Polymerization Technique Research Articles

RAFT Polymerization for Advanced Morphological Control: From Individual Polymer Chains to Bulk Materials.

Control of the morphology of polymer systems is achieved through reversible-deactivation radical polymerization techniques such as Reversible Addition-Fragmentation chain Transfer (RAFT). Advanced RAFT techniques offer much more than just "living" polymerization - the RAFT toolkit now enables morphological control of polymer systems across many decades of length-scale. Morphological control is explored at the molecular-level in the context of syntheses where individual monomer unit insertion provides sequence-defined polymers (single unit monomer insertion, SUMI). By being able to define polymer architectures, the synthesis of bespoke shapes and sizes of nanostructures becomes possible by leveraging self-assembly (polymerization induced self-assembly, PISA). Finally, it is seen that macroscopic materials can be produced with nanoscale detail, based on phase-separated nanostructures (polymerization induced microphase separation, PIMS) and microscale detail based on 3D-printing technologies. RAFT control of morphology is seen to cross from molecular level to additive manufacturing length-scales, with complete morphological control over all length-scales.

Achieving optimum balance between mechanical properties and gloss of acrylonitrile–styrene–acrylate resin through control of rubber particle size distribution

AbstractPreparation of acrylonitrile–styrene–acrylate (ASA) with high gloss and superior impact properties is still challenging. Here, we developed a new strategy for the preparation of ASA resins by a selective redox initiation method based on a semi‐continuous emulsion polymerization technique. A series of ASA core‐shell impact modifiers were firstly obtained by grafting styrene (St) and acrylonitrile (AN) onto poly(n‐butyl acrylate) (PBA) seeded latexes of different sizes. The ASA core‐shell impact modifier was then used to toughen the styrene–acrylonitrile copolymer (SAN). The synergistic effects between the single particle size of the rubber phase and different particle sizes were systematically investigated, and the mechanical properties of SAN‐toughened resins at various particle sizes of the rubber phase were analyzed. The results revealed that toughened SAN with small particle sizes possessed better gloss, and the impact strength of the doped small‐particle toughened SAN was much higher than that of the single particle size toughened SAN. The ASA graft powders synthesized from large particle PBA (particle size 316 nm) and small particle PBA (particle size 99 nm), respectively, were mixed at a 50/50 ratio and blended with SAN resin, a gloss level reaching 95, and an impact performance of 275 J/m values almost twice those of a single particle size toughened SAN.Highlights Acrylonitrile–styrene–acrylate resins with an impact strength of 275 J/m and gloss of 95 were prepared. The balance between mechanical properties and gloss of acrylonitrile–styrene–acrylate resin was obtained. Polymerization was initiated at low temperature.

Two-photon 3D printed fiber-optic Fabry–Perot probe for triaxial contact force detection of guidewire tips

The demand for real-time feedback and miniaturization of sensing elements is a crucial issue in the treating vascular diseases with minimally invasive interventions. Here, Fabry–Perot microcavities fabricated via direct laser writing using a two-photon polymerization technique on fiber tips are proposed, designed, simulated, and experimentally demonstrated as a miniature triaxial force sensor for monitoring real-time interactions between the tip of a guidewire and human blood vessels and tissues during minimally invasive surgeries. The sensor contains four fiber tip-based Fabry–Perot cavities, which can be seamlessly integrated into medical guidewires and achieves three-axis force decoupling through symmetrically arranged flexible structures. The results showed that the proposed sensor achieved a cross-sectional diameter of 890 μm and a high sensitivity of about 85.16 nm/N within a range of 0 to 0.5 N with a resolution of hundreds of micro-Newtons. The proposed triaxial force sensor exhibits high resolution, good biocompatibility, and electromagnetic compatibility, which can be utilized as an efficient monitoring tool integrated into minimally invasive surgical intervention devices for biomedical applications.

Scattering-Free and Fast Response Polymer Brush-Stabilized Liquid Crystals Beam Steering Using Surface-Initiated Polymerization Technique.

Nonmechanical fast response optical beam steering technology is increasingly essential for telecommunications, imaging systems, optical sensing, displays, and military applications. Polymer network liquid crystal (PNLC) beam steering can achieve submillisecond response times but faces limitations due to scattering issues arising from the refractive index mismatch between the polymer network and the liquid crystals (LCs). In this article, we demonstrate a scattering-free, fast-response LC beam steering by using polymer brushes to stabilize the gradient refractive index. First, the initiator is incorporated into the alignment layer and the monomer is mixed into the LC layer. Surface-initiated polymerization (SIP) is then employed to grow the polymer brushes exclusively on the substrate's surface, thus confining the polymer network's growth to the LC bulk and reducing interfacial scattering. For polymer brush stabilized liquid crystal (PBSLC) beam steering device with a period size of 225 μm and a cell gap of 7.2 μm, the average transmission rate reaches 88% in the visible light spectrum with a haze value of only 6.91. The steering angle is 0.16, and the diffraction efficiency is 80.3%. When a voltage of 35 Vrms is applied, the primary energy can be tuned to the zeroth order, with a response time close to 1 ms. By cascading two PBSLC beam steering devices with opposite steering directions, the primary energy of the beam can be adjusted between zeroth, +1, and -1 order. This method requires only a UV light source, a precision displacement stage, a power supply, and a mask, avoiding the need for expensive equipment and complex electrode fabrication. By adjustment of the phase change period, step width, and number of steps during fabrication, the steering angles and diffraction efficiency of the PBSLC beam steering device can be easily controlled, highlighting its significant potential for industrial production.

Tuning Supercapacitive Behavior of Eri Silk (Philosamiaricini)‐Polyanilne Nanocomposite for Electrodes Applications

ABSTRACTHerein, the synthesis of Polyaniline‐Eri nanosilk fibroin (PANI/ENSF) composite supercapacitor electrode material by utilizing Eri silk (Philosamiaricini) as a raw material and polyaniline (PANI) with H2SO4 as doping acid and (NH4)2S2O8 as an oxidant, via a simple in situ oxidative polymerization technique, with good performance characteristics is reported. The chemical composition of the composites have been studied by using XRD, FT‐IR, UV–vis spectroscopy, Raman spectroscopy, and morphology is studied by SEM. BET analysis reveals that the surface area of composite is 712.10 m2g−1, and BJH analysis shows that the pore size is mainly concentrated between 1.5 and 15.7 nm. The composite shows electrical conductivity of 17.33 × 10−2 Scm−1 (Keithley Model 2000). The electrochemical performances are evaluated by using CV, GCD, and EIS measurements. The three‐electrode system composite shows specific capacitance of about 310.12 Fg−1 at 0.1 Ag−1, which is the highest value being reported, compared to already available polyaniline‐silk composites. Further the studies have been extended to assemble a symmetrical two‐electrode supercapacitor device which also exhibits a high value of specific capacitance of 35 Fg−1 at 5 Ag−1 and 96.12% capacity retention over 5000 cycles. For the first time, this study reports using a Polyaniline‐Eri nanosilk composite to design an efficient supercapacitor electrode.

Green synthesis of boehmite-reinforced cashew gum/polypyrrole biopolymer blend for advanced biomaterials

Electrically conducting biopolymer blend nanocomposites based on different contents of boehmite (BHM) reinforced cashew gum (CG) /polypyrrole (PPy) blend is synthesized by an in situ polymerization technique using water as a green solvent. The resulting bio-blend nanocomposites underwent comprehensive analysis concerning their structural, morphology, thermal, and electrical properties, such as dielectric constant, dielectric loss, electric modulus, and AC conductivity. The Fourier transform infrared spectroscopy (FTIR) spectra revealed the presence of metal oxide stretching in the blended nanocomposite at 512 cm−1. Field emission scanning electron microscopy (FE-SEM) confirmed the attachment and uniform dispersion of BHM within the CG/PPy blend at 7 wt% loading, and beyond this loading, the nanoparticles get agglomerated in the biopolymer blend. The glass transition temperature and thermal stability of all the blended nanocomposites are higher than that of the pure CG/PPy blend and these thermal properties increase with the loading of nanoparticles. Conductivity experiments demonstrated that as the nanofiller content increases up to 7 wt%, there is a concurrent rise observed in AC conductivity, dielectric loss, and dielectric constant. There is a substantial difference of 1.21 Scm−1 between the maximum and minimum AC electrical conductivity, at 102 Hz. However, a decrease in electrical properties is observed at the highest loadings of BHM due to the agglomeration of nanoparticles in the polymer blend matrix. The lowest activation energy value (0.049 × 10−4 eV) is also exhibited by 7 wt% BHM nanocomposites. Furthermore, the electrical properties of both CG/PPy and CG/PPy/BHM nanocomposites exhibited a temperature-dependent behavior, progressively increasing until reaching maximum values. This study suggests that such bio-based polymer dielectrics could be promising materials for various applications, offering enhanced thermal and electrical properties through careful control of nanofiller content and dispersion.

A Novel Approach to the Development of Natural Resin‐Based Biopolymer in the Presence of a Reusable Catalyst: Characterization and Modeling of Material Properties

ABSTRACTThe rise in environmental and health concerns has led to increasing attention to nature‐derived materials. Natural resin (NR) is secreted by pine trees, and it is a great monomer source for synthesizing biopolymers. The objective of this study is to produce terpene rosin phenolic resin (TRPR) from NR, turpentine, and phenol by applying a novel polymerization technique. An environmentally friendly and reusable catalyst (Amberlyst15) was chosen instead of traditional ones. TRPR samples were chemically characterized using Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), and gel permeation chromatography (GPC) analysis. The average molecular weight (Mw) of TRPR was detected as 560 g/mol. Artificial neural network (ANN) modeling was designed with three inputs (pressure, temperature, and terpene/NR ratio) and four outputs (reaction yield, acid value, saponification value, and softening point). The highest TRPR yield was obtained with a terpene/NR ratio of (1/2) at 80°C and under 3 atm. The lowest acid and saponification values were calculated as 90.54 and 100.11 mg KOH/g, respectively. The softening point of TRPR reached 80°C and it was suggested for use in the paper, ink, and adhesive industries.

Fabrication and evaluation of eicosane/poly(styrene-co-butylacrylate) microencapsulated phase change materials through ultrasonicated mini-emulsion technique

This study reports the synthesis and characterization of Microencapsulated Phase Change Materials for the pertinence of latent heat storage. Eicosane/ Poly(Styrene-co-Butylacrylate) [ESE/Poly(Sty-co-BA)] microcapsules were synthesized by encapsulating n-Eicosane (n-ESE) with a shell made of Poly(Styrene-co-Butylacrylate) [Poly(Sty-co-BA)] via employing ultrasonic-assistant mini-emulsion polymerization technique. The properties of the synthesized ESE/Poly(Sty-co-BA) microcapsules were analyzed by Differential scanning calorimetry (DSC),Thermogravimetric analysis (TGA), Transmission electron microscopy (TEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR)spectroscopy. DSC results indicated that ESE/Poly(Sty-co-BA) exhibited a melting and crystallizing temperature of 35.72 and 32.27 °C, and latent heat of 220.53 and 218.57 J/g, respectively. The ESE/Poly(Sty-co-BA) microcapsules prepared in this work unveiled an effective encapsulation ratio (91.93 %), encapsulation efficiency (91.59 %) and displayed excellent thermal storage capacity (99.63 %). Various models such as Kissinger’s, Augis and Bennett’s approximation, Mahadevan and Arvami theory were employed to determine the effective activation energy value alongside the crystal growth of n-ESE and ESE/Poly(Sty-co-BA). TGA analysis revealed that ESE/Poly(Sty-co-BA) demonstrated three step degradation and exhibited good thermal stability. The findings of the work manifested a novel technique for producing the phase transition materials for TES that can be applied to a wide range of instances, including smart textiles, thermo-sensitized functional coatings, passive space cooling or heating.

Rewritable Surface‐Grafted Polymer Brushes with Dynamic Covalent Linkages

AbstractSurface grafting of polymer brushes drastically modifies surface properties, including wettability, compatibility, responsiveness, etc. A broad variety of functionalities can be introduced to the surface via different types of polymers. Bringing together properties of two or more types of polymer brushes to one surface opens up even more possibilities in brush‐modified materials. However, while it is generally feasible to introduce several chemical compositions along the brushes via copolymerization, it is challenging to vary the types of polymer brushes along a surface. Although previous studies have demonstrated binary brushes via orthogonal polymerization techniques or partial deactivation/regrafting, they commonly limit the number of polymer types to two. Here, we propose a strategy to introduce dynamic covalent diketoenamine linkages at the root of polymer brushes. The grafting density could be precisely tuned during surface functionalization. The surface‐anchored polymer brushes were cleaved by the addition of small molecule amines. New polymer brushes can be regrafted from the surface following refunctionalization of exposed sites. The maneuverability allows tuning of the types and densities of the polymer brushes, pointing the way to the preparation of a new generation of well‐defined brush‐modified materials with mixed grafts, with potential applications in the design of smart materials and surfaces.

Synthesis and Characterization of cellulose-derived superabsorbent hydrogel and its applications in the treatment of wastewater containing heavy metal ions

A cellulose xanthate (CX) based polymer hydrogel has been synthesized using free radical graft polymerization technique. Two monomers Acrylic Acid (AA) and Acrylonitrile (AN) were reacted with cellulose xanthate to synthesize the desired hydrogel CX-g-poly(AA-co-AN). The synthesized hydrogel has been characterized by various techniques viz. Thermo-gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), UV-visible spectroscopy (UV), Field emission scanning electron microscope (FESEM) and Point zero charge (PZC). This hydrogel has been employed for the removal of toxic metal ions from wastewater. The maximum percentage removal has been found to be 97.5 (±4.87)% for Cu2+ ions and 96.1 (±4.80)% for Co2+ ions under optimum pH 6. The calculated adsorption capacities have been found to be 330.03 (±35.3) mg/g for Cu2+ ions and 325.73 (±22.4) mg/g for Co2+ ions using the Langmuir Adsorption isotherm model. The thermodynamic parameters depicted that the process was endothermic, and spontaneous. The adsorption kinetics data shows excellent fit with pseudo-second-order kinetic model. The synthesized hydrogel exhibits a high swelling ratio of 846.85 (±42.36) g/g and retention ratio of 50.12 (±2.50) % in distilled water. Also, the synthesized hydrogel showed good reusability, exhibiting percentage removal 83.2% for Cu2+ ions and 81.3% for Co2+ ions in the fifth cycle.

Using zero nano-valent iron/thin film composite (ZNVI/TFC) membrane for brackish water desalination and purification

This study looked at the use of synthetic Zero Nano-valent Iron (ZNVI) particles in a unique interfacial polymerization technique on a polyamide thin film PA(TF) composite membrane for the treatment and desalination of brackish wastewater. Zero nano-valent iron (ZNVI) particles were created utilizing chemical reduction technique. ZNVI/PA(TF) NCs membrane is the outcome of advancing the PA(TF) membrane by combining with different concentration of ZNVI particles into the organic phase 1,3,5-benzenetricarbonyl trichloride (TMC). ZNVI/PA(TF) NCs membranes and ZNVI particles' surface properties were examined by the use of mechanical activity, contact angle, BET, FTIR, SEM, XRD, zeta potential, TEM analysis, and EDX studies. Using a variety of salt solutions, such as NaCl, Na2SO4, MgSO4, NaHCO3, CaSO4, CaCl2, and MgCl2, the ZNVI/PA(TF) NCs membrane performance towards salt rejection, flux (at varying pressure), anti-fouling activity, and ZNVI particles stability was assessed. This work investigated the removal efficiency of four dyes: methylene blue (MB), methyl orange (MO), Congo red (CR), and malachite green oxalate (MG). The water flux of the pristine PA(TF) membrane improved from 22 to 35 L/m2.h at 15 bar, indicating a 63% flux enhancement and the NaCl rejection was improved from 88.5 to 98.6%, indicating an 11.4% rejection improvement by incorporation of 0.3 wt.% of ZNVI particles into PA(TF) matrix. The ZNVI/PA(TF) NCs membrane's separation performances were evaluated using 5000 mg/L feed solutions of various salts at 15 bar. It was discovered that the water flux and salt rejection are, respectively, 33.4, 33, 32.7, 32, 31, 30 and 29 L/m2.h for CaSO4, MgSO4, Na2SO4, NaCl, CaCl2, MgCl2, and NaHCO3, and 97.4, 97, 96.5, 96, 94, 93.2, and 92.8%. It demonstrates that the flux recovery ratio (FRR) of the ZNVI/PA(TF) NCs membrane is greater than that of pristine PA(TF) (78%), coming in at 87%. High stability and fixing of the ZNVI particles on the modified membrane surface is indicated by the low overall ZNVI particles release rate over the course of the 10-day experiment.

Temperature-dependent dielectric measurements of polypyrrole/zinc cobalt oxide nanocomposites by impedance spectroscopy

This study characterizes the conduction mechanism in Zinc Cobalt oxide/Polypyrrole nanocomposites (ZCO/PPy NCs) concerning temperature (303–453 K) and frequency (100 Hz–1 MHz). To obtain the ZCO/PPy nanocomposites for the experiments, we used the in-situ chemical polymerization technique to disseminate varying weight percentages of ZCO nanoparticles (ZCO NPs) in the PPy matrix. The total electrical conductivity graph consists of a step-like feature of a plateau and dispersive regimes. The dispersive zone, which follows Jonscher's power law, correlates to AC conductivity, whereas the plateau region, which corresponds to DC conductivity, is thermally activated. The extracted DC conductivity values are of the order of 10‐4 S/m at 303 K. The conduction mechanism in ZCO/PPy nanocomposites is depicted by the Non-Overlapping Large Polaron Tunneling (NSPT) model. The dielectric studies confirm the non-Debye-like relaxation in PPy and ZCO/PPy NCs. In addition, the complex impedance and equivalent circuit analysis showed maximum contribution from grain and grain boundaries. The grain and grain boundary resistances are of the order of 103 Ω, depicting the electrical homogeneity in the PPy and ZCO/PPy nanocomposites.

Influence of light-polymerizing units and zirconia on the physical, chemical and biological properties of self-adhesive resin cements

BackgroundSelf-adhesive resin cements (SARCs) are widely used for fixed prostheses, but incomplete cleaning near the gingival margin can cause inflammation. However, the factors influencing cement properties and the biological response of gingival fibroblasts to cement eluates are not well understood. This study examines the impact of two light-polymerizing units (LPUs) on the physical and chemical properties of two SARCs under simulated clinical conditions, as well as the subsequent response of human gingival fibroblasts (hGFs) to these eluates.MethodsDental cement discs of SARCs were polymerized using Kerr DemiPlus and 3 M Elipar DeepCure-S LED LPUs with or without a 2-mm thick zirconia screen. Physical properties (microhardness, surface roughness, residual monomers) were evaluated. hGFs’ cell viability, wound healing potency, and gene expression were assessed.ResultsBoth Maxcem and RelyX exhibited reduced microhardness and increased surface roughness when polymerized through zirconia or with DemiPlus LPU. Higher residual monomers (HEMA and GDMA in Maxcem; TEGDMA in RelyX) concentration was observed with DemiPlus and zirconia polymerization. Maxcem polymerized with DemiPlus exhibited lower cell viability, impaired healing, and altered gene expression in hGFs compared to those polymerized with Elipar LPU. Gene expression changes included downregulated NRF2 and HO-1 and upregulated CCR-3.ConclusionsLight-polymerizing Maxcem through zirconia with DemiPlus LPU compromised SARCs’ properties, leading to higher residual monomers and negatively impacting hGFs’ viability, healing, and gene expression. Careful material selection and polymerization techniques are crucial to minimize adverse effects on surrounding tissues.Clinical significanceClinicians should exercise caution when using LPUs and SARCs, especially when polymerizing through zirconia. This will help optimize the physical and chemical properties of SARCs and minimize potential adverse effects on the surrounding gingival soft tissues.

Enhancement of interaction between Shenhua coal and GON-based dispersant with “surface-to-surface” adsorption by regulating the oxidation degree of GON: Experiments and simulations

The present study focuses on the synthesis of several graphene oxide nanosheet (GON)-based dispersants with an adsorption mode of “surface-to-surface” for the preparation of Shenhua coal (SC) water slurry (SCWS), achieved by grafting allyl polyoxyethylene ether (APEG) onto GON edges with varying degrees of oxidation using emulsion polymerization and esterification techniques. The impacts of the oxidation degree of GON on its structural characteristics and the performance of GON-based dispersants in SCWS were comprehensively assessed through a range of experimental techniques, alongside molecular dynamics (MD) simulations. Results demonstrated that with the increase in oxidation degree, there was an elevation of oxygen-containing groups, in which the content of COH decreased while the content of COC increased. Among all dispersants, GA-2, which was synthesized using GON-2 as the raw material with a graphite-to-KMnO4 mass ratio of 1:2.5, exhibited superior viscosity-reducing and stabilizing abilities compared to other dispersants. All SCWSs demonstrated pseudoplastic fluid behavior and showed good agreement with the Herschel-Bulkley model. After the adsorption of dispersants in SC, both the Zeta potential and surface wettability of SC significantly improved, especially with GA-2. The interaction mechanism between the dispersant and SC was analyzed by establishing and employing three adsorption models (M-1, M-2, and M-3). The interfacial adsorption structure confirmed that the dispersant exhibited “surface-to-surface” mode on coal through hydrophobic interaction, hydrogen bonding, and π–π interaction. Energy studies revealed that M-2 with the highest Eads (−105.31 kcal/mol) demonstrated superior adsorption strength compared to M-1 and M-3. Investigations into water molecule mobility revealed that the interaction between the GON-based dispersant and SC resulted in a reduction of water molecule mobility, thereby promoting water molecule aggregation to facilitate the formation of hydration films and enhance SCWS stability. In summary, an optimal oxidation degree of GON was found to be crucial for enhancing the performance of GON-based dispersants; higher oxidation levels may hinder dispersant adsorption on coal surfaces by converting hydroxyl and carboxyl groups into epoxide groups, thus impairing the conjugated structure.

Polymerization techniques on strength of denture base resins

Polymerization techniques on strength of denture base resins

Behind the scenes of green chemistry: Glories and shadows of atom transfer radical polymerization environmental impact (E-factor)

The paper presents the evaluation of environmental impact (E-factor) as green chemistry metric, calculated for polymer synthesis via one of the most useful tools of macromolecular chemistry, which is atom transfer radical polymerization (ATRP), belonging to the reversible deactivation radical polymerization (RDRP) techniques. For the first time, experimentally determined polymerization yields were included in the calculation, by analyzing the polymer synthesis process using various organic solvents, different methods of regenerating the catalytic complex (meaning ATRP approach), or using the miniemulsion system as eco-friendly reaction medium and presenting the possibility of effective solvent recovery and reuse. The majority of the values of E-factor were below 16, falling within the scope intended for fine chemicals (5–50). The significant and innovative part of the presented research involves verifying the feasibility of using higher concentrations of the dispersed phase in the case of miniemulsion polymerization (increased to as much as 100 % vs. aqueous phase from a typical 20 %), while the use of recycled water allowed a 3-fold reduction in E-factor value. Polymerization in a miniemulsion environment is also attractive due to its low cost, considering the price of distilled water, which is over 580-fold lower than that of DMSO – a typical organic solvent. These observations allow for the reduction of environmental impact and process cost. Importantly, the observed trends in E-factor changes allowed for the identification of ATRP development directions in line with green chemistry and the circular economy.

Poly(N-isopropylacrylamide)-chitosan nanogels for nanotechnological and catalytic applications

Polymer nanogels consisting of poly(N-isopropylacrylamide) and chitosan [P(NC)] were synthesized using a free radical precipitation polymerization technique in an aqueous environment. This process involved the polymerization of N-isopropylacrylamide (NIPAAM) with chitosan (CS) and a cross-linker. These P(NC) nanogels were utilized as nano-reactors for the synthesis of gold nanoparticles (AuNPs), which were formed within the polymeric network through an in-situ reduction process using chloroauric acid [H(AuCl4)] as precursor salt and sodium borohydride (NaBH4) as the reductant. Various analytical methods, including transmission electron microscopy (TEM), Thermogravimetric analysis (TGA), ultraviolet–visible spectroscopy (UV–Vis), and Fourier transform infrared spectroscopy (FTIR), were employed to confirm the formation of P(NC) nanogels and the incorporation and durability of AuNPs within the P(NC) nanogels. The AuNPs loaded P(NC) nanogels were utilized as catalysts for the reduction of 4-nitrophenol (4-NiP) into 4-aminophenol (4-AmP) in the presence of NaBH4. This system was also used to degrade a number of dyes including methylene blue (MB), methylene orange (MO), Rhodamine B (RhB), brilliant blue (BB) and eosin Y ((EY) by using NaBH4 as reducing agent. The Au-P(NC) catalyst exhibited remarkable efficiency, facilitating the fast reduction of 4-NiP and degradation of dyes within a very short interval of time. This system stands out for its economic usage, as even a small quantity of it can efficiently reduce toxic pollutants like 4-NiP and dyes. The results of the reactions highlighted exceptional yield, emphasizing the effectiveness and recyclability of the Au-P(NC) hybrid nanogels as highly capable catalysts.

Screening of the biphenyl polyamides nanofilms appropriate for molecular separation in organic solution feed

Developing polymeric separation membranes that combine excellent solvent stability, high permeability, and customizable molecular weight interception remains a challenge. Herein, thin-film composite (TFC) polyamide (PA) membranes with poly(ether ether ketone) (PEEK) support and biphenyl-centered polyamides active layer were fabricated through interfacial polymerization technique for the first time. Enhanced solvent stability was exhibited by the fabricated membranes due to the intrinsic resistance to organic solvents possessed by PEEK and biphenyl polyamides. The separation performance of the obtained membranes was systematically studied by relating to the properties of PA nanofilms in terms of nano-mechanical strength, morphologies, and microporosity. The organic solvent nanofiltration (OSN) performance of the resultant membranes in terms of permeability and molecular weight cut-off (MWCO) could be regulated. The optimized membrane exhibited a pure solvent permeability as high as 21.6 L m−2 h−1 bar−1 for acetonitrile and 14.0 L m−2 h−1 bar−1 for methanol. It also showed excellent long-term durability with almost unchanged permeability as well as solute retention remained above 97.8 % after a cumulative OSN operation of N, N-Dimethylformamide (DMF) based feed for 240 h. In particular, OSN membrane with targeted MWCOs covering the range of 170–370 g·mol−1 could be fabricated by selecting appropriate biphenyl acyl chlorides as building blocks. This approach offers a scalable and versatile platform for the development of solvent-stable, highly permeable, and customizable MWCO membranes for process-oriented OSN.

Bright Nanocomposites based on Quantum Dot‐Initiated Photocatalysis

Integrating quantum dots (QDs) into polymer matrix to form nanocomposites without compromising the QD photoluminescence (PL) is crucial to emerging QD light‐emitting and solar energy conversion fields. However, the most widely‐used bulk polymerization technique, where monomers serve as the QD solvent, usually leads to QD PL quenching caused by radical initiators. Here we demonstrate high‐brightness nanocomposites with near‐unity PL quantum yield (QY), through a novel QDs‐catalyzed (‐initiated) bulk polymerization without using any radical initiators. Different from previous reports where QDs were designed as photo‐sensitizers/catalysts (always with cocatalysts) and hence non‐emissive in catalytic conditions, our QDs combine high brightness with highly effective catalysis, a combination that was previously considered to be hardly possible. In our case, apart from emitting light (at a large probability), the photoexcited QDs act as ‘overall reaction’ catalysts by simultaneously employing photoexcited electrons and holes to produce active radicals without the need of any sacrificial agents. These active radicals, though with a small amount, are sufficient to initiate effective chain reaction‐dominated bulk polymerization, eliminating the requirement of extra radical initiators. This study provides new insights for understanding and development of QDs for energy applications.

Bright Nanocomposites based on Quantum Dot-Initiated Photocatalysis.

Integrating quantum dots (QDs) into polymer matrix to form nanocomposites without compromising the QD photoluminescence (PL) is crucial to emerging QD light-emitting and solar energy conversion fields. However, the most widely-used bulk polymerization technique, where monomers serve as the QD solvent, usually leads to QD PL quenching caused by radical initiators. Here we demonstrate high-brightness nanocomposites with near-unity PL quantum yield (QY), through a novel QDs-catalyzed (-initiated) bulk polymerization without using any radical initiators. Different from previous reports where QDs were designed as photo-sensitizers/catalysts (always with cocatalysts) and hence non-emissive in catalytic conditions, our QDs combine high brightness with highly effective catalysis, a combination that was previously considered to be hardly possible. In our case, apart from emitting light (at a large probability), the photoexcited QDs act as 'overall reaction' catalysts by simultaneously employing photoexcited electrons and holes to produce active radicals without the need of any sacrificial agents. These active radicals, though with a small amount, are sufficient to initiate effective chain reaction-dominated bulk polymerization, eliminating the requirement of extra radical initiators. This study provides new insights for understanding and development of QDs for energy applications.