METHOD FOR SYNTHESIZING A HYDROPHOBIC DEEP EUTECTIC SOLVENT
20220144669 · 2022-05-12
Inventors
- Jian Shi (Lexington, KY, US)
- Wenqi Li (Lexington, KY, US)
- Jameson Hunter (Lexington, KY, US)
- Yuxuan Zhang (Lexington, KY, US)
Cpc classification
International classification
Abstract
A method for synthesizing a hydrophobic deep eutectic solvent (DES) using one or more lignin-derived compounds is provided.
Claims
1. A method for synthesizing a hydrophobic deep eutectic solvent, comprising: mixing a first lignin-derived compound with a second lignin-derived compound to create a mixture; heating the mixture; and stirring the mixture until a homogenous liquid is obtained; wherein the first lignin-derived compound and the second lignin-derived compound are not the same compound.
2. The method according to claim 1, wherein at least one of the first lignin-derived compound and the second lignin-derived compound is aromatic.
3. The method according to claim 2, wherein the first lignin-derived compound is selected from one of: ##STR00010##
4. The method according to claim 2, wherein the first lignin-derived compound and the second lignin-derived compound are each aromatic.
5. The method according to claim 2, wherein at least one of the first lignin-derived compound and the second lignin-derived compound is phenolic.
6. The method according to claim 5, wherein the first lignin-derived compound is selected from one of: ##STR00011##
7. The method according to claim 5, wherein the first lignin-derived compound and the second lignin-derived compound are each phenolic.
8. The method according to claim 1, wherein the first lignin-derived compound and the second lignin-derived compound are each a monocyclic compound including at least one hydroxyl group attached to a ring structure of the monocyclic compound.
9. The method according to claim 1, wherein at least one of the first lignin-derived compound and the second lignin-derived compound is a terpenoid.
10. The method according to claim 1, wherein heating the mixture comprises increasing the temperature of the mixture to a value within a range of about 60° C. to about 100° C.
11. A method for synthesizing a hydrophobic deep eutectic solvent, comprising: mixing a first lignin-derived compound with a second lignin-derived compound to create a mixture; heating the mixture; and stirring the mixture until a homogenous liquid is obtained; wherein the first lignin-derived compound is aromatic, the second lignin-derived compound is a cyclic compound including at least one hydroxyl group attached to a ring structure of the cyclic compound, and the first lignin-derived compound and the second lignin-derived compound are not the same compound.
12. The method according to claim 11, wherein the first lignin-derived compound is selected from one of: ##STR00012##
13. The method according to claim 11, wherein the second lignin-derived compound is aromatic.
14. The method according to claim 11, wherein the second lignin-derived compound is a monocyclic compound.
15. The method according to claim 14, wherein the second lignin-derived compound is a terpenoid.
16. The method according to claim 15, wherein the second lignin-derived compound is selected from one of: ##STR00013##
17. The method according to claim 11, wherein the first lignin-derived compound is phenolic.
18. The method according to claim 17, wherein the first lignin-derived compound is selected from one of: ##STR00014##
19. The method according to claim 17, wherein the second lignin-derived compound is phenolic.
20. The method according to claim 11, wherein heating the mixture comprises increasing the temperature of the mixture to a value within a range of about 60° C. to about 100° C.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] The presently-disclosed subject matter will be better understood, and features, aspects and advantages other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such detailed description makes reference to the following drawings, wherein:
[0017]
[0018]
[0019]
[0020]
DESCRIPTION OF EXEMPLARY EMBODIMENTS
[0021] The details of one or more embodiments of the presently-disclosed subject matter are set forth in this document. Modifications to embodiments described in this document, and other embodiments, will be evident to those of ordinary skill in the art after a study of the information provided in this document. The information provided in this document, and particularly the specific details of the described exemplary embodiments, is provided primarily for clearness of understanding and no unnecessary limitations are to be understood therefrom. In case of conflict, the specification of this document, including definitions, will control.
[0022] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosure belongs. Any methods and materials similar to or equivalent to those described herein can be used in the practice or testing of the present disclosure, including the methods and materials described below.
[0023] Following long-standing patent law convention, the terms “a,” “an,” and “the” refer to “one or more” when used in this application, including the claims. Thus, for example, reference to “a cell” includes a plurality of cells, and so forth.
[0024] The terms “comprising,” “including,” and “having” are intended to be inclusive and mean that there may be additional elements other than the listed elements.
[0025] As used herein, the terms “optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
[0026] As used herein, the term “lignin-derived compound” means a compound which is either directly extracted from the lignin component of a lignocellulosic biomass or obtained directly from the lignin component of a lignocellulosic biomass by mechanically and/or chemically treating the lignocellulosic biomass, or which is synthesized from an intermediate compound that is directly extracted or obtained from the lignin component of a lignocellulosic biomass, such as m-Cresol and/or acetophenone.
[0027] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in this specification and claims are approximations that can vary depending upon the desired properties sought to be obtained by the presently-disclosed subject matter.
[0028] As used herein, the term “about,” when referring to a value or to an amount of mass, weight, time, volume, concentration, percentage, or the like is meant to encompass variations of in some embodiments ±50%, in some embodiments ±40%, in some embodiments ±30%, in some embodiments ±20%, in some embodiments ±10%, in some embodiments ±5%, in some embodiments ±1%, in some embodiments ±0.5%, and in some embodiments ±0.1% from the specified amount, as such variations are appropriate to perform the disclosed method.
[0029] As used herein, ranges can be expressed as from “about” one particular value, and/or to “about” another particular value. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.
[0030] All combinations of method or process steps as used herein can be performed in any order, unless otherwise specified or clearly implied to the contrary by the context in which the referenced combination is made.
[0031] As used herein, nomenclature for compounds, including organic compounds, can be given using common names, IUPAC, IUBMB, or CAS recommendations for nomenclature. When one or more stereochemical features are present, Cahn-Ingold-Prelog rules for stereochemistry can be employed to designate stereochemical priority, E1Z specification, and the like. One of skill in the art can readily ascertain the structure of a compound if given a name, either by systemic reduction of the compound structure using naming conventions, or by commercially available software, such as CHEMDRAW™ (Cambridgesoft Corporation, U.S.A.).
[0032] Provided herein is a method of synthesizing a hydrophobic deep eutectic solvent (DES) using one or more lignin-derived compounds. The hydrophobic DESs synthesized from the method disclosed herein may find utility in a variety of applications including, but not limited to, the extraction of plastic contaminants from water samples, the extraction of bioactive compounds, biomass fractionation, bioseparation, antimicrobial production, herbicidal applications, drug delivery applications, electrolyte for batteries, and formulating a two-phase reaction system.
[0033] Lignin is a phenolic polymer that is mainly composed of three phenolic monomers—namely, p-hydroxyphenyl, guaiacyl, and syringyl—making it promising for the production of aromatic chemicals via chemical or biological routes. In general, lignin can be used to directly produce phenols including phenol, benzene, and the three above-identified phenolic monomers. Through catalytic reactions, such as oxidation and hydrogenation, the phenols from lignin can be upgraded to phenolic or other hydroxylated compounds. Due to its high polarity, the hydroxyl group(s) of these lignin-derived compounds can easily provide or attract hydrogen to facilitate hydrogen bonding. Accordingly, a lignin-derived compound may act, in some DES systems, as a hydrogen bond donor (HBD), while, in other DES systems, the same lignin-derived compound may act as a hydrogen bond acceptor (HBA). For example, 2,6-dimethoxyphenol may serve as a HBD when used with thymol in the synthesis of a hydrophobic DES and may serve as a HBA when used with phenol in the synthesis of a hydrophobic DES.
[0034] In the method of the present disclosure, a hydrophobic DES is synthesized by initially mixing a lignin-derived compound (first compound or first lignin-derived compound) with a second compound that is different than the first compound to create a mixture, where, during synthesis of the hydrophobic DES, one compound of the mixture will act as a HBD and the other compound of the mixture will act as a hydrogen bond acceptor HBA. The mixture is subsequently heated and stirred using known heating and mixing means until a homogenous liquid is obtained, thus resulting in the synthesis of the hydrophobic DES.
[0035] As lignin-derived compounds are sourced from environmentally friendly renewable biomasses, it is generally preferred that the second compound used in the synthesis of the hydrophobic DES also be a lignin-derived compound. Accordingly, in one aspect, the presently disclosed subject matter is directed to a method of synthesizing a hydrophobic DES which utilizes a first lignin-derived compound and a second lignin-derived compound, wherein one of the first lignin-derived compound and the second lignin-derived compound acts as a HBD and the other of the first lignin-derived compound and the second lignin-derived compound acts as a HBA. The use of two lignin-derived compounds may prove particularly advantageous by helping to ensure the DES synthesized is hydrophobic. The hydrophobicity of a DES can be impacted by the properties of its components. For example, common quaternary ammonium salts, such as choline chloride, are highly soluble in water. Thus, DESs which are formed using such salts are more likely to be hydrophilic. Additionally, salts which have a low solubility in water are generally more expensive.
[0036] In some embodiments, the first lignin-derived compound and/or the second lignin-derived compound is aromatic (i.e., an aromatic compound) (
##STR00001##
2,6-dimethoxyphenol
##STR00002##
vanillin
##STR00003##
phenol
##STR00004##
1-phenylethanol
##STR00005##
guaiacol
##STR00006##
and 4-hydroxybenzyl alcohol
##STR00007##
In some embodiments, both the first lignin-derived compound and the second lignin derived compound are aromatic (
[0037] In some embodiments, the first lignin-derived compound and/or the second lignin-derived compound is phenolic (i.e., a phenolic compound) (
[0038] In some embodiments, the first lignin-derived compound and the second lignin-derived compound are each a monocyclic compound including at least one hydroxyl group attached to a ring structure of the monocyclic compound (
[0039] In one exemplary embodiment, the first lignin derived-compound is aromatic and the second lignin-derived compound is a cyclic compound including at least one hydroxyl group attached to a ring structure of the cyclic compound (
[0040] In some embodiments, the cyclic compound used as the second lignin-derived compound is aromatic (
##STR00008##
and thymol (
[0041] In some embodiments, the mixture created by mixing the first lignin-derived compound and the second lignin-derived compound is heated so that the temperature of the mixture is increased to a value of about 40° C. to about 120° C. In some embodiments, the mixture created from the first lignin-derived compound and the second lignin-derived compound is heated so that the temperature of the mixture is increased to a value of about 60° C. to about 100° C. In some embodiments, the first lignin-derived compound and the second lignin-derived compound may be mixed in a molar ratio of about 1:1, about 1:2, about 2:1, about 3:1, about 4:1, or about 5:1.
[0042] In another aspect, the presently disclosed subject matter is directed to a method of synthesizing a hydrophobic DES which utilizes only a single lignin-derived compound. In such embodiments, instead of utilizing a second lignin-derived compound within the mixture that is subsequently heated and stirred to synthesize the hydrophobic DES, a fatty acid which includes at least one carboxyl group is utilized. Due to its high polarity, the carboxyl group(s) of the fatty acid can easily provide or attract hydrogen to facilitate hydrogen bonding. Accordingly, the fatty acid may act, in some DES systems, as a hydrogen bond donor HBD, while, in other DES systems, the fatty acid may act as a HBA. In some embodiments, the fatty acid used in the mixture is decanoic acid
##STR00009##
In some embodiments, the lignin-derived compound with which the fatty acid is mixed is aromatic (
[0043] In some embodiments, the mixture created from the lignin-derived compound and the fatty acid is heated so that the temperature of the mixture is increased to a value of about 40° C. to about 120° C. In some embodiments, the mixture created from the lignin-derived compound and the fatty acid is heated so that the temperature of the mixture is increased to a value of about 60° C. to about 100° C. In some embodiments, the first lignin-derived compound and the second lignin-derived compound may be mixed in a molar ratio of about 1:1, about 1:2, or about 2:1.
[0044] The presently-disclosed subject matter is further illustrated by the following specific but non-limiting examples. The following examples may include compilations of data that are representative of data gathered at various times during the course of development and experimentation related to the presently-disclosed subject matter. Those skilled in the art will recognize, or be able to ascertain, using no more than routine experimentation, numerous equivalents to the specific substances and procedures described herein.
Examples
[0045] The following examples focus on the discoveries that (i) certain lignin-derived compounds can be combined with each other to synthesize a DES that exhibits hydrophobic properties and (ii) certain lignin-derived compounds can be combined with certain fatty acids to synthesize a DES that exhibits hydrophobic properties. More specifically, the following examples focus on the formulations outlined in Table 1 below, in which sample numbers 1-8, 9-16, 17-24, and 25-34 correspond to the number labels shown in
TABLE-US-00001 TABLE 1 Ratio (Compound A:Com- Sample Compound A Compound B pound B) 1 Menthol 2,6-dimethoxyphenol 1:1 2 Menthol 2,6-dimethoxyphenol 1:2 3 Menthol 2,6-dimethoxyphenol 2:1 4 Menthol phenol 1:1 5 Menthol phenol 1:2 6 Menthol phenol 2:1 7 Menthol 1-phenylethanol 1:1 8 Menthol guaiacol 1:1 9 Thymol vanillin 1:1 10 Thymol 2,6-dimethoxyphenol 1:1 11 Thymol 2,6-dimethoxyphenol 1:2 12 Thymol 2,6-dimethoxyphenol 2:1 13 Thymol phenol 1:1 14 Thymol phenol 1:2 15 Thymol phenol 2:1 16 Thymol guaiacol 1:1 17 Decanoic acid 2,6-dimethoxyphenol 1:1 18 Decanoic acid 2,6-dimethoxyphenol 1:2 19 Decanoic acid 2,6-dimethoxyphenol 2:1 20 Decanoic acid phenol 1:1 21 Decanoic acid phenol 1:2 22 Decanoic acid phenol 2:1 23 Decanoic acid guaiacol 1:1 24 Decanoic acid 1-phenylethanol 1:1 25 2,6-dimethoxyphenol 4-hydroxybenzyl alcohol 1:1 26 2,6-dimethoxyphenol 4-hydroxybenzyl alcohol 2:1 27 2,6-dimethoxyphenol 4-hydroxybenzyl alcohol 3:1 28 2,6-dimethoxyphenol 4-hydroxybenzyl alcohol 4:1 29 2,6-dimethoxyphenol 4-hydroxybenzyl alcohol 5:1 30 2,6-dimethoxyphenol vanillin 1:1 31 2,6-dimethoxyphenol vanillin 2:1 32 2,6-dimethoxyphenol phenol 1:1 33 2,6-dimethoxyphenol phenol 1:2 34 2,6-dimethoxyphenol phenol 2:1
[0046] Materials and Methods
[0047] In the examples described below, reference is made to the use of lignin-derived compounds including: menthol, thymol, 2,6-dimethoxyphenol, phenol, 1-phenylethanol, guaiacol, vanillin, 4-hydroxy benzyl alcohol. Menthol can naturally be obtained by freezing the oil of mint plants, followed by filtration to separate the menthol crystals or be produced through the Haarmann-Reimer process using lignin-derived m-Cresol as feedstock. Thymol can be extracted from thyme oil or be synthesized via alkylation of lignin-derived m-Cresol. 2,6-dimethoxyphenol, phenol, and guaiacol can each be obtained by subjecting a lignin sample to thermal decomposition. 1-phenylethanol can be obtained by the reduction or hydrogenation of lignin-derived acetophenone. Vanillin and 4-hydroxybenzyl alcohol can be obtained by the catalytic transformation of lignin or, alternatively, via extraction from cured vanilla beans.
[0048] In the examples described below, reference is also made to the use of the fatty acid compound of decanoic acid, which can be obtained by the fermentation of organic residues.
[0049] Menthol—2,6-Dimethoxyphenol DES
[0050] Three DESs were synthesized using the lignin-derived compound of menthol and the lignin-derived compound of 2,6-dimethoxyphenol (Table 1, samples 1-3). Three eutectic mixtures were initially created by mixing menthol and 2,6-dimethoxyphenol in 1:1, 1:2, and 2:1 molar ratios. Following the initial mixing of menthol and 2,6-dimethoxyphenol, each respective mixture was heated at 80° C. and constantly stirred for one hour until a homogenous transparent liquid was obtained, thus indicating formation of the DES. The hydrophobicity of each synthesized DES was then tested by introducing a small volume of water (1 mL) into a vial containing the synthesized DES (0.5 mL) and then mixing the contents of the vial (
[0051] Menthol—Phenol DES
[0052] Three DESs were synthesized using the lignin-derived compound of menthol and the lignin-derived compound of phenol (Table 1, samples 4-6). Three eutectic mixtures were initially created by mixing menthol and phenol in 1:1, 1:2, and 2:1 molar ratios. Following the initial mixing of menthol and phenol, each respective mixture was heated at 60° C. and constantly stirred for two hours until a homogenous transparent liquid was obtained, thus indicating formation of the DES. The hydrophobicity of each synthesized DES was then tested by introducing a small volume of water (1 mL) into a vial containing the synthesized DES (0.5 mL) and then mixing the contents of the vial (
[0053] Menthol—1-Phenylethanol DES
[0054] A single DES was synthesized using the lignin-derived compound of menthol and the lignin-derived compound of 1-phenylethanol (Table 1, sample 7). A eutectic mixture was initially created by mixing menthol and 1-phenylethanol in a 1:1 molar ratio. Following the initial mixing of menthol and 1-phenylethanol, the mixture was heated at 60° C. and constantly stirred for one hour until a homogenous transparent liquid was obtained, thus indicating formation of the DES. The hydrophobicity of the synthesized DES was then tested by introducing a small volume of water (1 mL) into a vial containing the synthesized DES (0.5 mL) and then mixing the contents of the vial (
[0055] Menthol—Guaiacol DES
[0056] A single DES was synthesized using the lignin-derived compound of menthol and the lignin-derived compound of guaiacol (Table 1, sample 8). A eutectic mixture was initially created by mixing menthol and guaiacol in a 1:1 molar ratio. Following the initial mixing of menthol and 1-phenylethanol, the mixture was heated at 60° C. and constantly stirred for one hour until a homogenous transparent liquid was obtained, thus indicating formation of the DES. The hydrophobicity of the synthesized DES was then tested by introducing a small volume of water (1 mL) into a vial containing the synthesized DES (0.5 mL) and then mixing the contents of the vial (
[0057] Thymol—Vanillin DES
[0058] A single DES was synthesized using the lignin-derived compound of thymol and the lignin-derived compound of vanillin (Table 1, sample 9). A eutectic mixture was initially created by mixing thymol and vanillin in a 1:1 molar ratio. Following the initial mixing of thymol and vanillin, the mixture was heated at 80° C. and constantly stirred for two hours until a homogenous transparent liquid was obtained, thus indicating formation of the DES. The hydrophobicity of the synthesized DES was then tested by introducing a small volume of water (1 mL) into a vial containing the synthesized DES (0.5 mL) and then mixing the contents of the vial (
[0059] Thymol—2,6-dimethoxyphenol DES
[0060] Three DESs were synthesized using the lignin-derived compound of thymol and the lignin-derived compound of 2,6-dimethoxyphenol (Table 1, samples 10-12). Three eutectic mixtures were initially created by mixing thymol and 2,6-dimethoxyphenol in 1:1, 1:2, and 2:1 molar ratios. Following the initial mixing of thymol and 2,6-dimethoxyphenol, each respective mixture was heated at 80° C. and constantly stirred for one hour until a homogenous transparent liquid was obtained, thus indicating formation of the DES. The hydrophobicity of each synthesized DES was then tested by introducing a small volume of water (1 mL) into a vial containing the synthesized DES (0.5 mL) and then mixing the contents of the vial (
[0061] Thymol—Phenol DES
[0062] Three DESs were synthesized using the lignin-derived compound of thymol and the lignin-derived compound of phenol (Table 1, samples 13-15). Three eutectic mixtures were initially created by mixing thymol and phenol in 1:1, 1:2, and 2:1 molar ratios. Following the initial mixing of thymol and phenol, each respective mixture was heated at 80° C. and constantly stirred for one hour until a homogenous transparent liquid was obtained, thus indicating formation of the DES. The hydrophobicity of each synthesized DES was then tested by introducing a small volume of water (1 mL) into a vial containing the synthesized DES (0.5 mL) and then mixing the contents of the vial (
[0063] Thymol—Guaiacol DES
[0064] A single DES was synthesized using the lignin-derived compound of thymol and the lignin-derived compound of guaiacol (Table 1, sample 16). A eutectic mixture was initially created by mixing thymol and guaiacol in a 1:1 molar ratio. Following the initial mixing of thymol and guaiacol, the mixture was heated at 100° C. and constantly stirred for one hour until a homogenous transparent liquid was obtained, thus indicating formation of the DES. The hydrophobicity of the synthesized DES was then tested by introducing a small volume of water (1 mL) into a vial containing the synthesized DES (0.5 mL) and then mixing the contents of the vial (
[0065] Decanoic Acid—2,6-Dimethoxyphenol DES
[0066] Three DESs were synthesized using the fatty acid decanoic acid and the lignin-derived compound of 2,6-dimethoxyphenol (Table 1, samples 17-19). Three eutectic mixtures were initially created by mixing decanoic acid and 2,6-dimethoxyphenol in 1:1, 1:2, and 2:1 molar ratios. Following the initial mixing of decanoic acid and 2,6-dimethoxyphenol, each respective mixture was heated at 100° C. and constantly stirred for two hours until a homogenous transparent liquid was obtained, thus indicating formation of the DES. The hydrophobicity of each synthesized DES was then tested by introducing a small volume of water (1 mL) into a vial containing the synthesized DES (0.5 mL) and then mixing the contents of the vial (
[0067] Decanoic Acid—Phenol DES
[0068] Three DESs were synthesized using the fatty acid decanoic acid and the lignin-derived compound of phenol (Table 1, samples 20-22). Three eutectic mixtures were initially created by mixing decanoic acid and phenol in 1:1, 1:2, and 2:1 molar ratios. Following the initial mixing of decanoic acid and phenol, each respective mixture was heated at 80° C. and constantly stirred for one hour until a homogenous transparent liquid was obtained, thus indicating formation of the DES. The hydrophobicity of each synthesized DES was then tested by introducing a small volume of water (1 mL) into a vial containing the synthesized DES (0.5 mL) and then mixing the contents of the vial (
[0069] Decanoic Acid—Guaiacol DES
[0070] A single DES was synthesized using the fatty acid decanoic acid and the lignin-derived compound of guaiacol (Table 1, sample 23). A eutectic mixture was initially created by mixing decanoic acid and guaiacol in a 1:1 molar ratio. Following the initial mixing of menthol and guaiacol, the mixture was heated at 80° C. and constantly stirred for one hour until a homogenous transparent liquid was obtained, thus indicating formation of the DES. The hydrophobicity of the synthesized DES was then tested by introducing a small volume of water (1 mL) into a vial containing the synthesized DES (0.5 mL) and then mixing the contents of the vial (
[0071] Decanoic Acid—1-Phenylethanol DES
[0072] A single DES was synthesized using the fatty acid decanoic acid and the lignin-derived compound of 1-phenylethanol (Table 1, sample 24). A eutectic mixture was initially created by mixing decanoic acid and 1-phenylethanol in a 1:1 molar ratio. Following the initial mixing of menthol and 1-phenylethanol, the mixture was heated at 60° C. and constantly stirred for two hours until a homogenous transparent liquid was obtained, thus indicating formation of the DES. The hydrophobicity of the synthesized DES was then tested by introducing a small volume of water (1 mL) into a vial containing the synthesized DES (0.5 mL) and then mixing the contents of the vial (
[0073] 2,6-Dimethoxyphenol—4-Hydroxybenzyl Alcohol DES
[0074] Five DESs were synthesized using the lignin-derived compound of 2,6-dimethoxyphenol and the lignin-derived compound of 4-hydroxybenzyl alcohol (Table 1, samples 25-29). Five eutectic mixtures were initially created by mixing 2,6-dimethoxyphenol and 4-hydroxybenzyl alcohol in 1:1, 2:1, 3:1, 4:1, and 5:1 molar ratios. Following the initial mixing of 2,6-dimethoxyphenol and 4-hydroxybenzyl alcohol, each respective mixture was heated at 100° C. and constantly stirred for one hour until a homogenous transparent liquid was obtained, thus indicating formation of the DES. The hydrophobicity of each synthesized DES was then tested by introducing a small volume of water (1 mL) into a vial containing the synthesized DES (0.5 mL) and then mixing the contents of the vial (
[0075] 2,6-Dimethoxyphenol—Vanillin DES
[0076] Two DESs were synthesized using the lignin-derived compound of 2,6-dimethoxyphenol and the lignin-derived compound of vanillin (Table 1, samples 30-31). Two eutectic mixtures were initially created by mixing 2,6-dimethoxyphenol and vanillin in 1:1 and 2:1 molar ratios. Following the initial mixing of 2,6-dimethoxyphenol and vanillin, each respective mixture was heated at 80° C. and constantly stirred for one hour until a homogenous transparent liquid was obtained, thus indicating formation of the DES. The hydrophobicity of each synthesized DES was then tested by introducing a small volume of water (1 mL) into a vial containing the synthesized DES (0.5 mL) and then mixing the contents of the vial (
[0077] 2,6-Dimethoxyphenol—Phenol DES
[0078] Three DESs were synthesized using the lignin-derived compound of 2,6-dimethoxyphenol and the lignin-derived compound of phenol (Table 1, samples 32-34). Two eutectic mixtures were initially created by mixing 2,6-dimethoxyphenol and phenol in 1:1, 1:2, and 2:1 molar ratios. Following the initial mixing of 2,6-dimethoxyphenol and phenol, each respective mixture was heated at 80° C. and constantly stirred for one hour until a homogenous transparent liquid was obtained, thus indicating formation of the DES. The hydrophobicity of each synthesized DES was then tested by introducing a small volume of water (1 mL) into a vial containing the synthesized DES (0.5 mL) and then mixing the contents of the vial (
[0079] All publications, patents, and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference, including the references set forth in the following references list:
REFERENCES
[0080] 1. Barnes, D. K. A., Invasions by marine life on plastic debris. Nature 2002, 416 (6883), 808-809. [0081] 2. Mason, S. A.; Kammin, L.; Eriksen, M.; Aleid, G.; Wilson, S.; Box, C.; Williamson, N.; Riley, A., Pelagic plastic pollution within the surface waters of Lake Michigan, USA. Journal of Great Lakes Research 2016, 42 (4), 753-759. [0082] 3. Wilcox, C.; Van Sebille, E.; Hardesty, B. D., Threat of plastic pollution to seabirds is global, pervasive, and increasing. Proceedings of the National Academy of Sciences 2015, 112 (38), 11899-11904. [0083] 4. Cózar, A.; Echevarria, F.; Gonzalez-Gordillo, J. I.; Irigoien, X.; Ubeda, B.; Hernandez-Leon, S.; Palma, A. T.; Navarro, S.; Garcia-de-Lomas, J.; Ruiz, A.; Fernandez-de-Puelles, M. L.; Duarte, C. M., Plastic debris in the open ocean. Proceedings of the National Academy of Sciences 2014, 111 (28), 10239-10244. [0084] 5. Borrelle, S. B.; Rochman, C. M.; Liboiron, M.; Bond, A. L.; Lusher, A.; Bradshaw, H.; Provencher, J. F., Opinion: Why we need an international agreement on marine plastic pollution. Proceedings of the National Academy of Sciences 2017, 114 (38), 9994-9997. [0085] 6. Gibb, B. C., Plastics are forever. Nature Chemistry 2019, 11 (5), 394-395. [0086] 7. Eriksen, M.; Lebreton, L. C. M.; Carson, H. S.; Thiel, M.; Moore, C. J.; Borerro, J. C.; Galgani, F.; Ryan, P. G.; Reisser, J., Plastic Pollution in the World's Oceans: More than 5 Trillion Plastic Pieces Weighing over 250,000 Tons Afloat at Sea. PLOS ONE 2014, 9 (12), e111913. [0087] 8. Geyer, R.; Jambeck, J. R.; Law, K. L., Production, use, and fate of all plastics ever made. Science Advances 2017, 3 (7), e1700782. [0088] 9. Ng, E.-L.; Huerta Lwanga, E.; Eldridge, S. M.; Johnston, P.; Hu, H.-W.; Geissen, V.; Chen, D., An overview of microplastic and nanoplastic pollution in agroecosystems. Science of The Total Environment 2018, 627, 1377-1388. [0089] 10. Cortés, C.; Domenech, J.; Salazar, M.; Pastor, S.; Marcos, R.; Hernandez, A., Nanoplastics as a potential environmental health factor: effects of polystyrene nanoparticles on human intestinal epithelial Caco-2 cells. Environmental Science: Nano 2020. [0090] 11. Revel, M.; Châtel, A.; Mouneyrac, C., Micro(nano)plastics: A threat to human health? Current Opinion in Environmental Science & Health 2018, 1, 17-23. [0091] 12. Mattsson, K.; Jocic, S.; Doverbratt, I.; Hansson, L.-A., Chapter 13—Nanoplastics in the Aquatic Environment. In Microplastic Contamination in Aquatic Environments, Zeng, E. Y., Ed. Elsevier: 2018; pp 379-399. [0092] 13. Gigault, J.; Halle, A. t.; Baudrimont, M.; Pascal, P.-Y.; Gauffre, F.; Phi, T.-L.; El Hadri, H.; Grassl, B.; Reynaud, S., Current opinion: What is a nanoplastic? Environmental Pollution 2018, 235, 1030-1034. [0093] 14. Hernandez, L. M.; Yousefi, N.; Tufenkji, N., Are There Nanoplastics in Your Personal Care Products? Environmental Science & Technology Letters 2017, 4 (7), 280-285. [0094] 15. da Costa, J. P.; Santos, P. S. M.; Duarte, A. C.; Rocha-Santos, T., (Nano)plastics in the environment—Sources, fates and effects. Science of The Total Environment 2016, 566-567, 15-26. [0095] 16. Koelmans, A. A., Proxies for nanoplastic. Nature Nanotechnology 2019, 14 (4), 307-308. [0096] 17. Wagner, S.; Reemtsma, T., Things we know and don't know about nanoplastic in the environment. Nature Nanotechnology 2019, 14 (4), 300-301. [0097] 18. Ter Halle, A.; Jeanneau, L.; Martignac, M.; Jardé, E.; Pedrono, B.; Brach, L.; Gigault, J., Nanoplastic in the North Atlantic Subtropical Gyre. Environmental Science & Technology 2017, 51 (23), 13689-13697. [0098] 19. Alimi, 0. S.; Farner Budarz, J.; Hernandez, L. M.; Tufenkji, N., Microplastics and Nanoplastics in Aquatic Environments: Aggregation, Deposition, and Enhanced Contaminant Transport. Environmental Science & Technology 2018, 52 (4), 1704-1724. [0099] 20. Shen, M.; Zhang, Y.; Zhu, Y.; Song, B.; Zeng, G.; Hu, D.; Wen, X.; Ren, X., Recent advances in toxicological research of nanoplastics in the environment: A review. Environmental Pollution 2019, 252, 511-521. [0100] 21. Nguyen, B.; Claveau-Mallet, D.; Hernandez, L. M.; Xu, E. G.; Farner, J. M.; Tufenkji, N., Separation and Analysis of Microplastics and Nanoplastics in Complex Environmental Samples. Accounts of Chemical Research 2019, 52 (4), 858-866. [0101] 22. Heddagaard, F. E.; Møller, P., Hazard assessment of small-size plastic particles: is the conceptual framework of particle toxicology useful? Food and Chemical Toxicology 2019, 111106. [0102] 23. Mao, Y.; Li, H.; Huangfu, X.; Liu, Y.; He, Q., Nanoplastics display strong stability in aqueous environments: Insights from aggregation behaviour and theoretical calculations. Environmental Pollution 2020, 258, 113760. [0103] 24. van Osch, D. J. G. P.; Zubeir, L. F.; van den Bruinhorst, A.; Rocha, M. A. A.; Kroon, M. C., Hydrophobic deep eutectic solvents as water-immiscible extractants. Green Chemistry 2015, 17 (9), 4518-4521. [0104] 25. Zhang, Q.; De Oliveira Vigier, K.; Royer, S.; Jérôme, F., Deep eutectic solvents: syntheses, properties and applications. Chemical Society Reviews 2012, 41 (21), 7108-7146. [0105] 26. Liu, Y.; Friesen, J. B.; McAlpine, J. B.; Lankin, D. C.; Chen, S.-N.; Pauli, G. F., Natural Deep Eutectic Solvents: Properties, Applications, and Perspectives. Journal of Natural Products 2018, 81 (3), 679-690. [0106] 27. Florindo, C.; Branco, L. C.; Marrucho, I. M., Development of hydrophobic deep eutectic solvents for extraction of pesticides from aqueous environments. Fluid Phase Equilibria 2017, 448, 135-142. [0107] 28. Cao, J.; Yang, M.; Cao, F.; Wang, J.; Su, E., Well-Designed Hydrophobic Deep Eutectic Solvents As Green and Efficient Media for the Extraction of Artemisinin from Artemisia annua Leaves. ACS Sustainable Chemistry & Engineering 2017, 5 (4), 3270-3278. [0108] 29. van Osch, D. J. G. P.; Dietz, C. H. J. T.; van Spronsen, J.; Kroon, M. C.; Gallucci, F.; van Sint Annaland, M.; Tuinier, R., A Search for Natural Hydrophobic Deep Eutectic Solvents Based on Natural Components. ACS Sustainable Chemistry & Engineering 2019, 7 (3), 2933-2942. [0109] 30. Ferreira, I.; Venancio, C.; Lopes, I.; Oliveira, M., Nanoplastics and marine organisms: What has been studied? Environmental Toxicology and Pharmacology 2019, 67, 1-7. [0110] 31. Mintenig, S. M.; Bauerlein, P. S.; Koelmans, A. A.; Dekker, S. C.; van Wezel, A. P., Closing the gap between small and smaller: towards a framework to analyse nano- and microplastics in aqueous environmental samples. Environmental Science: Nano 2018, 5 (7), 1640-1649. [0111] 32. Lambert, S.; Wagner, M., Characterisation of nanoplastics during the degradation of polystyrene. Chemosphere 2016, 145, 265-268. [0112] 33. Dawson, A. L.; Kawaguchi, S.; King, C. K.; Townsend, K. A.; King, R.; Huston, W. M.; Bengtson Nash, S. M., Turning microplastics into nanoplastics through digestive fragmentation by Antarctic krill. Nature Communications 2018, 9 (1), 1001. [0113] 34. Ekvall, M. T.; Lundqvist, M.; Kelpsiene, E.; Sileikis, E.; Gunnarsson, S. B.; Cedervall, T., Nanoplastics formed during the mechanical breakdown of daily-use polystyrene products. Nanoscale Advances 2019, 1 (3), 1055-1061. [0114] 35. Enfrin, M.; Lee, J.; Gibert, Y.; Basheer, F.; Kong, L.; Dumee, L. F., Release of hazardous nanoplastic contaminants due to microplastics fragmentation under shear stress forces. Journal of Hazardous Materials 2020, 384, 121393. [0115] 36. Hollóczki, 0.; Gehrke, S., Can Nanoplastics Alter Cell Membranes? Chem Phys Chem n/a (n/a). [0116] 37. Bergami, E.; Pugnalini, S.; Vannuccini, M. L.; Manfra, L.; Faleri, C.; Savorelli, F.; Dawson, K. A.; Corsi, I., Long-term toxicity of surface-charged polystyrene nanoplastics to marine planktonic species Dunaliella tertiolecta and Artemia franciscana. Aquatic Toxicology 2017, 189, 159-169. [0117] 38. Tallec, K.; Huvet, A.; Di Poi, C.; González-Fernandez, C.; Lambert, C.; Petton, B.; Le Goïc, N.; Berchel, M.; Soudant, P.; Paul-Pont, I., Nanoplastics impaired oyster free living stages, gametes and embryos. Environmental Pollution 2018, 242, 1226-1235. [0118] 39. Sendra, M.; Saco, A.; Yeste, M. P.; Romero, A.; Novoa, B.; Figueras, A., Nanoplastics: From tissue accumulation to cell translocation into Mytilus galloprovincialis hemocytes. resilience of immune cells exposed to nanoplastics and nanoplastics plus Vibrio splendidus combination. Journal of Hazardous Materials 2019, 121788. [0119] 40. Abraham, M. J.; Murtola, T.; Schulz, R.; Páll, S.; Smith, J. C.; Hess, B.; Lindahl, E., GROMACS: High performance molecular simulations through multi-level parallelism from laptops to supercomputers. SoftwareX 2015, 1-2, 19-25. [0120] 41. Luzar, A.; Chandler, D., Hydrogen-bond kinetics in liquid water. Nature 1996, 379 (6560), 55-57. [0121] 42. Bonomi, M.; Bussi, G.; Camilloni, C.; Tribello, G. A.; Banáš, P.; Barducci, A.; Bernetti, M.; Bolhuis, P. G.; Bottaro, S.; Branduardi, D.; Capelli, R.; Carloni, P.; Ceriotti, M.; Cesari, A.; Chen, H.; Chen, W.; Colizzi, F.; De, S.; De La Pierre, M.; Donadio, D.; Drobot, V.; Ensing, B.; Ferguson, A. L.; Filizola, M.; Fraser, J. S.; Fu, H.; Gasparotto, P.; Gervasio, F. L.; Giberti, F.; Gil-Ley, A.; Giorgino, T.; Heller, G. T.; Hocky, G. M.; Iannuzzi, M.; Invernizzi, M.; Jelfs, K. E.; Jussupow, A.; Kirilin, E.; Laio, A.; Limongelli, V.; Lindorff-Larsen, K.; Lohr, T.; Marinelli, F.; Martin-Samos, L.; Masetti, M.; Meyer, R.; Michaelides, A.; Molteni, C.; Morishita, T.; Nava, M.; Paissoni, C.; Papaleo, E.; Parrinello, M.; Pfaendtner, J.; Piaggi, P.; Piccini, G.; Pietropaolo, A.; Pietrucci, F.; Pipolo, S.; Provasi, D.; Quigley, D.; Raiteri, P.; Raniolo, S.; Rydzewski, J.; Salvalaglio, M.; Sosso, G. C.; Spiwok, V.; Sponer, J.; Swenson, D. W. H.; Tiwary, P.; Valsson, 0.; Vendruscolo, M.; Voth, G. A.; White, A.; The, P. c., Promoting transparency and reproducibility in enhanced molecular simulations. Nature Methods 2019, 16 (8), 670-673. [0122] 43. Kim K.; Dutta T.; Sun J.; Simmons B.; Singh S., Biomass Pretreatment Using Deep Eutectic Solvent From Lignin Derived Phenols. ResearchGate 2018, available at https://www.researchgate.net/publication/322345426_Biomass_Pretreatment_using_Deep_Eutectic_Solvent_from_Lignin_derived_Phenols (retrieved Oct. 26, 2020). [0123] 44. Kim K.; Dutta T.; Sun J.; Simmons B.; Singh S., Supplemental Material Biomass Pretreatment Using Deep Eutectic Solvent From Lignin Derived Phenols. ResearchGate 2018, available at http://www.rsc.org/suppdata/c7/gc/c7gc03029k/c7gc03029k1.pdf (retrieved Oct. 26, 2020).