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[Display omitted] Multifunctional micelles that permit both diagnosis and treatment present enormous advantage and potential for precision medicine. However, the inherent complexities and structural instability of these systems often cause unsatisfactory targeting and therapeutic performances. Herein, by ingenious design of a 2,5-bis(2-thienyl)pyrrole (SNS) modifier to covalently link with AS1411 aptamer and lipid segment, a simple strategy is proposed for one-step enzymatic preparation of interlocked aptamer-micelle (IApM) under bio-friendly conditions. The interlocked poly(SNS) skeleton in IApM can not only stabilize the micelle structure but also enhance near-infrared (NIR) absorption ability, thus further enhancing cellular internalization and photothermal therapy. In addition, the multivalent AS1411 aptamers tethered in the hydrophilic shell can simultaneously increase the specific binding affinity of DNA micelles and induce nucleus-targeted accumulation for DNA damage-triggered apoptosis. This DNA micelle achieves "best of both worlds" with enhanced biostability for cellular internalization and improved NIR photothermal conversion efficiency for nucleus-targeted therapy, which provides a promising formulation strategy for precision cancer treatment. [ABSTRACT FROM AUTHOR]

Introduction: Laccases are blue-multicopper containing enzymes that are known to play a role in the bioconversion of recalcitrant compounds. Their role in free radical polymerization of aromatic compounds for their valorization remains underexplored. In this study, we used a pBAD plasmid containing a previously characterized CotA laccase gene (abbreviated as Bli -Lacc) from Bacillus licheniformis strain ATCC 9945a to express this enzyme and explore its biotransformation/polymerization potential on β-naphthol. Methods: The protein was expressed from TOP10 cells of Escherichia coli after successful transformation of the plasmid. Immobilized metal affinity chromatography (IMAC) was used to generate pure protein. The biocatalytic polymerization reaction was optimized based on temperature, pH and starting enzyme concentration. 1H and 13C solution nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), and solid-state NMR (ssNMR) were used to characterize the formed polymer. A one-gram conversion reaction was done to explore applicability of the reaction in a pilot-scale. Results: The polymerization reaction generated a brown precipitate, and its chemical structure was confirmed using 1H and 13C NMR and FTIR. SsNMR revealed the presence of two different orientational hydroxyl functional groups in the polymer in addition to the presence of a very small amount of ether linkages (< 2%). This analysis elucidated that polymerization occurred mainly on the carbons of the aromatic rings, rather than on the carbons attached to the hydroxyl groups, resulting in a condensed ring or polynuclear aromatic structure. The reaction was optimized, and the highest yield was attained under conditions of 37°C, pH 10 and a starting enzyme concentration of 440 nM in 50 mM phosphate buffer. A one-gram conversion yielded 216 mg of polymer as dry mass. The crystal structure of the enzyme was solved at 2.7 Å resolution using X-ray crystallography and presented with a hexagonal space group. The final structure was deposited in the Protein Databank (PDB) with an ID−9BD5. Discussion: This article provides a green/enzymatic pathway for the remediation of phenolics and their valorization into potential useful polymeric materials. The comprehensive analysis of the formed polymer provides insight into its structure and functional moieties present. Based on the yield of the one-gram conversion, this synthetic method proves useful for a pilot-scale production level and opens opportunities to invest in using this polymer for industrial/environmental applications. [ABSTRACT FROM AUTHOR]

In this study, gallic acid-g-chitosan colored complex were produced using the HRP-catalyzed method. Then, these were used to successfully dye silk fabrics. The dyed silk fabrics were characterized through K/S, color fastness, and antibacterial tests. We studied the polymerization mechanism in detail using FT-IR and ESI-MS technologies, then the dyeing process and optimum reaction conditions were further investigated using the K/S values. Chitosan and gallic acid were polymerized to form a dark yellow polymer, which was successfully colored on silk fabrics. In addition, significant color differences were observed between fabrics dyed without chitosan and fabrics dyed in the presence of chitosan. In particular, the fabric treated with the pre-polymerization dyeing process showed high antibacterial properties, color fastness, and color depth compared to other dyeing processes. We found that the optimum reaction conditions for dyeing silk fabrics are as follows: 3-hour incubation period, 50 ℃ temperature, 3 mM gallic acid; 3 g/L chitosan. While the GA and CS pre-treatment or co-treatment process resulted in lower color fastness, the pre-polymerization approach offered enhanced fastness and overall performance. Based on the findings, the pre-polymerization process is recommended as the most effective method for dyeing silk fabrics with chitosan and natural dyes, optimizing both aesthetic and functional properties. [ABSTRACT FROM AUTHOR]

We successfully synthesized a new unnatural polysaccharide, 2-deoxy-β(1→3)-glucan, by β-1,3-glucan phosphorylase-catalyzed enzymatic polymerization of a D-glucal monomer from a cellobiose primer, owing to recognition of such non-native substrates by the enzyme. Because of solubility of the product in several high polar organic solvents, acetylation as an example of its derivatizations smoothly occurred using acetic anhydride in the presence of base/catalyst in a DMF solvent. The NMR analysis of the acetylated derivative strongly supported the β(1→3)-linked chain structure. [ABSTRACT FROM AUTHOR]

Here, we report the effects of peroxidase-mimicking activity of flower shaped hybrid nanobiocatalyst obtained from Viburnum-Opulus L. (Gilaburu) extract and Cu2+ ions on the polymerization of phenol and its derivatives (guaiacol and salicylic acid). The obtained nanoflowers exhibited quite high catalytic activity upon the polymerization of phenol and guaiacol. The yields and the number average molecular weights of the obtained polymers were significantly high. Due to solubility issue of salicylic acid in aqueous media, polymerization of salicylic acid resulted in very low yields. Free-horseradish peroxidase (HRP) enzyme is known to be losing its catalytic activity at 60 °C and above temperatures. However, the synthesized nanoflowers exhibited quite high catalytic activity even at 60 °C and above reaction temperatures. This provides notable benefits for reactions needed at high temperatures, and it is very important to use these kinds of nanobiocatalysts for both scientific studies and industrial applications. [ABSTRACT FROM AUTHOR]

IntroductionLaccases are blue-multicopper containing enzymes that are known to play a role in the bioconversion of recalcitrant compounds. Their role in free radical polymerization of aromatic compounds for their valorization remains underexplored. In this study, we used a pBAD plasmid containing a previously characterized CotA laccase gene (abbreviated as Bli-Lacc) from Bacillus licheniformis strain ATCC 9945a to express this enzyme and explore its biotransformation/polymerization potential on β-naphthol.MethodsThe protein was expressed from TOP10 cells of Escherichia coli after successful transformation of the plasmid. Immobilized metal affinity chromatography (IMAC) was used to generate pure protein. The biocatalytic polymerization reaction was optimized based on temperature, pH and starting enzyme concentration. 1H and 13C solution nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), and solid-state NMR (ssNMR) were used to characterize the formed polymer. A one-gram conversion reaction was done to explore applicability of the reaction in a pilot-scale.ResultsThe polymerization reaction generated a brown precipitate, and its chemical structure was confirmed using 1H and 13C NMR and FTIR. SsNMR revealed the presence of two different orientational hydroxyl functional groups in the polymer in addition to the presence of a very small amount of ether linkages (< 2%). This analysis elucidated that polymerization occurred mainly on the carbons of the aromatic rings, rather than on the carbons attached to the hydroxyl groups, resulting in a condensed ring or polynuclear aromatic structure. The reaction was optimized, and the highest yield was attained under conditions of 37°C, pH 10 and a starting enzyme concentration of 440 nM in 50 mM phosphate buffer. A one-gram conversion yielded 216 mg of polymer as dry mass. The crystal structure of the enzyme was solved at 2.7 Å resolution using X-ray crystallography and presented with a hexagonal space group. The final structure was deposited in the Protein Databank (PDB) with an ID−9BD5.DiscussionThis article provides a green/enzymatic pathway for the remediation of phenolics and their valorization into potential useful polymeric materials. The comprehensive analysis of the formed polymer provides insight into its structure and functional moieties present. Based on the yield of the one-gram conversion, this synthetic method proves useful for a pilot-scale production level and opens opportunities to invest in using this polymer for industrial/environmental applications.

Enzyme catalyzed reactions are known to be environmental friendly and easy method for many applications. However, utilization of enzymes in a variety of reactions is strictly limited due to their high cost, instability in aqueous solutions, denaturation in organic solvents and high temperatures. For this reason, it is important to discover new generation catalyst systems indicating enzyme‐like catalytic activity. Here, we report hybrid organic–inorganic flower‐shaped green tea‐Cu2+ nanobiocatalyst synthesized from green tea extract as an organic component and copper (II) ions (Cu2+) as inorganic component. The effect of the peroxidase‐mimicking activity of green tea‐Cu2+ nanobiocatalyst was investigated on the polymerization of phenol and derivatives (guaiacol and salicylic acid) through Fenton‐like reaction mechanism. Obtained successful outcomes showed that the synthesized nanobiocatalyst showed very high catalytic activity upon polymerization of phenol and guaiacol. The slight solubility of salicylic acid in water limited to achieve its polymerization under‐performed reaction conditions. The yields and molecular weights of the obtained polymers were found to be quite high. While free peroxidase enzymes like horseradish peroxidase (HRP) enzyme loses its catalytic activity at 60°C and above temperatures, green tea‐Cu2+ nanobiocatalyst exhibited very high catalytic activity upon polymerization reactions even at 60°C reaction temperature. This outcome provides significant advantages in some reactions requiring high temperatures. In order to understand the origin of the catalytic activity of the green tea‐Cu2+ nanoflowers, similar biocatalysts were also synthesized from caffeine and catechin alkaloids which are the active components of green tea. Caffeine‐Cu2+ and catechine‐Cu2+ nanobiocatalysts also exhibited quite high catalytic activity toward polymerization of phenol and derivatives. We suggest that green tea‐Cu2+ and similar types of nanobiocatalysts may expand their utilization in polymer chemistry as promising catalytic agents for radicalic polymerizations. [ABSTRACT FROM AUTHOR]

Hydrogels were prepared by Steglich esterification and by crosslinking pre-synthesized poly(sorbitol adipate)-graft-poly(ethylene glycol) mono methyl ether (PSA-g-mPEG) using different-chain-length-based disuccinyl PEG. PSA and PSA-g-mPEG were investigated for polymer degradation as a function of time at different temperatures. PSA-g-mPEG hydrogels were then evaluated for their most crucial properties of swelling that rendered them suitable for many pharmaceutical and biomedical applications. Hydrogels were also examined for their Sol-Gel content in order to investigate the degree of cross-linking. Physical structural parameters of the hydrogels were theoretically estimated using the modified Flory–Rehner theory to obtain approximate values of polymer volume fraction, the molecular weight between two crosslinks, and the mesh size of the hydrogels. X-ray diffraction was conducted to detect the presence or absence of crystalline regions in the hydrogels. PSA-g-mPEG hydrogels were then extensively examined for higher and lower molecular weight solute release through analysis by fluorescence spectroscopy. Finally, the cytotoxicity of the hydrogels was also investigated using a resazurin reduction assay. Experimental results show that PSA-g-mPEG provides an option as a biocompatible polymer to be used for pharmaceutical applications. [ABSTRACT FROM AUTHOR]

Polymers that can be extracted or manufactured from renewable resources such as sugars, natural acids, or terpenes are increasingly relevant. In this context, biobased lactones are a group of monomers that can be synthesized from renewable feedstocks and combine versatility with the ability to yield high-performing materials including both thermoplastics and thermosets. In this chapter, an overview of different kinds of catalytic ring-opening polymerization (ROP) mechanisms including coordination, organocatalyzed, and enzymatic reactions is discussed. ROP of renewable lactones to yield polyesters are classified by their origin. In particular, we report on recent advances in ROP of terpene-based precursors such as limonene and pinene that lead to a variety of caprolactone derivatives which are available for polymerization. Moreover, lactones that can be converted from sugars and natural acids (e.g., fatty acids, amino acids) will be discussed. [ABSTRACT FROM AUTHOR]

This review article presents the biomimetic helical inclusion of amylose toward hydrophobic polyesters as guests through a vine-twining polymerization process, which has been performed in the glucan phosphorylase (GP)-catalyzed enzymatic polymerization field to fabricate supramolecules and other nanostructured materials. Amylose, which is a representative abundant glucose polymer (polysaccharide) with left-handed helical conformation, is well known to include a number of hydrophobic guest molecules with suitable geometry and size in its cavity to construct helical inclusion complexes. Pure amylose is prepared through enzymatic polymerization of α-d-glucose 1-phosphate as a monomer using a maltooligosaccharide as a primer, catalyzed by GP. It is reported that the elongated amylosic chain at the nonreducing end in enzymatic polymerization twines around guest polymers with suitable structures and moderate hydrophobicity, which is dispersed in aqueous polymerization media, to form amylosic nanostructured inclusion complexes. As the image of this system is similar to how vines of a plant grow around a support rod, this polymerization has been named 'vine-twining polymerization'. In particular, the helical inclusion behavior of the enzymatically produced amylose toward hydrophobic polyesters depending on their structures, e.g., chain lengths and substituents, has been systematically investigated in the vine-twining polymerization field. Furthermore, amylosic supramolecular network materials, such as hydrogels, are fabricated through vine-twining polymerization by using copolymers, where hydrophobic polyester guests or maltooligosaccharide primers are covalently modified on hydrophilic main-chain polymers. The vine-twining polymerization using such copolymers in the appropriate systems induces the formation of amylosic nanostructured inclusion complexes among them, which act as cross-linking points, giving rise to supramolecular networks at the nanoscale. The resulting materials form supramolecular hydrogels, films, and microparticles. [ABSTRACT FROM AUTHOR]

Polysaccharide-based amphiphilic copolymers self-assemble in water to form micelle-like structures. They are expected to be used as nanocarriers in the biomedical field owing to their biocompatibility, biodegradability, and low toxicity. α-1,3-Glucan is a water-insoluble glucose homopolymer that can be generated through environmentally friendly enzymatic polymerization and easily purified without using organic solvents. Thus, it has attracted attention as a new bio-based material. In this study, we developed new nanomicelles based on α-1,3-glucan. Glycosyltransferase I from Streptococcus mutans was used to synthesize α-1,3-glucan, and a series of amphiphilic α-1,3-glucan-based graft copolymers (α-1,3-glucan-g-PLA) were synthesized with different L-Lactide supply ratios in the ionic liquid BmimCl. The results of FT-IR, 1H NMR, 13C NMR, XRD, and TGA verified that the reaction proceeded successfully. These amphiphilic α-1,3-glucan derivatives with low critical micelle concentrations can self-assemble to form core–shell structural micelles of various sizes (approximately 57–125 nm) in water. Furthermore, the self-assembled micelles were investigated as drug carriers using prednisone acetate (PA) as a model drug, and their sustained drug release behavior for 9 days was confirmed. These results revealed that the synthesized self-assembled micelles have promising potential as new carriers for the efficient delivery of hydrophobic drugs. [ABSTRACT FROM AUTHOR]

In the present work, 4-methylcatechol oligomer has been prepared by using enzyme-catalyzed polymerization in water and preliminary evaluations as stabilizing agent in polypropylene (PP) was performed. In comparison with intrinsic PP, the oxidation onset temperature of the 4-methylcatechol oligomer/PP composite increased by 66°C, and the oxidation induction time increased by 40 min. In addition, the mixing of a 4-methylcatechol oligomer with PP (i.e., in the formation of a 4-methylcatechol oligomer/PP composite) did significantly enhance the long-term stability of PP in a thermal oxidative environment. Moreover, the tensile strength of this composite did not significantly decrease after aging for 800 h in an air atmosphere at 120°C. These results show that the addition of a 4-methylcatechol oligomer will markedly delay the aging and degradation of PP materials, even under extreme conditions. Thus, an enzyme-catalyzed polymerization of phenol compounds may provide a new avenue toward the preparation of novel antioxidants.

The mechanisms of the enzymatic polymerization of flavonoids, including quercetin, rutin and catechins, have been fairly well researched, but the properties of polymeric forms of flavonoids still require in-depth analysis. The products of enzymatic polymerization are oligomeric flavonoids. The antioxidant and antimicrobial properties of many oligomeric flavonoids have been described in the literature. However, data on the thermal properties of oligomeric flavonoids are lacking and the supplementing of these deficiencies is a scientific novelty of this work. The aim of this study is to determine the effect of enzymatic polymerization on thermal stability of oligomeric flavonoids. As part of the work, oligomeric quercetin, rutin and catechin were prepared by the enzymatic polymerization reaction with laccase and horseradish peroxidase enzymes. The oligomeric structure of the flavonoids was confirmed by spectroscopic (Fourier transform infrared spectroscopy (FTIR) and UV–visible spectroscopy (UV–Vis)) as well as chromatographic (ultra-performance liquid chromatography (UPLC) and gel permeation chromatography (GPC)) methods. Thermal properties of oligomeric flavonoids were investigated using differential scanning calorimetry (DSC) and thermogravimetry (TG). Moreover, the antioxidant and antimicrobial properties of oligomeric forms of selected polyphenols were investigated. Based on DSC analysis, it was found that the common feature of all oligomeric flavonoids was a higher final oxidation temperature and a higher oxidation enthalpy than the reference flavonoids. Thermogravimetric analysis showed that oligomeric poly(flavonoids)-laccase had better thermal stability, which correlated with higher molar mass. [ABSTRACT FROM AUTHOR]

Gallic acid was synthesized using a new approach and arranged on three kind of templates (PEG, PEGMDE, Pluronic F68) using an horseradish peroxide (HRP)-catalyzed oxidative polymerization. The polymerization mechanism was investigated in detail using UV-Vis, FT-IR and HPLC-ESI-MS. In addition, the wettability, thermal properties and anti-UV activity of their corresponding dyed silk fabrics were investigated. The results confirmed that during the catalysis of gallic acid by HRP, the templates promoted the enzymatic polymerization in terms of the amount of poly(gallic acid) produced and the degree of polymerization. In addition, the template-treated silk fabrics exhibited enhanced wettability, anti-UV activity and color fastness than fabric treated with poly(gallic acid) in the absence of the templates. Upon analyzing the color depth, the K/S value of the silk fabrics dyed using the templates was significantly higher than that in the absence of the templates. The silk fabric dyed in the presence of templates showed higher fastness in all of the color fastness tests. This may expand the application range of natural phenols for textile dyeing and functionalization, and provide new outlooks for the environmentally friendly production of natural functional fabric.

Semi-conductive polymers have been used in a few area applications such as coatings, accumulators, solar cells, rechargeable batteries, ion sensors, photoreceptors, light-emitting diodes and electrochromic instruments. Poly(4-(trifluoromethyl)benzene-1,2-diamine)s of Poly(TFMBDA)-O and Poly(TFMBDA)-E were synthesized via chemical oxidative and enzymatic polymerization methods, respectively, using 4-(trifluoromethyl)benzene-1,2-diamine (TFMBDA) as monomer. FT-IR, UV-vis and 1H-NMR and 13C-NMR instruments were utilized in order to confirm the structures of all compounds. The Mw values of the polymers and their PDI values were found to be between 5000-7000 Da and 1.045-1.115, respectively, from GPC measurements. The glass temperature of phenazine-type structure of Poly(TFMBDA)-O was higher compared to that of Poly(TFMBDA)-E, which was composed of phenyl units linked with -NH bridges. As soon as Poly(TFMBDA)-O and Poly(TFMBDA)-E were excited by UV light, they had a quantum efficiency of 6.3% and 13.7%, respectively, in DMF for violet photoluminescence (PL) emission depending on photoluminescence measurement. SEM images revealed that Poly(TFMBDA)-O consisted of approximately 1-2 µm of uniform micro-spheres and a granular surface with different pore diameters. The enzymatic oxidation with HRP afforded Poly(TFMBDA)-E micro-rods of about 5-10 µm-long shape in their SEM images. [ABSTRACT FROM AUTHOR]

In this study, gallic acid-g-chitosan colored complexes were produced using the HRP-catalyzed method and successfully used to dye silk fabrics. The reaction mechanism was studied using FT-IR, 1H-NMR, and ESI-MS technologies; the dyed silk fabrics were characterized through K/S, color fastness, and antibacterial tests. In addition, an in situ staining process based on enzyme catalysis was explored to simplify the pretreatment process of chitosan. Chitosan and gallic acid were polymerized through O–Ph, Ph–Ph and amino-phenyl bonds to form a dark-yellow polymer that was successfully used to dye silk fabrics. In addition, significant color differences were observed between fabrics dyed without chitosan and dyed in the presence of chitosan. As a result, gallic acid-g-chitosan dyes polymerized via HRP catalysis improved the antimicrobial properties of the colored fabrics without significantly affecting the color fastness of the silk fabrics. [ABSTRACT FROM AUTHOR]

Hydrogels were prepared by Steglich esterification and by crosslinking pre-synthesized poly(sorbitol adipate)-graft-poly(ethylene glycol) mono methyl ether (PSA-g-mPEG) using different-chain-length-based disuccinyl PEG. PSA and PSA-g-mPEG were investigated for polymer degradation as a function of time at different temperatures. PSA-g-mPEG hydrogels were then evaluated for their most crucial properties of swelling that rendered them suitable for many pharmaceutical and biomedical applications. Hydrogels were also examined for their Sol-Gel content in order to investigate the degree of cross-linking. Physical structural parameters of the hydrogels were theoretically estimated using the modified Flory–Rehner theory to obtain approximate values of polymer volume fraction, the molecular weight between two crosslinks, and the mesh size of the hydrogels. X-ray diffraction was conducted to detect the presence or absence of crystalline regions in the hydrogels. PSA-g-mPEG hydrogels were then extensively examined for higher and lower molecular weight solute release through analysis by fluorescence spectroscopy. Finally, the cytotoxicity of the hydrogels was also investigated using a resazurin reduction assay. Experimental results show that PSA-g-mPEG provides an option as a biocompatible polymer to be used for pharmaceutical applications.

In this study, we successfully polymerized natural phenol (gallic acid, ferulic acid) and pyrrole (Py) monomers by oxidative polymerization of horseradish peroxidase (HRP). Then, we successfully colored silk fabrics using these chemicals. We analyzed the polymerization mechanism of polyphenol and polypyrrole complexes in detail using UV-Vis spectroscopy, Fourier transform infrared spectroscopy (FT-IR), and high-performance liquid chromatography/electrospray ionization mass spectrometry (HPLC/ESI-MS). In addition, we investigated the electrochemical activity, thermal properties and anti-UV activity of the colored silk fabrics. We found that the oxidative polymerization of phenol and Py on silk fibers under mild reaction conditions using HRP produced technically conductive silk fabrics that combine the superior chemical and physical properties of silk fabrics with superior levels of electrochemical activity and thermal stability. Upon analyzing the color depth of the fabrics, we found that silk fabrics treated with Py have a darker color than silk fabrics treated in the absence of Py. Additionally, the fabrics had slightly different levels of color fastness, but all were within the acceptable range. This technique expands the range of applications of natural phenols for textile dyeing and functionalization as well as providing new prospects for the enzymatically environmentally friendly production of natural functional fabric.

This study investigates inclusion behavior of amylose towards, poly(β-propiolactone) (PPL), that is a hydrophobic polyester, via the vine-twining process in glucan phosphorylase (GP, isolated from thermophilic bacteria, Aquifex aeolicus VF5)-catalyzed enzymatic polymerization. As a result of poor dispersibility of PPL in sodium acetate buffer, the enzymatically produced amylose by GP catalysis incompletely included PPL in the buffer media under the general vine-twining polymerization conditions. Alternatively, we employed an ethyl acetate–sodium acetate buffer emulsion system with dispersing PPL as the media for vine-twining polymerization. Accordingly, the GP (from thermophilic bacteria)-catalyzed enzymatic polymerization of an α-d-glucose 1-phosphate monomer from a maltoheptaose primer was performed at 50 °C for 48 h in the prepared emulsion to efficiently form the inclusion complex. The powder X-ray diffraction profile of the precipitated product suggested that the amylose-PPL inclusion complex was mostly produced in the above system. The 1H NMR spectrum of the product also supported the inclusion complex structure, where a calculation based on an integrated ratio of signals indicated an almost perfect inclusion of PPL in the amylosic cavity. The prevention of crystallization of PPL in the product was suggested by IR analysis, because it was surrounded by the amylosic chains due to the inclusion complex structure. [ABSTRACT FROM AUTHOR]

MXene-based functional textiles have been widely studied and applied in many fields. However, the service stability of MXene combined with textile substrates in the environment is far from ideal, which makes its practical application a great challenge. Here we introduced gallic acid (GA), as natural reactive polyphenol compound to silk fibers through enzymatic polymerization, which significantly improved the durability of its conductivity. The small molecules of GA can covalently bind to the titanium atoms on the MXene nanosheets, and the tyrosine residues from silk fibroins can be enzymatically oxidized by horseradish peroxidase (HRP) and further coupled with GA simultaneously, thus forming a covalent cross-linked network on the fiber surfaces. Furthermore, the durable MXene-based textile was used to manufacture smart dual-driven thermal devices with temperature monitoring, which can judge the real-time temperature during heating by changes in its apparent color. More importantly, the textile with smart temperature visualization also offers good EMI shielding and superior UV resistance, while retaining its inherent moisture-wicking, breathable and softness. The present work provides a new insight for the preparation of MXene-based multifunctional textile, and the smart visualization of dual-driven heating shows promising applications in practical personal thermal management. [Display omitted] • Enzymatic polymerization realizes the gallic acid (GA)-bridged attachment of MXene to the textile surface. • Conductivity stability and antioxidant properties of the MX@GA covalently-grafted textile are improved. • Smart textile can visualize real-time temperature monitoring while realizing electricity or solar heating. • Smart textile achieves multifunction while retaining their inherent breathable and softness properties. [ABSTRACT FROM AUTHOR]

After 2 h of reaction, the PGA/PEG and PGA/PM complexes exhibited polymerization rates two times faster than PGA and the PGA/PF68 complex showed a three times faster polymerization rate than PGA. Anti-UV activity of the treated silk fabrics HT

The use of natural plants for dyeing is a new green approach in the textile industry using eco-friendly, renewable, and non-toxic reductants for dyeing fabric. Recently, various templates have been reported to enhance the polymerization of natural phenols. In this paper, ferulic acid (FA) was synthesized using a new approach and arranged on poly(ethylene glycol) (PEG) templates using horseradish peroxide (HRP)-catalyzed oxidative polymerization. The polymerization mechanism was studied in detail using high-performance liquid chromatography-electrospray ionization mass spectrometry (HPLC-ESI-MS) analysis. In addition, the template effect of PEG on 13 natural phenols was also investigated. Upon analyzing the color depth, the K/S value of the silk fabric dyed using PEG as a template was significantly higher than that in the absence of PEG. The higher color depth of the poly(ferulic acid)/PEG-treated silk fabrics further validated the important role of PEG as a template. This study presents an environmentally friendly method for dyeing silk fabric under mild conditions and the polymerization mechanism. Compared to chemical polymerization reactions, this enzyme (HRP)-based synthesis is more environmentally friendly due to its milder reaction conditions. [ABSTRACT FROM AUTHOR]

This study investigates the formation and properties of vesicles produced via biocatalytic Polymerization-Induced Self-Assembly (bioPISA) as artificial cells. Methods for achieving size uniformity, including gentle centrifugation and sucrose gradient centrifugation, are explored, and the effects of stirring speed on vesicle morphology is investigated. The internal structure of the vesicles, characterized by a polymer-rich matrix, is analyzed using fluorescence correlation spectroscopy (FCS). Additionally, the feasibility of loading macromolecules into pre-formed vesicles is demonstrated using electroporation, and a fluorescent protein as well as enzymes for a cascade reaction were sucesfully incorporated into the fully assembled polymersomes. These findings provide a foundation for developing enzyme-synthesized polymeric vesicles with controlled morphologies for various applications, e.g., in synthetic biology., (© 2024 The Author(s). Advanced Biology published by Wiley‐VCH GmbH.)

Given the fossil fuel crisis and the steady consumption of finite resources, the use of green polymers is becoming necessary. However, the term “green” describes materials that present green properties (such as biological origin and/or biodegradability) and are produced via sustainable processes conducted under mild conditions and not requiring the use of chemical catalysts, toxic solvents or reagents. Truly green materials must combine these characteristics; consequently, enzymatically synthesized bio-based and/or biodegradable polymers can be characterized as truly green. The present review focuses on the most promising, commercially available aliphatic and alipharomatic polyesters that can be synthesized enzymatically. In particular, the recent developments in the enzymatic polymerization of PLA and PBS and alipharomatic furan-based polyesters (e.g., PBF) are herein analyzed. Based on this analysis, it can be concluded that important steps have been taken toward synthesizing sustainably green polymers. Still, it is necessary to evaluate the applied methods regarding their capability to be used on an industrial scale.

Cellular metabolism in multiple organelles utilizes compartmentalized multienzyme efficient catalysis to realize substance metabolism, energy conversion and immune defenses. The convenient and biomimetic design of artificial multienzymes has become an emerging research topic. Herein, we employ a facile enzyme-initiated radical polymerization to self-anchor multienzyme in cell-like hydrogels with mesoscale compartments. The dynamic assembly of glucose oxidase/cytochrome c (GOx/Cyt c) with methacrylate-modified hyaluronic acid can form nanoaggregates, where only the bound enzyme pairs with the adjacent position can catalyze the polymerization to compartmentalize multienzymes within hydrogel. Consequently, the cascade enzymes within hydrogel display 33.9 times higher activity compared to free enzymes, as well as excellent thermostability and multiple recyclability. The mechanism study indicates that the compartmental effect of the hydrogel and the anchoring effect of Cyt c synergistically enhance GOx/Cyt c activity. According to the density functional theory (DFT) calculation, Cyt c activity increment originates from its ligand changes of Fe(III) porphyrin, which has a smaller energy barrier of the catalytic reaction. This study provides a promising strategy for autonomous colocalization of multienzyme in biocompatible hydrogels which can be potentially applied in cascade enzyme induced catalysis applications. [ABSTRACT FROM AUTHOR]

In this study, 4‐amino‐3‐hydroxy‐1‐naphthalene sulfonic acid (Monomer) was converted to its enzyme‐catalyzed oxidative polymerization (Poly‐enz) in dioxane solvent by horseradish peroxidase enzyme (HRP) in the presence of hydrogen peroxide as oxidant. For the analysis of the monomer and its synthesized Poly‐enz, 1H‐NMR, 13C‐NMR, FT‐IR, TGA, and SEM measurements were determined. In addition, the optical ion sensor properties of Poly‐enz against metals such as Ag+, Cd2+, Co2+, Hg2+, Ni2+, Pb2+, Zn2+, Cu2+ were examined with UV‐Vis spectrophotometer. It was observed that Cu metal showed sensory properties. DNA cleavage and DNA binding activities of monomer and Poly‐enz were done using by agarose gel electrophoresis and UV‐Vis methods, respectively. It was seen that the Poly‐enz interacted with DNA electrostatically. This enzymatic polymer was found to cleave pBR322 plasmid DNA both hydrolytically and oxidatively as well. The antioxidant activities of the compounds were examined by three different methods (DPPH, ABTS, FRAP) and it was found that the Poly‐enz showed high antioxidant activity compared to its monomer. Antimicrobial activities were studied against various bacterial and yeast cultures by the minimum inhibition concentration (MIC) method. It was observed that the antimicrobial activities of the enzymatic polymer in different microorganisms increased depending on the concentration. [ABSTRACT FROM AUTHOR]

This study investigates vine-twining polymerization using poly(γ-butyrolactone) (PBL) as a new guest polyester to evaluate inclusion behavior of amylose toward PBL. The polymerization system was conducted by glucan phosphorylase (GP)-catalyzed enzymatic polymerization to produce amylose in the presence of PBL dispersed in aqueous acetate buffer at 50 °C for 48 h. The product was characterized by X-ray diffraction, 1H NMR, and IR measurements to support the structure of the amylose-PBL inclusion complex. Our previous study showed that the structural isomer of PBL, that is, poly[(R)-3-hydroxybutyrate] (PRHB) with a methyl substituent, was not included by amylose by the same operation and its oligomer with Mn = ~ 500 could form the inclusion complex with amylose only under specific conditions in the GP-catalyzed enzymatic polymerization. Accordingly, the present and previous results suggest that amylose includes PBL in its cavity more facilely than PRHB and its oligomer. [ABSTRACT FROM AUTHOR]

Naringenin is one of the flavonoids originating from citrus fruit. This polyphenol is mainly found in grapefruit, orange and lemon. The antioxidant and antimicrobial properties of flavonoids depend on their structure, including the polymeric form. The aim of this research was to achieve enzymatic polymerization of naringenin and to study the properties of poly(naringenin). The polymerization was performed by methods using two different enzymes, i.e., laccase and horseradish peroxidase (HRP). According to the literature data, naringenin had not been polymerized previously using the enzymatic polymerization method. Therefore, obtaining polymeric naringenin by reaction with enzymes is a scientific novelty. The research methodology included analysis of the structure of poly(naringenin) by NMR, GPC, FTIR and UV-Vis and its morphology by SEM, as well as analysis of its properties, i.e., thermal stability (DSC and TGA), antioxidant activity (ABTS, DPPH, FRAP and CUPRAC) and antimicrobial properties. Naringenin oligomers were obtained as a result of polymerization with two types of enzymes. The polymeric forms of naringenin were more resistant to thermo-oxidation; the final oxidation temperature To of naringenin catalyzed by laccase (poly(naringenin)-laccase) was 28.2 °C higher, and poly(naringenin)-HRP 23.6 °C higher than that of the basic flavonoid. Additionally, due to the higher molar mass and associated increase in OH groups in the structure, naringenin catalyzed by laccase (poly(naringenin)-laccase) showed better activity for scavenging ABTS+• radicals than naringenin catalyzed by HRP (poly(naringenin)-HRP) and naringenin. In addition, poly(naringenin)-laccase at a concentration of 5 mg/mL exhibited better microbial activity against E. coli than monomeric naringenin. [ABSTRACT FROM AUTHOR]

Conductive polyester non-woven fabric was prepared using horseradish peroxidase (HRP) catalytic agent, 3,4-ethylenedioxythiophene monomer and poly(p-styrenesulfonic acid) dopant. The electrical resistance of the prepared conductive polyester non-woven fabric was reduced to 1.3×104 Ω from 1014 Ω of the raw polyester non-woven fabric because of the addition of poly(3,4-ethylenedioxythiophene) the conductivity of conductive polyester non-woven fabric decreased by about 60 % after 300 bending cycles. Notably, the temperature of the conductive polyester non-woven fabric increased by 73.1 °C after 150 s of light irradiation from a lamp source, while that of the raw polyester non-woven fabric increased by only 19.4 °C under the same conditions. [ABSTRACT FROM AUTHOR]

The oxidative polymerizations of 2-methyl-m-phenylenediamine were performed to synthesize PMPDIA-A and PMPDIA-B polymers by H2O2 (35% aqueous solution) oxidant in acid-catalyzed ethanol and basic aqueous medium. Furthermore, PMPDIA-E polymer of 2-methyl-m-phenylenediamine was enzymatically synthesized by HRP (horseradish peroxidase) enzyme and H2O2 (35% aqueous solution) in dioxane/0.1 M phosphate tampon solution (pH = 7) mixture. The structures of 2-methyl-m-phenylenediamine and polymers were confirmed by FT-IR, NMR and UV–Vis spectrometer measurements. Molecular weight distributions, surface morphologies, thermal and fluorescence properties of polymers were determined from GPC, SEM, TG-DTA, DSC and fluorescence spectra analyses, respectively. CV and UV–Vis analyses were performed to determine the HOMO–LUMO energy levels, electrochemical (Eg′) and optical (Eg) band gaps values of MPDIA, PMPDIA-E, PMPDIA-A and PMPDIA-B. The electrochemical and optical band gaps values of polymers were lower than MPDIA, because of their polyconjugated structures. According to GPC measurements of polymers, the weight average molecular weights were between 5400 and 10400 Da. The fluorescence quantum yield of PMPDIA-E was calculated to be 9.15% in DMSO solution. The adsorption of methylene blue (MB) from aqueous solution on PMPDIA-B was studied. Adsorption isotherms and equilibrium adsorption capacities were determined by the fitting of the experimental data to two well-known isotherm models: Langmuir and Freundlich.

In this paper, we report that polysaccharide substrates bearing 2‐deoxygenated amylose chains are hydrophobic. A pure partially 2‐deoxygenated amylose was synthesized by the thermostable glucan phosphorylase‐catalyzed enzymatic copolymerization of d‐glucal, a non‐native monomer, with α‐d‐glucose 1‐phosphate, a native monomer from maltotriose, as a primer. A water contact angle on a cast film of the resulting polysaccharide confirms that it is hydrophobic. Enzymatic copolymerization using glycogen as a polymeric primer was used to investigate the possibility of engendering hydrophilic substrates with hydrophobicity by incorporating such polysaccharide chains; the resulting glycogen‐derived films with elongated partially 2‐deoxygenated amylose chains are strongly hydrophobic. [ABSTRACT FROM AUTHOR]

Surface‐independent smart antibacterial coatings with on‐demand antibiotics release profiles have attracted increasing attention in medical instruments, antibiotics delivery platforms, and implanted devices. Although several approaches have been well documented, the facile preparation of antibacterial coatings onto universal substrates with high antibiotics loading efficiencies, tunable drug release profiles, and excellent antibacterial performances is still met with many challenges, especially related to the redundant coating material synthesis and selective substrate fabrication process. To resolve this issue, the authors report a facile and robust fabrication method towards smart antibacterial coating surfaces on various substrates via a one‐pot integration of two types of naturally occurring building blocks, aminoglycosides and protocatechualdehyde in the presence of plant enzyme horseradish peroxidase. The simultaneous dynamic imine bonds formation and enzymatic polymerization within the system during the one‐pot reaction enable the facile fabrication of diverse surface‐independent smart antibacterial coatings, which can demonstrate several promising features including high drug loading and dynamic (i.e., pH‐responsive) properties, tunable and on‐demand antibiotics release behaviors, and efficient antibacterial activities both in vitro and in vivo. This work may offer new opportunities towards the robust and universal antibacterial coating materials by the bioinspired integration of all natural building blocks. [ABSTRACT FROM AUTHOR]

We have previously found that a partially 2-deoxygenated (P2D)-amylose, produced by glucan phosphorylase (GP)-catalyzed enzymatic copolymerization, shows hydrophobic nature. Based on this finding, the present study demonstrates hydrophobization of a strong hydrophilic polypeptide, i.e., poly(γ-glutamic acid) (PGA), by grafting of the P2D-amylose chains via GP-catalyzed enzymatic approach. After maltooligosaccharide primers for the enzymatic reaction were modified on the PGA chain, we performed GP-catalyzed copolymerization of d-glucan with α-d-glucose 1-phosphate as comonomers in different feed ratios from the primers to produce P2D-amylose-grafted PGAs. We analyzed the structures (chemical and crystalline) of the products, precipitated from reaction mixtures, by 1H NMR and powder X-ray diffraction measurements, respectively. The values of the water contact angle of the cast films, prepared from DMSO solutions of the products with different 2-deoxyglucose/glucose unit ratios, were greater than 100°, indicating efficient hydrophobization of the hydrophilic polypeptide by the present approach.

Deep eutectic solvents (DESs) are an alternative to traditional organic solvents for enzymatic reactions between compounds with poor solubility. Biocatalytic polymerization of the flavonoid (+)-catechin (CC) was carried out with laccase from the fungus Trametes hirsuta in a DES–buffer mixture (betaine/glycerol 60 vol %–buffer 40 vol %). The conditions for the synthesis of catechin oligomers (oligoCCs) soluble in organic solvents have been selected. According to the data from high-performance liquid chromatography, the oligoCCs had average molecular weights of 10 620 and 2540 g/mol with polydispersity indices of 1.1 and 1.09, respectively. The physicochemical properties of the obtained oligomers were studied via UV-visible, FTIR, 1H and 13C NMR spectroscopy. The resulting oligoCCs inhibited the α-glucosidase activity (IC50 ~ 8 μg/mL). [ABSTRACT FROM AUTHOR]

Properties of polymers were obtained by enzyme catalyzed oxidative polymerization varies according to oxidative polymerization products and thus polymeric materials with different properties are obtained. In this study, polymerization of 4-amino-2,6-dichlorophenol (ADCP), an aminophenol compound containing dihalogen, was carried out by two different methods and the two methods were compared with each other. One of the methods was oxidative polymerization in the presence of hydrogen peroxide with heating, and the other was enzyme-catalyzed oxidative polymerization that took place at room temperature in the presence of Horse Radish Peroxidase (HRP) enzyme and hydrogen peroxide. The structural characterization of the products obtained as a result of oxidative polymerization (PADCP-O) and as a result of enzyme catalyzed oxidative polymerization (PADCP-E) was performed by 1H-NMR, 13C-NMR, FT-IR, UV–Vis spectroscopy methods. The molecular masses of PADCP-O and PADCP-E were analyzed by GPC and the average molecular mass of PADCP-E was found to be higher than that of PADCP-O. Thermal properties were examined by TGA and it was determined that the thermal stability of the obtained polymers was higher than that of the monomer. Electrochemical and optical properties were determined by CV and UV–Vis spectroscopy methods, respectively. Electrochemical and optical band gap values were calculated as 1.61 and 1.33 eV, and 1.88 and 1.83 eV for PADCP-O and PADCP-E, respectively. In addition, it was observed that PADCP-O emitted green in UV light, while PADCP-E emitted red in DMSO. Surface properties and morphology of polymers were analyzed by SEM and it was observed that PADCP-O obtained by oxidative polymerization had a spongy structure, but the enzymatic polymerization product PADCP-E had a uniformly dispersed nanoparticle structure. [ABSTRACT FROM AUTHOR]

The in situ gelation of injectable precursors is desirable in the field of tissue regeneration, especially in the context of irregular defect filling. The current driving forces for fast gelation include the phase‐transition of thermally sensitive copolymers, click chemical reactions with tissue components, and metal coordination effect. However, the rapid formation of tough hydrogels remains a challenge. Inspired by aerobic metabolism, we herein propose a tissue‐fluid‐triggered cascade enzymatic polymerization process catalyzed by glucose oxidase and ferrous glycinate for the ultrafast gelation of acryloylated chondroitin sulfates and acrylamides. The highly efficient production of carbon radicals and macromolecules contribute to rapid polymerization for soft tissue augmentation in bone defects. The copolymer hydrogel demonstrated the regeneration‐promoting capacity of cartilage. As the first example of using artificial enzyme complexes for in situ polymerization, this work offers a biomimetic approach to the design of strength‐adjustable hydrogels for bio‐implanting and bio‐printing applications. [ABSTRACT FROM AUTHOR]

Preparation of oligo (aminophenols) was carried out by chemical oxidative and enzymatic oligomerization of 4-amino-2,6-dibromophenol (ADBP). The former method required hydrogen peroxide as catalyst in an aqueous sodium hydroxide solution and the latter method was catalyzed by an enzyme, horseradish peroxidase, in 1,4-dioxane resulting in the formation of (ADBP)-ox and (ADBP)-enz, respectively. For the structural confirmation for both of the synthesized oligomers were fulfilled using FT-IR, UV–vis and 1H NMR and 13C NMR instruments. The chemical oxidation with H 2 O 2 induced monodisperse particles in the sub-micron size. The thermal treatment of the oligomers at 1000 οC showed that the chemical oxidation resulted in (ADBP)-ox with higher residue% compared to enzymatic oxidation. Neutral ADBP underwent facile oxidation, leading to the formation of its corresponding oligomers, which were composed of head-to-tail or ortho -coupled constitutional moieties with lower optical and electrochemical band gaps than those of ADBP using two oligomerization routes. By analyzing the solvent effect on the absorption, lower optical band gaps of the synthesized oligomers were obtained in some selected solvents, pointing out them as semi-conductive material for the production of optoelectronic and electronic materials. By tuning the excitation wavelength, the fluorescence intensity of both of the oligomers was changed. DMF solution of (ADBP)-ox and (ADBP)-enz had a quantum yield of 17.6 % and 1.2 % for green and orange photoluminescence emission, respectively, with excellent photostability. [Display omitted] • Two oligo(aminophenols) were synthesized via chemical and HRP-catalyzed oxidative processes by 4-amino-2,6-dibromophenol. • E g values lowered depending on increase in the solvent polarity. • Oligomers exhibited QY of 17.6 % and 1.2 % for green and orange PL emission, respectively. • Oligomer with the higher thermal stability may serve as brominated flame retardant. [ABSTRACT FROM AUTHOR]

Bio-based star-shaped poly(ε-caprolactone)s (S-PCL) derived from sugar-based D-sorbitol as an initiator were obtained via solvent-free enzymatic ring-opening polymerization (eROP). The star S-PCL were converted into UV-curable maleates by employing maleic anhydride for subsequent crosslinking with tri(ethylene glycol) divinyl ether (DVE-3) in the presence of Darocur 1173 as a radical photoinitiator. The kinetics of the UV-induced radical copolymerization was monitored by real-time Fourier-Transform InfraRed (FTIR) spectroscopy, which revealed that the star S-PCL maleate/divinyl ether system was not scavenged by molecular oxygen (donor/acceptor polymerization). The UV-crosslinking reaction was fast (~10 s) to reach near quantitative conversions. The S-PCL maleate / divinyl ether liquid formulation cast on glass substrates successfully gave films upon UV-crosslinking. The thermal properties of the polymer films and their precursor polymers were characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Finally, the crosslinked polymer film demonstrated promising adhesive properties on steel, aluminum and glass substrates.

Due to the increasing importance of environmentally friendly processes, the development of monomer synthesis and its polymerization using enzymes has been investigated throughout the world. In this paper, the polymerization mechanism between silk fabrics and gallic acid (GA) in the presence of horseradish peroxidase (HRP) has been studied. The polymerization mechanism was studied in detail using UV-Vis and Fourier transform infrared spectroscopy (FT-IR), and high-performance liquid chromatography-electrospray ionization mass spectrometry (HPLC-ESI-MS) analysis. In addition, the dyeing properties and optimum reaction conditions were further investigated using the K/S values. The color fastness of the resulting silk fabrics has also been discussed. The results show that the dyeing mechanism for GA and silk fabric involved linking via the -NH2 and -OH groups in silk fiber and the -OH groups in GA. This was probably formed via the formation of phenyl-phenyl, oxygen-phenyl, or amino-phenyl linkages. HRP significantly improved the dyeing properties of GA dyes toward silk fabrics. The optimum reaction conditions for dyeing silk fabrics have been proposed (Incubation period, 5 h; temperature, 50 °C; GA dosage, 10 mM; HRP, 6 U/ml, and H2O2, 5 mM). The color fastness of the resulting silk fabrics displayed high colorfastness in all the colorfastness tests performed. [ABSTRACT FROM AUTHOR]