Search Results (109)

This study is aimed at developing a fibre-reinforced polymer composite with a high bio-based content and to investigate its mechanical properties. A novel basalt fibre-reinforced polymer (BFRP) composite with bio-based matrix modified with different contents of star-like n-butyl methacrylate (n-BMA) block glycidyl methacrylate (GMA) copolymer has been developed. n-BMA blocks have flexible butyl units, while the epoxide group of GMA makes it miscible with the epoxy resin and is involved in the crosslinking network. The effect of the star-like polymer on the rheological behaviour of the epoxy was studied. The viscosity of the epoxy increased with increase in star-like polymer content. Tensile tests showed no noteworthy influence of star-like polymer on tensile properties. The addition of 0.5 wt.% star-like polymer increased the glass transition temperature by 8.2 °C. Mode-I interlaminar fracture toughness and low-velocity impact tests were performed on star-like polymer-modified BFRP laminates, where interfacial adhesion and impact energy capabilities were observed. Interlaminar fracture toughness improved by 45% and energy absorption capability increased threefold for BFRP laminates modified with 1 wt.% of star-like polymer when compared to unmodified BFRP laminates. This improvement could be attributed to the increase in ductility of the matrix on the addition of the star-like polymer, increasing resistance to impact and damage. Furthermore, scanning electron microscopy confirmed that with increase in star-like polymer content, the interfacial adhesion between the matrix and fibres improves. Full article

A Monte Carlo study of the compatibilization of A/B polymer blends has been performed using the bond fluctuation model. The considered compatibilizers are copolymer molecules composed of A and B blocks. Different types of copolymer structures have been included, namely, linear diblock and 4-block alternating copolymers, star block copolymers, miktoarm stars, and zipper stars. Zipper stars are composed of two arms of diblock copolymers arranged in alternate order (AB and BA) from the central unit, along with two homogeneous arms of A and B units. The compatibilization performance has been characterized by analyzing the equilibration of repulsion energy, the simulated scattering intensity obtained with opposite refractive indices for A and B, the profiles along a coordinate axis, the radial distribution functions, and the compatibilizer aggregation numbers. According to the results, linear alternate block copolymers, star block copolymers, and zipper stars exhibit significantly better compatibilization, with zipper stars showing slightly but consistently better performance. Full article

For over four decades, carbon dioxide (CO₂) has been instrumental in enhancing oil extraction through advanced recovery techniques. One such method, water alternating gas (WAG) injection, while effective, grapples with limitations like gas channeling and gravity segregation. To tackle the aforementioned issues, this paper proposes an upgrade coupling method named alkaline-surfactant-polymer alternating gas (ASPAG). ASP flooding and CO₂ are injected alternately into the reservoir to enhance the recovery of the WAG process. The uniqueness of this method lies in the fact that polymers could help profile modification, CO₂ would miscible mix with oil, and alkaline surfactant would reduce oil–water interfacial tension (IFT). To analyze the feasibility of ASPAG, a couples model considering both gas flooding and ASP flooding processes is established by using the CMG-STARS (Version 2021) to study the performance of ASPAG and compare the recovery among ASPAG, WAG, and ASP flooding. Our research delved into the ASPAG’s adaptability across reservoirs varying in average permeability, interlayer heterogeneity, formation rhythmicity, and fluid properties. Key findings include that ASPAG surpasses the conventional WAG in sweep and displacement efficiency, elevating oil recovery by 12–17%, and in comparison to ASP, ASPAG bolsters displacement efficiency, leading to a 9–11% increase in oil recovery. The primary flooding mechanism of ASPAG stems from the ASP slug’s ability to diminish the interfacial tension, enhancing the oil and water mobility ratio, which is particularly efficient in medium-high permeability layers. Through sensitivity analysis, ASPAG is best suited for mid-high-permeability reservoirs characterized by low crude oil viscosity and a composite reverse sedimentary rhythm. This study offers invaluable insights into the underlying mechanisms and critical parameters that influence the alkaline-surfactant-polymer alternating gas method’s success for enhanced oil recovery. Furthermore, it unveils an innovative strategy to boost oil recovery in medium-to-high-permeability reservoirs. Full article

This review aims to highlight the most recent advances in the field of the synthesis of branched copolymers and nanogels using reversible addition-fragmentation chain transfer (RAFT) polymerization. RAFT polymerization is a reversible deactivation radical polymerization technique (RDRP) that has gained tremendous attention due to its versatility, compatibility with a plethora of functional monomers, and mild polymerization conditions. These parameters lead to final polymers with good control over the molar mass and narrow molar mass distributions. Branched polymers can be defined as the incorporation of secondary polymer chains to a primary backbone, resulting in a wide range of complex macromolecular architectures, like star-shaped, graft, and hyperbranched polymers and nanogels. These subcategories will be discussed in detail in this review in terms of synthesis routes and properties, mainly in solutions. Full article

The application of a biocompatible polymer nanocarrier can provide target delivery to tumor tissues, improved pharmacokinetics, controlled drug release, etc. Therefore, the proposed strategy was to use the water-soluble star-like copolymers with a Dextran core and Poly(N-isopropylacrylamide) grafts (D-g-PNIPAM) for conjugation with the widely used chemotherapy drugs in oncology–Cisplatin (Cis-Pt) and Doxorubicin (Dox). The molecular characteristics of the copolymer were received using size-exclusion chromatography. The physicochemical characterization of the D-g-PNIPAM-Cis-Pt (or Dox) nanosystem was conducted using dynamic light scattering and FTIR spectroscopy. Using traditional biochemical methods, a comparative analysis of the enhancement of the cytotoxic effect of free Cis-Pt and Dox in combination with D-g-PNIPAM copolymers was performed in cancer cells of the Lewis lung carcinoma line, which are both sensitive and resistant to Dox; in addition, the mechanism of their action in vitro was evaluated. Full article

The effect of colloidal nanoparticles on the phase changes of the amphiphilic AB linear diblock, A₁A₂B, and A₂B heteroarm star copolymers confined between two polymer brush substrates was investigated by using a real-space self-consistent field theory. By changing the concentrations of nanoparticles and polymer brushes, the phase structure of the amphiphilic AB copolymer transforms from lamellar to core-shell hexagonal phase to cylinder phase. The pattern of A₂B heteroarm star copolymer changes from core-shell hexagonal phases to lamellar phases and the layer decreases when increasing the density of the polymer brushes. The results showed that the phase behavior of the system is strongly influenced by the polymer brush architecture and the colloidal nanoparticle numbers. The colloidal nanoparticles and the soft confined surface of polymer brushes make amphiphilic AB copolymers easier to form ordered structures. The dispersion of the nanoparticles was also investigated in detail. The soft surfaces of polymer brushes and the conformation of the block copolymers work together to force the nanoparticles to disperse evenly. It will give helpful guidance for making some new functional materials by nano etching technology, nano photoresist, and nanoprinting. Full article

Star copolymer films were produced by using spin-coating, drop-casting, and casting deposition techniques, thus obtaining ultrathin and thick films, respectively. The morphology is generally flat, but it becomes substrate-dependent for ultrathin films where the planarization effect of films is not efficient. The indentation hardness of films was investigated by Force Volume Maps in both the air and liquid. In the air, ultrathin films are in the substrate-dominated zone and, thus, the elastic modulus E is overestimated, while E reaches its bulk value for drop-casted ultrathin and thick films. In liquid (water), E follows an exponential decay for all films with a minimum soaked time t₀ of 0.37 and 2.65 h for ultrathin and drop-casted ultrathin and thick films, respectively. After this time, E saturates to a value on average 92% smaller than that measured in the air due to film swelling. Such results support the role of film morphology in the antimicrobial activity envisaged in the literature, suggesting also an additional role of film hardness. Full article

Polymers, including non-linear copolymers, have great potential in the development of drug delivery systems with many advantages, but the design requires optimizing polymer–drug interactions. Molecular dynamics (MD) simulations can provide insights into polymer–drug interactions for designing delivery systems, but mimicking formulation processes such as drying is often not included in in silico studies. This study demonstrates an MD approach to model drying of systems comprising either hydrophilic tinidazole or hydrophobic clotrimazole drugs with amphiphilic hyperbranched copolyethers. The simulated drying protocol was critical for elucidating drug encapsulation and binding mechanisms. Experimentally, two polymers were synthesized and shown to encapsulate clotrimazole with up to 83% efficiency, guided by interactions with the hydrophobic core observed in simulations. In contrast, tinidazole is associated with surface regions, indicating capacity differences between drug types. Overall, this work highlights MD simulation of the drying process as an important tool for predicting drug–polymer complex behaviour. The modelled formulation protocol enabled high encapsulation efficiency and opened possibilities for the design of delivery systems based on computationally derived binding mechanisms. This demonstrates a computational–experimental approach where simulated drying was integral to elucidating interactions and developing optimized complexes, emphasizing the value of molecular modelling for the development of drug delivery formulations. Full article

Cannabidiol (CBD) is a promising drug candidate with pleiotropic pharmacological activity, whose low aqueous solubility and unfavorable pharmacokinetics have presented obstacles to its full clinical implementation. The rational design of nanocarriers, including niosomes for CBD encapsulation, can provide a plausible approach to overcoming these limitations. The present study is focused on exploring the feasibility of copolymer-modified niosomes as platforms for systemic delivery of CBD. To confer steric stabilization, the niosomal membranes were grafted with newly synthesized amphiphilic linear or star-shaped 3- and 4-arm star-shaped copolymers based on polyglycidol (PG) and poly(ε-caprolactone) (PCL) blocks. The niosomes were prepared by film hydration method and were characterized by DLS, cryo-TEM, encapsulation efficacy, and in vitro release. Free and formulated cannabidiol were further investigated for cytotoxicity and pro-apoptotic and anti-inflammatory activities in vitro in three human tumor cell lines. The optimal formulation, based on Tween 60:Span60:Chol (3.5:3.5:3 molar ration) modified with 2.5 mol% star-shaped 3-arm copolymer, is characterized by a size of 235 nm, high encapsulation of CBD (94%), and controlled release properties. Niosomal cannabidiol retained the antineoplastic activity of the free agent, but noteworthy superior apoptogenic and inflammatory biomarker-modulating effects were established at equieffective exposure vs. the free drug. Specific alterations in key signaling molecules, implicated in programmed cell death, cancer cell biology, and inflammation, were recorded with the niosomal formulations. Full article

Superparamagnetic iron oxide (SPIO) nanocrystals have been extensively studied as theranostic nanoparticles to increase transverse (T₂) relaxivity and enhance contrast in magnetic resonance imaging (MRI). To improve the blood circulation time and enhance the diagnostic sensitivity of MRI contrast agents, we developed an amphiphilic copolymer, PCPZL, to effectively encapsulate SPIO nanocrystals. PCPZL was synthesized by crosslinking a polyethylene glycol (PEG)-based homobifunctional linker with a hydrophobic star-like poly(ε-benzyloxycarbonyl-L-lysine) segment. Consequently, it could self-assemble into shell-crosslinked micelles with enhanced colloidal stability in bloodstream circulation. Notably, PCPZL could effectively load SPIO nanocrystals with a high loading capacity of 66.0 ± 0.9%, forming SPIO nanoclusters with a diameter of approximately 100 nm, a high cluster density, and an impressive T₂ relaxivity value 5.5 times higher than that of Resovist^®. In vivo MRI measurements highlighted the rapid accumulation and contrast effects of SPIO-loaded PCPZL micelles in the livers of both healthy mice and nude mice with an orthotopic hepatocellular carcinoma tumor model. Moreover, the magnetic micelles remarkably enhanced the relative MRI signal difference between the tumor and normal liver tissues. Overall, our findings demonstrate that PCPZL significantly improves the stability and magnetic properties of SPIO nanocrystals, making SPIO-loaded PCPZL micelles promising MRI contrast agents for diagnosing liver diseases and cancers. 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

The administration of poorly water-soluble drugs represents a relevant problem due to the low body fluids transport efficiency through hydrophilic hydrogels. Star-shaped co-polymers, i.e., amphiphilic polymers such as those with a hydrophobic core and a hydrophilic outer shell, can be used to improve weak interactions with drugs, with relevant benefits in terms of administration and controlled delivery. In this work, two different co-polymers, four-arm star-shaped PCL–PEG and six-arm star-shaped PCL–PEG, were synthesized via ring-opening polymerization to be loaded with ciprofloxacin. ¹H-NMR and FTIR analyses confirmed that PCL arms were successfully grafted to the mPEG backbone, while DSC analysis indicated similar crystallinity and melting point, ranging from 56 to 60 °C, independent of the different co-polymer architecture. Therefore, both star-shaped PCL-PEGs were investigated as cargo device for ciprofloxacin. No significant differences were observed in terms of drug entrapment efficiency (>95%) and drug release, characterized by a pronounced burst followed by a slow sustained release, only slightly affected by the co-polymer architecture. This result was also confirmed with curve fitting via the Korsmeyer–Peppas model. Lastly, good antibacterial properties and biocompatibility exhibited in both star-shaped PCL–PEG co-polymers suggest a promising use for oral delivery applications. Full article

The hydrogenated styrene–butadiene–styrene block copolymer (SEBS)/Polypropylene (PP)-blended thermoplastic elastomer (TPE) is an ideal material for automotive interior skin applications due to its excellent elasticity, weather resistance, and environmentally friendly characteristics such as low odor and low volatile organic compounds (VOC). As a thin-wall injection-molded appearance skin product, it requires both high fluidity and good mechanical properties with scratch resistance. To optimize the performance of the SEBS/PP-blended TPE skin material, an orthogonal experiment and other methods were employed to investigate the impact of the formula composition and raw material characteristics, such as the styrene content and molecular structure of SEBS, on the TPE’s final performance. The outcomes revealed that the ratio of SEBS/PP had the most significant influence on the mechanical properties, fluidity, and wear resistance of the final products. The mechanical performance was enhanced by increasing the PP content within a certain range. The degree of sticky touch on the TPE surface was increased as the filling oil content increased, causing the increase in sticky wear and the decrease in abrasion resistance. When the SEBS ratio of high/low styrene content was 30/70, the TPE’s overall performance was excellent. The different proportions of linear/radial SEBS also had a significant effect on the final properties of the TPE. The TPE exhibited the best wear resistance and excellent mechanical properties when the ratio of linear-shaped/star-shaped SEBS was 70/30. Full article

Multi-arm star-shaped block copolymers with precisely tuned nano-architectures are promising candidates for drug delivery. Herein, we developed 4- and 6-arm star-shaped block copolymers consisting of poly(furfuryl glycidol) (PFG) as the core-forming segments and biocompatible poly(ethylene glycol) (PEG) as the shell-forming blocks. The polymerization degree of each block was controlled by adjusting the feeding ratio of a furfuryl glycidyl ether and ethylene oxide. The size of the series of block copolymers was found to be less than 10 nm in DMF. In water, the polymers showed sizes larger than 20 nm, which can be related to the association of the polymers. The star-shaped block copolymers effectively loaded maleimide-bearing model drugs in their core-forming segment with the Diels–Alder reaction. These drugs were rapidly released upon heating via a retro Diels–Alder step. When the star-shaped block copolymers were injected intravenously in mice, they showed prolonged blood circulation, with more than 80% of the injected dose remaining in the bloodstream at 6 h after intravenous injection. These results indicate the potential of the star-shaped PFG-PEG block copolymers as long-circulating nanocarriers. Full article

The zwitterionic phospholipid polymer poly(2-methacryloyloxyethyl phosphorylcholine-co-n-butyl methacrylate) (PMB) is amphiphilic copolymer, and it has been reported to directly penetrate cell membranes and have good cytocompatibility. Conventional PMBs are linear-type random copolymers that are polymerized by a free radical polymerization technique. In contrast, star-shaped polymers, or simple branched-type polymers, have unique properties compared to the linear types, for example, a viscosity based on the effect of the excluded volume. In this study, a branched architecture was introduced into a PMB molecular structure, and a 4-armed star-shaped PMB (4armPMB) was synthesized by an atom transfer radical polymerization (ATRP) technique known as living radical polymerization. Linear-type PMB was also synthesized using ATRP. The effects of the polymer architecture on cytotoxicity and cellular uptake were investigated. Both 4armPMB and LinearPMB were successfully synthesized, and these polymers were verified to be water soluble. Pyrene fluorescence in the polymer solution indicated that the architecture had no effect on the behavior of the polymer aggregates. In addition, these polymers caused no cytotoxicity or cell membrane damage. The 4armPMB and LinearPMB penetrated into the cells after a short incubation period, with similar rates. In contrast, the 4armPMB showed a quicker back-diffusion from the cells than that of LinearPMB. The 4armPMB showed fast cellular internalization and exiting behaviors. Full article