Search Results (288)

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

Chain topology offers a chemistry-preserving route to tune block copolymer (BCP) self-assembly by modifying intrachain correlations and relaxation pathways without changing monomer interactions. Here, we perform a unit-matched comparison of four lamella-forming AB architectures reconstructed from an identical constitutive diblock unit ($N_0$): a linear diblock (DB), a linear multiblock (MB), a comb-like architecture (CB), and a star-like architecture (SB). Using dynamical density functional theory (DDFT), we quantify topology-dependent bulk ordering thresholds and show that architectural reconfiguration systematically stabilizes the ordered phase, reducing the order–disorder transition relative to DB (MB/CB/SB $\approx 0.793/0.762/0.752$ of the diblock value), in semi-quantitative agreement with random phase approximation (RPA) spinodal trends. We also compare topology-dependent directed self-assembly in a common trench geometry under matched reduced quench depth $\Delta \left(\chi N_0\right)=\chi N_0-{\left(\chi N_0\right)}_{\mathrm{ODT}}$, thereby isolating kinetic differences at comparable thermodynamic distance from bulk ordering. A Fourier-based alignment order parameter $\alpha \left(t\right)$ reveals sigmoidal alignment kinetics over decades in time and is well captured by a logistic form in $lnt$, enabling compact descriptors ($t_{50}$, $t_{90}$, and a steepness parameter k) that separate alignment onset from late-stage defect annihilation, while selective sidewalls robustly template sidewall-parallel lamellae across all topologies, the late-stage kinetics remain strongly connectivity dependent and can exhibit long-tailed completion associated with slow late-stage defect annihilation. These results demonstrate a dual role of topology in DSA: lowering the segregation strength required for bulk ordering while reshaping defect-mediated alignment pathways under confinement. Full article

Homopolymer addition is a widely used strategy to dilate the microdomain spacing of block copolymers, yet the attainable dilation is often limited by macrophase separation in conventional blends at elevated homopolymer loading. In this work, we investigate an architectural route to suppress macrophase separation while retaining homopolymer-driven dilation: a covalently hybridized bottlebrush copolymer (CH-BBC), a copolymacromer-like bottlebrush architecture in which symmetric AB diblock side chains and A-type homopolymer side chains are covalently grafted to a common backbone. Using dissipative particle dynamics (DPD) simulations, we directly compare the phase behavior of CH-BBC melts with that of composition-matched blends of symmetric AB diblocks and A-type homopolymers. Across the explored window, CH-BBC exhibits microphase morphologies and disorder without an observable two-phase region, whereas the corresponding blends show extensive two-phase coexistence at elevated homopolymer loading. Lamellar analysis and one-dimensional density decompositions further reveal that CH-BBC enables substantially larger microphase dilation and stronger selective swelling of the A-rich domain because tethered A-type homopolymer segments preferentially occupy and dilate the A-rich domain interior while diblock A segments remain localized near interfaces. Full article

Polymeric micelles have the potential to improve the efficacy and safety of drug delivery by improving drug solubility, enhancing bioaccumulation and reducing off-target toxicity. Despite excellent safety profiles, a major limitation with polymeric micelles is their inability to rapidly release their payload once they have reached their target, leading to the inadequate delivery of therapeutic doses. To address this limitation, we have developed a novel strategy to impart pH-responsiveness in non-responsive micelles through the co-encapsulation of oligoelectrolytes with drugs. Herein, we investigate the influence of copolymer composition and drug identity in combination with oligoelectrolyte—oligo(2-vinyl pyridine) (OVP)—loading on pH-triggered drug release from micelles and their cytotoxicity. A library of OVP-loaded micelles was prepared using conventional and well-established non-responsive block copolymers. Dynamic light scattering (DLS) was used to monitor the changes in the micelles as a function of pH. Regardless of the copolymer composition, an abrupt decrease in the hydrodynamic diameter (D_h) was observed as the pH was reduced due to OVP expulsion from the core, which was also confirmed by release studies. In general, co-encapsulation of OVP and model drugs (doxorubicin (DOX), gossypol (GP), paclitaxel (PX), and 7-ethyl-10-hydroxycamptothecin (SN38)) in the micelles provided good to excellent encapsulation efficiency percentage (EE%) values. In vitro studies revealed the pH triggered release of drugs from the OVP-loaded micelles regardless of the drug identity, which increased as the OVP loading increased. This general behaviour was observed in all cases, largely independent of the copolymer composition, albeit with subtle differences in the release profile for different drugs. Compared to their blank counterparts, the drug-loaded micelles displayed a slight increase in cytotoxicity against a panel of cancer cell lines, in a dose dependent manner. However, drug- and OVP-loaded micelles displayed a significant increase in cytotoxicity (up to 8-fold increase) that was independent of the copolymer composition. These results demonstrate the versatility of the oligoelectrolyte-mediated approach to furnish non-responsive micelles with a pH-trigger that allows the rapid release of drugs, regardless of the micelle composition or the drug identity. Full article

Herein, we report the synthesis via controlled reversible addition-fragmentation chain transfer (RAFT) polymerization of amphiphilic 2-vinylpyridine-b-styrene (2VPy-b-Sty) diblock copolymers of high molar masses (range: 52,100–304,000 g mol⁻¹) and various compositions (range: 2VP content 11.6–59.2 mol%) and their use for the fabrication of nanoporous membranes. The successful synthesis of the amphiphilic diblock copolymers was confirmed through the characterization of their molar masses, molar mass distribution, and composition using GPC and ¹H-NMR spectroscopy, respectively. Subsequently, membranes of the diblock copolymers were fabricated following the “phase inversion” technique. The resulting membranes were characterized via scanning electron microscopy which revealed the presence of sphere percolation networks morphology for all diblock copolymers with M_n ranging from 120 to 300 kDa and 2VPy content between 10 and 15 mol% at the optimal conditions. Afterward, the developed membranes were evaluated in terms of their permeability towards water and in terms of their ability to retain two different microorganisms, namely, Enterococcus faecalis and Escherichia coli, that are known to be harmful to human health. The experimental water flux for a membrane with pore size around 60 nm was equal to 31,400 L h⁻¹ m² and expectedly decreased with the decrease in membrane pore diameter. The retention ability of membranes for Enterococcus faecalis and Escherichia coli was higher than 90%. In particular, the retention ability for Enterococcus faecalis was equal to 98.9% and for Escherichia coli was 91.4%. The toxicity of the produced membrane was also determined, and the measured value was relatively low, at 17%. Full article

The nano-technological approach and supramolecular chemistry principles relation to the encapsulation of enzymes pave the way for creating next-generation nano-system-functionalized nano-compartments. The most promising approach for prophylaxis and the treatment of organophosphate (OP) poisoning is the use of stable, bioavailable nano-compartments containing OP-scavenging enzymes. Such enzymes, like butyrylcholinesterase (BChE), wild type and mutants, could also be used for the detoxification of other poisonous esters. There are two types of IRD-labeled human BChE-containing nano-scavengers: PEGylated liposomes and polyethyleneglycol–polypropylenesulfide polymersomes, which were developed with diameter close to 100 nm. BChE-polymersomes have higher encapsulation efficiency (95%) and slower release rate of enzymes (more than 7 days) compared to BChE-liposomes. The catalytic properties of encapsulated enzymes were analyzed for nano-compartment formulations, lipophilicity, the structure of block copolymers, and for different ester substrate polarity: positively charged butyrylthiocholine iodide, neutral phenyl acetate, and negatively charged aspirin. The highest k_cat (more than three times) compared to non-encapsulated BChE was for polymersomes based on diblock PEG-PPS polymersomes towards the neutral phenyl acetate substrate. Full article

Polylactide (PLA) was melt blended with block copolymers of ethylene glycol and propylene glycol: a triblock copolymer (PPG-b-PEG-b-PPG) with a molar mass of 2700 g/mol and 40 wt% PEG content, and a diblock copolymer (PPG-b-PEG) with a molar mass of 4000 g/mol and 50 wt% PEG content. The structure as well as the thermal and mechanical properties of both amorphous and crystallized blends were investigated. Due to the copolymers’ chemical composition and the resulting phase structure, the 10 wt% amorphous blends with PPG-b-PEG-b-PPG and PPG-b-PEG, with T_g values of 38 °C and 46 °C, respectively, exhibited relatively high yield stress, close to 45 MPa, along with remarkable elongation at break. Notably, the blend with the triblock copolymer showed a 70-fold increase in elongation at break compared to neat amorphous PLA. Furthermore, the tensile impact strength of the blend with the diblock copolymer surpassed that of neat PLA. Upon crystallization, the 10 wt% blends showed reduced yield stress and elongation at break; however, the elongation at break exceeded 7–25 times that of neat crystalline PLA. Furthermore, their tensile impact strength increased to more than three times the value of crystalline PLA. Full article

Τhe self-assembly behavior of a series of amphiphilic diblock copolymers, each consisting of a hydrophilic poly(N-vinyl pyrrolidone) (PNVP) block and a hydrophobic block derived from n-alkyl vinyl esters, namely poly(vinyl butyrate) (PVBu), poly(vinyl decanoate) (PVDc), and poly(vinyl stearate) (PVSt), in aqueous solutions was investigated. Dynamic and static light scattering (DLS and SLS) techniques were employed to monitor the micellization behavior. In addition, the self-assembled structures were observed with Transmission Electron Microscopy (TEM). The effect of the nature of the hydrophobic block, the copolymer composition and the copolymer molecular weight on the self-assembly properties was thoroughly examined. The encapsulation of curcumin and indomethacin within the dry cores of the micellar structures was conducted in aqueous solutions for all block copolymers at various curcumin/indomethacin-to-polymer mass ratios. UV-Vis spectroscopy was used to evaluate the drug-loading capacity and efficiency (%DLC and %DLE). In several cases, the encapsulation of both hydrophobic drugs was found to be nearly quantitative. Combined with the observed stability of the micellar structures, these findings suggest that the block copolymers demonstrate significant potential as carriers for drug delivery applications. Full article

Background: Encapsulating essential oils in polymer-based nanocarriers can improve their stability, solubility, and bioavailability, while maintaining the biological activity of the oil’s active ingredients. In this contribution, we investigated the antiviral activity of Oregano Essential Oil (OEO) in its pure form and encapsulated into nanosized polymeric micelles, based on a poly(ethylene oxide)-block-poly(ε-caprolactone) diblock copolymer. Methods: The effect of encapsulation was evaluated using three structurally different viruses: herpes simplex virus type 1 (HSV-1) (DNA—enveloped virus), human coronavirus (HCoV OC-43) (RNA—enveloped virus), and feline calicivirus (FCV) (RNA—naked virus). The effect on the viral replicative cycle was determined using the cytopathic effect inhibition (CPE) test. Inhibition of the viral adsorption step, virucidal activity, and protective effect on healthy cells were assessed using the final dilution method and were determined as Δlg compared to the untreated viral control. Results: In both studied forms (pure and nanoformulated), OEO had no significant effect on viral replication. In the remaining antiviral experiments, the oil embedded into nanocarriers showed a slightly stronger effect than the pure oil. When the oil was directly applied to extracellular virions, viral titers were significantly reduced for all three viruses, with the effect being strongest for HSV-1 and FCV (Δlg = 3.5). A distinct effect was also observed on the viral adsorption stage, with the effect being most significant for HSV-1 (Δlg = 3.0). Conclusions: Pretreatment of healthy cells with the nanoformulated OEO significantly protected them from viral infection, with the greatest reduction in viral titer for HCoV OC-43. Full article

Polymeric vesicles, characterized by enhanced colloidal stability, excellent mechanical properties, controllable surface functionality, and adjustable membrane thickness, are extremely useful in nano- and bio-technology for potential applications as nanosized carriers for drugs and enzymes. However, a few preparative steps are necessary to achieve a unilamellar vesicle with a narrow size distribution. Herein, we report the spontaneous formation of unilamellar polymeric vesicles with nanometer sizes (<50 nm), fabricated by simply mixing diblock copolymers (P(EO-AGE)(2K-2K) and P(EO-AGE)(0.75K-2K)) with differing hydrophilic mass fractions in aqueous solutions. Depending on the mixing ratio of block copolymers and the temperature, the block copolymer mixtures self-assemble into various nanostructures, such as spherical and cylindrical micelles, or vesicles. The self-assembled structures of the block copolymer mixtures were characterized by small-angle neutron scattering, resulting in a phase diagram drawn as a function of temperature and the mixing condition. Notably, the critical temperature for the micelle-to-vesicle phase transition can be easily controlled by altering the mixing conditions; it decreases with an increase in the concentration of one of the block copolymers. Full article

This study focuses on the synthesis and characterization of thermoresponsive hydrogels of poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG), PLA–PEG copolymers, aiming at the targeted and controlled release of deferoxamine (DFO), a clinically applied iron-chelating drug. Triblock (PLA-PEG-PLA) and diblock (mPEG-PLA) copolymers were synthesized using ring-opening polymerization (ROP) with five different PEGs with molecular weights of 1000, 1500, 2000, 4000, and 6000 g/mol and two types of lactide (L-lactide and D-lactide). Emulsions of the polymers in phosphate-buffered saline (PBS) were prepared at concentrations ranging from 10% to 50% w/w to study the sol–gel transition properties of the copolymers. Amongst the synthesized copolymers, only those that demonstrated thermoresponsive sol-to-gel transitions near physiological temperature (37 °C) were selected for further analysis. Structural and molecular confirmation was performed by Nuclear Magnetic Resonance (NMR) and Fourier-transform infrared spectroscopy (FTIR), while the molecular weights were determined via Gel Permeation Chromatography (GPC). The thermal transitions were studied by calorimetry (DSC) and crystallinity via X-ray diffraction (XRD) analysis. DFO-loaded hydrogels were prepared, and their drug release profiles were investigated under simulated physiological conditions (37 °C) for seven days using HPLC analysis. The thermoresponsive characteristics of these systems can offer a promising strategy for injectable drug delivery applications, where micelles serve as drug carriers and undergo in situ gelation, enabling controlled release. This alternative procedure may significantly improve the bioavailability of DFO and enhance patient compliance by addressing key limitations of conventional administration routes. Full article

Polymers and polymer composites offer versatile possibilities for engineering the physico-chemical properties of materials on micro- and macroscopic scales. This review provides an overview of polymeric and polymer-decorated particles that can serve as drug-delivery vectors: linear polymers, star polymers, diblock-copolymer micelles, polymer-grafted nanoparticles, polymersomes, stealth liposomes, microgels, and biomolecular condensates. The physico-chemical interactions between the delivery vectors and biological cells range from chemical interactions on the molecular scale to deformation energies on the particle scale. The focus of this review is on the structure and elastic properties of these particles, as well as their circulation in blood and cellular uptake. Furthermore, the effects of polymer decoration in vivo (e.g., of glycosylated plasma membranes, cortical cytoskeletal networks, and naturally occurring condensates) on drug delivery are discussed. Full article

In this article, we present a nonlocal Cahn–Hilliard (nCH) equation incorporating a space-dependent parameter to model microphase separation phenomena in diblock copolymers. The proposed model introduces a modified formulation that accounts for spatially varying average volume fractions and thus captures nonlocal interactions between distinct subdomains. Such spatial heterogeneity plays a critical role in determining the morphology of the resulting phase-separated structures. To efficiently solve the resulting partial differential equation, a Fourier spectral method is used in conjunction with a linearly stabilized splitting scheme. This numerical approach not only guarantees stability and efficiency but also enables accurate resolution of spatially complex patterns without excessive computational overhead. The spectral representation effectively handles the nonlocal terms, while the stabilization scheme allows for large time steps. Therefore, this method is suitable for long-time simulations of pattern formation processes. Numerical experiments conducted under various initial conditions demonstrate the ability of the proposed method to resolve intricate phase separation behaviors, including coarsening dynamics and interface evolution. The results show that the space-dependent parameters significantly influence the orientation, size, and regularity of the emergent patterns. This suggests that spatial control of average composition could be used to engineer desirable microstructures in polymeric materials. This study provides a robust computational framework for investigating nonlocal pattern formation in heterogeneous systems, enables simulations in complex spatial domains, and contributes to the theoretical understanding of morphology control in polymer science. Full article

Amphiphilic diblock copolymers comprising polyethylene glycol (PEG) and 1-vinyl imidazole (VIM) were synthesized using reversible addition–fragmentation chain transfer (RAFT) polymerization. The study focused on the synthesis of well-defined nanostructures with tunable composition and their functional modification for biomedical applications. The successful polymerization of PEG-b-PVIM diblock copolymers was confirmed via ¹H NMR spectroscopy, and their molecular weights were analyzed using gel permeation chromatography (GPC). The copolymers exhibited pH-responsive behavior, with effective pK values of approximately 4.2. To facilitate radiolabeling and in vivo tracking, a post-polymerization modification enabled the conjugation of a 1,4,7-Triazacyclononane-1,4,7-triacetic acid (NOTA) chelator via aminolysis. The final conjugates were purified and characterized, confirming successful functionalization. These findings highlight the potential of PEG_x-b-PVIM_y diblock copolymers for biomedical applications. Full article

Bacterially produced poly[(R)-3-hydroxybutyrate] (P3HB) was subjected to an alcoholysis reaction to produce low-molecular-weight (M_n ≈ 10,000 g mol⁻¹) hydroxy-terminated P3HB (LMPHB). Using diethyl zinc as a catalyst, LMPHB was reacted with the cyclic monomers ε-caprolactone and l-lactide in separate ring-opening polymerization (ROP) reactions to produce PHB-b-PCL (PHBCL) and PHB-b-PLA (PHBLA) AB-type crystalline–crystalline diblock copolymers with varying PCL and PLA block lengths. ¹H NMR and GPC were used to confirm the structure of the polymers. DSC was used to measure the thermal properties as well as assessing crystallization. A single-shifting T_g for PHBLA showed the two blocks to be miscible in the melt. The TGA results indicate enhanced thermal stability over the homopolymer P3HB. A study of the crystallization was undertaken by combining WAXD, a second DSC heating regime, and POM. POM showed that the crystallization in PHBCL to be dependent on the crystallization temperature more so than PHBLA, whose composition appeared to be the more definitive factor determining the spherulitic morphology. The results informed the crystallization temperatures used in the production of the melt-crystallized thin films that were imaged using AFM. AFM images showed unique surface morphologies dependent on the diblock copolymer composition, block length, and crystallization temperature. Finally, the enzymatic degradation studies showed these unique surface morphologies to influence how these block copolymers were degraded by enzymes. Full article