Search Results (36)

Molecularly Imprinted Microspheres (MIMs) or Microsphere Molecularly Imprinted Polymers represent an innovative design for the selective extraction of active compounds from natural products, showcasing effectiveness and cost-efficiency. MIMs, crosslinked polymers with specific binding sites for template molecules, overcome irregularities observed in traditional Molecularly Imprinted Polymers (MIPs). Their adaptability to the shape and size of target molecules allows for the capture of compounds from complex mixtures. This review article delves into exploring the potential practical applications of MIMs, particularly in the extraction of active compounds from natural products. Additionally, it provides insights into the broader development of MIM technology for the purification of active compounds. The synthesis of MIMs encompasses various methods, including precipitation polymerization, suspension polymerization, Pickering emulsion polymerization, and Controlled/Living Radical Precipitation Polymerization. These methods enable the formation of MIPs with controlled particle sizes suitable for diverse analytical applications. Control over the template-to-monomer ratio, solvent type, reaction temperature, and polymerization time is crucial to ensure the successful synthesis of MIPs effective in isolating active compounds from natural products. MIMs have been utilized to isolate various active compounds from natural products, such as aristolochic acids from Aristolochia manshuriensis and flavonoids from Rhododendron species, among others. Based on the review, suspension polymerization deposition, which is one of the techniques used in creating MIPs, can be classified under the MIM method. This is due to its ability to produce polymers that are more homogeneous and exhibit better selectivity compared to traditional MIP techniques. Additionally, this method can achieve recovery rates ranging from 94.91% to 113.53% and purities between 86.3% and 122%. The suspension polymerization process is relatively straightforward, allowing for the effective control of viscosity and temperature. Moreover, it is cost-effective as it utilizes water as the solvent. Full article

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. Full article

The solid polymer electrolyte is a promising candidate for solid-state lithium battery because of favorable interfacial contact, good processability and economic availability. However, its application is limited because of low ionic conductivity and insufficient mechanical strength. In this study, the delicate molecular structural design was realized via controlled / “living” radical polymerization in order to decouple the trade-off between ionic conductivity and mechanical strength. The random and triblock copolymer electrolytes were designed and synthesized to investigate the influence of molecular structure on ionic conduction, while a chemical cross-linking network was constructed via a semi-spontaneous post-crosslinking reaction. Compared with a random counterpart, the triblock copolymer electrolyte presented stronger chain segment motion and a liquid-like mechanical response due to the independent ion-conducting block, resulting in significantly improved ionic conductivity (from 6.29 ± 1.11 × 10⁻⁵ to 9.57 ± 2.82 × 10⁻⁵ S cm⁻¹ at 60 °C) and cell performance. When assembled with LiFePO₄ and lithium metal electrodes, the cell with triblock copolymer electrolyte showed significantly improved rate performance (150 mAh g⁻¹ at 1 C) and cycling life (200 cycles with 92.8% capacity retention at 1 C). This study demonstrates the advantages of molecular structure regulation on ionic conduction and mechanical support, which may provide new insights for the future design of solid polymer electrolytes. Full article

Styrene-based thermoplastic elastomers (TPEs) demonstrate excellent overall performance and account for the largest industrial output. The traditional methods of preparation styrene-based thermoplastic elastomers mainly focused on anionic polymerization, and strict equipment conditions were required. In recent years, controlled/living radical polymerization (CRP) has developed rapidly, enabling the synthesis of polymers with various complex topologies while controlling their molecular weight. Herein, a series of core crosslinked star-shaped poly(styrene-b-isoprene-b-styrene)s (SISs) was synthesized for the first time via reversible addition–fragmentation chain transfer (RAFT) polymerization. Meanwhile, linear triblock SISs with a similar molecular weight were synthesized as a control. We achieved not only the controlled/living radical polymerization of isoprene but also investigated the factors influencing the star-forming process. By testing the mechanical and thermal properties and characterizing the microscopic fractional phase structure, we found that both the linear and star-shaped SISs possessed good tensile properties and a certain phase separation structure, demonstrating the characteristics of thermoplastic elastomers. Full article

Rapid RAFT polymerization can significantly improve production efficiency of PAM with designed molecular structure. This study shows that ideal Reversible Addition–Fragmentation Chain Transfer (RAFT) polymerization of acrylamide is achieved in dimethyl sulfoxide (DMSO) solution at 70 °C. The key to success is the appropriate choice of both a suitable RAFT chain transfer agent (CTA) and initiating species. It is illustrated that dodecyl trithiodimethyl propionic acid (DMPA) is a suitable trithiocarbonate RAFT CTA and is synthesized more easily than other CTAs. Compared to other RAFT processes of polymers, the reaction system shortens reaction time, enhances conversion, and bears all the characteristics of a controlled radical polymerization. The calculation result shows that high concentrations can reduce high conversions, accelerate the reaction rate, and widen molecular weight distributions slightly. This work proposes an excellent approach for rapid synthesis of PAMs with a restricted molecular weight distribution. Full article

The abuse and residues of antibiotics have a great impact on the environment and organisms, and their determination has become very important. Due to their low contents, varieties and complex matrices, effective recognition, separation and enrichment are usually required prior to determination. Molecularly imprinted polymers (MIPs), a kind of highly selective polymer prepared via molecular imprinting technology (MIT), are used widely in the analytical detection of antibiotics, as adsorbents of solid-phase extraction (SPE) and as recognition elements of sensors. Herein, recent advances in MIPs for antibiotic residue analysis are reviewed. Firstly, several new preparation techniques of MIPs for detecting antibiotics are briefly introduced, including surface imprinting, nanoimprinting, living/controlled radical polymerization, and multi-template imprinting, multi-functional monomer imprinting and dummy template imprinting. Secondly, several SPE modes based on MIPs are summarized, namely packed SPE, magnetic SPE, dispersive SPE, matrix solid-phase dispersive extraction, solid-phase microextraction, stir-bar sorptive extraction and pipette-tip SPE. Thirdly, the basic principles of MIP-based sensors and three sensing modes, including electrochemical sensing, optical sensing and mass sensing, are also outlined. Fourthly, the research progress on molecularly imprinted SPEs (MISPEs) and MIP-based electrochemical/optical/mass sensors for the detection of various antibiotic residues in environmental and food samples since 2018 are comprehensively reviewed, including sulfonamides, quinolones, β-lactams and so on. Finally, the preparation and application prospects of MIPs for detecting antibiotics are outlined. Full article

The bacterial contamination of cutting boards and other equipment in the meat processing industry is one of the key reasons for reducing the shelf life and consumer properties of products. There are two ways to solve this problem. The first option is to create coatings with increased strength in order to prevent the formation of micro damages that are favorable for bacterial growth. The second possibility is to create materials with antimicrobial properties. The use of polytetrafluoroethylene (PTFE) coatings with the addition of metal oxide nanoparticles will allow to the achieving of both strength and bacteriostatic effects at the same time. In the present study, a new coating based on PTFE and Fe₂O₃ nanoparticles was developed. Fe₂O₃ nanoparticles were synthesized by laser ablation in water and transferred into acetone using the developed procedures. An acetone-based colloidal solution was mixed with a PTFE-based varnish. Composites with concentrations of Fe₂O₃ nanoparticles from 0.001–0.1% were synthesized. We studied the effect of the obtained material on the generation of ROS (hydrogen peroxide and hydroxyl radicals), 8-oxoguanine, and long-lived active forms of proteins. It was found that PTFE did not affect the generation of all the studied compounds, and the addition of Fe₂O₃ nanoparticles increased the generation of H₂O₂ and hydroxyl radicals by up to 6 and 7 times, respectively. The generation of 8-oxoguanine and long-lived reactive protein species in the presence of PTFE/Fe₂O₃ NPs at 0.1% increased by 2 and 3 times, respectively. The bacteriostatic and cytotoxic effects of the developed material were studied. PTFE with the addition of Fe₂O₃ nanoparticles, at a concentration of 0.001% or more, inhibited the growth of E. coli by 2–5 times compared to the control or PTFE without NPs. At the same time, PTFE, even with the addition of 0.1% Fe₂O₃ nanoparticles, did not significantly impact the survival of eukaryotic cells. It was assumed that the resulting composite material could be used to cover cutting boards and other polymeric surfaces in the meat processing industry. Full article

Precipitation polymerization (PP) is a powerful tool to prepare various types of uniform polymer particles owing to its outstanding advantages of easy operation and the absence of any surfactant. Several PP approaches have been developed up to now, including traditional thermo-induced precipitation polymerization (TRPP), distillation precipitation polymerization (DPP), reflux precipitation polymerization (RPP), photoinduced precipitation polymerization (PPP), solvothermal precipitation polymerization (SPP), controlled/‘‘living’’ radical precipitation polymerization (CRPP) and self-stabilized precipitation polymerization (2SPP). In this review, a general introduction to the categories, mechanisms, and applications of precipitation polymerization and the recent developments are presented, proving that PP has great potential to become one of the most attractive polymerization techniques in materials science and bio-medical areas. Full article

The aqueous Cu(0)-mediated reversible deactivation radical polymerization (RDRP) of triblock copolymers with two block sequences at 0.0 °C is reported herein. Well-defined triblock copolymers initiated from PHEAA or PDMA, containing (A) 2-hydroxyethyl acrylamide (HEAA), (B) N-isopropylacrylamide (NIPAM) and (C) N, N-dimethylacrylamide (DMA), were synthesized. The ultrafast one-pot synthesis of sequence-controlled triblock copolymers via iterative sequential monomer addition after full conversion, without any purification steps throughout the monomer additions, was performed. The narrow dispersities of the triblock copolymers proved the high degree of end-group fidelity of the starting macroinitiator and the absence of any significant undesirable side reactions. Controlled chain length and extremely narrow molecular weight distributions (dispersity ~1.10) were achieved, and quantitative conversion was attained in as little as 52 min. The full disproportionation of CuBr in the presence of Me₆TREN in water prior to both monomer and initiator addition was crucially exploited to produce a well-defined ABC-type triblock copolymer. In addition, the undesirable side reaction that could influence the living nature of the system was investigated. The ability to incorporate several functional monomers without affecting the living nature of the polymerization proves the versatility of this approach. Full article

Hydrogels obtained from combining different polymers are an interesting strategy for developing controlled release system platforms and tissue engineering scaffolds. In this study, the applicability of sodium alginate-g-(QCL-co-HEMA) hydrogels for these biomedical applications was evaluated. Hydrogels were synthesized by free-radical polymerization using a different concentration of the components. The hydrogels were characterized by Fourier transform-infrared spectroscopy, scanning electron microscopy, and a swelling degree. Betamethasone release as well as the in vitro cytocompatibility with chondrocytes and fibroblast cells were also evaluated. Scanning electron microscopy confirmed the porous surface morphology of the hydrogels in all cases. The swelling percent was determined at a different pH and was observed to be pH-sensitive. The controlled release behavior of betamethasone from the matrices was investigated in PBS media (pH = 7.4) and the drug was released in a controlled manner for up to 8 h. Human chondrocytes and fibroblasts were cultured on the hydrogels. The MTS assay showed that almost all hydrogels are cytocompatibles and an increase of proliferation in both cell types after one week of incubation was observed by the Live/Dead^® assay. These results demonstrate that these hydrogels are attractive materials for pharmaceutical and biomedical applications due to their characteristics, their release kinetics, and biocompatibility. Full article

This study examines the ab initio emulsion atom transfer radical polymerization (ATRP) initiated by an eco-friendly reducing agent to produce poly(methyl methacrylate) (PMMA) polymer with controlled characteristics in a 2 L stirred batch reactor. The effect of the reaction temperature, surfactant concentration, monomer to water ratio, and stirring speed was thoroughly investigated. The results showed that PMMA coagulation becomes quite severe at a certain temperature threshold. However, the coagulation could be avoided at mild reaction temperature, since the outcomes showed that loading more surfactant to the system under high mixing speed has balanced the polymer mixture and yielded high monomer conversion. The PMMA product was analyzed by gravimetry and GPC measurements and after 5 h of polymerization at a reaction temperature of 50 °C, monomer conversion of 64.1% was obtained, and PMMA polymer samples produced had an average molar mass of 4.5 kg/mol and a polydispersity index of 1.17. The structure of the PMMA polymer was successfully proved by FTIR and nuclear magnetic resonance (NMR) spectroscopy. The results confirm the living feature of MMA AGET ATRP in emulsion medium and recommend further investigation for other types of surfactant. Full article

Modern polymeric material design often involves precise tailoring of molecular/supramolecular structures which is also called macromolecular engineering. The available tools for molecular structure tailoring are controlled/living polymerization methods, click chemistry, supramolecular polymerization, self-assembly, among others. When polymeric materials with complex molecular architectures are targeted, it usually takes several steps of reactions to obtain the aimed product. Concurrent polymerization methods, i.e., two or more reaction mechanisms, steps, or procedures take place simultaneously instead of sequentially, can significantly reduce the complexity of the reaction procedure or provide special molecular architectures that would be otherwise very difficult to synthesize. Atom transfer radical polymerization, ATRP, has been widely applied in concurrent polymerization reactions and resulted in improved efficiency in macromolecular engineering. This perspective summarizes reported studies employing concurrent polymerization methods with ATRP as one of the reaction components and highlights future research directions in this area. Full article

Polymer nanocomposites have been synthesized by the covalent addition of bromide-functionalized graphene (Graphene-Br) through the single electron transfer-living radical polymerization technique (SET-LRP). Graphite functionalized with bromide for the first time via an efficient route using mild reagents has been designed to develop a graphene based radical initiator. The efficiency of sacrificial initiator (ethyl α-bromoisobutyrate) has also been compared with a graphene based initiator towards monitoring their Cu(0) mediated controlled molecular weight and morphological structures through mass spectroscopy (MOLDI-TOF) and field emission scanning electron microscopy (FE-SEM) analysis, respectively. The enhancement in thermal stability is observed for graphene-grafted-poly(methyl methacrylate) (G-g-PMMA) at 392 °C, which may be due to the influence ofthe covalent addition of graphene, whereas the sacrificial initiator used to synthesize G-graft-PMMA (S) has low thermal stability as analyzed by TGA. A significant difference is noticed on their glass transition and melting temperatures by DSC. The controlled formation and structural features of the polymer-functionalized-graphene is characterized by Raman, FT-IR, UV-Vis spectroscopy, NMR, and zeta potential measurements. The wettability measurements of the novel G-graft-PMMA on leather surface were found to be better in hydrophobic nature with a water contact angle of 109 ± 1°. Full article

The self-emulsifying acrylate-based emulsions with solid content 45 wt.% were prepared in 3.5 h by reverse iodine transfer polymerization (RITP), and the polymer molecular weight (M_n) could be 30,000 g·mol⁻¹. The influences of methacrylic acid (MAA) amount, soft/hard monomer mass ratio, and iodine amount on polymerization and latex were investigated. A moderate amount of ionized MAA was needed to stabilize the emulsion. Glass transition temperature (T_g) was decreased with the increasing mass ratio of soft/hard monomer. A higher iodine amount resulted in lower M_n. The increased M_n after chain extension of the polymer with water-insoluble monomers in iterative one-pot method proved the living of polymer. Compared with conventional emulsion polymerization, molecular weight (M_n) could be controlled, and M_n of polymer synthesized in RITP emulsion polymerization is higher; emulsion of polyacrylate-containing hydroxyl monomer units prepared by RITP emulsifier-free radical polymerization is more stable. Good properties, such as hardness, water resistance, adhesion, and increased value of maximum tensile of films modified by reaction of polyacrylate with melamine–formaldehyde (MF) resin, indicated potential application in baking coating. Full article

Polystyrene microparticles were covalently impregnated into the networks of functional polyelectrolyte chains designed via a tandem run of three reactions: (i) synthesis of water-soluble polyelectrolyte, (ii) fast azidation and (iii) a ‘click’ reaction, using the single-catalyst, single-pot strategy at room temperature in mild aqueous media. The model polyelectrolyte sodium polystyrenesulfonate (NaPSS) was synthesized via the well-controlled atom transfer radical polymerization (ATRP) whose halogen living-end was transformed to azide and subsequently coupled with an alkyne carboxylic acid through a ‘click’ reaction using the same ATRP catalyst, throughout. Halogen to azide transformation was fast and followed the radical pathway, which was explained through a plausible mechanism. Finally, the success of microparticle impregnation into the NaPSS network was evaluated through Kaiser assay and imaging. This versatile synthetic procedure, having a reduced number of discrete reaction steps and eliminated intermediate work-ups, has established a fast and simple pathway to design functional polymers required to fabricate stable polymer-particle composites where the particles are impregnated covalently and controllably. Full article