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A series of hexylamine modified polysuccinimide (PSI–HA) copolymers were synthesized by aminolysis of polysuccinimide (PSI) with hexylamine. FTIR and 1H NMR measurements confirmed the structure of the copolymers and the substitution degree of the N-hexyl aspartamide units ranged from 7 to 92 mol%. Stable nanoparticles formed when the DMF solution of PSI–HA copolymers was dropped into excess water, and the particle size reduced as increasing the substitution degree. 1H NMR analysis indicated that hexyl chain and succinimide units interacted to form the hydrophobic core, while, the nanoparticles were stabilized by the amide groups which formed hydrogen bonds with the surrounding water molecules. The nanoparticles became more compact at higher temperature due to the break of hydrogen bonds between amide groups and water molecules. Dynamic light scattering (DLS) and scanning electron microscopy (SEM) results showed that the nanoparticles were nearly spherical. Larger nanoparticles formed when the dispersion concentration increased from 0.1% to 1.0% according to the DLS and steady-state fluorescence measurements. After the nanoparticles formed in water, a sequential dilution can't influence the particles size of the nanoparticles any longer. [ABSTRACT FROM AUTHOR]

Oil-in-water nanoemulsions were prepared using a series of synthetic graft copolymers with a backbone of dextran (DEX) and a number of side chains of poly-ϵ-caprolactone (PCL). In this paper, we focus on the o/w emulsion stabilizing abilities of these novel PCL-DEX copolymers, using a recently developed optical analyzer (Turbiscan). The main advantage of Turbiscan is to detect the destabilization phenomena in non-diluted emulsion, much earlier than the naked eye’s operator, especially in the case of an opaque and concentrated system. This study shows that PCL-DEX copolymers successfully stabilized ethyl acetate-in-water emulsions, even in the absence of additional surfactants, whereas they were not efficient in stabilizing methylene chloride-in-water emulsions which coalesced fast and irreversibly. The ethyl acetate-in-water emulsion stabilizing ability of PCL-DEX seemed to be related to the localization of their blocks with regard to the oil–water interface. [Copyright &y& Elsevier]

When co-precipitated with amphiphilic copolymers from DMSO, poly(D,L-lactide)(PLA) can be readily converted into stable sub-200 nm nanoparticles by addition of an aqueous phase, free of any polymeric stabilizers such as poly(vinyl alcohol) or Poloxamer. In this work, the ability of random poly(methyl methacrylate-co-methacrylic acid) copolymers (PMMA-co-MA) to stabilize PLA nanoparticles was demonstrated, and the properties of PLA/PMMA-co-MA nanoparticles were investigated. When co-precipitated with PMMA-co-MA, PLA was totally converted into nanoparticles using a polymer concentration in DMSO (C[sub P]) below 17.6 mg ml[sup -1], and a PMMA-co-MA proportion above a critical value depending on the content of MA repeating units (X). For instance, the lowest PMMA-co-MA proportion required was 0.9 mg mg[sup -1] PLA for X = 12%, and 0.5 mg mg[sup -1] PLA for X = 25% (for C[sub PLA] = 16 mg ml[sup -1] DMSO). The nanoparticle diameter was essentially independent of X, the proportion of PMMA-co-MA, and the PLA molecular weight, except for oligomers for which the nanoparticle diameter was smaller. It decreased when the organic phase was diluted (126 ± 13 nm for C[sub P] = 17.6 mg ml[sup -1], and 81 ± 5 nm for C[sub P] = 5.6 mg ml[sup -1]). The timedependence of the stability and the degradation of PLA/PMMA-co-MA nanoparticles was discussed. One of the main advantages of this technique is the ability to control surface properties and to bring functional groups to otherwise non-functionalized PLA nanoparticles. To illustrate this, a conjugate of PMMA-co-MA25 and biotin was synthesized, and used to prepare biotinylated nanoparticles that could be detected by fluorescence and transmission electron microscopy after infiltration into ligatured rat small intestine. [ABSTRACT FROM AUTHOR]

Novel amphiphilic copolymers which contained poly(ethylene glycol) side-chain, long-chain alkyl pendant groups, and carboxyl groups have been synthesized by the conventional free-radical copolymerization of special monomers. The products were characterized by analysis of Fourier transform infrared spectroscopy (FT-IR), Gel Permeation Chromatography (GPC), and 1H NMR. Based on the measurement of surface tension of aqueous copolymer solutions with various concentrations at an air/water interface, the critical micelle concentrations (CMC) was found to be lower along with the increase of copolymer concentration. Experimental results showed that CMC of this kind of amphiphilic polymer appeared in the range of 0.01∼0.1 g/L. The amphiphilic polymer was mixed with an anionic surfactant (SDBS) in different proportions at aqueous solution and then successfully used in the preparation of alkyd emulsions. The results were compared with those of alkyd emulsions without polymeric surfactant. Steric stabilization of amphiphilic polymer was investigated by the observation of the stability of alkyd emulsions. The emulsions were stable after resting at ambient temperature for four months. [ABSTRACT FROM AUTHOR]

Advances in cryogenic electron microscopy (cryo-EM) enabled routine near-atomic structure determination of membrane proteins, while nanodisc technology has provided a way to provide membrane proteins with a native or native-like lipid environment. After giving a brief history of membrane mimetics, we present example structures of membrane proteins in nanodiscs that revealed information not provided by structures obtained in detergent. We describe how the lipid environment surrounding the membrane protein can be custom designed during nanodisc assembly and how it can be modified after assembly to test functional hypotheses. Because nanodiscs most closely replicate the physiologic environment of membrane proteins and often afford novel mechanistic insights, we propose that nanodiscs ought to become the standard for structural studies on membrane proteins., Competing Interests: Declaration of interests No interests are declared., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Amphiphilic copolymers consisting of alternating hydrophilic and hydrophobic units account for a major recent methodical breakthrough in the investigations of membrane proteins. Styrene–maleic acid (SMA), diisobutylene–maleic acid (DIBMA), and related copolymers have been shown to extract membrane proteins directly from lipid membranes without the need for classical detergents. Within the particular experimental setup, they form disc-shaped nanoparticles with a narrow size distribution, which serve as a suitable platform for diverse kinds of spectroscopy and other biophysical techniques that require relatively small, homogeneous, water-soluble particles of separate membrane proteins in their native lipid environment. In recent years, copolymer-encased nanolipoparticles have been proven as suitable protein carriers for various structural biology applications, including cryo-electron microscopy (cryo-EM), small-angle scattering, and conventional and single-molecule X-ray diffraction experiments. Here, we review the current understanding of how such nanolipoparticles are formed and organized at the molecular level with an emphasis on their chemical diversity and factors affecting their size and solubilization efficiency. [ABSTRACT FROM AUTHOR]

A series of anionic homopolymers, poly(sodium 2-(acrylamido)-2-methyl-1-propanesulfonate) (PAMPS) and amphiphilic copolymers of AMPS and sodium 11-(acrylamido)undecanoate (AaU), both block (PAMPS75-b-PAaUn), and random (P(AMPSm-co-AaUn)), were synthesized and their antiviral activity against Zika virus (ZIKV) was evaluated. Interestingly, while the homopolymers showed limited antiviral activity, the copolymers are very efficient antivirals. This observation was explained considering that under the conditions relevant to the biological experiments (pH 7.4 PBS buffer) the macromolecules of these copolymers exist as negatively charged (zeta potential about −25 mV) nanoparticles (4–12 nm) due to their self-organization. They inhibit the ZIKV replication cycle by binding to the cell surface and thereby blocking virus attachment to host cells. Considering good solubility in aqueous media, low toxicity, and high selectivity index (SI) of the PAMPS-b-PAaU copolymers, they can be considered promising agents against ZIKV infections. [ABSTRACT FROM AUTHOR]

Due to unique chelating and macrocyclic effects, crown ether compounds exhibit wide application prospects. They could be introduced into amphiphilic copolymers to provide new trigger mode for drug delivery. In this work, new amphiphilic random polymers of poly(lipoic acid-methacrylate-co-poly(ethylene glycol) methyl ether methacrylate-co-N-isopropylacrylamide-co-benzo-18-crown-6-methacrylamide (abbrev. PLENB) containing a crown ether ring and disulphide bond were synthesized via RAFT polymerization. Using the solvent evaporation method, the PLENB micelles were formed and then used to load substances, such as doxorubicin hydrochloride (DOX) and gold nanoparticles. The results showed that PLENB exhibited a variety of lowest critical solution temperature (LCST) in response to the presence of different ions, such as K+, Na+ and Mg2+. In particular, the addition of 150 mM K+ increased the LCST of PLENB from 31 to 37 °C and induced the release of DOX from the PLENB@DOX assemblies with a release rate of 99.84% within 12 h under 37 °C. However, Na+ and Mg2+ ions could not initiate the same response. Furthermore, K+ ions drove the disassembly of gold aggregates from the PLENB-SH@Au assemblies to achieve the transport of Au NPs, which is helpful to construct a K+-triggered carrier system. [ABSTRACT FROM AUTHOR]

• Porous polystyrene microspheres with the uniform size were fabricated. • Magnetic particles were modified on the polystyrene microspheres. • Amphiphilic copolymers layer was covered on the surface. • The magnetic polymer composite improved the extraction efficiency of safrole in the plasma. Polystyrene (PS) microsphere is a kind of attractive extracting medium due to its high stability in different matrices and its particle size can be controlled. The attachment of amphiphilic copolymers to the PS microsphere surface can overcome the drawback of PS relevant to its hydrophobic nature and low wettability. In our previous work, the magnetic composite based on PS microsphere (5 µm) and poly (divinylbenzene-co-N-vinylpyrrolidone, DVB-co-NVP) shell was successfully fabricated and applied for the extraction of safrole in cola drinks. However, the large size and ease of sedimentation limited its application in the enrichment of safrole from blood samples. Considering the adjustability of PS microsphere size, we synthesized the porous PS microspheres with the uniform size of 3 µm and then functionalized with Fe 3 O 4 nanoparticles and poly (DVB-co-NVP) layer in this work. Using the proposed material as extraction sorbent, a simple and fast magnetic solid phase extraction (MSPE) method coupled with HPLC was developed for quantification of safrole in the plasma. Under the optimized conditions, the response to safrole was linear in the range of 0.02–12 µg mL−1, and the limit of detection (LOD) was 0.006 µg mL−1. Satisfactory recoveries were obtained between 85.67% and 97.74% (spiked at 0.05, 0.2, 2 µg mL−1) and the relative standard deviations (RSDs) for the above spiked levels of the analyte were below 3.9% (n = 6). The adsorbent can be reused for 6 cycles without a significant loss of extraction capability. [ABSTRACT FROM AUTHOR]

[Display omitted] • Aggregation properties of T904 can be modulated through salt addition and changes in solution temperature. • Transition from loose cluster to compact micelles was accompanied with improved solubilization of quercetin (QN). • T904 offered superior QN solubilization in comparison to Pluronics. • QN molecules occupied the periphery of micelle core. There has been an enormous interest in improving the therapeutic efficacy of hydrophobic flavonoids through enhancement of their bioavailability. A carrier capable to effectively solubilize flavonoids is expected to support the chemical/structural integrity of flavonoid molecule, and hence, its antioxidant properties. In this paper, the effectiveness of saline solutions of an amphiphilic star block ethylene oxide-propylene oxide copolymer (Tetronic®T904) has been investigated for solubilizing quercetin (QN). T904 self-assembles in aqueous solution above its critical micellization temperature (CMT) that depends on solution concentration, temperature, pH and presence of salt. We have studied the solubilization of QN in T904 micelles at different temperature, concentration and salt (sodium chloride) concentration using scattering and spectral techniques. Our findings suggest that, at a given temperature, QN solubility is influenced by the concentration of salt and copolymer. When compared to its linear counterparts (the Pluronics®), T904 solutions offered superior solubilization. 2D NOESY NMR observations revealed that QN occupied the periphery of the hydrophobic core of micelles. Such an environment can protect the drug against oxidation in aqueous phase. [ABSTRACT FROM AUTHOR]

Chimeric or mixed nanosystems belong to the class of advanced therapeutics. Their distinctive characteristic compared with other types of nanoparticles is that they combine two or more different classes of biomaterials. These platforms have created a promising and versatile field of nanomedicine, incorporating materials that are biocompatible, such as lipids, but also functional, such as stimuli-responsive polymers. In the present work, thermoresponsive chimeric nanocarriers composed of l -α-phosphatidylcholine (Egg, Chicken) (EPC) phospholipids and poly(N-isopropylacrylamide)-b-poly(lauryl acrylate) (PNIPAM-b-PLA) block copolymers were designed and developed. Initially, model lipid bilayers with incorporated polymers and drug molecule TRAM-34 were built and studied for their thermodynamics, in order to assess the stability and functionality of the systems. Chimeric nanoparticles of EPC and PNIPAM-b-PLA were then developed and evaluated for their physicochemical properties in different medium conditions, as well as for their morphology. Polymer incorporation led to alterations in the properties and morphology of the nanoparticles, while interactions with serum proteins were absent. TRAM-34 was also incorporated inside the developed nanocarriers, followed by incorporation and release studies, which revealed the functionality of the system in elevated temperature conditions. Finally, in vitro studies on normal cells suggest the biocompatibility of these nanosystems. The proposed platforms are promising for further studies and applications in vitro and in vivo. [Display omitted] • Thermoresponsive chimeric nanocarriers with incorporated TRAM-34 were developed. • The thermotropic behavior of DPPC membranes is affected by PNIPAM-b-PLA and TRAM-34. • PNIPAM-b-PLA polymer stabilizes the membrane and leads to homogeneous nanoparticles. • EPC:PNIPAM-b-PLA nanocarriers release TRAM-34 in response to elevated temperature. • EPC:PNIPAM-b-PLA nanocarriers are biocompatible with HEK-293 cells. [ABSTRACT FROM AUTHOR]

Co-delivery of chemotherapeutics in cancer treatment has been proven essential for overcoming multidrug resistance and improving the outcome of therapy. We report the synthesis of amphiphilic copolymers of N -vinyl-2-pyrrolidone and allyl glycidyl ether of various compositions and demonstrate that they can form nanoaggregates capable of simultaneous covalent immobilization of doxorubicin by the epoxy groups in the shell and hydrophobic-driven incorporation of paclitaxel into the core of nanoparticles. The structure of the obtained copolymers was characterized by 13 C NMR, IR, and MALDI spectroscopy, as well as adsorption at the water/toluene interface. A linear increase in the number-average molecular weight of amphiphilic copolymers and a decrease in the number-average diameter of macromolecular aggregates with an increase in the ratio N -vinyl-2-pyrrolidone/allyl glycidyl ether were observed. The assembled nanocarriers were characterized by DLS. The reported novel nanocarriers can be of interest for delivery and co-delivery of a wide range of pharmacological preparations and combined therapy for cancer and other deceases.

In this research, the development and investigation of novel nanoobjects based on biodegradable random polypeptides and synthetic non-degradable glycopolymer poly(2-deoxy-2-methacrylamido-d-glucose) were proposed as drug delivery systems. Two different approaches have been applied for preparation of such nanomaterials. The first one includes the synthesis of block-random copolymers consisting of polypeptide and glycopolymer and capable of self-assembly into polymer particles. The synthesis of copolymers was performed using sequential reversible addition-fragmentation chain transfer (RAFT) and ring-opening polymerization (ROP) techniques. Amphiphilic poly(2-deoxy-2-methacrylamido-d-glucose)-b-poly(l-lysine- co -l-phenylalanine) (PMAG-b-P(Lys- co -Phe)) copolymers were then used for preparation of self-assembled nanoparticles. Another approach for the formation of polypeptide-glycopolymer particles was based on the post-modification of preformed polypeptide particles with an oxidized glycopolymer. The conjugation of the polysaccharide on the surface of the particles was achieved by the interaction of the aldehyde groups of the oxidized glycopolymer with the amino groups of the polymer on particle surface, followed by the reduction of the formed Schiff base with sodium borohydride. A comparative study of polymer nanoparticles developed with its cationic analogues based on random P(Lys- co -d-Phe), as well as an anionic one-P(Lys- co -d-Phe) covered with heparin--was carried out. In vitro antitumor activity of novel paclitaxel-loaded PMAG- b -P(Lys- co -Phe)-based particles towards A549 (human lung carcinoma) and MCF-7 (human breast adenocarcinoma) cells was comparable to the commercially available Paclitaxel-LANS.

Purpose. The aim of this work was to develop PEGylated poly(alkylcyanoacrylate) nanoparticles from a novel methoxypolyethyleneglycol cyanoacrylate-co-hexadecyl cyanoacrylate copolymer. Methods. PEGylated and non-PEGylated nanoparticles were formed by nanoprecipitation or by emulsion/solvent evaporation. Nanoparticles size, zeta potential and surface hydrophobicity were investigated. Surface chemical composition was determined by X-ray photoelectron spectroscopy. Nanoparticle morphology was investigated by transmission electron microscopy after freeze-fracture. Nanoparticles cytotoxicity was assayed in vitro, onto mouse peritoneal macrophages. Cell viability was determined through cell mitochondrial activity, by a tetrazolium-based colorimetric method (MTT test). Finally, the degradation of PEGylated and non-PEGylated poly(hexadecyl cyanoacrylate) nanoparticles was followed spectrophotometrically during incubation of nanoparticles in fetal calf serum. Results. Monodisperse nanoparticles with a mean diameter ranging between 100 and 200 nm were obtained using nanoprecipitation or emulsion/solvent evaporation as preparation procedures. A complete physico-chemical characterization, including surface chemical analysis, allowed to confirm the formation of PEG-coated nanoparticles. The PEGylation of the cyanoacrylate polymer showed reduced cytotoxicity towards mouse peritoneal macrophages. Furthermore, the presence of the PEG segment increased the degradability of the poly(hexadecyl cyanoacrylate) polymer in presence of calf serum. Conclusions. We succeeded to prepare PEGylated nanoparticles from a novel poly(methoxypolyethyleneglycol cyanoacrylate-co-hexadecyl cyanoacrylate) by two different techniques. Physico-chemical characterization showed the formation of a PEG coating layer. Low cytoxicity and enhanced degradation were also shown. [ABSTRACT FROM AUTHOR]

AB-type amphiphilic copolymers (abbreviated as LE) composed of poly (L-leucine) (PLL) as the A component and poly (ethylene oxide) (PEO) as the B component were synthesized by the ring-opening polymerization of L-leucine N-carboxy-anhydride initiated by methoxy polyoxyethylene amine (Me-PEO-NH2) and characterized. Core-shell type nanoparticles were prepared by the diafiltration method. Particle size distribution obtained by dynamic light scattering was dependent on PLL composition and the size for LE-1, LE-2 and LE-3 was 369.6±267, 523.4±410 and 561.2±364 nm, respectively. Shapes of the nanoparticles observed by transmission electron microscope (TEM) were almostly spherical. The critical micelle concentration (CMC) of the nanoparticles determined by a fluorescence probe technique was dependent on the composition of hydrophobic PLL, and the CMC for LE-1, LE-2 and LE-3 was 2. 0×10−6, 1.7×10−6 and 1.5×10−6 (mol/l), respectively. Clonazepam release from core-shell type nanoparticles in vitro was dependent on PLL composition and drug loading content. [ABSTRACT FROM AUTHOR]

The utilization of enzymes for catalysis in organic solvents, while exhibiting selectivity to different substrates, is a big challenge. We report an amphiphilic random copolymer system that self-assembles with enzymes in an organic solvent to form nanoreactors. These encapsulated enzymes are not denatured and they do preserve the catalytic activity. The cross-linkable functional groups in the hydrophobic compartments of the polymers offer to control accessibility to the enzyme. This varied accessibility due to the polymer host, rather than the enzyme itself, endows the nanoreactor with an unnatural selectivity. The findings here highlight the significant potential of simple polymer-based enzyme nanoreactors to execute selective organic reactions under non-native conditions., (© 2021 Wiley-VCH GmbH.)

[Display omitted] • Amphiphilic porous solid phase extraction materials were synthesized. • The materials were obtained by doping carbon nanotubes with HIPEs. • The materials had specific adsorption ability to triazine herbicides. • The materials were regulable, stable, and robustness. In this study, amphiphilic and porous copolymers were successfully prepared by doping a carboxylated carbon nanotube aqueous phase into a styrene and divinylbenzene oil phase, followed by a simple thermal polymerization to form high internalphase emulsions (polyHIPEs-CNTs). Hypercrosslinking and interconnecting chambers were formed with abundant open-cell pores with sizes ranging from 400 nm to 3.0 µm. Infrared spectroscopy, scanning electron microscopy, water contact angle measurements, and adsorption–desorption measurements were used to evaluate the characteristics of the material. The synthesized copolymers were demonstrated to be suitable for the separation of triazine herbicides from soil under optimized operating conditions. The maximum adsorption capacities of simazine, prometon, and prometryn were 25.4, 26.5, and 27.8 µg/g, respectively; the mean recoveries ranged from 87.56 to 97.67%, with a relative standard deviation lower than 4.5%. The polymers were stable, and the adsorption and desorption of the triazine herbicides were completed within a short period (10 min) without obvious interference. Adsorption isotherms revealed that the adsorption was co-determined by multiple effects between the adsorbents and compounds. An excellent reuse performance was observed, and the proposed polymers were believed to be potential materials for sample pretreatment in environmental science and pollutant cleaning engineering. [ABSTRACT FROM AUTHOR]

Vesicles, generally defined as self-assembled structures formed by single or multiple concentric bilayers that surround an aqueous core, have been widely used for biomedical applications. They can either occur naturally (e.g. exosomes) or be produced artificially and range from the micrometric scale to the nanoscale. One the most well-known vesicle is the liposome, largely employed as a drug delivery nanocarrier. Liposomes have been modified along the years to improve physicochemical and biological features, resulting in long-circulating, ligand-targeted and stimuli-responsive liposomes, among others. In this process, new nomenclatures were reported in an extensive literature. In many instances, the new names suggest the emergence of a new nanocarrier, which have caused confusion as to whether the vesicles are indeed new entities or could simply be considered modified liposomes. Herein, we discussed the extensive nomenclature of vesicles based on the suffix "some" that are employed for drug delivery and composed of various types and proportions of lipids and others amphiphilic compounds. New names have most often been selected based on changes of vesicle lipid composition, but the payload, structural complexity (e.g. multicompartment) and new/improved proprieties (e.g. elasticity) have also inspired new vesicle names. Based on this discussion, we suggested a rational classification for vesicles. [Display omitted] • A plethora of lipid vesicles for biomedical application are presented • The relationship between the nomenclature employed for these vesicles and modifications of classical liposomes is discussed • Full modification in the composition of lipid bilayers should be present in new vesicles • Concepts of composition, application and structural complexity are employed to categorize the vesicles [ABSTRACT FROM AUTHOR]

This article presents the evaluation of diblock and triblock poly(ethylene glycol)-b-poly(1,3-trimethylene carbonate) amphiphilic copolymers (PEG-PTMCs) as excipients for the formulation of long-acting injectables (LAIs). Copolymers were successfully synthesised through bulk ring-opening polymerisation. The concomitant formation of PTMC homopolymer could not be avoided irrespective of the catalyst amount, but the by-product could easily be removed by gel chromatography. Pure PEG-PTMCs undergo faster erosion in vivo than their corresponding homopolymer. Furthermore, these copolymers show outstanding stability compared to their polyester analogues when formulated with amine-containing reactive drugs, which makes them particularly suitable as LAIs for the sustained release of drugs susceptible to acylation. [ABSTRACT FROM AUTHOR]

Matrix-assisted laser/desorption ionization (MALDI) has become a very popular ionization technique for mass spectrometry of synthetic polymers because it allows high throughput analysis of low amounts of sample while avoiding the complexity introduced by extensive multiple charging of electrospray ionization. Yet, fundamental mechanisms underlying this ionization process are not fully understood, so development of sample preparation methods remains empirical. Reliable prediction for the optimal matrix/analyte/salt system is indeed still not possible for homopolymers and it becomes even more challenging in the case of amphiphilic block copolymers where conditions dictated by one block are not compatible with MALDI requirements of the second block. In order to perform MALDI of copolymers composed of poly (ethylene oxide) (PEO) and polystyrene (PS) blocks, it was postulated here that experimental conditions suitable for both species would also be successful for PEO- b -PS. Accordingly, designs of experiments based on Quantitative Structure Activity Relationship (QSAR) analysis were first implemented, studying the influence of 19 matrices and 26 salts on the laser fluence requested for successful MALDI. This analysis first permitted to highlight correlations between the investigated 10 descriptors of matrices and salts and the analytical response, and then to construct models that permits reliable predictions of matrix/salt couples to be used for one or the other homopolymer. Selected couples were then used for MALDI of a PEO- b -PS copolymer but no general trend was observed: experimental conditions expected to work often failed whereas ionic adducts of the copolymer were clearly detected with some matrix/salt systems that were shown to badly perform for constituting homopolymers. Overall, this rules out the working assumption stating that the MALDI behavior of chains composed of PEO and PS segments should combine the behavior of the two polymeric species. Yet, although requiring a dedicated design of experiments, MALDI of the amphiphilic PEO- b -PS copolymer was achieved for the first time., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Pizzala, Claeys-Bruno, Monnier, Sergent and Charles.)

Hydrated copolymers of N-vinylpyrrolidone (VP) with triethylene glycol dimethacrylate as a promising platform for biologically active compounds (BAC) were investigated by different physical chemical methods (dynamic light scattering, infrared spectroscopy, thermal gravimetric analysis, and differential scanning calorimetry) and the quantum chemical modeling of water coordination by the copolymers in a solution. According to the quantum chemical simulation, one to two water molecules can coordinate on one O-atom of the lactam ring of VP units in the copolymer. Besides the usual terminal coordination, the water molecule can form bridges to bind two adjacent C=O groups of the lactam rings of VP units. In addition to the first hydration shell, the formation of a second one is also possible due to the chain addition of water molecules, and its structure depends on a mutual orientation of C=O groups. We showed that N,N-dimethylbiguanidine hydrochloride (metformin) as a frontline drug for the treatment of type 2 diabetes mellitus can be associated in aqueous solutions with free and hydrated C=O groups of the lactam rings of VP units in studied copolymers. Based on the characteristics of the H-bonds, we believe that the level of the copolymer hydration does not affect the behavior and biological activity of this drug, but the binding of metformin with the amphiphilic copolymer will delight in the penetration of a hydrophilic drug across a cell membrane to increase its bioavailability. [ABSTRACT FROM AUTHOR]

• Amphiphilic sulfobetaine copolymer (ASC) coating were used to improve the antibiofouling capability of photobioreactor. • The contact angle of ASC modified EVA (EVA-ASC) film sharply decreased after immersed in water. • The EVA-ASC film either in dry, or in water swollen state exhibited excellent optical transparency in the visible light. • The density of absorbed protein and microalgae on the EVA-ASC film decreased 92% and 50% compared with those of EVA film. Biofouling is a critical challenge for the commercial application of photobioreactors for microalgae cultivation. In this work, a series of amphiphilic sulfobetaine copolymers (ASC) with different ratios of sulfobetaine (SBMA) and 2, 2, 2-trifluoroethyl methacrylate (TFMA) were synthesized via a monomer-starved seeded semi-continous emulsion polymerization method and were used to improve the antibiofouling capability of ethylene-vinyl acetate copolymer (EVA) film by surface coating method. Effects of the SBMA/TFMA ratio on the resultant ASC latexes and coating properties were investigated. With the increase of the SBMA/TFMA ratio, the particle diameter, polydispersity index and water uptake of ASC latexes and coating decreased from 261.8 nm to 144.9 nm, 0.198 to 0.054 and 26.28 % to 7.84 %, respectively, and increased afterwards. Fourier transform Infrared (FT-IR) spectra and X-ray photoelectron spectroscopy analysis (XPS) indicated that SBMA and TFMA were introduced onto the EVA film surface successfully. The contact angle of ASC modified EVA (EVA-ASC) film sharply decreased after immersed in water. The EVA-ASC film either in dry, or in water swollen state exhibited excellent optical transparency in the visible light. The adsorption of bovine serum albumin and Chlorella sp. on the EVA-ASC surface was investigated with protein and microalgae adsorption assay. It was shown that the EVA-ASC film had excellent protein and microalgae absorption resisting characteristic, the density of absorbed protein and microalgae decreased 92 % and 50 % compared with those of EVA film, respectively. [ABSTRACT FROM AUTHOR]

This work scrutinizes a versatile process during which amphiphilic copolymers (made of styrene and sulfobetaine methacrylate, ethylene glycol methacrylate or vinylpyrrolidone) are simultaneously copolymerized and coated on microporous poly (vinylidene fluoride) (PVDF) membranes. Changing the nature of the hydrophilic monomer and the reaction conditions, it is possible to regulate the wetting properties of the membranes by water and oil. The main surface physical properties of the membranes were not modified for a reaction/deposition bath containing up to 50% styrene monomer, but larger styrene amounts led to aggregate formation. A 50% molar ratio in hydrophobic/hydrophilic unit led to a suitable balance between stability and hydration, resulting in optimized water permeation and oil repellence. Gravity-driven separation of oily wastewaters was doable with all selected membranes (St50S50, St50P50 and St50V50) and oils tested (toluene, hexane, diesel). Nevertheless, it is highlighted that PEGylated surfaces offer the best overall compromise between separation kinetic and separation efficiency. Results also suggested that zwitterionization with larger amounts of zwitterionic monomers is not practical, possibly because it leads to a hydration layer too tight, which slows down the gravity-driven separation. This study demonstrates the effectiveness/versatility of this surface modification method to quickly hydrophilize PVDF membranes applied to energy-efficient separation of emulsions. Image 1 • A simultaneous polymerization/coating method is introduced. • The process is workable with a large variety of monomer units. • Modified membranes are applied to O/W gravity-driven separation. • PEGylated membranes offer the best flux/separation efficiency compromise. [ABSTRACT FROM AUTHOR]

Objective: Bile acid sequestrants (BAS) are used extensively in the treatment of hypercholesterolaemia. This brief review aimed to describe the design and evaluation of three types of BAS: amphiphilic copolymers, cyclodextrin/poly-cyclodextrin and molecular imprinted polymers. The mechanisms underlying the action of BAS are also discussed., Key Findings: BAS could lower plasma cholesterol, improve glycemic control in patients with type 2 diabetes and regulate balance energy metabolism via receptors or receptor-independent mediated mechanisms. Different types of BAS have different levels of ability to bind to bile acids, different stability and different in-vivo activity., Conclusions: A growing amount of evidence suggests that bile acids play important roles not only in lipid metabolism but also in glucose metabolism. The higher selectivity, specificity, stability and in-vivo activity of BAS show considerable potential for lipid-lowering therapy., (© The Author(s) 2021. Published by Oxford University Press on behalf of the Royal Pharmaceutical Society. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

Amphiphilic antimicrobial polymers display activity against the outer bacterial cell membrane, triggering various physiological effects. We investigated the regulation of ion transport across the lipid bilayer to understand differences in biological activity for a series of amphiphilic polymethyloxazoline - polyethyleneimine copolymers. The results confirmed that the tested structures were able to increase the permeability of the lipid bilayer (LB) membrane or its rupture. Black lipid membrane (BLM) experiments show that the triggered conductance profile and its character is strongly correlated with the polymer structure and zeta potential. The polymer exhibiting the highest antimicrobial activity promotes ion transport by using a unique mechanism and step-like characteristics with well-defined discreet openings and closings. The molecule was incorporated into the membrane in a reproducible way, and the observed channel-like activity could be responsible for the antibacterial activity of this molecule., (© 2020 Wiley-VCH GmbH.)

In this work, surface-modifying amphiphilic additives (SMAAs) were synthesized via hydrosilylation using various polymethylhydrosiloxanes (PMHS) and allyl-terminated polyethylene glycol monomethyl ethers (APEG) of varying molecular weights. The additives synthesized were incorporated into a hydrophobic, self-stratifying siloxane-polyurethane (SiPU) coating system to produce an amphiphilic surface. Contact angle experiments and atomic force microscopy (AFM), in a dry and hydrated state, were performed to assess changes in surface wettability and morphology. The antifouling and fouling-release (AF/FR) performances were evaluated by performing laboratory biological assays using the marine bacterium Cellulophaga lytica , the microalga Navicula incerta , the macroalga Ulva linza , the barnacle Amphibalanus amphitrite , and the marine mussel, Geukensia demissa . Several of the formulations showed improved AF/FR performance vs the base SiPU and performed better than some of the commercial standard marine coatings. Formulations containing SMAAs with a low grafting density of relatively high molecular weight PEG chains showed the best performance overall.

Biobased amphiphilic diblock copolymers are prepared thanks to the combination of reversible addition-fragmentation transfer (RAFT) polymerization and polymerization-induced self-assembly (PISA) in an eco-friendly solvent mixture. First, the formation of a poly(acrylic acid) macroRAFT agent (PAA-TTC) is performed in water at 70 °C. Then, in a series of experiments, the PAA-TTC macroRAFT agent is used directly, without purification, as both chain transfer agent and stabilizing agent in the RAFT-PISA of menthyl acrylate (MnA) in dispersion in an ethanol/water mixture. The polymerizations of MnA are fast with high final conversions and well-controlled amphiphilic diblock copolymers are synthesized. Stable, sub-micrometric spherical particles composed of the diblock copolymers are formed. The influence of the monomer concentration and the length of the solvophobic block on the diameter of the self-assemblies is studied by means of dynamic light scattering and cryogenic transmission electron-microscopy., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)