Functional Polymers Research Articles

Understanding, Mimicking, and Mitigating Radiolytic Damage to Polymers in Liquid Phase Transmission Electron Microscopy.

Advances in liquid phase transmission electron microscopy (LP-TEM) have enabled the monitoring of polymer dynamics in solution at the nanoscale, but radiolytic damage during LP-TEM imaging limitsits routine use in polymer science. This study focuses on understanding, mimicking, and mitigating radiolytic damage observed in functional polymers in LP-TEM. It is quantitatively demonstrated how polymer damage occurs across all conceivable (LP-)TEM environments,and the key characteristics and differences between polymer degradation in water vapor and liquid water are elucidated. Importantly, it is shown that the hydroxyl radical-rich environment in LP-TEM can be approximated by UV light irradiation in the presence of hydrogen peroxide, allowing the use of bulk techniques to probe damage at the polymer chain level. Finally, the protective effects of commonly used hydroxyl radical scavengers are compared, revealing that the effectiveness of graphene's protection is distance-dependent. The work provides detailed methodological guidance and establishes a baseline for polymer degradation in LP-TEM, paving the way for future research on nanoscale tracking of shape transitions and drug encapsulation of polymer assemblies in solution.

Catalytic Enantioselective Functionalization of Maleimides: An Update

Comprehensive SummaryMaleimide derivatives are well‐established reactive intermediates also found in natural products, synthetic pharmaceuticals and functional polymers. Their specific reactivity found widespread applications in the field of bioconjugation and allowed for the development of highly selective functionalizations based on simple additions and cycloadditions with the possible control of central and C–N axial chirality. These multisite‐reactive scaffolds have aroused a long‐standing interest throughout the scientific community more particularly as powerful electrophilic partners and more recently as nucleophilic partners in some specific transformations. The persistent interest in these easily accessible synthetic platforms over the last decade has enabled the development of new enantioselective transformations and the major advancements in this field are presented in this review. Key Scientists

Dynamically Switchable Global Chirality in Racemic Polymer Systems

Any polymers composed of racemic segments are obviously optically inactive and lack any chiroptical applications. Here, we present an intriguing method for precisely generating global chirality in racemic copolymer assemblies without any external asymmetrical intervention via step‐wise polymerization‐induced chiral self‐assembly (PICSA). Global supramolecular chirality of the nanoaggregates could be dynamically switched by the two diametrically opposed chiral conflict effects: “first come, first serve” effect and “late‐comer lives above” effect, which can be controlled by the precisely specified the number and sequence of enantiomeric segments. Significantly, the supramolecular stacking manners of the racemic mesogenic building units as well as the liquid crystallinity of the solvophobic core play a crucial role for the chiral communication pathway of enantiomeric mesogens. Furthermore, such switchable global chirality in racemic polymers is broadly applicable and well regulable. We propose that this research may challenge the notion that racemic systems lack optical activity while highlighting their potential applications in functional racemic polymer materials and providing insights into the evolution of racemates towards homochirality on early Earth.

Dynamically Switchable Global Chiralityin Racemic Polymer Systems.

Any polymers composed of racemic segments are obviously optically inactive and lack any chiroptical applications. Here, we present an intriguing method for precisely generating global chirality in racemic copolymer assemblies without any external asymmetrical intervention via step-wise polymerization-induced chiral self-assembly (PICSA). Global supramolecular chirality of the nanoaggregates could be dynamically switched by the two diametrically opposed chiral conflict effects: "first come, first serve" effect and "late-comer lives above" effect, which can be controlled by the precisely specified the number and sequence of enantiomeric segments. Significantly, the supramolecular stacking manners of the racemic mesogenic building units as well as the liquid crystallinity of the solvophobic core play a crucial role for the chiral communication pathway of enantiomeric mesogens. Furthermore, such switchable global chirality in racemic polymers is broadly applicable and well regulable. We propose that this research may challenge the notion that racemic systems lack optical activity while highlighting their potential applications in functional racemic polymer materials and providing insights into the evolution of racemates towards homochirality on early Earth.

Meta-connected Oligo-Azobenzenes Outperform Their Para Counterparts.

Systems with multiple photoswitchable units in one molecule have attracted considerable attention in the past years as they are useful for a broad variety of possible applications. Especially, linked azobenzenes sharing one benzene ring are of high interest since their direct linkage introduces an additional photoswitchable unit at only small increase in molecular weight. In this spirit, linear oligoazobenzenes had been synthesized, though their photochemical properties have only been investigated for short chain lengths. In this study, we use (time-dependent) density functional methodology for the evaluation of the excitations of meta- and para-connected oligo-azobenzenes to predict their switching ability. It becomes apparent, that the meta connection pattern enables each azobenzene subunit to act as an individual switchable unit, whereas they are strongly coupled and loose their individuality in para connection. Therefore, meta-oligo-azobenzenes are ideal candidates for future studies of azobenzene-based functional polymers, while para-oligo-azobenzenes are not.

Silica-reinforced Functional Composite Polymer Electrolyte with High Electrochemical Compatibility for Solid-State Lithium Metal Battery

Silica-reinforced Functional Composite Polymer Electrolyte with High Electrochemical Compatibility for Solid-State Lithium Metal Battery

SYNTHESIS AND CHARACTERIZATION OF POLYEPICHLOROHYDRIN DIOLS

Polyepichlorohydrin (PECH) is a functional polymer with high value in energy materials. Cationic ring-opening polymerization of epichlorohydrin (ECH) with a diol initiator and Lewis or protic acids catalyst, proceeds through an activated monomer mechanism (AM) allowing control of the polymer's average molecular weight and polydispersity index. In the present investigation, PECH diol was synthesized under the catalysis of boron trifluoride etherate, with the ECH monomer:ethylene glycol as an initiator molar ratio of 1:0.045, achieving a low molecular weight nM = 1935 g/mol, low polydispersity index PDI = 1.25, predominantly in the linear chain configuration with the terminal hydroxyl group.

Quantitative Effects of Ecuadorian Silicon-Aluminum Materials on the Degradation Rate and Mechanical Strength Enhancement of Recycled Polyethylene

This study presents an innovation in the use of a native Ecuadorian nanoporous material known as allophane for the reprocessing of greenhouse plastics to obtain a functional polymer that allows for reuse, improving its mechanical properties and/or increasing its lifespan. By achieving this objective, three problems are simultaneously addressed: 1) the need to recycle used plastics in a prominent Ecuadorian flower company committed to environmental preservation, 2) the scientific viability work carried out by the Central University of Ecuador, and 3) the industrial application of recycled plastics and pellet production. Blown film extrusion was used to prepare low-density polyethylene sheets with different amounts of Ecuadorian allophane microparticles (30±5 micrometers) (0.1%, 0.3%, and 0.5% by weight). Mechanical property studies were conducted following ASTM D 882 standards, and thermal stability was characterized using thermogravimetry. The results showed an increase in elongation at break and Young's modulus percentages as the concentration of the additive increased, demonstrating its physical-chemical compatibility. Additionally, the effect on the polymer’s thermal degradation was analyzed, resulting in a directly proportional relationship between activation energy and the concentration of the material. Finally, these results demonstrate that allophane as an additive enhances the mechanical properties of recycled low-density polyethylene (12-36%) and accelerates its thermal degradation process, reducing environmental impact.

Advanced functional polymer materials for biomedical applications

AbstractPolymer structures are essential in biomedical applications due to their biocompatibility, biodegradability, and ability to form intricate structures on micro‐ to nanometer scales. This review, emphasizing electrospinning and phase inversion techniques, examines the fabrication strategies and chemical design of polymer structures for biomedical use. Electrospinning, particularly needleless electrospinning, produces nanofibres with high porosity and flexibility and is widely applied in tissue engineering and drug delivery. Phase inversion, including thermal, nonsolvent‐, vapor‐ and evaporation‐induced phase separation, allows precise control over polymer properties but faces challenges in terms of cooling rates and solvent characteristics. Chemical design through doping, functionalization, cross‐linking and copolymerization enhances the biocompatibility, biodegradability and mechanical properties of polymers, facilitating advanced applications in drug delivery, tissue scaffolding and biosensors. Advanced functional polymers are revolutionizing biomedical fields, offering innovative solutions for therapeutic medicine delivery, disease detection, diagnostics, and regenerative medicine. Despite remarkable progress, challenges, such as scalability, cost‐effectiveness, and environmental impact, persist. This review underscores the transformative potential of advanced polymer materials in medical treatments and advocates for continuous research and interdisciplinary collaboration to overcome existing challenges and fully exploit the capabilities of these materials in improving patient care and medical outcomes. Future perspectives highlight enhancing precision control mechanisms, integrating phase inversion with other techniques and developing large‐scale production methods to advance the field further.

Non‐Fouling Multi‐Azide Polyoxazoline Brush‐co‐Polymers for Sensing Applications

Abstract One of the key parameters of an artificial biosensor is a high signal‐to‐noise ratio. This is achieved by limiting non‐specific interactions while simultaneously maximizing the targeted specific interaction. Here, it is combined non‐fouling characteristics of poly(2‐methyl‐2‐oxazoline) (PMOXA) coatings with an abundance of azide groups to create a multi‐azide containing poly(2‐methyl‐2‐oxazoline‐co‐2‐(3‐azidopropyl)‐2‐oxazoline) (PMCA) that can participate in bioorthogonal strain‐promoted azide‐alkyne cycloaddition (SPAAC) for functionalization. This functional polymer is made surface‐active using the PAcrAm™ technology to obtain well‐defined spontaneously adsorbed monolayers on gold surfaces. The resistance to non‐specific interactions is tested against full human serum (HS), analyzed via variable angle spectroscopic ellipsometry (VASE), and compared to equivalent coatings based on PMOXA and azido‐poly(ethylene glycol) (PEG‐N3). The specific interactions are investigated via VASE and quartz crystal microbalance with dissipation (QCM‐D) by immobilization of dibenzocyclooctyne‐PEG4‐biotin conjugate (DBCO‐biotin) and streptavidin. The new PMCA‐based coating shows superior resistance to non‐specific protein adhesion than equivalent coatings based on commercially available PEG‐N3 and significantly increases capacity for SPAAC. A proof of principle assay (biotin‐streptavidin/biotin‐BSA/anti‐BSA) shows improved binding for the new PMCA polymer compared with single azide PEG.

Long-Lived Charge Carrier Photogeneration in a Cooperative Supramolecular Double-Cable Polymer.

A newly designed C3-symmetric disc-shaped chromophore, BTT(NDI)3, features electron accepting naphthalene diimides linked to an electron donor BTT core. BTT(NDI)3 self-assembles in apolar solvents into highly ordered, chiral supramolecular fibers through π-π and 3-fold hydrogen-bonding interactions. This leads to a cooperative formation of plane-to-plane stacking of BTTs and J-aggregation of the outer NDIs. Such a structure ensures high charge mobility. Only photoexcitation of BTT in the BTT(NDI)3 polymers triggers a unidirectional electron transfer from BTT to NDI and results in (BTT•+-NDI•-) lifetimes that are by up to 3 orders of magnitude longer compared to (NDI•+-NDI•-) that is formed upon NDI photoexcitation. A multiphasic decay implies ambipolar pathways for charge carriers, that is, electron and hole delocalization along the respective BTT and NDI stacks. Our supramolecular approach offers potential for developing functional supramolecular polymers with continuous pathways for electrons and holes and, in turn, minimizing charge recombination losses in organic photovoltaic devices.

Polymer-Based Optical Guided-Wave Biomedical Sensing: From Principles to Applications

Polymer-based optical sensors represent a transformative advancement in biomedical diagnostics and monitoring due to their unique properties of flexibility, biocompatibility, and selective responsiveness. This review provides a comprehensive overview of polymer-based optical sensors, covering the fundamental operational principles, key insights of various polymer-based optical sensors, and the considerable impact of polymer integration on their functional capabilities. Primary attention is given to all-polymer optical fibers and polymer-coated optical fibers, emphasizing their significant role in “enabling” biomedical sensing applications. Unlike existing reviews focused on specific polymer types and optical sensor methods for biomedical use, this review highlights the substantial impact of polymers as functional materials and transducers in enhancing the performance and applicability of various biomedical optical sensing technologies. Various sensor configurations based on waveguides, luminescence, surface plasmon resonance, and diverse types of polymer optical fibers have been discussed, along with pertinent examples, in biomedical applications. This review highlights the use of biocompatible, hydrophilic, stimuli-responsive polymers and other such functional polymers that impart selectivity, sensitivity, and stability, improving interactions with biological parameters. Various fabrication techniques for polymer coatings are also explored, highlighting their advantages and disadvantages. Special emphasis is given to polymer-coated optical fiber sensors for biomedical catheters and guidewires. By synthesizing the latest research, this review aims to provide insights into polymer-based optical sensors’ current capabilities and future potential in improving diagnostic and therapeutic outcomes in the biomedical field.

Photoinduced Self-assembly: An Alternative Strategy for the Construction of Coordination Oligomers and Polymers.

Self-assembled oligonuclear and polynuclear complexes have numerous functionalities and potential applications. Generally, such compounds have been constructed by thermal substitution reactions with bridging ligands. Herein, we report bottom-up and photochemical construction of functional coordination oligomers and polymers by photosubstitution-induced self-assembly. The photosubstitution reactions of a ruthenium precursor complex with bridging ligands having pyrazole moieties afford mono-, di-, tri-, tetra-, and pentanuclear ruthenium complexes, Ru1-Ru5, which have one-dimensional architectures. Intramolecular hydrogen bonding between each bridging ligand is a key to construct the molecular nanowires. All the complexes have been isolated and thoroughly characterized. The photochemically synthesized ruthenium complexes act as synthons for longer metal-complex-based nanowires with a length of the order of tens-of nanometers. The multinuclear complexes are generated by photoinduced self-assembly in the presence of a base, and they undergo photoinduced disassembly in the presence of acid.

Structure, Properties, and Applications of Silica Nanoparticles: Recent Theoretical Modeling Advances, Challenges, and Future Directions.

Silica nanoparticles (SNPs), one of the most widely researched materials in modern science, are now commonly exploited in surface coatings, biomedicine, catalysis, and engineering of novel self-assembling materials. Theoretical approaches are invaluable to enhancing fundamental understanding of SNP properties and behavior. Tremendous research attention is dedicated to modeling silica structure, the silica-water interface, and functionalization of silica surfaces for tailored applications. In this review, the range of theoretical methodologies are discussed that have been employed to model bare silica and functionalized silica. The evolution of silica modeling approaches is detailed, including classical, quantum mechanical, and hybrid methods and highlight in particular the last decade of theoretical simulation advances. It is started with discussing investigations of bare silica systems, focusing on the fundamental interactions at the silica-water interface, following with a comprehensively review of the modeling studies that examine the interaction of silica with functional ligands, peptides, ions, surfactants, polymers, and carbonaceous species. The review is concluded with the perspective on existing challenges in the field and promising future directions that will further enhance the utility and importance of the theoretical approaches in guiding the rational design of SNPs for applications in engineering and biomedicine.

Sequence-sensitivity in functional synthetic polymer properties.

Recently, a new class of synthetic methyl methacrylate-based random heteropolymers (MMA-based RHPs) has displayed protein-like properties. Their function appears to be insensitive to the precise sequence. Here, through atomistic molecular dynamics simulation, we show that there are universal protein-like features of MMA-based RHPs that are insensitive to the sequence, and mostly depend on the overall composition. In particular, we find that MMA-based RHPs ``fold'' into globules with heterogeneous hydration patterns. However, the insensitivity to sequence identity observed in MMA-based RHPs dramatically changes when we substitute the backbone architecture with acrylate or replace the oxygen atom in the side chain with a nitrogen atom (methacrylamide or acrylamide). Using principal component analysis and an intersection-over-union based index, we demonstrate that different sequences may not overlap in the property space, meaning that their properties are controlled by the sequence rather than fixed composition. We further investigate the sequence-insensitive capability of the MMA-based RHPs as previously reported on bacterial phospholipase OmpLA stabilization through heterodimerization. As experimentally observed, such polymers enhance the stability of OmpLA as reliably as its native bilayer environment. The design of such MMA-based RHPs provides a sequence-insensitive alternative to protein-mimetic biomaterials that is orthogonal to the sequence-structure-function paradigm of proteins.

Sequence‐sensitivity in functional synthetic polymer properties

Recently, a new class of synthetic methyl methacrylate‐based random heteropolymers (MMA‐based RHPs) has displayed protein‐like properties. Their function appears to be insensitive to the precise sequence. Here, through atomistic molecular dynamics simulation, we show that there are universal protein‐like features of MMA‐based RHPs that are insensitive to the sequence, and mostly depend on the overall composition. In particular, we find that MMA‐based RHPs ``fold'' into globules with heterogeneous hydration patterns. However, the insensitivity to sequence identity observed in MMA‐based RHPs dramatically changes when we substitute the backbone architecture with acrylate or replace the oxygen atom in the side chain with a nitrogen atom (methacrylamide or acrylamide). Using principal component analysis and an intersection‐over‐union based index, we demonstrate that different sequences may not overlap in the property space, meaning that their properties are controlled by the sequence rather than fixed composition. We further investigate the sequence‐insensitive capability of the MMA‐based RHPs as previously reported on bacterial phospholipase OmpLA stabilization through heterodimerization. As experimentally observed, such polymers enhance the stability of OmpLA as reliably as its native bilayer environment. The design of such MMA‐based RHPs provides a sequence‐insensitive alternative to protein‐mimetic biomaterials that is orthogonal to the sequence‐structure‐function paradigm of proteins.

Development of functional polymer gel electrolytes and their application in next-generation lithium secondary batteries

Development of functional polymer gel electrolytes and their application in next-generation lithium secondary batteries

Synthesis of a perovskite surface-coated polymer brush by photo-induced atom transfer radical polymerization

Lead halide perovskite nanocrystals (PNCs) are expected to be applied in the field of optoelectronics due to their color tunability, high color purity, and near-unity photoluminescence quantum yields. Moreover, the construction of nanocomposite structures with functional polymers has been reported to improve the material stability as well as the ordered structure with high orientation and periodicity. In this study, we demonstrated the synthesis of polymethyl methacrylate (PMMA) on the PNCs by surface-initiated polymerization. We synthesized PMMA polymer brushes by photo-induced atom transfer radical polymerization (p-ATRP) after coordinating the initiator on the PNC surface. We succeeded in obtaining PMMA-PNCs with a degree of polymerization of 21. Moreover, thermal stability tests showed that PMMA-PNCs achieved improved thermal stability compared to pristine-PNCs. This work can provide guidance for developing polymer brush-PNCs via surface-initiated polymerization.

Self-Sustaining Triboelectric Nanosensors for Real-Time Urine Analysis in Smart Toilets.

Healthcare has undergone a revolutionary shift with the advent of smart technologies, and smart toilets (STs) are among the innovative inventions offering non-invasive continuous health monitoring. The present technical challenges toward this development include limited sensitivity of integrated sensors, poor stability, slow response and the requirement external energy supply alongside manual sample collection. In this article, triboelectric nanosensor array (TENSA) is introduced featuring electrodes crafted from laser-induced 3D graphene with functional polymers like polystyrene, polyimide, and polycaprolactone for real-time urine analysis while generating 50 volts output via urine droplet-based triboelectrification. Though modulating interfacial double-layer capacitance, these sensors exhibit exceptional sensitivity and selectivity in detecting a broad spectrum of urinary biomarkers, including ions, glucose, and urea with a classification precision of 95% and concentration identification accuracy of up to 0.97 (R2), supported by artificial neural networks. Upon exposure to urine samples containing elevated levels of Na+, K+, and NH4 +, a notable decrease (ranging from 32% to 68%) is observed in output voltages. Conversely, urea induces an increase up to 13%. Experimental validation confirms the stability, robustness, reliability, and reproducibility of TENSA, representing a significant advancement in healthcare technology, offering the potential for improved disease management and prevention strategies.

Fabrication of functionalized bio synthetic hydrogels using poly vinyl alcohol and Fucoidan

Abstract Background: Animal bodies are mostly made up of hydrogels, which are networks of hydrophilic polymers that have been permeated with water. These hydrogels make up the bulk of the cells and tissues in animals. Polyvinyl alcohol (PVA) hydrogels are of particular interest due to their various benefits such as biocompatibility, non-immunogenicity, and low biodegradability. Fucoidan is a sulfated polysaccharide molecule found in brown algae cell walls. They are nontoxic, non-irritating and bioactive. Rutin trihydrate is an antioxidant flavonoid and nitric oxide scavenger. The current study aimed to fabricate a functional biosynthetic polymer by combining fucoidan, PVA and Rutin trihydrate. This study also involves characterization and evaluation of antimicrobial activity of the obtained material. Commercial fucoidan(1g), PVA(0.5g) and Rutin (0.5g) was added to distilled water(50ml). The sample was kept in a magnetic stirrer for at 60°C,430 rpm for 30 min and dried in the hot air oven for 24hrs. The dried sample was studied by SEM and FTIR. Contact angle of the sample was also evaluated. Antimicrobial activity of the fabricated hydrogel was determined by agar diffusion method. The synthesized hydrogel is found to be hydrophilic in nature since the contact angle is 31.1°. The surface area of the synthesized hydrogel is found to be rough, irregular, porous and crystalline. Functional groups and compatibility between the polymers were determined by FTIR. Acceptable antimicrobial activity was demonstrated by the synthesized hydrogel against S.aureus and S.mutans (Zone of inhibition 12 mm and 12mm respectively). From the current study, it is concluded that the (Fucoidan- PVA) - Rutin, hydrogel fabricated is hydrophilic in nature and exhibits acceptable antimicrobial activity. Physical properties show that the hydrogel is suitable for drug delivery, tissue engineering and wound dressing.