Search Results (70)

Poly(9,9-di-n-octylfluorene) (PFO) suffers from interchain aggregation, which degrades its blue spectral stability and charge transport. To address this, a series of rod-coil diblock copolymers (PFO-b-PMMAs) with varying poly(methyl methacrylate) (PMMA) chain lengths were synthesized via Steglich coupling. The non-conjugated PMMA blocks act as bulky steric spacers in the solid state, effectively suppressing detrimental PFO aggregation and enhancing pure blue emission stability. Furthermore, moderate PMMA blocks (PFO-b-PMMA1 and PFO-b-PMMA2) promote favorable β-phase formation and ordered crystalline packing. This microstructural optimization yields a maximum electron mobility of 1.98 × 10⁻⁶ cm²/(V·s) for PFO-b-PMMA2, markedly higher than the PFO-2 homopolymer (4.13 × 10⁻⁷ cm²/(V·s)). However, an overlong PMMA block (PFO-b-PMMA3) introduces excessive steric hindrance (T_g = 66 °C) that disrupts crystallization, acting as an insulating barrier that reduces mobility. Thus, precisely tuning the non-conjugated block length effectively maximizes both the blue spectral stability and electron transport capabilities of PFO-based materials. Full article

Polymer coatings as thin films stand out as a commonly used strategy to modify biosensor surfaces for improving detection performance; however, nonspecific biomolecule interactions and the limited degree of ligand conjugation on the surface have necessitated the development of innovative methods for surface modification. To this end, methacrylated tethered telechelic polyethylene glycol (PEG-diMA) chains of three different molecular weights (2, 6, and 10 kDa) were synthesized herein and used for obtaining thiolated nanoparticles (NPs) upon adding excess amounts of a tetra-thiol crosslinker. Characterized according to their size, surface charge, morphology, and thiol amounts, these nanoparticles were immobilized on gold surfaces that mimicked gold-coated mass sensor platforms. The PEG-based nanoparticles, prepared especially by PEG6K-diMA polymers, were shown to result in the preparation of a monolayer and smooth coating of 80–120 nm thickness. Cysteine-modified NTS(8–13) peptide (RRPYIL) was conjugated to thiolated NP with reversible disulfide bonds and it was demonstrated that its cleavage with a reducing agent such as dithiothreitol (DTT) restores the NP-immobilized gold surface for at least two cycles. Together with its binding studies to NTSR2 antibodies, it was revealed that the peptide-conjugated NP-modified gold surface could be employed as a model for a reusable sensor surface for the detection of biomarkers of same or different types. Full article

This study explored the formation of soft colloidal particles from a diblock ionomer (DI) with the monomeric composition (acrylonitrile)_x-co-(glycidyl methacrylate)_y-b-(3-sulfopropyl methacrylate potassium)_z—abbreviated as (A_xG_y)S_z, where x >> z > y. A colloidal dispersion was generated by introducing water into the pre-prepared DMSO solutions of DI, which led to micelle formation and subsequent coagulation. The assembly of the hydrophobic (A_xG_y) blocks was influenced by water content and chain conformational flexibility (the ability to adopt various forms of conformation). The resulting microgel structure (in particle form) consists of coagulated micelles characterized by discrete internal hydrophobic gel domains and continuous external hydrophilic gel layers. Characterization methods included light scattering, zeta potential analysis, and particle size distribution measurements. In contrast, the copolymer (A_xG_y) chains form random coil aggregates in DMSO–H₂O mixtures, displaying a chain packing state distinct from the hydrophobic gel domains as aforementioned. Additionally, the amphiphilic glycidyl methacrylate (G) units within the (A_xG_y) block were found to modulate the microgel dimensions. Notably, the nanoscale hydrogel corona exhibits high accessibility to reactive species in aqueous media. The typical microgel has a spherical shape with a diameter ranging from 50 to 120 nm. It exhibits a zeta potential of −65 mV in a neutral aqueous medium; however, it may precipitate if the metastable colloidal dispersion state cannot be maintained. Its properties could be tailored through adjusting the internal chain conformation, highlighting its potential for diverse applications. Full article

The removal of surface residues from single-layer graphene (SLG), including poly(methyl methacrylate) (PMMA) polymers and Cl⁻ ions, during the transfer process remains a significant challenge with regard to preserving the intrinsic properties of SLG, with the process often leading to unintended doping and reduced electronic performance capabilities. This study presents a rapid and efficient surface treatment method that relies on an aqueous sodium nitrite (NaNO₂) solution to remove such contaminants effectively. The NaNO₂ solution rinse leverages reactive nitric oxide (NO) species to neutralize ionic contaminants (e.g., Cl⁻) and partially oxidize polymer residues in less than 10 min, thereby facilitating a more thorough final cleaning while preserving the intrinsic properties of graphene. Characterization techniques, including atomic force microscopy (AFM), Kelvin probe force microscopy (KPFM), and X-ray photoelectron spectroscopy (XPS), demonstrated substantial reductions in the levels of surface residues. The treatment restored the work function of the SLG to approximately 4.79 eV, close to that of pristine graphene (~4.5–4.8 eV), compared to the value of nearly 5.09 eV for conventional SLG samples treated with deionized (DI) water. Raman spectroscopy confirmed the reduced doping effects and improved structural integrity of the rinsed SLG. This effective rinsing process enhances the reproducibility and performance of SLG, enabling its integration into advanced electronic devices such as organic light-emitting diodes (OLEDs), photovoltaic (PV) cells, and transistors. Furthermore, the technique is broadly applicable to other two-dimensional (2D) materials, paving the way for next-generation (opto)electronic technologies. Full article

Tuning the critical solution temperature (CST) of thermoresponsive polymers is essential to exploit their immense potential in various applications. In the present study, the effect of PEG-methyl ether methacrylate with a higher molecular weight of 1100 g/mol (mPEGMA₁₁₀₀) as a comonomer was investigated for its suitability for the CST adjustment of LCST-type polymers. Accordingly, a library of mPEGMA₁₁₀₀-based copolymers was established with varying compositions (X_mPEGMA1100) using four main comonomers, namely di(ethylene glycol) ethyl ether acrylate, N-isopropyl acrylamide and methacrylamide, and mPEGMA₃₀₀, with different CST values (cloud points, T_CP, and clearing points, T_CL, by turbidimetry). It was found that less than 20 mol% of the mPEGMA₁₁₀₀ in the copolymers is practically sufficient for tuning the CST in the entire measurable temperature range, i.e., up to 100 °C, regardless of the CST of the homopolymer of the main comonomer (CST₀). Moreover, a predictive asymptotic model was developed based on the measured CST values, which strikingly revealed that the CSTs of mPEGMA₁₁₀₀-containing copolymers depend only on the two main parameters of these copolymers, X_mPEGMA1100 and the CST of the homopolymer of the main comonomer (CST₀), that is, CST = f(CST₀, X_mPEGMA1100). The revealed two-parameter relationship defines a surface in 3D plotting, and it is applicable to determine the CST of copolymers in advance for a given composition or to define the suitable composition for a required CST value. These unprecedented results on the dependence of CSTs on two major well-defined parameters enable to design a variety of novel macromolecular structures with tailored thermoresponsive properties. Full article

Background/Objectives: The endosomal escape of lipid nanoparticles (LNPs) is crucial for efficient mRNA-based therapeutics. Here, we present a cationic polymeric micelle (cPM) as a safe and potent co-delivery system with enhanced endosomal escape capabilities. Methods: We synthesized a cationic and ampholytic di-block copolymer, poly (poly (ethylene glycol)_4-5 methacrylate_a-co-hexyl methacrylate_b)_X-b-poly(butyl methacrylate_c-co-dimethylaminoethyl methacrylate_d-co-propyl acrylate_e)_Y (p(PEG_4-5MA_a-co-HMA_b)_X-b-p(BMA_c-co-DMAEMA_d-co-PAA_e)_Y), via reversible addition–fragmentation chain transfer polymerization. The cPMs were then formulated using the synthesized polymer by the dispersion–diffusion method and characterized by dynamic light scattering (DLS) and cryo-transmission electron microscopy (CryoTEM). The membrane-destabilization activity of the cPMs was evaluated by a hemolysis assay. We performed an in vivo functional assay of firefly luciferase (Fluc) mRNA using two of the most commonly studied LNPs, SM102 LNP and Dlin-MC3-DMA LNPs. Results: With a particle size of 61.31 ± 0.68 nm and a zeta potential of 37.76 ± 2.18 mV, the cPMs exhibited a 2–3 times higher firefly luciferase signal at the injection site compared to the control groups without cPMs following intramuscular injection in mice, indicating the high potential of cPMs to enhance the endosomal escape efficiency of mRNA-LNPs. Conclusions: The developed cPM, with enhanced endosomal escape capabilities, presents a promising strategy to improve the expression efficiency of delivered mRNAs. This approach offers a novel alternative strategy with no modifications to the inherent properties of mRNA-LNPs, preventing any unforeseeable changes in formulation characteristics. Consequently, this polymer-based nanomaterial holds immense potential for clinical applications in mRNA-based vaccines. Full article

A series of copolymers containing a thermo-responsive biocompatible first block of poly[di(ethylene glycol) methyl ether methacrylate)-co-(oligo(ethylene glycol) methyl ether methacrylate], P(DEGMA-co-OEGMA) were chain-extended to incorporate either poly(N-isopropylacrylamide), PNIPAAm or poly(N-isopropylacrylamide-co-butyl acrylate), P(NIPAAm-co-BA) as second thermo-responsive block using reversible addition–fragmentation chain transfer (RAFT) polymerization. P(DEGMA-co-OEGMA)-b-PNIPAAm copolymers showed two response temperatures at 33 and 43 °C in an aqueous solution forming stable aggregates at 37 °C. In contrast, P(DEGMA-co-OEGMA)-b-P(NIPAAm-co-BA) copolymers showed aggregation below room temperature due to the shift in response temperature provoked by the presence of hydrophobic butyl acrylate (BA) units, and shrinkage upon heating up to body temperature, while maintaining the second response temperature above 40 °C. The terminal trithiocarbonate group of the block copolymers was modified to a thiol functionality and used to stabilize gold nanorods (GNRDs) via the “grafting to” approach. The Localized Surface Plasmon Resonance (LSPR) absorption band of GNRDs with an aspect ratio of 3.9 (length/diameter) was located at 820 nm after surface grafting with block copolymers showing a hydrodynamic diameter of 160 nm at 37 °C. On the other hand, the stability of the P(DEGMA-co-OEGMA)-b-PNIPAAm@GNRDs and P(DEGMA-co-OEGMA)-b-P(NIPAAm-co-BA)@GNRDs nanohybrids was monitored for 8 days; where the LSPR absorption band did not shift or show any broadening. Aqueous dispersed nanohybrids were irradiated with a near-infrared laser (300 mW), where the temperature of the surroundings increased 16 °C after 16 min, where conditions for no precipitation were determined. These tailored temperature-responsive nanohybrids represent interesting candidates to develop drug nanocarriers for photo-thermal therapies. Full article

Aggregation-induced emission dyes (AIEs) have gained significant interest due to their unique optical properties. Upon aggregation, AIEs can exhibit remarkable fluorescence enhancement. These systems are ideal candidates for applications in bioimaging, such as image-guided drug delivery or surgery. Encapsulation of AIEs in polymeric nanocarriers can result in biocompatible and efficient nanosystems. Herein, we report the fabrication of novel nanoaggregates formulated by amino terpolymer and tetraphenylethylene (TPE) AIE in aqueous media. Poly(di(ethylene glycol) methyl ether methacrylate-co-2-(dimethylamino)ethylmethacrylate-co-oligoethylene glycol methyl ether methacrylate), P(DEGMA-co-DMAEMA-co-OEGMA) hydrophilic terpolymer was utilized for the complexation of the sodium tetraphenylethylene 4,4′,4″,4‴-tetrasulfonate AIE dye. Fluorescence spectroscopy, physicochemical studies, and self-assembly in aqueous and fetal bovine serum media were carried out. The finely dispersed nanoparticles exhibited enhanced fluorescence compared to the pure dye. To investigate the role of tertiary amino groups in the aggregation phenomenon, the polymer was quaternized, and quaternized polymer nanocarriers were fabricated. The increase in fluorescence intensity indicated stronger interaction between the cationic polymer analog and the dye. A stronger interaction between the nanoparticles and fetal bovine serum was observed in the case of the quaternized polymer. Thus, P(DEGMA-co-DMAEMA-co-OEGMA) formulations are better candidates for bioimaging applications than the quaternized ones, presenting both aggregation-induced emission and less interaction with fetal bovine serum. Full article

Aqueous solutions of a thermoresponsive diblock copolymer poly(di-[ethylene glycol] methyl ether methacrylate)-b-poly(2-[diisopropylamino] ethyl methacrylate) (PDEGMA-b-PDIPAEMA) were studied by static, dynamic and electrophoretic light scattering, small-angle X-ray scattering and differential scanning calorimetry. Thermoresponsive behavior of PDEGMA-b-PDIPAEMA was investigated at two pH values, pH = 2, at which the terminal carboxylic group of the PDEGMA chain and the PDIPAEMA block are protonated, and pH = 7, where the carboxyl terminal group is ionized while the PDIPAEMA block is partially deprotonated and more hydrophobic. Both at pH = 2 and 7, PDEGMA-b-PDIPAEMA copolymer underwent extensive association (the size of the aggregates was between 100 and 300 nm), indicating strong interchain interactions. While the measurements confirmed thermoresponsive behavior of PDEGMA-b-PDIPAEMA at pH = 7, no changes in the association with temperature were observed at pH 2 as the thermoresponsivity of PDEGMA was suppressed by hydrogen bonding between carboxylic groups and PDEGMA segments, as well as due to the increased hydrophilicity of the PDIPAEMA block. Fluorescence measurements with pyrene as a fluorescent probe showed that both at pH = 2 and pH = 7 the associates were able to solubilize hydrophobic substances. Full article

Brain-inspired flexible neuromorphic devices are of great significance for next-generation high-efficiency wearable sensing and computing systems. In this paper, we propose a flexible organic electrochemical transistor using poly[(bithiophene)-alternate-(2,5-di(2-octyldodecyl)- 3,6-di(thienyl)-pyrrolyl pyrrolidone)] (DPPT-TT) as the organic semiconductor and poly(methyl methacrylate) (PMMA)/LiClO₄ solid-state electrolyte as the gate dielectric layer. Under gate voltage modulation, an electric double layer (EDL) forms between the dielectric layer and the channel, allowing the device to operate at low voltages. Furthermore, by leveraging the double layer effect and electrochemical doping within the device, we successfully mimic various synaptic behaviors, including excitatory post-synaptic currents (EPSC), paired-pulse facilitation (PPF), high-pass filtering characteristics, transitions from short-term plasticity (STP) to long-term plasticity (LTP), and demonstrate its image recognition and storage capabilities in a 3 × 3 array. Importantly, the device’s electrical performance remains stable even after bending, achieving ultra-low-power consumption of 2.08 fJ per synaptic event at −0.001 V. This research may contribute to the development of ultra-low-power neuromorphic computing, biomimetic robotics, and artificial intelligence. Full article

Urethane acrylate (UA) was synthesized from various di-polyols, such as poly(tetrahydrofuran) (PTMG, Mn = 1000), poly(ethylene glycol) (PEG, Mn = 1000), and poly(propylene glycol) (PPG, Mn = 1000), for use as a polymer binder for paint. Polymethyl methacrylate (PMMA) and UA were blended to form an acrylic resin with high transmittance and stress-strain curve. When PMMA was blended with UA, a network structure was formed due to physical entanglement between the two polymers, increasing the mechanical properties. UA was synthesized by forming a prepolymer using di-polyol and hexamethylene diisocyanate, which were chain structure monomers, and capping them with 2-hydroxyethyl methacrylate to provide an acryl group. Fourier transform infrared spectroscopy was used to observe the changes in functional groups, and gel permeation chromatography was used to confirm that the three series showed similar molecular weight and PDI values. The yellowing phenomenon that appears mainly in the curing reaction of the polymer binder was solved, and the mechanical properties according to the effects of the polyol used in the main chain were compared. The content of the blended UA was quantified using ultravioletvisible spectroscopy at a wavelength of 370 nm based on 5, 10, 15, and 20 wt%, and the shear strength and tensile strength were evaluated using specimens in a suitable mode. The ratio for producing the polymer binder was optimized. The mechanical properties of the polymer binder with 5–10 wt% UA were improved in all series. Full article

Thin films of carbazole (Cz) derivatives are frequently used in organic electronics, such as organic light-emitting diodes (OLEDs). Because of the proximity of the Cz units, the excited-state relaxation in such films is complicated, as intermolecular pathways, such as singlet–singlet annihilation (SSA), kinetically compete with the emission. Here, we provide an investigation of two benchmark systems employing neat carbazole and 3,6-di-tert-butylcarbazole (t-Bu-Cz) films and also their thin film blends with poly(methyl methacrylate) (PMMA). These are investigated by a combination of atomic force microscopy (AFM), femtosecond and nanosecond transient absorption spectroscopy (fs-TA and ns-TA) and time-resolved fluorescence. Excitonic J-aggregate-type features are observed in the steady-state absorption and emission spectra of the neat films. The S₁ state shows a broad excited-state absorption (ESA) spanning the entire UV–Vis–NIR range. At high S₁ exciton number densities of about 4 × 10¹⁸ cm⁻³, bimolecular diffusive S₁–S₁ annihilation is found to be the dominant SSA process in the neat films with a rate constant in the range of 1–2 × 10⁻⁸ cm³ s⁻¹. SSA produces highly vibrationally excited molecules in the electronic ground state (S₀*), which cool down slowly by heat transfer to the quartz substrate. The results provide relevant photophysical insight for a better microscopic understanding of carbazole relaxation in thin-film environments. Full article

Self-healing nanocomposites can be generated by organic functionalization of inorganic nanoparticles and complementary functionalization of the polymer matrix, allowing reversible interactions between the two components. Here, we report on self-healing nanocomposites based on ionic interactions between anionic copolymers consisting of di(ethylene glycol) methyl ether methacrylate, sodium 4-(methacryloyloxy)butan-1-sulfonate, and cationically functionalized iron oxide nanoparticles. The materials exhibited hygroscopic behavior. At water contents < 6%, the shear modulus was reduced by up to 90%. The nanoparticle concentration was identified as a second factor strongly influencing the mechanical properties of the materials. Backscattered scanning electron microscopy and small-angle X-ray scattering measurements showed the formation of agglomerates in the size range of 100 nm to a few µm in diameter, independent of concentration, resulting in the disordering of the semi-crystalline ionic polymer blocks. These effects resulted in an increase in the shear modulus of the composite from 3.7 MPa to 5.6 MPa, 6.3 Mpa, and 7.5 MPa for 2, 10, and 20 wt% particles, respectively. Temperature-induced self-healing was possible for all composites investigated. However, only 36% of the maximum stress could be recovered in systems with a low nanoparticle content, whereas the original properties were largely restored (>85%) at higher particle contents. Full article

New amphiphilic VP-(di)methacrylate terpolymers of different monomer compositions and topologies have been synthesized by radical polymerization in toluene without any growth regulator of polymer chains. Their structures and properties in solid state and water solution were studied by double-detector size-exclusion chromatography; IR-, ¹H, and ¹³C NMR-spectroscopy; DLS, TEM, TG, and DSC methods. The composition of the VP-AlkMA-TEGDM monomer mixture has been established to regulate the topology of the resulting macromolecules. The studied terpolymers presented on TEM images as individual low-contrast particles and their conglomerates of various sizes with highly ordered regions; in general, they are amorphous structures. None of the terpolymers demonstrated cytotoxic effects for noncancerous Vero and tumor HeLa cells. Hydrophobic D-α-tocopherol (TP) was encapsulated in terpolymer nanoparticles (NPs), and its antioxidant activity was evaluated by ABTS (radical monocation 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid)) or DPPH (2,2′-diphenyl-1-picrylhydrazyl) methods. The reaction efficiency depends on the TP-NP type. The IC₅₀ values for the decolorization reaction of ABTS^•+ and DPPH inhibition in the presence of initial and encapsulated TP were obtained. 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