Radical Polymerization Reaction Research Articles

Two approaches to prepare cationic lignin‐based adsorbents for efficient removal of phosphate ion from wastewater

AbstractIn this work, two types of cationic lignin‐based adsorbents (AL‐METAC and AL‐GTA) were prepared through free radical polymerization or etherification reaction of alkali lignin with 2,3‐epoxypropyl‐3‐trimethylammonium chloride or methylacrylloxyethyl trimethyl ammonium chloride (METAC). The contents of quaternary ammonium groups in the adsorbents were adjusted by changing the dosages of 2,3‐epoxypropyl‐3‐trimethylammonium chloride and METAC to fabricate the adsorbents with excellent adsorption capacity. The structures, aqueous solubility, and physical properties of adsorbents were analyzed. Meanwhile, the effects of adsorbents dosage, pH value of solution, temperature, and ionic strength on the adsorption capacity of adsorbents were also analyzed. These two types of adsorbents exhibited outstanding affinity for phosphate, with a maximum removal efficiency of 51.8 and 73.2 mg/g, respectively. The adsorption processes followed pseudo‐second‐order and Langmuir models well. In addition, the AL‐GTA exhibited higher removal efficiency than AL‐METAC. Moreover, the AL‐METAC and AL‐GTA still retained 69.7% and 69.0% adsorption capacity after four times regeneration. The fabricated lignin‐based adsorbents have potential applications in the removal of phosphate from wastewater, which would promote the high‐value application of lignin.

Directional self-assembly of octavinyl polyhedral oligomeric silsesquioxane on the surface of melamine sponge: Establishing hydrophobic surfaces to improve oil–water separation performance

The continuous increase in industrial organic pollutants has seriously contaminated the natural environment, posing a threat to natural ecosystems and human survival. The preparation of hydrophobic materials with corrosion resistance is crucial for the efficient treatment of emulsified oil–water mixtures in industrial wastewater.Octavinyl polyhedral oligomeric silsesquioxane-coated melamine foam (OV-POSS@MF), possessing hydrophobic properties, was synthesized through a two-step process: initially, a sulfhydryl layer was built up on the surface of the melamine foam, followed by the subsequent assembly of octavinyl POSS onto the melamine foam’s surface via a free radical polymerization reaction between sulfhydryl groups and vinyl moieties. OV-POSS@MF achieves a static water contact angle of 141°, demonstrating its pronounced hydrophobic nature. Moreover, the corrosion resistance, adsorption capacity, oil–water separation efficiency, deformation resistance, and flame retardancy of OV-POSS@MF were thoroughly examined. The results indicate that OV-POSS@MF exhibits strong corrosion resistance and maintains good hydrophobicity even after prolonged exposure to highly acidic and alkaline conditions. Notably, OV-POSS@MF possesses the capability to efficiently and rapidly separate emulsified oil–water mixtures. Furthermore, it retains excellent hydrophobicity even after undergoing up to 100 consecutive compressions or distortions, highlighting its remarkable mechanical resilience. Additionally, OV-POSS@MF demonstrates superior flame retardant properties compared to unmodified melamine foam (MF).

Fabrication of dextran-grafted magnetic polymer microspheres with low nonspecific protein adsorption as carriers for chemiluminescence immunoassays

Inhibiting the nonspecific protein adsorption on the surface of magnetic microspheres has become a pressing challenge for immunoassays. In this paper, a novel dextran-modified sandwich-type magnetic polymer microsphere was developed and demonstrated to be a promising carrier for chemiluminescence immunoassay (CLIA). Dextran-modified sandwich-type magnetic polymer microspheres (PFS-PGDN) were synthesized by surface-initiated atom transfer radical polymerization (SI-ATRP) and ring-opening reaction of epoxy and aminodextran on the surface of magnetic P(GMA-MMA)-NH2@Fe3O4@SiO2 (PFS) microspheres. Then, carboxylated dextran-modified sandwich-type magnetic polymer microspheres (PFS-PGDC) were prepared by the surface carboxylation of the microspheres, which allowed the prepared microspheres to better couple with nucleic acids or antibodies. It is found that after grafting dextran, magnetic PFS-PGDC microspheres could significantly reduce the nonspecific protein adsorption by over 90 %. The chemiluminescence immunoassay assay showed a reduction of the background value to a very low level, indicating that the magnetic spheres showed significant advantages in improving the sensitivity of the chemiluminescence assay. Moreover, the chemiluminescence sensitivity and signal values of the synthesized magnetic microspheres have reached high levels. Therefore, the magnetic microspheres synthesized here hold great promise for applications in the field of CLIA.

Precise Regulation in Chain-Edge Structural Microenvironments of 1D Covalent Organic Frameworks for Photocatalysis.

Covalent organic frameworks (COFs) constitute a promising research topic for photocatalytic reactions, but the rules and conformational relationships of 1D COFs are poorly defined. Herein, the chain edge structure is designed by precise modulation at the atomic level, and the 1D COFs bonded by C, O, and S elements is directionally prepared for oxygen-tolerant photoinduced electron transfer-atom transfer radical polymerization (PET-ATRP) reactions. It is demonstrated that heteroatom-type chain edge structures (─O─, ─S─) lead to a decrease in intra-plane conjugation, which restricts the effective transport of photogenerated electrons along the direction of the 1D strip. In contrast, the all-carbon type chain edge structure (─C─) with higher intra-plane conjugation not only reduces the energy loss of photoexcited electrons but also enhances the carrier density, which exhibits the optimal photopolymerization performance. This work offers valuable guidance in the exploitation of 1D COFs for high photocatalytic performance. This work offers valuable guidance in the exploitation of 1D COFs for high photocatalytic performance.

Effect of rheological behaviors of polyacrylonitrile grafted sericin solution on film structure and mechanical properties

Sericin protein possesses excellent biocompatibility, antioxidation, and processability. Nevertheless, manufacturing large quantities of strong and tough pure regenerated sericin materials remains a significant challenge. Herein, we design a lightweight structural sericin film with high ductility by combining radical chain polymerization reaction and liquid-solid phase inversion method. The resulting polyacrylonitrile grafted sericin films exhibit the ability to switch between high strength and high toughness effortlessly, the maximum tensile strength and Young's modulus values are 21.92 ± 1.51 MPa and 8.14 ± 0.09 MPa, respectively, while the elongation at break and toughness reaches up to 344.10 ± 35.40 % and 10.84 ± 1.02 MJ·m−3, respectively. Our findings suggest that incorporating sericin into regenerated films contributes to the transformation of their mechanical properties through influencing the entanglement of molecular chains within polymerized solutions. Structural analyses conducted using infrared spectroscopy and X-ray diffraction confirm that sericin modulates the mechanical properties by affecting the transition of condensed matter conformation. This work presents a convenient yet effective strategy for simultaneously addressing the recycling of sericin as well as producing regenerated protein-based films that hold potential applications in biomedical, wearable, or food packaging.

Wood consolidation through an epoxy‐acrylic gamma‐crosslinked three‐dimensional system

AbstractEmerging technologies based on polymeric materials are progressively developed in order to preserve and consolidate cultural heritage artifacts. In this study, we aimed to obtain a hybrid polymer reliant on two types of thermosets that undergo irreversible crosslinking via ionizing radiation‐induced polymerization, the polymer's structure and characteristics being tailored using specific dose rates, doses, linear energy transfer and monomers ratio, in order to achieve the established performance requirements. Here, we demonstrate a covalently bonded 3D hybrid diepoxy‐triacrylic polymer that is chemically and dimensionally stable, intending to use it as a consolidant of highly degraded wooden artifacts in order to mitigate oxygen inhibition from radical chain reactions, to increase chemical and thermal stability, as well as to obtain a stiffer consolidated artifact, therefore more resistant to deformation. Various types of analytical techniques such as Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy, Mass Spectrometry or Thermal analysis were performed in order to support our strategy and predictions regarding the synergistic effect given by gamma irradiation‐driven crosslinking through simultaneous cationic and radical chain growth polymerization reaction mechanisms. We achieved a homogenous polymeric formulation and wood‐polymer composite materials with high modulus of elasticity, therefore providing up to a twofold increase in Young's modulus in the consolidated wood, a good chemical resistance to various solvents and outstanding thermal resistance up to 381°C. Consequently, the consolidation methodology, as well as mechanical testing, analytical and morphological characterization of the resulted composite will be discussed. Apart from consolidating cultural heritage wooden artifacts, this synthetic route and impregnation methodology provide opportunities for wood‐polymer composites in a wealth of applications as reinforced wood‐based materials.

Improved Approach for ab Initio Calculations of Rate Coefficients for Secondary Reactions in Acrylate Free-Radical Polymerization.

Secondary reactions in radical polymerization pose a challenge when creating kinetic models for predicting polymer structures. Despite the high impact of these reactions in the polymer structure, their effects are difficult to isolate and measure to produce kinetic data. To this end, we used solvation-corrected M06-2X/6-311+G(d,p) ab initio calculations to predict a complete and consistent data set of intrinsic rate coefficients of the secondary reactions in acrylate radical polymerization, including backbiting, β-scission, radical migration, macromonomer propagation, mid-chain radical propagation, chain transfer to monomer and chain transfer to polymer. Two new approaches towards computationally predicting rate coefficients for secondary reactions are proposed: (i) explicit accounting for all possible enantiomers for reactions involving optically active centers; (ii) imposing reduced flexibility if the reaction center is in the middle of the polymer chain. The accuracy and reliability of the ab initio predictions were benchmarked against experimental data via kinetic Monte Carlo simulations under three sufficiently different experimental conditions: a high-frequency modulated polymerization process in the transient regime, a low-frequency modulated process in the sliding regime at both low and high temperatures and a degradation process in the absence of free monomers. The complete and consistent ab initio data set compiled in this work predicts a good agreement when benchmarked via kMC simulations against experimental data, which is a technique never used before for computational chemistry. The simulation results show that these two newly proposed approaches are promising for bridging the gap between experimental and computational chemistry methods in polymer reaction engineering.

In vitro and in vivo assessment of gallic acid-chitosan/polycaprolactone conjugate electrospun nanofibers for wound healing

The development of innovative multifunctional wound healing materials based on natural bioactives has attracted a great deal of attention in recent years due to their ability to potentiate the healing process and minimize the challenges linked with conventional wound dressings. The current study demonstrates the development and evaluation of a novel nanofibrous wound healing mat made of Gallic acid-chitosan conjugate (GAC) incorporated within a polycaprolactone (PCL) matrix using an electrospinning technique. The GAC conjugate was synthesized by green synthesis using a free radical polymerization reaction to improve the chitosan's free radical scavenging properties. FTIR, DSC, XRD, and UV spectral analysis characterized the formation of GAC conjugate. The red shift observed in the UV spectrum suggested alterations in electronic transitions resulting from the creation of covalent bonds between Chitosan (CA) and Gallic acid (GA). The appearance of broader and weaker peaks in DSC and the reduced crystallinity in XRD spectrum, signify structural modifications, thereby providing valuable insights into the interaction and structural changes occurring in the GAC conjugates.The SEM image revealed a porous flake-like structural network of GAC conjugate due to the reduced intermolecular hydrogen bonding between them. The functional layer of the nanofibrous mat was produced by electrospinning GAC conjugate with polycaprolactone (PCL) to provide mechanical integrity to the nanofibrous mat. The electrospun nanofibers were characterized using FTIR, DSC, and SEM and evaluated for cell cytotoxicity, angiogenesis, and in vivo wound healing potential in female Wistar rats. The FTIR spectra confirmed the presence of GAC conjugate in the nanofibers, validating the conjugation process. The results demonstrated the successful incorporation of GAC conjugate within the PCL nanofibrous mat, thereby confirming the improvement in the biological properties of the mats. The nanofibrous mat showed angiogenesis activity in the yolk sac membrane assay confirming the property of nanofibers to facilitate cellular adhesion, migration and promotion of angiogenesis with no cytotoxic effect on the viability of mouse stromal cells. On the sixteenth day of therapy, wounds dressed with GAC/PCL nanofibrous mat exhibited a significant improvement in the percent wound closure (94.43%) as compared to the control group (p < 0.05). These results supported the application of GAC/PCL as a novel biomaterial for wound dressing to accelerate the process of wound healing.

Synthesis of thermo-responsive polymer gels composed of star-shaped block copolymers by copper-catalyzed living radical polymerization and click reaction

ABSTRACT In recent times, there has been a significant surge in research interest surrounding thermo-responsive water-soluble polyacrylamides, primarily due to their intriguing capability to undergo significant solubility changes in water. These polymers exhibit the remarkable ability to shift from a soluble to an insoluble state in response to temperature variations. The capacity of these polymers to dynamically respond to temperature changes opens up exciting avenues for designing smart materials with tunable properties, amplifying their utility across a spectrum of scientific and technological applications. Researchers have been particularly captivated by the potential applications of thermo-responsive water-soluble polyacrylamides in diverse fields such as drug delivery, gene carriers, tissue engineering, sensors, catalysis, and chromatography separation. This study reports the construction and functionalization of polymer gels consisting of a polymer network of polyacrylamide derivatives with nano-sized structural units. Specifically, thermo-responsive polymer gels were synthesized by combining well-defined star-shaped polymers composed of polyacrylamide derivatives with a multifunctional initiator and linking method through a self-accelerating click reaction. The polymerization system employed a highly living approach, resulting in polymer chains characterized by narrow molecular weight distributions. The method’s high functionality facilitated the synthesis of a temperature-responsive block copolymer gel composed of N-isopropyl acrylamide (NIPA) and N-ethyl acrylamide (NEAA). The resulting polymer gel, comprising star-shaped block copolymers of NIPA and NEAA, showcases smooth volume changes with temperature jumps.

Cellulose nanocrystal stabilized copper nanoparticles for grafting phase change materials with high thermal conductivity

Phase change materials (PCMs) have recently garnered significant attention for thermal energy storage applications. However, widely used PCMs, such as polyethylene glycol (PEG), suffer from low heat conductivity, poor thermal stability, and a tendency to leak, limiting their practical use. Therefore, the objective of this study is to develop a highly thermally conductive composite PCM using PEG and a thermally conductive nanomaterial, specifically cellulose nanocrystals supported by copper nanoparticles (CNC@Cu-NPs). The CNC@Cu-NPs nanocomposite material was used as a matrix to support polyethylene glycol (PEG), resulting in a shape-stable phase change material termed PEG/CNC@Cu-NPs. The obtained PEG/CNC@Cu-NPs were characterized using various analytical techniques. Fourier transform infrared spectroscopy (FTIR) analysis revealed the chemical linkages between PEG and cellulose nanocrystals through a radical polymerization reaction. Polarizing optical microscopy (POM) images of PEG/CNC@Cu-NPs exhibited spherocrystal morphology with smaller sizes compared to pure PEG, suggesting that CNC inhibited PEG side-chain mobility. According to differential scanning calorimetry, the suggested PEG/CNC@Cu-NPs demonstrated a temperature transition between 0.51 °C to 24.5 °C with enthalpies of fusion and crystallization measured at 92.19 and 98.54 J/g, respectively, while also exhibiting excellent cycling stability after 60 heating/cooling cycles. The addition of a modest amount of copper nanoparticles resulted in a remarkable improvement (>50 %) in the thermal conductivity of the PCM. Thermal imaging using an infrared camera showed that PEG/CNC@Cu-NPs exhibited a delay of 10 min in heating compared to pure CNC, confirming the good heat retention capacity of the developed composite material. Based on the aforementioned findings, the proposed PEG/CNC@Cu-NPs PCM offers promising application possibilities in the field of thermal energy storage.

Liquid Metal Nanocores Initiated Construction of Smart DNA‐Polymer Microgels with Programmable and Regulable Functions and Near‐Infrared Light‐Driven Locomotion

AbstractDue to their sequence‐directed functions and excellent biocompatibility, smart DNA microgels have attracted considerable research interest, and the combination of DNA microgels with functional nanostructures can further expand their applications in biosensing and biomedicine. Gallium‐based liquid metals (LMs) exhibiting both fluidic and metallic properties hold great promise for the development of smart soft materials; in particular, LM particles upon sonication can mediate radical‐initiated polymerization reactions, thus allowing the combination of LMs and polymeric matrix to construct “soft–soft” materials. Herein, by forming active surfaces under sonication, LM nanoparticles (LM NPs) initiated localized radical polymerization reactions allow the combination of functional DNA units and different polymeric backbones to yield multifunctional core/shell microgels. The localized polymerization reaction allows fine control of the microgel compositions, and smart DNA microgels with tunable catalytic activities can be constructed. Moreover, due to the excellent photothermal effect of LM NPs, the resulting temperature gradient between microgels and surrounding solution upon NIR light irradiation can drive the oriented locomotion of the microgels, and remote control of the activity of these smart microgels can be achieved. These microgels may hold promise for various applications, such as the development of in vivo and in vitro biosensing and drug delivery systems.

Liquid Metal Nanocores Initiated Construction of Smart DNA-Polymer Microgels with Programmable and Regulable Functions and Near-Infrared Light-Driven Locomotion.

Due to their sequence-directed functions and excellent biocompatibility, smart DNA microgels have attracted considerable research interest, and the combination of DNA microgels with functional nanostructures can further expand their applications in biosensing and biomedicine. Gallium-based liquid metals (LMs) exhibiting both fluidic and metallic properties hold great promise for the development of smart soft materials; in particular, LM particles upon sonication can mediate radical-initiated polymerization reactions, thus allowing the combination of LMs and polymeric matrix to construct "soft-soft" materials. Herein, by forming active surfaces under sonication, LM nanoparticles (LM NPs) initiated localized radical polymerization reactions allow the combination of functional DNA units and different polymeric backbones to yield multifunctional core/shell microgels. The localized polymerization reaction allows fine control of the microgel compositions, and smart DNA microgels with tunable catalytic activities can be constructed. Moreover, due to the excellent photothermal effect of LM NPs, the resulting temperature gradient between microgels and surrounding solution upon NIR light irradiation can drive the oriented locomotion of the microgels, and remote control of the activity of these smart microgels can be achieved. These microgels may hold promise for various applications, such as the development of in vivo and in vitro biosensing and drug delivery systems.

Fabrication of well-defined lignin-derived elastomers by atom transfer radical polymerization and Diels-Alder reaction towards sustainable, super-tough and high temperature-resistant hot-melt adhesives

Hot-melt adhesives synthesized from sustainable resource have attracted increasing attention in fields of home decoration, handicraft production, automotive industries, etc., due to their free of volatile organic compounds (VOCs) and environmentally friendly advantages. However, it is still challenging to fabricate super-tough and heat-resistant hot-melt adhesives with utilization of the inherited properties of sustainable resource as feedstock. Herein, a combination of photoinduced metal-free atom transfer radical polymerization (ATRP) and Diels-Alder (DA) reaction was applied to prepare lignin-derived elastomers for super-tough and high temperature-resistant hot-melt adhesives. Firstly, photoinduced metal-free ATRP of lauryl methacrylate (LMA) derived from fatty acids and furfuryl methacrylate (FMA) derived from furfural, were employed to fabricate sustainable well-defined multi-arm lignin-graft copolymers bearing furfuryl groups with the aid of lignin based macro-initiator (L-Br). The photoinduced metal-free ATRP in this work could be activated and deactivated by an “ON–OFF” ultraviolet (UV) light switch, and successfully achieved the precise control over the molecular weight and composition of lignin-graft copolymers. Then, Diels-Alder (DA) reaction was applied to functionalize the lignin-graft copolymers with dynamic crosslinked network and obtain the lignin-derived elastomers. Benefiting from the multi-arm structure and the dynamic crosslinked network, these lignin-derived elastomers exhibited favorable mechanical property, thermal stability, shape memory, self-healing and recycled properties. In addition, the lignin-derived elastomers could be used as hot-melt adhesives and their lap shear strengths could reach 5.95 MPa, while being bonded with aluminum plates. Moreover, the steel plate bonded with lignin-derived elastomers could remain stable even at 100 °C. We believe that this work will offer a new approach for designing lignin-derived elastomers towards sustainable, strong, super-tough and high-temperature-resistant hot-melt adhesives.

Development of a peptide microarray-based metal-enhanced fluorescence assay for ultrasensitive detection of multiple matrix metalloproteinase activities by using a gold nanorod-polymer substrate

Matrix metalloproteinases (MMPs) are attractive biomarkers for cancer diagnosis and treatment, while it is still a challenge to precise analysis of MMP activities owing to their very low abundance in the biological samples, especially at the early stages of tumors. Herein, a peptide microarray-based metal-enhanced fluorescence assay (PMMEFA) is proposed to simultaneously detect MMP-1, -2, -3, -7, -9, and -13 activities. The assay involves immobilization of Förster resonance energy transfer dye pair decorated peptides (FRET-peptides) on a poly(glycidyl methacrylate-co-2-hydroxyethyl methacrylate) coated gold nanorod modified glass slide (GNR@P(GMA-HEMA)). To fabricate the GNR@P(GMA-HEMA) slide, GNRs are self-assembled onto an aminated glass slide, and a polymer brush (P(GMA-HEMA)) is grown through a surface-initiated atom transfer radical polymerization reaction (SI-ATRP). Upon the addition of MMPs, the FRET pairs are broken due to the specific cleavage of FRET-peptides by enzymes, resulting in the recovery of fluorescence signals and further enhancement by the MEF of GNRs. The fluorescence recovery degree provides a direct indicator for MMP activity. The PMMEFA exhibits excellent sensitivity, which enables to detect MMP-1, -2, -3, -7, -9, and -13 activities, with low limits of detection (LODs) of 1.7 fg mL−1, 0.3 fg mL−1, 2.0 fg mL−1, 1.8 fg mL−1, 2.2 fg mL−1 and 14.0 fg mL−1, respectively. To substantiate the practicability of PMMEFA, MMP activities were measured in a range of matrices, encompassing cell culture medium, serum, and tumor tissue homogenate, and MMP activities can be detected only in 0.15 μL serum and 0.025 mg tumor tissue.

Preparation of acrylic metal salt resin containing capsaicin derivative structure and study of anti-fouling properties

Modifications of acrylic resins with environmentally friendly compounds often solve the problems of marine fouling. In this work, capsaicin derivatives-modified acrylic acid resins were successfully synthesized via free radical polymerization and condensation reactions of monomeric acrylic acid, capsaicin derivatives, metal salts and benzoic acid and structurally characterized by infrared spectroscopy and nuclear magnetism. The physicochemical properties of the synthesized resin coatings were tested with a rotary viscometer, gel permeation chromatography, video optical contact angle measurements and a laser confocal tester. The self-polishing and antifouling properties of the resins were investigated with dynamic simulation experiments, algae inhibitions, bacterial inhibition experiments and real sea antifouling experiments. By comparing with the acrylic resin without capsaicin derivatives, the acrylic resin with added capsaicin derivatives had good antifouling performance, and the optimal content was 2.5 %. In summary, the capsaicin derivative-modified acrylic metal salt resins have good self-polishing properties and antifouling properties.

Plasma-assisted surface functionalization of UHMWPE fiber for adhesion improvement with rubber matrix

A plasma-assisted surface modification method was introduced to enhance the interfacial adhesion of rubber composites reinforced with ultra-high molecular weight polyethylene (UHMWPE) fibers. First various reactive monomers were grafted onto the fiber surface via a plasma-assisted radical polymerization reaction. Subsequently, the grafted fibers underwent RFL (resorcinol-formaldehyde-latex) dipping process to bolster their interfacial adhesion with rubber. Compared with the original UHMWPE fibers, the modified fiber-reinforced rubber composites showed an increase in H pull-out force by 105.3 %–165.7 N and peel strength by 145.2 % to 10.3 N/mm, reaching the level of general-purpose fabric-core conveyor belt (≥4.5 N/mm). After the modification, the dynamic fatigue life and aging stability of the fiber-reinforced rubber composites were significantly improved, thereby enhancing the service life and safety of the composites. The results show that this method greatly improves the chemical activity, hydrophilicity, and surface roughness of UHMWPE fibers with minimal damage, rendering it a promising choice for industrial applications.

Acrylates Polymerization on Covalent Plasma-Assisted Functionalized Graphene: A Route to Synthesize Hybrid Functional Materials.

The modification of the surface properties of graphene with polymers provides a method for expanding its scope into new applications as a hybrid material. Unfortunately, the chemical inertness of graphene hinders the covalent functionalization required to build them up. Developing new strategies to enhance the graphene chemical activity for efficient and stable functionalization, while preserving its electronic properties, is a major challenge. We here devise a covalent functionalization method that is clean, reproducible, scalable, and technologically relevant for the synthesis of a large-scale, substrate-supported graphene-polymer hybrid material. In a first step, hydrogen-assisted plasma activation of p-aminophenol (p-AP) linker molecules produces their stable and covalent attachment to large-area graphene. Second, an in situ radical polymerization reaction of 2-hydroxyethyl acrylate (HEA) is carried out on the functionalized surface, leading to a graphene-polymer hybrid functional material. The functionalization with a hydrophilic and soft polymer modifies the hydrophobicity of graphene and might enhance its biocompatibility. We have characterized these hybrid materials by atomic force microscopy (AFM), X-Ray photoelectron spectroscopy (XPS) and Raman spectroscopy and studied their electrical response, confirming that the graphene/p-AP/PHEA architecture is anchored covalently by the sp3 hybridization and controlled polymerization reaction on graphene, retaining its suitable electronic properties. Among all the possibilities, we assess the proof of concept of this graphene-based hybrid platform as a humidity sensor. An enhanced sensitivity is obtained in comparison with pristine graphene and related materials. This functional nanoarchitecture and the two-step strategy open up future potential applications in sensors, biomaterials, or biotechnology fields.

Nanomotor-based H2S donor with mitochondrial targeting function for treatment of Parkinson's disease

Reduction of endogenous hydrogen sulfide (H2S) is considered to have an important impact on the progress of Parkinson's disease (PD), thus exogenous H2S supplementation is expected to become one of the key means to treat PD. However, at present, it is difficult for H2S donors to effectively penetrate the blood brain barrier (BBB), selectively release H2S in brain, and effectively target the mitochondria of neuron cells. Herein, we report a kind of nanomotor-based H2S donor, which is obtained by free radical polymerization reaction between l-cysteine derivative modified-polyethylene glycol (PEG-Cys) and 2-methacryloyloxyethyl phosphorylcholine (MPC). This kind of H2S donor can not only effectively break through BBB, but also be specifically catalyzed by cystathionine β-synthase (CBS) in neurons of PD site in brain and 3-mercaptopyruvate sulfurtransferase (3-MST) in mitochondria to produce H2S, endowing it with chemotaxis/motion ability. Moreover, the unique chemotaxis effect of nanomotor can realize the purpose of precisely targeting brain and the mitochondria of damaged neuron cytopathic diseases. This kind of nanomotor-based H2S donor is expected to enrich the current types of H2S donors and provide new ideas for the treatment of PD.

Thioxanthonation of 2-naphthalene-thioacetic acid as a visible-light photoinitiator: The investigation of photophysical and photochemical properties

Thioxanthonation of naphthalene thioacetic acid (TXNPSCH2COOH) resulted a visible light photoinitiator with the high molar absorptivity (ε405: 5680 L.mol−1.cm−1) in the visible spectral region and made this compound an attractive photoinitiator for free radical polymerization reactions. Low fluorescence quantum yield (ΦF: 0.06 in 2-MeTHF) and comparatively low triplet energy (186 kJ/mol in 2-MeTHF) was in favorable for efficient intersystem crossing to the triplet state which is necessary for production of initiating radicals. Indeed, photopolymerization of methyl methacrylate along with TXNPSCH2COOH (1 × 10−3 M) and a tertiary amine namely MDEA yielded nearly 25% conversion of monomer to polymer. All spectrophotometric studies including laser flash photolysis which gives triplet lifetime of initiator which is very important information for initiation mechanism of photoinitiators, indeed a long enough triplet lifetime of TXNPSCH2COOH (τT: 1000 ns) allows for efficient reactions with co-initiators to generate radicals.

Design and Synthesis of Co-initiators via Base-Catalysed Sequential Conjugate Addition: Application in Photoinduced Radical Polymerisation Reaction.

Applications of photochemistry are becoming very popular in modern-day life due to its operational simplicity, environmentally friendly and economically sustainable nature in comparison to thermochemistry. In particular photoinduced radical polymerisation (PRP) reactions are finding more biological applications and especially in the areas of dental restoration processes, tissue engineering and artificial bone generation. A type-II photoinitiator and co-initiator-promoted PRP turned out to be a cost-effective protocol, and herein we report the design and synthesis of a new efficient co-initiator for a PRP reaction via a barrierless sequential conjugate addition reaction. Experimental mechanistic observations have been further complemented by computational data. Time for newly synthesised 1,2-benzenedithiol (DTH) based co-initiator promoted polymerisation of urethane dimethacrylate (UDMA, 70 %) and triethylene glycol dimethacrylate (TEGDMA, 30 %) in presence of 450 nm LED (15 W) under the aerobic conditions is 38 seconds. Polymeric material has high glass transition temperature, improved mechanical strength (860 BHN) and longer in-depth polymerisation (3 cm).