Defining structure–mechanical activity relationships (SMARs) is essential for understanding how molecular structure controls force-coupled reactivity and for designing mechanophores with predictable mechanical responses. In this study, we conducted a systematic SMAR study to engineer dithienylphenanthrene derivatives into a functional mechanophore platform. These studies revealed that the mechanochemical reactivity of DTPs is governed by regiochemical control and by a previously unrecognized design principle that we term the “resisting moment-arm effect,” wherein distal steric congestion creates an opposing torque resisting the conformational adjustments required for the stereochemical conversion and thereby modulates mechanical activity. These SMARs guided the rational design of DTP5-p as a promising molecular force sensing probe and established dithienylphenanthrene as a new platform for atropisomer mechanochemistry, and revealed that structural modification remote from the force-transmission pathway can be leveraged to control mechanochemical reactivity.

Radical and anionic polymerizations are two major routes to synthetic macromolecules, yet they have remained largely separate due to their distinct underlying mechanisms. To bridge these traditionally exclusive methods, we report a strategy that combines the complementary strengths of both methods, fueled by Earth-abundant alkali metal Lewis base and hydrosilanes. Central to this approach is a hydrogen atom-coupled electron transfer (HCET) process that transforms radical-driven initiation into anionic propagation. This method enables the synthesis of a broad spectrum of polymers, demonstrated here by polystyrene homopolymers and poly(styrene)-block-poly(methyl methacrylate) copolymers, under user-friendly conditions that tolerate air and use unpurified commodity chemicals. The operational simplicity, oxygen tolerance, and scalability of this method hold promise for sustainable and industrially relevant polymer synthesis.

A simple, 1-pot synthesis approach is presented that produces segmented thermoplastic polyurethanes with increased molecular weight and crystallinity, shape memory properties, and the ability to form fibrous scaffolds with high strength.

Enzymes play an important role in numerous natural processes and are increasingly being utilized as environmentally friendly substitutes and alternatives to many common catalysts. Their essential advantages are high catalytic efficiency, substrate specificity, minimal formation of byproducts, and low energy demand. All of these benefits make enzymes highly desirable targets of academic research and industrial development. This review has the modest aim of briefly overviewing the classification, mechanism of action, basic kinetics and reaction condition effects that are common across all six enzyme classes. Special attention is devoted to immobilization strategies as the main tools to improve the resistance to environmental stress factors (temperature, pH and solvents) and prolong the catalytic lifecycle of these biocatalysts. The advantages and drawbacks of methods such as macromolecular crosslinking, solid scaffold carriers, entrapment, and surface modification (covalent and physical) are discussed and illustrated using numerous examples. Among the hundreds and possibly thousands of known and recently discovered enzymes, hydrolases and oxidoreductases are distinguished by their relative availability, stability, and wide use in synthetic applications, which include pharmaceutics, food and beverage treatments, environmental clean-up, and polymerizations. Two representatives of those groups—laccase (an oxidoreductase) and lipase (a hydrolase)—are discussed at length, including their structure, catalytic mechanism, and diverse usage. Objective representation of the current status and emerging trends are provided in the main conclusions.

Macromolecules obtained from renewable natural sources are gaining increasing attention as components for a vast variety of sustainable polymer-based materials. Natural raw materials can facilitate continuous-flow production due to their year-round availability and short replenishment period. They also open new opportunities for chemists and biologists to design and create "bioreplacement" and "bioadvantaged" polymers, where complex structures produced by nature are being modified, upgraded, and utilized to create novel materials. Bio-based macromonomers are expected not only to compete with but to replace some petroleum-based analogs, as well. The development of novel sustainable materials is an ongoing and very dynamic process. There are multiple strategies for transforming natural macromolecules into sophisticated value-added products. Some methods include chemical modification of macromolecules, while others include blending several components into one new system. One of the most promising approaches for incorporating renewable macromolecules into new products is the synthesis of hybrid networks based on one or more natural components. Each one has unique characteristics, so its incorporation into a network brings new sustainable materials with properties that can be tuned according to their end-use. This article reviews the current state-of-the-art and future potential of renewable natural macromolecules as sustainable building blocks for the synthesis and use of hybrid polymer networks. The most recent advancements and applications that involve polymers, such as cellulose, chitin, alginic acid, gellan gum, lignin, and their derivatives, are discussed.

Pollution with organic dyes is one of the most typical environmental problems related to industrial wastewater. The removal of these dyes opens up new prospects for environmental remediation, but the design of sustainable and inexpensive systems for water purification is a fundamental challenge. This paper reports the synthesis of novel fortified hydrogels that can bind and remove organic dyes from aqueous solutions. These hydrophilic conetworks consist of chemically modified poly(ethylene glycol) (PEG-m) and multifunctional cellulose macromonomers ("cellu-mers"). Williamson etherification with 4-vinylbenzyl chloride (4-VBC) is used to modify PEGs of different molecular masses (1, 5, 6, and 10 kDa) and cellobiose, Sigmacell, or Technocell™ T-90 cellulose (products derived from natural renewable resources) with polymerizable/crosslinkable moieties. The networks are formed with good (75%) to excellent (96%) yields. They show good swelling and have good mechanical properties according to rheological tests. Scanning electron microscopy (SEM) reveals that cellulose fibers are visibly embedded into the inner hydrogel structure. The ability to bind and remove organic dyes, such as bromophenol blue (BPB), methylene blue (MB), and crystal violet (CV), from aqueous solutions hints at the potential of the new cellulosic hydrogels for environmental cleanup and clean water safeguarding.

We report a new method to shape double-network (DN) hydrogels into customized microscale 3D structures that exhibit superior mechanical properties in both tension and compression. A one-pot prepolymer formulation containing photo-cross-linkable acrylamide and thermo-reversible sol-gel κ-carrageenan with a suitable crosslinker, and photo-initiator/absorbers are optimized. A new TOPS system is utilized to photo-polymerize the primary acrylamide network into a 3D structure above the sol-gel transition of κ-carrageenan (80°C), while cooling down generates the secondary physical κ-carrageenan network to realize tough DN hydrogel structures. 3D structures, printed with high lateral (37μm) and vertical (180μm) resolutions and superior 3D design freedoms (internal voids), exhibit ultimate stress and strain of 200 kPa and 2400% respectively under tension, and simultaneously exhibit high compression stress of 15 MPa with a strain of 95%, both with high recovery rates. The roles of swelling, necking, self-healing, cyclic loading, dehydration, and rehydration on the mechanical properties of printed structures are also investigated. To demonstrate the potential of this technology to make mechanically reconfigurable flexible devices, we print an axicon lens and show that a Bessel beam can be dynamically tuned via user-defined tensile stretching of the device. This technique can be broadly applied to other hydrogels to make novel smart multifunctional devices for a range of applications.

This study describes the synthesis of novel amphiphilic linear-dendritic block copolymers and their self-assembly in water to form supramolecular nanoreactors capable of catalyzing Suzuki-Miyaura coupling reactions under "green" conditions. The block copolymers were formed through copper(I)-catalyzed alkyne-azide cycloaddition between azide functionalized poly(benzyl ether) dendrons as the perfectly branched blocks, as well as bis-alkyne modified poly(ethylene glycol), PEG, as the linear block. A first-generation poly(benzyl ether) dendron (G1) was coupled to a bis-alkyne modified PEG with molecular mass of 5 kDa, forming an ABA copolymer (G1)2-PEG5k-(G1)2 (yield 62%), while a second-generation dendron (G2) was coupled to a 11 kDa bis-alkyne modified PEG to produce (G2)2-PEG11k-(G2)2 (yield 49%). The structural purity and low dispersity of the linear-dendritic copolymers were verified by size-exclusion chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Their self-assembly was studied by dynamic light scattering, showing that (G1)2-PEG5k-(G1)2 and (G2)2-PEG11k-(G2)2 formed single populations of micelles (17 nm and 37 nm in diameter, respectively). The triazole rings located at the boundaries between the core and the corona are efficient chelating groups for transition metals. The ability of the micelles to complex Pd was confirmed by 1H NMR, transmission electron microscopy, and inductively coupled plasma. The catalytic activity of the supramolecular linear-dendritic/Pd complexes was tested in water by model Suzuki-Miyaura reactions in which quantitative yields were achieved within 3 h at 40 °C, while, at 17 °C, a yield of more than 70% was attained after 17 h.

Organic coatings provide an effective way to improve the corrosion resistance of metals. Traditional organic varnishes, however, either contain highly polluting or toxic components or lack self-healing ability. In this article, we report a feasible method of preparing polyaniline-modified halloysite nanotubes (PANI@HNTs). They were loaded with a corrosion inhibitor, benzotriazole (BTA), and were tested as multifunctional anticorrosion additives for environmentally friendly epoxy waterborne coatings. The PANI@HNTs were formed via the in situ polymerization of aniline in the presence of halloysites. The BTA loading was then carried out and reached up to 14.5 wt.%. The BTA retention ability of the PANI@HNTs was significantly improved in comparison to that of pure HNT. Electrochemical impedance spectroscopy (EIS) tests of the coatings immersed in a 3.5 wt.% NaCl solution showed that the barrier and corrosion inhibition effects were enhanced by two to four orders of magnitude with the incorporation of BTA-loaded PANI@HNTs. The salt spray tests on artificially scratched coatings revealed that the surfaces protected by varnishes doped with the BTA-loaded PANI@HNTs exhibited the lowest degree of corrosion compared to the control samples, illustrating the self-healing potential of the modified coatings.

In this paper, we describe a novel method for preparation of polymer composites with homogeneous dispersion of natural fibers in the polymer matrix. In our approach, Williamson ether synthesis is used to chemically modify cellulose with polymerizable styrene moieties and transform it into a novel multifunctional cellu-mer that can be further crosslinked by copolymerization with styrene. Reactions with model compounds (cellobiose and cellotriose) successfully confirm the viability of the new strategy. The same approach is used to transform commercially available cellulose nanofibrils (CNFs) of various sizes: Sigmacell and Technocell™ 40, 90 and 150. The styrene-functionalized cellulose oligomers and CNFs are then mixed with styrene and copolymerized in bulk at 65 °C with 2,2′-azobisisobutyronitrile as initiator. The resulting composites are in a form of semi-interpenetrating networks (s-IPN), where poly(styrene) chains are either crosslinked with the uniformly dispersed cellulosic component or entangled through the network. Non-crosslinked poly(styrene) (31–41 w%) is extracted with CHCl3 and analyzed by size-exclusion chromatography to estimate the extent of homopolymerization and reveal the mechanism of the whole process. Electron microscopy analyses of the networks show the lack of cellu-mer agglomeration throughout the polymer matrix. The homogeneous distribution of cellulose entities leads to improved thermal and mechanical properties of the poly(styrene) composites compared to the physical mixtures of the same components and linear poly(styrene) of similar molecular mass.

This study reports the first attempt to employ a potassium–graphite intercalation compound (KC24) as an initiator for the one-pot synthesis of a multi-block copolymer. The results obtained show that KC24 successfully initiated the copolymerization, leading to a copolymer consisting of poly(styrene), poly(methyl methacrylate) and poly(ethylene oxide) blocks. When all three comonomers were introduced simultaneously or in a specific sequence, the resulting copolymers had molecular masses in the range between 170,000 Da and 280,000 Da. Their composition was investigated by size-exclusion chromatography with triple detection (dRI/UV/IR) and 1H-NMR. The analyses indicated that all copolymers were enriched in methyl methacrylate (50–66 mol%) despite the fact that the comonomers were added in equimolar amounts. Due to the layered structure of the initiator, the polymerization took place in the graphite interlayer spaces and lead to extensive delamination, indicating at the potential to produce in situ graphite/copolymer composite materials.

This study targets the synthesis of novel semi-interpenetrating networks and amphiphilic conetworks, where hydrophilic soft matter (Gellan Gum, GG) was combined with hydrophobic rigid poly(styrene), PSt. To achieve that, GG was chemically modified with 4-vinyl benzyl chloride to form a reactive macromonomer with multiple double bonds. These double bonds were used in a copolymerization with styrene to initially form semi-interpenetrating networks (SIPNs) where linear PSt was intertwined within the GG-PSt conetwork. The interpenetrating linear PSt and unreacted styrene were extracted over 3 consecutive days with yields 18–24%. After the extraction, the resulting conetworks (yields 76–82%) were able to swell both in organic and aqueous media. Thermo-mechanical tests (thermal gravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis) and rheology indicated that both SIPNs and conteworks had, in most cases, improved thermal and mechanical properties compared to pure poly(styrene) and pure GG gels. This crosslinking strategy proved that the reactive combination of a synthetic polymer and a bio-derived constituent would result in the formation of more sustainable materials with improved thermo-mechanical properties. The binding ability of the amphiphilic conetworks towards several organic dyes was high, showing that they could be used as potential materials in environmental clean-up.

This study reports the first enzymatic synthesis leading to several oligomer analogues of poly[3-(3,4-dihydroxyphenyl)glyceric acid]. This biopolymer, extracted from plants of the Boraginaceae family has shown a wide spectrum of pharmacological properties, including antimicrobial activity. Enzymatic ring opening polymerization of 2-methoxycarbonyl-3-(3,4-dibenzyloxyphenyl)oxirane (MDBPO) using lipase from Candida rugosa leads to formation of poly[2-methoxycarbonyl-3-(3,4-dibenzyloxyphenyl)oxirane] (PMDBPO), with a degree of polymerization up to 5. Catalytic debenzylation of PMDBPO using H2 on Pd/C yields poly[2-methoxycarbonyl-3-(3,4-dihydroxyphenyl)oxirane] (PMDHPO) without loss in molecular mass. Antibacterial assessment of natural polyethers from different species of Boraginaceae family Symhytum asperum, S. caucasicum,S. grandiflorum, Anchusa italica, Cynoglossum officinale, and synthetic polymers, poly[2-methoxycarbonyl-3-(3,4-dimethoxyphenyl)oxirane (PMDMPO) and PMDHPO, reveals that only the synthetic analogue produced in this study (PMDHPO) exhibits a promising antimicrobial activity against pathogenic strains S.aureus ATCC 25923 and E.coli ATCC 25922 the minimum inhibitory concentration (MIC) being 100 µg/mL.

A key challenge to the creation of chemically responsive electro-functionality of nonconductive, hydrophobic, and free-contacted textile or fibrous network materials is how to impart the 3D structure with functional filaments to enable responsive structure sensitivity, which is critical in establishing the fibrous platform technology for sensor applications. We demonstrate this capability using an electrospun polymeric fibrous substrate embedded with nano-filaments defined by size-tunable gold nanoparticles and structurally sensitive dendrons as crosslinkers. The resulting interparticle properties strongly depend on the assembly of the nano-filaments, enabling an interface with high structure sensitivity to molecular interactions. This is demonstrated with chemiresistive responses to vaporous alcohol molecules with different chain lengths and isomers, which is critical in breath and sweat sensing involving a high-moisture or -humidity background. The sensitivity scales with the chain length and varies with their isomers. This approach harnesses the multifunctional tunability of the nano-filaments in a sensor array format, showing high structure sensitivity to the alcohol molecules with different chain lengths and isomers. The high structure sensitivity and its implications for a paradigm shift in the design of textile sensor arrays for multiplexing human performance monitoring via breath or sweat sensing and environmental monitoring of air quality are also discussed.

Bacteria can colonize essentially any surface and form antibiotic resistant biofilms, which are multicellular structures embedded in an extracellular matrix secreted by the attached cells. To develop better biofilm control technologies, we recently demonstrated that mature biofilms can be effectively removed through on-demand shape recovery of a shape memory polymer (SMP) composed of tert-butyl acrylate (tBA). It was further demonstrated that such a dynamic substratum can sensitize the detached biofilm cells to antibiotics. However, this SMP can undergo shape change only once, limiting its application in long-term biofilm control. This motivated the present study, which aimed to prove the concept that biofilm can be effectively removed by repeated on-demand shape recovery. Reversible shape memory polymers (rSMPs) containing poly(ε-caprolactone) diisocyanatoethyl dimethacrylate (PCLDIMA) of varying molecular masses and butyl acrylate (BA) as a linker were synthesized by using benzoyl peroxide (BPO) as a thermal initiator. By comparison of several combinations of PCLDIMA of different molecular masses, a 2:1 weight ratio mixture of 2000 and 15000 g/mol PCLDIMA was the most promising because it had a shape transition (at 36.7 °C) close to body temperature. The synthesized rSMP demonstrated good reversible shape recovery and up to 94.3 ± 1.0% removal of 48 h Pseudomonas aeruginosa PAO1 biofilm cells after three consecutive shape recovery cycles. Additionally, the detached biofilm cells were found to be 5.0 ± 1.2 times more susceptible to 50 μg/mL tobramycin than the static control.

This paper reports the creation of hydroxyapatite/polyester nanografts by "graft-from" polymerization of d,l-lactide with [Ca5(OH)(PO4)3]2 as the initiator and tin(II)-2-ethylhexanoate as the catalyst. Model polymerizations were performed with cyclooctanol as initiator to confirm the grafting on the surface of the hydroxyapatite nanocrystals. Polymers with the highest molecular mass (Mn) between 4250 Da (cyclooctanol) and 6100 Da (hydroxyapatite) were produced. In both cases the molecular mass distributions of the polymers formed were monomodal. The materials obtained were characterized by size-exclusion chromatography, NMR and FT-IR spectroscopy, and thermal methods. Their suitability as additives for commercial bone cement (Simplex P Speedset, Stryker Orthopaedics) has been confirmed by thermal analysis techniques and mechanical testing. The results obtained show that addition of the hydroxyapatite/ polyester nanografts improved both thermal and mechanical properties of the bone cement.

This study reports the first enzyme-mediated polymerization of dendritic macromonomers. The enzyme substrates are prepared by "click" conjugation between tyrosine and hydrophilic triethylene glycol (TrEG)-based dendrons of three generations (G1, G2, and G3). The resulting enzyme-polymerizable dendrons are defect-free as revealed by mass spectrometry, size-exclusion chromatography, and spectroscopic techniques. The phenol-containing macromonomers are water soluble and their polymerizations into dendronized polymers (denpols) are catalyzed by laccase (an oxidoreductase) under benign conditions (45 °C and aqueous medium at pH = 4.0) with copolymer yields between 30 and 40%. The resulting denpols consist of unnatural poly(tyrosine) backbones and dendritic poly(ether-ester) side chains and have molecular masses up to ∼13 000 Da (generation 1), ∼20 000 Da (generation 2), and ∼36 000 Da (generation 3) determined by matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) analyses. They display amphiphilic properties and self-assemble in aqueous solutions to form aggregates with generation-dependent morphologies.

Herewith we report the first attempt towards non-covalent immobilization of Trametes versicolor laccase on neat and magnetically responsive highly porous polyamide 6 (PA6) microparticles and their application for catechol oxidation. Four polyamide supports, namely neat PA6 and such carrying Fe, phosphate-coated Fe and Fe3O4 cores were synthesized in suspension by activated anionic ring-opening polymerization (AAROP) of ε-caprolactam (ECL). Enzyme adsorption efficiency up to 92% was achieved in the immobilization process. All empty supports and PA6 laccase complexes were characterized by spectral and synchrotron WAXS/SAXS analyses. The activity of the immobilized laccase was evaluated using 2,2’-Azino-bis-(3- ethylbenzothiazoline-6-sulfonic acid (ABTS) and compared to the native enzyme. The PA6 laccase conjugates displayed up to 105% relative activity at room temperature, pH 4, 40 °C and 20 mM ionic strength (citrate buffer). The kinetic parameters of the ABTS oxidation were also determined. The reusability of the immobilized laccase-conjugates was proven for five consecutive oxidation cycles of catechol.

Freeze-thaw poly(vinyl alcohol) hydrogels (PVAH) offer great potential for several biomedical applications due to their biomimetic mechanical properties and biocompatibility. Despite these advantages, the use of PVA-H for load bearing applications has been limited due to poor performance in boundary lubrication compared to natural tissue such as articular cartilage. Recently, zwitterionic polymer brushes have been shown to act as effective boundary lubricants on rigid substrates; however, to the best of our knowledge, the synergistic effects of zwitterionic brushes coupled with the biomimetic fluid load support exhibited by hydrogels have not been reported. We report here on our investigation involving the synthesis and characterization of two unique types of polymer brush functionalized PVA hydrogels. The zwitterionic polymers that were compared contained either [2-(methacryloyloxy)ethyl]dimethyl-3-sulfopropylammonium hydroxide, PMEDSAH, or 2-methacryloyloxyethylphosphorylcholine, PMPC, repeating units. Both hydrogels coated with zwitterionic polymers were found to be cytocompatible. We report further on micrometer-scale surface properties via water contact angle goniometry, surface roughness measurements, and scanning electron microscopy. Finally, the impact of brush functionalization on the mechanics of the tribologically enhanced gels is reported with comparison to natural articular cartilage within the context of Hertzian contact theory.