Patent Application
20180352820
The present invention relates to a gelling agent made from modified konjac flour and methods for making those modifications. More specifically, this application discloses modifying the konjac flour in an alkali-alcohol solution so that the modified konjac glucomannan can be recovered and prepared to be a ready to gel konjac flour.
Konjac, Amorphophallus konjac, is a plant native to warm subtropical and tropical regions of East Asia. The plant produces large corms whose principle polysaccharide is glucomannan. Konjac is used to create flour, jelly, and the like, and can be used as a vegan substitute for gelatin.
Glucomannan is a long, branched polysaccharide comprising glucose and mannose. The structure, in relevant part is depicted in
This specification discloses a method for processing konjac glucomannan to make a gelling agent. In embodiments native konjac flour is mixed with an alkali-alcohol solution and is heated to sufficient temperature and for sufficient time to modify the konjac glucomannan so that it forms a gelling agent. Compared to the prior art, the method allows for the modified konjac gelling agent to be easily recovery so that it can be milled to form a powdered gelling agent.
In an embodiment the process comprises mixing konjac flour with an alkali-alcohol solution to modify the konjac flour, neutralizing the solution, recovering the modified konjac glucomannan, rinsing it with an alcohol, drying it, and further milling it to obtain a powdered modified konjac glucomannan gelling agent (also called a ready-to-gel konjac flour). The reaction is run in basic solutions having a pH above 7 and preferably above 10, more preferably in a range between 12 and 13. The reaction can be run at temperatures between ambient and near boiling. In embodiments the reaction is run at ambient temperature, between 20° C. and 25° C. In other embodiments the reaction is run at high temperature, between 90° C. and 99° C.
This specification also discloses a gelling agent made from konjac glucomannan. To make the gelling agent, konjac flour is modified so that it has fewer acetyl groups attached to the polysaccharide backbone than native konjac glucomannan. In one embodiment the modified konjac glucomannan has an acetylation of less than 1.2%, preferably less than 0.5%, and more preferably between 0.25% and 0.10%.
This specification also discloses methods of making gels from the konjac glucomannan gelling agent. The modified konjac flour forms viscous sols in water. To make gels, the aqueous modified konjac flour solution is stirred and heated to above an activation temperature. In embodiments, the solution is heated to between 90 and 99° C. for more than 1 minute. The solution forms gels without cooling.
This specification also discloses products made from the gels as well as processes for making such product. Such products included foodstuffs, cosmetics and industrial products. The products are made by mixing the modified konjac flour gelling agent with an aqueous solution to form a viscous sol and heating the sol to above an activation temperature to form a gel.
This specification discloses an improved process for modifying konjac flour that allows for more easily working with the flour in solution, more easily modifying the flour to make a gelling agent, and then more easily recovering the gelling agent. In one embodiment of the process konjac flour is mixed with an alkali-alcohol solution. The mixture is heated to sufficient temperature for sufficient time to modify the konjac flour to be a gelling agent.
In embodiments, the modified konjac flour is recovered by a filtration process or evaporative process.
In embodiments, the recovered modified konjac flour is neutralized by washing it in a buffered acidic solution until the pH of the recovered modified konjac flour is about neutral (i.e. pH between about 6 and about 8).
In embodiments, the gelling agent can then be washed and dried to form a powder.
More particularly, konjac flour is mixed in an alkali-alcohol solution. Any commonly available alcohol is suitable for the process. For example, methy, etheyl, propyl, and isopropyl alcohols may be used. The pH of the alcohol solution may be adjusted prior to or after the konjac flour is added. The reaction is run in basic solution (i.e. having pH greater than 7). Reaction time and yield improves with increased pH. In embodiments the pH is greater than 7.5. In embodiments the solution has pH greater than 10. In other embodiments the pH is greater than 11. In other embodiments the pH is between 12 and 13.
Konjac flours have different amounts of glucomannan. Standard commercial variants have between 55% and 85% glucomannan. The amount of glucomannan in the flour affects the yield of the gelling agent. So, konjac flours having higher glucomannan content are preferred.
In embodiments of the method, alcohol concentrations in the solution should be sufficiently high to minimize dissolution of konjac flour, and to aid in controlling the viscosity of the solution. In embodiments of the invention the alcohol concentration is at least 20% by volume (i.e between about 20% and about 100%). In embodiments it is about 50% by volume of alcohol. Konjac flour is mixed with the alcohol solution in a ratio of at least 1:2 and more typically in a 1:4 ratio.
Persons of ordinary skill in the art understand how to mix the alcohol and alkali solution to reach the desired pH range. For food applications, suitable food grade bases for use in the pH adjustment step include sodium hydroxide, sodium carbonate, sodium citrate, tetrasodium pyrophosphate, ammonium orthophosphate, disodium orthophosphate, trisodium phosphate, calcium carbonate, calcium hydroxide, potassium carbonate, potassium hydroxide, and potassium citrate. Particularly useful food grade bases are sodium hydroxide, sodium carbonate and potassium citrate.
Without being bound by theory, it is proposed that konjac glucomannan is deacetylated in solution. Native konjac glucomannan has an acetylation percentage of around 2%. Gels can be successfully made if the amount of acetylation is reduced to about 1.25% or less. More effective gelling agents are made with lower amounts of acetylation—i.e. stronger gels can be made with less gelling agents. So preferred amounts of acetylation are below 1%, more preferably below 0.5% and more preferably between about 0.25% and 0.10%
A person of ordinary skill in the art will understand that reaction times will vary with conditions. In embodiments konjac flours (85% glucomannan) having acetylation levels of between 0.25% and 0.20% were obtained by mixing with 50% ethanol solution (v/v, 80 g) at pH between 12 and 13 and heating to between about 25° C. to about 95° C. for between 1 to 3 hours.
The time to deacetylate the konjac flour will vary based on temperature and pH, typical reactions run for between 5 minutes and 3 hours. In one embodiment the reaction is run at temperatures between about 20° C. and about 25° C. for between about 2 and about 3 hours at pH of about 12.5 and above. In another embodiment the reaction is run at temperatures between 90° C. and 99° C. for between about 1 and about 2 hours at pH between about 11 and about 12.5.
The konjac may also be further modified, for example, chemically, enzymatically or physically to further adjust properties of the konjac.
Modified konjac flour is recovered by neutralizing the solution and filtering the suspended modified konjac flour. The recovered modified konjac flour is then washed in a suitable alcohol, such as methanol, ethanol, propanol, or isopropanol. The recovered modified konjac flour can be milled and sieved to make modified konjac glucomannan flour that acts a gelling agent.
Disclosed herein is a process for making gels from modified konjac flour. The modified konjac flour is water soluble, forming a viscous solution. A person of ordinary skill in the art would understand that gel strength and sol viscosity can be adjusted by using different amounts of the konjac flour gelling aging. In embodiments about 0.25% to about 10% (w/w) konjac gelling agent is added to water, preferably between about 0.5% and about 5% and more preferably between about 1% and about 3%. The modified konjac flour in solution is mixed for between about 0.5 and about 4 hours to develop viscosity.
To form a gel, the aqueous modified konjac solution is heated at sufficient temperature and for sufficient time to activate the modified konjac flour (i.e. enable it to form gels). In embodiments the aqueous konjac solution is heated to temperatures of 50° C., but more typically between 90° C. and 99° C. (the activation temperature). In embodiments the modified konjac flour solution is maintained at or above the activation temperature for between 1 minute and about 60 minutes until the gel forms. Gels form at high temperature without cooling. In an exemplary embodiment a 1.5%, by weight, modified konjac flour/water slurry that was heated to 90° C. for 30 minutes formed a firm set, elastic, opaque gel.
The gelling agents made using the disclosed method can be used to form gels useful in various food applications. Examples include, but are not limited to, imitation cheeses, soups, desserts, sauces, gravies, pie fillings, yogurts, puddings, dressings, sausage casings, jellies, and gelatinized snack, and to replace gelatin, gums, and alginates in food.
The gelling agents may also be used in non-comestible applications, such as in cosmetics, personal hygiene or industrial detergents and conditioners, or in industrial, and in pharmaceutical or nutraceutical applications where gelling agents are of use. As examples, in addition to gels, konjac flour may be used to form suspensions, emulsions, and encapsulating compounds that are useful for making beadlets, microcapsules, capsules, tablets, solutions etc. that preserve and deliver active pharmaceutical ingredients, vitamins, minerals, nutritional supplements, conditioning agents, detergents, fragrances, colorants, ingredients for textile sizing, etc.
End products, whether comestible or not, using the konjac gelling agent are made using the konjac gelling agent alone in combination with other ingredients. The other ingredients will be dictated by the end use. Such ingredients may include modified and unmodified dairy products and proteins; sweeteners, including sugars, syrups, and their derivatives; fruit or fruit pectin etc.; seasoning salts, emulsifying salts and other, preservative salts; and animal and vegetable fats. Additionally, the konjac flour may be mixed with other starches, flours, protein concentrates and isolates that are modified (chemically, physically, or enzymatically) or not. The base flour may come from various sources, including pulses, wheat, oats, corn, sorgum, arrowroot, sago, potato, tapioca, rice, and waxy and high amylose variants. The modified konjac flour can be used as the sole gelling agent, or in combination with other gelling agents such as gelatin or modified and unmodified gums starches, fibers, and proteins. The konjac flour also may be combined with or plasticizers, including polyols (sorbitol, mannitol, glycerol, etc.). The gelling agent will be added as per the needs of the application but generally in amounts of between 0.1% and 50% flour (w/w) based on the end product, and all ranges in between.
Certain aspects of the present invention are further described by way of the following examples, which are provided as illustrations and should not be construed to limit the scope of the invention in any way. Persons of ordinary skill in the art will recognize that routine modifications may be made to the methods and materials used in the examples, which would still fall with in the spirit and scope of the present invention.
konjac flour was prepared according to the following methods to remove the acetyl group. Konjac flour (85% glucomannan, 20 g) was mixed in a 1:4 ratio with 50% ethanol solution (80 g) at pH 11-12.5 (adjusted using 50% NaOH solution) at room temperature (about 22° C.) or at 95° C. for 1.5-2.5 hrs. The treated konjac flour was neutralized, washed with ethanol several times, and then dried in a hood at room temperature.
The amount of acetyl groups in the konjac flour was measured according to following method: Konjac flour was solubilized by an acid (4%, w/w, DCl/D2O) in a pressure cooker. The solubilized samples were analyzed using a proton NMR spectrometer (Bruker AV-400). The acetyl levels of konjac flour samples are summarized in Table 1.
As seen, the native Konjac flour had 1.86% acetyl groups, which is higher than any of the alkali-alcohol treated samples. The four alkali-alcohol samples, samples 1, 2, 3, and 4, have acetyl levels of 0.23%, 1.13%, 0.15%, and 0.16%, respectively. This suggests that the treatment removes the acetyl group from the konjac glucomannan. Further, consideration of the results shows that higher pH solutions remove the acetyl group more efficiently. (Compare Sample 2, with Sample 3). Also, Sample 4 shows that sufficiently high pH the acetyl groups can be removed at room temperature.
solutions made with modified and unmodified konjac flour were tested for the ability to form gels. The solutions were 1.5% konjac flour (w/w) in water. The solution was stirred for about 2.5 h at room temperature. Both treated and native solutions attained the high viscosity characteristic of konjac glucomannan sols. The solutions were then covered with foil and then heated in a boiling water bath for 30 min.
