WO2002014374A2

WO2002014374A2 - Method for improving cold water solubility of pectins with a very low degree of esterification

Info

Publication number: WO2002014374A2
Application number: PCT/US2001/022594
Authority: WO
Inventors: Timothy C. Gerrish; Susan C. Forman; Jan A. Staunstrup
Original assignee: Cp Kelco Aps
Priority date: 2000-08-15
Filing date: 2001-08-13
Publication date: 2002-02-21
Also published as: AU2001282907A1; WO2002014374A3

Abstract

A hydrocolloid, having desirable bulk density, which is soluble in aqueous systems at cold temperatures, a method for preparing same, and compositions incorporating the hydrocolloid. The method includes dissolving a precursor hydrocolloid in a hot aqueous system which is substantially free of sugars, precipitating it out of the aqueous system, and then drying. The compositions include pharmaceutical formulations, personal care products, beverages, and foodstuffs. In addition, a method of preparing and cooking foodstuffs incorporating the hydrocolloid.

Description

METHOD FOR IMPROVING COLD WATER SOLUBILITY OF PECTINS WITH A VERY LOW DEGREE OF ESTERIFICATION

BACKGROUND OF THE INVENTION I. FIELD OF THE INVENTION

The present invention relates to hydrocolloids which are soluble in aqueous systems at temperatures below about 50 °C and to methods for producing such cold temperature soluble hydrocolloids. The present invention also relates to products containing these cold temperature soluble hydrocolloids. More particularly, the present invention relates to pectins having a low degree of esterifϊcation which are soluble in an aqueous system at a temperature below about

50 °C, and products containing them. II. BACKGROUND OF THE INVENTION AND RELATED INFORMATION

There is a need, in a variety of applications, for hydrocolloids that are soluble in an aqueous system at cold temperatures, i.e., those below about 50 °C. In the food processing industry, for example, the use of heated process water is prohibited by various health regulations.

In addition to compliance with regulatory prohibitions, cold temperature soluble hydrocolloids are advantageous in that they reduce energy expense as no heated process water is required, and further, cold temperature soluble hydrocolloids reduce equipment cost. Moreover, as is discussed below, current cold temperature soluble pectins are co-dried with sugars and are useful in jellies and the like. In some applications to which this invention is germane, however, sugar is an unwanted excipient.

Various hydrocolloids, and particularly pectins with a low degree of esterification, i.e., between about 0% and 50%, are often difficult or impossible to dissolve at cold temperatures. As such, a number of attempts have been undertaken to prepare pectins which are soluble in aqueous systems at cold temperatures. These approaches include co-drying with sugars, other protective hydrocolloids, or salts, agglomeration, granulation, and instantizing.

For instance, United States Patent No. 4,268,533, to Williams et al., discloses a cold temperature soluble quick-setting low methoxyl pectin dry mix composition providing smooth, continuous and uniform gels having good texture and mouth-feel characteristics. This composition is prepared by combining a low methoxyl pectin which has been co-dried with a protective amount of buffer and a solubilizing amount of sugar with: 1) a slowly soluble calcium ion source in an amount sufficient for gel formation; and 2) a slowly dissolving edible acid in an amount which will provide a final pH of from about 3.5 to 4.5 upon dissolution of the mix in water.

Similarly, U.S. Patent No. 2,856,288, to Peebles, describes a pectin which is moistened, aggregated, and dried in such a manner as to leave the aggregates intact. This patent, more particularly, describes mixing the pectin with lactose powder before the moistening and aggregating operation.

U.S. Patent No. 2,673,157, to Shepard et al., further, discloses drying a low methoxyl pectin, which is cold temperature soluble. This pectin is prepared by co-drying the pectin with a sugar, such as sucrose, lactose, or dextrose. The pectin is then incorporated into a single-pack mix comprising the co-dried pectin/sugar composition and a source of calcium ions. Additionally, a Japanese patent, i.e., JP 8116890A to Okawa et al., describes a soluble pectin powder which dissolves at a low temperature. This composition is obtained by dissolving low methoxy pectin in hot water, mixing the solution with dextrin, and drying.

EP 517423 Al, to Eng et al., also describes hydrocoUoid agglomerates which are easily dispersable in cool liquids. The agglomerates are prepared by wetting fine particles of hydrocoUoid material, such as pregelatinized starch or pectin, with a solution of water and a wetting agent, e.g., triacetin or glycerol, and then agglomerating. The agglomeration can take place in a fluidized bed, for example. This patent further describes agglomeration of the hydrocoUoid in the presence of sugar to increase the ease of dispersion.

An article in International Food Marketing and Technology, i.e., Hesse D (8 (6), 12-14 (1994)), discloses instant pectins which are produced by granulation of standardized pectin powder to form larger, more porous particles with better dispersion and solubility properties.

For the foregoing reasons, there is a need for a hydrocoUoid which is soluble in aqueous systems at cold temperatures.

SUMMARY OF THE INVENTION A hydrocoUoid which is soluble in aqueous systems at cold temperatures, i.e. , those below about 50 °C, and a method for preparing same is disclosed. Additionally, products incorporating the hydrocoUoid are disclosed.

In an embodiment, a precursor hydrocoUoid is dissolved in a hot aqueous system, i.e., at a temperature above about 50°C, which is substantially free of sugars. The hydrocoUoid is then precipitated out of the aqueous system with a non-solvent, which can be diluted or mixed with water. Thereafter, the hydrocoUoid is dried at typical industry conditions. The hydrocoUoid of this method has a desirable bulk density and is soluble in an aqueous system at a temperature below about 50 °C. Products incorporating the hydrocoUoid, i.e., pharmaceutical formulations, personal care products, beverages, and foodstuffs, are further disclosed, as is a method of preparing and cooking the batter coated foodstuff.

For example, pharmaceutical formulations containing the hydrocoUoid, such as tablets, capsules, topical gels, extracts, wound dressings, and syrups are disclosed. Likewise, personal care products of the hydrocoUoid, including hair shampoos and conditioners, lipstick, perfumes, sun tan lotions, sun screen lotions, body lotions, deodorants, and antiperspirants, are disclosed as part of this invention. Further, beverages containing the hydrocoUoid, e.g., milk, alcoholic beverages, fruit juices, carbonated drinks, still drinks, powdered drinks, and condensed compositions to be diluted, are disclosed.

According to the present invention, a method for preparing a hydrocoUoid having a clarity of about 85% in a first aqueous system at a temperature below about 50 °C is provided. The method includes: 1) dissolving a precursor hydrocoUoid in a second aqueous system at a temperature above about 50°C; 2) precipitating the hydrocoUoid with a non-solvent; and 3) drying the hydrocoUoid. Additionally, the method disclosed herein is performed substantially in the absence of a sugar selected from at least one of sucrose, dextrose, lactose, maltose, fructose, glucose, corn syrup, maple syrup, maple sugar, brown sugar, high fructose com syrup, invert sugar, and honey. In one aspect of the present invention, the first aqueous system is water.

According to another aspect, the precursor hydrocoUoid may be added to the second aqueous system in a ratio of about 120 grams per liter of the second aqueous system, or further, the precursor hydrocoUoid may be added to the second aqueous system in a ratio of about 60 grams per liter of the second aqueous system. In another embodiment, the precursor hydrocoUoid may be added to the second aqueous system in a ratio of about 30 grams per liter of the second aqueous system. Further, the non-solvent may be one or more of isopropyl alcohol, ethanol, and methanol.

According to other features of the invention, the non-solvent may be mixed with water in a ratio of about 60:40 to about 100:0 by weight percent, or the non-solvent and water may be mixed in a ratio of about 65:35 to about 90: 10 by weight percent. Additionally, the non-solvent may be mixed with water in a ratio of about 70:30 to about 80:20 by weight percent.

In the present invention, the hydrocoUoid is at least one of pectin, partially methoxylated galacturonic acid, polysaccharide gum, pregelatinized starch, agar, alginate, carrageenan, gum arabic, gum tragacanth, gum karaya, gellan gum, carboxymethyl cellulose, methyl cellulose, hydroxypropylmethyl cellulose, hydroxypropyl cellulose, modified starch, xanthan, konjac gum, locust bean gum, guar gum, dextran, curdlan, and pullulan. In another aspect of the invention, the hydrocoUoid may be a pectin selected from one of high methoxy pectin, high methoxy amidated pectin, low methoxy pectin, low methoxy amidated pectin, polygalacturonic acid, polygalacturonate salt, pectic acid, pectic acid salt, pectate, pectate salt, pectinic acid, pectinic acid salt, pectinate, and pectinate salt. Further, the molecular weight of the pectin may be from about 5,000 daltons to about 150,000 daltons, or alternatively, the molecular weight of the pectin may be from about 15,000 daltons to about 100,000 daltons.

In one embodiment, the pectin may have a degree of esterification from about 0 to about 80, and in another aspect, the pectin may have a degree of esterification from about 0 to about 50. According to another aspect, the pectin may have a degree of esterification from about

0 to about 25. Also, the pectin may have a clarity in the first aqueous system from about 70%o to about 100%, or alternatively, the pectin may have a clarity in the first aqueous system from about 80% to about 100%. Further, the pectin may have a clarity in the first aqueous system from about 85% to about 100%. The pectin may also have a bulk density from about 0.3 to about 1, or the pectin may have a bulk density from about 0.4 to about 0.75.

In another embodiment, the first aqueous system is at a temperature from about 0°C to about 50 °C, and in another embodiment, the first aqueous system is at a temperature from about 5°C to about 35°C.

According to other features the invention, the hydrocoUoid may have a degree of esterification from about 0 to about 80, or according to another, the hydrocoUoid may have a degree of esterification from about 0 to about 50. Alternatively, the hydrocoUoid may have a degree of esterification from about 0 to about 25. As a further feature of the invention, the hydrocoUoid may have a clarity in the first aqueous system from about 70% to about 100%, or alternatively, the hydrocoUoid may have a clarity in the first aqueous system from about 80% to about 100%. Further, the hydrocoUoid may have a clarity in the first aqueous system from about

85% to about 100%.

In another aspect of the invention, the bulk density of the hydrocoUoid may be from about 0.3 to about 1, or alternatively, the bulk density of the hydrocoUoid is from about 0.4 to about 0.75. According to the invention, the hydrocoUoid has the thermal fingerprint depicted in Figure

4 and the general formula:

Where: is an alpha (α) or a beta (β) glycosidic bond;

N is an integer from 10 to 10,000;

O O

X is - C - OM or C - NH₂;

M is H⁺ , a cation, a polyvalent cation, or CH₃;

CH,

R is H, CH₃, C₂H₅ -, - (CH₂- CH₂- O)_y - H, or CH₂ - CH - OH - ; and y is 1 or 2.

In another embodiment, a method for preparing a pectin having a bulk density from about 0.4 to about 0.75, a degree of esterification from about 0% to about 25%, and a clarity of about 85%o to about 100% in a first aqueous system at a temperature below 50°C, is disclosed. The method includes: 1) dissolving a precursor hydrocoUoid in a second aqueous system at a temperature above about 50 °C; 2) precipitating the hydrocoUoid with a non-solvent comprising isopropyl alcohol; and 3) drying the hydrocoUoid. The method may performed substantially in the absence of a sugar selected from at least one of sucrose, dextrose, lactose, maltose, fructose, glucose, corn syrup, maple syrup, maple sugar, brown sugar, high fructose corn syrup, invert sugar, and honey.

According to the present invention, a hydrocoUoid, having a clarity of about 85% to about 100% in a first aqueous system at a temperature below about 50 °C, a degree of esterification from about 0% to about 25%, and a bulk density from about 0.4 to about 0.75, is provided. Another aspect being that the hydrocoUoid is substantially free of a sugar selected from at least one of sucrose, dextrose, lactose, maltose, fructose, glucose, corn syrup, maple syrup, maple sugar, brown sugar, high fructose corn syrup, invert sugar, and honey.

Another feature of the present invention is a foodstuff incorporating the hydrocoUoid: including food batter, foodstuffs coated with the food batter, processed meat products, chicken, fish, onion rings, potatoes, matrix meat, vegetables, or vegetable foods.

In yet another aspect, a pharmaceutical formulation incorporating the hydrocoUoid is disclosed. The disclosed pharmaceutical compositions include tablets, wound dressings, capsules, topical gels, extracts, or syrups.

Additionally, personal care products, such as hair shampoos and conditioners, lipstick, perfumes, sun tan lotions, sun screen lotions, body lotions, deodorants, or antiperspirants, incorporating the hydrocoUoid are part of the present invention.

Further provided as part of the present invention are beverages incorporating the hydrocoUoid; for example, milk, alcoholic beverages, fruit juices, carbonated drinks, still drinks, or condensed compositions to be diluted.

In another embodiment of the invention, a method of inhibiting oil adsorption/ absoφtion of a food product cooked in oil is disclosed. The method includes the following steps: 1) coating a foodstuff with a batter composition, including a calcium reactive hydrocoUoid having a bulk density from about 0.4 to about 0.75, a degree of esterification from about 0% to about 25%, and a clarity of about 85% to about 100% in a first aqueous system at a temperature below about 50 °C, to produce a batter-coated foodstuff; and 2) coating the batter-coated foodstuff with a calcium salt enriched crumb composition to obtain a batter and crumb-coated food product having a calcium-hydrocoUoid film resulting from the inaction of the calcium reactive hydrocoUoid and the calcium salt at the interface between the crumb composition and the batter coated foodstuff. Additionally, the batter composition may be substantially free of a sugar selected from at least one of sucrose, dextrose, lactose, maltose, fructose, glucose, corn syrup, maple syrup, maple sugar, brown sugar, high fructose corn syrup, invert sugar, and honey.

According to the invention, a method of inhibiting oil absorption/adsorption of a foodstuff, such as chicken, fish, onion rings, potatoes, processed meat, matrix meat, vegetables, or vegetable foods, cooked in oil is provided. The method includes: 1) coating a foodstuff with a batter composition to produce a batter-coated foodstuff; 2) applying an aqueous solution comprising a hydrocoUoid having a bulk density from about 0.4 to about 0.75, a degree of esterification from about 0%> to about 25%, and a clarity of about 85% to about 100% in a first aqueous system at a temperature below about 50 °C; and 3) drying the coated foodstuff. Additionally, the hydrocoUoid may be substantially free of sugar selected from at least one of sucrose, dextrose, lactose, maltose, fructose, glucose, corn syrup, maple syrup, maple sugar, brown sugar, high fructose corn syrup, invert sugar, and honey. According to another aspect, a method for cooking a battered foodstuff, like chicken, fish, onion rings, potatoes, processed meat, matrix meat, vegetables, or vegetable foods, with reduced oil or fat adsoφtion is disclosed. This method includes: 1) coating the foodstuff with a batter composition to produce a batter coated foodstuff; 2) applying an aqueous solution including a hydrocoUoid having a bulk density from about 0.4 to about 0.75, a degree of esterification from about 0% to about 25%, and a clarity of about 85% to about 100% in a first aqueous system at a temperature below about 50 °C; 3) drying the foodstuff; and 4) frying the dried, coated foodstuff, in cooking oil or fat in a temperature range of about 100°C to about 200 °C to form a batter coated foodstuff having reduced oil or fat content. The hydrocoUoid, further, may be substantially free of sugar selected from at least one of sucrose, dextrose, lactose, maltose, fructose, glucose, corn syrup, maple syrup, maple sugar, brown sugar, high fructose corn syrup, invert sugar, and honey.

These and other features, aspects, and advantages of the present invention will become better understood with reference to the following description and appended claims.

BRIEF DESCRIPTION OF DRAWINGS

The foregoing and other features and advantages of the invention will be apparent from the following more particular description of the preferred embodiments, as illustrated in the accompanying drawings, in which reference characters refer to the same, or like, parts throughout the various views, and wherein:

Figure 1 depicts the weight loss profiles (as temperature is increased 5 °C/minute over a range of 0°C to 1000°C) of a control pectin (untreated - Slendid 440™) and the pectin of the present invention (soluble pectin);

Figure 2 depicts the weight loss profiles (as temperature is increased 0.5°C/minute over a range of 0°C to approx. 350°C) of vacuum dried samples of a control pectin (untreated - Slendid 440™) and the pectin of the present invention (soluble pectin);

Figure 3 depicts the deconvoluted degradation peaks of the vacuum dried control pectin (untreated - Slendid 440™) weight loss profile from Figure 2; and

Figure 4 depicts the deconvoluted degradation peaks of the vacuum dried pectin of the present invention (soluble pectin) weight loss profile from Figure 2.

DF/TATLED DESCRIPTION OF THE INVENTION

The present invention is directed to a, substantially sugar free, hydrocoUoid that is soluble in a cold aqueous system. I. DEFINITIONS

As used herein, the term "precursor hydrocoUoid" refers to a hydrocoUoid obtained by separation of hydrocoUoid from plant material. The precursor hydrocoUoid can preferably be obtained from citrus peel, apple juices, apple ciders, apple pomade, sugar beets, sunflower heads, vegetables, or waste products from plants such as apples, sugar beets, sunflowers, and citrus fruits. More preferably, the precursor hydrocoUoid can be obtained from apples and citrus plants, and most preferably, the precursor hydrocoUoid can be obtained from citrus plants such as limes, lemons, grapefruits, and oranges. Examples of the precursor hydrocoUoid are Slendid 440™ (LM1912 CSZ), which is manufactured by Hercules Incoφorated, and GENU® pectin (citrus) type USP-H, which is also manufactured by Hercules Incoφorated.

The hydrocoUoid of the present invention, depending upon its end use, may also be calcium reactive, termed as calcium sensitive. That is, the hydrocoUoid cross-links with a calcium salt, which is a source of free cations. As used herein, the term "calcium salt" includes calcium nitrate, calcium chloride, calcium hydroxide, calcium acetate, calcium propionate, calcium oxide, calcium gluconate, calcium lactate, and calcium carbonate.

Additionally, as used herein, the term "sugar" or the phrase "sugar free" refers to a sugar selected from at least one of sucrose, dextrose, lactose, maltose, fructose, glucose, corn syrup, maple syrup, maple sugar, brown sugar, high fructose corn syrup, invert sugar, and honey.

Further, "soluble" or "solubility" refers to a hydrocoUoid' s ability to dissolve in an aqueous system, and, with respect to the present invention, solubility is quantified in terms of clarity. That is, a hydrocoUoid is soluble if, when placed in an aqueous system, it has a clarity of about 70%) to about 100%>, and preferably, if it has a clarity of about 80%> to about 100%). Most preferably, a hydrocoUoid is soluble if it has a clarity of about 85% to about 100%.

The procedure for determining clarity is as follows. Measure 1 g of hydrocoUoid, and place it in a 250 mL beaker. Wet the hydrocoUoid in the beaker with 3 mL of isopropyl alcohol and place a magnetic stirrer in the beaker. Position the beaker on a magnetic stirrer plate and add 99 mL of distilled water to the beaker, while stirring the contents of the beaker. Continue stirring until the hydrocoUoid is dissolved. Take a sample of the hydrocolloid-IPA mixture and measure its transmission or absorbance on a spectrometer at 655 nm. The results are given as %T (transmission).

As employed herein, the term "cold aqueous system" represents an aqueous system which is preferably at a temperature from about 0°C to about 50°C, and more preferably at a temperature from about 5 °C to about 35 °C. Additionally, the term "degree of esterification" (DE) refers to the extent to which free carboxylic acid groups contained in the polygalacturonic acid chain of the pectin have been esterified, e.g., by methylation, or in other ways rendered non-acidic, e.g., by amidation. As such, the term "low degree of esterification" in the present invention refers to a DE below about 50%).

The method for determination of degree of esterification (DE) and galacturonic acid (GA) in non-amide pectin employed herein is a modification of the FCC-and FAO/WHO method for determination of %> DE and % GA in pectin which does not contain amide and acetate ester.

To conduct this analysis, the following Apparatus are required: 1) Analytical balance; 2) Glass beaker, 250 mL, 5 pcs; 3) Measuring glass, 100 mL; 4) Vacuum pump; 5) Suction flask; 6) Glass filter crucible no. 1 (Bϋchner funnel and filter paper); 7) Stop watch; 8) Test tube; 9) Drying cabinet at 105°C; 10) Desiccator; 11) Magnetic stirrer and magnets; 12) Burette (10 mL, accuracy ± 0.05 mL); 13) Pipettes (20 mL: 2 pcs, 10 mL: 1 pc); and 14) pH-meter/autoburette or phenolphtalein.

Additionally, the following chemicals are required to perform the analysis: 1) Carbon dioxide-free water; 2) Isopropanol (IPA), 60% and 100%; 3) Hydrochloride (HCl), 0.5 N and fuming 37%; 4) Sodium hydroxide (NaOH), 0.1 N (corrected to four decimals, e.g., 0.1002), 0.5 N; 5) Silver nitrate (AgNO₃), 0.1 N; 6) Nitric acid (NHO₃), 3 N; and 7) Indicator, phenolphtalein, 0.1%.

Once all the devices and chemicals are obtained, the degree of esterification deteimination is conducted according to the following protocol.

1. Weigh 2.0000 g pectin in a 250 mL glass beaker.

2. Add 100 mL acid alcohol and stir on a magnetic stirrer for 10 min. (Please note: acid alcohol is 100 mL 60% IPA + 5 mL HCl fuming 37%)

3 Filtrate through a dried, weighed glass filter crucible.

4 Rinse the beaker completely with 6 x 15 mL acid alcohol.

5, Wash with 60%> IPA until the filtrate is chloride-free* (approx. 500 mL).

6 Wash with 20 mL 100% IPA.

7 Dry the sample for 2 14 hours at 105 °C.

8, Weigh the crucible after drying and cooling in desiccator.

9 Weigh accurately 0.4000 g of the sample in a 250 mL glass beaker.

10 Weigh two samples for double determination.

11 Wet the pectin with approx. 2 mL 100%) IPA and add approx. 100 mL carbon dioxide-free water while stirring on a magnetic stirrer. *(Chloride test: Transfer approx. 10 mL filtrate to a test tube, add approx. 3 mL 3 N HNO₃, and add a few drops of AgNO₃. The filtrate will be chloride-free if the solution is clear, otherwise there will be a precipitation of silver chloride).

Please note that if only % DE is to be calculated, the procedure can be changed as follows: Ref. item 3 : Replace "weighed glass filter crucible" with "Buchner funnel and filter paper type strong, viscous, super rapid, or similar." Ref. item 7: Replace "Dry the sample for 2 ! hours at 105°C" with approx. 15 min.'s drying on Buchner funnel with vacuum suction." Ref. item 9: Replace "accurately 0.4000 g" with "approx. 0.4000 g." Ref. item 11 : Replace "carbon dioxide free water" with "deionized water."

At this point, the sample is now ready for titration, either by means of an indicator or by using a pH-meter/autoburette.

If an the indicator method is employed, the following protocol should be used.

1. Add 5 drops of phenolphtalein indicator and titrate with 0.1 N NaOH until change of color (record it as Vj titer).

2. Add 20.00 mL 0.5 NNaOH while stirring. Let stand for exactly 15 min. When standing the sample must be covered with foil.

3. Add 20.00 mL 0.5 N HCl and stir on a magnetic stirrer until the color disappears.

4. Add 3 drops of phenolphtalein and titrate with 0.1 N NaOH until change of color (record ' it as V₂ titer).

Blind test (Double determination is carried out)

1. Add 5 drops phenolphtalein to 100 mL carbon dioxide-free water, and titrate in a 250 mL glass beaker with 0.1 N NaOH until change of color (1-2 drops)

2. Add 20.00 mL 0.5 N NaOH and let the sample stand untouched for exactly 15 min. When standing the sample must be covered with foil.

3. Add 20.00 mL 0.5 N HCl and 3 drops phenolphtalein, and titrate until change of color with 0.1 NNaOH (record it as Bj). Maximum amount allowed for titration is 1 mL 0.1 N NaOH. If titrating with more than 1 mL, 0.5 N HCl must be diluted with a small amount of deionized water. If the sample has shown change of color on addition of 0.5 N HCl, 0.5 N NaOH must be diluted with a small amount of deionized water. Maximum allowed dilution with water is such that the solutions are between 0.52 and 0.48 N. If alternatively, the pH-meter/Autoburette method is employed, use the following protocol. 1. Titrate with 0.1 N NaOH to pH 8.5 (record the result as Y_x titer). 2. Add 20.00 mL 0.5 N NaOH, and let the sample stand untouched for exactly 15 min. When standing the sample must be covered with foil.

3. Add 20.00 mL 0.5 N HCl and stir on a magnetic stirrer until pH is constant.

4. Subsequently, titrate with 0.1 N NaOH to pH 8.5 (record the result as N₂ titer). Blind test (Double determination is carried out)

1. Titrate 100 mL carbon dioxide-free water to pH 8.5 with 0.1 Ν ΝaOH (1-2 drops).

2. Add 20.00 mL 0.5 Ν ΝaOH and let the blind test sample stand untouched for exactly 15 min. When standing the sample must be covered with foil.

3. Add 20.00 mL 0.5 Ν HCl, and stir on a magnetic stirrer until pH is constant. 4. Titrate to pH 8.5 with 0.1 Ν ΝaOH (record it as Bj). Maximum amount allowed for titration is 1 mL 0.1 Ν ΝaOH. If titrating with more than 1 mL, 0.5 Ν HCl must be diluted with a small amount of deionized water. If pH does not fall to below 8.5 on addition of 0.5 Ν HCl, 0.5 Ν ΝaOH must be diluted with a small amount of deionized water. Maximum allowed dilution with water is such that the dilutions are between 0.52 and 0.48 Ν.

Upon obtaining the data form the above referenced protocol, the following equation is employed to determine the degree of esterification. V_t ^ + CV B,)

% DE (Degree of esterification) = fV₂-B₁) x l00 V_t

% of DF A (Degree of free acid) = 100 - % DE

% GA* (Degree of galacturonic acid) = 194.1 x V_t x Ν x 100

400 *On ash-and moisture- free basis

194.1: Molecular weight for GA

N: Corrected normality for 0.1 N NaOH used for titration (e.g. 0.1002 N) 400: weight in mg of washed and dried sample for titration

% Pure pectin = acid washed, dried amount of pectin x 100 weighed amount of pectin Further, the molecular weight of the hydrocoUoid of the present invention is preferably calculated by measuring the relative viscosity of a 0.1% pectin solution using Na- hexametaphosphate. The apparatus used in this calculation are (1) at least two Witeg-Ostwald- viscosimeters or similar viscometers with 100 to 150 sec. outlet time for water (25°C); (2) a transparent thermostated water bath (25.0°C ± 0.3 °C); and (3) a digital stop watch.

The reagent used in calculating the molecular weight of the pectin is Na- hexametaphosphate which is prepared by: (a) dissolving 20.0 g of Na-hexametaphosphate in 1,800 mL ion exchanged deaerated (boiled) water; (b) adjusting the pH to 4.50 ± 0.05 with 1 M HCl; and (c) diluting the solution with ion exchanged deaerated (boiled) water until 2,000 mL.

The procedure for calculating the molecular weight of the hydrocoUoid is as follows: (1) clean the viscosimeters; (2) measure the outlet time on the viscosimeters for (i) each freshly prepared hexametaphosphate solution and (ii) every new working day where pectin solutions are being measured (filter the hexametaphosphate solution through a glass filter #3 immediately before measuring the necessary quantity of hexametaphosphate solution); (3) determine the hydrocoUoid sample system as follows: (a) acid wash the hydrocoUoid; (b) weigh approximately 90 g hexametaphosphate solution in a tared beaker with stirring magnet; (c) gradually add 0.1 g acid washed hydrocoUoid to the 90 g hexametaphosphate solution in a tared beaker while stirring; (d) heat the solution to 70 °C while stirring until the hydrocoUoid is completely dissolved; (e) cool the solution to 25 °C; (f) q.s. (weigh up) to 100.0 g with hexametaphosphate solution; and (g) filter through a glass filter #3; (4) measure the outlet time for every molecular weight determination on two different viscosimeters; and (5) calculate the molecular weight separately for each viscosimeter using the latest measured outlet time for hexametaphosphate solution on the viscosimeter in question. If the difference between two calculated molecular weights is less than 3,500, the mean value is calculated by rounding off the value to the nearest multiple of

1,000. If the difference between the two calculated molecular weights is 3,500 or more, clean the viscosimeters and measure a new outlet time for the hexametaphosphate solution.

The outlet time is measured via the following procedure: (1) rinse the viscosimeter twice with the sample; (2) pour 5.00 mL of the sample in the viscosimeter and place it in the thermostated water bath at 25.0°C ± 0.3 °C for at least 15 minutes prior to measuring; and (3) measure time on the two outlets. If the difference between the times is more than 0.2 seconds on measuring hexametaphosphate solution or 0.4 seconds on measuring samples, the measuring is repeated until there are three outlet times which differ no more than 0.2 seconds on measuring hexametaphosphate solution or 0.4 seconds on measuring samples. The outlet time which is needed for further calculations is the mean value of the above mentioned two or three identical or almost identical measuring results.

The relative viscosity is calculated as follows: n_r = (t₀- K t₀) / (t_h- K/t_h) wherein t₀ and t_h are the outlet times for hydrocoUoid solution and hexametaphosphate solution, respectively, wherein K = (Q • t^) / (Q + (0.226 ^• L ^• , and wherein Q = volume of viscosimeter bulb in cm³, L = length of capillary tube in cm, and = outlet time for water in seconds.

The molecular weight of hydrocoUoid is then calculated as follows:

M = 1.277 ^• 10⁶ (n, ^1/6-l) g/mol.

Additionally, the hydrocoUoid of the present invention has a bulk density from about 0.3 to about 1, and preferably from about 0.4 to about 0.75. As used herein, bulk density is determined in the following manner.

The apparatus used are (1) a 250 mL graduated cylinder; (2) a magnetic type electric vibrator attached to the vertical support rod of a ring stand (with weighted stand) approximately 1 ft (0.3 m) above the base; and (3) a condenser clamp of sufficient size to hold a 250 mL, which should be attached to the above rod.

To calculate the bulk density, first, weigh out 50 g of a powdered sample, and then place the sample in a 250 mL graduated cylinder. Place the graduated cylinder in the condenser clamp.

Thereafter, turn on the vibrator and allow the cylinder to vibrate for 3 minutes. Alternatively, the sample may be compacted manually. To do so, tap the cylinder (containing sample) on a hard surface by dropping it repeatedly from a height of about 1 in. (25 mm), until the volume of the sample remains constant. In order to prevent cylinder breakage, cover the tapping surface with a 1/8 to 1/4 in. (3-6 mm) thick rubber sheet, or use a plastic graduated cylinder.

After compacting the sample, record the level (in millimeters) to which the sample has been compacted. Then calculate the density of the sample using the following equation.

_W_S_ = Density (g/mL)

N * s where: W_s = weight of sample (50 g) V_s = observed reading (mL) Report the bulk density of the sample to the nearest 0.001 g/mL.

As used herein, the term "thermal fingeφrint" refers to a mass change curve or weight loss profile generated via thermogravimetric techniques. Preferably, the apparatus employed to perform these thermogravimetric dynamic weight loss studies is the TA Instruments Thermogravimetric Analyzer 2950 operating under UHP/zero grade nitrogen atmosphere at a flow rate of 100 ml/min.

The apparatus is calibrated in terms of weight and temperature based on the standard procedures. Weight calibration is done manually using a two-point calibration. Certified mass standards of 100 mg and 1000 mg are used for the calibration.

Temperature calibration is conducted using a five point calibration process and following the basic outline of the American Society for Testing and Materials (ASTM) method designation E 1582-93, "Standard Practice for Calibration of Temperature Scale for Thermogravimetry," which is incoφorated herein by reference. This five-point calibration is conducted using room temperature, a calibrated thermometer, and the four certified standards listed below which have the indicated transition temperatures: Alumel 154.28°C

Nickel 358.28 °C Perkalloy 596.08 °C

Iron 770.00 °C

Temperature calibration is conducted at a time-temperature ramp rate of 10 °C per minute. Vacuum dried pectin samples are prepared for analysis by first drying to remove any moisture. This drying step is completed by drying the sample under vacuum (5 kPa) at 70 °C for 6 hours in a vacuum oven. Next, five to fifteen milligrams of the oven dried pectin samples are placed into tared, open platinum sample pans. The pectin samples are then manually loaded into the instrument furnace. The weight loss studies are conducted under an Ultra High Pure (UHP)/zero grade nitrogen atmosphere at a flow rate of 100 ml/min. Each sample is evaluated at two different time-temperature ramps: 5.0°C/min, room temperature to 1000°C; and

0.5°C/min, room temperature to 375 °C.

The apparent weights (and weight loss) with respect to temperatures are recorded automatically and the data is presented graphically as the rates of weight loss (in wt % per second) versus temperatures (in °C). This graphical representation is generally know as a mass change curve or a weight loss profile.

Each peak represents a degradation stage and the peak maximum denotes the inflection point of the degradation range. The overlapping degradation peaks can be further de-convoluted using the constrained Gaussian amplitude function in SPSS Science Peakfit software.

Further, the term "substantially the same thermal fingeφrint," as used herein indicates that the pectin has degradation peaks which are substantially similar to those in Figure 4. Stated differently, the pectin's thermal fingeφrint should exhibit a substantial number of the differences between the control pectin (Figure 3) and the pectin of the invention (Figure 4), so that one skilled in the art would recognize it to be the pectin of the present invention. Both of these definitions are intended to be subsumed under Figure 4.

II. METHOD OF PREPARING THE HYDROCOLLOD3

The present invention relates to a method for preparing cold temperature soluble hydrocolloids, which are substantially sugar free. That is, hydrocolloids which are readily soluble in an aqueous system at a temperature from about 0°C to about 50 °C, and preferably in an aqueous system at a temperature from about 5°C to about 35 °C.

The hydrocoUoid of the present invention is prepared by dissolving a precursor hydrocoUoid in an aqueous system at a temperature above about 50 °C, precipitating it out with a non-solvent, and then drying it. The precursor hydrocoUoid may be any hydrocoUoid which is insoluble in an aqueous system at a temperature below about 50°C.

According to the invention, the precursor hydrocoUoid is added to the aqueous system at a temperature above about 50 °C in a ratio (gram hydrocoUoid per liter aqueous system) of about 120 g hydrocoUoid per liter, and preferably at a ratio of about 60 g hydrocoUoid per liter. Most preferably, the precursor hydrocoUoid is added at a ratio of 30 g per liter.

The cold temperature soluble hydrocoUoid is then precipitated out of the precursor containing aqueous system with a non-solvent. The non-solvent may be either isopropyl alcohol, ethanol, or methanol. Preferably, the non-solvent is one that is listed in 184 C.F.R. 184.1588 as approved for or in the isolation of pectin from aqueous systems.

Further, the non-solvent can be mixed with water in ratios (non-solvent to water) ranging from about 60%-40% to 100%-0%, preferably from about 65%-35% to 90%- 10%, and most preferably from about 70%-30% to 80%-20%.

Thereafter, the precipitated hydrocoUoid is then dried, substantially in the absence of sugars, under conditions typical in the industry. That is, under conditions of controlled temperature, humidity, air velocity, and duration, which may be more or less advantageous to the cold temperature solubility performance of the hydrocoUoid.

III. COMPOSITION

The present invention further relates to a, substantially sugar free, hydrocoUoid that is soluble in a cold aqueous system, i.e., a hydrocoUoid which is soluble in an aqueous system at a temperature from about 0°C to about 50°C, and preferably from about 5 °C to about 35 °C. The hydrocoUoid may be at least one of pectin, partially methoxylated galacturonic acid, gelatin, polysaccharide gum, pregelatinized starch, agar, alginate, carrageenan, gum arabic, gum tragacanth, gum karaya, gellan gum, carboxymethyl cellulose, methyl cellulose, hydroxypropylmethyl cellulose, hydroxypropyl cellulose, modified starch, xanthan, konjac gum, locust bean gum, guar gum, dextran, curdlan, and pullulan.

By way of description, the hydrocoUoid of the present invention has a degree of esterification from about 0 to 80, and preferably the hydrocoUoid has a degree of esterification from about 0 to 50. More preferably, the hydrocoUoid of the present invention has a degree of esterification from about 0 to 25. Further, when dissolved in a cold aqueous system, the hydrocoUoid has a clarity from about 70%> to about 100%>, and more preferably the hydrocoUoid has a clarity, in a cold aqueous system, of about 80% to about 100%). The hydrocoUoid also has a bulk density from about 0.3 to about 1. Preferably, the hydrocoUoid has a bulk density from about 0.4 to about 0.75. The hydrocoUoid further has the following general formula.

Wherein: is an alpha (α) or a beta (β) glycosidic bond;

N is an integer from 10 to 10,000;

O O

X is - C - OM or - C -NH₂;

M is H* , a cation, a polyvalent cation, or CH₃; and

CH,

R is H, CH₃, C₂H₅ -, - (CH₂ - CH₂ - O)_y - H, or CH₂ - CH - OH - ; and y is 1 or 2.

Further, the hydrocoUoid preferably has substantially the thermal fingeφrint, obtained by thermogravimetric techniques, which is depicted in Figures 1, 2, and 4.

The weight loss profile depicted in Figure 1 illustrates the thermal degradation events of a control pectin and the pectin of the present invention over a temperature range from room temperature to 1,000°C at a time-temperature ramp increase rate of 5°C/min., and Figure 2 illustrates the weight loss profiles of a control pectin and the pectin of the present invention over a range from room temperature to 50° C at a time-temperature ramp increase rate of 0.5°C/min. This smaller time-temperature ramp increase rate allows for a better separation (and identification) of the degradation events. The weight percent used in the Figures is presented in the dry basis. The moisture content and the residual weight at 1,000°C for the samples can be found in Table 1 below. Table 1. Water Content and Residual Weight of Pectin Samples at 1000°C.

Figure 1 illustrates degradation events or the thermal finger print which can helpful in identifying the pectin of the present invention. These events occur at approximately 180, 198, 220, 240, 260, and 930 °C, with the event at 930 °C. being more pronounced. The degradation events at lower temperatures, however, are more evident when a slower time-temperature ramp increase rate is employed as is shown in Figure 2. From this, the pectin of the present invention exhibits degradation events at approximately 180, 198, 220, 240, and 260 °C.

In order to further identify the chemical components of the pectin of the present invention (or which chemical components are removed during the process of the present invention), the overlapping degradation events are further deconvoluted (as is shown in Figures 3 and 4). At least five degradation events, at 180, 198, 220, 240, and 260°C, are evidenced for both the pectin of the present invention and untreated samples in the temperature range of 150 to 300°C. As can be seen, the intensities (area) of the peaks (derivative of wt%> versus temperature) are reduced for the pectin of the present invention sample as compared to the untreated sample. As discussed below, this reduced intensity indicates that amounts of certain chemical components are removed from the pectin of the present invention as the intensity is directly proportional to the concentration of the species in the sample.

Not wishing to be bound by theory, the dynamic weight loss profiles indicates that certain chemical components are reduced or removed from the pectin of the present invention as compared to the untreated pectin, Slendid 440™. The chemical components that are reduced in concentration have the degradation temperature (the temperature at the reflection point of the degradation process) of 180, 198, 220, 240, and 260 °C respectively. The first 5 temperatures are related to the degradation of the organic components, with the major weight loss at 198 °C being attributable to the loss of linear pectin molecules. The highest temperature degradation represents the degradation of an inorganic or organic salt. As such, the component that is removed from the Slendid™ 440 is either an inorganic or organic salt that is thermally degraded at approximately 930°C. Another difference is the residual weight of the respective samples at 1,000°C: the untreated pectin sample has a higher value than that of the pectin of the present invention. This suggests that the former might contain a higher concentration of inorganic or organic salts that would not degrade at the test temperature.

A specific embodiment of the present invention also relates to a, substantially sugar free, pectin that is soluble in a cold aqueous system, i.e., a pectin which is soluble in an aqueous system at a temperature from about 0 ° C to about 50 ° C, and preferably from about 5 ° C to about 35 °C. Examples of pectins are high methoxy pectin, high methoxy amidated pectin, low methoxy pectin, low methoxy amidated pectin, polygalacturonic acid, polygalacturonate salt, pectic acid, pectic acid salt, pectate, pectate salt, pectinic acid, pectinic acid salt, pectinate, or pectinate salt.

By way of description, the pectin of the present invention has a degree of esterification from about 0 to 80, preferably the pectin has a degree of esterification from about 0 to 50, and more preferably the pectin has a degree of esterification from about 0 to 25. Further, when dissolved in a cold aqueous system, the pectin has a clarity from about 70% to about 100%, and more preferably the pectin has a clarity, in a cold aqueous system, of about 80%> to about 100%. The pectin also has a bulk density from about 0.3 to about 1. Preferably, the pectin has a bulk density from about 0.4 to about 0.75. Further, the pectin is of the general formula:

Wherein: is an alpha (α) glycosidic bond;

N is an integer from 10 to 10,000; and O O

X is - C - OM or - C -NH₂; and

M is H^1" , a cation, a polyvalent cation or CH₃.

In addition, the pectin preferably has substantially the same thermal fingeφrint, obtained by thermogravimetric techniques, which is depicted in Figures 1, 2, and 4. IV. USES AND INDUSTRIAL APPLICABILITY

The present invention is contemplated for use with typical coated foodstuffs, pharmaceutical compositions, personal care products, and beverages. For example, any foodstuff which is coated with bread crumbs and is intended to be deep-fat fried or pan fried would be included in this invention. Such foodstuffs include fish, seafood, red meat, pork, fruits, and vegetables. Additionally, in pharmaceutical compositions, the present invention may be used as an encapsulating agent, a stabilizing agent, as a thickening agent, or it may be used to affect the dissolution rate of an active ingredient. Examples of these pharmaceutical compositions include tablets, capsules, topical gels, and wound dressings. With personal care products, the present invention is useful, as a thickening or emulsifying agent, in products such as skin moisturizing lotions, hair shampoos and conditioners, and the like. The present invention is further useful as a thickening and stabilizing agent in both powdered and liquid beverages, including powdered drinks, liquid fruit juices and dairy products, and liquid carbonated beverages.

The foodstuffs, such as vegetable, meat, fish, or poultry, are first coated with at least one coating and fried to form low fat food. The foodstuff is coated with hydrocoUoid, dried, and fried to produce a low oil product. Frying is carried out in cooking oil. As used herein, oil refers to cooking oil and/or fat. The coating may be applied as a powder or as a solution. The solvent of the solution may be water or a more volatile liquid to increase the rate of drying.

Initially, the coating is an aqueous system including the hydrocoUoid and a cross-linking agent such as polyvalent cations, for example calcium salts. The coating at least partially encases the outer the surface of the foodstuff, and it is dried prior to frying. The dried coating is adapted to substantially impede the penetration of oil into the foodstuff, and as such, the coated fried products have a low concentration of cooking oil.

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent.

The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.

EXAMPLES EXAMPLE 1 - HYDROCOLLOID PREPARATION (lab)

Add 300 g of LM1912 CSZ pectin to 15 liters of water at 90°C. Then mix the pectin - water system for 15 minutes to ensure that the pectin is completely dissolved in the water. After mixing the pectin - water system, cool the solution to 40 °C. Divide the cooled solution into two samples, and precipitate the pectin from the solution using an IP A/water mixture.

Precipitate the first sample using a 80/20 IP A/water mixture, and precipitate the second sample using a 50/50 IP A/water mixture. The results are tabulated in the following table.

*Clarity (%T) Control Method 48501 EXAMPLE 2 - HYDROCOLLOID PREPARATION (pilot plant)

Prepare a 2 kg batch of 5% LM1912 solution and cooled to room temperature. LM1912 CSZ 100 g

Water, deionized 1,900 g

To prepare the pectin, heat the water to approximately 90 °C, and, while agitating the water with an overhead mixer, slowly add the pectin. Once the pectin is completely dissolved, remove the heat source, and continue shear for approximately 10 minutes. Thereafter, cool the solution to room temperature. Divide the pectin solution into three 500 g batches. Then extract and wash the pectin using three different solutions of IP A/water.

Then precipitate the pectin out of solution in accordance with the following instruction.

1. Using the overhead mixer to agitate the system, pour the pectin solution into an IP A/water mixture. Shear the system to expose as much pectin surface area as possible. Then strain the system through cheese cloth and squeeze out the excess IP A/water mixture.

2. Repeat pectin washing step #1 , using an overhead mixer to mix the pectin and IP A/water system. Thereafter, strain the system through cheese cloth and squeeze out any excess IP A/water mixture.

3. Repeat pectin washing step #1, and squeeze out the excess IP A/water mixture as above. Then transfer the pectin to a glass or aluminum pan and dry at 50 °C. Remove pectin from oven, grind pectin in Wiley Mill, and return pectin to oven.

Once the pectin is dried, prepare an 1%> solution from the pectin above dried pectin by adding pectin to water at room temperature, i.e., 50°C, using a magnetic stirrer plate. That is, slowly disperse the pectin into agitated water, and continue agitating for 15 minutes. All three pectin batches, i.e., 1 through 3, dissolve in deionized water at room temperature. EXAMPLE 3 - FOODSTUFF COMPRISING THE HYDROCOLLOID POTATO STRIPS (French fries) CONTROL I Prefried

Fresh Idaho russet potatoes referred to by size as Idaho 100's (100 potatoes per 50 pound box) are sliced with a manual potato slicing device which produces consistent 7.95 mm by 7.95 mm (0.313 by 0.313 inch) strips. Twenty-five grams of strips are then washed in a large volume of cold water to remove surface starch and sugars. The washed strips are trimmed to 2.5 to 3.0 inches in length to form prefried strips. The strips are blanched by heating at 85 ° C for 8 minutes in water. The strips are then dried in a mechanical convection oven at 150° C for 10 minutes. Fried

Strips are then fried in two (2) gallons of oil at 170° C for three (3) minutes. At the completion of frying, the frying basket is removed from the oil and shaken by hand 5 seconds over the hot oil. The strips are then removed to paper towels to drain until cool.The product has

9.1 g of oil per 100 g product. FOODSTUFFS CONTAINING THE HYDROCOLLOID

Prefried

The potato strips are treated as in Control I but with the use of 0.5% aqueous solution of calcium chloride as blanch water. The strips are then are soaked in a 5% aqueous solution of low molecular weight, low ester (calcium reactive), pectin for 5 minutes at 37° C. The strips are then dried in a convection oven at 150° C for 10 minutes. Fried

Strips are then fried in two (2) gallons of oil at 170° C for three (3) minutes. At the completion of frying, the frying basket is removed from the oil and shaken by hand 5 seconds over the hot oil. The strips are then removed to paper towels to drain until cool. These product strips have an oil content of 6.1 g oil per 100 g of product.

EXAMPLE 4 - PROCESS FOR PREPARING AND COOKING BATTERED FOODSTUFF PECTIN TREATED BATTERED AND BREADED FISH PORTIONS: CALCIUM BAKED-IN INTO AMERICAN BREAD CRUMB

Tempered frozen fish portions are dusted with a pre-dust composition typical in the industry and then dipped in a commercially available adhesion batter (Kerry Ingredients, Golden Dipt Coating Division designation #G6046) using a Stein batter application unit. The battered fish portion is then coated with bread crumbs (Kerry Ingredients, Golden Dipt Coating Division designation ABC #J0570-T01) into which calcium chloride had been baked at a level of 1 ,200 mg per pound of crumbs. After breading, the fish portions are immersed into a 1.0% aqueous solution of calcium reactive pectin at 50° C or lower for 5 seconds. The pectin of this invention is suitable for this purpose. During the pectin 5 second dip, the food product will typically absorb approximately 0.35 to 0.55 grams of pectin per 100 square centimeters of battered and breaded surface area. The battered and breaded fish portions are then either frozen raw or par fried for 30 seconds at approx. 200 °C using a Stein continuous fryer and then frozen. The raw frozen fish portions are reconstituted for consumption by deep fat frying in a 50 pound Stein batch fryer for 4 minutes at 180°C. The oil level of this product is 4.3 g of fat per 100 g of product. The par fried fish portions are reconstituted for consumption by deep fat frying in a 50 pound Stein batch fryer for 4 minutes at 180°C. The oil level of this product is 7.5 g of fat per 100 g of product. The par fried fish portions are reconstituted for consumption by baking in a convection oven for 12 minutes at 235 °C. The oil level of this product is 7.2 g of fat per 100 g of product.

EXAMPLE 5 - PECTIN FIBER FOR WOUND DRESSINGS

A wet spinning method is illustrated in 30% calcium chloride by this example. Spinning conditions are as follows:

Flow rate 22 J mL/hour Diameter of nozzle 252 micrometers

Length of nozzle 1 cm

Coagulation bath 30 percent w/v calcium chloride (optionally the coagulation bath may contain non-solvent for pectins, such as ethanol, methanol, isopropyl alcohol, or the like)

Pectin concentration 2 percent w/v Pectin

The pectin is dissolved in deionized (DI) water at 50° C or lower to form a solution, centrifuged at 8,000 rpm, and filtered through a 5 micron filter. Using a syringe pump, this filtered solution is pumped at a flow rate of 22.1 mL/hr through a nozzle into a coagulation bath containing 30% of calcium chloride. The nozzle is located at the bottom of the bath with the opening of the nozzle pointed toward the top of the bath. Fibers that are formed are removed from the top of the bath and have a wet tensile strength of 1 J kg/mm². The wet fibers are rinsed first in DI water and then isopropyl alcohol; the fibers are then dried overnight under vacuum. The soft white pectin fibers produced after drying have an average diameter of about 44 micrometers and tensile strengths of 28.0 kg/mm² . Since a relatively high concentration of calcium chloride is used to induce rapid fiber formation, a solvent is not needed or used in this example to aid in phase separation of the pectin from solution. This example demonstrates that the use of solvents during the spinning process (not necessarily the drying process) can be avoided.

EXAMPLE 6 - FRUIT BEVERAGE To prepare a fruit drink containing the pectin of the present invention, obtain the following ingredients and combine them in the following manner.

First, mix ingredients (A) very carefully. Then, premix ingredients (B), very carefully, and disperse ingredients (B) in the mix (A). The mixture of (A) and (B) may be at room temperature. Thereafter, homogenize the mixture at 75-100 bars, and fill bottles (of any size) with the homogenized mixture. Finally, pasteurize the filled bottles at 85 °C for 10 minutes.

Please note that the use level of calcium chloride will depend on the calcium content in the fruit.

EXAMPLE 7 - POWDERED FRUIT BEVERAGE

To prepare a powdered fruit drink containing the pectin of the present invention, obtain the following ingredients and mix them in quantities set forth below. The mixed Fruit Drink Powder (Final Fruit Drink) can then be added to cold water to obtain a cold fruit drink.

the hydrated fruit drink powder mix. Soluble solids add to viscosity and mouth feel, and as such, higher amounts of soluble solids consequently reduce the need for pectin. Sugar free fruit drinks need the highest concentration of pectin.

EXAMPLE 8 - SKIN CREME

A skin cream (oil in water type) formulation according to the present invention is outlined below.

HydrocoUoid 0.50

Magnesium Aluminum Silicate 0.75

Cocoa Butter 1.25

Squalene 1.05

Isostearyl Isononanoate 2.25

DC Silicone Fluid 200®(50 CST) 1.25

DC Silicone Fluid 200®(100 CST) 0.50 Butylene Glycol 3.00

Glycerin 2.50

Sodium Hyaluronate 0.50

Tridecyl Salicylate 5.00

Glycereth-7 Hydroxystearate 1.50

Stearic Acid 3.50

Cetyl/Stearyl Alcohol 2.55

Sodium PCA 2.10

Glyceryl Hydroxystearate 1.25

Tocopherol 0.35

Methylparaben 0.20

Propylparaben 0.10

Glydant ® 0.30

Steareth-20 1.20

Disodium EDTA 0.05

Triethanolamine 1.50

Deionized Water quantum sufficit

EXAMPLE 9 - SUN SCREEN A protective skin lotion with sunscreen formulation according to the present invention is outlined below.

HydrocoUoid 0.15

Seppigel 501 ® 1.50

Shea Butter 1.50

Squalene 2.00

Coco Caprylate/Caprate 2.25

Propylene Glycol 3.55

Dicaprylate Dicaprate

DC Silicone Fluid 200®(20 CST) 0.50

DC Silicone Fluid 200®(350 CST) 1.00

Butylene Glycol 3.00

Glycerin 1.00

Sodium Hyaluronate 0.35

Tridecyl Salicylate 3.00 Cetyl Alcohol 1.00

DEA-Cetyl Phosphate 1.25

Parsol MCX ® 6.00

Benzophenone-3 3.00

Ceteth-2 0.50

Ceteareth-20 1.20

Methylparaben 0.30

Propylparaben 0.15

Glydant ® 0.20

Aloe Vera Gel 2.00

Tocopheryl Acetate 0.30

Disodium EDTA 0.05

Deionized Water quantum sufficit The preceding examples can be repeated with similar success by substituting the generically and specifically described constituents and/or operating conditions of this invention for those used in the preceding examples. From the foregoing descriptions, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt to various usages and conditions.

This application claims priority of U.S. Application No. 09/638,030, filed August 15, 2000, the disclosure of which is incoφorated by reference herein in its entirety.

Although the invention has been described with reference to particular means, materials and embodiments, it is to be understood that the invention is not limited to the particulars disclosed, and extends to all equivalents within the scope of the claims.

Claims

What is claimed is

1. A method for preparing a hydrocoUoid, said hydrocoUoid having a clarity of about 85% in a first aqueous system at a temperature below about 50°C, the method comprising:

(a) dissolving a precursor hydrocoUoid in a second aqueous system at a temperature above about 50 °C;

(b) precipitating said hydrocoUoid with a non-solvent; and

(c) drying said hydrocoUoid.

2. The method recited in claim 1, wherein said method is performed substantially in the absence of a sugar selected from at least one of sucrose, dextrose, lactose, maltose, fructose, glucose, com syrup, maple syrup, maple sugar, brown sugar, high fructose com syrup, invert sugar, and honey.

3. The method recited in claim 2, wherein said first aqueous system comprises water.

4. The method recited in claim 3, wherein said first aqueous solution consists of water.

5. The method recited in claim 3, further comprising adding said precursor hydrocoUoid to said second aqueous system in a ratio of about 120 grams per liter of the second aqueous system.

6. The method recited in claim 5, further comprising adding said precursor hydrocoUoid to said second aqueous system in a ratio of about 60 grams per liter of the second aqueous system.

7. The method recited in claim 6, further comprising adding said precursor hydrocoUoid to said second aqueous system in a ratio of about 30 grams per liter of the second aqueous system.

8. The method recited in claim 3, wherein the non-solvent comprises one or more of isopropyl alcohol, ethanol, and methanol.

9. The method recited in claim 8, wherein said non-solvent consists of isopropyl alcohol.

10. The method recited in claim 8, further comprising a ratio of said non-solvent and water in a range of about 60:40 to about 100:0 by weight percent.

11. The method recited in claim 10, further comprising a ratio of said non-solvent and water in a range of about 65:35 to about 90:10 by weight percent.

12. The method recited in claim 11, further comprising a ratio of said non-solvent and water in a range of about 70:30 to about 80:20 by weight percent.

13. The method recited in claim 3, wherein said hydrocoUoid is at least one of pectin, partially methoxylated galacturonic acid, polysaccharide gum, pregelatinized starch, agar, alginate, carrageenan, gum arabic, gum tragacanth, gum karaya, gellan gum, carboxymethyl cellulose, methyl cellulose, hydroxypropylmethyl cellulose, hydroxypropyl cellulose, modified starch, xanthan, konjac gum, locust bean gum, guar gum, dextran, curdlan, and pullulan.

14. The method recited in claim 13, wherein said hydrocoUoid is pectin.

15. The method recited in claim 14, wherein said pectin is at least one of high methoxy pectin, high methoxy amidated pectin, low methoxy pectin, low methoxy amidated pectin, polygalacturonic acid, polygalacturonate salt, pectic acid, pectic acid salt, pectate, pectate salt, pectinic acid, pectinic acid salt, pectinate, and pectinate salt.

16. The method recited in claim 15, wherein said pectin is at least one of high methoxy pectin, high methoxy amidated pectin, low methoxy pectin, low methoxy amidated pectin, polygalacturonic acid, polygalacturonate salt, pectic acid, and pectate salt.

17. The method recited in claim 14, wherein the molecular weight of said pectin is about 5,000 daltons to about 150,000 daltons.

18. The method recited in claim 17, wherein the molecular weight of said pectin is about 15,000 daltons to about 100,000 daltons.

19. The method recited in claim 17, wherein said pectin has a degree of esterification from about 0 to about 80.

20. The method recited in claim 19, wherein said pectin has a degree of esterification from about 0 to about 50.

21. The method recited in claim 20, wherein said pectin has a degree of esterification from about 0 to about 25.

22. The method recited in claim 19, wherein said pectin has a clarity in said first aqueous system from about 70%) to about 100%.

23. The method recited in claim 22, wherein said pectin has a clarity in said first aqueous system from about 80% to about 100%.

24. The method recited in claim 23, wherein said pectin has a clarity in said first aqueous system from about 85% to about 100%_>.

25. The method recited in claim 22, wherein the bulk density of said pectin is from about 0.3 to about 1.

26. The method recited in claim 25, wherein the bulk density of said pectin is from about 0.4 to about 0.75.

27. The method recited in claim 23, wherein said first aqueous system is at a temperature from about 0°C to about 50°C.

28. The method recited in claim 27, wherein said first aqueous system is at a temperature from about 5°C to about 35 °C.

29. The method recited in claim 13, wherein said hydrocoUoid has a degree of esterification from about 0 to about 80.

30. The method recited in claim 29, wherein said hydrocoUoid has a degree of esterification from about 0 to about 50.

31. The method recited in claim 30, wherein said hydrocoUoid has a degree of esterification from about 0 to about 25.

32. The method recited in claim 29, wherein said hydrocoUoid has a clarity in said first aqueous system from about 70% to about 100%).

33. The method recited in claim 32, wherein said hydrocoUoid has a clarity in said first aqueous system from about 80% to about 100%>.

34. The method recited in claim 33, wherein said hydrocoUoid has a clarity in said first aqueous system from about 85% to about 100%.

35. The method recited in claim 32, wherein the bulk density of said hydrocoUoid is from about 0.3 to about 1.

36. The method recited in claim 35, wherein the bulk density of said hydrocoUoid is from about 0.4 to about 0.75.

37. The method recited in claim 32, wherein said first aqueous system is at a temperature from about 0°C to about 50 °C.

38. The method recited in claim 37, wherein said first aqueous system is at a temperature from about 5°C to about 35 °C.

39. The method recited in claim 35, wherein said hydrocoUoid has the general formula:

Wherein: is an alpha (α) or a beta (β) glycosidic bond;

N is an integer from 10 to 10,000;

O O

X is - C - OM or - C -NH₂;

M is H⁺, a cation, a polyvalent cation, or CH₃;

CH,

R is H, CH₃, C₂H₅-, - (CH₂- CH₂- O)_y - H, or - CH₂ - CH - OH - ; and y is 1 or 2.

40. The method recited in claim 39, wherein said hydrocoUoid has substantially the thermal fingeφrint of Figure 4.

41. A method for preparing a pectin having a bulk density from about 0.4 to about 0.75, a degree of esterification from about 0% to about 25%, and a clarity of about 85% to about 100% in a first aqueous system at a temperature below 50 °C, said method comprising:

(b) precipitating said hydrocoUoid with a non-solvent comprising isopropyl alcohol; and

(c) drying said hydrocoUoid.

42. The method recited in claim 41, wherein said method is performed substantially in the absence of a sugar selected from at least one of sucrose, dextrose, lactose, maltose, fructose, glucose, com symp, maple symp, maple sugar, brown sugar, high fructose com symp, invert sugar, and honey.

43. A hydrocoUoid, having a clarity of about 85%> to about 100%> in a first aqueous system at a temperature below about 50 °C, a degree of esterification from about 0% to about 25%o, and a bulk density from about 0.4 to about 0.75.

44. The hydrocoUoid recited in claim 43, said hydrocoUoid being substantially free of a sugar selected from at least one of sucrose, dextrose, lactose, maltose, fructose, glucose, com symp, maple symp, maple sugar, brown sugar, high fructose com symp, invert sugar, and honey.

45. The hydrocoUoid recited in claim 44, said hydrocoUoid having the general formula:

Wherein: is an alpha (α) or a beta (β) glycosidic bond;

N is an integer from 10 to 10,000;

O O

X is - C - OM or - C -NH₂;

M is FfJ a cation, a polyvalent cation, or CH₃;

CH,

R is H, CH₃, C₂H₅ -, - (CH₂ - CH₂ - O)_y - H, or - CH₂ - CH - OH - ; and y is 1 or 2.

46. The method recited in claim 45, wherein said hydrocoUoid has substantially the thermal fingeφrint of Figure 4.

47. A foodstuff comprising the hydrocoUoid of claim 43.

48. The foodstuff recited in claim 47, wherein said foodstuff comprises one of food batter, foodstuffs coated with said food batter, processed meat products, chicken, fish, onion rings, potatoes, matrix meat, vegetables, or vegetable foods.

49. A pharmaceutical formulation comprising the hydrocoUoid of claim 43.

50. The pharmaceutical formulation recited in claim 49, wherein said pharmaceutical composition comprises one of tablets, wound dressings, capsules, topical gels, extracts, or syrups.

51. A personal care product comprising the hydrocoUoid of claim 43.

52. The personal care product recited in claim 51, wherein said personal care product comprises one of hair shampoos and conditioners, lipstick, perfumes, sun tan lotions, sun screen lotions, body lotions, deodorants, or antiperspirants.

53. A beverage comprising the hydrocoUoid of claim 43.

54. The beverage recited in claim 53, wherein said beverage comprises milk, alcoholic beverages, fruit juices, carbonated drinks, still drinks, or condensed compositions to be diluted.

55. A method of inhibiting oil adsoφtion/ absoφtion of a food product cooked in the oil, the method comprising the steps: a) coating a foodstuff with a batter composition, including a calcium reactive hydrocoUoid having a bulk density from about 0.4 to about 0.75, a degree of esterification from about 0% to about 25%, and a clarity of about 85% to about 100%) in a first aqueous system at a temperature below about 50 °C, to produce a batter-coated foodstuff; and b) coating the batter-coated foodstuff with a calcium salt enriched crumb composition to obtain a batter and cmmb-coated food product having a calcium-hydrocoUoid film resulting from the inaction of the calcium reactive hydrocoUoid and the calcium salt at the interface between the cmmb composition and the batter coated foodstuff.

56. The method in claim 55, said batter composition being substantially free of a sugar selected from at least one of sucrose, dextrose, lactose, maltose, fructose, glucose, com symp, maple symp, maple sugar, brown sugar, high fructose com syrup, invert sugar, and honey.

57. The method recited in claim 56, wherein said hydrocoUoid has the general formula:

Wherein: is an alpha ( ) or a beta (β) glycosidic bond;

N is an integer from 10 to 10,000;

O O

X is - C - OM or - C -NH₂;

M is Ε , a cation, a polyvalent cation, or CH₃;

CH,

R is H, CH₃, C₂H₅-, - (CH₂- CH₂- O)_y - H, or CH₂ - CH - OH - ; and y is 1 or 2.

58. The method recited in claim 57, wherein said hydrocoUoid has substantially the thermal fingeφrint of Figure 4.

59. A method of inhibiting oil absoφtion/adsoφtion of a foodstuff cooked in oil, comprising:

(a) coating a foodstuff with a batter composition to produce a batter-coated foodstuff;

(b) applying an aqueous solution comprising a hydrocoUoid having a bulk density from about 0.4 to about 0.75, a degree of esterification from about 0% to about 25%>, and a clarity of about 85% to about 100% in a first aqueous system at a temperature below about 50 °C; and

(c) drying the coated foodstuff.

60. The method recited in claim 59, said hydrocoUoid being substantially free of sugar selected from at least one of sucrose, dextrose, lactose, maltose, fructose, glucose, com syrup, maple symp, maple sugar, brown sugar, high fructose com symp, invert sugar, and honey.

61. The method recited in claim 60, wherein the battered foodstuff is at least one of chicken, fish, onion rings, potatoes, processed meat, matrix meat, vegetables, or vegetable foods.

62. The method recited in claim 60, wherein said hydrocoUoid has the general formula:

Wherein: is an alpha (α) or a beta (β) glycosidic bond;

N is an integer from 10 to 10,000;

O O

X is - C - OM or - C - NH₂;

M is Ff^" , a cation, a polyvalent cation, or CH₃;

CH,

R is H, CH₃, C₂H₅ -, - (CH₂ - CH₂ - O)_y - H, or - CH, - CH - OH - ; and y is 1 or 2.

63. The method recited in claim 62, wherein said hydrocoUoid has substantially the thermal fingeφrint of Figure 4.

64. A method for cooking a battered foodstuff with reduced oil or fat adsoφtion, said method comprising:

(a) coating said foodstuff with a batter composition to produce a batter coated foodstuff;

(b) applying an aqueous solution comprising a hydrocoUoid having a bulk density from about 0.4 to about 0.75, a degree of esterification from about 0% to about 25%>, and a clarity of about 85%o to about 100% in a first aqueous system at a temperature below about 50 °C;

(c) drying said foodstuff; and

(d) frying the dried, coated foodstuff, in cooking oil or fat in a temperature range of about 100°C to about 200 °C to form a batter coated foodstuff having reduced oil or fat content.

65. The method recited in claim 64, said hydrocoUoid being substantially free of sugar selected from at least one of sucrose, dextrose, lactose, maltose, fructose, glucose, com symp, maple symp, maple sugar, brown sugar, high fructose com symp, invert sugar, and honey.

66. The method recited in claim 65, said foodstuff comprising at least one of chicken, fish, onion rings, potatoes, processed meat, matrix meat, vegetables, or vegetable foods.

67. The method recited in claim 65, wherein said hydrocoUoid has the general formula:

Wherein: is an alpha (α) or a beta (β) glycosidic bond;

N is an integer from 10 to 10,000;

O O

X is - C - OM or C -NH M is H⁺ , a cation, a polyvalent cation, or CH₃;

CH,

68. The method recited in claim 67, wherein said hydrocoUoid has substantially the thermal fingeφrint of Figure 4.

69. The method recited in claim 26, wherein said pectin has the general formula:

Wherein: is an alpha ( ) glycosidic bond;

N is an integer from 10 to 10,000;

O O

X is - C - OM or - C - NH₂; and

M is H⁺ , a cation, a polyvalent cation, or CH₃.