Search Results (55)

This study presents a novel strategy for designing photocurable resins tailored for the additive manufacturing of smart thermoset materials. A quaternary formulation was developed by integrating bis(2-methacryloyl)oxyethyl disulfide (DADS) with an epoxy/thiol-ene system (ETES) composed of diglycidyl ether of bisphenol A (EP), pentaerythritol tetrakis(3-mercaptopropionate) (PTMP), and 4,4′-methylenebis(N,N-diallylaniline) (ACA4). This unique combination enables the simultaneous activation of four polymerization mechanisms: radical photopolymerization, thiol-ene coupling, thiol-Michael addition, and anionic ring-opening, within a single resin matrix. A key innovation lies in the exothermic nature of DADS photopolymerization, which initiates and sustains ETES curing at room temperature, enabling 3D printing without thermal assistance. This represents a significant advancement over conventional systems that require elevated temperatures or post-curing steps. The resulting hybrid poly(acrylate–co-ether–co-thioether) network exhibits enhanced mechanical integrity, shape memory behavior, and intrinsic self-healing capabilities. Dynamic Mechanical Analysis revealed a shape fixity and recovery of 93%, while self-healing tests demonstrated a 94% recovery of viscoelastic properties, as evidenced by near-overlapping storage modulus curves compared to a reference sample. This integrated approach broadens the design space for multifunctional photopolymers and establishes a versatile platform for advanced applications in soft robotics, biomedical devices, and sustainable manufacturing. Full article

Adhering to the principles of green analytical chemistry (GAC) is crucial for advancing sample pretreatment. In this work, we developed a green in-tube solid-phase microextraction (IT-SPME) material utilizing non-toxic cyclodextrin and zwitterionic polymers as co-functioning monomers. The hybrid monolithic material was synthesized within 38 min via an efficient epoxy ring-opening reaction and free radical polymerization. Comprehensive characterization confirmed a rigid framework with strong anti-swelling properties, good permeability, and high enrichment efficiency on the polymers. When coupled with HPLC-UV, the optimized IT-SPME method enabled highly sensitive detection of polypeptides (vancomycin and teicoplanin) in aqueous matrices, achieving detection limits as low as 15.0–20.0 μg L⁻¹, a wide linear range (60–800 μg L⁻¹, R² > 0.99), and good precision (RSDs = 5.9–8.2%). The prepared material demonstrated remarkable performance in real complex water samples, achieving recovery rates of up to 95.4%. Density functional theory (DFT) calculations indicated that the adsorption mechanism primarily involves hydrogen bonding and electrostatic interactions. This study presents an effective approach for the development of green chemical synthesis of extraction materials and offers a sustainable platform for monitoring trace contaminants in environmental waters. Full article

Background/Objectives: Biodegradable and pH-responsive nanocarriers using zwitterionic moieties represent a promising avenue for targeted delivery of chemotherapeutics. The present study addresses this by developing zwitterionic nanoparticles based on polylactic acid/poly(ethylene adipate) (PLA/PEAd) copolymers grafted with SBMA, designed to combine acid-triggered drug release with stealth-like biocompatibility. Methods: A series of polylactic acid/poly(ethylene adipate) (PLA/PEAd) copolymers with varying compositions (95/5, 90/10, and 75/25 w/w) were synthesized via ring-opening polymerization, followed by controlled radical grafting of the zwitterionic monomer [2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA), which was then successfully grafted upon their backbone. The resulting zwittenionic copolymers were thoroughly characterized for their structural and physicochemical properties, displaying tunable molecular weights of 3200–4900 g/mol, enhanced hydrophilicity and controlled degradation, with mass loss ranging from 8% to 83% over 30 days, depending on PEAd content and pH. Paclitaxel-loaded nanoparticles of spherical shape with sizes ranging from 220 to 565 nm were then fabricated. Drug release was pH-dependent with significantly higher release at pH 5.0 (up to ~79% for PLAPEAd7525-SBMA) compared to pH 7.4 (~18–35%). Hemolysis assays demonstrated excellent hemocompatibility, and cytotoxicity studies showed strong anticancer activity (>80% cell death in MDA-MB-231) with lower toxicity toward iMEFs, especially for PEAd-rich formulations. Conclusions: Our findings underline the potential of SBMA-functionalized PLA/PEAd nanoparticles as effective nano-carriers for tumor-targeted chemotherapy. Full article

Acrylated silicone elastomers for UV-curing 3D printing have gathered considerable attention in biomedical applications due to their exceptional mechanical and thermal stability. However, traditional manufacturing methods for these resins often face challenges such as stringent conditions and self-polymerization. In this study, various acrylate silicone resins (LMDT-AE) and silicone oils (PDMS-AE) were synthesized through ring-opening hydrolysis-polycondensation. The structures of LMDT-AE and PDMS-AE, with varying AE contents (molar ratio of organic groups to silicon atoms), were characterized using FTIR, ¹H NMR, ¹³C NMR, and GPC. Additionally, their physical properties, including viscosity, density, refractive index, and transparency, were thoroughly examined. The 3D-AE silicone resin composed of LMDT-AE-2.0 and PDMS-AE-20/1, in a mass ratio of 2:1, demonstrated superior mechanical properties, thermal stability, and curing shrinkage rate compared to other formulations. This curing silicone resin is capable of producing 3D physical entities with smooth surfaces and well-defined contours. It is shown that the successful preparation of transparent and high-strength UV-cured silicone resin based on free radical polymerization can provide a potential path for high-precision biological 3D printing. Full article

The valorization of agricultural waste has gained attention due to the need for sustainable technologies addressing environmental and economic challenges. The aim of this work is to investigate the electrochemical transformation of anacardic acid, a major component of cashew nut shell liquid (CNSL), into organic acids and polymeric materials. Cyclic voltammetry (CV) was carried out on ethanolic anacardic acid solutions with NaOH as the supporting electrolyte to induce oxidation reactions. CV, FTIR spectroscopy, and electrochemical impedance spectroscopy (EIS) were used to analyze the transformation processes. The results revealed oxidation sequences involving phenoxyl radicals, hydroquinones, and benzoquinones, leading to ring-opening reactions and the production of low-molecular-weight organic acids, including propionic, formic, oxalic, lactic, and acetic acids, as confirmed by HPLC. Polymerization processes were also observed, leading to the attainment of polymeric materials. FTIR spectra showed changes in phenol and carboxylic acid bands, confirming chemical transformations. CV and EIS indicated irreversible oxidation processes with charge transfer coefficients between 0.397 and 0.414 controlled by diffusion–adsorption. This work demonstrates the feasibility of electrochemical oxidation as a green method for producing organic acids from anacardic acid, aligning with circular economy principles and reducing reliance on petrochemical sources. It highlights the potential of electrochemical approaches for sustainable biomass utilization and fine chemical synthesis. Full article

Recently, the radical ring-opening polymerization of cyclic monomers has become one of the most important topics because it can impart degradability to vinyl polymers by introducing functional groups and heteroatoms into the main chain through copolymerization with vinyl monomers. In this study, we investigated the possibility of the ring-opening polymerization of the cyclic sulfone compounds, including sulfolane and sulfolene derivatives. First, the reactions of 2,5-dimethyl-3-sulfolene (DMS) were predicted using density functional theory (DFT) calculations, and the reaction product was actually examined after heating in the presence of a radical initiator. Next, we synthesized and polymerized 2-vinylsulfolane (2VS), which has been reported to undergo radical ring-opening polymerization in the literature and tried to modify the resulting polymers containing the unsaturated groups in the main chain via post-polymerization reaction by ene–thiol additions. We also examined the decomposition behavior of the polymer of 2VS before and after hydrogenation. Furthermore, we discussed the reactivity of 3-exomethylenesulfolane (3EMS), which is expected to exhibit radical ring-opening polymerization similar to 2VS, as well as the structure and reactivity of the corresponding polymer. Full article

The development of biomaterials with gradient surface modification capable of spatially controlled cell adhesion and migration is of great importance for tissue engineering and regeneration. In this study, we proposed a method for the covalent modification of PLA-based materials with a cationic polypeptide (polylysine, PLys) via a thiol-ene click reaction carried out under a light gradient. With this aim, PLA-based films were fabricated and modified with 2–aminoethyl methacrylate (AEMA) as a double bond source. The latter was introduced by reacting pre-formed and activated surface carboxyl groups with the amino group of AEMA. The success of the modification was confirmed by ¹H NMR, Raman and X-ray photoelectron spectroscopy data. A further photoinduced thiol-ene click reaction in the presence of a photosensitive initiator as a radical source was further optimized using cysteine. For grafting of PLys via the thiol-ene click reaction, PLys with a terminal thiol group was synthesized by ring-opening polymerization using Cys(Acm) as an amine initiator. Deprotection of the polypeptide resulted in the formation of free thiol groups of Cys-PLys. Successful gradient grafting of Cys-PLys was evidenced by covalent staining with the fluorescent dye Cy3-NHS. In addition, PLys gradient-dependent adhesion and migration of HEK 293 cells on PLys-PLA-based surfaces was confirmed. Full article

We report a one-pot synthesis of well-defined A₅B and A₈B miktoarm star-shaped polymers where N,N-dimethylaminoethyl methacrylate (DMAEMA) and various cyclic esters such as ε-caprolactone (ε-CL), lactide (LA) and glycolide (GA) were used for the synthesis. Miktopolymers were obtained by simultaneously carrying out atom transfer radical polymerization (ATRP) of DMAEMA, ring-opening polymerization (ROP) of cyclic esters, and click reaction between the azide group in gluconamide-based (GLBr₅-Az) or lactonamide-based (GLBr₈-Az) ATRP initiators and 4-pentyn-1-ol. The relatively low dispersity indices of the obtained miktoarm stars (Đ = 1.2–1.6) indicate that control over the polymerization processes was sustained despite almost complete monomers conversions (83–99%). The presence of salts from phosphate-buffered saline (PBS) in polymer solutions affects the phase transition, increasing cloud point temperatures (T_CP) values. The critical aggregation concentration (CAC) values increased with a decreasing number of average molecular weights of the hydrophobic fraction. Hydrolytic degradation studies revealed that the highest reduction of molecular weight was observed for polymers with PCL and PLGCL arm. The influence of the composition on the miktopolymers hydrophilicity was investigated via water contact angle (WCA) measurement. Thermogravimetric analysis (TGA) disclosed that the number of arms and their composition in the miktopolymer affects its weight loss under the influence of temperature. Full article

Dermatology and cosmetology currently prioritize healthy, youthful-looking skin. As a result, research is being conducted worldwide to uncover natural substances and carriers that allow for controlled release, which could aid in the battle against a variety of skin illnesses and slow the aging process. This study examined the biological and physicochemical features of novel hydrogels containing cannabidiol (CBD) and α-terpineol (TER). The hydrogels were obtained from ε-caprolactone (CL) and poly(ethylene glycol) (PEG) copolymers, diethylene glycol (DEG), poly(tetrahydrofuran) (PTHF), 1,6-diisocyanatohexane (HDI), and chitosan (CHT) components, whereas the biodegradable oligomers were synthesized using the enzyme ring-opening polymerization (e-ROP) method. The in vitro release rate of the active compounds from the hydrogels was characterized by mainly first-order kinetics, without a “burst release”. The antimicrobial, anti-inflammatory, cytotoxic, antioxidant, and anti-aging qualities of the designed drug delivery systems (DDSs) were evaluated. The findings indicate that the hydrogel carriers that were developed have the ability to scavenge free radicals and impact the activity of antioxidant enzymes while avoiding any negative effects on keratinocytes and fibroblasts. Furthermore, they have anti-inflammatory qualities by impeding protein denaturation as well as the activity of proteinase and lipoxygenase. Additionally, their ability to reduce the multiplication of pathogenic bacteria and inhibit the activity of collagenase and elastase has been demonstrated. Thus, the developed hydrogel carriers may be effective systems for the controlled delivery of CBD, which may become a valuable tool for cosmetologists and dermatologists. Full article

Polymerization-induced self-assembly (PISA) is a powerful and versatile technique for producing colloidal dispersions of block copolymer particles with desired morphologies. Currently, PISA can be carried out in various media, over a wide range of temperatures, and using different mechanisms. This method enables the production of biodegradable objects and particles with various functionalities and stimuli sensitivity. Consequently, PISA offers a broad spectrum of potential commercial applications. The aim of this review is to provide an overview of the current state of rational synthesis of block copolymer particles with diverse morphologies using various PISA techniques and mechanisms. The discussion begins with an examination of the main thermodynamic, kinetic, and structural aspects of block copolymer micellization, followed by an exploration of the key principles of PISA in the formation of gradient and block copolymers. The review also delves into the main mechanisms of PISA implementation and the principles governing particle morphology. Finally, the potential future developments in PISA are considered. Full article

This study explores the synthesis, characterization, and application of a heterofunctional initiator derived from 2-hydroxypropyl cyclodextrin (HP-β-CD), having eight bromoester groups and thirteen hydroxyl groups allowing the synthesis of mikto-arm star-shaped polymers. The bromoesterification of HP-β-CD was achieved using α-bromoisobutyryl bromide as the acylation reagent, modifying the cyclodextrin (CD) molecule as confirmed by electrospray ionization mass spectrometry (ESI-MS), nuclear magnetic resonance (NMR), attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy analysis, and differential scanning calorimetry (DSC) thermograms. The initiator’s effectiveness was further demonstrated by obtaining star-comb and mikto-arm polymers via an enzymatically assisted atom transfer radical polymerization (ATRP) method and subsequent ring-opening polymerization (ROP). The ATR polymerization quality and control depended on the type of monomer and was optimized by the way of introducing the initiator into the reaction mixture. In the case of ATRP, high conversion rates for poly(ethylene oxide) methyl ether methacrylate (OEOMA), with molecular weights (Mn) of 500 g/mol and 300 g/mol, were achieved. The molecular weight distribution of the obtained polymers remained in the range of 1.23–1.75. The obtained star-comb polymers were characterized by different arm lengths. Unreacted hydroxyl groups in the core of exemplary star-comb polymers were utilized in the ROP of ε-caprolactone (CL) to obtain a hydrophilic mikto-arm polymer. Cloud point temperature (T_CP) values of the synthesized polymers increased with arm length, indicating the polymers’ reduced hydrophobicity and enhanced solvation by water. Atomic force microscopy (AFM) analysis revealed the ability of the star-comb polymers to create fractals. The study elucidates advancements in the synthesis and utilization of hydrophilic sugar-based initiators for enzymatically assisted ATRP in an aqueous solution for obtaining complex star-comb polymers in a controlled manner. Full article

Syntheses of novel bifunctional poly(methyl methacrylate) (PMMA)-, poly(styrene) (PS)-, and (poly ε-caprolactone) (PCL)-based atom transfer radical polymerization (ATRP) macroinitiators derived from p-xylene-bis(1-hydroxy-3-thia-propanoloxy) core were carried out to obtain ABA-type block copolymers. Firstly, a novel bifunctional ATRP initiator, 1,4-phenylenebis(methylene-thioethane-2,1-diyl)bis(2-bromo-2-methylpropanoat) (PXTBR), synthesized the reaction of p-xylene-bis(1-hydroxy-3-thia-propane) (PXTOH) with α-bromoisobutryl bromide. The PMMA and PS macroinitiators were prepared by ATRP of methyl methacrylate (MMA) and styrene (S) as monomers using (PXTBR) as the initiator and copper(I) bromide/N,N,N′,N″,N″-pentamethyldiethylenetriamine (CuBr/PMDETA) as a catalyst system. Secondly, di(α-bromoester) end-functionalized PCL–based ATRP macronitiator (PXTPCLBr) was prepared by esterification of hydroxyl end groups of PCL-diol (PXTPCLOH) synthesized by Sn(Oct)₂–catalyzed ring opening polymerization (ROP) of ε-CL in bulk using (PXTOH) as initiator. Finally, ABA-type block copolymers, PXT(PS-b-PMMA-b-PS), PXT(PMMA-b-PS-b-PMMA), PXT(PS-b-PCL-b-PS), and PXT(PMMA-b-PCL-b-PMMA), were synthesized by ATRP of MMA and S as monomers using PMMA-, PS-, and PCL-based macroinitiators in the presence of CuBr/PMDETA as the catalyst system in toluene or N,N-dimethylformamide (DMF) at different temperatures. In addition, the extraction abilities of PCL and PS were investigated under liquid–liquid phase conditions using heavy metal picrates (Ag⁺, Cd²⁺, Cu²⁺, Hg²⁺, Pb²⁺, and Zn²⁺) as substrates and measuring with UV-Vis the amounts of picrate in the 1,2–dichloroethane phase before and after treatment with the polymers. The extraction affinity of PXTPCL and PXTPS for Hg²⁺ was found to be highest in the liquid–liquid phase extraction experiments. Characterizations of the molecular structures for synthesized novel initiators, macroinitiators, and the block copolymers were made by spectroscopic (FT–IR, ESI–MS, ¹H NMR, ¹³C NMR), DSC, TGA, chromatographic (GPC), and morphologic SEM. Full article

A fluorescent and colorimetric poly (acrylamide)-based copolymer probe P(AAm-co-RBNCH) has been designed via free radical polymerization of a commercial acrylamide monomer with a rhodamine-functionalized monomer RBNCH. Metal ion selectivity of RBNCH was investigated by fluorescence and colorimetric spectrophotometry. Upon addition of Fe³⁺, a visual color change from colorless to red and a large fluorescence enhancement were observed for the ring-opening of the rhodamine spirolactam mechanism. The monomer gives a sensitive method for quantitatively detecting Fe³⁺ in the linear range of 100–200 μM, with a limit of detection as low as 27 nM and exhibiting high selectivity for Fe³⁺ over 12 other metal ions. The hydrogel sensor was characterized by FTIR, and the effects of RBNCH amount on gel content and swelling properties were explored. According to the recipe of 1.0 mol% RBNCH to the total monomers, the fabricated hydrogel sensor displayed a good swelling property and reversibility performance and has potential for application in the imaging of Fe³⁺ level in industrial wastewater. Full article

Due to their diverse and unique physical properties, miktoarm star copolymers (μ-SCPs) have garnered significant attention. In our study, we employed α-monobomoisobutyryl-terminated polydimethylsiloxane (PDMS-Br) to carry out styrenics-assisted atom transfer radical coupling (SA ATRC) in the presence of 4-vinylbenzyl alcohol (VBA) at 0 °C. By achieving high coupling efficiency (χ_c = 0.95), we obtained mid-chain functionalized PDMS-VBA_m-PDMS polymers with benzylic alcohols. Interestingly, matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF MS) analysis revealed the insertion of only two VBA coupling agents (m = 2). Subsequently, the PDMS-VBA₂-PDMS products underwent mid-chain extensions using ε-caprolactone (ε-CL) through ring-opening polymerization (ROP) with an efficient organo-catalyst at 40 °C, resulting in the synthesis of novel (PDMS)₂-μ-(PCL)₂ μ-SCPs. Eventually, novel (PDMS)₂-μ-(PCL)₂ μ-SCPs were obtained. The obtained PDMS-μ-PCL μ-SCPs were further subjected to examination of their solid-state self-assembly through small-angle X-ray scattering (SAXS) experiments. Notably, various nanostructures, including lamellae and hexagonally packed cylinders, were observed with a periodic size of approximately 15 nm. As a result, we successfully developed a simple and effective reaction combination (Є) strategy (i.e., SA ATRC-Є-ROP) for the synthesis of well-defined PDMS-μ-PCL μ-SCPs. This approach may open up new possibilities for fabricating nanostructures from siloxane-based materials. Full article

Medical titanium alloy Ti-6Al-4V (TC4) has been widely used in the medical field, especially in human tissue repair. However, TC4 has some shortcomings, which may cause problems with biocompatibility and mechanical compatibility in direct contact with the human body. To solve this problem, physical gels are formed on the surface of TC4, and the storage modulus of the formed physical gel matches that of the human soft tissue. 2-bromoisobutyryl bromide (BIBB) and dopamine (DA) were used to form initiators on the surface of hydroxylated medical titanium alloy. Different initiators were formed by changing the ratio of BIBB and DA, and the optimal one was selected for subsequent reactions. Under the action of the catalyst, L-lactide and D-lactide were ring-opened polymerized with hydroxyethyl methacrylate (HEMA), respectively, to form macromolecular monomers HEMA-PLLA₂₉ and HEMA-PDLA₂₉ with a polymerization degree of 29. The two macromolecular monomers were stereo-complexed by ultrasound to form HEMA-stereocomplex polylactic acid (HEMA-scPLA₂₉). Based on two monomers, 2-(2-methoxyethoxy) ethyl methacrylate (MEO₂MA) and oligo (ethylene oxide) methacrylate (OEGMA), and the physical crosslinking agent HEMA-scPLA_29, physical gels are formed on the surface of TC4 attached to the initiator via Atom Transfer Radical Addition Reaction (ATRP) technology. The hydrogels on the surface of titanium alloy were characterized and analyzed by a series of instruments. The results showed that the storage modulus of physical glue was within the range of the energy storage modulus of human soft tissue, which was conducive to improving the mechanical compatibility of titanium alloy and human soft tissue. Full article