Title of Invention

A PROCESS FOR THE PREPARATION OF WATER-SOLUBLE CHILI COLORANT FORMULATION HAVING INCREASED FADING-RESISTANCE TO UV LIGHT

Abstract

Chili color consists of carotenoids of which Capsorubin and Capsanthin are the major pigments. These pigments are fat-soluble and have poor stability to oxygen and light. Earlier, preparation of water-soluble colorant using emulsifiers has been reported. But this preparation has poor light stability. Chili color is a natural color in good demand in food processing industries. There is a need for a photostable water-soluble chili colorant. A process for the preparation of a pungency-free water-soluble natural colorant using the pungent and water-insoluble chili oleoresin is hereby described. Pungency is removed from chili oleoresin with selected solvent mixtures get a colour enriched fraction free from pungency. This is made water-soluble by the use of appropriate emulsifiers. The stabilization of this preparation is achieved by incorporating Tertiary Butyl HydroQuinone (TBHQ) a permitted synthetic antioxidant and piperine from black pepper.

Full Text

The present invention relates to a process for the preparation of water-soluble chillli colorant. Carotenoids, capsorubin and capsanthin in the form of its lauryl esters are the coloring principles in capsicums and its oleoresin. These molecules are fat-soluble and have poor solubility in water-based products. They are also known to lose color upon exposure to air and light due to oxidation of the pigments. Degradation is dependent on the conditions of exposure and get accelerated upon exposure to high heat and intense light conditions. Use of ethoxyquin as an antioxidant in ground paprika has been allowed by FDA but at a level of no more than 0.01%. However, due to its possible toxicological effects, its use is not permitted as a direct additive to foods or oleoresin paprika. Encapsulation of the pigment by dissolving it in an organic solvent like ethanol and using wall materials like various plant gums and subsequent spray drying of the resultant oil-in-water emulsion does afford some protection to the pigments but to a lesser degree. While bisulfite used to prevent degradation is objectionable as a stabilizer, thiopropionates as antioxidants are not permitted in foods. Polyoxyethylene derivatives combined with BHA and BHT are useful for making stable liquid combinations of the pigment but these formulations are not stable in the presence of oxygen. The prior art shows use of emulsifiers in condimental combinations of seasonings including oleoresin of paprika to achieve mutual compatibility as well as dispersability in both oil and water. These systems do not impart the required stability of the pigments against oxidative and thermal stress and often found to be disadvantageous from this point of view. Hence, there is need for development of a system to preserve the color of paprika and its oleoresin when used in the manufacture of food is well preserved even when subjected to light and heat exposure. The present invention relates to the preparation of a water-soluble chili colorant that is also photo-stable. The main uses of the invention are (i) the colorant would be soluble in water as well as water-based formulations and foods (ii) and the colorant has higher stability when exposed to UV light. Reference may be made to the patent (JP57205453, IWAI YOSHIO et al.,), wherein a starch hydrolyzate containing saccharide solution was added to the water-insoluble chlorophyll or paprika color, and the mixture after emulsification was dried and ground to afford a water-soluble product . The main draw-back of this procedure is that the process does not impart any enhanced stability to the pigment especially against exposure to light. Reference may be made to the patent (JP56011960, INAMI OSAMU et al) wherein paprika color preparation is described which involves extraction of the oleo-resin with alcohol followed by suitable steps of saponification, acidification and extraction with an organic solvent like acetone. The main draw-back of this procedure is that the process is related to paprika color preparation which is not water-soluble. Reference may be made to the patent (JP56011961, INAMI OSAMU et al.,), wherein the color preparation was achieved by mixing and emulsifying a mixture of deodorized paprika color separated from paprika oleo-resin with caproic acid triglyceride and an aqueous system containing sorbitan fatty acid ester and/or a protecting colloid such as gum arabic. The main draw-back of this procedure is that the process is related to paprika color preparation which is water-soluble but does not possess any improved stability characteristics on exposure of the color preparation to light. Reference may be made to the patents (Anderson , et al., US 5,258,194; US 5,139,800), wherein a browning composition was prepared by mixing an oil phase containing an emulsifier with an aqueous phase containing a colorant under shear conditions to form a dispersion of the aqueous phase in the oil phase. The drawback of this patent is that the colorants are mixtures of pigments from the group of caramel, paprika, food grade dyes, beet powder, carmine, water-soluble annatto, turmeric, and saffron and the objective was to obtain a browning composition. Reference may be made to the patents (Todd, Jr., et al. US 4,283,429; US 4,285,981; 4,343,823), wherein a homogeneous liquid oil as well as water-soluble condimental composition was prepared by various combinations of emulsifiers like lecithin, fatty acid mono- and ploy-glyceryl esters along with the oleoresin/essential oil/edible coloring principles. The drawback of this patent is that the said products are useful in flavoring and coloring foods and beverages with no claims on the stability of the constituent color substances towards exposure to UV light. Reference may be made to a patent (Bruno, Jr. et al., 4,560,564), wherein paprika color and oleoresin were used to flavor and color a tomato sauce product in order to obtain a product with optimal color. The drawback of this patent is that it employs a combination of high-temperature commercial sterilization and hot-fill-hold processing with more emphasis on incorporation of texture and protein into the product along with color. Reference may be made to a patent (Todd, Jr. 5,084,293), wherein activated ascorbic acid antioxidant compositions embodying propylene glycol or a nonionic surface-active agent have been shown to impart increased antioxidant activity in fats, oils, carotenoids and foods stabilized therewith. The patent has emphasis on anti-oxidant action of the derivatives and as such is not aimed at the development of a color formulation. Reference may be made to a patent (Todd, Jr. 5,059,437), wherein color-stabilized paprika compositions containing certain surface-active agents which impart resistance to color fading in foods exposed to oxidative stress as well as a method of stabilizing paprika pigment against oxidative discoloration are described. The former include mono and diglyceride esters of dibasic organic acids like citric and lactic acids. The antioxidants employed encompass a wide range of compounds and extracts like, Labiatae extract, tea extract, rosemary or sage extract, ascorbyl palmitate / stearate and tocopherol. The patent does not highlight the synergistic effect, if any, of these constituents towards protection against degradation caused on exposure to UV light. Reference may made to a Patent ( Naik J.P. et al 20040191384 ) wherein pungency free enriched color is prepared using a commercial grade pungency free chili oleoresin as the starting material using any one of the alcoholic solvents .mixture of alcoholic solvents, mixture of alcohol-ketonic solvent. The drawback of the patent is that it does not deal with the preparation of water solubilization or improving photo stability of the color. The main objective of the present invention is to develop 'a water- soluble and photo-stable formulation of carotenoids from chili spice (Capsicum annum)', which obviates the aforesaid drawbacks of the processes described in the prior art. Especially the prior art does not deal; with methods for stabilizing the pigments against degradation when exposed to UV light. Accordingly the present invention provides a process for preparation of water-soluble chili colorant, which comprises, a) subjecting chili oleoresin prepared by conventional solvent extraction technique to extraction with aqueous low molecular weight straight chain and branched chain alkanol of 40-90 per cent alkanol content, to separate into two fractions, namely a pigment-enriched fraction with reduced natural pungency and a pungency enriched fraction with substantially lower colour value than the starting oleoresin wherein effective mass transfer of constituents from chili oleoresin to aqueous low molecular weight straight chain and branched chain alkanol is achieved by vigorous mixing, b) physical separation of the colour layer and pungency -rich layer by manual draining or by centrifugation at 3,000 -10,000 rpm to separate pungent and color fraction and followed by repeated extractions of the color rich layer, with aqueous low molecular weight straight chain and branched chain alkanol of 40-60 per cent. c) desolventization of the colour- rich layer using conventional distillation techniques to get a deep red colored resinous preparation almost free from pungency and with residual methanol in the preparation being within the permissible limit of 30-50 parts per million , d) desolventisation of the pooled pungent extracts to get a pungency enriched resinous preparation of low colour value, as a by product, e) mixing the pungency-free chili oleoresin from step 1 (c) with the surface active agent of the type polyoxyethylene sorbitan fatty acid esters (Tweens) preferably polyoxyethylene sorbitan mono-sterate (Tween 60) in the proportion of 0.1:1 to 1:1 by weight along with the permitted synthetic antioxidant Tertiary butyl hydroquinone (TBHQ) at a level of 0.2 to 5% by weight of the formulation, preferably at 0.5 to 4 % by weight and piperine at a level of 0.2 to 5% by weight of the formulation also preferably at 0.5 to 4% by weight wherein TBHQ and piperine are solubilized in Tween 60 with warming up to 50° C and gentle mixing to get a homogenous formulation, f) cooling the formulation rapidly to room temperature to get a homogenous water-soluble chili colorant formulation possessing increased resistance to fading especially under UV light exposure. In an embodiment of the invention, natural piperine isolated from the spice black pepper (Piper nigrum) can be used along with TBHQ in the formulation In another embodiment of the invention, defatted and deodourised black pepper oleoresin preferably defatted and deodourised oleoresin from white pepper containing 60-90 per cent piperine, can be used with TBHQ in the formulation In yet another embodiment of the invention a water- soluble chili colour formulation typically consists of (i) pungency-freed chilli colour fraction: (A) (ii) polyoxyethylene sorbitan monosterate (tween 60): (B) (iii) tertiary butyl hydroquinone (C ) and (iv) natural or synthetic piperine /defatted and deodourised pepper oleoresin containing 60-90 percent piperine (D) Wherein A+B+C+D are blended in proportions of 10 to 50+ 50 to 90+0.5 to 4+ 0.5 to 4 by weight respectively to get color formulations of different pigment strengths ranging in color from 10,000 to 80,000 color units. In yet another embodiment of the invention, a colorant preparation soluble only in fat (but not water soluble) is prepared essentially in the same manner as described under 1(f), but omitting the surface active agent Tween 60 from the formulation but incorporating only TBHQ and piperine with the pungency freed colour fraction prepared as described under 1 (a) to 1 (d) In yet another embodiment of the invention, TBHQ and piperine can be used singly or in combination essentially as described under 1(f) In yet another embodiment of the invention, the water soluble chilli colorant formulations can be used to impart attractive orange to orange-red shades of color in a variety of food products such as tomato jams and jellies, dairy products like ice-cream and flavoured milk, cakes, beverage, sweetmeats and savouries. The process employs chili oleoresin as the starting raw material. Chili oleoresin is conventionally prepared mainly from solvent extraction process wherein powdered chili is extracted with solvents such as acetone/ethylene di chloride / hexane, under controlled extraction conditions which is followed by desolventisation of the extract to obtain a deep red viscous preparation which contains in a concentrated form the natural carotenoid pigments as well as pungent and aromatic constituents in a matrix of mainly fatty oil and resinous matter The coloring principles are mainly the oxygenated carotenoids, capsanthin (fig 1) and capsorubin (fig 2) in esterified form with fatty acids. The pungency is due to capsainoids mainly capsaicin (fig 3), di hydro capsaicin and nor di hydro capsaicin. The presence of pungent constituents in chili oleoresin renders it unsuitable for direct use as a colorant (orange to orange red shade) in foods.The present patent deals with a method for removing the pungent constituents followed by solubilization of the color fraction and its stabilization against degradation in UV light. The chili oleoresin is extracted with aqueous low molecular weight straight chain, branched chain alkanols under conditions designed for effective transfer of pungent constituents into the alkanol layer. Repeated extraction is done to ensure almost complete removal of pungent constituents. The color fraction is soluble in fat but insoluble in water. It is rendered water soluble by mixing with selected emulsifiers in the right proportions. Also the permitted antioxidants tertiary butylhydroquinone (fig 4) and piperine (fig 5) from pepper are added, to the formulation which confers the property of resistance to fading of chili pigments when exposed to ultra violet light. Novelty The novelty lies in the preparation of a natural colorant suitable for varied applications using the pungent and water insoluble spice extractive namely chilli oleoresin which consists of (a) selective removal of pungent constituents from chili oleoresin using specific solvent mixtures to get a color enriched fraction free from pungency (b) rendering the color enriched fraction water soluble with the help of suitable emulsifiers (c) enhancing the stability of the water soluble colorant towards UV light, by the incorporation of a novel mixture consisting of the synthetic antioxidant.Tertiary butyl hydroquinone (TBHQ) and a phytochemical namely piperine added in suitable proportions which is an innovative step of the process. The invention has been explained with the help of following examples and should not be construed to limit the scope of the invention Example 1 Preparation of chili oleoresin and separation of color fraction: Dry red chili (1 Kg) of Byadag'i variety was spread on metallic trays and dehydrated in an electric drier at the temperature of 50 + 5 °C for 2 hrs. The crisp dry chili was crushed into flakes using a hammer type mill and sieved to separate the skin (pericarp) from the seeds and stalk. The pericarp (0.5kg) was ground to a powder passing through 30 mesh sieve. The powder was loaded to a suitable glass column and extracted with acetone as the solvent using a material to solvent ratio 1:8. The pooled extract was desolventised initially using a glass distillation apparatus over a water bath to remove most of the solvent. The extract was transferred to a rotary evaporator and desolventization was carried out taking care to see that the temperature did not exceed 50 °C, and applying vacuum up to 26" mercury towards the end of distillation for effective removal of the solvent to get a deep red colored viscous resin (45g) free of acetone odour which was subjected to further extraction of pungent resin as described further. This chili oleoresin was extracted with 270 ml of isopropanol containing 30 % v/v water in a separating funnel with shaking and settling followed by separation of layers. The color layer was re-extracted with aqueous isopropanol till it was almost free from pungency. The color layer was subjected to de-solventization under reduced pressure using a rotary evaporator as described earlier to get the color fraction weighing 35 g and having a color value 1,60,000 E.OAunits (EOA specification 239, 1980). This was used as the starting material for the preparation of water-soluble chili colorant with increased resistance to fading when exposed to UV light. Example 2 Chili colorant (5 gm) was mixed with polyoxyethylene sorbitan mono sterate (45 g) with warming and stirring to get a homogeneous formulation. The resultant water-soluble preparation (Formulation 1) was stored in glass test tubes and its stability was studied at room temperature. The pigment stability in the sample was monitored by suitable dilution with acetone, measurement of the absorbance at 458 nm and calculation of the color value by EOA method. Table 1 .Chili color stability studies under diffused day light (Table Removed) Example 3 Chili colorant (5 g) was mixed with polyoxyethylene sorbitan mono sterate (45 g) containing piperine with warming and stirring to get a homogeneous formulation. The resultant water-soluble preparation with piperine at 1 % level (Formulation 2) was stored in glass test tubes and its stability was studied at room temperature. The pigment stability in the sample was monitored by suitable dilution with acetone, measurement of the absorbance at 458 nm and calculation of the color value by EOA method, Table 2. Chili color stability studies under diffused day light (Table Removed) Example 4 Chili colorant (5 g) was mixed with polyoxyethylene sorbitan mono sterate (45 g) containing TBHQ with warming and stirring to get a homogeneous formulation. The resultant water-soluble preparation with TBHQ at 1 % level (Formulation 3) was stored in glass test tubes and its stability was studied at room temperature. The pigment stability in the sample was monitored by suitable dilution with acetone, measurement of the absorbance at 458 nm and calculation of the color value by EOA method. Table 3.Chili color stability studies under diffused day light (Table Removed) Example 5 Chili colorant (5 gm) was mixed with polyoxyethylene sorbitan mono sterate (45 g) containing piperine and TBHQ with warming and stirring to get a homogeneous formulation. The resultant water-soluble preparation with a combination of piperine and TBHQ at 0.5 % level (Formulation 4) was stored in glass test tubes and its stability was studied at room temperature. The pigment stability in the sample was monitored by suitable dilution with acetone, measurement of the absorbance at 458 nm and calculation of the color value by EOA method. Table 4.Chili color stability studies under diffused day light (Table Removed) Example 6 Chili colorant (5 gm) was mixed with polyoxyethylene sorbitan mono sterate (45 g) with warming and stirring to get a homogeneous formulation. The resultant water-soluble preparation (Formulation 1) was stored in glass test tubes and its stability was studied under simulated accelerated conditions by exposing the colorant to UV light of 366 nm wavelength. The pigment stability in the sample was monitored at different time periods by suitable dilution with acetone, measurement of the absorbance at 458 nm and calculation of the color value by EOA method. Table 5.Chili color stability under exposure to UV light (Table Removed) Example 7 Chili colorant (5 gm) was mixed with polyoxyethylene sorbitan mono sterate (45 g) containing piperine with warming and stirring to get a homogeneous formulation. The resultant water-soluble preparation with piperine at 1 % level (Formulation 2) was stored in glass test tubes and its stability was studied under simulated accelerated conditions by exposing the colorant to UV light of 366 nm wavelength.. The pigment stability in the sample was monitored by suitable dilution, measurement of the absorbance at 458 nm and calculation of the color value by EOA method. Table 6.Chili color stability in presence of piperine under exposure to UV light (Table Removed) Example 8 Chili colorant (5 gm) was mixed with polyoxyethylene sorbitan mono sterate (45 g) containing TBHQ with warming and stirring to get a homogeneous formulation. The resultant water-soluble preparation with TBHQ at 1 % level (Formulation 3) was stored in glass test tubes and its stability was studied under simulated accelerated conditions by exposing the colorant to UV light of 366 nm wavelength. The pigment stability in the sample was monitored by suitable dilution with acetone, measurement of the absorbance at 458 nm and calculation of the color value by EOA method. Table 7 .Chili color stability in presence of TBHQ under exposure to UV light (Table Removed) Example 9 Chili colorant (5 gm) was mixed with polyoxyethylene sorbitan mono sterate (45 g) containing piperine and TBHQ with warming and stirring to get a homogeneous formulation. The resultant water-soluble preparation with a combination of piperine and TBHQ, each at 0.5 % level (Formulation 4) was stored in glass test tubes and its stability was studied under simulated accelerated conditions by exposing the colorant to UV light of 366 nm wavelength. The pigment stability in the sample was monitored by suitable dilution with acetone, measurement of the absorbance at 458 nm and calculation of the color value by EOA method. Table 8.Chili color stability in presence of TBHQ and piperine under exposure to UV light (Table Removed) EXAMPLE 10 The pungency-free chilli oleoresin is mixed at the proportion of 10%(w/w) with polyoxyethylene sorbitan fatty acid esters (Tweens) selected from polyoxyethylene sorbitan monosterate (Tween 60) at the proportion of 89%(w/w); synthetic antioxidant selected from tertiary butyl hydroquinone (TBHQ) at the proportion 0.5%(w/w) and piperine at the proportion of 0.5%(w/w) in order to get the said chilli colorant formulation 4. Tertiary butyl hydroquinone (TBHQ) and piperine are solubilized in Tween-60 followed by warming at the temperature of about 50 deg C and gentle mixing to obtain homogeneous formulation. EXAMPLE 11 The pungency-free chilli oleoresin is mixed at the proportion of 40%(w/w) with polyoxyethylene sorbitan fatty acid esters (Tweens) selected from polyoxyethylene sorbitan monosterate (Tween 60) at the proportion of 52%(w/w); synthetic antioxidant selected from tertiary butyl hydroquinone (TBHQ) at the proportion 4%(w/w) and piperine at the proportion of 4%(w/w) in order to get the said chilli colorant formulation 4. Tertiary butyl hydroquinone (TBHQ) and piperine are solubilized in Tween-60 followed by warming at the temperature of about 50 deg C and gentle mixing to obtain homogeneous formulation. EXAMPLE 12 The pungency-free chilli oleoresin is mixed at the proportion of 45%(w/w) with polyoxyethylene sorbitan fatty acid esters (Tweens) selected from polyoxyethylene sorbitan monosterate (Tween 60) at the proportion of 50%(w/w); synthetic antioxidant selected from tertiary butyl hydroquinone (TBHQ) at the proportion 1%(w/w) and piperine at the proportion of 4%(w/w) in order to get the said chilli colorant formulation 4. Tertiary butyl hydroquinone (TBHQ) and piperine are solubilized in Tween-60 followed by warming at the temperature of about 50 deg C and gentle mixing to obtain homogeneous formulation. EXAMPLE 13 The pungency-free chilli oleoresin is mixed at the proportion of 10%(w/w) with polyoxyethylene sorbitan fatty acid esters (Tweens) selected from polyoxyethylene sorbitan monosterate (Tween 60) at the proportion of 85.5%(w/w); synthetic antioxidant selected from tertiary butyl hydroquinone (TBHQ) at the proportion 0.5%(w/w) and piperine at the proportion of 4%(w/w) in order to get the said chilli colorant formulation 4. Tertiary butyl hydroquinone (TBHQ) and piperine are solubilized in Tween-60 followed by warming at the temperature of about 50 deg C and gentle mixing to obtain homogeneous formulation. Advantages of the process are: 1. Makes use of an abundantly available edible raw material, namely chili for colorant preparation 2. Overcomes the limitation of the usage of the chili as a food colorant because of its pungent taste, by selectively extracting out the pungent constituents. 3. Overcomes the limitation of the chili pigments of not being soluble in water 4. Enhances the photo-stability of the formulation by a novel approach involving the addition of TBHQ and piperine 5. A marginal increase in the pigment stability of the formulations when stored in diffused day-light was noticed in comparison to control. However, the present proposal does not make any claims for enhancing the thermal stability of the carotenoid pigments present in the formulations. We claim: 1. A process for the preparation of water-soluble chili colorant formulation having increased fading-resistance to UV light which comprises the steps of: (a) extracting chilli oleoresin from dry red chilli by conventional solvent extraction technique, (b) extracting the chilli oleoresin with aqueous isopropanol in order to get two separate layers namely pigment enriched layer having reduced natural pungency and pungency enriched layer having low color value, (c) separating the pigment layer from the pungent layer (d) re-extracting the pigment layer repeatedly with aqueous isopropanol in order to remove pungency, (e) de-solventizing the color layer in order to get the red colored oleoresin fraction having color value of 1,60,000 E.O.A. units to obtain yield turn-over in the range of 6-8 (w/w) per cent dried raw chilli, (f) mixing the pungency-free chilli oleoresin obtained in step (e) in a proportion in the range of 10-50%(w/w) with polyoxyethylene sorbitan fatty acid esters (Tweens) selected from polyoxyethylene sorbitan monosterate (Tween 60) in the proportion in the range of 50-90%(w/w); synthetic antioxidant selected from tertiary butyl hydroquinone (TBHQ) in the proportion in the range of 0.5-4%(w/w) and piperine at the proportion in the range of 0.5-4%(w/w) in order to get the said chilli colorant formulation. 2) A process as claimed in claim 1, wherein tertiary butyl hydroquinone (TBHQ) and piperine used are solubilized in Tween-60 followed by warming at the temperature of 50 deg C followed by gentle mixing to obtain homogeneous formulation. 3) A process as claimed in claims 1 and 2, wherein aqueous isopropanol used is in the ratio of 6:1 (v/w) and at the concentration of 70 % (v/v) in water. 4) A process as claimed in claims 1-3, wherein pungent layer obtained in step (c) is desolventized in order to get pungency enriched resinous preparation of low colour value, as a by product. 5) A process as claimed in claims 1-4, wherein the colour layer and pungency -rich layer is physically separated by draining or by centrifugation at an angular speed in the range of 3,000-10,000 rpm. 6) A process as claimed in claims 1-5, wherein the red chilli used is a Byadagi variety. 7) A process as claimed in claims 1-6, wherein piperine used is selected from natural piperine or prepared synthetically by known methods. 8) A process as claimed in claims 1-7, wherein natural piperine used is obtained from pepper selected from black pepper (Piper nigrum) and white pepper. 9) A process as claimed in claims 1-8, wherein the natural piperine used is a defatted and deodorized pepper oleoresin containing 60-90 percent piperine. 10) A process as claimed in claims 1-9, wherein a water-soluble chilli colour formulation obtained is represented by compositions having different pigment strengths ranging from 10,000 to 18,000 color units. 11) A process as claimed in claims 1-10, wherein a water-soluble chilli colour formulation as claimed in claim 1, comprises of; in %(w/w) (i) pungency-freed chilli colour fraction- 10 (ii) polyoxyethylene sorbitan monosterate (tween 60)- 89 (iii) tertiary butyl hydroquinone- 0.5 (iv) piperine -0.5 12) A process as claimed in claims 1-11, wherein a water-soluble chilli colour formulation as claimed in claim 1 comprises of; in % (w/w) (i) pungency-freed chilli colour fraction -45 (ii) polyoxyethylene sorbitan monosterate (tween 60) -50 (iii) tertiary butyl hydroquinone -1 (iv) piperine -4

Documents:

730-del-2005-abstract.pdf

730-DEL-2005-Claims-(29-03-2011).pdf

730-DEL-2005-Claims-(30-04-2012)..pdf

730-DEL-2005-Claims-(30-04-2012).pdf

730-del-2005-claims.pdf

730-DEL-2005-Correspondence Others-(29-03-2011).pdf

730-DEL-2005-Correspondence Others-(30-04-2012)..pdf

730-DEL-2005-Correspondence Others-(30-04-2012).pdf

730-del-2005-correspondence-others.pdf

730-DEL-2005-Description ( Complete) -(29-03-2011).pdf

730-del-2005-description (complete).pdf

730-del-2005-description (provisional).pdf

730-del-2005-drawings.pdf

730-DEL-2005-Form-1-(29-03-2011).pdf

730-del-2005-form-1.pdf

730-del-2005-form-18.pdf

730-DEL-2005-Form-2-(29-03-2011).pdf

730-del-2005-form-2.pdf

730-DEL-2005-Form-3-(29-03-2011).pdf

730-del-2005-form-3.pdf

730-del-2005-form-5.pdf