| Title of Invention | "AN APPARATUS FOR MAKING A STERILIZED ARTI CLE FROM A NON-STERILIZED ARTICLE BY USING HYDROGEN PEROXIDE VAPOR" |
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| Abstract | An apparatus and process for hydrogen peroxide vapor sterilization of medical instruments and similar devices make use of hydrogen peroxide vapor released from an inorganic hydrogen peroxide complex. The peroxide vapor can be released at room temperature and atmospheric pressure; however, the pressure used can be less than 50 torr and 5 the temperature greater than 86°C to facilitate the release of hydrogen peroxide vaper. Preferred hydrogen peroxide complexes for use in the invention include Na4P207-3H202 and KH2P04-H202. The heating rate can be greater than 5°C. Optionally, a plasma can be used in conjunction with the vapor. |
| Full Text | Background of tne Invention Frold of the invention This invention relates to an apparatus and prococs for wofr hydrogen peroxide sterilization of articles such as medical instruments, and more particularly to the use of an inorganic hydrogen peroxide complex for such a process. Description of the Related Art Medical instruments have traditionally been sterilized using either heat, such as is provided by steam, or a chemical, such as formaldehyde or ethylene oxide in the gas or vapor state. Each of these methods has drawbacks. Many medical devices, such as fiber optic devices, endoscopes, power tools, etc. are sensitive to heat, moisture, or both. Formaldehyde and athylene oxide are both toxic gases that pose a potential hazard to healthcare workers. Problems with ethylene oxide are particularly severe, because its use requires long aeration times to remove the gas from articles that have been sterilized. This makes the sterilization cycle time undesirably long. In addition, both formaldehyde and ethylene oxide require the presence of a substantial amount of moisture in the system. Thus, devices to be sterilized must be humidified before the chemical is introduced or the chemical and moisture must be introduced simultaneously. Moisture plays a role in sterilization with a variety of other chemicals in the gasor vapor state, in addition to ethylene oxide and formaldehyde, as shown in Table 1. Table 1 ve Humidity Requirements Literature for Optimal Efficacy Reference 25-50% 1 25-50% 1 7590% 2 >75% 1 80-90% 3 60-80% 4 40-70% 1 >75% 1 40-80% 5 Chemic3l Ethylene oxide Propylene oxide Ozone Formaldehyde Glutaraldehyde Chlorine dioxide Methyl bromide /? Pr opiolactone Peracetic acid 1. Bruch, C. W. Gaseous Sterilization, Ann. Rev. Microbiology 15:245 262 (1961). 2. Janssen, D. W. and Schneider, P.M. Overview of Ethylene Oxide Alternative Steiilization Technologies, Zentralsterilisation 1:16-32 (1993). 3. Bovallius, A. and Anas, P. Surface-Decontaminating Action of Glutaraldehyde in the Gas-Aerosol Phase. Applied and Environmental Microbiotcgy, 129-134 (Aug. 1977J. 4. Knapp, J. E. et al. Chlorine Dioxide As a Gaseous Sterilant, Medical Device & Diagnostic Industry, 48-51 (Sept. 1986). 5. Partner, D.M. and Hoffman, R.K. Sporicidal Effect of Peracetic Acid Vapor, Applied Microbiology 16:17821785 11968). -2- Sterilization using hydrogen peroxide vapor has been shown to have some advantages ever other chemical sterilization processes (SOB, e.g., U.S. Pat. Nos. 4,169,123 and 4,169,124), and the combination of hydrogen peroxide with a plasma provides additional advantages, as disclosed in U.S. Pat. 4,543,878. In these disclosures the hydrogen peroxide vapor is generated from an aqueous solution of hydrogen peroxide, which ensures that there is moisture present in the system. These disclosures, together with those summarized in Table 1, teach that moisture is required for hydrogen peroxide in the vapor phase to be effective or to exhibit its maximum sporicidai activity. However, the uss of aqueous solutions of hydrogen peroxide to generate hydrogen peroxide vapor for sterilization may cause problems. At higher pressures, such as atmospheric pressure, excess water in the system can cause condensation. Thus, one must reduce the relative humidity in a sterilization enclosure before introducing the aqueous hydrogen peroxide vapor. The sterilization of articles containing diffusion-restricted areas, such as long narrow lumens, presents a special challenge for hydrogen peroxide vapor that has been generated from an aqueous solution of hydrogen peroxide, because: 1. Water has a higher vapor pressure than hydrogen peroxide and will vaporize faster* than hydrogen peroxide from an aqueous solution. 2. Water has a lower molecular weight than hydrogen peroxide and will diffuse faster than hydrogen peroxide in the vapor state. Because of this, when art aqueous solution nf hydrogen peroxide is vaporized, the water reaches the items to be sterilized first and in higher concentration. The water vapor therefore restricts penetration of hydrogen peroxide vapor into diffusion restricted areas, such as small crevices and long narrow lumens. Removing water from the aqueous solution arid using moie concentrated hydrogen peroxide can be hazardous, due to the oxidizing nature of the solution. U.S. Patents 4,642,165 and 4,744,951 attempt to solve this problem. The former discloses metering small increments of a hydrogen peroxide solution onto a heated surface to ensure that each increment is vaporized before the next increment is added. Although this helps to eliminate the difference in the vapor pressure and volatility between hydrogen peroxide and water, it does not address the fact that water diffuses -aster than hydrogen peroxide in the vapor state. The latter patent describes a process for concentrating hydrogen peroxide from a relatively dilute solution of hydrogen peroxide and water and supplying the concentrated hydrogen peroxide in vapor form to a sterilization chamber. The process involves vaporizing a major portion of the water from the solution and removing the water vapor produced before injecting the concentrated hydrogen peroxide vapor into the sterilization chamber. The preferred range for the concentrated hydrogen peroxide solution is 50% to 80% by weight. This process has the disadvantage of working with ' solutions that are in the hazardtsus range; i.e., greater than 85% hydrogen peroxide, and also does not remove all of the water from the vapor state. Since water is still present in the solution, it will vaporize first, diffuse faster, and reach the items to be sterilized first. This effect will be especially pronounced in long narrow lumens. U.S. Pat. 4,943,414 discloses a process in which a vessel containing a small amount of a vaporizable liquid sterilaot solution is attached to a lumen, and the sferilant vaporizes and flows directly into the lumen of the article as the pressure is reduced during the sterilization cycle. This system has the advantage that the water and hydrogen peroxide vapor are pulled through the lumen by the pressure differential that exists, increasing the sterilization rate for -3- lumens, but it has the disadvantage that the vessel needs to be attached to each lumen ;o be sterilized. In addition, water is vaporized faster and precedes Hie hydrogen peroxide vapor into the lumen. U.S. Pat. No. 5,008,106 discloses that a substantially anhydrous complex of PVP and H]0, is useful for reducing the microbial content of surfaces. The complex, in the form of a fine white powder, is used to form ' HjO; is released upon contact with water present on the surfaces containing the microbes. Thus, this method too requires the presence of moisture to effect sterilization. Ceilain inorganic hydrogen peroxide complexes have been reported including examples within the following classes: alkali metal and ammonium carbonates, alkali metal oxalates, alkali metal phosphates, alkali metal pyrophosphates, fluorides and hydroxides. U.S.S.fl. patent document No. SU 1681860 (Nikolskaya et al.) discloses that surfaces can be decontaminated, although not necessarily sterilized, using ammonium fluoride peroxohydrate (NH"F#H?0;). However, this inorganic peroxide complex provides decontamination only within the very narrow temperature range of 70-86°C. Even within this range, decontamination times were quite long, requiring at least two hours. Additionally, it is known that ammonium fluoride decomposes to ammonia and hydrofluoric acid at temperatures above 40°C. Due to its toxicity and reactivity, hydrofluoric acid is undesirable in most sterilization systems. Moreover, Nikolskaya et at disclose that despite the release of 90% of its hydrogen peroxide at 60°C, NH4F"H:0: is ineffective at decontamination of surfaces at this temperature. Thus, it appears that a factor other than hydrogen peroxide is responsible for the decontamination noted. Hydrogen peroxide is capable of forming complexes with both organic and inorganic compounds. The binding in these complexes is attributed to hydrogen bonding between electron rich functional groups in the complexing compound and the peroxide hydrogen. The complexes have been used in commercial and industrial applications such as bleaching agents, disinfectants, sterilizing agents, exidizing reagents in organic synthesis, and catalysts for free-radical mduced polymerization reactions. Generally, these types of compounds have been prepared by the crystallization of the complex from an aqueous solution. For example, urea hydrogen peroxide complex was prepared by Lu et at. U, An. Chem. Soc. 63(11:1507-1513 (1941)) in the liquid phase by adding a solution of urea to a solution of hydrogen peroxide and allowing the complex to crystallize under the proper conditions. U.S. Pat. No. 2,986,448 describes the preparation of sodium carbonate hydrogen peroxide complex by treating a saturated aqueous solution of N3jC03 with a solution of 50 to 90% H:O; in a closed cyclic system at 0 to 5°C for 4 to 12 hours. More recently, U.S. Pat. No. 3,870,783 discloses the preparation of sodium carbonate hydrogen peroxide complex by reacting aqueous sclutions of hydrogen peroxide and sodium carbonate in a batch or continuous crystallizer. The crystals are separated by filtration or centrifugation and the liquors used to produce more sodium carbonate solution. Titova et al. \Zhvmal Neorg. Khim., 30:2222-2227, 1985) describe the synthesis of potassium carbonate peroxyhydrate(K,C03*3H;0;) by reaction of solid potassium carbonate with an aqueous solution of hydrogen peroxide at low temperature followed by crystallization of the complex from ethanol. These methods work well for peroxide complexes that form stable, crystalline free flowing products from aqueous solution. -4- U.S. Pat. HQS. 3,376,110 and 3,480,557 disclose the preparation of a complex of hydrogen peroxide with a polymeric Nvinylheterocyclic compound (PVP) from aqueous solution. The resultant complexes contained variable amounts of hydrogen peroxide and substantial amounts of water. U.S. Pat. No. 5,008,093 teaches that free-flowing, stabte, substantially anhydrous complexes of PVP and H,0, could bo obtained hy reading a suspension of PVP and a solution ' of HJOJ in an anhydrous organic solvent like ethyl acetate. More recently, U.S. Pat. No. 5,077,047 describes a commercial process for producing the PVP-hydrogen peroxide product by adding finely divided droplets of a 30% to 80% by weight aqueous solution of hydrogen peroxide to a fluidized bed of PVP maintained at a temperature of ambient to 60DC. The resultant product was found to be s stable, substantially anhydrous, free flowing powder with a hydrogen peroxide concentration of 15 to 24%. U.S. Pat. No. 5,030,380 describes the preparation of a solid polymeric electrolytic complex with hydrogen peroxide by first forming a complex in aqueous solution and then drying the reaction product under vacuum or by spray drying at a low enough temperature to avoid thermal degradation sf the product. Titova 2t al. {Ross. J. tnorg. Cheat., 40:384-387, 1995) formed a Na4Pj07*3Hj0j complex by mixing N3,P;Q;'1O H;D with a 30-90% HjO2 solution followed by vacuum drying. The complex was observed to partially decompose under isothermic exposure for two hours at 120°C and 14Q°C. All of these previous methods of preparing hydrogen peroxide complexes use solutions of hydrogen peroxide. Either the complex is formed in a solution containing hydrogen peroxide or droplets of a hydrogen peroxide solution are sprayed onto a fluidized bed of the reactant material. Vapor phase and gas phase reactions are well known synthesis methods. For example, U.S. Pat. No. 2,812,244 J discloses a solid-gas process for dehydrogenation, thermal cracking, and d&methanation. Fujimoto et al. U Catalysis, 133:370-382 (1992)) described a vapor-phase carsoxylation sf methane!. Zeilers et al. {Anal Chem.t 82:1222-122? (1990)) discussed the reaction of styrene vapor with a square plannar organoplatinum complex. These prior art vapor- and gas-phase reactions, however, were not used to form hydrogen peroxide complexes. Summary of the Invention One aspect of the present invention relates to an apparatus for hydrogen peroxide sterilization of an article. This apparatus includes a container for holding the article to be sterilized, and a source of hydrogen peroxide vapor in fluid communication with the container. The source includes an inorganic hydrogen peroxide complex which does not decompose to form a hydrohalic acid, and is configured so thai the vapor can contact the article to effect1 sterilization.. The apparatus optionally includes a breathable barrier. The source of hydrogen peroxide vapor can be located within the container, or can also be located in m enclosure which is in fluid communication with the container. If art enclosure is provided, a valve can be included between the enclosure and the container. A heater can be included which is adapted to heat the inorganic hydrogeu peroxide complex. Where the complex is within the container, ? heater ten also be adapted to heat the container. Alternatively, where an enclosure is provided containing the peroxide complex, a heater zm be adapted to heat the enclosure. Thus, a preferred embodiment encompasses three heaters, one for heating each of the container, the complex and the enclosure. Another optional element of the apparatus is a pump to evacuate the container. If an enclosure is provided, the pump can be adapted to evacuate the container and the enclosure, preferably independently. Thus, ths apparatus ego also include tws pumps, one adapted iu evacuate the container and a second pump adapted to evacuate the enclosuie. A vent valve is also optionally included which is adapted to vent the container. I! an enclosure is included, a first vent vaiva can be adapted to vent the container and a second vent valve can be adapated to vent the enclosure independently of the first vent valve. Stil! another optional component of the apparatus is a mechanism for generating a plasma. The plasma can be generated within the container or outside thereof. A variety of complexes can be used. The complex is preferably in a solid phase. In one embodiment, the complex is a hydrogen peroxide complex of a phosphate or condensed phosphate salt. In other embodiments, the complex is a hydrogen peroxide complex of an oxalate salt, a carbonate salt, a suifate salt or a silicate salt. Another aspect of the present invention relates to 8 method for hydrogen peroxide vapor sterilization of an article. This method includes the step of contacting the article with hydrogen peroxide vapor released from en inorganic hydrogen peroxide complex to sterilize the article. The peroxide complex u^ does not decompose to a hydrohafic acid. Preferably, the complex has less than 10% water and is performed at a temperature of 25°C m lesi When using certain complexes, the complex can be heated so as to facilitate the release of ths vapor from the complex, for many of these complexes, the complex is preferably heated to a temperature greater than 85°C. Preferably, ths heating is performed at a rate of at least 5*Cfcntnute, more preferably at least 10uClminute, sti more preferably at least 50°C/minute] and most preferably at a rate of at least lOQQ'C/mintfte; In one ambodtment, the heating is accomplished by contacting tha complex with a prs-haated heater. Ths method can be performed at atmospheric or subatmotpheric pressure. In certain embodiments, the container is'evacuated before introducing the vapor into the container. If the container is evacuated, it is preferably brought to a pressure of less than 50 torr, more preferably less than 20 torr, and most preferably less than 10 torr. The peroxide complex can be provided within an enclosure, in which case, the pressures of the container and the enclosure can be the same Of different The evacuating step is preferably conducted before the step of contacting the article with the vapor. An optional step is generating a plasma around the article after introducing the vapor into the container. Such a plasma can be generated inside the container or the plasma can be generated outside the container and flowed inside the container and around the article. Other optional steps are pressure pulsing of the vapor during the contacting step, or venting to a pressure less than or equal to atmospheric pressure. A variety of inorganic complexes can be used, in one preferred embodiment, ths complex is a complex of a phosphate or condensed phosphate salt with hydrogen peroxide, such as a salt of potassium or sodium, magnesium or calcium, (n this embodiment, one preferred complex is a hydrogen peroxide complex with Na^PjQ,, preferably one with two or more molecules of hydrogen peroxide, more preferably still Na,P;0,"3H;0,. Other preferred complexes are a hydrogen peroxide complex with NaaP04, Na^HPO* Na5P30,0, KjPO* K"P,O, (especially one having two or more H20; molecules), K,HPG,, KH;P0, (especially KH,P04>H?0J) and Ca?P2O7, Mp,jP,O7. In another embodiment, the inorganic compfex is a complex of hydrogen peroxide with an oxalate salt. A preferred oxalate salt complex is a hydrogen peroxide complex with KJCJO*, especially K?Cj04"H,Q,. The inorganic complex can also be a complex of hydrogen peroxide with 8 carbonate salt, such as one sf sodium, potasssium or rubidium. Preferred carbonat salt complexes include N3jC03 (especially NajC03"U-H,0?), KjC03, NaHCO> KHCO3 and Rb^COj. In another embodiment, the complex is a complex of hydrogen peroxide with a suifate salt, such as a sodium or potassium salt thereof. Preferred sultate salt complexes include ¦6 complexes of hydrogen peroxide with Na?S04 and K;S04. Still another embodiment is where the inorganic complex is a complex of hydrogen peroxide with a silicate salt, such as a sodium sal; thereof. Preferred silicate salt complexes include complexes of hydrogen peroxide with Na3Si03 or Na,fci3O,. Many of the preferred complexes, and others, release hydrogen peroxide at atmospheric pressure and room temperature. However, for some complexes the peroxide is released at a pressure less than atmospheric pressure. In an alternative embodiment, the contacting step includes the hydrogen peroxide from a second source thereof. The second source can be a second hydrogen peroxide complex, including an organic hydrogen peroxide complex. In some embodiments, a mixture of hydrogen peroxide complex provides the source of peroxide vapor. This mixture C3n be either a physical mixture or 3 chemical mixture, as those terms srs defined herembetow. A further aspect of the invention relates to another method for hydrogen peroxide vapor sterilization of an. article. This method includes contacting the article with hydrogen peroxide vapor released from a N3"P207 hydrogen peroxide complex by heating the complex so as to produce hydrogen peroxide vapor that cart contact and sterilize the article. !n a preferred embodiment, the N^PjO, complex is Na4Pj07-3HjQ7. The contacting step can be conducted at atmospheric pressure, or the container can be evacuated, such that when the vapor i& into the container, the container is at a pressure of less than 50 torr. The complex can also be heated to a temperature of approximately !75°C to effectively release the vapor. The article can be placed into a container prior to the contacting step. Still another aspect of the invention is yet another method for hydrogen peroxide sterilization of an article. This method includes placing the article in a container, placing a hydrogen peroxide complex with an inorganic salt which does not decompose to form a hydrchalic acid into vapor communication with the container, and allowing the container to r stand at a temperature below about 70°C for a time sufficient to release hydrogen peroxide vapor from the complex to effect sterilization of the article. The container can be any of a number of types of containers, including a pouch, chamber or room. In one preferred embodiment, the inorganic salt is a salt of a phosphate or condensed phosphate. In other embodiments, the inorganic salt is a salt of an flxalate, a carbonate, a sulfate or a silicate. In certain embodiments of this aspect of the invention, the container is allowed to stand at a pressure less than atmospheric pressure and/or at a temperature below about 4Q°C. In certain embodiments, the complex is heated to a temperature greater than 23°C to facilitate release of the vapor. The hydrogen peroxide complex can come in a variety of forms, including a powder and a tablet. In some embodiments, the hydrogen peroxide complex is within an enclosure. If an enclosure is provided, the enclosure can he either inside or outside the container. The enclosure can be selectively separated from the container by a valve, and in some embodiments can be detached from container. The container can be sealed, preferably with a gas permeable material. Preferred gas permeable materials include TVVEKm, CSR wrap and paper. An optional step is exposing the article to plasma, and when a detachable enclosure is provided, the article is preferably exposed to plasma after detaching the enclosure from the container. Yet one more aspect of the present invention relates to a method for hydrogen peroxide sterilization of an article having an exterior and a narrow lumen therein. This method includes connecting a vessel containing a hydrogen peroxide complex to the lumen at the article, placing the article within 3 container, evacuating the container, and contacting the lumen of the article with hydrogen peroxide vapor released from the hydrogen peroxide complex. The hydrogen peroxide ¦7- compJojf is a complex which docs not ducomposo to farm e hydrohalic acid. Any of a number of such complexes can be used, such as a complox of a phosphate or condensed phosphate salt an oxalate salt, a carbonate salt, a tulfata salt u:\tl a s:IJc*jto sail. Optionally. Urn 0*tuner of ihu orticlu can bo contact with a second source of sterilant, which can Li. j;,y uf o rumour ol suiuLiiQ siunkinis, such as ihu samu hydrogon poroxide complex as in the vessel, a different 5 liyirorjen peroxide complex as in the vesiul, Kguid hydrogon peroxide or chlorine dioxide. Another optional step is to expose the arnclo to plasma. Brief Description of tte Accompanying Drawings FIGURE 1 is a schematic of a vapor s:erili;ation apparatus or the present invention. FIGURE 2 is a schematic of a vapor sterilization apparatus of the present invention which includes an electrode 10 winch is optionally used to generate plasma. FIGURE 3A is a schemaiie of a device which can be used for heating peroxide complexes. FIGURE 3S is a schematic of a preferred container for holding the peroxide sourpe for sterilization according !c UIIJ present invention. FIGURE 4 is d (jraijli ^UJJ.Ctun; tiiy luiujse uf liytlfogun purondo vapor from a vacuum unstable non-aqueous lii (jlvcine anhydride peroxide compiex. FIGURE 5 is a schematic cf a pressure control system of a differential scanning calorimeter (DSC) used to deturrr.ir.c hydrogen peroxide- release or decomposition properties of inorganic peroxide complexes according to the prasent invention, FIGURE 6 is a graph show my the effect of pressure on hydrogen peroxide release from potassium oxalate /3 ptfyjticJ;.1 complex with one small tiolu on a lid coveiinrj the complex. FIGURE 7A is a schematic view of a bellows for injecting peroxide vapor into a chamber in accordance with l!;e ;;i'i.icnt invention before inircdiiCiion uf tfic peroxide vapor. FIGURE 78 is a schematic view of the bellows of FIGURE 7A showing a heated plate in contact with a peroxide co(t:;:!i.'x duriny introduction. 25 FIGURE 8 is a schematic view of a sterilization chamber and heating appratus for inorganic hydrogen peroxide complexes. FIGURE 9 is a schematic view of a diffuso packaged layer of hydrogen peroxide complex for use in vapor sterilisation. FIGURE 10 shows the effect cf an open aluminum pan and a pan with two holes on a lid covering the complex 2'i on ik USC curves cf K7CrOj'HjC; at aimcspU'nc pressure. FIGURE 11A is a DSC prohle of No,P70,-2H70; and Na,P;0,-3H:02 at 760 torr. o FIGURE 11B is a DSC profile o! N34P,0,-4H,C, at 760 tcr. FIGURE 12 is a OSC profile of NdjP04-5Hj0, at 760 torr. 7 lorr and 0.35 torr. FIGURE 13 shows DSC profiles of Na.HI'tVIHjO, and Na,HP04-2Hj0, at 760 torr. J^ HGUHE 14 shows a DSC piuhlu of NjiHjO.u-HjO, at 760 torr. FIGURE 15 shows a DSC profile of K3P04-3.34H?0, at 760 torr, 7 torr and 1 torr. -8- FIGURE 16 is a DSC profile of K^O^HjO, at 760 torr and 7 torr. FIGURE 17 shows a DSC profile of K,HP04-3.15Hj0r at 760 torr and at 1 torr. FIGURE 18 shows a DSC profile of KH:P04-H;0; at 760 torr. FIGURE 19 shows a DSC profile of Na,C03-1.5H:02 at 7G0 torr and at 7 torr. FIGURE 20 shows a DSC profile of Ca;P2C7"3.42H;07 at 760 torr. FIGURE 21 is a DSC profile of MgjP,07"4.60HiO, at 760 torr and 7 torr. FIGURE 22 is a DSC profile of NajSO^USHjO, at 760 torr. FIGURE 23 is a DSC profile of M04"0.62H:0; at 760 torr. FIGURE 24 is a DSC profile of Na;Si03*2.15HI0; at 760 torr, 1 torr and 0.5 torr. FIGURE 25 is a DSC profile of Na7Si307"0.68H?0, at 760 torr. Detailed Description of the Invention Hydrogen peroxide sterilizers that have been used in the past invariably used an aqueous solution of hydrogen peroxide as their source of sterilant. These sterilizers have disadvantages caused by the presence of water in the system. At higher pressure, such as atmospheric pressure, the excess water in the system can cause condensation. This requires that an extra step be performed to reduce the relative humidity of the atmosphere in an enclosure to be sterilized to an acceptable level before the aqueous hydrogen peroxide vapor is introduced. These sterilizers also have drawbacks caused by the facts that water, having a higher vapor pressure, vaporizes more quickly than hydrogen peroxide from an aqueous solution; and water, having a lower molecular weight, diffuses faster than hydrogen peroxide. When a medical device Of trie like is enclosed in a sterilizer, the initial sterilant that reaches the device from the hydrogen peroxide source is diluted in comparison to the concentration of the source. The dilute sterilant can be a barrier to sterilant that arrives later, particularly if rhe device being sterilized is an article, such as an endoscope, that has narrow lumens. Using a concentrated solution of hydrogen peroxide as the source in an attempt to overcome these drawbacks is unsatisfactory, because such solutions are hazardous. In the present invention, the shortcomings of hydrogen peroxide sterilizers of the prior art are overcome by using a substantially non-aqueous (i.e., substantially anhydrous) source of hydrogen peroxide which releases a substantially non-aqueous hydrogen peroxide vapor. In a preferred embodiment, the substantially non-aqueous hydrogen peroxide vapor is produced directly from a substantially nonaqueous hydrogen peroxide complex. However, the substantially non-aqueous hydrogen peroxide vapor can also be generated from an aqueous complex which is processed during* vaporization to remove water, such as under vacuum. Thus, where an aqueous hydrogen peroxide complex is used, the aqueous complex can be converted to a substantially non-aqueous hydrogen peroxide complex while carrying out the process of the present invention. Preferably, the substantially non-aqueous hydrogen peroxide complexes contain less than about 20% water, more preferably nc more than about 10% water, still more preferably no more than about 5% water, and most preferably no more than about 2% water. As is apparent from the preferred percentages of water in the substantially non-aqueous hydrogen peroxide complexes used in the present invention, as provided above, the most preferred hydrogen peroxide complex and the peroxide vapor generated therefrom are substantially water free. Nevertheless, as is also apparent from these figures. 9- some water can be present in the system. Some of this water may derive from the decomposition of hydrogen peroxide to form W3tsr and oxygen as byproducts and some hydrogen binding of this water to the complex can occur. The effect of water was measured in a series of tests, with a sterilization chamber maintained at various relative humidities. Test conditions were those described in Example 1, below, with spores supported on stainless steel (SS) blades in 3mm x 50cm stainless steel lumens. As shown in Table 2, under the test conditions, 5% relative humidity has no effect on efficacy but 10% relative humidity decreases the sterilization rate. This example shows that small amounts of moisture can be allowed in the system with the hydrogen peroxide generated from the non-aqueous peroxide complex and the presence of water in the system can be overcome by increasing the exposure time. Table 2 Effects of Relative Humidity OR Efficacy SS Blades in 3mm x 50cm SS Lumens 5 10 15 30 Diffusion Time Sterility Results (Positive/Samples) t%RH 013 5%RH 0/3 !0%RH 3/3 0/3 0/3 2/3 0/3 0/3 0/3 0/3 0/3 0/3 A primary criterion for the composition of the hydrogen peroxide seurce is the relationship between ks stability and hydrogen peroxide evaporation rate as a function of temperature and pressure. Depending on the parameters of the sterilization process-e.g. pressure, temperature, etc.-3 higher sr lower peroxide evaporation fats may be preferred, and heating the peroxide source may or may not be required. The need for heating of the peroxide complex depends on the tfapor pressure of the complex. Same peroxide complexes have 3 sufficiently high vapor pressure that a significant amount of hydrogen peroxide vapor can be released without heating the complex. In general, heating the complex increases the vapor pressure of hydrogen peroxide and accelerates the release of peroxide from the complex. To provide a desirably high evaporation rate, the source should preferably have a large surface area. Thus the source may be a fine powder or a coating on a material that has a large surface area. Of course, safety, availability, and cost of the material are also important criteria. The release of hydrogen peroxide from hydrogen peroxide complexes with urea, polyvinylpyrrolidone, nylon-6, glycine anhydride, and 1,3 dimethyl urea were evaluated. The complexes of hydrogen peroxide with urea, poiyvinylpyfrolidone, nylort-8, and giycine anhydride are solids. The 1,3 dimethyl urea peroxide complex is a liquid. The glycine anhydride hydrogen peroxide complex is a less stable complex under reduced pressure than the other complexes evaluated, and under vacuum conditions, most of the hydrogen peroxide can be released from the complex without the need for additional heating. Urea hydrogen peroxide complex is available in tablet form from Ruka Chemical Corp., Ronkonkoma, NY and in powder form from Aldrich Chemical Co., Milwaukee, Wl. This complex is also known as urea peroxide, hydrogen ¦10- peroxide urea complex, peroxide urea, peroxide urea adduct, urea peroxide adrfuct. percarbamide, carbamide perhydrate, and carbamide peroxide. As used herein, the term "urea peroxide" encompasses all of the foregoing terms. The polyvinylpyrrolidone hydrogen peroxide complex (PVP-H,O,t can be prepared by the method disclosed in International Application Pub. No. WO 92/17158. Alternatively, the complexes with PVP, with nylon-6, with 1,3 dimethylurea and with glycine anhydride, as well as with other organic and inorganic compounds can be prepared by the method disclosed m detail below. Achieving suitable evaporation rates of anhydrous peroxide vapor from the source may be facilitated by elevated temperatures and/or reduced pressure. Thus, a heater for the peroxide source and/or a vacuum pump to evacuate the sterilization chamber are preferably a part of the sterilizer. Preferably, the source is covered with a layer of gas permeable material, such as TWER™ nonwoven polyethylene fabric, nonwoven polypropylene such as SPUNGUARO™, or similar material, which permits the peroxide vapor to pass but not the peroxide complexing material. Perforated aluminum or other suitable perforated material could also be used as a cover. '¦ FIGURE 3A shows a device 80 that can be used to measure release of hydrogen peroxide from hydrogen peroxide complexes under various temperature conditions. In this device, an aluminum pan 90 is covered with a gas permeable layer 92, such as a layer of medical grade TYVEK". The pan 90 is placed on top of a heating pad 94 which is placed in a pyrex pan G6. A thermocouple thermometer 98 is placed on the outside of the pan 90 approximately 1 cm from the bottom thereof. In a preferred embodiment, aluminum pan 90 is open to the atmosphere to allow greater release of the postassium oxalate hydrogen peroxide complex at atmospheric pressure. A preferred container 99 for holding the peroxide source is illustrated in FIGURE 3B. The container 99 comprises E metal plate 100, e.g. an aluminum plate, with an optional attached heater used to heat the solid peroxide complex. A temperature monitor 101, such as a thermometer, can be placed on tho plate 100 to monitor the temperature. Ths peroxide complex is placed directly on the plate 100. Alternatively, in order to provide even heating of all the peroxide complex, the peroxide complex can be placed between one or more aluminum screens 102, 104 placed on top of the plate 100. The aluminum screens 102, 104 provide greater surface area and even heating of the complex when larger amounts of peroxide complex are being used. The peroxide complex, or the screen or screens 102, 104, are then covered with a gas permeable layer 106, such as"a layer of medical grade TYVEK1" or SPUNGUARD™, so that the hydrogen peroxide released from the complex passes through the covering 106 before diffusing into the rest of the chamber. A perforated aluminum plate 108 is optionally placed on top of the TYVEK™ or SPUNGUARDV layer 106 to provide pressure to keep the complex in contact with the heated plate 100 and tc ensure even heating of the peroxide complex. The device just described provides even heating of the complex, which results in an increased amount of hydrogen peroxide vapor being released from the peroxide complex. FIGURE 1 depicts a schematic of a hydrogen peroxide vapor sterilization apparatus of the present invention. Chamber 10 holds an article 12 which is to be sterilized and which, for convenience, is placed on shelf 14. Ooor 16 provides access to the interior of chamber 10. A non-aqueous source of hydrogen peroxide 18 is depicted on optional heater 20, which is controlled by temperature controller 22. The peroxide concentration can be monitored by optional .11- monitor 24. If desired, chamber 10 can be evacuated using pump 28; however, sterilization can also be accomplished at atmospheric pressure. The container that holds the articles to be sterilized can be a conventional sterilization chamber, which is evacuated, or it can be a container for a room) at atmospheric pressure. The time required to sterilize the articles depends on the nature, number and packaging of the articles and their placement in the chamber. Alternatively, it may be the chamber itself {or an entire room} that is being sterilized. In any case, optimum sterilization times can be determined empirically. The use of pressure poising to enhance the penetration and antimicrobial activity of stedlant gases, which is well known in the sterilization art, can also be applied to the non-aqueous hydrogen peroxide process. One exemplary process of pressure pulsing, which can be adapted for use in connection with the methods and apparatuses described herein, is described in U.S. Patent No. 5,527,508. As described in additional detail hereinbelow, plasma can also be used to further enhance activity and/or to remove residuals. At the conclusion of the sterilization process excess hydrogen peroxide can be removed from devices that have an affinity for peroxide by exchanging the air in contact with the devices. This can be accomplished by flowing warm air over the devices for an extended time or by evacuating the chamber. Articles that have previously been sterilized by exposure to hydrogen peroxide vapor may also be exposed to the plasma to remove residual hydrogen peroxide that may remain on the articles. Since the hydrogen peroxide is decomposed into non-toxic products during the plasma treatment, the sterilized articles may be used without the need for any additional steps. It may be desirable to isolate the peroxide source from the sterilizer after the peroxide vapor is released to avoid reabsorpiion of the vapor or, when a plasma is used, to avoid exposing the source to the plasma. Isolation is also advantageous when the complex used is not stable under vacuum. Isolation can be accomplished using valves or other isolating devices well known in the art. FIGURE 2 depicts a schematic of a hydrogen peroxide plasma sterilization system of the present invention. Sterilization can be achieved with or without the use of plasma. The plasma can be used to enhance the sporicida! activity of the peroxide vapor, and/or to remove any residual hydrogen peroxide remaining on the sterilized articles. . Sterilization is carried out in chamber 3Q, which includes a door or opening 32 through which articles to be sterilized can be introduced. The chamber 3D includes an autlet 34 to a vacuum pump 36, through which the chamber can be evacuated. The outlet 34 contains a valve 38 to isolate the chamber from the vacuum pump 36. The chamber 30 also includes an inlet 40 attached to sn enclosure 42 that contains the hydrogen peroxide complex. Inlet 40 contains a valve 44 that allows enclosure 42 to be isolated from the chamber. The sterilization system also contains an inlet 41 which connects the enclosure 42 and the vacuum pnmp 38: which contains a valve 43. This system allows the simultaneous evacuation of both enclosure 42 and chamber 30, or the independent evacuation of either enclosure 42 or chamber 30. Evacuation is controlled by the opening and closing of the valves 38, 44, and 43. As will be apparent to one having ordinary skill in the art, two pumps, one for each chamber, could also be employed in this system. -12 The enclosure 42 contains an optional heater 49 attached to a temperature controller 46 to control the temperature of the hydrogen peroxide complex. The hydrogen peroxide complex concentration in the vapor stats can is monitored by an optional peroxide monitor 48. The interior of the chamber contains a radio frequency (RF) electrode 50, to which is attached a matching network 52 and so RF power sypjjiy 54. A convenient form for ths sfeeffotis is a perforated cylinder, surrounding the samples and open at both end. The general operation of the presort! procass is as fsftows: 1. The articles 56 to be sterilized are placed in the chamber 30. 2. The chamber 30 may bs st atmospheric pressure or, alternatively, may fee evacuated to facilitate penstration of the hydrogen peroxide. Evacuation is accomplished by opening valve 38 and turning on vacuum pump 38. Alternatively, ostb tha chamber 30 and the enclosure 42 may ba svacuatad by opening valves 38 and 44, and/or 43. 3. The valves 38 and 43 are rissetf to isolate the vacuum pump 3S from ths chamber 30 and enclosure 42, and the valve 44 is opened. Hydrogen peroxide vapor is delivered into chamber 30 from the hydrogen peroxide source, which may se healed 15 facilitate the release si ths hydrsgen prsjttde vapor. Optionafiy, sir or m issft gas may also be added. 4. The articles 5S to be ster2sied are either treated with peroxide vapor tmtiJ sterilized er pretreated with peroxide vapor in the chamber 30 before plasma with sufficient power to slenlire is generated. If necessary, chamfagr 30 may be evacuated a! this time to facilitate generation of the plasma. The duration sf the prs-piasma holding period depends on the type of package used, the nsture and number af items to be sterilieed, and the placement of the items In iris chamber. Optimum times can be determined empirically. 5. The articles 56 arc subjected ts 3 plasma by applying pswer frsm the fiF power supply 54 to ike HF electrode 50. The RF energy used to generate the plasma may be pulsed or continuous. Trie articles 56 remain in the plasma for a period to effect complete steriiiration aadfsr to remove residua! hydrogen peroxide. In certain embsdimersts, 5 to 30 minutes of plasma is used. However, optimum tirntss can be determined empirically. When used in the present specification mi claims, the term "plasma" is intended to mdude any psrtion of tfts gas or vapor that contains electrons, ions, free radicals, dissociated and/or excited atoms or molecules produced as a result fif ars appJied electric fie&t wcfcdwg any accompanying radialiQR that might be produced. The apoiisd field may cover a broad frequency range; however, a radio frequency or microwaves are commonly used. The nan-aqueous hydrogss peroxide delivery system disclssBd in iris present invention can also be used with plasmas generated by the method disclosed in the previously msntioneo1 U.S. Pat, 4*643,876. Alternatively, it may be tissd with ptaias described to U.S. Patent 5,f 15,166 or 5,087,418, in which the article to be sterilized is located in 3 chamber that is separated from the plasms source. The device just described is particularly advantageous when using peroxide complexes that are not stable under vacuum. There are a* feast two possible methods that can he used to minhfttze the tess sf hydrogen psroxide during the vacuum stage, first, the small chamber can be evacuated independently. Second, if a small enough chamber is used, there is ns need to evacuate :ne smsii chsmfc-er af ait ¦13- Gne such uastabis non-aqueous peroxide complex is glyrirm anhydfide-p&foxide. This compound releases hydrogen peroxide vapor when placed under vacuum. FIGURE 4 is a graph illustrating the release of hydrogen peroxide vapor from glycine anhydride-peroxide complex under vacuum. The procedure used to release Ihe hydrogen peroxide from the glycine anhydride complex is as follows: (1) The main chamber 30 was evacuated with valves 43 and 44 closed. (2) The chamber containing the hydrogen peroxide complex 42 was evacuated with valves 33 and 44 closed and valve 43 open. (3) Valve 43 was closed and valve 44 was opened and hydrogen peroxide vapor was allowed to diffuse into chamber 30, As shown by the graph, hydrogen peroxide vapor is released from the mmpkt as the pressure is reduced, even without additional heating. As illustrated in FIGURE 4, release of peroxide vapor is significantly increased by heating the complex to a higher temperature. Thus, even unstable peroxide complexes are useful in the sterilization method of the present invention. The present invention provides at least four advantages over earlier hydrogen peroxide sterifealion systems: 1. The use of concentrated, potentially hazardous hydrogen peroxide solutions is circumvented. 2. The need to reduce beforehand the relative humidity of areas to be sterilized in arder to prevent condensation is eliminated. 3. Water is substantially eliminated from the systsm, so that there is little competition between water and hydrogen peroxide for diffusion into long narrow lumens. 4. The need to attach a special vessel to deliver sterilant gases into long narrow lumens can often he eliminated. That sterilization can be effected using hydrdgen peroxide vapor in the substantial absence of moisture is one of thg surprising discoveries of the present invention. The prior art teaches that the presence of water is required to achieve sterilization in chemical gas or vapor state sterilization processes. Advantageously, the present invention substantially eliminates water from the system, which results in faster, more efficient and effective sterilization. The sterilization efficacy of various rton-aqueaus hydrogen peroxide complexes was determined as described below in Examples 1-4. Example 1 Efficacy d3ta was obtained with hydrogen peroxide vapor released from substantially anhydrous urea peroxide, complex using Bacillus svbtllis var. fn/gsrj spores in metai and TEFION1" elastic lumens as the biological challenge. A. Test Procedures 1. Equipment Four grams of crushed hydrogen peroxide urea adduct tablet (Fluka Chemical Corp, Ronkonkoma, NY) were placed in an aluminum pan 90, as described in FIGURE 3A. the top of the pan 90 was covered with medical grade TYVEK™ 92 (a breathable spunbond polyethylene fabric) so that any hydrogen peroxide released from the complex would need to pass through the TYVEK™ covsring before diffusing into the rest of the chamber. The aluminum pan 80 was ' placed on a heating pad 94 in a pyrex dish 96 located in the bottom of an aluminum sterilization chamber (see FIGURE 1). The sterilization chamber, which had an approximate volume of 173 liters, also contained: ¦14 o A hydrogen peroxide monitor for measuring hydrogen peroxide concentration m the vapor phase. o A temperature controller for controlling the temperature of the heating pad. o An injection port through which liquid hydrogen peroxide could be injected into the chamber. o A metal shelf on which a plastic tray containing lumen devices were placed for testing. o Electrical resistance heaters on lhe exterior of the chamber walls, which maintained the chamber temperature at 45°C during the efficacy testings. 2. Biological Challenge and Test To evaluate the efficacy of the non-aqueous peroxide delivery system, a biological challenge consisting of 1.04 x 106 8. subtilis var. fniger} spores on a stainless steel scalpel blade was placed equally distant from each and of the stainless steel lumens of dimensions 3mm ID * 40cm length, 3mm 10 * 50cm length, and 1mm ID * 50cm length. These IQ's and lengths are typical for metal lumens used in medical devices. The compartment in the middle of each iumen that contained the biological test piece had the dimensions 13mm ID x 7.8cm length. In the biological testing with metal lumens, a total of 9 lumens were evaluated per test. These included 3 lumens from each of the 3 different sets of IP's and lengths available. Similar tests were conducted with a biological challenge consisting of 4.1 * 10* B, subtttis var. {niger} spores on a papef strip {8mm * 4mm Whatman #1 chromatography paper} located equally distant from the ends of TEFLON™ lumens of dimensions 1mm ID * 1 meter length, 1mm ID * 2 meter length, 1mm ID * 3 meter length, and 1mm ID * 4 mater length. The center compartment of these lumens that contained the biolcgrcal test piece had the dimensions 15mm ID * 7.8cm length. In the biological testing with TEflONrw lumens, a total of 12 lumens were evaluated per test, 3 lumens from each of the 4 different lengths available. The lumens containing the biological test samples were placed in a plastic tray that was then placed sn the shelf in the sterilization chamber. The chamber door was then closed and the chamber evacuated to 0.2 Torr pressure with a vacuum pump. The aluminum pan containing the hydrogen peroxide urea adduct was then heated to 80 to 81 °C for a period of 5 minutes, as measured by a thermocouple thermometer placed on the side wall of the aluminum pan approximately 1 cm from the Bottom of the pan. During this time the concentration of hydrogen peroxide in the chamber increased to 6mg(L as measured by the peroxide monitor. The biological test samples were exposed to the hydrogen peroxide vapor for periods of 5, 10, 15, 20, and 25 minutes. After exposure to the hydrogen peroxide vapor, the biological test samples were asepticaiiy'transferred into 15mL af trypticase soy broth containing 277 units of catalase to neutralize any hydrogen peroxide residuals that may remain on the test samples. All samples were incubated for 7 days at 32°C and observed for growth. Comparative studies were also conducted in which a 50% aqueous solution of hydrogen peroxide was injected into the sterilization chamber and vaporized from a heated injector fa heated metal surface). The volume of hydrogen peroxide solution injected produced a vapor phase concentration of hydrogen peroxide of Gmg/L. The test lumens and biological test samples used in these tests were identical to those used in the non-aqueous hydrogen peroxide tests. The handling of the biological test samples after exposure to the hydrogen peroxide was also identical. -15- B. Test Results The results of these tests with stainless steel and TEFLON1" lumens, which are presented in Tables 3 and 4, respectively, illustrate the advantages of the non-aqueous peroxide delivery system with both matai and non-metal lumens. Total kill of the bacterial spores was achieved within 5 minutes with the non-aqueous peroxide delivery system for the smallest ID and the longest lumens evaluated. At the same time, total kill was not achieved even after 25 minutes of diffusion time with the 50% hydrogen peroxide solution. Table 3 Aqueous/Non-Aqueaus Efficacy Comparison SS Blades in SS Lumens STERILITY RESULTS (POSITIVE/SAMPLES) SOURCE OF DIFFUSION PEROXIDE TIME mm) 3mm x 40cm 3mm x 50cm 1mm x 50cm 5 3/3 3/3 3/3 10 013 213 313 50% SOLUTION 15 1/3 1/3 1/3 20 0/3 0/3 1/3 25 0/3 0/3 1/3 5 0/3 0/3 013 10 0/3 0/3 0/3 UREA PEROXIDE 15 0/3 0/3 0/3 20 0/3 0/3 0/3 25 0/3 0/3 0/3 -16-Table 4 Aquaous/fJon-Aqueous Efficacy Comparison 8mm x 4mm Paper strip in TEFLON™ lumens STERILITY RESULTS {POSITIVE/SAMPLES} SOURCE OF DIFFUSION PEROXIDE TIME 10 313 3/3 3/3 313 50% SOLUTION 15 0/3 1/3 1/3 2/3 20 013 0/3 1/3 1/3 25 0/3 0/3 0/3 1/3 5 013 0/3 0/3 0/3 UREA 10 013 0/3 0/3 0/3 PEROXIDE 15 0/3 0/3 0/3 0/3 20 0/3 0/3 0/3 0/3 25 0/3 "0/3 0/3 0/3 The fact that rapid sterilization can be accomplished in the absence of substantial amounts of water is surprising, in 0§ht cf the fact that moisture has generally been present during chemical gas/vapor phase sterilization by various sterilants other than hydrogen peroxide. Since vapor phase hydrogen peroxide sterilization systems have used aqueous solutions of hydrogen peroxide, there has been moisturs present in those systems as well. To test the sterilization efficacy of various other peroxide complexes, the following experiments were performed. Examples 2. 3 and 4 The apparatus of Example 1 was used to test the efficacy of polyvinylpyrrolidone-hydrogen peroxide complex (Example 2)t nylon 6-hydrogen peroxide complex (Example 3), and 1,3 dimethylurea hydrogen peroxide complex (Example 4). These compounds were synthesized according to the method disclosed below in Examples 12 and 13. Test parameters were as follows: 17- Chamber Temp. Initial Pressure Wt. % of peroxide Peroxide concentration Wt. of complex used per cycle Temp to release peroxide Example 2 Exemole 3 Example 4 45°C 45°C 45°C 0-2 Terr 1.0 Torr 10 Torr 17% 10.5% 26.6% 6mg/L 6mg/L 6mg/L 18g 6g no°c 110°C 80°C In each case, spore supports were 6mm * 4mm paper substrates in plastic lumens and stainless steel blades in stainless steel lumens. The results of this efficacy testing appear below in Table 5. Table 5 Efficacy of Complexes with PVP, nylon 6, and 1,3 dimethylurea STERILITY RESULTS (POSITIVE/SAMPLES) With 5 Minutes Exposure TYPE OF SIZE OF LUMEN LUMENS Example 2 Example 3 Example 4 1mm * 1m 0/3 0/3 0/3 1mm x 2m 0/3 0/3 0/3 TEFLON* 1mm x 3m 0/3 0/3 0/3 1mm x 4m 0/3 0/3 0/3 3mm x 40cm 0/3 0/3 0/3 STAINLESS 3mm x 50cm 0/3 0/3 0/3 STEEL 1mm x 50cm 0/3 0/3 0/3 The results appearing in Table 5 show that each of the tested hydrogen peroxide complexes generate peroxide vapor which provides efficient sterilization after only five minutes exposure. The temperature required to release the hydrogen peroxide vapor from the solid complex which is shown above is the temperature measured by a thermocouple thermometer located on the outside of the aluminum pan approximately 1 cm from the bottom of the pan. Further testing using a thermometer, such as a fluoroptic thermometer, placed on the inside bottom of the pan indicated thai the temperature at the bottom of the pan was approximately 30-35°C higher, as described in Example 5 below. Thus, in the previous example, the temperature at the bottom of thft pan was approximately 110 115ftC when ti>e thermocouple thermometer read 80°C, and the temperature at the bottom of the pan was approximately 140 -145°C when the thermocouple thermometer read 110°C. ¦18- Example 5 To determine the temperature at the bottom of the aluminum pan used to contain the solid peroxide complex, a fluoroptic thermometer was taped to the inside bottom of the aluminum pan. An Omega™ thermocouple thermometer was placed on the outside of the aluminum pan approximately 1 cm from the bottom of the pan. Three different readings of the thermometers were taken. Each time the pan was heated to the desired temperature indicated by the thermometer placed on the side of the pan, allowed to cool, and then re-heated to the desired temperature. The recorded temperatures are listed below: Temp, at Temp. at bottom of pan 1 °C) side of pan 1st 2nd 3rd ava 80°C 100°C 110.9 131.5 110.6 132.6 110.6 132.0 110.7 132.0 The results show that the temperature at the bottom of the aluminum pan was approximately 30-35°C higher than the temperature indicated by the thermocouple thermometer located at the side of the pan. Further testing was performed to compare the efficacy data obtained using an aqueous and non-aqueous source of peroxide in an open (non-lumen) system. The experiments are described in detail below. Example 6 The apparatus of Example 1 was used with a biological challenge that consisted of 6.8 * 10s B. subtitis var (niger) spores on a 6mm * 4mm strip of Whatman #1 chromatography paper packaged in a TYVEK^/MYtAR™ envelope. (TYVEK™ is a gas permeable fabric made of polyethylene. MYLAR™ is a non-gas permeable polyester material). Packaged biological challenge strips were placed in the front, middle and back of a polyphenylene oxide tray that contained a flexible fiberoptic sigmoidoscope. The tray was placed in a polyphenylene oxide container that had one port in the top and two ports in the bottom to allow for diffusion. The four-inch diameter ports were covered with a breathable polypropylene packaging material (SPUNGUARD™ Heavy Duty Sterilization Wrap, Kimberly-Clark, Dallas, TX) to maintain the sterility of the contents of the container after sterilization. The container was placed in the apparatus of Example 1 and the pressure in the chamber was reduced to 0.2 Torr. The aluminum pan containing 2 grams of hydrogen peroxide urea adduct (Fluka Chemical Corp.) was then heated to 80 to 81 °C, as measured byVthermocouple thermometer placed on the outside of the aluminum pan approximately 1 cm from the bottom of the aluminum pan, for 5 minutes to provide 3mg/L of hydrogen peroxide vapor in the chamber. The biological test samples were exposed to the hydrogen peroxide vapor for periods of 5 and 10 minutes. After exposure the test samples were handled in the same way as were those in Example 1. Comparative studies were also conducted in which a 50% aqueous solution of hydrogen peroxide was injected into the sterilization chamber and vaporized from a heated injector. The volume of hydrogen peroxide solution injected produced a vapor phase concentration of 3mg/L The test configuration, the composition of the biological test samples, -19- md the handling of the biological test samples after exposure were all identical to those used in the non-aqueous iydrogen peroxide tests. The results of these tests are presented in Table 6. Source of Peroxide 50% solution Urea Peroxide Table 6 Aqueous/Non Aqueous Efficacy Comparison in Open System (Non-Lumen Test) Diffusion Sterility Time Results (min) (positive/samples) 5 3/3 10 3/3 5 1/3 10 0/3 The results of these tests demonstrate the greater efficacy of the non-aqueous when compared with the aqueous hydrogen peroxide process in an "open" system in which the biological sample was not placed in a lumen. Again, it was surprisingly discovered that a non-aqueous system provided superior sterilization even when diffusion of hydrogen peroxide into a long and narrow lumen is not required. This suggests that the mode of action of hydrogen peroxide is not the same for systems with and without water. Further testing was performed to determine the efficacy a non-aqueous peroxide vapor at normal, not reduced, pressure. This testing is detailed below. Example 7 Efficacy tests were conducted with the hydrogen peroxide vapor released from the urea peroxide complex in an open system at atmospheric pressure. In this test the biological challenge of 1.04 * 10*5. subtilis var. (niger) spores on the stainless steel surgical blades were packaged in a TYVEK™/MYLAR™ envelope. Packaged biological challenge blades were placed on the front, middle, and back of a polyphenylene oxide tray. The tray was placed in the apparatus of Example 1 and the chamber door was closed. The aluminum pan containing 4.0 gm of urea peroxide (Fluka Chemical Corp.) was heated to 80° to 81 °C, as measured by a thermocouple thermometer placed on the side of the aluminum oan approximately 1 cm from the bottom of the pan, for the duration of the test. The biological test samples were jxposod to the hydrogen peroxide vapor for periods of 5, 10, 20 and 30 minutes. After exposure the test samples were landled the same way as those in Example 1. The results of these tests are presented in Table 7 and demonstrate the sfficacy of the non-aqueous peroxide process in an open system at atmospheric pressure. ¦20- Table 7 Efficacy of non aqueous peroxide process in open system al atmospheric pressure Source of Peroxide Urea Peroxide Diffusion Time (minutes) Sterility Results (Dositivefsamoles) 5 3/3 10 1/3 20 0/3 30 0/3 Further tests were conducted to determine the approximate amount of peroxide released from the hydrogen peroxide urea complex at various temperatures. This testing is described in Example 8. Example 8 Urea peroxide powder, obtained from crushing the commercially available tablets IFIuka Chemical Corp.), was placed between two aluminum screens in an apparatus according to FIGURE 3B having dimensions 12.7 cm * 12.7 cm. The aluminum plate was then heated and the temperature was monitored using a thermometer located near a corner of the aluminum plate. Table 8 lists the approximate percent of peroxide released at various temperatures after healing for five minutes. The data show that approximately 100% of the peroxide is released from the complex at a temperature of 140°C. Lesser percentages of peroxide are released at lower temperatures. Table 8 Release of non-aqueous peroxide at various temperatures Heatina Temperature 80° C 100' >c 120' 'C 130' >C 140' 'C % Peroxide Released -25% -65% -80% -90% -100% Peroxide complexes having the ability to release hydrogen peroxide vapor at roum temperature and atmospheric pressure, such as the urea peroxide complex, allows them to be effective for use in various sterilization applications. Not only can they be used in the sterilization apparatus of the present invention described above, the compounds of the ¦21- present invention can also be used as part of sett sterilising packaging materials, or applied onto supports such as gauze, sponge, cotton, and the like. The compounds allow for sterilization of sealed packages at room temperature or at elevated temperatures, and are particularly useful for the sterilization of packaged medical or surgical products. Particular uses of the compounds of the present invention are described in the examples which follow. The peroxide complex used in the following examples was urea peroxide in the form of a tablet (Fluka Chemical Corp.) of in the form of 3 powder obtained by crushing the tablets. Example 9 A self-steriliiifig pouch was assembled as follows: A surgical scalpel having 3.8 * 16* 8. subtifis var. niger spores on its surface was placed in a sterile petri dish. The dish was placed in a larger petri dish, together with 1 gm urea peroxide complex in either tablet or powder form. The larger petfi dish was then inserted Into a pouch formed of TYVEtr/MYlAR"1 (gas permeable, Table 9). MYLAR™/MYLARn Each pouch was exposed to various temperatures for various time periods, as shown in Tables 9 and 10 below. Tha biological test samples were evaluated for sterilization as described in Example 1. Ths results are included in Tables 9 and 10, with a " + " sign indicating bacterial growth. Table 9 Self-Sterilizing Pouches With Breathable Barrier (TYVEK™/MYLAR™) Temperature Peroxide Type 1 hf. 2 hr. 3hr. 4hr. 23°C powder o tablet o*o o 40°C powder tablet - - 60°C powder - tablet - Table 10 lists the efficacy data for sell-sterilizing pouches with (Paper/MYLAR1*}* and without (MYLARS/MYLAR™) a breathable barrier. The pouches were assembled as described above, however tha peroxide vapor source was urea peroxide in powder form only. ¦22- Table 10 Self Sterling Pouches With & Without Breathable Barrier Temperature Packaging Type 2 hr. 4 hr. 23°C MYLAR/MYLAR ¦ ¦ Paper/MYLAR + o 4Q°C MYLAR/MYLAR o Paper/MYLAR 60°C MYLAR/MYLAR ¦ Paper/MYLAR - Results from this testing show that the urea peroxide complex of the present invention included in a pouch with and without a breathable barrier provides effective sterilization to an article inside the pouch in the absence of moisture at room temperature and atmospheric pressure after only 2 to 3 hours. At higher temperatures, sterilization is effected after only one hour. To determine the efficacy of the sterilization system of the present invention in a closed container, the following experiment was performed. Example 10 A self-sterilizing container was assembled as follows: A stainless steel support having either 3.6 * 10* B. subtifis var. niger spores on its surface (Table 11) or having 9.2 * ID* B. subtilis var. niger spores on its surface (Table 12), was placed inside a small polyethylene (PE) vial having 20 holes (3/16" in size) in its surface. The vial was placed in a larger PE vial, which was covered with either an air tight cap, or a gas permeable layer of SPUNGUARO® (CSR Wrap). Also included in the larger vial was a second PF vial, also having 20 holes 13/16" in size) in its surface. This vial contained 1 gm urea peroxide in either powder or tablet form, and was sealed in either a SPUNGUARD™ (CSR wrap) or TYVEK1* pouch. Each container was exposed to various temperatures for various time periods, as shown in Tables 11 and 12 below. The biological test samples were evaluated for sterilization as described in Example 1. The results are included in Tables 11 and 12, with a "?" sign indicating bacterial growth. ¦23- 1MB 11 Self-Sterilizing Containers Without Breathable Window Temperature Packaging Type 2hr. Bhr. 23°C Unpacfsagsd tablet - C/C" packaged tablet - CJC packaged pswdsr + ¦ 40eC Unpackaged tablet - C?C psekaged lablst o o C/C packaged powder o o eo°c Unpackaged tsblst C/C packaged tablet - C/C paekagsd powder - pouth formed from CSR wrap ¦24 Table 12 Self Sterilizing Containers With Breathable CSR Window Temperature Packaging Type 0.5 hr. 1.0 hr. 1.5 hr. 2.0 hr. 3.0 hr. 4.0 hr. 23°C Unpackaged tablet ? + o o Unpackaged powder + + o o T/T* packaged tablet + + + + - T/T packaged powder + ? + o o C/C** packaged tablet + + ¦ o C/C packaged powder + o o 4O°C Unpackaged tablet ¦ o Unpackaged powder o o T/T packaged tablet + ¦ ¦ ¦ T/T packaged powder o ¦ C/C packaged tablet o o ¦ C/C packaged powder o o 60°C Unpackaged tablet - o Unpackaged powder T/T packaged tablet ¦ T/T packaged powder C/C packaged tablet C/C packaged powder o ¦ pouch formed from TYVfK™ *" ¦ pouch formed from CSR wrap Results from this testing show that the non-aqueous urea peroxide complex included in a container with and without a breathable barrier provides effective sterilization at room temperature after only 3-4 hours. At higher temperatures, sterilization is effected after as little as one half hour. The non-aqueous peroxide complexes which release peroxide vapor have been found to be useful in the sterilization of articles at room temperature, and more effectively, at higher temperatures. These complexes can be placed in a pouch, container, chamber, room or any area capable of being sealed, where they release peroxide vapor which effectively sterilizes the articles. The complexes can be heated to facilitate the release of vapor, and to provide sterilization in less time than that required for room temperature sterilization. The compounds of the present invention are therefore useful in a variety of applications where steriluation is desired. Simply by placing the complex in a sealed ¦25- area containing an article or articles to be sterilized, sterilization can be achieved. By contrast with prior art methods, there is no need for contact with moisture to provide activation of the hydrogen peroxide. To confirm that sterilization can be effected using non-aqueous peroxide complexes in (ess time at lower pressures, the following experiment was performed. Example 11 A self-sterilizing container was assembled as follows: A stainless steal support having 8.2 * 1(F B. tubtiBs w.n/ger spores on its surface was placed inside a small PE vial having 20 hole* (3/16" in size) in its surface. The vial was placed in a larger PE vial, which was covered with a gas permeable layer of CSR wrap (SPUNGUARD™). Also included in the larger vial was a second PE vial, also having 20 holes (3/16" in size) in its surface. This vial contained 1 gm urea peroxide in either powder or tablet form. The vial was then sealed in a CSR wrap or TYVEK™ pouch. The large vials were placed in either a 4.5 L sterilization chamber or a 173 L sterilization chamber. Each container was exposed to 100 torr pressure and 23°C temperature for 2 hours, as shown in Table 13.* The biological test samples were evaluated for sterilization as described in Example 1. The results are included in Table 13. Table 13 Self-Sterilizing Containers With Breathable Window In Reduced Pressure Conditions Temperature Packaging Type - 4.5 L chamber 173 L chamber 23°C Unpackaged powder ¦ o T/T packaged powder o C/C packaged powder ¦ o These results show that non-aqueous urea peroxide complex included in a container with a breathable barrier provides effective sterilization at 100 torr and room temperature after only 2 hours. These results, when compared with the results in Table 12, demonstrate that the peroxide complexes of the present invention provide sterilization at reduced pressures in less time than that required to effect sterilization at atmospheric pressure. Thus, the hydrogen peroxide complexes of the present invention can provide effective sterilization in significantly shorter periods of time. In addition, as discussed above, plasma can also be used to enhance the sterilization activity of the hydrogen peroxide vapor. The articles to be sterilized are subjected to a plasma after exposure to the peroxide vapor, and remain in the plasma for a period of time sufficient to effect complete sterilization. Articles that have been sterilized by exposure to hydrogen peroxide vapor can be expused to a plasma to remove any residual hydrogen peroxide remaining on the articles. Because the residual hydrogen peroxide is decomposed into non-toxic products during the plasma treatment, the sterilized articles are ready for use following treatment, without the need for any additional steps. Non-aqueous peroxide complexes are useful in a variety of applications, including as a component of self-sterilizing packaging. In addition, the complexes are suitable for use in various methods for vapor sterilization of articles. ¦26- such as the method disclosed in U.S. Patent No. 4,943,414. This patent discloses a process in which a vassal containing a small amount of a vapor liable liquid sterilant solution is attached to a lumen, and the sterilant vaporizes and flows directly into the lumen of the article as the pressure is reduced duiing the sterilization cycle. The method disclosed in the patent can be modified to allow for use of a non-aqueous peroxide compound. The compound is placed in a vessel ' and connected to the lumen of the article to be sterilized. The article is then placed within a container and the container evacuated. The lumen of the article and the exterior of the article are contacted by the hydrogen peroxide vapor released from the non-aqueous compound. A plasma can optionally be generated and used to enhance sterilization and/or to remove any todiferibvofrqea^eadadfouwiufejMictethe system just described overcomes the disadvantage that the water in the aqueous solution is veporized faster and precedes the hydrogen peroxide vapor into the lumen. Thus, more effective sterilization is achieved and less time is required to effect sterilization. Hydrogen peroxide complexes such as gtycine anhydride are especially advantageous since they release a significant amount of hydrogen peroxide at reduced pressure without the need for additional heating of the complex. Synthesis of Non-Aqueous Hydrogen Peroxide Complexes The present invention further provides a process for preparing non-aqueous hydrogen peroxide complexes that are useful as the source in a hydrogen peroxide vapor sterilizer, or as a component of self-sterilizing packaging, as was described above. Of course, the hydrogen peroxide complexes can be used for other applications, such as for bleaching agents, contact lens solutions, catalysts, and other applications which will be well known by those having ordinary skill in the art. The general procedure for preparing the hydrogen peroxide complexes of this invention is as follows: (1) Place the reactant material in the chamber. The material to be reacted with the hydrogen peroxide can be a solid in various forms, (e.g., powder, crystal, film etc., preferably having high surface area to increase the reaction rate}. The reactant material can also be present as a solution in water or another solvent, if sufficient time is allowed to evaporate the solvent after the pressure is reduced in the chamber. The material may also be a liquid whose boiling point is higher than that of hydrogen peroxide (150°C). Since reaction rates are faster at elevated temperature, the chamber is preferably heated whether before or after the reactant composition is introduced. However, the temperature should not be so high that the reactant boils or vaporizes. The reactant composition may be contained in any container that provides access to the peroxide'vapor. If it is in the form of a powder or other form that may be blown about when the chamber is evacuated, then the reactant may be retained in a permeable container, which allows hydrogen peroxide to diffuse into the coniainer. |2) Evacuate the chamber, In certain embodiments, the chamber is evacuated to a pressure below atmospheric pressure, such as a pressure that is below the vapor pressure of the hydrogen peroxide (which depends on its concentration and temperature), in order to assure that all of the peroxide is in the vapor phase. The vapor pressure increases with increasing temperature and decreases with increasing peroxide concentration. For most of the experiments, the chamber was evacuated to about 0.2 Torr and the temperature was ambient or above. ¦27- Generate hydrogen peroxide vapor. The hydrogen peroxide vapor can be generated from a hydrogen peroxide solution or from a substantially anhydrous hydrogen peroxide complex. The latter yields dry hydrogen peroxide in the vapor state, which is an advantage if either the material to be reacted with the vapor or the complex to be formed is hygroscopic. Another advantage of generating the hydrogen peroxide vapor from a substantially water-free complex is that the percent of hydrogen peroxide in the complex being formed is higher than if the vapor is generated from an aqueous solution of H2O7. This is probably due to the competition between water molecules and H;O. molecules for bonding sites on the complex when an aqueous solution is used to generate the H;O; vapor. The peroxide vapor can be generated within the same chamber that houses the reactant material or in another ' chamber separated from it by t vacuum valve. (4) React the reactant material with hydrogen peroxide. The time required for the reaction depends, of course, on the reaction rate of the reactant'wrth hydrogen peroxide. It can be empirically determined by monitoring the pressure, which decreases during the binding of peroxide to the reactant material. Typically, the reaction time is about 5 30 minutes. The concentration of vaporized hydrogen peroxide and the weight of the starting material determine the weight percentage of peroxide in the final reaction product. As the weight ratio of reactant to hydrogen peroxide increases, the weight percentage of hydrogen peroxide in the complex decreases. The reaction can tie repeated multiple times to increase the concentration of hydrogen peroxide in the complex. (5) Evacuate the chamber again. At the end of the reaction period, trie chamber is further evacuated to about 2 Torr to remove any unreacted hydrogen peroxide. (6} Vent the chamber and retrieve the hydrogen peroxide complex. The mechanism by which the hydrogen peroxide forms a complex with the reactant material is not completely understood. The formation of the complex is believed to involve hydrogen bond formation between the hydrogen peroxide and electron rich functional groups containing oxygen and/or nitrogen on the reactant material. It is not known if this is the only mode of binding; however, materials with a wide range of functional groups have been found to form complexes with hydrogen peroxide. The advantages of the vapor phase reaction over earlier methods of hydrogen peroxide complex formation include: 1. The ratio of hydrogen peroxide to reactant material can be accurately controlled by varying the amount of hydrogen peroxide present in the vapor state or the amount of reactant material exposed to the vapor. 2. The need to remove solvent from the reaction product is eliminated. 3. Peroxide complexes can be formed that are liquid or solids, such as powders, crystals, films, etc. 4. Peroxide complexes of hygroscopic materials can be prepared. The synthesis of the nan aqueous peroxide complexes according to the present invention is further described in the following examples. Many of these compounds have utility as catalysts, in addition to having the utilities 28 described in greater detail herein, as will be readily appreciated by those having ordinary skill in the art. The examples represent embodiments of the compositions and processes of the invention, but they are not in any way intended to limit the scope of the invention. Example 12 A hydrogen peroxide complex of glycine anhydride was prepared as follows: A 1.0 gram sample of gtycine anhydride (Aldhch Chemical Co., Milwaukee, Wl) was placed in an aluminum tray in a 173 liter chamber maintained at a temperature of 45°C. The top of the aluminum tray was covered wrth TYVEK™ nonwoven fabric, which prevented the gfycine anhydride from coming out of the tray when the pressure in the chamber was reduced but was breathable and did not absorb hydrogen peroxide. The chamber door was closed and the pressure in the chamber was reduced to 9 0.2 Torr by evacuating the chamber with a vacuum pump. A hydrogen peroxide concentration of 10 mg/liter was created by evaporation of an appropriate volume of a 70% aqueous solution of hydrogen peroxide (FMC Corp., Philadelphia, PA} into the chamber. The hydrogen peroxide vapor was maintained in contact with the glycine anhydride for 20 minutes. At the end of the reaction period, the chamber pressure was reduced to 2 Torr and then returned to atmospheric pressure. The reaction product was removed from the chamber and analyzed for weight percent hydrogen peroxide by i the following iodometric titration reactions. H2O, ? 2KI "- HjS04 > I: + K^SO, ? 2H,0 l2 f 2Na7S,0, > Na2S406 + 2Nal A starch indicator was used in the iodine sodium thiosulfate titration reaction to enhance the color change at tha end point. The percentage by weight of hydrogen peroxide was calculated by the following equation: wt% H2Oj - [(ml of Na^SjOjl'Inormality of Na?S:O:) *1.7|/(samplc weight in grams} The weight percentage of hydrogen peroxide in the glycine anhydride complex was found to be 24.3%. Example 13 The hydrogen peroxide complexes of a wide variety of organic and inorganic complexes were prepared using the procedure of Example 12. In each case, the reaction conditions were the same as those in Example 12, except 1.0 i gram of each one of the compounds presented in Table 14 was used in place of glycine anhydride. -29- TeblB 14 COMPOUNDS EVALUATED AND WEIGHT PERCENT HYDROGEN PEROXIDE PRESENT IN COMPLEXES FORMED BY VAPOR PHASE SYNTHESIS I PROCESS Wt% After Chemical Chemical Peroxide Name Structure Treatment Cateaorv Polylvinyl alcohol) [-CH2CH{OH)i 18.9% Alcohol Poly(vinyl methyl ether) I-CH,CH(OCH3)i 22.0% Ether Polylvinyl methyl Ketone) [.CHrCH(C0CH3a 13.9% Ketone Polyfacrylic acid) |-CH2CH{C00H)-]n 5.1% Acid Glycine H2C(NH2) (COOH) 20.7% Amino Acid L-Nistidine tN=CHNHCH=C] CHjCH (NH3) COOH I I 14.1% Amino Acid Polyfvinyl acetate) E-CH2CH{OCOCH3)-]n 9.1% Ester Cellulose acetate 10.9% Ester Sodium alginate 27.7% Organic Salt Cellulose sulfate, sodium salt 18.2% Organic Salt Poly(4-Vinylpyridine) [¦CH2CH(p-CBH4N).]n 21.8% Aromatic amine Histamins [N=CHNHCH=C-] CHJCHJ (NH,) 13.2% A mine Propionamide (C2H6)C0NH2 31.8% Amide Urea (HjN)2C0 17.9% Urea 1,3-dimethylurea (H3C)HNCONH(CH3) 31.7% Urea Biuret (H2N)CO(NH)CO(NH2) 13.7% Bioret Polyacrylamide [-CH2CH{CONH2Mn 30.1% Polyamide Polyvinylpyrrolidone [-CHaCH(-N(CHa),CO) -]" I I 29.9% Polyamide Nylon 6 [NHICHACO-],, 17.1% Polyamide Nylon 6,6 film [NH(CH2)sNHC0(CH,)4C0-In 16.6% Polyamide Polyetherpolyurethane |-RHNC00R'-]n 9.5% Polyurethane Sodium carbonate Na2CO3 14.3% Inorganic Potassium carbonate K2CQ3 33.9% Inorganic Rubidium carbonate Rb2CO3 37.0% Inorganic Calcium hydroxide Ca(OH)2 23.4% Inorganic ' Sodium bicarbonate NaHCO3 10.7% Inorganic Tetrasodium pyrophosphate Na4P,07 18.9% Inorganic The organic complexes formed cover the following range of functional groups that are capable of forming hydrogen bonds with hydrogen peroxide: alcohols, ethers, ketones, acids, amino acids, esters, organic salts, amines, amides, poiyamides, polyurethanes, ureas, and biuret. The inorganic complexes include carbonates with sodium, potassium, and rubidium cations, as well as sodium bicarbonate. In addition, the hydrogen peroxide complexes of calcium hydroxide and tetrasodium pyrophosphate were also prepared. The starting materials were finely divided powers or 30- slightly larger crystalline materials, except for nylon 6,6, which was processed as a film with a thickness of 0.12 mm, and polyvinyl methyl ether, which was a 50% by weight aqueous solution. The hydrogen peroxide complexes obtained with these materials under the test conditions were solids, except for polyvinylpyrrolidone, histamine, polyfvinyl methyl ether), polyfvinyl methyl katonel.propionamide. and 1,3-dimethylurea. The 1,3 dime thy luiea and propionamide hydrogen peroxide complexes were free flowing liquids that were easily handled in the vapor phase synthesis process, since no solvent needed to be removed to obtain the final product. The histamine, pofyvinylpyrrolidone, polyfvinyl methyl ether), and poiyWinyl methyl ketone) complexes were gummy materials that were not as easy to handle. Examples 14 and 15 describe additional studies with polyvinylpyrrolidone under different process conditions to obtain the peroxide complex as a free flowing solid product. Example 14 Hydrogen peroxide complexes with polyvinylpyrrolidone wsre prepared in which the percent hydrogen peroxide in the polyvinylpyrrolidone complex was varied by changing the ratio of the weight of polyvinylpyrrolidone to the concentration of hydrogen peroxide in the vapor state. The conditions in these tests were identical to those in Example 12, except !he weight of polyvinylpyrrolidone was increased from 1.0 gram to 3.0 grams to 5.0 grams. In all tests, the concentration of hydrogen peroxide was held constant at 10.0 mg/liter of chamber volume. The results of these tests are presented in Table 15. Example 15 A hydrogen peroxide complex of PVP was prepared in which the hydrogen peroxide was delivered from a complex of hydrogen peroxide with urea. When hydrogen peroxide is delivered in this manner, it is substantially water free. In this test, 5 grams of PVP was placed in the reaction chamber and 10 mg H:O:/liter of chamber volume was delivered into the reaction chamber by heating about 7 grams of a 35% complex of H20? with urea to a temperature of about 110°C for approximately 5 minutes. The rest of the conditions in this test were the same as those in Example 12. The percentage hydrogen peroxide in the PVP complex and the physical state of the complex are presented in Table 15. Table 15 EFFECT OF RATIO OF POtYVINYlPYRROUDONE TO HYDROGEN PEROXIDE IN THE VAPOR STATE ON % HYDROGEN PEROXIDE IN COMPLEX AND PHYSICAL STATE OF PRODUCT Wt% H,O, in Complex 29 .9 23. .5 ¦ 17. ,7 Weight Wt% H,O, Physical State Ex. 14 1 29.9 Soft gummy product 3 23.5 Hard gummy product 5 17.7 Free flowing solid Ex. 15 5 19.7 Free flowing solid PVPJnJ in Complex of Product ¦31 The results of these tests demonstrate that a free flowing solid can be obtained with the PVP hydrogen peroxide complex by controlling the ratio of PVP to hydrogen peroxide in the vapor state and, alternatively, by using a substantially water-free hydrogen peroxide vapor source. INORGANIC HYDROGEN PEROXIDE COMPLEXES Inorganic hydrogen peroxide complexes are also suitable for use as stehlanls as described in detail hereinabeve for organic hydrogen peroxide complexes. Peroxide vapor car. be released from these inorganic complexes at atmospheric pressure and room temperature. However, as described in greater detail below, substantial amounts of hydrogen peroxide vapor can be released from inorganic peroxide complexes upon rapid heating to a particular release temperature under both atmospheric and reduced pressure. In order to effectively release hydrogen peroxide from inorganic peroxide, the heating rate of the inorganic peroxide complexes is preferably at least 5°C/min; more preferably it is at least 10°C per minute; still more preferably at least 50°C/min.; and most preferably, it is at least 1000°C per minute. A representative listing of these inorganic peroxide complexes, and the weight percent hydrogen peroxide, is presented in Table 16. Preferred inorganic complexes are those which do not decompose to form a hydro ha lie acid. Thus, especially preferred complexes contain no halogens. It is also possible to provide a mixture of peroxide complexes as a source of peroxide vapor. Such a mixture can be a "physical mixture" in which two different pre-preparBd peroxide complexes are physically mixed, or a "chemical mixture" in which the compounds in the complex are mixed prior to preparation of peroxide complexes therefrom. The titration procedure used to determine the weight percent of H,O? in the complexes was as described in Example 12. Sodium carbonate H,O7 complex was purchased from Fluka Chemical Corp. The vapor-phase synthesis procedure used for synthesizing the inorganic peroxide complexes was the same as that disclosed in Example 12, with the exceptions that 10g of the solid inorganic sample instead of 1 5g. and two reaction cycles versus one, were employed. Example 16 The reaction procedure for liquid phase synthesis of inorganic hydrogen peroxide complexes was essentially as described by Jones et al. U Chem. Soc, Dalian, 12:2526 2532, 1980). Briefly, inorganic solids were first dissolved in a 30% aqueous solution of hydrogen peroxide to make a saturated solution, followed by dropwise addition of ethanol. For the potassium oxalate and rubidium carbonate complexes, the white peroxide precipitates were formed as the amourit of ethanol added was gradually increased. For potassium carbonate, potassium pyrophosphate and sodium'pyrophosphate, the saturated solutions were incubated at -1Q°C for several hours to facilitate crystalline peroxide complex formation. The complexes were separated from the liquid by vacuum filtration, washed with ethanol at least throe times and dried by vacuum. COMPOUNDS EVALUATED AND WEIGHT PERCENT HYDROGEN PEROXIDE PRESENT IN COMPLEXES Chemical Chemical Wt % HJQJ Name formula in Complexes1 Purchased1 Vapor3 liquid3 Sodium Carbonate Na,C03 27.35 Potassium Carbonate K,CO3 7.43 22.70 Robidium Carbonate Rh3CO3 20.31 26.78 Potassium Oxafaie KA04 16.13 18.42 Sodium Pyrophosphate Na4P,O, 11.48 23.49 Potassium Pyrophosphate K4P1O1 20.90 32.76s Sodium Orthophosphate Na3P04 15.67 Potassium Onhophosphaie K3PO" 1811 1. The titration procedure employed to determine the weight percent of H?0; in the complexes is the same as the one slated in the previous patent application. 2. Sodium carbonate hydrogen peroxide complex was purchased from Ftuks Chemical Corp. 3. The vapor and liquid phase procedures were used for synthesizing the inorganic peroxide. A differential scanning calorimeter (DSC) (Model PDSC 2920, TA and Metier-Toledo Model DSC 27HP instruments) was used to determine HjO? release or decomposition properties of the inorganic peroxide complexes. The DSC was run at a heating ramp of 1Q"C/min and at a temperature range of between 30°C and 22Q°C under both atmospheric and varying vacuum pressure conditions. Referring now to FIGURE 5, tha DSC comprises a sample chamber 110. heating plate 112 and pressure control system. The pressure control system comprises a pressure transducer 114 connected to a pressure gauge 116. The pressure gauge 116 is connected to a controller 118 which is, in turn, connected t>> a pressure control valve 120. The pressure transducer 114 is in fluid communication with pressure control valve 120 end with pump 122. Potassium osalate hydrogen peroxide complex synthesized as described hecemabove was placed in 3 DSC and subjected to a particular vacuum pressure over a temperature range of 50°C to 170°C. As can be seen in FIGURE 6, under these DSC conditions with one hole on the lid of the sample pan, greater release of H-.O?, an endothermic process/ occurred at lower pressures, while the exothermic decomposition of H20, was favored at higher pressures. However, as shown in FIGURE 10, partial release of peroxide may also occur at atmospheric pressure when the same experiment was repeated without any cover on the pan (i.e. open pan). Thus, (or certain hydrogen peroxide complexes, a mote open system andioc reduced pressure can facilitate release ol H,0, from the complex. 33- In the use of the inorganic peroxide complexes for sterilization, it is critical to complex stability that heating occur rapidly which may be effected by preheating the aluminum plate prior to contacting with tl.e inorganic peroxide composition. In the use of the inorganic peroxide compounds, rt is also preferred that the temperature be higher than 86°C. As discussed above, it is preferred that the inorganic hydrogen peroxide complex be heated rapidly, i.e. as rapidly as 1000°C/minute or more. This can be accomplished by contacting the peroxide with a preheated haatmg plate. A preferred embodiment for accomplishing such rapid heating is shown in FIGURES 7A and 7B. Referring to FIGURE 7A, there is shown an apparatus 125 for injecting peroxide vapor into a sterilization chamber 131 in a dosed position. The inorganic hydrogen peroxide complex is incorporated into a peroxide disk 132. The disk 132 comprises five layers: three layers of CSR wrap, peroxide complex powder and aluminum fail coated with polypropylene. The disk 132 is heat sealed around its edge to retain the peroxide complex powder. The peroxide disk 132 is placed underneath a perforated aluminum plate 130 which is attached to housing 150 by aluminum attachment pieces 142. The disk'132 is loosely held in place between O-rings 151. Prior to introduction of peroxide vapor into the chamber, a heated aluminum platen 134 is apart from the peroxide disk 132 and is attached to an aluminum plate 136. A spring (not shown) within the bellow 138 holds the plate 136 down in the closed position. When the chamber 131 is evacuated, the bellow 138 is also evacuated. The plate 136 is seated against 0 rinps 148, thus separating a peroxide release chamber 152 from passageways 158. The apparatus is held in place and attached to a sterilization chamber 131 by bolts 144, 146, 154 and 156. Referring to FIGURE 7B, in order to bring the platen 134 up to contact the peroxide disk 132, the bellow 138 is vented. Once the pressure is increased, the bellow 138 moves upward, thereby propelrng the heated aluminum platen 134 against the peroxide disk 132. In a preferred embodiment, the aluminum platen 134 is preheated to 175°C; however other temperatures can be used. Peroxide vapor is then released from the powder through the CSP layers, passes through the perforations 160 in the perforated aluminum plate 130, and enters the peroxide release chamber 152. The upward movement of the heated aluminum platen 134 also opens the peroxide release chamber 152, allowing peroxide vapor to enter passageways 158 which are in fluid communication with the sterilization chamber. Heferring now to FIGURE 8, there is illustrated a sterilization chamber 170 containing a plurality of glass rods 172 orthogonally arranged therein. Stainless steel scalpel blades 174 and 176 placed at the top and bottom, respectively, of chamber 170 contain Bacillus stearothermophilus inoculated thereon. Contained within the sterilization chamber 170 and shown to the right thereof is an apparatus 178 used for heating the hydrogen peroxide complexes, which for exemplary purposes were sodium pyrophosphate (Na4P]0r- 3H,0:) and potassium oxalate (KJC^-HJOJ) hydrogen peroxide complexes. An apparatus 178 comprises a pyrex bowl 180 at the bottom of chamber 170. A pyrex dish 182 is disposed on top of the pyrex bowl 180. An aluminum plate 184 with a heating pad 186 is placed on top of the pyrex dish 182. The peroxide complex is placed on the aluminum plate 184. A power coid 188 is attached to the heating pad 186 and a thermocouple 190 is attached to the aluminum plate 184. Scalpel blades 174 are placed two inches above the aluminum plate 184. o34- In certain embodiments, the hydrogen peroxide complexes are provided within a separate enclosure in fluid communication with the container in which the article to be sterilized is located. The pressures within the enclosure and the container can be the same or different. A positive pressure difference in the enclosure will facilitate movement of the peroxide vapor released from the peroxide complex within the enclosure into the container. Such positive pressure would be particularly useful where the container is large, such es when it is an entire room. In another preferred embodiment, the peroxide complex in powder farm is appGed to an adhesive surface. Preferred adhesive surfaces include high temperature rated adhesive tapes such as A1O and A25 adhesive tapes (3M Corp., Minneapolis, MN). These peroxide complex powder-coated adhesive tapes are then heated to effect peroxide release therefrom using the apparatus shown in, for example, FIGURES 3A, 7A and 8. Referring to FIGURE 9, high temperature rated adhesive tape 200 having peroxide complex powder 202 is disposed on aluminum foil layer 204. One or more CSR layers 206 is layered on top of adhesive tape layer 200. This arrangement can take the form oi individual sheets of material, or a roll can be formed from the material. The inorganic peroxide complexes used in Examples 17 and 18 to determine the amount of peroxide release and sterilization efficacy were potassium pyrophosphate (K Release of Peroxide from SC, PO and PP The ideal temperature at which H:O, was released from SC, PO and PP was determined by OSC. The actual amount of H20z released from 2 g of each of these complexes was determined at various temperatures using a 75 liter chamber and the apparatus shown in FIGURES 7A and 7B. The amount of H;O, released from PP at 175°C was greater than for SC and PO. Although SC released the least amount of H;0, at 175°C, significantly more release was seen whan the amount of sample was increased. o35- Table V7 RELEASE OF PEROXIDE IN 75 LITER CHAMBER SC PO PP Temp, to release H,Oj (by DSC) 170°C 15Q°C 130°C With 2 grams sample At 125°C 0.3 mg/L 0.8 mg/L 1.0 mg/L At 150°C 1.2 mg/L 2.0 mg/L 1.5 mg/L At 175°C 1.8 mg/L 2.5 mg/L 3.4 mg/L With 3 grams sample At 175°C 2.3 mg/L With 4 grams sample At 175°C 2.9 mo/L Example 18 Efficacy tests using SC. PO and PP 2 x 106 B. subtilis var. niger spores were inoculated on a SS blade. Three inoculated blades were first placet) in the front, middle and back positions of a Spunguard wrapped 1Q"x 21 "x 3.5" polyphenylene oxide tray. The wrapped tray was then placed in a 75 liter vacuum chamber having an initial vacuum pressure of 0.2 torr. A 5.5" peroxide disk was made by heat-sealing the SC, SO or PP inorganic peroxide powders between three layers of Spunguard and one layer of aluminum foil coated with polypropylene film. The peroxide was released by contacting the disk for 2 minutes with an aluminum plate which had been preheated to 175°C, followed by an additional diffusion time of 8 minutes for a total exposure time of 10 minutes. After treatment, the three blades were separately placed in Trypticase Soy Broth (TSB) at 32°C for 7 days and scored for bacterial growth. The results are summarized in Table 18. ¦38- Table 16 EFFICACY UST RESUITS Peroxide Complex Weight of Complex Peroxide Cone. Sterility (Wall) PP 2 grams 3.4 mg/1 0/3 PO 2 grams 2.5 mg/l 0/3 sc 2 grams 1.8 mg/i m sc 3 grams 2.3 mg/l 0/3 sc 4 urams 2.9 mg/l 0/3 As can he seen in Table 18, no growth of spores was observed with the exception of 2 g SC {1/3). However, when the amount of SC subjected to vaporization was increased to 3 grams, no bacterial growth was observed. These results underscore the efficacy of sterilization using inorganic hydrogen peroxide complexes. inorganic hydrogen peroxide compfexes can be readily incorporated into the sterilisation procedures described heremabove in connection with organic peroxide complexes. For example, inorganic complexes can be used in connection with 3 plasms sterilization method, or in connection with a self-sterili/mg enclosure where peroxide is slowly released from the complex, Similarly, inorganic complexes can also be used in the sterilization of articles having narrow lumens, wheieby s vessel containing the inorganic peroxide pompfex is connected tc (he lumen. In addition, pressure pulsing of the vapor released from organic peroxide complexes can be employed. Other examples of the use of inorganic complexes for sterilization will be apparent to one having ordinary skill in the art upon reference to the present specification. Synthesis of Fhosahate aad Condensed Phosphate Peroxide Complexes Some phosphate and condensed phosphate pnroxide complexes, along with procedures for their synthesis reported in the literature, are summarized in Table 19. In general, these complexes can be synthesized by mixing the phosphate salts with aqueous hydrogen peroxide solution (either adding solid to peroxide solution or adding the peroxide solution to the solid). Since the heat generated by the reaction may result in decomposition of hydrogen peroxide, attempts have been made to control the reaction temperature by slowly mixing solid with the peroxide solution or using cooled peroxida solution (e.g., 0°C). Peroxide complexes have also been formed by dissolving the hydraje-of phosphate er condensed phosphate salts in peroxide solution. o37- Table 13 Starting Compounds Synthesis Complex Formula Ref. solids Na4P2O? 2:85% adding Na4P]0, to HjQ| so!, slowly to control temp, faelow 5GeC N84PA"nH,0j n-2, 3 or higher 1 Na,PjO7 £.50% reacting 3 mol. 50% H,O2 with 1 mol. Nd"PjO,, drying in fluidized bed at lower temp. Ni4P,0T"3H,0, 2 Na4Pj0,"10H,0 30-90% adding Na4P;07*10H:0 to H,O, sol and drying in vacuum at 2O°C 3 Na3PO4"12H,0 30% adding Na3P04"12H,Q to HJOJ sol and drying in vacuum at 2Q°C Na3PO4"5H,0, 4 NajHPO^IZHjO 4-78% adding Na,HP04*12H20 to H20: sol and drying in vacuum at 20°C NajHPO^nHjO; n-1,2 4 Na,P3010 60% spraying H;0; sol onto NasP30,0 in fluidized bed at 40-50°C, then drying in the bed. NasP3010"nH,0, n KjPQ""7H,0 65-70% dissolving K3PQ""7H,O to H,0, sol at 0°C , maintaining temp, balow 70°C. K,P04"nHj0, n-1.2.4 6 K"P,O7 6090% adding K.P^, slowly to H:0; sol to maintain temp. below 60°C. The results showed that no complex was farmed using this procedure when large quantity of staring solid (e.g.174g)was employed. K^O^nHjO, n-5.35. 7 7 1. Richmond, Howard, PCT Publication No. WO 95/05341 2. Xiao et al., faming Zhuanli Shenqing Gcngkai Shoumingshu, CN 1,097,798, 2b Jan 1995. 3. Titava et a!. Buss. J. foorg. Chem. 40131:384 (1995). 4. Titova et a!., Buss. J. Inorg. Chem. 39151:754 El 994). 5. Kudo, I., Japan Kokai, (C1.C01B), Aug. 29, 1975, Appl. 74 15,389, Feb. 08, 1974. 6. Kirsanova, M. P., Bogdanov, G. A., Oymova, Z. N., Safonov, V. V., Uv. Vyssh. Ucheb. Zsvad. Kjim, Khim. Tskfmol 1SI2M83-6 09721. 7. Majewski, H. W., U.S. Patent No. 3,650,750. Sorav method Procedures similar to those previously described in the literature were performed to determineJhe ease and limitations of the procedures for preparing phosphate and condensed phosphate complexes. In general, complexes were prepared by spraying peroxide solution onto evenly spread solid saits, followed by vacuum or oven drying. Table 20 summarizes the complexes synthesized by the spray method. Na4P,0,-3HIO? could not be synthesized using a 30% H2O, solution which is consistent with the prior art. The K3P0, peroxide complex could not be prepared by directly adding H20, solution to anhydrous K3P04 at room temperature. Detailed synthesis conditions are provided in Examples 21 to 38 below. 38 Table 20 Starting Compounds Synthesis Complex Formula Examples solids Na4P,07 >50% spraying H:07 sol. onto Na4PjO7 Na4P,0,"nH20i n-3, or higher 21-27 Na4P,0, 30% spraying H?0, sol. onto Na4P:0; Na4P,0,"nH,0, n Na,P04 30-70% spraying H:0: sol. onto Na,PO4 NajP04"5Hj0? 28 NajHP04 3070% spraying H:O; sol. onto Na,HP0, Na,HP04"nH70, n-1, 2 29 N3sP3010 30-70% spraying H;0; sol. onto NasP3010 NajPjO^-nHjO, n-1-2 30 59% spraying H,07 sol. onto K3P04 no complex formed 31 K.PA 59-70% spraying H:O2 sol. onto K4P,O, K^O^nHjO, n-4-7 32 KjHPO. 59% spraying H2O, sol. onto K:HP04 K2HP04"3.15Hj02 33 KH,PQ4 59% spraying H:Q: sol. onto KHjPO4 KHJPO,"1HJO, 34 Ca:P3O7 59% spraying H;O: sol. onto Ca7P,O7 Ca,P:0,"3.42H,0? 35 M0;P?O7 59% spraying H3O2 sol. onto Mg^O; MB?P,D;"4.60H:0I 36 ' UQU id-Spray Synthesis of Na.P^-nHiO, In general, an anhydrous complex of sodium pyrophosphate and hydrogen peroxide (Na4P;07-nH;03} was synthesized using a liquid solid phase reaction followed by vacuum and/or oven drying. A number of parameters were varied in connection with the liquid-spray synthesis of a complex of sodium pyrophosphate and hydrogen peroxide, as described below in Examples 21-27. Concentrated hydrogen peroxide solution (30-90% H;0;) was sprayed onto sodium pyrophosphate [98%, A Id rich) dropwise. The mixture was incubated at 10°C, 25°C or 45°C for 1-16 hours, followed by vacuum drying at 25°C-60°C and/or oven drying at 60°C. H;0; concentration, starting H}0, to Na4P;O7 molar ratio, solid to liquid ratio, incubation time and temperature, drying mode, drying temperature and quantity of starting materials were varied as described in the following examples to determine their effect on product composition. Examples 21 to 23 show the effec; of drying processes (vacuum drying at 30°C, yacuum drying at 60°C, and oven drying at 60°C, respectively} on final wt % of H;0; in the resulting complex with a 2 hour reaction time at 25°C. Example 24 shows the reaction time effect with vacuum drying at 25°C. The results indicate that a one hour reaction period is sufficient for forming a 1:3 ratio of sodium pyrophosphate to H?07 in the complex. o39- Exampie 25 shows the reaction temperature effect en peroxide complex formation'. The results indicate that the complex with about a 1:3 ratio could still be formed at a temperature below 45°C when a small quantity of starting materials was employed. Example 26 shows the effect of hydrogen peroxide concentration on the composition of the resulting peroxide complex using liquid spray synthesis. As indicated in Table 26, when 30% H,0; was sprayed onto sodium pyrophosphate solid, even at a starting Ha02 to SP molar ratio of 4:1, the resulting complex, Na4P?G7"1-84H?Qj, had a HJOJ to SP ratio of fess than 2:1 (bisperoxyhydrate). The trisperoxyhydrate (Na4P}07'3HI0;) could be formed when the concentration of HJOJ was greater than 45%, preferably greater than 50%. The composition of Na(Pj0F4H;0J( with a HJOJ to SP ratio of 4:1, was only stable at a temperature below 60°C. Example 27 shows that the sodium pyrophosphate tris-peroxyhydrate complex could not be successfully prepared by the liquid-spray method when a larger quantity of Na^Q, was used. Example 21 Vacuum drying at 30°C HJQJ (59%! was mixed with sodium pyrophosphate (SP) at a solid to liquid ratio of 1:0.8, 1:0.8 and 1:1.1 by weight, incubated at 25°C for 2 hours and driad under vacuum at 30°C for 4 hours or at 30°C for 4 hours followed by 60°C for 15 hours. The product yield ranged from 84% to 09%. The results are summarized in Table 21. Table 21 Vacuum dry at ou L SP Starting Compounds 59% HA HJOJ/SP molar ratio Reaction Time at 25°C Product Weight Weight % H2Q2 Vac-30°C 4h f80°C 15 h (9) (g) (91 4hs Sealed1 Open2 10 88 3.7 2h 13.5 26.81 26.11 26.18 10 g Sg 4.2 2h 13.9 27.75 26.95 26.SS 2h 5.1 10 g 11.7 11 g 27.75 I. For sealed condition, the complex was in a lightly capped plastic bottle; I For open condition, the complex was in an open petri dish. 26.61 26.88 Example 22 Vacuum drying at 60°C HjO; 159%) was mixed with sodium pyrophosphats at a solid to liquid ratio of 1:0.8, 1:0,9 and 1:1.1 by weight, uubated at 25°C for 2 hours and dried under vacuum at 60°C for 4 hours. The results are summarized in Table 22. 40-Tabla 22 Starting Compounds Reaction Time Reaction Temp. Weight % H,O? SP 59% H,Oa H,O,iSP molar ratio Vacuum dry at 60 6C Vac-60°C 4 h * 8Q°C 15 h (g) (0) Ihrs) TO 4h Open 10 8 3.? 2 25 28,54 25,53 10 S 4.2 2 25 28,92 28-38 10 11 5.1 2 25 26,83 2C.28 Example 23 Oven drying at 6D°C HjO, (59%) was mixed with sodium pyrophosphate at a solid to liquid ratio of 1:0,8,1:0.9 and 1:1,1 fcy weight, incubated at 25°C for 2 hours and oven dried at 60°C far either 6 hours or 21 hours. The results are summarized in Table 23. Tabfa 23 Starling Compounds Reaction Tims Reaction Temp. Weight % HA SP 59% H,O; H,Oj/SP molar ratio Oven-dry at 60°C to) tfl) Chr$) rci 6h 21 h 10 3 37 2 25 27.22 26,63 10 9 4.2 2 25 27.10 26.87 10 11 5.1 2 25 29.5? 26.74 Examste 24 Reaction time effect HJOJ C53%) was mixed with sodium pyrophosphate at a solid ts liquid ratio ol 1:0.8 fey weight, incubated at 25°C for 1, 2 and 16 hours and dried under vacuum at 25°C for 4 hours. The results are summarized in Table 24. o41-Table 24 Starting Compounds Reaction Time Reaction Temp Weight % H,O, SP 59% HA HJOJ/SP molar ratio Vacuum dry at 25°C Vac-25°C 4 h + 60°C 15 h (g) (11) (hrs) I°C) 4h Open 10 8 3.7 1 25 27.45 26.77 10 8 4.2 2 25 26.81 26.18 10 8 5.1 16 25 27.01 26.96 25* 20 3.7 16 25 27.12 26.90 oThis sample was used for the thermal stability study in Example 39. Example 25 Reaction temperature effect HjO; {59%} was mixed with sodium pyrophosphate at a solid to liquid ratio of 1:0.8, 1:1.1 or 1:1.3 by weight, incubated at 10°C, 25°C or 45°C, and dried under vacuum. The results are summarized in Table 25. Table 25 Starting Compounds Reaction Time Reaction Temp Weight % H2O; SP 59% HA H20>/SP molar ratio Vacuum dry at 25°C Vacuum dry at 45°C (g) 10 8 3.7 2 10 27.81 10 8 4.2 2 25 26.81 25 27 5.0 1.5 45 26.07 25 32.5 * 6.0 1.5 45 27.23 Example 26 Effect of H,O, concentration H,Oj solution having different concentrations was added to sodium pyrophosphate lAldrich, 98%) dropwise. The mixture was incubated at 25°C for 2 hours, then vacuum dried at 25°C for 4 hours, followed by oven drying at 60°C for 15 hours with the exception of the sample in the last row of Table 26, which was vacuum dried at 25°C for 4 hours, then oven dried at 40°C for 9 hours. The results are summarized in Table 26 and indicate that higher concentrations of peroxide are required to make a peroxide complex having a H2O7 to SP molar ratio of about 1:3. -42- Table 26 Starting Compounds Complexes SP wt of HJOI H;Oj cone. HjQ2l$? molar ratio Weight % HI02 Composition (8) (0* (%) 10 15.8 , 30 3.7 15.69 N8,?,07.-1.4BHA 10 17.2 30 4.0 17.36 NaJV), o1.64HA 10 11 45 4.0 25.48 HatP2Q7 o2,87H2O2 10 B 59 3.7 26.18 Na4P,07 o2.7BH,0, 10 9 59 4.2 28.98 Na4Pj0, o2.89K,Ql 10 12 90 5.8 27.18 Na,P2G7 '2.928^2 10 12 90 5.6 34.44* * The sample was dried under vacuum at 25°C for 4 hours and then in an oven at 40"C for 9 hours. Example 27 Effect of quantity of starting compound 59% H2O2 solution at room temperature was slowly sprayed onto sodium pyrophosphate solid; however, the temperature of the mixture increased. When 59% H;02 was added to 300 grams SP, the temperature of the mixture climbed to over 60°C, thus, larger quantities of SP do not appear to work as well as smaller quantities. The results are summarized in Table 27. Table 27 Starting Compounds Temp, during mixing (°Ci Incubation Time at 25°C Drying condition Weight % H2O, SP 59% HA H2Dj/SP molar ratio (8) (9) (hours) 10 8 3.7 -35 1 vac-25°C3.5h* oven -60°C 15 h 26.7J,, 100 80 3.7 -45 3 vac-25°C 3.5 h+ avert -80°C 15 rt 25.86 300 250 3.7 over 60 3 vac45°C 15 h 19.98 Several additional liquid-spray syntheses of additional peroxide complexes are described irt Examples 28-34 below, -43- Example 23 Liquid-spray synthesis of Na]P04-5H,0I Aqueous hydrogen persside solutions having hydrogen peroxide concentrations of 30%, 59% arid 70% were sprayed onto solid sodium orthophosphate, tribasic (SPT; 96%, Aldfich) to form a paste. The mixture was incubated for 2 haws at 25°Cf then vacuum dried at 25°C. The results are summarized in Table 28. Table 28 Starting Compounds Complexes Na3P04 wt of H,0, HjO; cone. H,07 Na3P04 molar ratio Weight % HA . Composition m 5 34.6 30 10 51.70 Na3P04"5.16H70j 5 17.8 59 10 52.23 Na3P04 o5.27HjOj 5 14.8 70 to 48.81 Na3PO4 oA.mlQ, Examola 29 Liquid synthesis of Na2HPO,-HjO: and NtjHPO^aHjOj Sodium phosphate, dibasic solid (99.95%, Aldrich) was dissolved in aqueous hydrogen peroxide solution and incubated at 25°C for t ftour, then dried under vacuum at 25°C. The resulting product was a gel having a NaiHPDi/HiO, ratio of about 1:2. Further drying of the gel resulted in a powder having a Na*HPO4/M;0j ratio of about 1:1. The results are summarized in Table 29. 44-Table 29 Starting Compounds Complexes Na3HPO4 wt of H2O2 cone. H302/ Na2HPO4 molar ratio Weight %H3O2 Composition Weight %HA Composition fg) (a) m in get form in powdar form ¦ 5 12.0 30 3.Q 20.37 Na2HP04 o 1.07H;02 5 19.8 30 5.0 33.72 &3.HP0* o2.12H2O? 23.01 NazHP04 o1.25H,O2 5 6.1 59 3.0 27.88 Na2HP0 5 10.2 59 5,0 35.33 Na,HP04 o2.28H30j 20.85 Na;HPO4._ oI.IOHJOJ 5 5.1 70 3.0 31.31 NajHPO* o 1.92H20j 5 8.5 70 5.0 35.13 Na,HP04 o22BH7Q3 21.49 Na2HP04 oM4H20" Example 30 Liquid-spray synthesis of NasP]O,o-l-2H1O2 Concentrated hydrogen peroxide solution was sprayed onto sodium tripoiyphosphate {85%, Aldnch) (STP) dropwise. The mixture was incubated at 25°C for 1 hour, vacuum dried at 25°C, and then oven dried at 60nC. Results are shown in Table 30. Table 3D Starting Compounds Complexes Na5Pa010 wt of H2O2 H20; cone. Ha02/ NasP3010 molar ratio Weight % HA Composition * (9) (0) - (%) 10 ^ 13.0 30 5-0 ¦10.58 Na6P3010 o1.40HaO2 10 . 8.6 59 5.0 12.58 Na5P3O10 oU2Ha0, 10 5.6 70 5.0 13.40 NasP30l0"1.73HA Examc le 31 Liquid-spray synthesis of K3PO 59% H3Q2 at room temperature was adrfeii dropwise to potassium phosphate, tribasic (97%, AJdrich). The temperature of the reaction mixture during the spraying climbed to about 80°C. The paste mixture was dried under o45- vacuum for A hours. The results are summarized in Table 31 and indicate that the majority of peroxide in the complex" decomposed due to the high reaction temperature. Table 31 Starting Compounds Reaction product K3P04 Wt Of H;0j HjO2 cone. H3Q2/ K3P0" molar ratis Weight % HA Composition (fl" (8) (%) 10 8 59 3.0 0.34 Example 32 liquid-spray synthesis sf ^PjOj-sHjOj Aqueous hydrogen peroxide solution having a concentration of 59% or 70% was sprayed onto potassium pyrsshssphatgiPP) |37%, Al&kh) ts form 3 paste, the ismjmraturg of which was about 30*C Is 35°C during spraying. The mixture was incubated at 25°C tor 2 hours, then dried under vacuum at 25°C. The results are summarized in Table 32. Table 32 Starting Compounds Complexes K"PA wt 10 8.0 58 4.8 28.74 K4P2O? *3.81H3O2 10 9.5 59 5.4 33.70 K,P207 o4.74HJ0I 10 11.0 59 8.4 38.30 K4P,0, o5.6?HaO! 10 17.5 59 10 41.84 W), o8.93H3Oj 10 21,0 59 12 41.48 K4P2O? oB.99H3O! 10 14.7 70 10 42.80 K4P3Q7 o7.28H!O2 10 17.6 70 12 41.11 K4P2O7 o6.78H202 Example 33 Liquid-spray synthesis of KJHP04-3HJ0, Concentrated hydrogen peroxide solution was sprayed onto potassium hydrogen phosphate (98%, Aldrich) (PHP} dropwise. The mixture was incubated 3f 25°C for 1 hoar and vacuiim dried ai 25°C. Ths results 3f8 shown in Tabfe 33. -46-Table 33 Starting CsmpoymJs Compisx K,HPO4 Wt Of H;02 H;0j cone. HA' KjHPO4 molar ratio Weight % HA Composition Eg) 5 4.97 ¦ 59 3,0 38.04 KjHP04"3,15H2O, Example 34 liquid-spray synthesis of KH^Q^Oj Concentrated hydrogen peroxide solution was sprayed onto potassium dihydrogen phosphate (98%, Aldrich} (POHPI dropwtss. The mixture was Incubated at 25°C for 1 hour and vacuum dried at 25°C. Tha rasult* are shown in Table 34. Table 34 Starting Compounds Complex KHjP04 wt of KJOJ H,0, cone. H3Dj/ KH,P04 mstar ratio Weight % HA' Composition Example 35 liquid-Spray Synthesis of C8IPJOJ*3.42HJO2 59% aqueous hydrogen peroxide solution was sprayed onto solid calcium pyrophosphate (Aldrich). The miiiure wss fflcobatetl fsf 1 hsur at 25°C, thm vacuum tfiisd at 25°C. The results are summarized in Tabte 35. Table 35 Starting Compounds Complex CaiP,Q, wt of fyOj . HJOJ cone. H,O,/ Ca;P?07 molar ratio Weight % HA Composition txampie 36 Liquid-Spray Synthesis of Ma,P)0,"4.60HJ01 59% aqueous hydrogen pstuUs soiutisn was spraysd onto ssfid magnesiym pyrsphsssphate lAWrish). TJJS mixture was incubated for 1 hour at 25°C, then vacuum dried at 25°C The results are summarized in Table 36. ¦47-Table 36 Starting Compounds Complex wt of HJOJ H,Oj cone. H,0,/ Mg,P,0, molar ratio Weight % H,03 Composition (g> (8) i%) 5 10 53 7.72 41.28 MglPlQ;"4;6QHIG* Although several phosphate peroxide complexes have been described, no general method of synthesis for producing stable complexes is known. The reaction between hydrogen peroxide solution and s phesphatt or condensed phosphate is an exothermic reaction. The heat produced by this exothermic reaction can result in decomposition of the hydrogen peroxide. As a result, the complex may be unstable, Of may have a lower ratio of peroxide to phosphate or condensed phosphate than desired. This problem is particularly pronounced when a large quantity of complex is prepared. Paste Method In an effort to control the heat produced by reaction of hydrogen peroxide solution with the phosphate or condensed phosphate, we have developed a variety of synthesis methods. One such method we call the "paste" method because s paste is initially formed from the phosphate or condensed phosphate with water. This paste liquid synthetic method for inorganic hydrogen peroxide complexes comprises mixing the desired inorganic compound with water to form a soft paste. The pasts is allowed to cool, and aqueous hydrogen peroxide solution is added to the inorganic paste. The resulting mixture is dried to remove water, yielding the inorganic hydrogen peroxide complex. The main advantage of this synthetic scheme is thai while the reaction of inorganic compound with water is exothermic, very little heat is generated during formation of the inorganic peroxide complex, thus avoiding the degradation a! hydrogen peroxide during the synthesis. This is a significant improvement over previous methods in which significant amounts of heat are generated which degrade the hydrogen peroxide. The resulting crystals of the inorganic peroxide complex are finer and more stable than those produced according to other procedures and lower concentrations of H;O, can also be used. Without wishing to be bound by any particular theory or mechanism of action, we believe that a hydrate is tniliafiy formed upon formation of the paste, and that the wstef from these hydrates is then replaced with peroxide to form the inorganic peroxide complexes. Examples 37 and 38 provide exemplary methods for the production of two different phosphate peroxide complexes. Example 37 Paste liquid synthesis of Na4P,D,*2-3 HjQ, using different HSO, cones. Sodium pyrophosphate solid (98%. Aldrich] was mixed w>th deioni/ed water and slowly stirred, resulting in formation of a soft paste. Because this reaction is eioiherrmc, the paste was allowed to cool to room temperature 48 Aqueous H70? solution having different H,O, concentrations was mixed with the paste. No temperature increase occurred. The mixture was incubated at 25°C for 1 hour, then vacuum dried at 25°C. The vacuum dried samples were further oven dried at 60°C to remove any remaining water. The results are summarized in Table 37. Table 37 Starting Compounds Complexes SP wt of H,0 wt of H*O7 HA cone. H,O2/SP molar rstto Weight % Composition ffl) (0) (Q) (%) 5 5 24.4 12 4.6 26.60 Na.P,0, o2.84HJ0, 5 5 9.8 30 4.6 27.92 Na4P;0, o3.03H70I 6 5 2.4 59 2.2 17.16 Na4P:0, o1.62HI0j 5 5 3.0 S3 2.8 19.67 Na^O; o1.92H;0j 5 5 3.2 59 3.2 24.43 Na4P,0f o2.53H,0: 5 5 4 59 3.7 26.02 Na4Pj0f o2.75H!O, 5 5 5 59 4.6 28.10 Na4Pj07 o3.G6H?O; 50* 50 50 59 4.6 27.40 Na,P,0, o2.95H,O; 200 200 200 59 4.6 28.31 Na4Pj0, *3.01H,0, * This sample was used for the thermal stability study in Example 39. Table 37 shows several advantages of the paste method for the preparation of hydrogen peroxide complexes: 1. The starting concentration of H,0, was not restricted to greater than 50% in order to prepare sodium pyrophosphate tris peroxyhydrats (Na4P?0;-3H20j}. The complex could hs prepared when as low as 12% HJQ3 solution was employed. 2. Na(PiQj-3H?O2 could ba successfully prepared using larger quantities of starting materials (e.g. 2Q0 g SP), because no temperature increase occurred during mixing of H:0: solution with SP-water paste. 3. Peroxide complexes having different compositions can easily be prepared by controlling the H20j to SP molar ratio in the starting mixture. Example 38 Paste-liquid synthesis of KjP0 Potassium phosphate, Irisasic (97%, Aldrich) (PPT) was mixed with deianized water and slowly stirred, resulting in formation of a soft paste which was allowed to cool to room temperature. Aqueous H;0; solution (59%) was mixed with the paste. No temperature increase was observed. The mixture was incubated at 25°C for 2 hours and dried under vacuum at 25°C. The results are summarized in Table 38. Potassium phosphate peroxide could not be formed by the liquid spray procedure (as shown in Example 31) which is ysed far most phosphate-peroxide complex syntheses. ¦49 When a hydrogen peroxide solution was sprayed onto solid potassium phosphate, the temperature of !he reaction mixture climbed to about 80°C. This high tempefaturontost iikeiy results in the decomposition of hydrogen peroxide so that minimal incorporation of hydrogen peroxide into potassium phosphate occurred. The paste method is ctsariy superior to the liquid-spray method for the preparation of the K3P04-3H30, complex. Table 38 Starting Compounds Complex K3P04 wi of , wt of HA HA cone. H^/ K3PG4 molar tatio Weight % HA Composition (g) (gJ (a) m 5 2 8.8 58 5.0 34.57 KjP04 o3.34H&. Cxamste 33 Thermal stability al NB/JO^-SHJO; prepared using spray method anil pasts method Approximately 0,3 g complex sample was stored in 8 5 ml plastic bottla which was either left unscrewed (open, ondition 1) or tightly capped (sealed, condition 2). Trie open and sealed bottles were placed in a 23°C, 50% relates humidity (RH1 incubator or a 60°C oven. The H30? content of the complex was then determined. The results are summarized m Table 33, Table 39 Synthesis mathod Storage condition* Testing condition wt % H,0s 0) 23°C, 50% m 60°C, in oven 1w 2w 3w 4w 6w 28.35 25.76 27.04 24.57 28.10 20.39 28.38 21.22 NIA N/A SPRAY f2) 23°C, 50% RH 80% in oven 28.86 28.70 26.71 25.10 28.87 23.ST 26.81 21.33 26.84 17.70 (1) 23°C, 50% RH 80°€, in even 26.85 26.84 2693 28.29 26.73 25.58 26.64 24.78 26.98 23.73 PASTE (2) 23aC, 50% RH 6QeC, in oven 27.15 28.87 27.04 27.74 26.98 28.1? 26.72 28.10 27.33 25.71 Storage condition: (1) unscrewed plastic bottle: (2) tightly capped plastic bottle. ¦50- Comparing the results reported in Table 39, the stability of the complex produced via the spray method was less stable at 60°C than the complex prepared via the paste method. However, the stability at 23°C and 50% relative humidity was roughly comparable. Thus, the paste method offers unexpected stability under adverse storage conditions, such as commonly occur during shipping. Hydrate Method As discussed above, we believe that the paste method initially produces a hydrate of the phosphate or condensed phosphate. For many phosphate or condensed phosphate compounds, hydrates can either be readily produced using techniques well known to those having ordinary skill in (he art, or are commercially available. Thus, we tried a hydrate mBthod of synthesis for peroxide complexes which omits the initial paste-formation of the past method, substituting instead a prepared hydrate. As is believed to occur in the past method, the water molecules of the hydrate are replaced by peroxide. Example 40 below provides an exemplary hydrate synthesis method. Example 40 Hydrate synthesis of Na4Pt0,-3H,O, Sodium pyrophosphate decahydrate solid (99%, Aldrich) was mixed with 12%, 30% or 59% aqueous hydrogen peroxide solution, incubated for one hour at 25°C, then vacuum dried at 25°C. The results are summarized in Table 40. Thus, this complex can be prepared with less than 30% hydrogen peroxide solution. Table 40 Starting Compounds Complex Na4P70,"10H,0 wt of HA HA cone. H^ Na4P,0, ratio Weight % HA Composition fg) (g) (%) 8.4 24.5 12 4.6 25.87 Na"PA o2.78H,O, 8.4 10.0 30 4.6 28.04 Na4PA o3.05H,0j 200 120 59 4.6 27.57 Na4PA o2.97HIOI Synthesis of Sulfate Peroxide Complexes We have also synthesized hydrogen peroxide complexes of sulfate salts for use in connection with the sterilization methods described herein. Examples 41 and 42 provide synthetic details for two exemplary sulfate salt complexes. ExamplB 41 Liquid-Spray Synthesis of NaIS0,"1.28H;O! 59% aqueous hydrogen peroxide solution was sprayed onto solid sodium sulfate (99% + , Aldrich}. The mixture was incubated for 1 hour at 25°C, then vacuum dried at 25°C. The results are summarized in Table 41. 51-Table 41 Starting Compounds Complex wt af HjO HA cone. H,0,/ Na,SO, molar ratio Weigh! % HA Composition (9) (g) (%) 10 10 S9 2,46 23.4? Na*SQ,"1.28HA Example 42 Liqttid*Sprcy Synthesis of KISO 59% aqueous hydrogen peroxide solution was sprayed onto solid potassium sulfate (99%+, Aldrich). The mixture was incubated for 1 hour at 25°C, then vacuum dried at 25°C. The results are summarized in Table 42. Tablet 42 Starting Compounds Complex K3S04 wt of HjO HA cone. HjO,/ K;SO" molar ratio Weight % HA Composition Cgl {%) 10 7 59 2.12 10.82 K?S0i*0.62HJ02 Synthesis of Silicate Peroxide Complexes We have also synthesized hydrogen peroxide complexes of silicate salts for use in connection with the sterilization methods described herein. Examples 43 and 44 provide synthetic details for two exemplary silicate salt complexes. Example 43 Paste liquid Synthesis of NajSiO^nHA Sslid ssdrum melasiltcate (NajSiO^. Aldrich) was mixed with water, resulting in formation of a soft paste, which was allowed to cool to room temperature. Aqueous hydrogen peroxide solution (12%} was mixed with the paste. The temperature during the mixing was 30-35DC, The mixture was incubated for 1 hour at 25°C, then vacuum dried at 25°C. The results are summarized in Table 43. Table 43 Starting Compounds Complexes Na;SiO3 wt of H20 wt of HA HA cone. NajSiO3 motar ratio Weight % HA Composition (a) ig) {%} 5 5 23.22 12 2.0 24.74 N3jSiO3"-1.18HA 5 5 34.83 12 3.0 37.45 NajSi03*2.15H?0j 5 r 5 4B.45 12 4.0 37.64 Na2Si0,"2.17HA ¦52- Example 44 Hydrate Synthesis of Na,SijO,"0.68HiO, 5S% aqueous hydrogen peroxide solution was sprayed onto solid sodium irisilicate hydrate (Na2Si307* *H;O, Aldrich). The mixture was incubated for 1 hour at 25°C, then vacuum dried at 25°C. The results are summarized in Table 44. Table 44 Starting Compounds Complex NaiSiA'xH wt of H:02 HA cone. H:0,/ Na,Si3O7 molar ratio Weight % HA Composition (9) (8) (%) 5 4.76 59 4.0 8.73 Na;Si:07"0.68H,0, Thus, we have shown that hydrogen peroxide complexes of a wide variety of inorganic salts can be produced. We believe that successful release of H;0? in connection with the sterilization methods disclosed herein can be achieved using a large number of salts of anions capable of hydrogen bonding, such as those that include at least one oxygen and/or nitrogen atom. See, Table 14, supra, for examples of organic complexes and additional inorganic complexes which can be used in connection with the methods of the present invention. Release of Peroxide from Complexes The DSC curves shown in previous examples, e.g. FIGURE 6, were conducted with one hole on a covered pan at both atmospheric and reduced pressure. With only one small hole on the lid, an exothermic peak was observed in DSC at one atomphere for potassium oxalate percxide complex. The same test was repeated under atmospheric pressure to determine whether more peroxide can be released using a more open system, as shown below in Example 45. Example 45 HjO: Release from K,C,04 peroxide complex at atmospheric pressure Potassium oxalate hydrogen peroxide complex (KiC?04+J70?) was heated at atmospheric pressure using the apparatus shown in FIGURE 5, having either two holes in the sealed lid of a sample pan on the heating plate 112 or with an aluminum pan open to the atmosphere. The DSC profile is shown in FIGURE 10. A large endothermic peak followed by a small exothermic peak indicated partial release of HjO, if the pan was open. A small endothermic peak followed by a large exothermic peak indicated that some release, but mostly degradation, had occurred when the pan had a lid with two holes. In view of the results of Example 45 that a significant amount of H^O; release could occur with an open pan but not using a lid with two holes, we conducted the remainder of our testing of release of peroxide fiom complexes at atmospheric pressure using an open pan and under reduced pressure using a pan covered with a lid with one hole in DSC. The DSC profiles of a number of inorganic complexes are shown in FIGURES 11-25 and a summary of the thermal behavior of peroxide complexes in DSC studies is shown in Table 45. FIGURE J1A is a DSC profile of Na4P,07-2H70j and Na4P:0,-3H?0? at 760 torr. As can be seen, one endothermic peak was observed, indicating that near complete release had occurred. 53 FIGURE 11B is a DSC profile of.NaJMMHjO, at 760 torr. As can be seen, two andothermic paaks were observed, indicating near complete release occurred, FIGURE 12 is a DSC profile of Na3P0.-5Hj02 3f 760 torr, 1 torr and 0.35 torr. The complex wax synthesized using the liquid-spray procedure. As can be seen, exothermic peaks followed by 3 small exothermic peak indicated that partial release had occurred a! one atmosphere. But, under vacuum, a broad eniioihermic effect indicated near complete release had occurred. FIGURE 13 shows DSC profiles of Na?HP0"-1H,0j and Na^HPO^HjO* al 760 torr. Both complexes showed m sndothefmic effect in DSC, indicating near total release occurred at atmospheric pressure. FIGURE 14 shows a DSC profile of Na5P3010-H,(]; at 760 torr. Several endothermic peaks indicated near total release had occurred under atmospheric pressure. FIGURE 15 shows a DSC profile of K3PO4 *3.34H,0: at 760 torr, 7 torr and 1 torr. One exothermic peak in DSC at atmospheric pressure indicated that most H,O? had decomposed at atmospheric pressure, but "partial release occurred under vacuum since an endothermic peak was observed before the exothermic peak under vacuum. FIGURE 16 is 3 DSC profile of K*PjO?-7H;O? at ?60 torr snd 7 torr. Based on independently obtained weight Isss data, art endothermh: peak is likely canceled out by an exothermic peak in the range J4O°C-1BO°C at atmospheric pressure. Thus, the DSC shows that partial release occurred at atmospheric pressure. Several endothermic peaks under vacuum indicated near total release under those conditions. FIGURE 17 shows a DSC profile of K,HPO-3.15H,O7 at 760 torr and at 1 torr. Several endothermic peaks followed by exothermic peaks indicated that par'.ia! release occurred at atmospheric pressure, but ns exothermic peaks were observed under vacuum, indicating near total release under those conditions. FIGURE 18 shows a DSC profile of KH;P04-Hj0j 3t 760 torr. Two endothermic peaks were observed, indicating near total release occurred under atmospheric pressure. FIGURE 19 shows 3 OSC profile of NajC03-1.SHj0? at both 780 torr and at 7 torr. The endothermic peak ai 90-100°C is believed to be release of H,0 under both atmospheric and vacuum conditions. The exothermic peak at approximately 150°C wider atmospheric pressure indicated msstly HjO; decomposition. However, the exothermic peak became endoiheirnic followed by a small exothermic peak under vacuum conditions, indicating that most HJOJ was released. FIGURE 20 shows a DSC profile of CaiP;0;"3.42H303 at 760 torr. An endothsrmic psak Infested mm complete release of H:0, had occurred. FIGUfiE 21 is a DSC profile of MgjP?0?"4.60H;Oj at 760 torr and 7 torr. An endothermic peak followed by an exothermic peak indicated partial release of H:0: occurred at atmospheric pressure, but a large endothermic peak observed under vacuum indicated neat total release under vacuum, FIGURE 22 is a OSC profile of Na?S04*1.28Hj07 at 760 torr. An endothermic peak indicated that near complete release had occurred under atmospheric conditions. FIGURE 23 is a OSC profile of K3S0 -54- FIGURE 24 is a DSC profile of Na,SiOs"2.15H?O, at 760 torr, 1 lorr and 0.5 larr. Exothermic peaks under atmospheric sad reduced pressure indicated that most of the H?Oj had decomposed under these conditions, FIGURE 25 is a DSC profile af Na;Si3Q7"0.688,0; at 760 lorr. An exothermic peak indicated that most of the H20; had decomposed under atmospheric pressure. Table 45 below summarizes the thermal behavior of peroxide complexes in DSC studies. Table 45 Complex Thermal behavior in OSC figure No. at 1 atmosphere {760 torr) under vacuum endo+exo endo 10 n-2, 3, 4, endo endo IIAand 11 8 Na/O^H,^ endo+exo endo 12 NajHPO.TiH^ n-U endo pndo 13 n-1-2 endo ando 14 exo endo * exo 15 ends* exo endo 18 K,HP04"3.15H,0, endo + exo enda 17 KHaP04-1H,0, endo endo 18 Na2C03"1.5Hj0, exo endo+exo 19 Ca,H307"3.42Hj0; endo endo 20 MfljPj0,"4.60H,0, eodg*8xs . ends 21 Na^04"1.2eH30, endo endo 22 KjSO^o.eaHjO, endo endo 23 Na,Si03"2.15H,0, exo exo 24 Na7Si307"0.68HsOj e*o exs 25 Efficacy Test Results Previous examples, e.g. Examples 17 and 18, demonstrated that inorganic percxide complexes were capable of providing sterilization in connection with the techniques described herein and elesewhere under vacuum conditions. In order to demonstrate that those inorganic complexes were capable of providing sterilization under atmospheric conditions, we tested the sierifoat'on efficacy of a number of compounds. Example 48A provides results in which the sterilization occurred at one atmosphere and low tempefstme! £ 80°C) for a complex with an endothermit peak only in OSC at one atmasphere. Example 48S provides the results in which the sterilization occurred at one atmosphere and fow temperature |^60°C) far a complex with both exothermic and exothermic peaks in OSC at @ne atmosphere. Example 48C provides the results in which the sterilization occurred at one atmasphere and low temperature ( ¦55 exothermal penk only in DSC at uiie atmosphere. Exampie 4? provides the resuils in which the sierilrjation occurred a! one atmosphere and the compta* was heated using o complei with an only endothsrmic peak in DSC at one atmosphere. Example 48 provides the results in which the sterilization occurred at one atmosphere and the complex was healed using e complex with both endothefmic 8nd exothermic peaks at one atmosphere. As seen below, under these condition*, efficacious sterilization could be achieved at one atmosphere pressure using these complexes, even for a complex having only an exothermic peak in DSC. As discussed above, it is believed that in certain instances art endothermic peak is masked by an exothermic peak occurring within the same temperature range, accounting for the efficacious sterilization sesn using complexes exhibiting only an exothermic peak on DSC. Example 46A Sterilization using KHjPO4-H?O, peroxide complex (1 stm. and low temperature) A self stenluing pouch was assembled as follows: A stamless steel blade having 7.7 % 1£? S. stmothermophifys spcres in rts surface was placed in a sterile petn dish {60 x Ib mm). 2 grams of KHjPQ4-H,0j complex powder (containing 20.31% wt of H,0, was placed in another pefri dish. Both dishes were inserted together into a 100 x 250 mm pcutrs formed ol TYVEK^/MYIAS™. The pouch was sealed and exposed to room temperature (appro*. 23°C), 40°C (m an incubator) and GITC (in an oven) for different time periods. The sterility test results are summarized m Tabfe 46A. Table 48A Exposure Temperature Exposure Tims (pajitivei/samplcs} I h 2h 4h 6h 8h 23 °C (RT) + + 40°C + 60°C 4- Example 46B Sterilization using K,C,Ot-Hj0j peroxide complex (1 atm and low temperature) A self stonli/iEig pouch was assem&ied as follows: A stainless steel blade having 1.34 * !£? 8. sobtHis *ar. J6 niger spore: on its surface was placed in a sterile petn riish (60 x 15 mm). 2 grams of KiC704-H,0, complex powder {containing 14.21% wt of H>0;) was placed m another petn dish. Both dishes were inserted together into a 100 t 250 mm pouch formed ot MYLARS/MYLAR1". The pouch was sealed and exposed lo 40°C (in an incubator) and 60°C (in an oven) for different time periods. The sterility test results are summarised in Table 46B -56 Table 46B Exposure Temperature Exposure Time (positives/samples) 81, 16h 24h 48h 72h 40°C N/A N/A + + . 60°C + Example 46C Sterilization using Na,C0,-1.5H,0, peroxide complex (1 atm and low temperature) A self sterilizing pouch was assembled as follows: A stainless steel blade having 1.34 x WfjB. subtilis var. niger spores on its surface was placed in a sterile petri dish (60 x 15 mm). 2 grams of N3jC03-1.5^0;, complex powder (containing 27.78% wt of H;0;, Fluka) was placed in another petri dish. Both dishes were inserted together into a 100 x 250 mm pouch formed of MYLARS/MYLAR™ The pouch was sealed and exposed to 60°C (in an oven) for different time periods. The sterility test results are summarized in Table 46C. Table 46C Exposure Temperature Exposure Time (positives/samples) 24h 48h 72h 60°C + Example 47 Sterilization using Na,P,0,'3H,0, peroxide complex (1 atm and elevated complex temperature) Na(P:07-3H?0; (wt % - 27%) was used in the sterilization apparatus shown in FIGURE 6. The sterilization parameters were as follows: size of chamber - 6.25" x 6.25" x 7" (4.5 liters); temperature of chamber - 40°C; pressure of chamber - 760 torr; heating temperature - 175-180°C. B. stearothermophilus{\5 x lOfyscalpel blade) was used as the inoculant. The results are summarized in Tables 47A and 47B. As evidenced by Table 47A, complete sterilization of the scalpel blades located two inches above the heating apparatus was achieved with just 0.01 g of the complex. In contrast, in the inoculates located at the bottom of the chamber, 0.3 g of the complex was required for 26 complete sterilization. 57 Table 47A Sterility remits (positives/samples) with samples located 2" above the heated plete Wt. of Complex 2/10 cyrle" 2/1b cycle 2/30 cycle 0.0 g 2/2 2/2 2/2 0.01 g 0/2 0/2 0/2 0.03 g 0/2 0/2 0/2 0.05 g 0/2 0/2 0/2 Cycle Time - Heating time (min.l/total exposure time (min.) Table 47B Sterility results (positives/samples) with temples located on the bottom of the chamber Wt. of Complex 2/10 cycle' 2/15 cycle 2/30 cyrle 0.0 g 2/2 2/2 2/2 0.1 g 2/2 2/2 2/2 0.2 g 1/2 1/2 1/2 0.3 g 0/2 0/2 0/2 0.5 g 0/2 0/2 0/2 o : Cycle Time - Heating time (mm.)/total exposure time (mm.) Example 48 Sterilization using K;C;04-HjO, peroxide complex (1 atm and elevated complex tempereture) K,C,tVH,O, (wt % - 16.3%) was used in the sterilization apparatus shown in FIGURE 8. The sterilisation parameters were as outlined in Example 47. with the exception that the heating temperature was 155 160°C. In this experiment, inoculated scalpel blades were placed only above the heating plate. The results are summarized in Table 48. ¦58-Table 48 Sterility results {poiit!vei/samples) with samples located 2" above the healed pleta Wt. of Complex 2/10 cycle* 2H5 cycle 2/3G evefe 0.0 8 212 2/2 m a.mB h2 - 1/2 012 0.03 g m S/2 012 0.05 B 0/2 0/2 012 0-1 8 0/2 ¦ 012 ' 0/2 0.2 g 0/2 8/2 012 o: Cycle Time - Heating lime fmirUltota! eiposure time ImiiU With the potassium oxatate comptex, complete starvation occurred using 0.01 g with 30 minutes exposure. Complete sterilization was seen with 0.Q3 g of the complex in ail three cycles. In summary, H30j can be released from the complex at a pressure of one atmosphere and at room tempsraiars. This release can be facilitated with elevated temperature and reduced pressure. System far Retease of tfaffor from Hydrogen Persjtitfe Conmfexss The apparatus discussed above in connection with FIGURES 7 A and 7B can be used in a system for the relaase of hydrogen peroxide vapor from hydregsn peroxide complexes. Such m apparatus can fee used in connection with peroxide complexes formed into disks. Nevertheless, we have found that vapor can be more thoroughly and efficiently released when used in powdered form. Powder zm be placed into the apparatus asmg tha same mechanism described above in connection with FIGURES ?A and 7B. However, another method of introduction of powder is accomplished by mhisWy applying the powdsr to 3 high temperature adhesive tape. FOE example, the 3M Corporation manufactures high temperature tape 9489 which makes use of their adhesive A1O. Tha powder can be dusted onto the adhesive and tha tape imieduced into the chamber for release of hydregeti peroxide vapar. Another exemplary adhesive tape for this purpose can be formed of 3M tape §485 with 3M adhesive A2S. Ceftclusion ft should be noted that the present invention is no* limited to only those embodiments dsscribed in the Detailed Description. Any embodiment which retains the spirit of the present invention should fee considered to be within its scops. However, the invention is only fimitgd by the scope of the following claims. O-113'3000-6-93 - 59 - We claim:- 1. An apparatus for hydrogen peroxide sterilization of an article, comprising: a container for holding the article to be sterilized; and a source of hydrogen peroxide vapor in fluid communication with said container, said source comprising an inorganic hydrogen peroxide complex which does not decompose to form a hydrohalic acid^ said source configured so that said vapor can contact said article to effect sterilization. 2. The apparatus of claim 1, wherein said apparatus includes a breathable barrier. 3" The apparatus of claim 1, wherein said source of hydrogen perixide vapor is located within the container. 4. The apparatus of claim 1t wherein said source of hydrogen peroxide vapor is located in an enclosure which is in fluid communication with the container. 5. The apparatus of claim 4, additionally comprising a valve between said enclosure and said container. 6. The apparatus of claim 1, further comprising a heater adapted to heat the inorganic hydrogen peroxide complex. 7. The apparatus of claim 1, wherein the inorganic hydrogen peroxide complex is within said container, said apparatus further comprising a heater adapted to heat the container. - 60 - 8. The apparatus or claim 4f further comprising a heater adapted to heat the enclosure, 9* The apparatus of claim 4t further comprising a heater adapted to heat the complex. 10, The apparatus of claim 1" further comprising a pump to evacuate the container^ 11 o The apparatus of claiia 4, further comprising a pump adapted to evacuate the container and the enclosure. 12. The apparatus of claim 11, whereby the pump is adapted to evacuate the container independently of the enclosure. 13. The apparatus of claim 4, further comprising a first pump adapted to evacuate the container and a second pump adapted to evacuate the enclosure. 14. The apparatus of claim 10, additionally comprising a first vent valve adapted to vent the container* 15. The apparatus of claim 11, additionally comprising a first vent valve adapted to vent the container and a second vent valve adapted to vent the enclosure independently of the first vent valve. 16. The apparatus of claim 1, further comprising a mechanism for generating a plasma. 17. The apparatus of claim 16, whereby the plasma is generated within the container. D-t13-"00C.1tt&7 - 61 - 18, The apparatus of claim 1, wherein said complex is a hydrogen peroxide complex of a phosphate or condensed phosphate salt, 19, The apparatus of claim 1, wherein said complex is a hydrogen peroxide complex of an oxalate salt, 20, The apparatus of claim 1f wherein said complex is hydrogen peroxide complex of a carbonate salt, 21, The apparatus of claim 1, wherein said complex is a hydrogen peroxide complex of a sulfate salt. 22, The apparatus of claim 1, wherein said complex is a o¦ hydro gen peroxide complex of a silicate salt, 23" The apparatus of claim 1, wherein said complex is a solid phase, 24. The apparatus of claim 1, wherein said container is at a pressure of less than 50 torr, and said inorganic hydrogen peroxide complex is at a temperature greater than 86°C, 25" The apparatus of claim 24, wherein said pressure is less than 20 torr. 26, The apparatus of claim 24, wherein said pressure is less than 10 torr, 27# The apparatus of claim 24, wherein said source is located within said container, 28, The apparatus of claim 24, further comprising an enclosure disposed outside of said container in which said complex is located, D-113-3000-6-98 - 62 - and an inlet providing fluid communication between said container and said enclosure, such that vapor released from said complex travels along said inlet and into said container to effect sterilization. 29. The apparatus of claim 24, wherein Said inorganic hydrogen peroxide complex is a complex of sodium carbonate, potassium pyrophosphate or potassium oxalate© 30. The apparatus of claim 24, further comprising a heater located within said container, whereby said complex is placed on said heater and heated to facilitate the release of said vapor from said complex. 31. The apparatus of claim 30, wherein said heater is heated prior to contacting with said complex. 32. The apparatus of claim 24, further comprising a vacuum pump in fluid communication with said container for evacuating the container. 33" The apparatus of claim 24 further comprising an electrode adapted to generate a plasma around said article. 34. The apparatus of claim 33" wherein Said electrode is inside said container. 35. The apparatus of claim 33, wherein said electrode is spaced apart from said container and is adapted to flow plasma generated thereby towards and around said article. D-113-3000-6-98 - 63 - 36. The apparatus of claim 24, wherein said complex is in'a solid phase. 37. A sealed enclosure containing a sterile product and an inorganic hydrogen peroxide complex capable of releasing hydrogen peroxide vapor. An apparatus and process for hydrogen peroxide vapor sterilization of medical instruments and similar devices make use of hydrogen peroxide vapor released from an inorganic hydrogen peroxide complex. The peroxide vapor can be released at room temperature and atmospheric pressure; however, the pressure used can be less than 50 torr and 5 the temperature greater than 86°C to facilitate the release of hydrogen peroxide vaper. Preferred hydrogen peroxide complexes for use in the invention include Na4P207-3H202 and KH2P04-H202. The heating rate can be greater than 5°C. Optionally, a plasma can be used in conjunction with the vapor. |
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02056-cal-1998-correspondence.pdf
02056-cal-1998-description(complete).pdf
02056-cal-1998-letters patent.pdf
02056-cal-1998-priority document.pdf
| Patent Number | 201934 | ||||||||||||
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| Indian Patent Application Number | 2056/CAL/1998 | ||||||||||||
| PG Journal Number | 08/2007 | ||||||||||||
| Publication Date | 23-Feb-2007 | ||||||||||||
| Grant Date | 23-Feb-2007 | ||||||||||||
| Date of Filing | 23-Nov-1998 | ||||||||||||
| Name of Patentee | ETHICON ,INC. | ||||||||||||
| Applicant Address | NEW BRUNSWICK, NEW JERSY 08933-7003 | ||||||||||||
Inventors:
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| PCT International Classification Number | A 61 L 9/00 | ||||||||||||
| PCT International Application Number | N/A | ||||||||||||
| PCT International Filing date | |||||||||||||
PCT Conventions:
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