Functional Polymers Research Articles

In Situ Synthesis and Assembly of Functional Materials and Devices in Living Systems.

ConspectusIntegrating functional materials and devices with living systems enables novel methods for recording, manipulating, or augmenting organisms not accessible by traditional chemical, optical, or genetic approaches. (The term "device" refers to the fundamental components of complex electronic systems, such as transistors, capacitors, conductors, and electrodes.) Typically, these advanced materials and devices are synthesized, either through chemical or physical reactions, outside the biological systems (ex situ) before they are integrated. This is due in part to the more limited repertoire of biocompatible chemical transformations available for assembling functional materials in vivo. Given that most of the assembled bulk materials are impermeable to cell membranes and cannot go through the blood-brain barrier (BBB), the external synthesis poses challenges when trying to interface these materials and devices with cells precisely and in a timely manner and at the micro- and nanoscale─a crucial requirement for modulating cellular functions. In contrast to presynthesis in a separate location, in situ assembly, wherein small molecules or building blocks are directly assembled into functional materials within a biological system at the desired site of action, has offered a potential solution for spatiotemporal and genetic control of material synthesis and assembly.In this Account, we highlight recent advances in spatially and temporally targeted functional material synthesis and assembly in living cells, tissues and animals and provide perspective on how they may enable novel probing, modulation, or augmentation of fundamental biology. We discuss several strategies, starting from the traditional nontargeted methods to targeted assembly of functional materials and devices based on the endogenous markers of the biological system. We then focus on genetically targeted assembly of functional materials, which employs enzymatic catalysis centers expressed in living systems to assemble functional materials in specific molecular-defined cell types. We introduce the recent efforts of our group to modulate membrane capacitance and neuron excitability using in situ synthesized electrically functional polymers in a genetically targetable manner. These advances demonstrate the promise of in situ synthesis and assembly of functional materials and devices, including the optogenetic polymerization developed by our lab, to interface with cells in a cellular- or subcellular-specific manner by incorporating genetic and/or optical control over material assembly. Finally, we discuss remaining challenges, areas for improvement, potential applications to other biological systems, and novel methods for the in situ synthesis of functional materials that could be elevated by incorporating genetic or material design strategies. As researchers expand the toolkit of biocompatible in situ functional material synthetic techniques, we anticipate that these advancements could potentially offer valuable tools for exploring biological systems and developing therapeutic solutions.

Fabrication of polydopamine-modified cellulose hydrogel for controlled release of α-mangostin.

Hydrogels are notable for their outstanding absorbent qualities, satisfactory compatibility with biological systems, ability to degrade, and inherent safety, all of which contribute to their high demand in the field of biomedicine. This study focuses on the fabrication of hydrogels using environmentally friendly cellulosic material. Cellulose hydrogel beads were prepared by physical cross-linking in a NaOH/urea medium. Furthermore, nano polydopamine was integrated into the hydrogel matrix as functional polymers and α-mangostin was employed as an active pharmaceutical ingredient. The physicochemical properties were comprehensively analyzed using Fourier-transform infrared spectrometer, 13C cross-polarization/magic angle spinning nuclear magnetic resonance, thermogravimetric analysis, and scanning electron microscope. The drug delivery properties, including water content, swelling ratio, and drug release profiles, were evaluated. In vitro cytotoxicity against MC3T3-E1 cells was assessed using sulforhodamine B staining. All test hydrogels exhibited inhibitory activity against the growth of MC3T3-E1 cells. These results indicated the potential use of these hydrogels as a drug delivery carrier for α-mangostin in the treatment of ankylosing spondylitis.

O/S Exchange Reaction in Synthesizing Sulfur-Containing Polymers.

Using carbon disulfide (CS2) and carbonyl sulfide (COS) as sulfur-containing and one-carbon feedstocks to make value-added products is paramount for both pure and applied chemistry and environmental science. One of the practical strategies is to copolymerize these bulk chemicals with epoxides to produce sulfur-containing polymers. This approach contributes to improving the sustainability of polymer manufacturing, provides highly desired functional polymer materials, and has attracted much attention. However, these copolymerizations invariably exhibit the intensely complicated chemistry of O/S exchange reaction, leading to sulfur-containing polymers with diverse architectures. As the understanding of O/S exchange continues to deepen, recent efforts have guided significant advances in the synthesis of CS2- and COS-based polymers. This review examines the O/S exchange chemistry and summarizes the recent progress in this field to promote the further advance of synthesizing sulfur-containing polymers from CS2 and COS.

Cardiac Troponin I-Responsive Nanocomposite Materials for Voltammetric Monitoring of Acute Myocardial Infarction.

Acute myocardial infarction (AMI) is a severe cardiovascular disease characterized by heart muscle damage due to inadequate blood supply, leading to a life-threatening risk of heart attack. Herein, we report on the design of polyaminophenol-based thin film functional polymers and their thorough optimization by electrochemical, spectroscopic, and microscopic techniques to develop a high-performance point-of-care voltammetric monitoring system. Molecularly imprinted polymer-based cTnI-responsive nanocomposite materials were prepared on an electrode surface by imprinting a specific cTnI epitope, integrating polyaminophenol electrodeposition, along with gold nanoparticles (AuNPs) and graphene quantum dots (GQDs). The characterization techniques, including cyclic and square wave voltammetries, electrochemical impedance spectroscopy, atomic force microscopy, fluorescence microscopy, attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), and contact angle measurements proved the efficient fabrication of the voltammetric monitoring system relying on cTnI-responsive functional thin films. The sensing platform prepared with the optimized nanocomposite composition of AuNPs, GQDs, and molecularly imprinted polymers exhibited very high sensitivity, reproducibility, specificity, and affinity toward cTnI. The sensor showed a storage stability of 30 days, demonstrating great potential for use in early and point-of-care diagnosis of AMI with its 18 min detection time.

Nanomaterial-Based Sensors for Coumarin Detection.

Sensors are widely used owing to their advantages including excellent sensing performance, user-friendliness, portability, rapid response, high sensitivity, and specificity. Sensor technologies have been expanded rapidly in recent years to offer many applications in medicine, pharmaceuticals, the environment, food safety, and national security. Various nanomaterial-based sensors have been developed for their exciting features, such as a powerful absorption band in the visible region, excellent electrical conductivity, and good mechanical properties. Natural and synthetic coumarin derivatives are attracting attention in the development of functional polymers and polymeric networks for their unique biological, optical, and photochemical properties. They are the most abundant organic molecules in medicine because of their biological and pharmacological impacts. Furthermore, coumarin derivatives can modulate signaling pathways that affect various cellular processes. This review covers the discovery of coumarins and their derivatives, the integration of nanomaterial-based sensors, and recent advances in nanomaterial-based sensing for coumarins. This review also explains how sensors work, their types, their pros and cons, and sensor studies for coumarin detection in recent years.

Intrinsically Safe Lithium Metal Batteries Enabled by Thermo-Electrochemical Compatible In Situ Polymerized Solid-State Electrolytes.

In situ polymerized solid-state electrolytes have attracted much attention due to high Li-ion conductivity, conformal interface contact, and low interface resistance, but are plagued by lithium dendrite, interface degradation, and inferior thermal stability, which thereby leads to limited lifespan and severe safety hazards for high-energy lithium metal batteries (LMBs). Herein, an in situ polymerized electrolyte is proposed by copolymerization of 1,3-dioxolane with 1,3,5-tri glycidyl isocyanurate (TGIC) as a cross-linking agent, which realizes a synergy of battery thermal safety and interface compatibility with Li anode. Functional TGIC enhances the electrolyte polymeric level. The unique carbon-formation mechanism facilitates flame retardancy and eliminates the battery fire risk. In the meantime, TGIC-derived inorganic-rich interphase inhibits interface side reactions and promotes uniform Li plating. Intrinsically safe LMBs with nonflammability and outstanding electrochemical performances under extreme temperatures (130°C) are achieved. This functional polymer design shows a promising prospect for the development of safe LMBs.

Special Issue: Functional Polymer Materials

Special Issue: Functional Polymer Materials

Bis(imino)pyridyliron incorporated with NO2, F and benzhydryl substituents as thermostable precatalysts for vinyl-terminated polyethylenes

The electronic and steric properties of ligands are of great importance in late transition metal catalyst mediated ethylene polymerization to tune the catalytic performance. In this contribution, strong electron-withdrawing groups—fluoro and nitro—along with benzhydryl as a steric component, were incorporated into the parent bis(imino)pyridine ligand structure to prepare a series of iron (II) chloride complexes: 2-[MeC=N{2-(Ph2CH)-4-NO2-6-F}C6H2]-6-[MeC=N(Ar)C6H2]C5H3N–FeCl2 (Ar = 2,6-Me2C6H3Fe2Me, 2,6-Et2C6H3Fe2Et, 2,6-iPr2C6H3Fe2iPr, 2,4,6-Me3C6H2Fe3Me and 2,6-Et2-4-MeC6H2Fe2Et,Me). Apart from the structural characterization of all complexes executed via FTIR and elemental analysis, X-ray diffraction analysis unveiled distorted square pyramidal geometry for Fe2Me (τ5 = 0.21) and Fe2Et (τ5 = 0.28). Upon in situ activation with either MAO or MMAO cocatalysts, all iron complexes displayed distinguished polymerization performance, especially in terms of thermo-stability. In particular, the less hindered Fe2Me exhibited high activity: 20.4 × 106 g mol−1 h−1 at 70 °C, 1.5 × 106 g mol−1 h−1 at 110 °C, and 0.6 × 106 g mol−1 h−1 at 120 °C. Whereas, the sterically more hindered Fe2iPr proved to be more productive in generating high molecular weight polyethylene (Mw up to 410.7 kg mol−1 at 70 °C). Moreover, by adjusting the reaction temperature and ligand structure, the chain termination reaction could be modulated from a high proportion of vinyl-terminated polyethylene to saturated polyethylene rich product [CH2CH(CH2)nCH3/CH3(CH2)nCH3 = 0.7/0.3–0.39/0.61], as confirmed by high-temperature 1H/13C NMR spectra. Low molecular weight vinyl-terminated polyethylenes are of significant importance in the synthesis of functional polymers and can serve as valuable additives in lubricants.

Insights into the silica scaling behaviors in membrane distillation and anti-scaling mechanism of functional polymers

Silica scaling imposes a significant limitation on the efficacy of membrane distillation (MD) in the treatment of hypersaline wastewater. The complex dynamic behaviors of silica at the membrane-water-air interface and the poor understanding of molecular-level anti-scaling mechanism hampers the development of effective antiscalants for mitigating silica scaling in MD. Despite using functional polymers to prevent silica polymerization, the inhibition mechanisms are unclear. Here, the kinetic process of silica scaling during MD and the potential anti-scaling mechanism of poly-ethylenimine (PEI) were investigated at the molecular level via molecular dynamics simulations. The investigation reveals that silica scales were more likely to adhere to the water-PTFE interface with a free energy potential well of -40.0 kJ mol−1 than that of the water-air interface with a -11.4 kJ mol−1 potential well. Silica scales falling at the water-air interface also migrated on the water-air interface until captured by the PTFE membrane. In this work, a representative functional amino-rich polymer PEI was constructed as silica inhibitors and its scale inhibition mechanism was elucidated. Notably, the inclusion of PEI increased the free-energy barriers for the silica polymerization reaction from 72.0 kJ mol−1 to 86.1 kJ mol−1, compared to scenarios without the antiscalants. Moreover, quantitative structure-activity relationships (QSAR) model of ΔGwater−silica was developed to predict the anti-scaling efficiencies of typical antiscalants based on machine learning method. These findings provide valuable insights into enhancing the efficiency of silica scaling mitigation strategies.

Group transfer polymerization of polar conjugated monomers using pinacolborane and thiourea anions

AbstractGroup transfer polymerization (GTP) plays a crucial role in polymerizing (methyl) acrylate. The utilization of cheap and easily synthesized thiourea anion (TUA) combined with pinacolborane (HBpin) undergoes controlled GTPs of methyl methacrylate (MMA), methacrylate (MA), and α‐methylenebutyrolactone (MBL) at ambient temperature. The mechanistic study reveals that the TUA′‐1 having ‐NEt2 moiety works out as a cocatalyst to assist HBpin undergoes the 1,4‐hydroboration reaction with α, β‐unsaturated acrylates to in situ generate a boron enolate (boryl ketene acetal [BKA]). Different from typical GTP, in which silyl ketene acetal (SKA) is used as an initiator, this work shows that BKA could act as an initiator with the assistance of the cocatalyst TUA′‐1 to generate the polymer. The chain end groups of the obtained polymer are characterized by MALDI‐TOF‐MS, indicating one of the chain ends features a hydride from the HBpin and another chain end has a linear or back‐biting cyclic structure. Moreover, the polymerization process is strongly supported by density functional theory (DFT) calculations. The application of BKA expands the research area of GTP reactions. The tunable and structural properties of TUA/hydroboranes significantly broaden the types of initiators in the GTP and pave a new methodology to achieve functional polymers.

Density Function Theory Study on the Energy and Circular Dichroism Spectrum for Methylene-Linked Triazole Diads Depending on the Substitution Position and Conformation.

Since the discovery of metal-catalyzed azide-alkyne cycloadditions, 1,2,3-triazoles have been widely used as linkers for various residues. 1,2,3-Triazole is an aromatic five-membered cyclic compound consisting of three nitrogen and two carbon atoms with large dipoles that absorb UV light. In the past decade, we have been working on the synthesis of dense triazole polymers possessing many 1,2,3-triazole residues linked through a carbon atom in their backbone as a new type of functional polymer. Recently, we reported that stereoregular dense triazole uniform oligomers exhibit a circular dichroism signal based on the chiral arrangement of two neighboring 1,2,3-triazole residues. In this study, to investigate the chiral conformation of two neighboring 1,2,3-triazole residues in stereoregular dense triazole uniform oligomers, density functional theory (DFT) calculations were performed using 1,2,3-triazole diads with different substitution positions and conformations as model compounds and compared with our previous results.

Functional Technical Textile-Based Polymer Nanocomposites with Adsorbent Properties of Toxins and Dyes also Have Antibacterial Behavior.

This is the first study of non-woven fabrics elaborated by melt-blowing from polymer nanocomposites made of Nylon 6 and nanoclay (Cloisite 20A) modified with an amine (1,4 diaminobutane dihydrochloride). Morphological and physical characteristics, adsorption capacity, and antibacterial properties are presented. From the X-ray diffraction (XRD) results, it was possible to observe a displacement of the signals to other 2θ angles, due to an α to ϒ phase shift. The scanning electron microscopy (SEM) images showed that the mean diameter of fiber decreased as the content of nanoclay increased. The mechanical tests showed that the tear strength force of neat nylon was 1.734 N, but this characteristic increased to 2.135 N for the sample with 0.5% modified nanoclay. The inulin adsorption efficiency of the Nylon 6/C20A 1.5% and Nylon 6/C20A 2% samples at 15 min was 75 and 74%, respectively. The adsorption capacity of Nylon 6/C20A 1.5% and Nylon 6/C20A 2% for methylene blue and methyl orange remained above 90% even after four adsorption cycles. In addition, non-woven fabrics present antibacterial activity against E. coli.

Mussel-inspired polydopamine modified mica with enhanced mechanical strength and thermal performance of poly(lactic acid) coating

Polylactic acid (PLA), as a green functional polymer, has been useful in various coating applications. However, due to the low mechanical strength and thermal stability of PLA, it needs to be improved in order to expand its application areas. In this work, a series of polylactic acid (PLA) nanocomposite films were prepared through introducing polydopamine-modified mica (PDA@MICA) as a self-assemble nanofiller to enhance its mechanical and thermal properties. The results demonstrated that PLA/PDA@MICA shows excellent mechanical properties. Tensile tests showed that PLA/PDA@MICA exhibits a 58.3 % increase in tensile strength and a 16.8 % increase in Young's modulus compared to pure PLA. Meanwhile, thermal performance testing shown the introduction of PDA@MICA led to an increase in crystallinities (Xc = 24.78 %). And the thermal decomposition temperature of PLA/PDA@MICA film (374 °C) was slightly higher than that of PLA film (367 °C). The simultaneous improvement of the mechanical and thermal properties was attributed to the formation of hydrogen bonds between PLA and PDA@MICA. In addition, the parallel arrangement of PDA@MICA and PLA macromolecular chains forms a unique “brick and mortar” structure in the coating, which enhances the mechanical properties of PLA/PDA@MICA composite coatings. This study reports a successful approach to simultaneously address the drawbacks of PLA, specifically its low thermal stability and mechanical strength, thereby promoting its widespread application in the coatings industry.

Poly(2-isopropenyl-2-oxazoline) as a Versatile Functional Polymer for Biomedical Applications.

Functional polymers play an important role in various biomedical applications. From many choices, poly(2-isopropenyl-2-oxazoline) (PIPOx) represents a promising reactive polymer with great potential in various biomedical applications. PIPOx, with pendant reactive 2-oxazoline groups, can be readily prepared in a controllable manner via several controlled/living polymerization methods, such as living anionic polymerization, atom transfer radical polymerization (ATRP), reversible addition-fragmentation transfer (RAFT) or rare earth metal-mediated group transfer polymerization. The reactivity of pendant 2-oxazoline allows selective reactions with thiol and carboxylic group-containing compounds without the presence of any catalyst. Moreover, PIPOx has been demonstrated to be a non-cytotoxic polymer with immunomodulative properties. Post-polymerization functionalization of PIPOx has been used for the preparation of thermosensitive or cationic polymers, drug conjugates, hydrogels, brush-like materials, and polymer coatings available for drug and gene delivery, tissue engineering, blood-like materials, antimicrobial materials, and many others. This mini-review covers new achievements in PIPOx synthesis, reactivity, and use in biomedical applications.

Cobalt-Catalyzed Cascade C-H Activation/Annulation Polymerizations toward Diversified and Multifunctional Sulfur-Containing Fused Heterocyclic Polymers.

Transition-metal-catalyzed C-H activation has greatly benefited the synthesis and development of functional polymer materials, and the construction of multifunctional fused (hetero)cyclic polymers via novel C-H activation-based polyannulations has emerged as a charming but challenging area in recent years. Herein, we report the first cobalt(III)-catalyzed cascade C-H activation/annulation polymerization (CAAP) approach that can efficiently transform readily available aryl thioamides and internal diynes into multifunctional sulfur-containing fused heterocyclic (SFH) polymers. Within merely 3 h, a series of SFH polymers bearing complex and multisubstituted S,N-doped polycyclic units are facilely and efficiently produced with high molecular weights (absolute Mn up to 220400) in excellent yields (up to 99%), which are hard to achieve by traditional methods. The intermediate-terminated SFH polymer can be used as a reactive macromonomer to controllably extend or modify polymer main chains. The structural diversity can be further enriched through facile S-oxidation and N-methylation reactions of the SFH polymers. Benefiting from the unique structures, the obtained polymers exhibit excellent solution processability, high thermal and morphological stability, efficient and readily tunable aggregate-state fluorescence, stimuli-responsive properties, and high and UV-modulatable refractive indices of up to 1.8464 at 632.8 nm. These properties allow the SFH polymers to be potentially applied in diverse fields, including metal ion detection, photodynamic killing of cancer cells, fluorescent photopatterning, and gradient-index optical materials.

Recyclable Alloy Nanocatalyst-Mediated Photo-Controlled Synthesis of Functional Polymers for Toxic Metal and Dye Removal

Recyclable Alloy Nanocatalyst-Mediated Photo-Controlled Synthesis of Functional Polymers for Toxic Metal and Dye Removal

Anthranilic Acid: A Versatile Monomer for the Design of Functional Conducting Polymer Composites

Polyaniline has been utilized in various applications, yet its widespread adoption has often been impeded by challenges. Composite systems have been proposed as a means of mitigating some of these limitations, and anthranilic acid (2-aminobenzoic acid) has emerged as a possible moderator for use in co-polymer systems. It offers improved solubility and retention of electroactivity in neutral and alkaline media, and, significantly, it can also bestow chemical functionality through its carboxylic acid substituent, which can greatly ease post-polymer modification. The benefits of using anthranilic acid (as a homopolymer or copolymer) have been demonstrated in applications including corrosion protection, memory devices, photovoltaics, and biosensors. Moreover, this polymer has been used as a versatile framework for the sequestration of metal ions for water treatment, and, critically, these same mechanisms serve as a facile route for the production of catalytic metallic nanoparticles. However, the widespread adoption of polyanthranilic acid has been limited, and the aim of the present narrative review is to revisit the early promise of anthranilic acid and assess its potential future use within modern smart materials. A critical evaluation of its properties is presented, and its versatility as both a monomer and a polymer across a spectrum of applications is highlighted.

Recent Advances in Biomedical Nanotechnology Related to Natural Products.

Natural product processing via nanotechnology has opened the door to innovative and significant applications in medical fields. On one hand, plants-derived bioactive ingredients such as phenols, pentacyclic triterpenes and flavonoids exhibit significant pharmacological activities, on another hand, most of them are hydrophobic in nature, posing challenges to their use. To overcome this issue, nanoencapsulation technology is employed to encapsulate these lipophilic compounds and enhance their bioavailability. In this regard, various nano-sized vehicles, including degradable functional polymer organic compounds, mesoporous silicon or carbon materials, offer superior stability and retention for bioactive ingredients against decomposition and loss during delivery as well as sustained release. On the other hand, some naturally occurring polymers, lipids and even microorganisms, which constitute a significant portion of Earth's biomass, show promising potential for biomedical applications as well. Through nano-processing, these natural products can be developed into nano-delivery systems with desirable characteristics for encapsulation a wide range of bioactive components and therapeutic agents, facilitating in vivo drug transport. Beyond the presentation of the most recent nanoencapsulation and nano-processing advancements with formulations mainly based on natural products, this review emphasizes the importance of their physicochemical properties at the nanoscale and their potential in disease therapy.

Advances in 3D printing for polymer composites: A review

AbstractThe potential of three‐dimensional (3D) printing technology in the fabrication of advanced polymer composites is becoming increasingly evident. This review discusses the latest research developments and applications of 3D printing in polymer composites. First, it focuses on the optimization of 3D printing technology, that is, by upgrading the equipment or components or adjusting the printing parameters, to make them more adaptable to the processing characteristics of polymer composites and to improve the comprehensive performance of the products. Second, it focuses on the 3D printable novel consumables for polymer composites, which mainly include the new printing filaments, printing inks, photosensitive resins, and printing powders, introducing the unique properties of the new consumables and different ways to apply them to 3D printing. Finally, the applications of 3D printing technology in the preparation of functional polymer composites (such as thermal conductivity, electromagnetic interference shielding, biomedicine, self‐healing, and environmental responsiveness) are explored, with a focus on the distribution of the functional fillers and the influence of the topological shapes on the properties and functional characteristics of the 3D printed products. The aim of this review is to deepen the understanding of the convergence between 3D printing technology and polymer composites and to anticipate future trends and applications.image

Molding Process Retaining Gold Nanoparticle Assembly Structures during Transfer to a Polycarbonate Surface.

The immobilization of gold nanoparticle (AuNP) linear surface assemblies on polycarbonate (PC) melt surface via molding is investigated. The order of the particle assemblies is preserved during the molding process. The assemblies on PC exhibit plasmonic coupling features and dichroic properties. The structure of the assemblies is quantified based on Scanning Electron Microscopy (SEM) and image analysis data using an orientational order parameter. The transfer process from mold to melt shows high structural fidelity. The order parameter of around 0.98 reflects the orientation of the lines and remains unaffected, independent of the injection direction of the melt relative to the particle lines. This is discussed in the frame of fountain flow during injection molding. The particles were permanently fixed and withstood the injection molding process, detachment of the substrate, and extraction in boiling ethanol. The plasmonic particles coupled strongly within the dense nanoparticle lines to produce anisotropic optical properties, as quantified by dichroic ratios of 0.28 and 0.52 using ultraviolet-visible-near-infrared (UV-Vis-NIR) spectroscopy. AuNP line assemblies on a polymer surface may be a basis for plasmonic devices like surface-enhanced Raman scattering (SERS) sensors or a precursor for nanowires. Their embedding via injection molding constitutes an important link between particle-self-assembly approaches for optically functional surfaces and polymer processing techniques.