DEACETYLATION AND CROSSLINKING OF CHITIN AND CHITOSAN IN FUNGAL MATERIALS AND THEIR COMPOSITES FOR TUNABLE PROPERTIES

Abstract

Fungal crosslinked structures, fungal crosslinking systems, and methods for crosslinking a fungal material. The crosslinked fungal material described herein comprises a variety of crosslinkers, crosslinking sites, and various combinations of crosslinks, each forming unique structures. The crosslinked fungal material comprises at least one crosslinking compound attached to a bonding site. The fungal crosslinking system includes a preparation unit, an impregnating unit, a crosslinking unit and a rinsing unit. The preparation unit may partially deacetylate chitin within the fungal material and within chitin nanowhiskers. The impregnating unit impregnates the fungal material with chitin nanowhiskers. The crosslinking unit is configured to crosslink the fungal material and chitin nanowhiskers via genipin to create a composite material. The rinsing unit rinses and removes unreacted genipin material thereby rendering a crosslinked composite material. The resulting crosslinked composite material is stronger and more flexible than the original fungal material with improved chemical and mechanical properties.

Claims

1. A method for crosslinking a fungal material utilizing a fungal crosslinking system to create a crosslinked composite material stronger and more flexible than the original fungal material, the method comprising the steps of: a) providing the fungal crosslinking system having a preparation unit, an impregnating unit, a crosslinking unit and a rinsing unit; b) partially deacetylating chitin within the fungal material and within chitin nanowhiskers in the deacetylating unit by submerging chitin nanowhiskers and the fungal material in an aqueous solution of sodium hydroxide at an optimal temperature for a deacetylating time period; c) impregnating the fungal material with chitin nanowhiskers through soaking and agitation in the impregnating unit; d) crosslinking the fungal material and chitin nanowhiskers in the crosslinking unit by (i) dissolving a genipin material in acetic acid to create a genipin first mixture, (ii) mixing the genipin first mixture with a mixing solution to generate a genipin second mixture and (iii) applying the genipin second mixture to the fungal material at a genipin utilization rate at an incubation condition with agitation to create a composite material; e) rinsing the composite material in the rinsing unit with water thereby neutralizing the composite material to an optimum pH value; and f) removing unreacted genipin material to generate a crosslinked composite material.

2. The method of claim 1 wherein the optimal temperature for partial deacetylation of chitin is around 80 degrees and the deacetylating time period ranges from one minute to ten hours.

3. The method of claim 1 wherein the mixing solution has a pH rate ranging from 2 to 3.

4. The method of claim 1 wherein the genipin utilization rate ranges from 0.05%-4% w/w to the weight of the genipin polymer.

5. The method of claim 1 wherein the incubation condition for incubating the genipin fungal mixture includes an incubation time ranging from 40 minutes to several hours and an incubation temperature of 25 degree Celsius.

6. The method of claim 1 wherein the composite material is neutralized at the optimum pH value of 7.

7. A method for crosslinking a fungal material utilizing a fungal crosslinking system, the method comprising the steps of: a) providing the fungal crosslinking system having a deacetylating unit, an impregnating unit, a crosslinking unit and a rinsing unit; b) partially deacetylating chitin within the fungal material and within chitin nanowhiskers in the deacetylating unit by submerging chitin nanowhiskers and the fungal material in an aqueous solution of sodium hydroxide at an optimal temperature for a deacetylating time period; c) impregnating the fungal material with chitin nanowhiskers through soaking and agitation in the impregnating unit; d) crosslinking the fungal material and chitin nanowhiskers in the crosslinking unit by (i) dissolving a genipin material in acetic acid to create a genipin first mixture, (ii) mixing the genipin first mixture with a mixing solution to generate a genipin second mixture and (iii) applying the genipin second mixture to the fungal material at a genipin utilization rate to create a genipin fungal mixture that being incubated at an incubation condition with agitation to create a composite material; e) rinsing the composite material in the rinsing unit with water thereby neutralizing the composite material to an optimum pH value; and f) removing unreacted genipin material to generate a crosslinked composite material with improved strength and flexibility.

8. A fungal crosslinking system comprising: a deacetylating unit for partially deacetylating chitin within a fungal material and within chitin nanowhiskers; an impregnating unit for impregnating the fungal material with chitin nanowhiskers; a crosslinking unit for crosslinking the fungal material and chitin nanowhiskers, the crosslinking unit being configured to dissolve a genipin material in acetic acid to create a genipin first mixture, to mix the genipin first mixture with a mixing solution thereby generating a genipin second mixture and to apply the genipin second mixture to the fungal material at a genipin utilization rate to create a genipin fungal mixture that being incubated at an incubation condition with agitation to create a composite material; and a rinsing unit for rinsing the composite material with water thereby generating a crosslinked composite material with increased strength and flexibility.

9. The fungal crosslinking system of claim 8, wherein the deacetylating unit partially deacetylates chitin within the fungal material and within chitin nanowhiskers by submerging chitin nanowhiskers and the fungal material in an aqueous solution of 40% by weight of sodium hydroxide at an optimal temperature for a deacetylating time period.

10. The fungal crosslinking system of claim 8 wherein the crosslinking unit utilize bonding at hydroxyl group sites, amine group sites including syntan tannins, carbon-carbon bond sites, aldehyde group sites including formaldehyde and glutaraldehyde, phenolic group sites including vegetable tannins and polysaccharides and metal complex sites.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Elements in the figures have not necessarily been drawn to scale in order to enhance their clarity and improve understanding of these various elements and embodiments of the invention. Furthermore, elements that are known to be common and well understood to those in the industry are not depicted in order to provide a clear view of the various embodiments of the invention. Thus, the drawings are generalized in form in the interest of clarity and conciseness.

[0020] FIG. 1 illustrates a block diagram of a fungal crosslinking system in accordance with one embodiment of the present invention;

[0021] FIG. 2 illustrates a high-level flowchart of a method for crosslinking a fungal material utilizing the fungal crosslinking system in accordance with the preferred embodiment of the present invention;

[0022] FIG. 3 illustrates a flowchart of the method for crosslinking the fungal material in accordance with the preferred embodiment of the present invention;

[0023] FIG. 4 is an SEM image illustrating the chainlike filamentous fiber structure of the hyphae that are comprised of chitin;

[0024] FIG. 5 illustrates a simple crosslinking system between a pair of chitin fibers such as would be present in fungal materials and their composites;

[0025] FIG. 6 illustrates the acetamide group, or amine group, bonding site for the various crosslinking molecules in accordance with several embodiments of the present invention;

[0026] FIG. 7 illustrates the hydroxyl bonding sites for the different crosslinking molecules in accordance with several embodiments of the present invention;

[0027] FIG. 8 illustrates the process of deacetylation of chitin into chitosan in accordance with one embodiment of the present invention; and

[0028] FIG. 9 illustrates the enhanced tensile strength of polysaccharide material crosslinked with vegetable tannin versus natural polysaccharide material.

DETAILED DESCRIPTION OF THE DRAWINGS

[0029] In the following discussion that addresses a number of embodiments and applications of the present invention, reference is made to the accompanying drawings that form a part hereof, and in which is shown by way of illustration specific embodiments in which the invention may be practiced. It is to be understood that other embodiments may be utilized and changes may be made without departing from the scope of the present invention.

[0030] Various inventive features are described below that can each be used independently of one another or in combination with other features. However, any single inventive feature may not address any of the problems discussed above or only address one of the problems discussed above. Further, one or more of the problems discussed above may not be fully addressed by any of the features described below.

[0031] As used herein, the singular forms “a”, “an” and “the” include plural referents unless the context clearly dictates otherwise. “And” as used herein is interchangeably used with “or” unless expressly stated otherwise. As used herein, the term “about” means +/−5% of the recited parameter. All embodiments of any aspect of the invention can be used in combination, unless the context clearly dictates otherwise.

[0032] Unless the context clearly requires otherwise, throughout the description and the claims, the words “comprise”, “comprising”, and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of “including, but not limited to”. Words using the singular or plural number also include the plural and singular number, respectively. Additionally, the words “herein,” “wherein”, “whereas”, “above,” and “below” and words of similar import, when used in this application, shall refer to this application as a whole and not to any particular portions of the application.

[0033] The description of embodiments of the disclosure is not intended to be exhaustive or to limit the disclosure to the precise form disclosed. While the specific embodiments of, and examples for, the disclosure are described herein for illustrative purposes, various equivalent modifications are possible within the scope of the disclosure, as those skilled in the relevant art will recognize.

[0034] Referring to FIG. 1, a method for crosslinking a fungal material utilizing a fungal crosslinking system 10 for crosslinking a fungal material and/or fungal composite material with itself and/or each other is illustrated. Crosslinking allows for control of many useful fungal properties, including mechanical properties such as tensile strength, tear strength, abrasion resistance and other chemical properties such as dye fixation. FIG. 9 exemplifies this increase in strength, showing the strength increase of a cellulosic, polysaccharide material that was crosslinked with vegetable tannin versus a natural polysaccharide material.

[0035] The fungal crosslinking system 10 comprises a preparation unit 12, which in the preferred embodiment is a deacetylation preparation unit, an impregnating unit 14, a crosslinking unit 16 and a rinsing unit 18. In one embodiment, the preparation unit 12 partially deacetylates chitin within the fungal material. If the impregnating unit calls for the addition of the composite material, chitin nanowhiskers and the fungal material are submerged in an aqueous solution of 40% by weight of sodium hydroxide at an optimal temperature for a deacetylating time period. In the preferred embodiment, the optimal temperature is 80 degrees Celsius and the deacetylating time period ranges from one minute to ten hours to achieve degrees of acetylation from 1% to 50% as desired.

[0036] The impregnating unit 14 is configured to impregnate the fungal material with chitin nanowhiskers and the crosslinking unit 16 through soaking and agitation. In a first embodiment, the crosslinking unit 16 is designed to crosslink the fungal material and composite material (such as cellulosic textiles) with themselves and each other. In said first embodiment, crosslinking is also achieved without the addition of a deacetylating agent such as genipin.

[0037] In a second embodiment, the crosslinking unit 16 is designed to crosslink the fungal material and composite (such as cellulosic textiles) with themselves and each other using genipin material. In order to create a genipin first mixture, commercially available genipin powder is dissolved in acetic acid. The genipin first mixture is then mixed with a mixing solution to generate a genipin second mixture. The mixing solution has a pH rate ranging from 2 to 3. In said second embodiment of the invention, the genipin second mixture is applied to the fungal material at a genipin utilization rate to create a genipin fungal mixture which is incubated at an incubation condition with agitation to create a composite material. The genipin utilization rate ranges from 0.05%-4% w/w to the weight of the genipin polymer. Preferably, the incubation condition for incubating the genipin fungal mixture includes an incubation time of 40 minutes to several hours and an incubation temperature of 25 degrees Celsius with agitation.

[0038] The rinsing unit 18 rinses the composite material with water thereby neutralizing the composite material to an optimum pH value of 7 and removes unreacted genipin material to generate a crosslinked composite material. The resulting crosslinked composite material is stronger and more flexible than the original fungal material and comprises improved chemical and mechanical properties.

[0039] FIG. 2 illustrates a high-level flowchart of a chemical method for crosslinking the fungal material utilizing genipin material. As illustrated in FIG. 2, the method of the second embodiment of the present invention commences by partially deacetylating chitin within the fungal material and within chitin nanowhiskers in the deacetylating unit as shown in block 20. Next, the fungal material is applied with chitin nanowhiskers in the impregnating unit as shown in block 22. Thereafter, the fungal material and chitin nanowhiskers are crosslinked to create the composite material in the crosslinking unit as shown in block 24. Finally, the rinsing unit rinses the composite material thereby generating the crosslinked composite material as shown in block 26.

[0040] FIG. 3 illustrates a flowchart that describes the method for crosslinking the fungal material in detail. The crosslinking method starts by providing the fungal crosslinking system as shown in block 30. Next, chitin within the fungal material and within chitin nanowhiskers is partially deacetylated in the deacetylating unit as indicated at block 32. In this step of partial deacetylation, chitin nanowhiskers and the fungal material are submerged in the aqueous solution of sodium hydroxide at the optimal temperature for the deacetylating time period.

[0041] Thereafter, the fungal material is impregnated with chitin nanowhiskers through soaking and agitation in the impregnating unit as shown in block 34. Next, the fungal material and chitin nanowhiskers are crosslinked in the crosslinking unit by dissolving the genipin material in acetic acid to create a genipin first mixture as shown in block 36. Then, the genipin first mixture is mixed with the mixing solution to generate the genipin second mixture as shown in block 38. Upon generating the genipin second mixture, the genipin second mixture is applied to the fungal material at the genipin utilization rate to create the genipin fungal mixture as indicated at block 40. Next, the genipin fungal mixture is incubated at the incubation condition with agitation to create the composite material as shown in block 42. Thereafter, the composite material is rinsed in the rinsing unit with water thereby neutralizing the composite material to the optimum pH value as shown in block 44. Finally, the unreacted genipin material is removed to generate the crosslinked composite material as indicated at block 46.

[0042] In some embodiments, the above-described crosslinking methods are applied to leather-like fungus-based materials or composites with the aim of increasing tensile strength, tear strength, flexibility and other desirable qualities within that material. Notably, the present structures and methods control the chemical and mechanical properties of fungal materials and their composites for applications in textiles, packaging, building materials, and other industries where such materials are utilized.

[0043] The physical crosslinking of fungal material is achieved by chemically linking the branched, filamentous fibers contained in fungal material. As shown in the SEM image of FIG. 4, the strands of mycelium, also called Hyphae, comprise spaghetti-like strands made of chitin. A simple diagrammatic representation of the crosslinking of chitin is shown in FIG. 5.

[0044] A third embodiment of the present invention comprises a crosslinked fungal composite material wherein the acetamide groups on the chitin chain are targeted for modification, as shown in FIG. 6. The acetamide groups on the chitin are utilized to create a bonding site for compounds that attach through an amide bond. Compounds that attached through an amide bond include glutaraldehyde, metal-complex tannins, and synthetic tannins (“syntans” or “syntan compounds”). In some embodiments, the acetamide groups are deacetylated into amine groups. Notably, deacetylated chitin is also referred to as chitosan.

[0045] A fourth embodiment of the present invention comprises a crosslinked fungal composite wherein the links are created by phenolic compounds such as vegetable tannins, among polysaccharides (sugar molecules) which exist on the hyphal cells. Such a crosslinked fungal material would exhibit links between bonding sites on the hydroxyl groups of the polysaccharides. Such hydroxyl groups of the polysaccharides are highlighted by a dashed circle in FIG. 7. These polysaccharide bonding sites may also be on the cellulosic material that is used as the composite along with the fungal material, such as a cotton textile layer. As described above, links may also be created by the partial degradation of chitin molecules into chitosan followed by a reaction with genipin.

[0046] Another embodiment of the present invention utilizes bonding sites on the carbonaceous backbone of the chitin molecule itself. Binding to the carbonaceous backbone may be achieved by various methods known to persons skilled in the art and as described herein.

[0047] Further embodiments of the present invention comprise combinations of the above bonding mechanisms, wherein a crosslinking compound or molecule acts as a bridge between dissimilar bonding sites, resulting in crosslinked chitin or chitosan fibers. Bonding between dissimilar bonding sites may include: hydroxyl to carbon bonding, hydroxyl to amine bonding, carbon to carbon bonding, carbon to amine bonding, and the like.

[0048] A summary of distinct embodiments of crosslinked fungal composites is provided in Table 1 below:

TABLE-US-00001 TABLE 1 Crosslinking Compound or Molecule Link A Link B Bonding-site Glutaraldehyde Chitinand/or Chitinand/or Hydroxyl and/or (condensation) Polysaccharide Polysaccharide Amine Groups Vegetable Extract Polysaccharide Polysaccharide Hydroxyl Groups (phenolic or and/or Chitin and/or Chitin polyphenolic compounds) Syntans (synthetic Chitinand/or Chitinand/or Amine Groups tannins) Polysaccharide Polysaccharide Metal Complex Deacetylated Deacetylated Carboxyl Groups (Mineral) Chitin Chitin Genipin Deacetylated Deacetylated Amine Group on Chitin Chitin Chitosan Carbon-Carbon Carbon Carbon Covalent Bonding Combinations of the above

[0049] Table 1 shows that chitin-containing and/or polysaccharide-containing compositions may include crosslinking compounds attached to bonding sites. If a bonding site comprises, for example, a hydroxyl group and/or an amine group, then a glutaraldehyde crosslinking compound may serve as a suitable crosslinking molecule. Also, if a hydroxyl group bonding site is present, then phenolic compounds such as those found in vegetable extracts may serve as a suitable crosslinking molecule. Another embodiment illustrated in Table 1 involves an amine group bonding site. If an amine group bonding site is present, then a syntan compound (synthetic tannins) may serve as a suitable crosslinking molecule.

[0050] Yet another embodiment illustrated in Table 1 comprises a carboxyl group bonding site. If a carboxyl group bonding site is present, then a metal complex may serve as a suitable crosslinking molecule. In addition, covalent carbon-carbon bonds may be formed using carbonaceous linker segments. As described in Table 1, various combinations of the above-described crosslinking compounds and bonding sites are contemplated in the present invention.

[0051] Further to the above, crosslinking may be facilitated by a secondary constituent and a tertiary crosslinking compound. Said tertiary compound may form a crosslink between the fungal material and the secondary constituent. While said fungal material crosslinks to the secondary constituent, it may also crosslink to itself. Similarly, the secondary material may crosslink to itself. Finally, the tertiary compound may agglomerate into larger, polymeric chains that are then bonded to the fungal material and/or the secondary constituent. As a direct result of these heterogeneous conformational and chemical arrangements, the resulting crosslinked materials often exhibit tensile strength that is greater than the sum of the fungal material and secondary constituent alone, as exemplified in FIG. 9.

[0052] The foregoing description of the preferred embodiment of the present invention has been presented for the purpose of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications and variations are possible in light of the above teachings. It is intended that the scope of the present invention not be limited by this detailed description, but by the claims and the equivalents to the claims appended hereto.