rexresearch
rexresearch1

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Takuzo AIDA, et al.
Supramolecular Plastic

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https://www.riken.jp/en/news_pubs/research_news/pr/2024/20241122_1/index.html
Bye-bye microplastics: new plastic is recyclable and fully ocean-degradable

Researchers led by Takuzo Aida at the RIKEN Center for Emergent Matter Science (CEMS) have developed a durable plastic that won’t contribute to microplastic pollution in our oceans. The new material is as strong as conventional plastics and biodegradable, but what makes it special is that it breaks down in seawater. The new plastic is therefore expected to help reduce harmful microplastic pollution that accumulates in oceans and soil and eventually enters the food chain. The experimental findings were published Nov 22 in Science.

Scientists have been trying to develop safe and sustainable materials that can replace traditional plastics, which are non-sustainable and harm the environment. While some recyclable and biodegradable plastics exist, one big problem remains. Current biodegradable plastics like PLA often find their way into the ocean where they cannot be degraded because they are water insoluble. As a result, microplastics—plastic bits smaller than 5 mm—are harming aquatic life and finding their way into the food chain, including our own bodies.

In their new study, Aida and his team focused on solving this problem with supramolecular plastics—polymers with structures held together by reversible interactions. The new plastics were made by combining two ionic monomers that form cross-linked salt bridges, which provide strength and flexibility. In the initial tests, one of the monomers was a common food additive called sodium hexametaphosphate and the other was any of several guanidinium ion-based monomers. Both monomers can be metabolized by bacteria, ensuring biodegradability once the plastic is dissolved into its components.

“While the reversable nature of the bonds in supramolecular plastics have been thought to make them weak and unstable,” says Aida, “our new materials are just the opposite.” In the new material, the salt bridges structure is irreversible unless exposed to electrolytes like those found in seawater. The key discovery was how to create these selectively irreversible cross links.

As with oil with water, after mixing the two monomers together in water, the researchers observed two separated liquids. One was thick and viscous and contained the important structural cross linked salt bridges, while the other was watery and contained salt ions. For example, when sodium hexametaphosphate and alkyl diguanidinium sulfate were used, sodium sulphate salt was expelled into the watery layer. The final plastic, alkyl SP2, was made by drying what remained in the thick viscous liquid layer.

The “desalting” turned out to be the critical step; without it, the resulting dried material was a brittle crystal, unfit for use. Resalting the plastic by placing it in salt water caused the interactions to reverse and the plastic’s structure destabilized in a matter of hours. Thus, having created a strong and durable plastic that can still be dissolved under certain conditions, the researchers next tested the plastic’s quality.

The new plastics are non-toxic and non-flammable—meaning no CO2 emissions—and can be reshaped at temperatures above 120°C like other thermoplastics. By testing different types of guanidinium sulfates, the team was able to generate plastics that had varying hardnesses and tensile strengths, all comparable or better than conventional plastics. This means that the new type of plastic can be customized for need; hard scratch resistant plastics, rubber silicone-like plastics, strong weight-bearing plastics, or low tensile flexible plastics are all possible. The researchers also created ocean-degradable plastics using polysaccharides that form cross-linked salt bridges with guanidinium monomers. Plastics like these can be used in 3D printing as well as medical or health-related applications.

Lastly, the researchers investigated the new plastic’s recyclability and biodegradability. After dissolving the initial new plastic in salt water, they were able to recover 91% of the hexametaphosphate and 82% of the guanidinium as powders, indicating that recycling is easy and efficient. In soil, sheets of the new plastic degraded completely over the course of 10 days, supplying the soil with phosphorous and nitrogen similar to a fertilizer.

“With this new material, we have created a new family of plastics that are strong, stable, recyclable, can serve multiple functions, and importantly, do not generate microplastics,” says Aida.

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Takuzo Aida, Group Director
Emergent Soft Matter Function Research Group

https://www.riken.jp/en/research/labs/cems/emerg_soft_matter_funct/
RIKEN Center for Emergent Matter Science
https://www.riken.jp/en/research/labs/cems/
#101 Frontier Research Laboratory, 2-1 Hirosawa, Wako, Saitama 351-0198 Japan
E-mail：takuzo.aida[at]riken.jp

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https://www.science.org/doi/10.1126/science.ado1782
Mechanically strong yet metabolizable supramolecular plastics by desalting upon phase separation
Yiren Cheng, et al
Editor’s summary
A strong, glassy supramolecular polymer has been shown to prevent the formation of marine microplastics by slowly dissolving in salt water into metabolizable compounds. Cheng et al. show that salt bridging between sodium hexametaphosphate or sulfated polysaccharides and guanidinium sulfates expels sodium sulfate to create a cross-linked network that is stable until the electrolytes are added back. The dried material is a moldable and recyclable thermoplastic that can be water stabilized with hydrophobic coatings. —Phil Szuromi
Abstract
Plastics that can metabolize in oceans are highly sought for a sustainable future. In this work, we report the noncovalent synthesis of unprecedented plastics that are mechanically strong yet metabolizable under biologically relevant conditions owing to their dissociative nature with electrolytes. Salt-bridging sodium hexametaphosphate with di- or tritopic guanidinium sulfate in water forms a cross-linked supramolecular network, which is stable unless electrolytes are resupplied. This unusual stability is caused by a liquid-liquid phase separation that expels sodium sulfate, generated upon salt bridging, into a water-rich phase. Drying the remaining condensed liquid phase yields glassy plastics that are thermally reshapable, such as thermoplastics, and usable even in aqueous media with hydrophobic parylene C coating. This approach can be extended to polysaccharide-based supramolecular plastics that are applicable for three-dimensional printing.

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https://www.justhaveathink.com/
https://www.youtube.com/watch?v=zRYZymbchM4
New plastic gamechanger. NO FOSSIL FUELS! NO MICROPLASTICS!

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WO2024135791
Mechanically robust sustainable plastics and their green, non-covalent manufacturing method
[ PDF ]

The present invention relates to mechanically robust, sustainable plastics and methods for their production.

Various plastics such as polyethylene terephthalate, polycarbonate, polymethacrylate, polyolefin, and polyurethane are used in our daily lives.
Since 1950, over 8.3 billion tons of plastic have been produced, of which 6.3 billion tons have been discarded as waste (Non-Patent Document 1), and the impact of used plastics on the environment, such as the ocean and soil, is becoming a problem.

Laws regulating plastics have been enacted both domestically and internationally, such as the 2021 Basel Convention on the Import and Export of Plastics and Japan's Act on Promotion of Resource Circulation Related to Plastics. Plastic regulations are being strengthened, and there is a demand for the use of plastics with low environmental impact.

Although efforts are being made to recycle plastics, the recycling rate is only about 9% of the total production volume worldwide (Non-Patent Document 1), and the majority of used plastics is still incinerated. Although recycling of polyethylene terephthalate has progressed relatively well, it is difficult to decompose and recycle it.

Various types of polymers that can be recycled using catalysts (Non-Patent Document 2) and biodegradable polymers (Non-Patent Document 3) have been developed, but recycling plastics has problems such as the many recycling steps and costs, the cost of using catalysts such as precious metals to regenerate plastics, and the difficulty of decomposing plastics into monomers.

On the other hand, supramolecular polymers, in which monomers are bonded to each other by non-covalent bonds, are bonded to each other by weak, reversible interactions, and can be recycled by self-repairing even if they are separated by external stimuli or rebonded, making them promising new materials with low environmental impact.
For example, Non-Patent Document 4 discloses a photoresponsive supramolecular polymer glass having high stiffness and good self-repairing properties, which is composed of an assembly of 1,1,1-tris(hydroxymethyl)propane monomers having three ureido-4-pyrimidinone groups.

Non-Patent Document 5 discloses metallosupramolecular copolymers constructed by combining a monomer having three 2,6-bis(1'-methylbenzimidazolyl)pyridines bound to a 1,3,5-tris(alkyl)benzene core or a monomer having two 2,6-bis(1'-methylbenzimidazolyl)pyridines bound to poly(ethylene-co-butylene) with Zn(NTf₂)₂.
However, conventional photoresponsive supramolecular polymer glasses have poor mechanical strength.

The problem to be solved by the present invention is to provide a mechanically robust composite that can be green-synthesized and molded in an aqueous solvent.

The present invention encompasses the embodiments described below.
Item 1.
A complex comprising: an organic cation formed by ionization of a compound having at least two amino groups or guanidino groups; and an oxyanion, wherein the organic cation and the oxyanion are bonded together by ionic bonds and hydrogen bonds.

Item 2.
Item 2. The complex according to item 1, wherein the organic cation and the oxyanion are bonded to each other through an ionic bond and a hydrogen bond represented by one or more of the following formulas (1) to (4):

In each of formulas (1) to (4), R is any monovalent organic group.

Item 3.
Item 2. The complex according to item 1, wherein the organic cation is an ionized organic cation of a guanidine compound represented by the following formula (6):
(In the formula, R represents a substituted or unsubstituted hydrocarbon chain, and when the hydrocarbon chain is substituted, some of the methylene groups of the hydrocarbon chain are replaced with a group selected from the group consisting of -NH-, -N(alkyl group)-, -O-, -COO-, -O-COO-, -NHCO-, -S-, cycloalkane, cycloalkanone, benzene, a group represented by formula (7), and substituted or unsubstituted -N(guanidyl alkylene group)-, and when the -N(guanidyl alkylene group) is substituted, some of the methylene groups of the guanidyl alkylene group are replaced with the same group as the group substituting some of the methylene groups of the hydrocarbon chain.）

(In the formula, R₁ and R₂ each independently represent an alkyl group or a phenyl group having 1 to 6 carbon atoms, R₃ and R₄ each independently represent an alkyl group or a phenyl group having 1 to 6 carbon atoms, m is 1 to 6, n is 1 to 6, p is an integer in the range of 0 to 20, and q is an integer in the range of 0 to 20, with the proviso that p+q is an integer of 1 or greater.)
Section 4.
Item 4. The conjugate according to item 3, wherein the guanidine compound comprises a compound of formula (I), a compound of formula (II), or both.
(I) A compound represented by formula (6), in which A is a substituted or unsubstituted hydrocarbon chain, and when the hydrocarbon chain is substituted, part of the methylene groups of the hydrocarbon chain is substituted with a group selected from the group consisting of -NH-, -N(alkyl)-, -O-, -COO-, -O-COO-, -NHCO-, -S-, cycloalkane, cycloalkanone, benzene, and a substituted or unsubstituted -N(guanidyl alkylene group)-, and when the -N(guanidyl alkylene group) is substituted, part of the methylene groups of the guanidyl alkylene group is substituted with the same group as the group substituting part of the methylene groups of the hydrocarbon chain, excluding compounds in which part of the methylene groups of the hydrocarbon chain is substituted with a group represented by formula (7). (II) A compound represented by formula (6), in which A is a substituted hydrocarbon chain, and part of the methylene groups of the hydrocarbon chain is substituted with a group represented by formula (7). 　Item 2. The complex according to item 1, wherein the oxyanion is an oxyanion of sulfur, phosphorus, silicon, or carbon. Item 6. 　Item 6. The complex according to Item 5, wherein the oxyanion is a polyoxyanion. Item 7. 　Item 6. The complex according to Item 5, wherein the oxyanion is a cyclic phosphate anion represented by the following formula (10), a linear phosphate anion represented by the following formula (11), an anion of phytic acid, or an anion of carboxylate:

(Wherein, n is 1 or 4)
(wherein n is an integer from 1 to 1000) Item 8.
　Item 6. The complex according to Item 1 or 5, wherein the oxyanion is an oxyanion generated by ionization of a polysaccharide having an anionic functional group.
Item 9.
　Item 2. The complex according to item 1, which is insoluble in organic solvents.
Item 10. 　Item 2. The composite according to item 1, which is processable in water at 20° C. Item 11. 　Item 2. The composite according to item 1, which has self-repairing properties. Item 12. 　Item 2. The composite according to item 1, wherein the composite has a thickness of 0.5 mm and has a light transmittance of 90% or more at 400 to 800 nm. Item 13. 　Item 2. The composite according to item 1, which is a supramolecular plastic. Item 14. 　Item 2. The composite according to item 1, which is a supramolecular polymer glass. Item 15. 　Item 15. A composition comprising the complex according to any one of items 1 to 14. Item 16. 　Item 15. An article comprising the composite according to any one of items 1 to 14. Item 17. 　A method for producing a complex, comprising: mixing a compound having at least two amino groups or guanidino groups with an oxyanion-containing compound in water or an aqueous solution; and producing a complex in which an organic cation formed by ionizing the compound having at least two amino groups or guanidino groups and an oxyanion formed by ionizing the oxyanion-containing compound are bonded by ionic bonds and hydrogen bonds. Item 18. 　Use of a compound having at least two amino or guanidino groups and an oxyanion-containing compound of sulfur, phosphorus, silicon, or carbon to prepare a supramolecular polymer composite.

　According to the present invention, it is possible to provide a mechanically robust composite body whose manufacture and processing involves little or no environmental impact.

Schematic showing the polymer network of a supramolecular polymer glass (SPG).
Photograph showing liquid-liquid phase separation during the production of supramolecular polymer glass (SPG).
Micrograph of supramolecular polymer micelles. Graph showing the optical transparency of various plastics and first generation supramolecular polymer glass. PMMA: polymethylmethacrylate, PC: polycarbonate, PET: polyethylene terephthalate, PS: polystyrene, Glass: inorganic glass, SPG: supramolecular polymer glass. A photograph of a weight placed on the first-generation supramolecular polymer glass formed by hot pressing. Graph showing the Young's modulus of various plastics and first generation supramolecular polymer glass. Second from the right: First generation monomer ^GuM^Gen.I-(9-2) was used. Far right: First generation monomer NER10MNER11-(9-4) was used. Rubber: Rubber, PVA: Polyvinyl acetate, PTFE: Polytetrafluoroethylene, PP: Polypropylene, PET: Polyethylene terephthalate, PS: Polystyrene, PMMA: Polymethyl methacrylate, PEEK: Aromatic polyether ketone, Nylon: Nylon, SPG: Supramolecular polymer glass. A graph showing the tensile strength of various plastics and first generation supramolecular polymer glass. Second from the right: First generation monomer NER12MNER13-(9-2) was used. Far right: First generation monomer NER14MNER15-(9-4) was used. Rubber: rubber, PVA: polyvinyl acetate, PTFE: polytetrafluoroethylene, PP: polypropylene, PET: polyethylene terephthalate, PS: polystyrene, PMMA: polymethyl methacrylate, PEEK: aromatic polyether ketone, Nylon: nylon, SPG: supramolecular polymer glass Young's modulus of the first generation supramolecular polymer glass (^Gen.1SPG, far right), the second generation supramolecular polymer glass (^Gen.2SPG, far left), and three third generation supramolecular polymer glasses (^Gen.2SPG and ^Gen.1SPG, three bars in the middle).
The mixed molar ratio of the guanidine compounds (referred to as M1 and M2, respectively) used in the preparation of each of the third generation supramolecular polymer glasses was changed. From left to right, the molar ratios of M1:M2 are 4:1, 1:1, and 1:4. (A) (B) Photographs showing the underwater processability of first generation supramolecular polymer glasses. (A) 10 s after immersion in water, (B) 2 h after immersion in water. Synthesis of supramolecular polymer glasses using diamines and sodium hexametaphosphate. Measurement results of an indentation experiment of an SPG consisting of ^GuM^Gen.II-1 and phytic acid. Force: Force, Displacement: Displacement. Measurement results of an indentation experiment of an SPG consisting of ^GuM^Gen.I-2 and phytic acid. Force: Force, Displacement: Displacement. Measurement results of an indentation experiment of an SPG consisting of diamine and alginic acid. Measurement results of a pressing experiment on an SPG made of guanidine and alginate. Measurement results of an indentation experiment of an SPG consisting of diamine/guanidine, alginic acid, and hexametaphosphate. Photograph of the supramolecular polymer emulsion produced by mixing chondroitin sulfate with first generation monomers (^GuM^Gen.I). Photograph of the supramolecular polymer glass synthesized in Example 6. Photograph of the supramolecular polymer emulsion formed by mixing sodium heparin sulfate with first generation monomers (^GuM^Gen.I). Photograph of the supramolecular polymer glass synthesized in Example 7. Photograph of the supramolecular polymer emulsion produced by mixing sodium dextran sulfate with first generation monomers (^GuM^Gen.I). A photograph of the supramolecular polymer glass synthesized in Example 8. A photograph of the supramolecular polymer emulsion produced by mixing β-cyclodextrin substituted with -SO₃Na and (first generation monomer (^GuM^Gen.I).
The inset on the left shows the glass tube containing the emulsion. Photograph of the supramolecular polymer glass synthesized in Example 9.

　As used herein, the terms "contain" and "include" are concepts that also encompass the term "consist of."

In the numerical ranges described in stages in this specification, the upper limit or lower limit of a numerical range of a certain stage can be arbitrarily combined with the upper limit or lower limit of a numerical range of another stage.
Furthermore, in any numerical range described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in an example or a value that can be unambiguously derived from an example.
Furthermore, in this specification, a numerical value connected with "to" means a numerical range including the numerical values before and after "to" as the lower and upper limits.

As used herein, a "composite" refers to a material that is made up of two or more substances bonded together.
Each substance constituting the complex may be referred to as a "monomer." A complex formed by binding two or more types of molecules is sometimes called a "molecular assembly."

As used herein, "supramolecular polymer" refers to a polymer formed by two or more types of monomers linked together through reversible interactions.
Reversible interactions include non-covalent bonds such as hydrogen bonds, ionic bonds, hydrophobic interactions, electrostatic interactions, and/or van der Waals forces.

As used herein, "supramolecular plastic" refers to a polymer or a composition containing the same, in which two or more types of monomers are bonded together through reversible interactions.
A "supramolecular plastic" may be the same as a "supramolecular polymer" or may include substances other than a "supramolecular polymer." The "supramolecular plastic" may be a synthetic resin.

As used herein, "glass" refers to an amorphous solid material.
Amorphous is also called amorphous, and refers to a disordered atomic arrangement in which no clear diffraction phenomenon is observed in X-ray diffraction.

As used herein, "organic cation" refers to a cation whose structure contains at least one carbon atom.

As used herein, "oxyanion" refers to an anion having oxygen bound to a non-metal.

According to a first aspect of the present disclosure, there is provided a complex comprising an organic cation formed by ionizing a compound having at least two amino groups or guanidino groups, and an oxyanion, wherein the organic cation and the oxyanion are bonded to each other via an ionic bond and a hydrogen bond.

To facilitate understanding of the invention, FIG. 1 shows a schematic diagram of an example of a complex that is a supramolecular polymer. The physical properties of the supramolecular polymer described below can be applied to the complex of the present invention.

The supramolecular polymer (1) is composed of an organic cation (2) obtained by ionizing a compound having at least two amino groups or a compound having at least two guanidino groups, and an oxyanion (3) bonded by a non-covalent bond. This results in a strong bond between these monomers, and the mechanical strength of the supramolecular polymer is higher than that of conventional supramolecular polymers.
In addition, since the organic cation and the oxyanion can be separated more easily than in the case where the monomers are covalently bonded to each other, the recyclability is excellent.
The organic cation and the oxyanion can be separated, for example, by immersing the material in a polar medium, such as water or an aqueous solution, for a certain period of time or more.
It should be noted that the compound having at least two amino groups excludes a compound having at least two guanidino groups.

In some embodiments, the organic cation and the oxyanion are bonded by ionic bonds and hydrogen bonds represented by one or more of the following formulas (1) to (4):

In each of formulas (1)-(4), R is any monovalent organic group. As used herein, an organic group refers to a group having one or more carbon atoms.
When two or more R are present in one molecule, the R may be the same or different.
As shown in formulas (1) and (2), hydrogen bonds are formed between hydrogen atoms derived from two amino groups of the amine compound and oxygen atoms of the oxyanion, and an ionic bond is formed between the ammonium cation and the oxyanion.
Alternatively, as shown in formulas (3) and (4), hydrogen bonds are formed between the hydrogen atoms derived from the two guanidino groups of the guanidine compound and the oxygen of the oxyanion, and an ionic bond is formed between the guanidinium cation and the oxyanion. This improves the mechanical strength of the supramolecular polymer. On the other hand, the bond between an organic cation and an oxyanion is easier to separate than a covalent bond.

In some embodiments, the compound having at least two amino groups is an amine compound represented by the following formula (5):
(In the formula, R represents a substituted or unsubstituted hydrocarbon chain, and when the hydrocarbon chain is substituted, part of the methylene groups of the hydrocarbon chain is substituted with a group selected from the group consisting of -NH-, -N(alkyl group)-, -O-, -COO-, -O-COO-, -NHCO-, -S-, cycloalkane, cycloalkanone, benzene, a group represented by formula (7), and substituted or unsubstituted -N(guanidyl alkylene group)-, and when the -N(guanidyl alkylene group) is substituted, part of the methylene groups of the guanidyl alkylene group is substituted with the same group as the group substituting part of the methylene groups of the hydrocarbon chain.）
(In the formula, R₁ and R₂ are each independently an alkyl group or a phenyl group having 1 to 6 carbon atoms, R₃ and R₄ are each independently an alkyl group or a phenyl group having 1 to 6 carbon atoms, m is 1 to 6, n is 1 to 6, p is an integer in the range of 0 to 20, and q is an integer in the range of 0 to 20, with the proviso that p+q is an integer of 1 or greater.）

The hydrocarbon chain of R may be an aliphatic hydrocarbon chain, a cycloaliphatic hydrocarbon chain, an aromatic hydrocarbon chain, or a combination thereof.
The aliphatic hydrocarbon chain may be a saturated linear aliphatic hydrocarbon chain or an unsaturated aliphatic hydrocarbon chain, and may be a linear or branched chain.
Preferably, the hydrocarbon chain is a linear or branched saturated hydrocarbon chain.

When some of the methylene groups in the hydrocarbon chain are substituted, the number of substituted methylene groups is not limited, but is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5.

In certain embodiments, the alkyl group of the --N(alkyl) which is a substituent of a methylene group of a hydrocarbon chain is preferably a straight or branched chain alkyl having from 1 to 6 carbon atoms. In a particular embodiment, the alkylene group of the -N (guanidyl alkylene group) which is a substituent of the methylene group of the hydrocarbon chain is preferably a straight or branched alkylene having 1 to 6 carbon atoms.

In formula (7), the alkyl group having 1 to 6 carbon atoms represented by R₁ and R₂ may be a straight chain, branched chain, or cyclic chain.
The alkyl group having 1 to 6 carbon atoms represented by R₃ and R₄ may be a straight chain, branched chain, or cyclic chain.
In certain embodiments, the alkyl groups having 1 to 6 carbon atoms of R₁, R₂, R₃, and R₄ are each independently a linear alkyl group having 1 to 6 carbon atoms. In certain embodiments, p and q are both integers ranging from 1-20. In certain embodiments, one of p and q is an integer in the range of 1 to 20, and one of p and q is 0.

The compound having at least two amino groups may have two, three, four or more amino groups in one molecule.

When an amine compound has three amino groups in one molecule, the mechanical strength is usually greater than when it has two amino groups in one molecule.
Furthermore, when the guanidine compound has a nitrogen atom in the hydrocarbon chain with a --NH-- substituent, the guanidine compound has improved solubility in water and is more likely to assume an amorphous form.

In some embodiments, the compound having at least two guanidino groups is a guanidine compound represented by the following formula (6):

(In the formula, R represents a substituted or unsubstituted hydrocarbon chain, and when the hydrocarbon chain is substituted, part of the methylene groups of the hydrocarbon chain is substituted with a group selected from the group consisting of -NH-, -N(alkyl group)-, -O-, -COO-, -O-COO-, -NHCO-, -S-, cycloalkane, cycloalkanone, benzene, a group represented by formula (7), and substituted or unsubstituted -N(guanidyl alkylene group)-, and when the -N(guanidyl alkylene group) is substituted, part of the methylene groups of the guanidyl alkylene group is substituted with the same group as the group substituting part of the methylene groups of the hydrocarbon chain.）

(In the formula, R₁ and R₂ each independently represent an alkyl group or a phenyl group having 1 to 6 carbon atoms, R₃ and R₄ each independently represent an alkyl group or a phenyl group having 1 to 6 carbon atoms, m is 1 to 6, n is 1 to 6, p is an integer in the range of 0 to 20, and q is an integer in the range of 0 to 20, with the proviso that p+q is an integer of 1 or greater.) The hydrocarbon chain of R may be an aliphatic hydrocarbon chain, a cycloaliphatic hydrocarbon chain, an aromatic hydrocarbon chain, or a combination thereof. The aliphatic hydrocarbon chain may be a saturated linear aliphatic hydrocarbon chain or an unsaturated aliphatic hydrocarbon chain, and may be a linear or branched chain.
Preferably, the hydrocarbon chain is a linear or branched saturated hydrocarbon chain.

When some of the methylene groups in the hydrocarbon chain are substituted, the number of substituted methylene groups is not limited, but is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5.

In certain embodiments, the alkyl group of the --N(alkyl) which is a substituent of a methylene group of a hydrocarbon chain is preferably a straight or branched chain alkyl having from 1 to 6 carbon atoms. In a particular embodiment, the alkylene group of the -N (guanidyl alkylene group) which is a substituent of the methylene group of the hydrocarbon chain is preferably a straight or branched alkylene having 1 to 6 carbon atoms.

In formula (7), the alkyl group having 1 to 6 carbon atoms represented by R₁ and R₂ may be a straight chain, branched chain, or cyclic chain.
The alkyl group having 1 to 6 carbon atoms represented by R₃ and R₄ may be a straight chain, branched chain, or cyclic chain. In certain embodiments, the alkyl groups having 1 to 6 carbon atoms of R₁, R₂, R₃, and R₄ are each independently a linear alkyl group having 1 to 6 carbon atoms. In certain embodiments, p and q are both integers ranging from 1-20. In certain embodiments, one of p and q is an integer in the range of 1 to 20, and one of p and q is 0.

The guanidine compound having at least two guanidino groups may have two, three, four or more guanidino groups in one molecule. When a guanidine compound has three guanidino groups in one molecule, the mechanical strength is usually greater than when the guanidino compound has two guanidino groups in one molecule. Furthermore, when the guanidine compound has a nitrogen atom in the hydrocarbon chain with a --NH-- substituent, the guanidine compound has improved solubility in water and is more likely to assume an amorphous form.

In some embodiments, the guanidine compound is a guanidine compound of formula (I) below, a guanidine compound of formula (II) below, or includes both a guanidine compound of formula (I) and a guanidine compound of formula (II).

Guanidine compound (I): A compound represented by formula (6), in which A is a substituted or unsubstituted hydrocarbon chain, and if the hydrocarbon chain is substituted, part of the methylene groups of the hydrocarbon chain is substituted with a group selected from the group consisting of -NH-, -N(alkyl group)-, -O-, -COO-, -O-COO-, -NHCO-, -S-, cycloalkane, cycloalkanone, benzene, and substituted or unsubstituted -N(guanidyl alkylene group)-, and if the -N(guanidyl alkylene group) is substituted, part of the methylene groups of the guanidyl alkylene group is substituted with the same group as the group substituting part of the methylene groups of the hydrocarbon chain. However, this does not include compounds in which some of the methylene groups in the hydrocarbon chain are substituted with a group represented by formula (7).

Guanidine compound (II): A compound represented by formula (6), in which A is a substituted hydrocarbon chain, and a part of the methylene groups of the hydrocarbon chain is substituted with a group represented by formula (7).

The supramolecular polymer produced using the guanidine compound (I) has high mechanical strength, but is easily soluble in water and has high processability in water.

Specific examples of the organic cation formed by protonating the guanidine compound (I) include the following organic cations.

The supramolecular polymer produced using the guanidine compound (II) has a lower solubility in water than the supramolecular polymer produced using the guanidine compound (I), but tends to have a lower mechanical strength.

Therefore, a supramolecular polymer produced using both the guanidine compound (I) and the guanidine compound (II) can improve the mechanical strength of the supramolecular polymer produced using the guanidine compound (II) while suppressing the solubility in water of the supramolecular polymer produced using the guanidine compound (I).

In the supramolecular polymer produced using both the guanidine compound (I) and the guanidine compound (II), each of the guanidine compound (I) and the guanidine compound (II) may be any combination of the guanidine compound (I) and the guanidine compound (II) disclosed herein. The guanidine compound (I) and the guanidine compound (II) may each be one type or two or more types.

The molar ratio of the guanidine compound (I) to the guanidine compound (II) for producing the supramolecular polymer is not particularly limited, but is preferably 90:10 to 10:90, more preferably 20:80 to 80:20.

Specific examples of the organic cations formed by protonating the guanidine compound (II) include organic cations represented by the following formulas (9-1) to (9-10).(In each of formulas (9-1) to (9-6), n is an integer from 1 to 100. In formula (9-2), m is an integer from 1 to 100

Guanidine is a highly safe substance that is also present in the body. The guanidine compound may be synthesized by a known method, or a commercially available product may be used.

An oxyanion refers to an anion having a structure consisting of a central element and oxygen bonded to the central element.
The central element is not particularly limited and may be a metallic element or a non-metallic element, but from the standpoint of safety and low environmental impact, sulfur, phosphorus, silicon, or carbon is more preferred.

In some embodiments, the oxyanion is an oxyanion of sulfur, phosphorus, silicon, or carbon.
Oxyanions are generated by ionization of oxyanion-containing compounds of sulfur, phosphorus, silicon, or carbon.
Sulfur, phosphorus, silicon, or carbon oxyanion-containing compounds include, but are not limited to, salts selected from the group consisting of sulfates, sulfites, sulfonates, protonated phosphates, phosphates, polyphosphates, metaphosphates, phosphonites, oxyphosphates, silicates, carboxylates, carbonates, and combinations thereof.
The salt is preferably a metal salt, and preferred metals constituting the metal salt include, but are not limited to, sodium, potassium, lithium, calcium, strontium, barium, magnesium, and the like.
The supramolecular polymer may contain one type of oxyanion, or may contain two or more types of oxyanions.
Alternatively, the sulfur, phosphorus, silicon, or carbon oxyanion-containing compounds include, but are not limited to, salts selected from the group consisting of sulfate esters, phosphodiesters, silicate esters, and carboxylate esters, combinations thereof.

In some embodiments, the oxyanion is a polyoxyanion having two or more central elements in one molecule.
When the oxyanion is a divalent or higher anion, it can bond to the organic cation, which is the partner molecule, at two or more positions, and a network structure can be formed by bonding between the organic cation and the oxyanion.

In some embodiments, the oxyanion is a cyclic phosphate anion represented by formula (10), a linear phosphate anion represented by formula (11), an anion of phytic acid, or an anion of a carboxylate. (wherein n is an integer from 1 to 4). (wherein n is an integer from 1 to 1000).

In the cyclic phosphate anion of formula (10), n is preferably 1 or 4, and more preferably n is 4.
Sodium hexametaphosphate, which is used as a source of hexaphosphate ion when n is 4, is a compound approved by the U.S. Food and Drug Administration (FDA) and is highly safe.
In order to obtain a supramolecular polymer having high mechanical strength, an oxyanion in which n is 4 is more preferable. The upper limit of n is preferably 100.
The linear phosphate anion represented by formula (11) preferably has n in the range of 1 to 1,000.
The sulfur, phosphorus, silicon, or carbon oxyanion-containing compound may be synthesized by a known method, or a commercially available product may be used.
The anion of phytic acid is an anion generated by deprotonating phytic acid represented by formula (12).
Carboxylic acid anions, also known as carbanions, include, but are not limited to, anions generated by deprotonation of carboxylic acids represented by formulas (13-1) and (13-2) and an anion of alginic acid represented by formula (14).

In some embodiments, the oxyanion-containing compound is a polysaccharide, and the oxyanion is an oxyanion resulting from ionization of the polysaccharide.
Preferably, the polysaccharide is a polysaccharide having an anionic functional group, more preferably an acidic polysaccharide having an anionic functional group.
Such anionic functional groups include acid groups, salts, acid esters, or combinations thereof.
When the anionic functional group is a salt, it includes, but is not limited to, salts selected from the group consisting of sulfates, sulfites, sulfonates, protonated phosphates, phosphates, polyphosphates, metaphosphates, phosphonites, oxyphosphates, silicates, carboxylates, carbonates, and combinations thereof.
The salt is preferably a metal salt, and preferred metals constituting the metal salt include, but are not limited to, sodium, potassium, lithium, calcium, strontium, barium, magnesium, and the like.
Preferred anionic functional groups include, for example, sulfate groups, sulfate salts, sulfate esters, carboxy groups, carboxylates, carboxylate esters, sulfo groups, sulfonate salts, sulfonate esters, phosphoric acid groups, phosphate salts, phosphate esters, phosphonic acid groups, phosphonate salts, phosphonate esters, or combinations thereof.
More preferably, the polysaccharide is a polysaccharide having at least two anionic functional groups selected from the group consisting of sulfate groups, sulfate salts, sulfate ester salts, carboxy groups, carboxylate groups, carboxylate esters, sulfo groups, sulfonate salts, sulfonate esters, phosphoric acid groups, phosphate salts, phosphate esters, phosphonic acid groups, phosphonate salts, phosphonate esters, and phosphodiesters.
The at least two anionic functional groups may be of the same type or of different types.
　The polysaccharide having an anionic functional group preferably contains one anionic functional group per monomer unit which is a constituent unit of the polysaccharide.
All of the monomer units may have an anionic functional group, or only a part of the monomer units may have an anionic functional group.
The at least two anionic functional groups may be directly bonded to a five- or six-membered ring containing carbon of a monomer unit that is a constituent unit of the polysaccharide, or may be bonded to the five- or six-membered ring via a substituted or unsubstituted hydrocarbon chain.
Hydrocarbon chains include, but are not limited to, alkylene groups (eg, methylene groups).
　Examples of groups obtained when the at least two functional groups are ionized include a sulfate ester group (-O-SO₃^-), a sulfonic acid group (-SO₃^-), a carboxylate group (-COO^-), a phosphate group (-O-PO₃^2-), and a phosphoryl group (-PO₃^2-).
　The polysaccharide having an anionic functional group may be a natural polysaccharide or a synthetic polysaccharide.
The polysaccharide having an anionic functional group may be any of linear, branched, and cyclic polysaccharides.
Examples of polysaccharides include, but are not limited to, carboxymethylcellulose, gellan gum, alginic acid, sulfated alginic acid, carrageenan, xanthan gum, chondroitin sulfate, heparin, hyaluronic acid, pectinic acid, gum arabic, agar, tragacanth gum, sodium dextran sulfate, and sodium sulfate of cyclodextrin.
　The number of monomer units in polysaccharides that ionize to generate oxyanions, particularly polysaccharides having anionic functional groups, is not particularly limited, but is preferably 2 to 100,000.
　The molecular weight of polysaccharides that ionize to generate oxyanions, particularly polysaccharides having an anionic functional group, is not particularly limited, but is preferably 1,000 to 10,000,000, more preferably 5,000 to 1,000,000 in weight average molecular weight.
The weight average molecular weight of the polysaccharide can be calculated by gel permeation chromatography (GPC) measurement. 　The oxyanions generated from the above-mentioned polysaccharides that ionize to generate oxyanions, particularly polysaccharides having anionic functional groups, can form complexes by bonding through ionic bonds and hydrogen bonds with organic cations formed by ionization of any compound having at least two amino groups or guanidino groups described herein. 　In some embodiments, the Young's modulus of the supramolecular polymer measured under the following measurement conditions for the indentation experiment is 5 GPa or more, preferably 10 GPa or more, more preferably 15 GPa or more, and more preferably 20 GPa or more. Measurement conditions: The supramolecular polymer is cut into a sample having a length and width of 1 cm x 1 cm and a thickness of 0.5 mm. The sample was subjected to an indentation hardness test using an ENT-NEXUS (ELIONIX Inc.) indentation hardness tester at a measurement temperature of 20°C. ) was used to determine Young's modulus. A diamond indenter tip was used for indentation. The test load was 50 mN, the loading time was 20,000 msec, the holding time was 5,000 msec, and the unloading time was 20,000 msec.

Many of the known synthetic resins polymerized by covalent bonds, such as polytetrafluoroethylene, polypropylene, polyethylene terephthalate, polystyrene, polymethyl methacrylate, and aromatic polyether ketone, have a Young's modulus of 5 GPa or less, but the Young's modulus of supramolecular polymer glass (SPG) can be made larger than the Young's modulus of such synthetic resins.

In some embodiments, the tensile strength of the supramolecular polymer measured under the following measurement conditions is preferably 5 MPa or more and 50 MPa or less.
These values are comparable to the tensile strength of several known covalently polymerized synthetic resins, and may make the tensile strength of supramolecular polymer glasses (SPGs) equal to or greater than the tensile strength of such synthetic resins. Measurement conditions: The supramolecular polymer is cut into a sample having a length and width of 2 mm x 35 mm and a thickness of 0.5 mm. The test speed was 10 mm/s. The tension machine sensor indicated 500N. The measurement temperature is 20°C.

In some embodiments, supramolecular polymer glasses (SPGs) are processable in water at 20°C.
Supramolecular polymer glass (SPG) is made by bonding organic cations and the oxyanions through ionic and hydrogen bonds. When placed in water for a certain period of time, the supramolecular polymer bonds with water, swells, softens, and can be processed by hand or machine. Adding an electrolyte such as sodium chloride to the water further promotes dissociation into monomers. Also, for example, the supramolecular polymer can be wetted with water and molded into any shape, such as a plate or sphere. Moreover, the molded supramolecular polymer can be dried to maintain the shape of the molded supramolecular polymer. The supramolecular polymer of this embodiment may be 100% decomposable in water, and such a supramolecular polymer is advantageous in that it has a low environmental impact.

In some embodiments, supramolecular polymer glasses (SPGs) can be molded into a variety of shapes above their glass transition temperature.

In some embodiments, supramolecular polymer glasses (SPGs) are self-healing.
For example, if a supramolecular polymer is broken into two pieces, the two pieces will bond together if the broken surfaces are moistened with water and the two broken surfaces are allowed to come into contact and allowed to stand for a period of time.

In some embodiments, the Young's modulus of the supramolecular polymer at 20° C. is 5 GPa or more, preferably 10 GPa or more, more preferably 15 GPa or more, more preferably 20 GPa or more, and the tensile strength of the supramolecular polymer at 20° C. is 5 MPa or more and 50 GPa or less.
A supramolecular polymer having such a structure has high rigidity and high mechanical strength against tension.

In some embodiments, the supramolecular polymer glass (SPG) is insoluble in organic solvents.
Examples of the organic solvent include dichloromethane, chloroform, methanol, ethanol, acetone, hexane, dimethylformamide, dimethylsulfoxide, ethyl acetate, diethyl ether, and tetrahydrofuran.

In some embodiments, the optical transmittance of a 0.5 mm thick supramolecular polymer glass between 400 and 800 nm is 95% or greater.
Such supramolecular polymers have excellent transparency.

The supramolecular polymer, which is a complex according to the first aspect of the present invention, has one or more of the following advantages [1] to [8].
Particularly preferred embodiments have all advantages except for [5] or have all advantages of [1] to [8].

[1] Quantitative Green Synthesis: An organic cation formed by ionizing a compound having at least two amino or guanidino groups is non-covalently bonded to an oxyanion in a 1:1 molar ratio to produce a supramolecular polymer.
Supramolecular polymers can be synthesized without the need for heat or pressure.
Moreover, the supramolecular polymer can be synthesized in water or an aqueous solvent, and no organic solvent is required. [2] Green processing: Supramolecular polymers can be processed in water. No heating is required for processing. [3] Ultra-tough: The supramolecular polymer has a Young's modulus at 20°C of 5 GPa or more, and/or a tensile strength at 20°C of 5 MPa or more and 50 GPa or less. [4] Self-repair: If a supramolecular polymer is broken into two pieces, the two pieces will bond when the broken surfaces are moistened with water and placed in contact with each other. [5] Water resistance: The supramolecular polymer produced using the guanidine compound (II) has lower solubility in water than the supramolecular polymer produced using the guanidine compound (I). [6] Organic solvent resistance: Supramolecular polymers are insoluble in organic solvents. Examples of the organic solvent include dichloromethane, chloroform, methanol, ethanol, acetone, hexane, dimethylformamide, dimethylsulfoxide, ethyl acetate, diethyl ether, and tetrahydrofuran. [7] Complete recycling: Unlike conventional plastic polymers, recycling of the SPG of this embodiment does not require catalysts or energy-consuming procedures. Immersion of SPG in aqueous solutions of ammonium chloride or acid destroys the salt-bridge interactions between the guanidino and phosphodiester groups, allowing complete conversion back to the starting monomer. The monomer can be recovered by purification techniques such as ion exchange resins. This will enable resource circulation and realize a microplastic-free ocean. This will change the way we think about plastics.

In some embodiments, the organic cation oxyanion in the complex of the first aspect may be bound by additional covalent or non-covalent bonds other than ionic and hydrogen bonds.
Such further covalent or non-covalent bonds can be formed by introducing functional groups into the organic cation and/or the oxyanion in a known manner.

In some embodiments, the complex of the first aspect is a supramolecular polymer.
In some embodiments, the composite of the first aspect is a supramolecular plastic. In some embodiments, the composite of the first aspect is a supramolecular polymer glass. It is preferable that the complex is a supramolecular polymer, since the production and processing of the complex imposes less or no environmental burden.

According to a second aspect of the present disclosure, there is provided a composition containing the complex of the first aspect.
The composition may further comprise a polymer, such as a synthetic resin, an elastomer, or a rubber. The composition may also contain further additives other than the polymer. Examples of additives include, but are not limited to, synthetic resins, elastomers, rubbers, surfactants, lubricants, dispersants, antioxidants, light stabilizers, ultraviolet absorbers, colorants, preservatives, and fragrances.

According to a third aspect of the present disclosure, there is provided an article comprising the composite of the first aspect.
The article may comprise a component other than the composite of the first aspect. Examples of goods include, but are not limited to, containers, packaging, metal machinery and industrial products (industrial machinery, electrical machinery, precision machinery, electrical machinery), home appliances, personal computers and mobile phones, kitchen utensils, cleaning supplies, stationery, toys, sporting goods, furniture, clothing, detergents, pharmaceuticals, cosmetics, coatings, building materials, vehicles (light vehicles, vehicles) and their parts

According to a fourth aspect of the present disclosure, there is provided a method for producing a complex, comprising: mixing a compound having at least two amino groups or guanidino groups with an oxyanion-containing compound in water or an aqueous solution; and generating a complex in which an organic cation formed by ionization of the compound having at least two amino groups or guanidino groups and an oxyanion formed by ionization of the oxyanion-containing compound are bonded by ionic bonds and hydrogen bonds.
The complex may be the complex of the first aspect above. In some embodiments, the complex is a supramolecular polymer. In some embodiments, the composite is a supramolecular polymer glass.

The compound having at least two amino groups or guanidino groups, the oxyanion-containing compound, and the complex are as described for the complex of the first embodiment.
In particular, the supramolecular polymer, which is the complex of the first embodiment, can be prepared in one step.

When a compound having at least two amino groups or guanidino groups is mixed with an oxyanion-containing compound in water or an aqueous solution, an organic cation formed by ionization of the compound having at least two amino groups or guanidino groups and an oxyanion formed by ionization of the oxyanion-containing compound form ionic bonds and hydrogen bonds to form a supramolecular polymer, and an anion generated by ionization of the compound having at least two amino groups or guanidino groups and an organic cation generated by ionization of the oxyanion-containing compound are neutralized and dissolved in water.
Since the supramolecular polymer undergoes liquid-liquid phase separation from the solvent, the supramolecular polymer can be easily separated or recovered from the water or aqueous solution by known methods such as centrifugation and recovery. The resulting supramolecular polymer is then dried to give a supramolecular polymer in which the monomer molecules are non-covalently bonded but which has high mechanical strength. After the supramolecular polymer is separated or recovered from the water or aqueous solution, it can be molded into any shape, such as a plate or sphere. As the molding method, any molding method such as press molding, injection molding, extrusion molding, etc. can be used.

The method for producing the composite of this embodiment can be carried out in an aqueous system, and is environmentally friendly in that it can avoid the use of organic solvents.
Additionally, no heat or pressure is required and the composite can be produced at temperatures between 5 and 40° C. and under ambient or atmospheric pressure. In addition, the process is low cost because it does not require the use of expensive rare earth metal catalysts.

According to a fifth aspect of the present disclosure, there is provided a use of a compound having at least two amino or guanidino groups and a sulfur, phosphorus, silicon or carbon oxyanion-containing compound for preparing a supramolecular polymer composite.
The compound having at least two amino groups or guanidino groups, and the compound containing an oxyanion of sulfur, phosphorus, silicon or carbon are as described for the complex of the first embodiment.

The disclosures of all patent applications and publications cited herein are hereby incorporated by reference in their entireties.　The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these.

Example 1: Synthesis of guanidinium-based monomer (^GuM) 1.
Synthesis of first generation monomer 1 (NER67M-NER68-1)
To a mixture of water and ethanol (v/v 1:1, 500 mL) was added diethyltriamine (54 mL, 0.5 mol) and S-methylisothiourea 0.5 H₂SO₄ (139.2 g, 1 mol).
The reaction mixture was stirred at room temperature for 16 hours, giving rise to a white precipitate.
The crude product was filtered, rinsed with ethanol, and recrystallized in a mixture of water and isopropanol to give ^GuM^Gen.I-1 (yield: 93% based on diethyltriamine).
The product was identified by ¹H NMR and ¹³C NMR.
¹H NMR (600 MHz, 298 K, D₂O): δ 3.32 (t, 4H, NH-C H₂-CH₂), 2.81 (t, 4H, C H₂-NH-CH₂) ppm. ¹³C NMR (150 MHz, 298 K, D₂O): δ 157.07 ( C =NH), 46.62 ( C H₂-NH-CH₂), 40.63 (NH- C H₂-CH₂) ppm.

Synthesis of first generation monomer 2 (NER87M-NER88-2)
In an oven-dried 1 L three-neck round-bottom flask, S-methylisothiourea·1/2H₂SO₄ (250.5 g, 1.8 mol) was dissolved in 700 mL Milli-Q water.
To this solution was added 70 mL of norspermidine.
The reaction mixture was refluxed for 72 h. The reaction mixture was cooled to room temperature. The flask was placed in a freezer at 4° C. for 12 hours, allowing a white precipitate to form. The crude product was filtered, washed with ice water, and recrystallized with mL Milli-Q water to give ^GuM^Gen.I-2. (Yield: 95% based on norspermidine). The product was characterized by ¹H NMR and ¹³C NMR. ¹H NMR (600 MHz, 298 K, D₂O): δ 2.04 (p, 4H; CH₂C H₂CH₂), 3.16 (t, 4H; C H₂-NH-C H₂), 3.64 (t, 4H; NH-C H₂-CH₂) ppm. ¹³C NMR (150 MHz, 298 K, D₂O): δ 159.73 ( C =NH), 47.85 ( C H₂-NH- C H₂), 41.04 (NH- C H₂-CH₂), 27.83 (CH₂- CH₂-CH₂) ppm.

Synthesis of first generation monomer 3 (NER113-M NER114-3)
In an oven-dried 100 mL three-neck round-bottom flask, S-methylisothiourea·0.5 H₂SO₄ (12.53 g, 0.09 mol) was dissolved in 35 mL Milli-Q water.
To this solution was added 4 mL of spermidine.
The reaction mixture was refluxed for 72 h. The reaction mixture was cooled to room temperature. The crude residue was filtered, washed with ice water, and recrystallized in a mixture of water and ethanol (v/v 1:1) to give ^GuM^Gen.I-3 (yield: 53% based on spermidine). The product was identified by ¹H NMR and ¹³C NMR. ¹H NMR (600 MHz, 298K, D₂O): δ 3.31 (t, 2H, NH-C H₂-(CH₂)₂-NH-CH₂), 3.24 (t, 2H, NH-C H₂-(CH₂)₃-NH-CH₂), 3.12 (m, 2H, NH-(CH₂)₂-CH₂-NH-CH₂), 3.09 (m, 2H, NH-(CH₂)₃-C H₂-NH-CH₂), 2.00 (tt, 2H, NH-CH₂-C H₂-CH₂-NH), 1.76 (m, 2H, NH-(CH₂)₂-C H₂-CH₂-NH-CH₂), 1.67 (m, 2H, NH-CH₂-C H₂-(CH₂)₂-NH-CH₂) ppm. ¹³C NMR (150 MHz, 298K, D₂O): δ 156.9 ( C =NH), 47.21 (NH-(CH₂)₃- C H₂-NH-CH₂), 44.83 (NH-(CH₂)₂- C H₂-NH-CH₂), 40.41 (NH- C H₂-(CH₂)₃-NH-CH₂), 38.19 (NH- C H₂-(CH₂)₂-NH-CH₂), 25.03 (NH-CH₂- C H₂-(CH₂)₂-NH-CH₂), 24.95 (NH-CH₂- C H₂-CH₂-NH), 22.83 (NH-(CH₂)₂- C H₂-CH₂-NH-CH₂) ppm.

Synthesis of first generation monomer 4 (NER183-M NER184-4)
In an oven-dried 200 mL three-neck round-bottom flask, S-methylisothiourea·0.5 H₂SO₄ (13.9 g, 0.1 mol) was dissolved in a mixture of water and ethanol (v/v 1:3).
To this solution was added 16 mL of ethylenediamine. The reaction mixture was stirred for 24 h, resulting in the formation of a white precipitate. The crude residue was washed with ethanol and recrystallized from a mixture of water and ethanol (v/v 1:1) to give transparent crystals of ^GuM^Gen.I-4 (yield: 96% based on ethylenediamine). The product was identified by ¹H NMR and ¹³C NMR. ¹H NMR (600 MHz, 298K, D₂O): δ 3.44 (s, 4H, C H₂-C H₂). ¹³CNMR (150 MHz, 298K, D₂O): δ 159.95 ( C =NH), 42.95 ( C H₂- C H₂).

Synthesis of first generation monomer 5 (^GuM^Gen.I-5) ^GuM^Gen.I-5 was synthesized via the following two steps:
Step I: In an oven-dried 200 mL three-neck round-bottom flask, S-methylisothiourea·0.5 H₂SO₄ (13.9 g, 0.1 mol) was dissolved in 50 mL of a mixture of water and ethanol (v/v 1:3). To this solution was added 10 mL of 1,3-diaminopropane. After stirring for several minutes, a mixed solution of water and ethanol (v/v 1:3) was poured in, and stirring was continued for an additional 30 minutes. The crude residue was filtered, washed with water and recrystallized to give the desired product as crystals (yield: 72% based on 1,3-diaminopropane). The product was identified by ¹H NMR. ¹H NMR (600 MHz, 298K, D₂O): δ 3.31 (t, 4H, CH₂-NH), 3.08 (p, 2H, CH₂-NH₂), 1.98 (p, 2H, CH₂-C H₂-CH₂) ppm. Step II: The product obtained in Step I (7.4 g) and S-methylisothiourea · 0.5 H₂SO₄ (4.81 g, 34.5 mmol) were dissolved in 50 mL of water. To this mixture was added 1.5 mL of aqueous sodium hydroxide solution (5 M) dropwise and refluxed for 8 hours. The reaction mixture was cooled to room temperature. The flask was placed in a freezer at 4° C. for 12 hours, allowing a white precipitate to form. The crude product was filtered, washed with water and recrystallized to give ^GuM^Gen.I-5 (yield: 38% based on 1,3-diaminopropane). The product was identified by ¹H NMR and ¹³C NMR. ¹H NMR (600 MHz, 298K, D₂O): δ 3.28 (t, 4H, CH₂-NH), 1.89 (p, 2H, CH₂-C H₂-CH₂) ppm.
¹³C NMR (150 MHz, 298K, D₂O): δ 156.85 ( C =NH), 38.34 ( C H₂-NH), 26.97 (CH₂- C H₂-CH₂) ppm.

Synthesis of first generation monomers 6, 7, and 8 (NER232-M, NER233-6, NER234-M, NER235-7, and NER236-M, NER237-8)
This series of guanidinium monomers (^GuM^Gen.I-6 to ^GuM^Gen.I-8) followed the same synthetic protocol as ^GuM^Gen.I-5.
To a solution of S-methylisothiourea·0.5 H₂SO₄ (250.5 g, 1.8 mol) was added an aliphatic diamine (0.5 mol), and the reaction mixture was stirred at 105° C. for 3 days.
The reaction mixture was cooled to room temperature. The flask was placed in a freezer at 4° C. for 12 hours, allowing a white precipitate to form. The crude products were filtered, washed with water and recrystallized to give the desired products (^GuM^Gen.I-6 to ^GuM^Gen.I-8). The product was identified by ¹H NMR and ¹³C NMR. ^GuM^Gen.I-6 (n = 3)
¹H NMR (600 MHz, 298K, D₂O): δ 3.22 (t, 4H, C H₂-NH), 1.56 (t, 4H, CH₂-C H₂-C H₂-CH₂) ppm.
NER261MNER262-7(n = 4)
¹H NMR (600 MHz, 298K, D₂O): δ 3.19 (t, 4H, CH₂-NH), 1.62 (t, 4H, CH₂-C H₂-CH₂-C H₂-CH₂), 1.41 (p, 2H, CH₂-CH₂-C H₂-CH₂-CH₂) ppm.
¹³CNMR (150 MHz, 298K, D₂O): δ 156.76 ( C =NH), 40.89 ( C H₂-NH), 26.97 (CH₂-C H₂-CH₂-C H₂-CH₂), 22.90 (CH₂-CH₂-C H₂-CH₂-CH₂) ppm.
NER289MNER290-8(n = 5)

¹H NMR (600 MHz, 298K, D₂O): δ 2.60 (t, 4H, C H₂-NH), 1.44 (t, 4H, NH-CH₂-C H₂), 1.33 (p, 6H, NH-CH₂-CH₂-C H₂-C H₂-C H₂) ppm.
¹³CNMR (150 MHz, 298K, D₂O): δ 156.73 ( C =NH), 41.20 ( C H₂-NH), 27.82 (NH-CH₂- C H₂), 27.73 (NH-CH₂-CH₂- C H₂), 25.63 (NH-CH₂-CH₂-CH₂-CH₂) ppm.

Synthesis of first generation monomer 9 (NER313MNER314-9)
In an oven-dried 200 mL three-neck round-bottom flask, S-methylisothiourea·0.5 H₂SO₄ (13.9 g, 0.1 mol) was dissolved in Milli-Q water.
To this solution was added 5 mL of bis(2-aminoethyl)ethane-1,2-diamine.
The reaction mixture was refluxed for 24 h, resulting in the formation of a white precipitate.
The crude residue was washed with ethanol and recrystallized from Milli-Q water to give transparent crystals ^GuM^Gen.I-9 (yield: 96% bis(2-aminoethyl)ethane-1,2-diamine). The product was identified by ¹H NMR and ¹³C NMR. ¹H NMR (600 MHz, 298K, D₂O): δ 3.29 (t, 4H, C H₂-NH), 2.70 (t, 4H, N-C H₂-CH₂) ppm. ¹³CNMR (150 MHz, 298K, D₂O): δ 156.93 ( C =NH), 52.33 ( C H₂-NH), 38.92 (N- C H₂-CH₂) ppm.

Synthesis of first generation monomer 10 (NER331MNER332-10)
In an oven-dried 300 mL three-neck round-bottom flask, S-methylisothiourea·0.5 H₂SO₄ (13.9 g, 0.1 mol) was dissolved in 80 mL of Milli-Q water.
To this solution was added 30.6 mL of 2,2'-thiobis(ethan-1-amine) (0.25 mol).
The mixture was refluxed for 3 days. The reaction mixture was cooled to room temperature, giving rise to a white precipitate. The precipitate was aspirated and recrystallized from water to give white crystals of ^GuM^Gen.I-10 (yield: 72% based on 2,2'-thiobis(ethan-1-amine)). The product was identified by ¹H NMR and ¹³C NMR. ¹H NMR (600 MHz, 298 K, D₂O): δ 3.43 (t, 4H; NH-C H₂), 2.83 (t, 4H; C H₂-S) ppm. ¹³C NMR (150 MHz, 298 K, D₂O): δ 156.90 ( C =N), 40.50 (NH- C H₂) 30.27 ( C H₂-S) ppm.
．
Synthesis of first generation monomer 11 (NER347MNER348-11)
In an oven-dried 300 mL three-neck round-bottom flask, S-methylisothiourea·0.5 H₂SO₄ (13.9 g, 0.1 mol) was dissolved in 80 mL Milli-Q water.
To this solution was added 40 mL of 2,2'-disulfanediyldiethaneamine (0.25 mol).
The mixture was refluxed for 24 hours. The reaction mixture was cooled to room temperature, giving rise to a white precipitate. The precipitate was aspirated and recrystallized from water to give white crystals, ^GuM^Gen.I-11 (yield: 96% based on 2,2'-disulfanediyldiethanamine). The product was identified by ¹H NMR and ¹³C NMR. ¹H NMR (600 MHz, 298 K, D₂O): δ 3.60 (t, 4H; NH-C H₂), 3.38 (t, 4H; C H₂-S) ppm. ¹³C NMR (150 MHz, 298 K, D₂O): δ 156.90 ( C =N), 39.77 (NH- C H₂), 36.11 (NH-CH₂- C H₂) ppm.

Synthesis of first generation monomer 12 (NER364MNER365-12)
In an oven-dried 300 mL three-neck round-bottom flask, 2,2'-(ethane-1,2-diylbis(oxy)bis(ethan-1-amine) (38.5 mL, 0.25 mol) was added to a solution of S-methylisothiourea·1/2H₂SO₄ (13.9 g, 0.1 mol) in Milli-Q water. The mixture was refluxed for 24 hours. After concentrating using a small evaporator, the mixture was allowed to stand at 4°C for 3 days. A clear precipitate formed which was washed with cold ethanol. Recrystallization from water/ethanol gave clear crystals ^GuM^Gen.I-12 (yield: 32% based on 2,2'-(ethane-1,2-diylbis(oxy)bis(ethan-1-amine)). The product was identified by ¹H NMR and ¹³C NMR. ¹H NMR (600 MHz, 298 K, D₂O): δ 3.72 (t, 4H; NH-C H₂), 3.70 (p, 4H; NH-CH₂- C H₂-O), 3.41 (t, 4H; O-C H₂-C H₂-O) ppm. ¹³C NMR (150 MHz, 298 K, D₂O): δ 157.30 ( C =N), 69.68 ( C H₂-O) 68.81 (O- C H₂- C H₂-O), 41.16 (NH- C H₂) ppm.

Synthesis of second generation monomer 1 (NER385-M NER386-1)
In an oven-dried 1000 mL three-neck round-bottom flask, S-methylisothiourea·0.5 H₂SO₄ (40 g, 0.3 mol) was dissolved in 700 mL Milli-Q water.
To this solution was added 14 mL of 1,3-bis(3-aminopropyl)tetraethylsiloxane. The reaction mixture was refluxed for 24 hours. The reaction mixture was cooled to room temperature and the crude residue was filtered and washed with cold water to give ^GuM^Gen.II-1 (yield: 53% based on 1,3-bis(3-aminopropyl)tetraethylsiloxane). The product was identified by ¹H NMR and ¹³C NMR. ¹H NMR (600 MHz, 298 K, D₂O): δ 3.18 (t, 4H; NH-C H₂), 1.62 (p, 4H; NH-CH₂-C H₂), 0.61 (t, 4H; C H₂-O-Si), 0.14 (s, 12H; Si-C H₃) ppm. ¹³C NMR (150 MHz, 298 K, D₂O): δ 156.67 ( C =N), 43.70 (NH- C H₂), 22.14 (NH-CH₂- C H₂), 14.10 ( C H₂-O-Si), 0.70 (Si- C H₃) ppm.

Synthesis of second generation monomer 2 (NER407-M NER408-2)
In an oven-dried 100 mL three-neck round-bottom flask, 3,3'-(1,1,3,3,5,5,7,7,9,9,11,11-dodecamethylhexasiloxane-1,11-diyl)bis(propan-1-amine) (5.4 mL, 10 mmol) was dissolved in hydrochloric acid (1.5 mL, wt. % = 36.5%) in ethanol (20 mL). To this solution was added cyanamide (1.6g, 0.04 mol). The reaction mixture was refluxed for 4 hours. The reaction mixture was cooled to room temperature and then evaporated to dryness under reduced pressure to give a viscous liquid. The resulting viscous liquid was rinsed with warm water (70 °C 100 mL × 3) to obtain liquid ^GuM^Gen.II-2 (yield: 12% based on 3,3'-(1,1,3,3,5,5,7,7,9,9,11,11-dodecamethylhexasiloxane-1,11-diyl)bis(propan-1-amine). The product was identified by ¹H NMR. ¹H NMR (600 MHz, 298 K, MeOD): δ 2.92 (t, 4H; NH-C H₂), 1.71 (p, 4H; NH-CH₂-C H₂), 0.64 (t, 4H; C H₂-O-Si), 0.12 (m, 36H; Si-C H₃) ppm.

Example 2: Synthesis of supramolecular polymer glass (SPG) 1.
Synthesis of first-generation supramolecular polymer glass (^Gen.ISPG) The first-generation supramolecular polymer glass is synthesized using the first-generation monomer prepared in Example 1. The synthesis of this first generation supramolecular polymer glass can be carried out in an aqueous system and does not involve any organic solvents or expensive rare earth metal catalysts. In the following Examples 2, and 4 to 9, unless otherwise specified, the supramolecular polymer glass was synthesized in a flask as in Example 1.

To an aqueous solution of sodium hexametaphosphate (or sodium trimetaphosphate), an aqueous solution of each of the guanidinium-based first generation monomers (NER419MNER420) prepared in Example 1 was added so that the theoretical molar ratio of the guanidinium monomer to the phosphate diester was 1:1.
When any of the first-generation monomers was used, the mixed aqueous solution immediately underwent liquid-liquid phase separation, resulting in a turbid supramolecular polymer emulsion (FIGS. 2A and 2B; in FIG. 2A, phase separation occurs at the interface 12 between the water layer 10 and the layer of viscous liquid 11 consisting of the supramolecular polymer glass). The supramolecular polymer emulsion was concentrated by centrifugation to a viscous liquid, which was rinsed with pure water and dried in vacuum to obtain the first generation supramolecular polymer glass (^Gen.ISPG) in 98% yield.

Synthesis of second-generation supramolecular polymer glass (^Gen.IISPG) Second-generation supramolecular polymer glass is synthesized using second-generation monomers.

To an aqueous solution of sodium hexametaphosphate (or sodium trimetaphosphate), an aqueous solution of each of the guanidinium-based second generation monomers (^GuM^Gen.II) prepared in Example 1 was added so that the theoretical molar ratio of the guanidinium monomer to the phosphate diester was 1:1.
When any of the second generation monomers was used, the mixed aqueous solution immediately underwent liquid-liquid phase separation to produce a turbid supramolecular polymer emulsion. The supramolecular polymer emulsion was concentrated by centrifugation to a viscous liquid, which was rinsed with pure water and dried in vacuum to obtain the second generation supramolecular polymer glass (^Gen.IISPG) in 72% yield.

Synthesis of the third generation supramolecular polymer glass (^Gen.IIISPG) The third generation supramolecular polymer glass is synthesized using both first and second generation monomers.

An aqueous solution of sodium hexametaphosphate (or sodium trimetaphosphate) was added with a mixture of the guanidinium-based first generation monomer (^GuM^Gen.I) and each second generation monomer (^GuM^Gen.II) prepared in Example 1 in a theoretical molar ratio of guanidinium monomer to phosphate diester of 1:1. The mixed aqueous solution immediately underwent liquid-liquid phase separation to produce a turbid supramolecular polymer emulsion. The supramolecular polymer emulsion was concentrated by centrifugation to a viscous liquid, which was rinsed with pure water and dried in vacuum to obtain the third generation supramolecular polymer glass (^Gen.IIISPG) in a 90% yield.

Example 3: Evaluation of the physical properties of supramolecular polymer glass (SPG) 1.
Optical transmittance of supramolecular polymer glass (SPG) SPG films measuring 100 mm in length, 100 mm in width, and 0.5 mm in thickness were produced, and the optical transmittance of the SPG films was measured using the transmission mode of an ultraviolet-visible spectrometer. (Results) As a result, the optical transmittance of the SPG film was found to be in the range of 90% to 97%, depending on the molecular structure of the monomer, and was comparable to that of commercially available transparent resin films (polymethyl methacrylate (PMMA)), polycarbonate (PC), polyethylene terephthalate (PET), polystyrene (PS), and inorganic glass (Glass) (Figure 3).

Mechanical Properties of Supramolecular Polymer Glass (SPG) SPG films with dimensions of 100 mm in length, 100 mm in width, and 0.5 mm in thickness were produced. The film was placed on a metal plate and tested using an indentation hardness tester, ENT-NEXUS (ELIONIX Inc.) ) was used to determine Young's modulus. A diamond indenter tip was used for the indentation test. The maximum load was 50 mN, and the loading/unloading speed was 2.5 mN/s. The duration of the maximum load was 5 s. From the unloading curves, the Young's modulus and indentation hardness were determined using a testing machine. The measurement temperature was 25°C.

The tensile strength of commercially available materials was reported on Wikipedia and in other published literature. The tensile strength was measured by preparing a sample having a length of 35 mm, a width of 2 mm, and a thickness of 0.5 mm, and using a tensile machine at a test speed of 10 mm/s. (Results) As shown in Figure 4, the first-generation supramolecular polymer glass maintains its shape and can withstand the load even when a weight is placed on it.

As shown in FIG. 5, unexpectedly, the Young's modulus of the SPG films exceeded 5 Gpa for the second-generation supramolecular polymer glass and exceeded 15 Gpa for the first-generation supramolecular polymer glass, both of which were higher than those of the commercial resin films.

As shown in FIG. 6, the tensile strength of the first and second generation supramolecular polymer glasses was in the range of 20 to 50 Gpa, which was comparable to that of commercially available resin films.

Mechanical properties of third-generation supramolecular polymer glass (SPG) The third-generation SPG is also described in "2. The Young's modulus was measured under the same conditions as in "Mechanical Properties of Supramolecular Polymer Glass (SPG)".  However, the measurement temperature was 30°C. (Results) As shown in Figure 7, the Young's modulus is low for the second-generation SPG (^Gen.2SPG, far left) and high for the first-generation SPG (^Gen.1SPG, far right); however, the Young's modulus could be adjusted by mixing the first and second-generation SPGs.

Processability of supramolecular polymer glass (SPG) The glass transition temperatures (Tg) of the first to third generation SPGs produced in Example 2 ranged from 35°C to 125°C. Each SPG could be processed into various shapes or patterns by hot pressing at temperatures around T_g, similar to conventional synthetic resins such as PET.

Self-healing property of supramolecular polymer glass (SPG) The SPG based on ^GuM^Gen.I-2 produced in Example 2 was able to completely self-heal after being broken into two pieces by applying pressure under ambient conditions (20 °C, humidity 60%). After self-healing, the mechanical properties of the SPG were not compromised. Additionally, all of the SPGs prepared in Example 2 are capable of self-healing with the assistance of water or moisture. Specifically, the first-generation supramolecular polymer glass, NER437_SPG, was able to self-repair by pressing it under high humidity (RH 80%) conditions for 30 minutes, and the second-generation supramolecular polymer glass, NER438_SPG, was able to self-repair by pressing it under water spray for 20 minutes.

Underwater processability of first-generation supramolecular polymer glass (^Gen.ISPG) When each of the first-generation supramolecular polymer glasses, ^Gen.ISPG, produced in Example 2, was immersed in water, it gradually softened (Figure 8 (A)) and after several hours became a viscous supramolecular polymer liquid (Figure 8 (B)). This viscous liquid was dried in a Teflon container under vacuum at 80° C. for 6 hours to give ^Gen.ISPG with mechanical strength without any loss of monomer or mechanical properties. NER442 SPG can also be softened and viscous by spraying it with water, allowing it to be molded into a variety of structures.

Example 4: Synthesis of supramolecular polymer glass using ammonium-based monomers The ammonium groups of ammonium-based molecules interact with oxyanions such as carboxylate and phosphodiester groups to form cross-linked supramolecular networks, giving rise to SPGs. As a typical example, commercially available small molecules bearing di/tri/tetraamino groups can form supramolecular polymers with oxyanions via salt bridges.

As shown in FIG. 9, a diamine monomer was dissolved in ethanol at 0.06 M, and a 0.2 M sodium hexametaphosphate solution was added to the prepared diamine monomer solution.
The solution immediately became cloudy, and liquid-liquid phase separation was observed instantaneously. When the mixture was centrifuged at 1000 rpm for 10 minutes, a clear liquid-liquid phase separation was observed as shown by the dotted line in the lower left photograph of FIG.  The lower viscous liquid was washed three times with 50 mL of deionized water. After drying in vacuum at 80°C for 3 hours, a transparent glass was obtained with a yield of about 98%.

Example 5: Synthesis of SPGs using renewable feedstock monomers Water-soluble small biomolecules or biopolymers are abundantly stored on Earth, and these could also be used to form SPGs using our strategy. In this example, SPG was prepared using two renewable raw materials, phytic acid and alginic acid, as raw material monomers for oxoanions.

Phytic acid is a hexahydrogen phosphate ester of inositol and is the major storage form of phosphorus in cereals, legumes, oilseeds, and nuts.
Alginic acid is a naturally occurring edible polysaccharide purified from naturally occurring brown algae and certain bacterial genera.
It is rich in carboxyl groups and can form salt bridges with ammonium and guanidinium groups. Alginate can also be incorporated into ^Gen.1SPG and ^Gen.2SPG as an additive to enhance the mechanical properties of SPG.

Phytic acid-based SPG: An aqueous solution of a guanidinium-based monomer was added to an aqueous solution of phytic acid so that the stoichiometric molar ratio of guanidino groups to phosphate groups (guanidinium ions to phosphate ions) was 1:1. This mixed aqueous solution instantly underwent liquid-liquid phase separation, yielding a cloudy supramolecular polymer emulsion. This supramolecular polymer emulsion was concentrated into a viscous liquid by centrifugation, and the viscous liquid was washed with Milli-Q water and then vacuum dried to obtain supramolecular polymer glass (SPG). SPG could be processed into various shapes and patterns by hot pressing.

Characteristics of phytic acid-based SPG The mechanical properties of the SPG film produced in 1-1 were as described in Example 3, section 2. Under the same measurement conditions as ENT-NEXUS (ELIONIX Inc. ) was determined by indentation testing. A Berkovich-shaped diamond indenter tip was used for the indentation experiments. For the combination of phytic acid and ^GuM^Gen.II-1, the Young's modulus of SPG was 5.5 GPa (Figure 10A). Furthermore, when SPGs were prepared using ^GuM^Gen.I-2 instead of ^GuM^Gen.II-1, the Young's modulus of the SPGs increased to 10 GPa (Figure 10B).

Alginic acid-based SPG: Amine or guanidine monomers were added to a diluted aqueous solution of alginic acid so that the stoichiometric molar ratio of guanidino group/amino group to carboxyl group (guanidinium ion/ammonium ion) to carboxylate ion) was 1:1. This mixed aqueous solution instantly underwent liquid-liquid phase separation, yielding a cloudy supramolecular polymer emulsion. The supramolecular polymer emulsion was concentrated by centrifugation into a viscous liquid, which was washed with Milli-Q water and then dried under vacuum to obtain a supramolecular polymer glass.

Alginic acid-reinforced SPG: Amine or guanidine monomers were added to a mixed aqueous solution of alginic acid and hexametaphosphoric acid so that the stoichiometric molar ratio of guanidino group/amino group to carboxyl group (guanidinium ion/ammonium ion) to carboxylate ion) was 1:1. This mixed aqueous solution instantly underwent liquid-liquid phase separation, yielding a cloudy supramolecular polymer emulsion. The supramolecular polymer emulsion was concentrated by centrifugation into a viscous liquid, which was washed with Milli-Q water and then dried under vacuum to obtain a supramolecular polymer glass.

Results The mechanical properties of the SPG film were as described in Example 3, section 2. Under the same measurement conditions as ENT-NEXUS (ELIONIX Inc. ) was determined by indentation testing. A Berkovich-shaped diamond indenter tip was used for the indentation experiments. The mechanical properties of alginate-based and alginate-reinforced SPG are shown in Figures 11A-C.

In all samples, the Young's modulus of SPG was high, exceeding 10 Gpa (12.21 Gpa, 17.51 Gpa, and 16.16 GPa in Figures 11A, 11B, and 11C, respectively).

Example 6
Synthesis of SPG using natural polysaccharides An aqueous solution of chondroitin sulfate and an aqueous solution of each of the guanidinium-based first generation monomers (NER451MNER452) produced in Example 1 were mixed so that the theoretical mixing molar ratio of the guanidinium monomer to the anionic functional group in the chondroitin sulfate was 1:1.
The mixed aqueous solution underwent liquid-liquid phase separation to produce a turbid supramolecular polymer emulsion (Figure 12).
The supramolecular polymer emulsion was concentrated by centrifugation to a viscous liquid, which was rinsed with pure water and dried in vacuum to obtain a supramolecular polymer glass in a yield of 95% (Figure 13).

Example 7
Synthesis of SPG using natural polysaccharides An aqueous solution of sodium heparin sulfate and an aqueous solution of each of the first generation guanidinium-based monomers (NER453MNER454) produced in Example 1 were mixed so that the theoretical molar ratio of the guanidinium monomer to the anionic functional groups in sodium heparin sulfate was 1:1.
The mixed aqueous solution underwent liquid-liquid phase separation to produce a turbid supramolecular polymer emulsion (Figure 14).
The supramolecular polymer emulsion was concentrated by centrifugation to a viscous liquid, which was rinsed with pure water and dried in vacuum to obtain a supramolecular polymer glass in a yield of 98% (Figure 15).

Example 8
Synthesis of SPG using synthetic polysaccharides An aqueous solution of dextran sodium sulfate and an aqueous solution of each of the guanidinium-based first generation monomers (NER455MNER456) produced in Example 1 were mixed so that the theoretical molar mixing ratio of the guanidinium monomer to the anionic functional group in the dextran sodium sulfate was 1:1.
The mixed aqueous solution underwent liquid-liquid phase separation to produce a turbid supramolecular polymer emulsion (Figure 16).
The supramolecular polymer emulsion was concentrated by centrifugation to a viscous liquid, which was rinsed with pure water and dried in vacuum to obtain a supramolecular polymer glass in 100% yield (FIG. 17).

Example 9
Synthesis of SPG using synthetic polysaccharides An aqueous solution of β-cyclodextrin (product number CAS7585-39-9) in which some of the hydrogen atoms of the hydroxyl groups had been replaced with -SO₃Na and an aqueous solution of each of the guanidinium-based first generation monomers (^GuM^Gen.I) produced in Example 1 were mixed so that the theoretical molar ratio of the guanidinium monomer to the anionic functional groups in the β-cyclodextrin was 1:1. The mixed aqueous solution underwent liquid-liquid phase separation to produce a turbid supramolecular polymer emulsion (Figure 18). The supramolecular polymer emulsion was concentrated by centrifugation to a viscous liquid, which was rinsed with pure water and dried in vacuum to obtain a supramolecular polymer glass in a yield of 98% (Figure 19).

The synthesis of the supramolecular polymer glasses of Examples 2, 4-9 could be carried out at atmospheric pressure without the need for heating or cooling of the samples.

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