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It has been shown that amphiphilic polymers (AP) (Pluronic F108 and polyvinylpyrrolidone) increase the activity of rose bengal (RB) in the photogeneration of 1O2 in vitro and in vivo conditions. In particular, in the presence of AP, the intensity of luminescence of 1O2 generated by exited RB increased. Perhaps RB forms loosely bound complexes with AP, which promotes disaggregation of the dye. According to x-ray diffraction data, the degree of crystallinity of pluronic decreases during crystallization from joint solutions with RB and a large period in the packing of its crystallites is disrupted. This may indicate the localization of the dye in the intercrystalline amorphous regions of pluronic due to complexation RB + F108. In vitro experiments showed that the phototoxicity of the dye against A549 lung carcinoma cells increases in the presence of F108 and PVP. Under photodynamic exposure to model wounds in rats using the RB + F108 complex as a PS, there was an increase in reparative processes in the wounds, while pluronic F108 weakened the negative impact of RB on microvessels and prevented the development of a local hemorrhagic reaction. Thus, the photosensitizing systems based on RB + AP complexes are promising for treating local foci of oncological and non-oncological nature using PDT. [ABSTRACT FROM AUTHOR]

Polymersomes, also known as polymeric vesicles, have high potential in the field of biomedicines due to their high stability and ability to carry hydrophilic and hydrophobic materials to the targeted sites without any loss. The self‐assembly of amphiphilic block copolymers into hollow spherical structures, known as polymersomes, has opened up new frontiers in biomedicine and other bio‐related applications. These structures harness the unique properties of biopolymers such as polyethylene glycol (PEG), polycaprolactone (PCL), and polypeptides, which contribute to their biocompatibility and functionality. The need for efficient materials for applications in the field of targeted drug delivery, theranostics, and bio‐imaging is increasing day by day so that scientists are in search of efficient polymersomes by making modifications in their structures. This review outlines various block copolymers from which polymersomes can be made, the types of polymersomes, the ways to prepare the materials along with the biomedical applications that the polymersomes can be opted for. Here we discuss about self‐assembly techniques like solvent switch, microfluid, pH tuning and polymerization induced self‐assembly. The present paper provides an overview of stimuli‐responsive polymersomes. Towards the end of the review, several applications of polymersomes are covered, such as drug administration, imaging, theranostics, and usage as nanoreactors. [ABSTRACT FROM AUTHOR]

Cancer is still ranked among the top three causes of death in the 30- to 69-year-old age group in most countries and carries considerable societal and macroeconomic costs that differ depending on the cancer type, geography, and patient gender. Despite advances in several pharmacological approaches, the lack of stability and specificity, dose-related toxicity, and limited bioavailability of chemotherapy (standard therapy) pose major obstacles in cancer treatment, with multidrug resistance being a driving factor in chemotherapy failure. The past three decades have been the stage for intense research activity on the topic of nanomedicine, which has resulted in many nanotherapeutics with reduced toxicity, increased bioavailability, and improved pharmacokinetics and therapeutic efficacy employing smart drug delivery systems (SDDSs). Polymeric micelles (PMs) have become an auspicious DDS for medicinal compounds, being used to encapsulate hydrophobic drugs that also exhibit substantial toxicity. Through preclinical animal testing, PMs improved pharmacokinetic profiles and increased efficacy, resulting in a higher safety profile for therapeutic drugs. This review focuses on PMs that are already in clinical trials, traveling the pathways from preclinical to clinical studies until introduction to the market. [ABSTRACT FROM AUTHOR]

Encapsulation with polymers is a well-known strategy to stabilize and functionalize nanomaterials and tune their physicochemical properties. Amphiphilic copolymers are promising in this context, but their structural diversity and complexity also make understanding and predicting their behavior challenging. This is particularly the case in complex media which are relevant for intended applications in medicine and nanobiotechnology. Here, we studied the encapsulation of gold nanoparticles and quantum dots with amphiphilic copolymers differing in their charge and molecular structure. Protein adsorption to the nanoconjugates was studied with fluorescence correlation spectroscopy, and their surface activity was studied with dynamic interfacial tensiometry. Encapsulation of the nanoparticles without affecting their characteristic properties was possible with all tested polymers and provided good stabilization. However, the interaction with proteins and cells significantly depended on structural details. We identified statistical copolymers providing strongly reduced protein adsorption and low unspecific cellular uptake. Interestingly, different zwitterionic amphiphilic copolymers showed substantial differences in their resulting bio-repulsive properties. Among the polymers tested herein, statistical copolymers with sulfobetaine and phosphatidylcholine sidechains performed better than copolymers with carboxylic acid- and dimethylamino-terminated sidechains. [ABSTRACT FROM AUTHOR]

The effect of the diphenylalanine (Phe-Phe) amino acid on the rate of tryptophan photooxidation catalyzed by photosensitizers (PS) of different natures: dimegin (DMG), fluorinated tetraphenylporphyrin (FTPP), photoditazine (PD) and methylene blue (MB) was studied. It was shown that in the presence of Phe-Phe, the effective constant of photooxidation of the substrate catalyzed by DMG, PD and MB in the aqueous phase decreases. However, the introduction of the amphiphilic polymer Pluronic F127 into the systems allows not only to restore, but also to increase the activity of the PS in the processes of photosensitized oxidation. In particular, the activity of dimegin solubilized by Pluronic F127 in the presence of Phe-Phe is higher than the activity of both pure porphyrin and solubilized DMG. In addition, the activity of the hydrophobic FTPP solubilized by Pluronic also increases. At the same time, a study of the luminescence of singlet oxygen generated by solubilized FTPP in the absence and presence of Phe-Phe revealed that the dipeptide does not influence the processes of 1О2 generation. It was suggested that micellar catalysis influences the activity of solubilized PS in the presence of a biologically active dipeptide. [ABSTRACT FROM AUTHOR]

pH-sensitive amphiphilic diblock polyphosphoesters containing lactic acid units were synthesized by multistep one-pot polycondensation reactions. They comprise acid-labile P(O)-O-C and C(O)-O-C bonds, the cleavage of which depends on the pH of the medium. The structure of these copolymers was characterized by 1H, 13C {H}, 31P NMR, and size exclusion chromatography (SEC). The newly synthesized polymers self-assembled into the micellar structure in an aqueous solution. The effects of the molecular weight of the copolymer and the length of the hydrophobic chain on micelle formation and stabilityand micelle size were studied via dynamic light scattering (DLS). Drug loading and encapsulation efficiency tests using doxorubicin revealed that hydrophobic drugs can be delivered by copolymers. It was established that the molecular weight of the copolymer, length of the hydrophobic chain and content of lactate units affects the size of the micelles, drug loading, and efficiency of encapsulation. A copolymer with 10.7% lactate content has drug loading (3.2 ± 0.3) and efficiency of encapsulation (57.4 ± 3.2), compared to the same copolymer with 41.8% lactate content (1.63%) and (45.8%), respectively. It was demonstrated that the poly[alkylpoly(ethylene glycol) phosphate-b-alkylpoly(ethylene glycol)lactate phosphate] DOX system has a pH-sensitive response capability in the result in which DOX was selectively accumulated into the tumor, where pH is acidic. The results obtained indicate that amphiphilic diblock polyphosphoesters have potential as drug carriers. [ABSTRACT FROM AUTHOR]

Cancer is still ranked among the top three causes of death in the 30- to 69-year-old age group in most countries and carries considerable societal and macroeconomic costs that differ depending on the cancer type, geography, and patient gender. Despite advances in several pharmacological approaches, the lack of stability and specificity, dose-related toxicity, and limited bioavailability of chemotherapy (standard therapy) pose major obstacles in cancer treatment, with multidrug resistance being a driving factor in chemotherapy failure. The past three decades have been the stage for intense research activity on the topic of nanomedicine, which has resulted in many nanotherapeutics with reduced toxicity, increased bioavailability, and improved pharmacokinetics and therapeutic efficacy employing smart drug delivery systems (SDDSs). Polymeric micelles (PMs) have become an auspicious DDS for medicinal compounds, being used to encapsulate hydrophobic drugs that also exhibit substantial toxicity. Through preclinical animal testing, PMs improved pharmacokinetic profiles and increased efficacy, resulting in a higher safety profile for therapeutic drugs. This review focuses on PMs that are already in clinical trials, traveling the pathways from preclinical to clinical studies until introduction to the market.

The aim of our work is the preparation of cellulose nanofibrils or nanocrystals made from cellulose that is recovered from sugarcane bagasse agricultural waste (SC) as a dispersant instead of commercial cellulose for oil spill cleanup. In the current study, carboxymethyl cellulose was prepared by cellulose mercerization, which was then esterified by oxalic acid to create nanocellulose. Incorporation of oxalate into carboxymethyl cellulose (CMC) was verified by 1H‐NMR spectroscopy by the appearance of a new peak at 8.15 ppm for CMC–oxalate. The degree of substitution (DS) of oxalate was 0.17. The synthesized nanocellulose formed particles were roughly the same size and shape as both cellulose nanofibrils (CNFs) and cellulose nanocrystals (CNCs): measuring 321–480 nm in length and 4–5 nm in width. Emulsions of paraffins made from CMC–oxalate are stable up to 10 months without undergoing precipitation. CMC–oxalate had great thermal stability and worked well as a paraffin oil dispersant. CMC–oxalate provided a barrier around the oil droplet surface, which prevented droplets from coalescing. This hypothesis is supported by the contact angle measurement for the O/W emulsion formed by CMC–oxalate being 0°, which is lower than the value for emulsions formed by underivatized CMC, 37.20°. From transmission electron microscopy observations, O/W emulsions of paraffin oil were spherical in shape, and separated from each other by a distance of 30–100 nm. This study shows that CMC–oxalate can be prepared by a low‐cost method, yielding nanocellulose with characteristics that resemble CNFs and CNCs, thereby opening up new potential applications for cellulose nanomaterials. [ABSTRACT FROM AUTHOR]

Comb‐shape, block copolymers from hydrophilic poly(ethylenglycol) monomethyl ether acrylate (mPEGA, A) and hydrophobic 2‐ethylhexyl acrylate (EHA, B) are synthesized by copper(0)‐mediated single‐electron transfer living radical polymerization (SET‐LRP) via sequential addition of the two monomers, resulting in different compositions (AB, ABA, BAB, BA), molar masses, and mPEGA/EHA ratios. All polymers show narrow molar mass distributions and molecular weights of 7.7–25.50 kg mol−1, demonstrating precise control over the polymerization and molecular weights through the utilization of SET‐LRP. Kinetic experiments are conducted to investigate the polymerization behavior of mPEGA and EHA in N,N‐dimethylformamide as a rather uncommon solvent for SET‐LRP further underlining a living‐type polymerization. Amphiphilic properties are investigated by critical micelle concentration (CMC) measurements and formation of micelles in water. A reverse relation between mPEGA/EHA ratio and CMC values reveals that an increased hydrophobicity leads to decreased CMC values. The self‐assembly behavior of polymers in water confirms the formation of uniform and stable micelles in water with a size between 12 and 184 nm depending on the composition of the polymers. With increased hydrophilicity, micelle sizes increase as well. In vitro tests of the obtained polymers show excellent biocompatibility even at high concentrations further affirming their suitability for drug delivery applications. [ABSTRACT FROM AUTHOR]

Amphiphilic photopolymerized network films are prepared, based on a hexyl acrylate (HA) hydrophobic matrix containing varied amounts of urethane dimethacrylates bearing a hydrophilic poly(ethylene glycol) segment and terminated with hydrophobic, low surface energy groups, i.e., a short perfluorohexyl chain (for EF) or a fluorine‐free heptamethyltrisiloxane group (for ES). These films are extensively characterized in bulk and at the surface by thermal, mechanical, solvent and water uptake, contact angle, and X‐ray photoelectron spectroscopy measurements. On one hand, surface characterizations reveal that the amphiphilic chains of the additives enrich the topmost layer of the films, thus generating a water‐responsive surface. The reconstruction process is found to be faster for the perfluorinated additive EF and slower for the fluorine‐free ES ones. On the other hand, HA provides a hydrophobic matrix with low elastic modulus, dimensional stability, and adhesion to the substrates even after the absorption of water after prolonged immersion. A field immersion trial carried out in a touristic harbor in Leghorn points out that the films, although being ineffective in preventing organism settlement, are easily cleaned by a water jet after three months of immersion, showing a final residual coverage of panels as low as 15%. [ABSTRACT FROM AUTHOR]

Recently, bioabsorbable vascular stents (BVSs) are actively studied owing to their ability to dissolve within the human body. However, despite their advantages, BVSs often dislodge from the expandable balloon‐based delivery system when transported to the lesion site. In this study, a novel methodology aiming at increasing the retention force between the stent and the delivery system is presented. The breath‐figure method is adopted to form a porous structure and enhance adhesion. Additionally, numerical and experimental methods are used to evaluate the effect of surface tension between two immiscible fluids (polymeric solutions and droplets). To control the interfacial tension between the solution and droplets, an amphiphilic polymer and NaCl‐added vapor are used. By selecting the appropriate parameters, a sponge‐like structure is prepared on the stent delivery system. To verify its applicability, the two types of structures presented in this study are experimentally compared. These findings provide valuable guidelines for understanding the mechanism of breath‐figure patterns. Thus, the innovative methodology developed in this study demonstrates simplicity and scalability for large‐area production, making it potentially applicable to industrial technologies and offering new insights into biomedical engineering. [ABSTRACT FROM AUTHOR]

Polymeric bowl‐shaped nanoparticles (BNPs) are anisotropic hollow structures with large openings on the surface, which have shown advantages such as high specific area and efficient encapsulation, delivery and release of large‐sized cargoes on demand compared to solid nanoparticles or closed hollow structures. Several strategies have been developed to prepare BNPs based on either template or template‐free methods. For instance, despite the widely used self‐assembly strategy, alternative methods including emulsion polymerization, swelling and freeze‐drying of polymeric spheres, and template‐assisted approaches have also been developed. It is attractive but still challenging to fabricate BNPs due to their unique structural features. However, there is still no comprehensive summary of BNPs up to now, which significantly hinders the further development of this field. In this review, the recent progress of BNPs will be highlighted from the perspectives of design strategies, preparation methods, formation mechanisms, and emerging applications. Moreover, the future perspectives of BNPs will also be proposed. [ABSTRACT FROM AUTHOR]

Multistep one-pot polycondensation reactions synthesized amphiphilic diblock polyphosphoesters containing lactic acid units in the polymer backbone. At the first step was synthesized poly[poly(ethylene glycol) H-phosphonate–b-poly(ethylene glycol)lactate H-phosphonate] was converted through one pot oxidation into poly[alkylpoly(ethylene glycol) phosphate-b-alkylpoly(ethylene glycol)lactate phosphate]s. They were characterized by 1H, 13C {H},31P NMR, and size exclusion chromatography (SEC). The effects of the polymer composition on micelle formation and stability, and micelle size were studied via dynamic light scattering (DLS). The hydrophilic/hydrophobic balance of these polymers can be controlled by changing the chain lengths of hydrophobic alcohols. Drug loading and encapsulation efficiency tests using Sudan III and doxorubicin revealed that hydrophobic substances can be incorporated inside the hydrophobic core of polymer micelles. The micelle size was 72–108 nm when encapsulating Sudan III and 89–116 nm when encapsulating doxorubicin. Loading capacity and encapsulation efficiency depend on the length of alkyl side chains. Changing the alkyl side chain from 8 to 16 carbon atoms increased micelle-encapsulated Sudan III and doxorubicin by 1.6- and 1.1-fold, respectively. The results obtained indicate that these diblock copolymers have the potential as drug carriers. [ABSTRACT FROM AUTHOR]

We review the considerable progress during the recent decade in the endeavours of designing, optimising, and utilising carrier particle systems for structural and functional studies of membrane proteins in near-native environments. New and improved systems are constantly emerging, novel studies push the perceived limits of a given carrier system, and specific carrier systems consolidate and entrench themselves as the system of choice for particular classes of target membrane protein systems. This review covers the most frequently used carrier systems for such studies and emphasises similarities and differences between these systems as well as current trends and future directions for the field. Particular interest is devoted to the biophysical properties and membrane mimicking ability of each system and the manner in which this may impact an embedded membrane protein and an eventual structural or functional study. • We review the biophysical properties of commonly encountered carrier systems for handling membrane proteins in solution. • We review trends and recent developments in membrane protein carrier systems. • We discuss and compare the impact of carrier systems on membrane protein stability, activity, and regulation. [ABSTRACT FROM AUTHOR]

Amphiphilic fluorinated copolymers PEGMAx‐co‐FAy and TEGMAx‐co‐FAy are prepared by activators regenerated by electron transfer atom transfer radical polymerization (ARGET‐ATRP). All polymers present a reversible thermoresponsive lower critical solution temperature‐type behavior, and a cloud point temperature (Tc) in the range of 30–60 °C strictly dependent on the length of the oxyethylene side chain, the content of the hydrophobic counits, and the concentration of the solution. Combined small angle X‐ray scattering (SAXS) and dynamic light scattering measurements are used to study the self‐assembly behavior in water, organic solvents (tetrahydrofuran [THF] and dimethylformamide [DMF]), and a fluorinated solvent (hexafluorobenzene [HFB]). SAXS confirms the formation of compact‐globular single‐chain self‐folded unimer micelles in water below Tc, which generally presents small hydrodynamic diameters (Dh ≤ 8 nm) as a result of the folding of the hydrophobic perfluorohexylethyl acrylate counits. The copolymers are also able to form reverse unimer micelle in HFB. The copolymers are not able to self‐assemble in unimer micelles in THF or DMF solutions, in which they adopt conventional random coil conformations. [ABSTRACT FROM AUTHOR]

The aim of this study is to synthesize new amphiphilic chitosan containing myristic acid as the hydrophobic tail and tertiary amine groups as the hydrophilic head and to evaluate the gene delivery efficiency. In this context, the primary amine groups of chitosan were first modified with myristic acid (Chi-M), followed by the modification of the methylol groups with 3-dimethylamino-1-propyl chloride hydrochloride. The chemical characterization of this chitosan formulation (Chi-MA) was determined using nuclear magnetic resonance (NMR), Fourier-transform infrared spectroscopy (FTIR) analysis and gel permeation chromatography-size exclusion chromatography. Chi-MA nanoparticles were prepared via ionic gelation, and particle size, polydispersity and zeta potential were determined. The nanoparticles were evaluated for their proton buffering capacity and gene complexing capacity. Additionally, the cytotoxicity of Chi-MA on HEK293T cells was determined via MTT assay, and the transfection efficiency of Chi-MA was analyzed by a flow cytometer. The results indicate a significant increase in gene complexing capacity (8-fold) and nanoparticle formation ability of Chi-MA compared to other chitosan formulations. Chi-MA nanoparticles showed no toxicity against HEK293T cells and exhibited the highest transfection efficiency with significantly lower nanoparticle: gene ratios compared to previous studies. These findings demonstrate the effective use of amphiphilic Chi-MA as a gene carrier. [Display omitted] • New amphiphilic chitosan, Chi-MA, synthesized with myristic acid and tertiary amine. • Chi-MA exhibited high proton buffering capacity. • Chi-MA revealed significantly increased gene complexing capacity. • Chi-MA demonstrates potential as an effective and safe gene delivery vector. [ABSTRACT FROM AUTHOR]

The structure of model compounds for the amphiphilic copolymer poly(diisobutylene‐alt‐maleic acid), DIBMA, is investigated with (gas phase) B3LYP/6‐31G** and PM7 calculations. It is found that in the monoprotonated state of the repeating unit strong (about 70 kJ mol−1) ionic hydrogen bonds are formed within the hydrogen succinate rings, which impart partial structural rigidity on the backbone of the copolymer. Based on literature pKa values of the first and second deprotonation step of the succinic acid units, it is argued that the ionic hydrogen bonds are likely to be present in aqueous solution as well. The main chain conformation depends strongly on the stereochemical configuration of the carbon atoms in the hydrogen succinate rings. The possible consequences of the hydrogen bonding for the mechanism of membrane solubilization by maleic acid‐based amphiphilic copolymers are discussed. [ABSTRACT FROM AUTHOR]

The properties of polymer brushes based on three macromonomers were investigated in aqueous and organic solutions. Methacrylic monomers with different compositions of the oligo(oxyalkylene) substituents and arrangements of the oligo(ethylene glycol) and oligo(propylene glycol) blocks were used for the synthesis of polymers. There were methoxy [oligo(ethylene glycol)10.3-block-oligo(propylene glycol)4.7] methacrylate, methoxy [oligo(propylene glycol)8.3-block-oligo(ethylene glycol)6.6] methacrylate, and methoxy oligo(propylene glycol)4.2 methacrylate. Molecular brushes were investigated by the methods of molecular hydrodynamics and optics in dilute solutions in acetonitrile, chloroform, and water. The peculiarities of behavior of poly[oligo(oxyalkylene) methacrylates] in aqueous solutions and water-toluene systems have been found; in particular, the solubility of the polymers in water and organic solvents, the polymers equilibrium distribution between the phases, and the surface activity in the water-toluene system have been established. The thermo-responsibility in aqueous solutions and values of a critical concentration of micelle formation were shown. Depending on the arrangement of blocks in the side chains of molecular brushes, they are characterized by different intramolecular density. [ABSTRACT FROM AUTHOR]

Polymeric high internal phase emulsions decorated with covalent organic frameworks (polyHIPEs-COFs) were synthesized and used as the sorbent for cyantraniliprole and chlorantraniliprole. Pickering high internal phase emulsions stabilized by covalent organic frameworks solid particles and liquid surfactants (Span80 and polyvinylpyrrolidone) endow the composites with open-cell structures and superwettability. The amphiphilicity and open-cell structures enable rapid adsorption and desorption for cyantraniliprole and chlorantraniliprole, and the solid-phase extraction process can be completed in 5 min. The adsorption efficiencies of polyHIPEs-COFs for cyantraniliprole and chlorantraniliprole are above 85.19%, but lower than 10% for fenvalerate, anti-aphid, and chlorpyrifos, demonstrating the good adsorption selectivity for cyantraniliprole and chlorantraniliprole. The adsorption efficiencies of cyantraniliprole and chlorantraniliprole using a same polyHIPEs-COFs and five different batches of polyHIPEs-COFs range from 94.25 to 100.00%, revealing the good reproducibility of the sorbent. In addition, the polyHIPEs-COF-based solid-phase extraction combined with high-performance liquid chromatography-ultraviolet detector (HPLC-UV) was developed for determination of bisamide insecticides in vegetable (eggplants, tomatoes, and peppers) samples. Results showed that the method was feasible to determine the cyantraniliprole and chlorantraniliprole in real vegetable samples with a linear range of 0.012-1.2 μg/kg and limits of detection of 0.0075-0.0090 μg/kg. The recoveries of cyantraniliprole and chlorantraniliprole spiked in vegetable samples ranged from 85.00 to 100.00% with relative standard deviations less than 3.52%. The study indicates the feasibility of amphiphilic polyHIPEs-COFs in extraction and enrichment of bisamide insecticides from vegetable samples for HPLC-UV analysis., Competing Interests: Declarations. Ethical approval: This research did not involve human or animal samples. Competing interests: The authors declare no competing interests., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

The influence of chitosan (CS) and amphiphilic polymers (AP: pluronic F108 and polyvinylpyrrolidone (PVP)) on the photocatalytic activity of rose bengal (RB) in a model reaction of tryptophan photo-oxidation in phosphate-buffered saline (PBS) was studied. It was shown that in the presence of CS, the effective rate constant keff of tryptophan photo-oxidation catalyzed by RB in PBS solution decreases by a factor of two. This is due to the ionic interaction of the RB with the chitosan. Rose bengal in a slightly acidic environment (pH 4.5) passes into a neutral lactone form, which sharply reduces the photosensitizing properties of the dye. It was demonstrated that the introduction of AP into a solution containing RB and CS prevents direct interaction between RB and CS. This is evidenced by the presence of photocatalytic activity of the dye in the RB-AP-CS systems, as well as bathochromic shifts of the main absorption bands of the dye, and an increase in the optical density and luminescence intensity of the RB when AP is introduced into a buffer solution containing RB and chitosan. The presence of RB-CS and RB-AP interaction in aqueous and PBS media is confirmed by the increase in the degree of fluorescence anisotropy (r) of these binary systems. In an aqueous solution, the value of r for the RB-F108-CS system decreases by a factor of 3.5 (compared to the value of r for the RB-CS system), which is associated with the localization of the dye in pluronic micelles. In PBS, the fluorescence anisotropy is practically the same for all systems, which is related to the stability of the dye structure in this medium. The presence of interaction between RB and AP in aqueous solutions was confirmed by the proton NMR method. In addition, the formation of RB-F108 macromolecular complexes, which form associates during solution concentration (in particular, during evaporation), was shown by AFM. Such RB-AP-CS systems may be promising for practical application in the treatment of local foci of infections by aPDT. [ABSTRACT FROM AUTHOR]

The synthesis and solution properties of thermoresponsive polymer molecular brushes based on five novel diblock macromonomers (methoxy [oligo(ethylene glycol)e-block-oligo(propylene glycol)p] methacrylates, OEGeOPGpMA, where e = 7.0–10.3 and p = 2.8–10.3) have been studied. The effect of synthesis conditions on the rate of radical solution polymerization in ethyl acetate, maximum conversions of macromonomers, and molecular weight characteristics of polymers has been shown. Homopolymers of OEGeOPGpMA exhibited pronounced surface-active properties. The influence of the length of oligo(propylene glycol) block on the degree of reduction of surface (air–water) and interfacial (hexane-water) tension was shown. The aggregation behavior of polymers was investigated by dynamic light scattering and fluorimetry using pyrene as a fluorescent probe. The dependence of critical micelle concentration on the length of the oligo(propylene glycol) block was shown. The polymers have a critical solution temperature within the range of 34–71 °C depending on the length of oligo(oxyalkylene) blocks and polymer concentration. The relationship between the distribution coefficient of macromonomers in water–oil systems and the LCST of polymers based on them has been established. [ABSTRACT FROM AUTHOR]

Using a novel strategy, amphiphilic polyphosphoesters based on poly(oxyethylene H-phosphonate)s (POEHP) with different poly(ethylene glycol) segment lengths and aliphatic alcohols with various alkyl chain lengths were synthesized using polycondensation reactions. They were characterized by 1H NMR, 13C {H} NMR 31P NMR, IR, and size exclusion chromatography (SEC). The effects of the polymer structure on micelle formation and stability, micelle size, and critical micelle temperature were studied via dynamic light scattering (DLS). The hydrophilic/hydrophobic balance of these polymers can be controlled by changing the chain lengths of hydrophilic PEG and hydrophobic alcohols. A solubilizing test, using Sudan III, revealed that hydrophobic substances can be incorporated inside the hydrophobic core of polymer associates. Loading capacity depends on the length of alkyl side chains. The results obtained indicate that these structurally flexible polymers have the potential as drug carriers. [ABSTRACT FROM AUTHOR]

A method was developed for the conjugation of aminopropyl spacer-bearing carbohydrates with epoxy groups on the crown of nanoparticles consisting of a copolymer of N-vinyl-2-pyrrolidone and allyl glycidyl ether in basic buffer, opening prospects for the design of vectorized nanocomposite drug forms. A conjugate of the above copolymer and trisaccharide A, a synthetic blood group antigen, was synthesized. Meglumine was used to bind any unreacted epoxide groups of the allyl glycidyl fragment. One- and two-dimensional NMR spectroscopy showed quantitative opening of the epoxide ring as a result of carbohydrate immobilization. By integrating the characteristic signals in the 1H NMR spectrum, we determined the molar ratio of the immobilized vector and meglumine, as well as the composition and number-average molecular weight of the carrier copolymer. The results obtained point to the interesting possibilities in the further study of the polymer–carbohydrate ligand system as a platform for the development of several drug carriers and theranostics based on them. [ABSTRACT FROM AUTHOR]

In recent years, polymers with stimuli-responsive properties have been increasingly reported on due to their diverse applications. However, most of the studies have only focused on the performance of polymers under specific scenarios. The laws of changes in the properties in response to various external stimuli have been less systematically and quantitatively studied. In this paper, we prepared an amphiphilic polymer (PadaMX and PAdaM3QA−X) with temperature-, pH-, ion-, and β-cyclodextrin (β-CD)-responsive properties. According to the cloud point tested by the UV-Vis method, the lower critical soluble temperature (LCST) of PAdaM3QA−10% was more sensitive to a change in pH and less sensitive to a change in ions compared with PadaM3 due to quaternized side chains with a stronger intramolecular mutual repulsion. We then fabricated the coatings with responsive properties by immobilizing the adamantyl groups on β-CD-modified surfaces. The hydrophilicity of the coatings was improved after quaternization, as proven by the water contact angle (WCA) measurement. The antifouling and antibacterial performance was further evaluated via the fluorescence intensity of bovine serum albumin (BSA) adsorbed on the surfaces and the spread plate method. A 78.4% BSA desorption rate and a 96.8% sterilization rate were achieved by the PAdaM3QA−10% coating. In summary, this work prepared a multiple-stimuli-responsive amphiphilic copolymer for antifouling and antibacterial functionality via a "resistance–kill–release" mechanism. [ABSTRACT FROM AUTHOR]

Multistep one-pot polycondensation reactions synthesized amphiphilic diblock polyphosphoesters containing lactic acid units in the polymer backbone. At the first step was synthesized poly[poly(ethylene glycol) H-phosphonate–b-poly(ethylene glycol)lactate H-phosphonate] was converted through one pot oxidation into poly[alkylpoly(ethylene glycol) phosphate-b-alkylpoly(ethylene glycol)lactate phosphate]s. They were characterized by 1H, 13C {H},31P NMR, and size exclusion chromatography (SEC). The effects of the polymer composition on micelle formation and stability, and micelle size were studied via dynamic light scattering (DLS). The hydrophilic/hydrophobic balance of these polymers can be controlled by changing the chain lengths of hydrophobic alcohols. Drug loading and encapsulation efficiency tests using Sudan III and doxorubicin revealed that hydrophobic substances can be incorporated inside the hydrophobic core of polymer micelles. The micelle size was 72–108 nm when encapsulating Sudan III and 89–116 nm when encapsulating doxorubicin. Loading capacity and encapsulation efficiency depend on the length of alkyl side chains. Changing the alkyl side chain from 8 to 16 carbon atoms increased micelle-encapsulated Sudan III and doxorubicin by 1.6- and 1.1-fold, respectively. The results obtained indicate that these diblock copolymers have the potential as drug carriers.

Chrysophanol and hesperidin are natural nutraceuticals that exhibit synergistic bioactivities, but their hydrophobicity limits their applications, and it is unclear whether coencapsulation can improve their solubility and release behaviors. The objective of this work was to coencapsulate chrysophanol and hesperidin by octenylsuccinated β -glucan aggregates (OS β G-Agg) and to reveal how coencapsulation improves their release and bioaccessibility. Mechanisms underlying the hypothesis of beneficial effects in coloading, corelease and bioaccessibility were revealed. The solubilization of OS β G-Agg was due to hydrogen-bonding among β -glucan moieties of OS β G and hydroxyl groups of chrysophanol and hesperidin and hydrophobic interactions among octenyl chains of OS β G and hydrophobic moieties of chrysophanol and hesperidin. Structural analyses confirmed the hypothesis that chrysophanol molecules were nearly embedded deeper into the interior of hydrophobic domains, and most of hesperidin molecules were incorporated into the exterior of the hydrophobic domains of OS β G-Agg due to the strength of these interactions, but they interacted in OS β G-Agg with a dense and compact structure rather than existing in isolation. The combined effects delayed their release and enhanced their bioaccessibility because of dynamic equilibrium between the favorable interactions and unfavorable structural erosion and relaxation of OS β G-Agg. Overall, OS β G-Agg is effective at codelivering hydrophobic phenolics for functional foods and pharmaceuticals. [Display omitted] • Coloading improved the release and bioaccessibility of chrysophanol and hesperidin. • Hydrodynamic, hydrophilic and hydrophobic structures of OS β G-aggregates were revealed. • Chrysophanol and hesperidin loaded in different domains of OS β G-aggregates. • Coloading caused transition from a loose structure to a compact aggregating structure. • Coencapsulation of chrysophanol and hesperidin was due to Multiple interactions. [ABSTRACT FROM AUTHOR]

Semiconducting polymers with amphiphilic properties can play an increasing role in future organic and unimolecular electronic devices, especially due to their excellent processability and ease of self-assembly into thin films, but they could also be used as intermediate layers to improve electron transport in metal-organic junctions. In this work, we synthesized a homologous series of amphiphiles by copolymerization of aniline with aniline-N-propanesulfonic acid. The polymerization was first initiated with aniline, and the latter monomer was added at different time intervals: 2, 10, 20, 30, 40, and 60 min, spaced from the time of initiation. Thus, the poly(aniline-co-aniline-N-propanesulfonic acid) (PANi-co-PANs) homologous series of copolymers obtained had the same length of the water soluble PANs chain, and a variable length of the water insoluble PANi chain. We demonstrated that there is a strong structure–activity relationship in the homologous series of PANi-co-PANs copolymers, evidenced in the tensiometry and wettability studies, as well as in-depth conductivity with frequency and temperature investigations. We observed a gradual change in solubility, interfacial activity, and conductivity in the homologous series of amphiphiles within the boundaries set by the electrically insulating, hydrophilic PANs chain and the semiconducting, hydrophobic PANi chains; representing a viable platform toward designing polymers with tunable conductivity. [ABSTRACT FROM AUTHOR]

A study is performed of the effect such amphiphilic polymers (APs) as pluronics F-127 and F-108, poly-N-vinylpirrolidone (PVP), and polyethylene glycol (PEG) have on the photocatalytic activity of Rose Bengal, a xanthene dye, in the photooxidation of tryptophan in water. Rose Bengal (RB) is an efficient photosensitizer (PS) in the regeneration of singlet 1О2 oxygen and is present in a solution in the form of associates. It is shown that all of the above APs raise the effective rate constant of tryptophan photooxidation, which is usually explained by the partial disaggregation of such associates. The strongest effect is in this case observed when using pluronic F-108. When using APs, the electron absorption and fluorescence spectra of the xanthene dye is transformed somewhat. A bathochromic shift (5–15 nm) of the dye absorption bands and an increase in RB photoluminescence (2–5 times) are observed. RB fluorescence is the strongest strongest when PVP is added. Dynamic light scattering shows that the size of RB particles is reduced 1.3–1.5 times when using pluronic F-108 and PVP. The observed patterns indicate there is interaction between the xanthene dye and APs. Such RB–AP based systems are promising for use as preparations for theranostics (i.e., visualizing fluorescence and treating oncological and nononcological tumors by means of photodynamic therapy). [ABSTRACT FROM AUTHOR]

Atherosclerosis, a leading cause of mortality in developed countries, is characterized by the buildup of oxidized low-density lipoprotein (oxLDL) within the vascular intima, unregulated oxLDL uptake by macrophages, and ensuing formation of arterial plaque. Amphiphilic polymers (AMPs) comprised of a branched hydrophobic domain and a hydrophilic poly(ethylene glycol) (PEG) tail have shown promising anti-atherogenic effects through direct inhibition of oxLDL uptake by macrophages. In this study, five AMPs with controlled variations were evaluated for their micellar and structural stability in the presence of serum and lipase, respectively, to develop underlying structure-atheroprotective activity relations. In parallel, molecular dynamics simulations were performed to explore the AMP conformational preferences within an aqueous environment. Notably, AMPs with ether linkages between the hydrophobic arms and sugar backbones demonstrated enhanced degradation stability and storage stability, and also elicited enhanced anti-atherogenic bioactivity. Additionally, AMPs with increased hydrophobicity elicited increased atheroprotective bioactivity in the presence of serum. These studies provide key insights for designing more serum-stable polymeric micelles as prospective cardiovascular nanotherapies.

In this work, a block copolymer (BCP) consisting of poly((butyl methacrylate‐co‐benzophenone methacrylate‐co‐methyl methacrylate)‐block‐(2‐hydroxyethyl methacrylate)) (P(BMA‐co‐BPMA‐co‐MMA)‐b‐P(HEMA)) is prepared by a two‐step atom‐transfer radical polymerization (ATRP) procedure. BCP membranes are fabricated applying the self‐assembly and nonsolvent induced phase separation (SNIPS) process from a ternary solvent mixture of tetrahydrofuran (THF), 1,4‐dioxane, and dimethylformamide (DMF). The presence of a porous top layer of the integral asymmetric membrane featuring pores of about 30 nm is confirmed via scanning electron microscopy (SEM). UV‐mediated cross‐linking protocols for the nanoporous membrane are adjusted to maintain the open and isoporous top layer. The swelling capability of the noncross‐linked and cross‐linked BCP membranes is investigated in water, water/ethanol mixture (1:1), and pure ethanol using atomic force microscopy, proving a stabilizing effect of the UV cross‐linking on the porous structures. Finally, the influence of the herein described cross‐linking protocols on water‐flux measurements for the obtained membranes is explored. As a result, an increased swelling resistance for all tested solvents is found, leading to an increased water flux compared to the pristine membrane. The herein established UV‐mediated cross‐linking protocol is expected to pave the way to a new generation of porous and stabilized membranes within the fields of separation technologies. [ABSTRACT FROM AUTHOR]

Microwave irradiation is applied to rapidly prepare highly ordered lamellar structures of amphiphilic comb‐shaped polymers via nanophase separation. Amphiphilic comb‐shaped polymer of poly(N‐dodecyl acrylamide) (pDDA) is synthesized by free radical polymerization. Differential scanning calorimetry (DSC) and X‐ray diffraction results indicate that pDDA is amorphous at room temperature. Exposing pDDA powder to microwave irradiation in the presence of water (microwave–humidity annealing) converts the structure into lamellae. The water molecules absorb the microwaves, and their temperature rapidly increases above the glass‐transition temperature (Tg) of pDDA. Moreover, a fraction of the heated water is adsorbed at the amide moiety, which increases the nanosegregation with the alkyl side chains. As a result, pDDA forms a lamellar structure by nanophase separation between the main chain with water‐containing amide moieties and the alkyl side chains. The rapid increase in temperature results in a fast formation (a few tens of seconds) of the lamellae. Moreover, the microwave–humidity annealing of pDDA thin films on Si substrates results in a uniaxial lamellar structure. These results indicate that microwave–humidity annealing is a simple method to rapidly form a self‐assembled structure in homopolymers by nanophase separation. [ABSTRACT FROM AUTHOR]

Macromolecular engineering presents a pleasant tactic for planning the construction of desired molecular architectures from nano to macro configurations. The mechanistic pathways and synthetic features of macromolecular designs mostly rely on the precursor composition, topology, functionality, and complexity in architectures. Specifically, macromolecular design with biomolecular conjugation has attracted remarkable attention due to its typical biochemical and physiological affirmative traits. In this review article, it is intended to highlight the major progress on the macromolecular designs and synthesis of polymers comprising bile acid (BA) as the biomolecular colleague. BAs are steroidal biocomposites, produced through cholesterol metabolism in the bile of mammals and vertebrates. They are low priced, biocompatible, abundant, trivially toxic, and structurally unique for facewise amphiphilicity, which make them suitable for designing BA‐based polymers (BAPs) to be utilized in biomedical fields. The major aim of this review article is to summarize the recent progress (2015–present) on the requisite necessity of BA in BAPs toward design and synthetic avenues. In particular, the design of various polymers with primary and secondary BAs at side chain, main chain, chain end, crosslinking zone, and core confined area are illustrated in this review article via numerous reported methods. [ABSTRACT FROM AUTHOR]

Abstract Aggregation‐induced emission (AIE) is a phenomenon in which fluorescence is enhanced rather than quenched upon molecular assembly. AIE fluorogens (AIEgens) are flexible, conjugated systems that are limited in their dynamics when assembled, which improves their fluorescent properties. This intriguing feature has been incorporated in many different molecular assemblies and has been extended to nanoparticles composed of amphiphilic polymer building blocks. The integration of the fascinating AIE design principle with versatile polymer chemistry opens up new frontiers to approach and solve intrinsic obstacles of conventional fluorescent materials in nanoscience, including the aggregation‐caused quenching effect. Furthermore, this integration has drawn significant attention from the nanomedicine community, due to the additional advantages of nanoparticles comprising AIEgenic molecules, such as emission brightness and fluorescence stability. In this regard, a range of AIEgenic amphiphilic polymers have been developed, displaying enhanced emission in the self‐assembly/aggregated state. AIEgenic assemblies are regarded as attractive nanomaterials with inherent fluorescence, which display promising features in a biomedical context, for instance in biosensing, cell/tissue imaging and tracking, as well as (photo) therapeutics. In this review, we describe recent strategies for the design and synthesis of novel types of AIEgenic amphiphilic polymers via facile approaches including direct conjugation to natural/synthetic polymers, polymerization, post‐polymerization and supramolecular host−guest interactions. Their self‐assembly behavior and biomedical potential will be discussed.

Influenza virus (IV) infection currently poses a serious and continuing threat to the global public health. Developing effective prevention strategies is important to defend against infection and spread of IV. Here, we developed a triple-protective nanoshield against IV infection in the lungs, formed by self-assembling DSPE-PEG amphiphilic polymers encapsulating the flu-preventive antiviral drug Arbidol internally. The preventive effect of the nanoshield against virus infection includes increasing the viscosity in the surrounding environment to physically defend against viral entry, forming a hydrated layer to block the interaction between viruses and cells, and inhibiting virus replication. Our finding suggested that a single inhalation of the nanoshield provides effective protection against IV infection for at least 8 h. Thus, this nanoshield may be a potential pandemic protection agent against IV, especially in viral environments, where no prophylactic or therapeutic measures are available.

Amphiphilic copolymer molecular brushes of three different types with side chains consisting of alkyl and oligo(ethylene glycol) blocks based on higher alkoxy oligo(ethylene glycol) methacrylates (HAOEGM), methoxy oligo(ethylene glycol) methacrylates (MOEGM) and dodecyl(meth)acrylate have been successfully synthesized via conventional radical polymerization in toluene. In case of the copolymerization of HAOEGM with MOEGM, the monomer reactivity ratios were independent of the structure of higher alkyl groups (C12–C18) and the degree of ethoxylation (n = 6–11) and were equal to 0.76–0.81 and 1.19–1.27, respectively. In case of the copolymerization of HAOEGM or MOEGM with dodecyl methacrylate, the reactivity ratios were even closer to each other (1.00–1.17). Applicability of the reactivity ratios calculated at low conversions for estimating copolymer compositions at high conversions was shown. In all systems, compositionally homogeneous copolymers with a narrow molecular weight distribution were formed. For the HAOEGM (C12, n = 9)—dodecyl acrylate monomer system, the reactivity ratios were 0.88 and 0.25 and the resulting copolymers had high compositional heterogeneity. [ABSTRACT FROM AUTHOR]

This review is devoted to the star‐shaped polylactide‐b‐poly(ethylene glycol) (PLA‐b‐PEG) polymers with hydrophobic‐hydrophilic arms. Star‐shaped polymers have a more compact structure as compared to linear counterparts but what is more important contain more end‐groups. If end‐groups are hydrophilic (such as hydroxyl groups), it may shift the hydrophilic‐hydrophobic balance of hydrophobic polymer such as PLA. Additional improvement of hydrophilicity may be achieved by introducing poly(ethylene glycol) segments. In this review, we are discussing synthetic approaches and basic properties of star‐shaped polylactide‐b‐poly(ethylene glycol) (PLA‐b‐PEG). The introduction of hydrophilic fragments (PEG) into hydrophobic chains (PLA) causes the considerable change of many properties of PLA polymers and extends their applications, particularly biomedical. The influence of the architecture and the number of arms of synthesized polymers as well as the content of hydrophilic and hydrophobic blocks on their properties is also discussed. Particular emphasis is placed on researches on the obtained polymers (in vitro and in vivo) as potential materials for biomedical applications. [ABSTRACT FROM AUTHOR]

Amphiphilic coatings have garnered significant attention in the realm of fouling resistance due to their potential to reduce fouling adhesion and enhance fouling release. However, developing anti-fouling amphiphilic surfaces with robust mechanical properties remains a formidable challenge. Herein, a series of norbornene-based amphiphilic copolymers (PNPFE-PEG-x) with varying NPEG mass fractions (0–50 wt%) were well-designed and fabricated via living ring-opening metathesis polymerization (ROMP) employing norbornene-based fluorinated monomer (NPFE) and poly(ethylene glycol) (NPEG) monomer. The water absorption, surface wettability, and mechanical properties of the amphiphilic copolymers can be regulated by adjusting the NPEG contents. Particularly, dry PNPFE-PEG-10 % films exhibited exceptional tensile strength of 14.36 MPa and breaking elongation of 376 %. The wet PNFPE-PEG-H 2 O samples exhibited a unique hydration-induced stiffening phenomenon. Even in the water swelling state, wet PNPFE-PEG-50 % films still demonstrated remarkable tensile strength of 8.05 MPa and breaking elongation of 74.81 %. Furthermore, increasing the NPEG content effectively resisted bovine serum albumin and fibrinogen protein adsorption on the coatings, with PNPFE-PEG-50 % showing the lowest protein adsorption at 19 μg/cm2 and 27 μg/cm2, respectively, indicating excellent anti-fouling properties. In addition, PNPFE-PEG-x exhibited anti-icing property through rational molecular design. These high-performance anti-fouling coatings are equipped to meet diverse application needs in marine anti-fouling, biomedical instruments, and other relevant fields. [Display omitted] • Well-designed norbornene-based amphiphilic copolymers prepared by ROMP polymerization • Amphiphilic polymers with simultaneous mechanical robustness and fouling resistance • Possessing anti-icing property through rational molecular design [ABSTRACT FROM AUTHOR]

The influence of chitosan (CS) and amphiphilic polymers (AP: pluronic F108 and polyvinylpyrrolidone (PVP)) on the photocatalytic activity of rose bengal (RB) in a model reaction of tryptophan photo-oxidation in phosphate-buffered saline (PBS) was studied. It was shown that in the presence of CS, the effective rate constant keff of tryptophan photo-oxidation catalyzed by RB in PBS solution decreases by a factor of two. This is due to the ionic interaction of the RB with the chitosan. Rose bengal in a slightly acidic environment (pH 4.5) passes into a neutral lactone form, which sharply reduces the photosensitizing properties of the dye. It was demonstrated that the introduction of AP into a solution containing RB and CS prevents direct interaction between RB and CS. This is evidenced by the presence of photocatalytic activity of the dye in the RB-AP-CS systems, as well as bathochromic shifts of the main absorption bands of the dye, and an increase in the optical density and luminescence intensity of the RB when AP is introduced into a buffer solution containing RB and chitosan. The presence of RB-CS and RB-AP interaction in aqueous and PBS media is confirmed by the increase in the degree of fluorescence anisotropy (r) of these binary systems. In an aqueous solution, the value of r for the RB-F108-CS system decreases by a factor of 3.5 (compared to the value of r for the RB-CS system), which is associated with the localization of the dye in pluronic micelles. In PBS, the fluorescence anisotropy is practically the same for all systems, which is related to the stability of the dye structure in this medium. The presence of interaction between RB and AP in aqueous solutions was confirmed by the proton NMR method. In addition, the formation of RB-F108 macromolecular complexes, which form associates during solution concentration (in particular, during evaporation), was shown by AFM. Such RB-AP-CS systems may be promising for practical application in the treatment of local foci of infections by aPDT.

Using a novel strategy, amphiphilic polyphosphoesters based on poly(oxyethylene H-phosphonate)s (POEHP) with different poly(ethylene glycol) segment lengths and aliphatic alcohols with various alkyl chain lengths were synthesized using polycondensation reactions. They were characterized by 1H NMR, 13C {H} NMR 31P NMR, IR, and size exclusion chromatography (SEC). The effects of the polymer structure on micelle formation and stability, micelle size, and critical micelle temperature were studied via dynamic light scattering (DLS). The hydrophilic/hydrophobic balance of these polymers can be controlled by changing the chain lengths of hydrophilic PEG and hydrophobic alcohols. A solubilizing test, using Sudan III, revealed that hydrophobic substances can be incorporated inside the hydrophobic core of polymer associates. Loading capacity depends on the length of alkyl side chains. The results obtained indicate that these structurally flexible polymers have the potential as drug carriers.

In recent years, polymers with stimuli-responsive properties have been increasingly reported on due to their diverse applications. However, most of the studies have only focused on the performance of polymers under specific scenarios. The laws of changes in the properties in response to various external stimuli have been less systematically and quantitatively studied. In this paper, we prepared an amphiphilic polymer (PadaMX and PAdaM3QA−X) with temperature-, pH-, ion-, and β-cyclodextrin (β-CD)-responsive properties. According to the cloud point tested by the UV-Vis method, the lower critical soluble temperature (LCST) of PAdaM3QA−10% was more sensitive to a change in pH and less sensitive to a change in ions compared with PadaM3 due to quaternized side chains with a stronger intramolecular mutual repulsion. We then fabricated the coatings with responsive properties by immobilizing the adamantyl groups on β-CD-modified surfaces. The hydrophilicity of the coatings was improved after quaternization, as proven by the water contact angle (WCA) measurement. The antifouling and antibacterial performance was further evaluated via the fluorescence intensity of bovine serum albumin (BSA) adsorbed on the surfaces and the spread plate method. A 78.4% BSA desorption rate and a 96.8% sterilization rate were achieved by the PAdaM3QA−10% coating. In summary, this work prepared a multiple-stimuli-responsive amphiphilic copolymer for antifouling and antibacterial functionality via a “resistance–kill–release” mechanism.

Hybrid macromolecular antioxidants has evolved into a mature research field last three decades. The main concept of this area was to design polymer conjugates that combine in one structure the hydrophilic properties of a polymer backbone and biological efficiency of hydrophobic antioxidants. Over the years, the understanding of different aspects of such approach has grown. In general, meticulous selection of each component is essential to obtain the conjugate with required properties. This review overview a plethora of hybrid macromolecular antioxidants synthesized over the last 20 years, together with the discussion their physicochemical properties and application for biomedical purposes. [ABSTRACT FROM AUTHOR]

Bottom‐surface defect passivation of perovskite film, lagging far behind easily conducted bulk and top‐surface passivations in perovskite solar cells (PSCs), remains rather challenging because most passivation molecules/groups can be eroded by polar solvents used for the subsequent perovskite deposition. In this work, an effective bottom‐surface passivation is enabled for enhanced performance of inverted PSCs by covalently attaching a passivation group (hydroxyl) to a hole transporting polymer. A short linker (methylene) between the hydroxyl and the conjugated backbone bearing hydrophobic long alkyl chains is adopted to improve the resistance of the resultant amphiphilic polymer to polar solvents. A solvent evaporation‐induced self‐assembly of the amphiphilic hole transporting polymer is developed to enrich hydroxyl groups on the film surface, passivating defects of the upper perovskite layer via interactions with undercoordinated Pb2+ and I– sites. Inverted PSCs based on this hole transporting film are superior in efficiency (20.12%), reproducibility, large‐area fabrication, and stability to its classical poly(bis(4‐phenyl)(2,5,6‐trimethylphenyl)amine) counterpart. This work demonstrates that rational introduction of passivation groups into the hole transporting layer combined with self‐assembly‐modulated component distributions is useful to realize bottom‐surface passivation of the perovskite layer for improved photovoltaic performance. [ABSTRACT FROM AUTHOR]

In recent years, polymeric micelles have been extensively utilized in pre-clinical studies for delivering poorly soluble chemotherapeutic agents in cancer. Polymeric micelles are formed via self-assembly of amphiphilic polymers in facile manners. The wide availability of hydrophobic and, to some extent, hydrophilic polymeric blocks allow researchers to explore various polymeric combinations for optimum loading, stability, systemic circulation, and delivery to the target cancer tissues. Moreover, polymeric micelles could easily be tailor-made by increasing and decreasing the number of monomers in each polymeric chain. Some of the widely accepted hydrophobic polymers are poly(lactide) (PLA), poly(caprolactone) (PCL), poly(lactide- co -glycolide) (PLGA), polyesters, poly(amino acids), lipids. The hydrophilic polymers used to wrap the hydrophobic core are poly(ethylene glycol), poly(oxazolines), chitosan, dextran, and hyaluronic acids. Drugs could be conjugated to polymers at the distal ends to prepare pharmacologically active polymeric systems that impart enhanced solubility and stability of the conjugates and provide an opportunity for combination drug delivery. Their nano-size enables them to accumulate to the tumor microenvironment via the Enhanced Permeability and Retention (EPR) effect. Moreover, the stimuli-sensitive breakdown provides the micelles an effective means to deliver the therapeutic cargo effectively. The tumor micro-environmental stimuli are pH, hypoxia, and upregulated enzymes. Externally applied stimuli to destroy micellar disassembly to release the payload include light, ultrasound, and temperature. This article delineates the current trend in developing polymeric micelles combining various block polymeric scaffolds. The development of stimuli-sensitive micelles to achieve enhanced therapeutic activity are also discussed. [Display omitted] • Polymeric micelles are self-assembled nano-aggregates of amphiphilic b- co -polymers. • Micelles load drugs physico-chemically, tumor-targeted by active/passive phenomena. • The review focusses on various lipophilic and hydrophilic micellar building blocks. • Micelles sensitive to stimuli, pH, hypoxia, temperature, and light are discussed. [ABSTRACT FROM AUTHOR]

This article describes synthesis, characterization, antimicrobial, drug-releasing and anti-cancer activity of acrylate monomer and its polymer containing chalcone moiety. The synthesized polymers were characterized through IR, 1H NMR and UV–visible spectroscopy techniques. The molecular weight of the obtained polymer is found to be around 4000 g/mol. The synthesized polymers are thermally stable up to 260 °C. The monomer and its polymer show higher activity against gram-negative bacteria and these compounds show remarkable activity over breast cancer cells. The synthesized monomer and polymers showed higher anticancer activity. The inhibitory potential of monomers and polymers premeditated using optimized in vitro evaluation MTT assay and live cell images. The drug release potential was controlled through co-monomer, pH and temperature. [ABSTRACT FROM AUTHOR]

Ocular neovascularization is a hallmark of several sight-threatening diseases, including diabetic retinopathy and age-related macular degeneration. Currently, available treatments are limited and often associated with side effects. Therefore, a novel approach to ocular neovascularization treatment through utilization of polymersomes from self-assembled sphingosine-grafted hyaluronic acid (HA-Sph) amphiphilic polymers is presented. The polymersomes are generated in spherical morphologies and sizes between 97.95 - 161.9 nm with homogenous size distributions. Experiments reveal that HA-Sph polymersomes, with concentrations ≥150 µg mL -1 , significantly inhibit the proliferation of human umbilical vein endothelial cells (HUVECs), while concurrently promoting the proliferation of retinal pigment epithelial cells. The polymersomes demonstrate gradual disintegration in vitro, leading to sustained release of sphingosine, which prolongs the inhibition of HUVEC proliferation (from 87.5% at 24 h to 35.2% viability at 96 h). The efficacy of polymersomes in inhibiting angiogenesis is confirmed through tube formation assay, revealing a substantial reduction in tube length compared to the control group. The findings also validate the ocular penetration capability of polymersomes through ex vivo whole porcine eye ocular penetration study, indicating their suitability for topical administration. Potentially, HA-Sph polymersomes can be harnessed to develop intricate drug delivery systems that protect the retina and effectively treat ocular diseases., (© 2024 The Authors. Macromolecular Bioscience published by Wiley‐VCH GmbH.)