Search Results (16)

Access to clean water remains a critical global challenge, exacerbated by population growth, industrial activity, and climate change. In response, this study presents the development and characterization of thermo-responsive and salt-adaptive ultrafiltration membranes functionalized with a poly(N-isopropylacrylamide)–co-poly(dimethylacrylamide) (PNIPAM-co-PDMAC) copolymer. By combining the thermo-responsive properties of PNIPAM with the hydrophilic characteristics of PDMAC, these membranes exhibit dual-stimuli responsiveness to temperature and ionic strength, allowing for precise control of permeability and fouling resistance. The experimental results demonstrated that the copolymer’s hydration state and dynamic pore size modulation are sensitive to changes in salinity and temperature, with sodium chloride (NaCl) significantly influencing the transition behavior. Preliminary fouling tests confirmed the antifouling capabilities of these membranes, with salt-triggered hydration transitions effectively reducing irreversible fouling and extending membrane durability. The membranes’ reversible properties and adaptability to dynamic operating conditions highlight their potential to enhance the efficiency and sustainability of water treatment processes. Future investigations will focus on scaling up the fabrication process and assessing the long-term stability of these membranes under real-world conditions. This study underscores the promise of smart membrane systems for advancing global water sustainability. Full article

In this study, novel triblock copolymers, including poly(N-isopropylacrylamide)-block-poly(ε-caprolactone)-block-poly(N-isopropylacrylamide) (PNIPAM-b-PCL-b-PNIPAM), poly(N-vinyl-pyrrolidone)-block-poly(ε-caprolactone)-block-poly(N-vinyl-pyrrolidone) (PNVP-b-PCL-b-PNVP), poly(N-isopropylacrylamide-co-N,N-dimethylaminoethyl methacrylate)-block-poly(ε-caprolactone)-block-poly(N-isopropylacrylamide-co-N,N-dimethylaminoethyl methacrylate) (P(DMAEMA-co-NIPAM)-b-PCL-b-P(NIPAM-co-DMAEMA)), and poly(N,N-dimethylacrylamide)-block-poly(ε-caprolactone)-block-poly(N,N-dimethylacrylamide) (PDMA-b-PCL-b-PDMA), were synthesized via a combination of ring-opening polymerization (ROP) and reversible addition–fragmentation chain transfer (RAFT) polymerization. The synthesis was performed using novel bifunctional PCL-based RAFT macro chain transfer agents (macroCTAs; MXTPCL-X1 and MXTPCL-X2) with a m-xylene-bis(2-mercaptoethyloxy) core. Initially, m-xylene-bis(1-hydroxy-3-thia-propane) (MXTOH), which has not previously been used in lactone polymerization, was synthesized via the reaction of α,α′-dibromo-m-xylene with 2-mercaptoethanol in the presence of sodium in ethanol. Subsequently, Sn(Oct)₂-catalyzed ROP of ε-caprolactone (ε-CL) using MXTOH as an initiator yielded PCL-diol (MXTPCLOH). The resulting PCL-diol underwent further functionalization through esterification and substitution reactions, leading to the formation of PCL-based RAFT macroCTAs. Triblock copolymers were synthesized using these macroCTAs with AIBN as an initiator. The synthesized products, along with their intermediates, were characterized using FTIR and ¹H NMR spectroscopy. The number average molecular weight (M_n) and polydispersity index (Ð) of PCL-based macroCTAs were determined by using GPC analysis. The sensor capabilities of the synthesized novel triblock copolymers were investigated on the determination of syringic acid and it was determined that the most sensitive polymer was PNVP-b-PCL-b-PNVP (MXTP2). The working range was between 1.5 µg/mL and 15 µg/mL and the limit of detection (LOD) was found to be 0.44 µg/mL using DPV on MXTP2 polymer sensor. Full article

Poly(2-hydroxyethylmethacrylate-co-2-(dimethylamino)ethyl methacrylate), P(HEMA-co-DMAEMAx), copolymers were quaternized through the reaction of a part of (dimethylamino)ethyl moieties of DMAEMA units with 1-bromohexadecane. Antimicrobial coatings were further prepared through the cross-linking reaction between the remaining DMAEMA units of these copolymers and the epoxide ring of poly(N,N-dimethylacrylamide-co-glycidyl methacrylate), P(DMAm-co-GMAx), copolymers. The combination of P(HEMA-co-DMAEMAx)/P(DMAm-co-GMAx) copolymers not only enabled control over quaternization and cross-linking for coating stabilization but also allowed the optimization of the processing routes towards a more facile cost-effective methodology and the use of environmentally friendly solvents like ethanol. Careful consideration was given to achieve the right content of quaternized units, qDMAEMA, to ensure antimicrobial efficacy through an appropriate amphiphilic balance and sufficient free DMAEMA groups to react with GMA for coating stabilization. Optimal synthesis conditions were achieved by membranes consisting of cross-linked P(HEMA78-co-DMAEMA9-co-qDMAEMA13)/P(DMAm-co-GMA42) membranes. The obtained membranes were multifunctional as they were self-standing and antimicrobial, while they demonstrated a distinct fast response to changes in humidity levels, widening the opportunities for the construction of “smart” antimicrobial actuators, such as non-contact antimicrobial switches. Full article

The group-transfer polymerization (GTP) of N,N-bis(2-methoxyethyl)acrylamide (MOEAm) initiated by Me₂EtSiH in the hydrosilylation-promoted method and by silylketene acetal (SKA) in the conventional method proceeded in a controlled/living manner to provide poly(N,N-bis(2-methoxyethyl)acrylamide) (PMOEAm) and PMOEAm with the SKA residue at the α-chain end (MCIP-PMOEAm), respectively. PMOEAm-b-poly(N,N-dimethylacrylamide) (PDMAm) and PMOEAm-s-PDMAm and PMOEAm-b-poly(N,N-bis(2-ethoxyethyl)acrylamide) (PEOEAm) and PMOEAm-s-PEOEAm were synthesized by the block and random group-transfer copolymerization of MOEAm and N,N-dimethylacrylamide or N,N-bis(2-ethoxyethyl)acrylamide. The homo- and copolymer structures affected the thermoresponsive properties; the cloud point temperature (T_cp) increasing by decreasing the degree of polymerization (x). The chain-end group in PMOEAm affected the T_cp with PMOEAm_x > MCIP-PMOEAm_x. The T_cp of statistical copolymers was higher than that of block copolymers, with PMOEAm_x-s-PDMAm_y > PMOEAm_x-b-PDMAm_y and PMOEAm_x-s-PEOEAm_y > PMOEAm_x-b-PEOEAm_y. Full article

Multiple responsive hydrogels are usually constructed by the addition of many different functional groups. Generally, these groups have different responsive behaviors which lead to interleaved and complex modes of the multi-response system. It is difficult to get a practical application. In this study, we show that multi-response hydrogels can also be constructed using dynamic bonds as crosslinks. The multiple responsive hydrogel films with thicknesses on the sub-micrometer or micrometer scale can be fabricated from P(DMAA-3-AAPBA), a copolymer of N,N-dimethylacrylamide, 3-(acrylamido)phenylboronic acid, and poly(vinylalcohol) (PVA) though a simple layer-by-layer (LbL) technique. The driving force for the film build up is the in situ-formed phenylboronate ester bonds between the two polymers. The films exhibit Fabry–Perot fringes on their reflection spectra which can be used to calculate the equilibrium swelling degree (SD_e) of the film so as to characterize its responsive behaviors. The results show that the films are responsive to temperature, glucose, and fructose with simple and practical linear response modes. More importantly, the speed of which the films respond to glucose or fructose is quite fast, with characteristic response times of 45 s and 7 s, respectively. These quick response films may have potential for real-time, continuous glucose or fructose monitoring. With the ability to bind with these biologically important molecules, one can expect that hydrogels may find more applications in biomedical areas in the future. Full article

This contribution reports the syntheses, structural analyses and properties of europium (Eu³⁺)- and terbium (Tb³⁺)-based coordination complexes of poly(N-isopropyl,N-methylacrylamide-stat-N,N-dimethylacrylamide) (poly(iPMAm-stat-DMAm)) copolymer, named as poly-Eu(III) and poly-Tb(III), respectively. In greater detail, poly(iPMAm₈₅-stat-DMAm₁₅) is first prepared by random copolymerization of N-isopropyl,N-methylacrylamide (iPMAm) and N,N-dimethylacrylamide (DMAm) via group transfer polymerization (GTP). Next, poly(iPMAm₈₅-stat-DMAm₁₅) is used as the polymer matrix for chelating with Eu³⁺ and Tb³⁺ cations at its side amide groups, to produce poly-Eu(III) and poly-Tb(III). Their structural characterizations by FT-IR spectroscopy and XPS confirm the formation of polymeric complexes. The study on their fluorescence emission characteristics and luminescence lifetime demonstrates that Poly-Eu(III) shows four strong emission peaks at 578, 593, 622, and 651 nm, which are responsible for the electron transitions from the excited ⁵D₀ state to the multiplet ⁷F_J (J = 0, 1, 2, 3) states, respectively, and poly-Tb(III) also displays four emission peaks at 489, 545, 588, and 654 nm, mainly due to the electron transitions of ⁵D₄ → ⁷F_i (i = 6, 5, 4, 3). The luminescence lifetimes of poly-Eu(III) (τ_poly-Eu(III)) and poly-Tb(III) (τ_poly-Tb(III)) are determined to be 4.57 and 7.50 ms, respectively. In addition, in aqueous solutions, poly-Eu(III) and poly-Tb(III) are found to exhibit thermoresponsivity, with their cloud temperatures (T_cs) locating around 36.4 and 36.8 °C, respectively. Finally, the cytotoxicity study on the human colon carcinoma cells LoVo and DLD1 suggests that the luminescent Eu³⁺ and Tb³⁺ in the chelated state with poly(iPMAm-stat-DMAm) show much better biocompatibility and lower toxicity than their inorganic salts. Full article

In this work, sensing behaviors and mechanisms of two crosslinked copolymers with dimethylamine and dimethylamide functional groups were compared and investigated for their ability to detect hydrogen chloride (HCl) gas. The crosslinked copolymer films were photopolymerized on quartz crystal electrodes using a micro-contact printing technique. The gas sensing behaviors were analyzed by measuring resonant frequency (Δf) of quartz crystal microbalance (QCM). The HCl binding capacity of photopolymerized films, with a mass between 4.6 and 5.9 μg, was optimized. Under optimized film mass conditions, the poly(2-dimethylaminoethyl methacrylate-co-ethylene glycol dimethacrylate) (DMAEMA-co-EGDMA), poly(DMAEMA-co-EGDMA), film, C2-DMA, showed a 13.9-fold higher binding capacity than the poly(N,N-dimethylacrylamide-co-ethylene glycol dimethacrylate, poly(DMAA-co-EGDMA), film, C0-DMA, during HCl gas adsorption. HCl gas was effectively adsorbed on the C2-DMA film because of the formation of tertiary amine salts through protonation and strong ionic bonding. Furthermore, the C2-DMA film exhibited excellent sensitivity, of 2.51 (ng/μg) (1/ppm), and selectivity coefficient (k* = 12.6 for formaldehyde and 13.5 for hydrogen fluoride) compared to the C0-DMA film. According to the experimental results, and due to its high functionality and stability, the C2-DMA film-coated QC electrode could be used as an HCl gas sensor, with low-cost and simple preparation, in future endeavors. Full article

We have previously demonstrated that poly(N-cyanomethylacrylamide) (PCMAm) exhibits a typical upper-critical solution temperature (UCST)-type transition, as long as the molar mass of the polymer is limited, which was made possible through the use of reversible addition-fragmentation chain transfer (RAFT) radical polymerization. In this research article, we use for the first time N-cyanomethylacrylamide (CMAm) in a typical aqueous dispersion polymerization conducted in the presence of poly(N,N-dimethylacrylamide) (PDMAm) macroRAFT agents. After assessing that well-defined PDMAm-b-PCMAm diblock copolymers were formed through this aqueous synthesis pathway, we characterized in depth the colloidal stability, morphology and temperature-responsiveness of the dispersions, notably using cryo-transmission electron microscopy (cryo-TEM), dynamic light scattering (DLS), small angle X-ray scattering (SAXS) and turbidimetry. The combined analyses revealed that stable nanometric spheres, worms and vesicles could be prepared when the PDMAm block was sufficiently long. Concerning the thermoresponsiveness, only diblocks with a PCMAm block of a low degree of polymerization (DP_n,PCMAm < 100) exhibited a UCST-type dissolution upon heating at low concentration. In contrast, for higher DP_n,PCMAm, the diblock copolymer nano-objects did not disassemble. At sufficiently high temperatures, they rather exhibited a temperature-induced secondary aggregation of primary particles. In summary, we demonstrated that various morphologies of nano-objects could be obtained via a typical polymerization-induced self-assembly (PISA) process using PCMAm as the hydrophobic block. We believe that the development of this aqueous synthesis pathway of novel PCMAm-based thermoresponsive polymers will pave the way towards various applications, notably as thermoresponsive coatings and in the biomedical field. Full article

Application-oriented hydrogel properties can be obtained by modifying the synthesis conditions of the materials. The purpose of this study is to achieve customized properties for sensing applications of hydrogel membranes based on poly(2-hydroxyethyl methacrylate), HEMA and N,N-dimethylacrylamide, DMAa. Copolymer p(HEMA-co-DMAa) hydrogels were prepared by varying the DMAa monomer ratio from 0–100% in 20% increments. Hydrogel membranes were characterized by attenuated infrared spectroscopy. Swelling and sorption were evaluated using cation solutions. Copolymers were also synthesized on the gold surface of quartz crystal microbalances (QCM) as coating membranes. A proof of concept was conducted for approaching the design and development of QCM sensors based on P(DMAa-co-HEMA)-membranes. Results showed that the water and ion adsorption capacity of hydrogel membranes increased with higher DMAa content. Membranes are not selective to a specific location but did show different transport features with each cation. The QCM coated with the selected membrane presented linear relationships between resonance frequency and ions concentration in solution (10–120 ppm). As a consequence, hydrogel membranes obtained are promising for the development of future biosensing devices. Full article

Due to a strong retardation effect of o-nitrobenzyl ester on polymerization, it is still a great challenge to prepare amphiphilic block copolymers for polymersomes with a o-nitrobenzyl ester-based hydrophobic block. Herein, we present one such solution to prepare amphiphilic block copolymers with pure poly (o-nitrobenzyl acrylate) (PNBA) as the hydrophobic block and poly (N,N’-dimethylacrylamide) (PDMA) as the hydrophilic block using bulk reversible addition-fragmentation chain transfer (RAFT) polymerization of o-nitrobenzyl acrylate using a PDMA macro-RAFT agent. The developed amphiphilic block copolymers have a suitable hydrophobic/hydrophilic ratio and can self-assemble into photoresponsive polymersomes for co-loading hydrophobic and hydrophilic cargos into hydrophobic membranes and aqueous compartments of the polymersomes. The polymersomes demonstrate a clear photo-responsive characteristic. Exposure to light irradiation at 365 nm can trigger a photocleavage reaction of o-nitrobenzyl groups, which results in dissociation of the polymersomes with simultaneous co-release of hydrophilic and hydrophobic cargoes on demand. Therefore, these polymersomes have great potential as a smart drug delivery nanocarrier for controllable loading and releasing of hydrophilic and hydrophobic drug molecules. Moreover, taking advantage of the conditional releasing of hydrophilic and hydrophobic drugs, the drug delivery system has potential use in medical applications such as cancer therapy. Full article

Micellar catalysts with a switchable core are attractive materials in organic synthesis. However, little is known about the role of the shell forming block on the performance of the catalyst. Thermoresponsive block copolymers based on poly(N-isopropylacrylamide-co-vinyl-4,4-dimethylazlactone) attached to different permanently hydrophilic blocks, namely poly(ethylene glycol), poly(N,N-dimethylacrylamide), and poly(2,3-dihydroxypropyl acrylate), were successfully synthesized via reversible addition/fragmentation chain transfer radical polymerization (RAFT). Post-polymerization attachment of an amino-functionalized L-prolineamide using the azlactone ring-opening reaction afforded functionalized thermoresponsive block copolymers. Temperature-induced aggregation of the functionalized block copolymers was studied using dynamic light scattering. It was shown that the chemical structure of the permanently hydrophilic block significantly affected the size of the polymer self-assemblies. The functionalized block copolymers were subjected to an aldol reaction between p-nitrobenzaldehyde and cyclohexanone in water. Upon temperature-induced aggregation, an increase in conversion was observed. The enantioselectivity of the polymer-bound organocatalyst improved with an increasing hydrophilic/hydrophobic interface as a result of the different stability of the polymer aggregates. Full article

Crosslinked polymeric materials based on a quaternary trimethylammonium compound were developed and evaluated as potential antifouling coatings. For this purpose, two water-soluble random copolymers, poly(4-vinylbenzyltrimethylammonium chloride-co-acrylic acid) P(VBCTMAM-co-AAx) and poly(N,N-dimethylacrylamide-co-glycidylmethacrylate) P(DMAm-co-GMAx), were synthesized via free radical polymerization. A water based approach for the synthesis of P(VBCTMAM-co-AAx) copolymer was used. Coatings of the complementary reactive copolymers in different compositions were obtained by curing at 120 °C for one day and were used to coat aquaculture nets. These nets were evaluated in respect to their release rate using Total Organic Carbon (TOC) and Total Nitrogen (TN) measurements. Finally, the antifouling efficacy of these newly-composed durable coatings was investigated for 14 days in accelerated conditions. The results showed that this novel polymeric material provides contact-killing antifouling activity for a short time period, whereas it functions efficiently in biofouling removal after high-pressure cleaning. Full article

The influence of the macromolecular architecture of block copolymers containing poly(N,N-dimethyl acrylamide) (PDMA) on the optical characteristics and sensing properties of corresponding thin films is discussed. Series of hydrophilic PDMA-based copolymers of different chemical composition and chain architecture such as triblock, star-shaped, and branched were synthesized. The copolymers were characterized using conventional spectroscopic techniques as well as methods for characterization of copolymer macromolecular characteristics in solution, namely size-exclusion chromatography and static light scattering. Thin films of the copolymers of nanometer scale thickness were deposited on silicon substrates by the spin-coating method. The refractive index and extinction coefficient of the copolymer films were calculated from the reflectance spectra by using non-linear curve fitting methods and the composition-structure-optical properties relationships were evaluated. Humidity-sensing properties of the films were studied by measuring reflectance spectra of the films at a relative humidity range from 5 to 95%RH. The implementation of the copolymer films as optical sensors of humidity is justified and discussed. Full article

A series of copolymers with an adamantyl side group (poly(NIPAM-co-AdMA) and poly(DMAM-co-AdMA)) were prepared by radical copolymerization of N-isopropylacrylamide (NIPAM) and N,N-dimethylacrylamide (DMAM) with a 2-methyl-2-adamantylmethacrylate (AdMA) monomer. The structure and composition of the as-synthesized copolymers were characterized by Fourier transform infrared (FT-IR) spectroscopy, proton nuclear magnetic resonance (¹H NMR) spectroscopy, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), and elemental analysis. Temperature and recognition dual responsivity of the copolymers was investigated by cloud point (T_cp) and dynamic light scattering (DLS), respectively. The results show that the as-synthesized copolymers are a kind of temperature-responsive polymer with a lower critical solution temperature (LCST). T_cp was approximately consistent with the critical temperature of intermolecular copolymer association (T_ass) from DLS. For these copolymers, T_cp decreases with increasing content of AdMA unit in the copolymers. After the addition of β-cyclodextrins (β-CD), T_cp increases, and the increment of T_cp values gradually became large with increasing content of AdMA in the copolymers. It is host-guest molecular recognition of β-CD and adamantyl groups that endows the as-synthesized copolymers with recognition-tunable thermosensitivity. Full article

The combination of reversible addition–fragmentation chain transfer (RAFT) and emulsion polymerization has recently attracted much attention as a synthetic tool for high-molecular-weight block copolymers and their micellar nano-objects. Up to recently, though, the use of thermoresponsive polymers as both macroRAFT agents and latex stabilizers was impossible in aqueous media due to their hydrophobicity at the usually high polymerization temperatures. In this work, we present a straightforward surfactant-free RAFT emulsion polymerization to obtain thermoresponsive styrenic block copolymers with molecular weights of around 100 kDa and their well-defined latexes. The stability of the aqueous latexes is achieved by adding 20 vol % of the cosolvent 1,4-dioxane (DOX), increasing the phase transition temperature (PTT) of the used thermoresponsive poly(N-acryloylpyrrolidine) (PAPy) macroRAFT agents above the polymerization temperature. Furthermore, this cosolvent approach is combined with the use of poly(N,N-dimethylacrylamide)-block-poly(N-acryloylpiperidine-co-N-acryloylpyrrolidine) (PDMA-b-P(APi-co-APy)) as the macroRAFT agent owning a short stabilizing PDMA end block and a widely adjustable PTT of the P(APi-co-APy) block in between 4 and 47 °C. The temperature-induced collapse of the latter under emulsion polymerization conditions leads to the formation of RAFT nanoreactors, which allows for a very fast chain growth of the polystyrene (PS) block. In dynamic light scattering (DLS), as well as cryo-transmission electron microscopy (cryoTEM), moreover, all created latexes indeed reveal a high (temperature) stability and a reversible collapse of the thermoresponsive coronal block upon heating. Hence, this paper pioneers a versatile way towards amphiphilic thermoresponsive high-molecular-weight block copolymers and their nano-objects with tailored corona switchability. Full article