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Natural single‐chain nanoparticles (SCNPs) such as proteins have inspired research into the formation and application of synthetic SCNPs. Although the latter can mimic general aspects of the self‐assembly behavior of their biological counterparts, these systems remain relatively understudied. In this respect, a systematic series of amphiphilic statistical copolymers (ASC) of different molecular weights, with a hydrophilic comonomer (methacrylic acid) and varying hydrophobic comonomer to encompass methacrylates of different hydrophobicity, are synthesized. Small‐angle X‐ray scattering studies confirmed that SCNPs are achieved for each copolymer series when dispersed in basified water at 1% w/w. When the aggregation number of the ASC nanoparticles is close to unity the particle shape elongates resulting in a larger particle surface area to volume ratio, allowing more hydrophilic groups to locate on the particle surface tending to keep the particle surface charge density (PSC) constant. Thus, within a series, particle elongation increases with copolymer molecular weight. Structural parameters of SCNPs formed by ASCs composed of hydrophobic components with low partition coefficients are well consistent with predictions obtained from the PSC model. These results highlight the main parameters, namely molecular weight and acid content, responsible for the SCNP formation and provide insight into how specific particle morphology can be targeted. [ABSTRACT FROM AUTHOR]

A series of novel amphiphilic alternating CPEG copolymers were synthesized through an amine–epoxy click reaction comprising aliphatic amine and polyethylene glycol diglycidyl ether (PEGDE). These polymers were characterized in detail via nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), Fourier-transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA) to confirm the successful synthesis. Due to their amphiphilic structure, these polymers display thermoresponsiveness, with tunable cloud points (Tcps) that are adjustable from 20.8 °C to 46.8 °C by altering the side-chain length of the aliphatic amine, varying the mixing ratios of copolymers, the solution's pH, and salt additions. This tunable thermoresponsive behavior positions CPEG copolymers as promising candidates for a range of functional material applications. [ABSTRACT FROM AUTHOR]

We have constructed the phase diagrams in water of two commercial additives for coatings consisting of polyether‐modified polydimethylsiloxanes. These aqueous systems form a liquid crystal mesophase (LC) at copolymer concentrations higher than 60 wt%. At low copolymer concentrations, this LC coexists with a diluted aqueous phase. Small angle x‐ray scattering (SAXS) measurements and polarized optical microscope observations indicate that the structure of the mesophase is lamellar, with an interlayer spacing that increases linearly with the concentration of water in the system. The lamellar liquid crystals display temperature‐dependent viscoelastic behavior, with the copolymer with longer spacing showing a much lower elastic modulus. Since one of the copolymer has terminal acryl groups, its lamellar phase can be crosslinked to produce gelled liquid crystals. Other cross‐linked self‐assembled structures, such as bicontinuous microemulsions, are envisaged. [ABSTRACT FROM AUTHOR]

Amphiphilic copolymers (ACs) are versatile systems with self-assembling and aggregating properties, enabling the formation of nanomaterials (NMs) such as micelles, vesicles, nanocapsules, and nanogels. These materials have been extensively explored for the delivery of various drugs and active compounds, enhancing the solubility and permeation of poorly water-soluble drugs into skin tissue. This improvement facilitates the treatment of skin diseases, including chronic conditions like cancer, as well as infections caused by bacteria, fungi, and viruses. This review summarizes recent applications of ACs in skin treatment, with a particular focus on their use in anti-cancer drug therapy. It covers the synthesis, classification, and characterization of ACs using various experimental techniques. Additionally, it discusses recent research on different drug delivery pathways using ACs, including encapsulation efficiency, release behavior, characteristics, applications, and responses to various chemical and physical stimuli (both in vivo and in vitro). Furthermore, this review provides a comprehensive analysis of the effects of ACs NMs on several skin diseases, highlighting their potential as alternative treatments. [ABSTRACT FROM AUTHOR]

The aqueous solution of binary mixtures of amphiphilic copolymers is a potential platform for fabricating mixed polymeric micelles for pharmaceutical applications, particularly in developing drug delivery depots for a poorly water-soluble compound. This study fabricated and investigated binary mixtures of poloxamer 403 (P403) and poloxamer 407 (P407) at varying P403:P407 molar ratios to develop a vehicle for the poorly water-soluble compound, using ibuprofen as a model drug. The cooperative formation of mixed micelles was obtained, and the solubility of ibuprofen in the binary mixtures was enhanced compared to the solubility in pure water and an aqueous single P407 solution. The binary mixture with the P403:P407 molar ratio of 0.75:0.25 at a total polymer concentration of 19% w/v exhibited the temperature dependence of micellization and sol-to-gel characteristics of the thermosensitive mixed micellar gels. It possessed suitable micellization and gelation characteristics for in situ gelling systems. The release of ibuprofen from the thermosensitive mixed micellar depots was sustained through a diffusion-controlled mechanism. The findings can aid in formulating binary mixtures of P403 and P407 to achieve the desired properties of mixed micelles and micellar gels. [ABSTRACT FROM AUTHOR]

Luminescent Ag nanoclusters (Ag NCs) are a promising probe material for sensing and bioimaging applications. However, the intrinsic obstacle of poor water stability and photostability greatly restrict their practical application in biological systems. Herein, we report the intracellular hypochlorite (ClO−) detection with amphiphilic copolymer-modified luminescent Ag NCs with good biocompatibility and photostability. The Ag NCs were synthesized by using chemically inert hydrophobic ligands and then modified with an amphiphilic (1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(poly(ethylene glycol))-2000]) (DSPE-PEG-2000) and sodium dodecyl sulfonate (SDS) for phase transfer. It was found that the approach of the removal of organic solvents during the phase transfer has remarkable influences on the properties of the Ag NCs, including their size, luminescence property, and aqueous stability. Furthermore, the silver core of Ag NCs could be oxidatively damaged by ClO−, thereby causing photoluminescence (PL) quenching. The ClO−-induced PL quenching was specific over the other common reactive oxygen species (ROS) as well as some common interferences. Finally, they have been successfully applied as a fluorescent nanoprobe for detecting exogenous and endogenous ClO− in living cells. [ABSTRACT FROM AUTHOR]

In this work, nine amphiphilic acrylamide copolymers were synthesized using three surface-active co-monomers based on polyethoxylated sorbitan monoesters. The prepared co-monomers and copolymers were characterized by FT-IR, 1H-NMR, and viscosity average molecular weight. Surface/interfacial activities, contact angles, and rheological properties for aqueous solutions of the prepared copolymers were determined. Also, the influence of salts' concentration and temperature variation was investigated. The results showed that incorporating the prepared co-monomers into the copolymers backbone enhanced their properties and capabilities. This improvement was enlarged by increasing the feed ratio and chain length of the attached co-monomers. The copolymers PT20S-3, PT40S-3, and PT60S-3 showed better results and the latter exhibited the best values. They were 37.6 mN.m−1, 6.4 mN.m−1, 15.678° and 338.48 mPa.s for γST, γIFT, CA, and ηapp respectively. The copolymer PT60S-3 was expected to have a prospective use as a chemical EOR agent. [ABSTRACT FROM AUTHOR]

This study focused on synthesizing and characterizing PEGylated amphiphilic block copolymers with pendant linoleic acid (Lin) moieties as an alternative to enhance their potential in drug delivery applications. The synthesis involved a two‐step process, starting with ring‐opening polymerization of ε‐caprolactone (CL) and propargylated cyclic carbonate (MCP) to obtain PEG‐b‐P(CL‐co‐MCP) copolymers, which were subsequently modified via click chemistry. Various reaction conditions were explored to improve the yield and efficiency of the click chemistry step. The use of anisole as a solvent, N‐(3‐azidopropyl)linoleamide as a substrate, and a reaction temperature of 60°C proved to be highly efficient, achieving nearly 100% conversion at a low catalyst concentration. The resulting copolymers exhibited controlled molecular weights and low polydispersity, confirming the successful synthesis. Furthermore, click chemistry allows for the attachment of Lin moieties to the copolymer, enhancing its hydrophobic character, as deduced from their significantly lower critical micelle concentration than that of traditional PEG‐b‐PCL systems, which is indicative of enhanced stability against dilution. The modified copolymers exhibited improved thermal stability, making them suitable for applications that require high processing temperatures. Dynamic light scattering and transmission electron microscopy confirmed the formation of micellar structures with sizes below 100 nm and minimal aggregate formation. Additionally, 1H NMR spectroscopy in deuterated water revealed the presence of core‐shell micelles, which provided higher kinetic stability against dilution. [ABSTRACT FROM AUTHOR]

This manuscript serves as the starting point for in-depth research of multicomponent, statistical, methacrylate-based copolymers that potentially mimic the behavior of proteins in aqueous solutions. These synthetic macromolecules are composed of specially chosen comonomers: methacrylic acid (MAA), oligoethylene glycol methyl ether methacrylate (OEGMA475), 2-(dimethylamino)ethyl methacrylate (DMAEMA) and benzyl methacrylate (BzMA). Monomer choice was based on factors such as the chemical nature of pendant functional groups, the polyelectrolyte/polyampholyte and amphiphilic character and the overall hydrophobic–hydrophilic balance (HLB) of the obtained quaterpolymers. Their synthesis was achieved via a one-pot reversible addition fragmentation chain transfer (RAFT) polymerization in two distinct compositions and molecular architectures, linear and hyperbranched, respectively, in order to explore the effects of macromolecular topology. The resulting statistical quaterpolymers were characterized via 1H-NMR and ATR-FTIR spectroscopies. Their behavior in aqueous solutions was studied by dynamic (DLS) and electrophoretic light scattering (ELS) and fluorescence spectroscopy (FS), producing vital information concerning their self-assembly and the structure of the formed aggregates. The physicochemical studies were extended by tuning parameters such as the solution pH and ionic strength. Finally, the quaterpolymer behavior in FBS/PBS solutions was investigated to test their colloid stability and biocompatibility in an in vivo-mimicking, biological fluid environment. [ABSTRACT FROM AUTHOR]

This manuscript presents the synthesis of hyperbranched amphiphilic poly (lauryl methacrylate-co-tert-butyl methacrylate-co-methacrylic acid), H-P(LMA-co-tBMA-co-MAA) copolymers via reversible addition fragmentation chain transfer (RAFT) copolymerization of tBMA and LMA, and their post-polymerization modification to anionic amphiphilic polyelectrolytes. The focus is on investigating whether the combination of the hydrophobic characters of LMA and tBMA segments, as well as the polyelectrolyte and hydrophilic properties of MAA segments, both distributed within a unique hyperbranched polymer chain topology, would result in intriguing, branched copolymers with the potential to be applied in nanomedicine. Therefore, we studied the self-assembly behavior of these copolymers in aqueous media, as well as their ability to form complexes with cationic proteins, namely lysozyme (LYZ) and polymyxin (PMX). Various physicochemical characterization techniques, including size exclusion chromatography (SEC) and proton nuclear magnetic resonance (1H-NMR), verified the molecular characteristics of these well-defined copolymers, whereas light scattering and fluorescence spectroscopy techniques revealed promising nanoparticle (NP) self- and co-assembly properties of the copolymers in aqueous media. [ABSTRACT FROM AUTHOR]

Luminescent Ag nanoclusters (Ag NCs) are a promising probe material for sensing and bioimaging applications. However, the intrinsic obstacle of poor water stability and photostability greatly restrict their practical application in biological systems. Herein, we report the intracellular hypochlorite (ClO−) detection with amphiphilic copolymer-modified luminescent Ag NCs with good biocompatibility and photostability. The Ag NCs were synthesized by using chemically inert hydrophobic ligands and then modified with an amphiphilic (1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(poly(ethylene glycol))-2000]) (DSPE-PEG-2000) and sodium dodecyl sulfonate (SDS) for phase transfer. It was found that the approach of the removal of organic solvents during the phase transfer has remarkable influences on the properties of the Ag NCs, including their size, luminescence property, and aqueous stability. Furthermore, the silver core of Ag NCs could be oxidatively damaged by ClO−, thereby causing photoluminescence (PL) quenching. The ClO−-induced PL quenching was specific over the other common reactive oxygen species (ROS) as well as some common interferences. Finally, they have been successfully applied as a fluorescent nanoprobe for detecting exogenous and endogenous ClO− in living cells.

Giant unilamellar vesicles (GUVs) are microcompartments serving to confine reactions, allow signaling pathways, or design synthetic cells. Polymer GUVs are composed of copolymer membranes mimicking cell membranes, and present advantages over lipid-based GUVs, such as higher mechanical stability and chemical versatility. Such microcompartments are essential for understanding reactions/signaling occurring in cells, which are difficult to study by in vivo approaches due to the cell's complexity. However, the lack of control over their production, stability, and membrane diffusion properties is still limiting their use for bio-related applications. Here, polymer GUVs produced by microfluidics and permeabilized with DNA-origami nanopores (DoNs) that present a high level of control over these essential properties are introduced. After systematic optimization of conditions, DoN-GUVs reveal a narrow size distribution, allow for high encapsulation efficiencies, and are stable for weeks, protecting encapsulated biomolecules. The kinetics of diffusion of molecules through the GUV's membrane is tuned by insertion of DoNs with a controlled 3D-structure. DNA polymerase I, encapsulated as model for bioreactions, successfully produced DNA duplex strands with spatiotemporal control. DoN-GUVs loaded with active molecules open new avenues in bioreactions, from the detection of biomolecules, over the tuning of molecular transport rates, to the investigation of cellular processes/signaling. [ABSTRACT FROM AUTHOR]

Synthetic anion transporters are potential therapeutics for a plethora of cellular ailments including cystic fibrosis, cancer resistance, epilepsy, etc. In this context, cationic macromolecular amphiphiles are gaining revived interest because of their easy synthesis and ample ion channelization through the membrane barrier. Herein, side chain alanine containing cationic polymer amphiphiles with steroid/fatty acid decoration was established to be an efficient anion‐selective artificial ionophore. The facile amphiphilicity‐assisted assembly makeover of cholic acid containing copolymers channelized the better transmembrane anion transport and efficiency with the maximum selectivity found with NO2− ion. [ABSTRACT FROM AUTHOR]

Mixed micelles from copolymers in aqueous media have emerged as a valuable tool for producing functional polymer nanostructures with applications in nanomedicine, including drug delivery and bioimaging. In this review, we discuss the basics of mixed copolymer micelles’ design, structure, and physicochemical properties. We also focus on their utilization in biomedical applications using examples from recent literature.

The physicochemical properties of “smart” or stimuli-sensitive amphiphilic copolymers can be modeled as a function of their environment. In special, pH-sensitive copolymers have practical applications in the biomedical field as drug delivery systems. Interactions between the structural units of any polymer-drug system imply mutual constraints at various scale resolutions and the nonlinearity is accepted as one of the most fundamental properties. The release kinetics, as a function of pH, of a model active principle, i.e., Curcumin, from nanomicelles obtained from amphiphilic pH-sensitive poly(2-vinylpyridine)-b-poly(ethylene oxide) (P2VP-b-PEO) tailor-made diblock copolymers was firstly studied by using the Rietger-Peppas equation. The value of the exponential coefficient, n, is around 0.5, generally suggesting a diffusion process, slightly disturbed in some cases. Moreover, the evaluation of the polymer-drug system’s nonstationary dynamics was caried out through harmonic mapping from the usual space to the hyperbolic one. The kinetic model we developed, based on fractal theory, fits very well with the experimental data obtained for the release of Curcumin from the amphiphilic copolymer micelles in which it was encapsulated. This model is a variant of the classical kinetic models based on the formal kinetics of the process.

[Display omitted] • Henry's constant is obtained from the results of Self-Consistent field calculations to compare the surface affinity of amphiphilic copolymers of various architectures. • Spatial distribution of adsorbing segments along polymer chains has great influence on their adsorption and ultimately on colloidal stabilising properties, when used as dispersants. • For star-like polymers with identical chemical compositions, the surface affinity decreases with increasing number of arms. • For amphiphilic copolymers of the same chemical composition, dendritic polymers have the highest surface affinity. Polymer architecture is known to have significant impact on its adsorption behaviour. Most studies have been concerned with the more concentrated, "close to surface saturation" regime of the isotherm, where complications such as lateral interactions and crowding also additionally affect the adsorption. We compare a variety of amphiphilic polymer architectures by determining their Henry's adsorption constant (k H), which, as with other surface active molecules, is the proportionality constant between surface coverage and bulk polymer concentration in a sufficiently dilute regime. It is speculated that not only the number of arms or branches, but also the position of adsorbing hydrophobes influence the adsorption, and that by controlling the latter the two can counteract each other. The Self-consistent field calculation of Scheutjens and Fleer was implemented to calculate the adsorbed amount of polymer for many different polymer architectures including linear, star and dendritic. Using the adsorption isotherms at very low bulk concentrations, we determined the value of k H for these. It is found that the branched structures (star polymers and dendrimers) can be viewed as analogues of linear block polymers based on the location of their adsorbing units. Polymers containing consecutive trains of adsorbing hydrophobes in all cases showed higher level of adsorption compared to their counterparts, where the hydrophobes were more uniformly distributed on the chains. While increasing the number of branches (or arms for star polymers) also confirmed the known result that the adsorption decreased with the number of arms, this trend can be partially offset by the appropriate choice of the location of anchoring groups. [ABSTRACT FROM AUTHOR]

Hydrophilic chitosan (CHT) and hydrophobic polyε‐caprolactone (PCL) are well‐known biocompatible and biodegradable polymers that have many applications in the biomedical and pharmaceutical fields. But the mixtures of these two compounds are considered incompatible, which makes them not very interesting. To avoid this problem and to further extend the properties of these homopolymers, the synthesis of a new graft copolymer, the fully biodegradable amphiphilic poly(ε‐caprolactone‐g‐chitosan) (PCL‐g‐CHT) is described, with an unusual "reverse" structure formed by a PCL backbone with CHT grafts, unlike the "classic" CHT‐g‐PCL structure with a CHT main chain and PCL grafts. This copolymer is prepared via a copper‐catalyzed 1,3‐dipolar Huisgen cycloaddition between propargylated PCL (PCL‐yne) and a new azido‐chitosan (CHT‐N3). In order to obtain an amphiphilic copolymer regardless of the pH, chitosan oligomers, soluble at any pH, are prepared and used. The amphiphilic PCL‐g‐CHT copolymer spontaneously self‐assembles in water into nanomicelles that may incorporate hydrophobic drugs to give novel drug delivery systems. [ABSTRACT FROM AUTHOR]

The copolymerization of 1,1,1,3,3,3-hexafluoroisopropylacrylate (HFIPA) and 2,2,3,3,4,4,5,5-octafluoropentyl acrylate (OFPA) with N-vinylpyrrolidone (NVP) in the presence of S,S'-dibenzyl trithiocarbonate (BTC) and polymeric RAFT agents based on fluoroacrylates were investigated. The copolymerization process proceeds in a control mode at any conditions investigated that was confirmed by the first order of reaction by monomer and SEC curves. Reactivity ratios of monomers were determined by the Fineman-Ross and Kelen-Tudos models. Aggregation behavior of copolymers at the air/water interface was studied by the Langmuir film balance technique. The influence of the composition and pH of the subphase on the surface properties of copolymers is considered. With the rise of subphase pH, as well as an increase in the mole fraction of NVP in the copolymer, the pressure of the plateau formation process increases. The morphology of LB films of various compositions was studied by atomic force microscopy. With the elevation in the proportion of NVP, a change in the size of micelles is traced. [ABSTRACT FROM AUTHOR]

In this work, amphiphilic polymers synthesized from carboxylated carbon nanotubes stabilized high internal phase emulsions are demonstrated to be capable of direct extracting zearalenone and zearalanone in samples consisting of an oil‐water emulsion system. Under optimal conditions, the maximum adsorption capacities for zearalenone and zearalanone are 17.27 and 13.26 mg/g. The adsorption is mainly attributed to π‐π interaction, hydrophobic interaction, and hydrogen‐bonding interaction for zearalenone and zearalanone. The adsorption isotherms reveal that the adsorption of zearalenone and zearalanone on amphiphilic polymers synthesized from carboxylated carbon nanotubes stabilized high internal phase emulsions follows Freundlich model with multilayer and heterogeneous adsorption due to the presence of multiple kinds of adsorption sites. The relative recoveries of the spiked zearalenone and zearalanone in corn juice samples range from 85% to 93% with relative standard deviations lower than 3.52%. The results manifest the high efficiency of amphiphilic polymers synthesized from carboxylated carbon nanotubes stabilized high internal phase emulsions for the adsorption and separation of analytes in the oil‐water emulsion system. This study provides a new perspective on adsorbent engineering for the adsorption application in heterogeneous media. [ABSTRACT FROM AUTHOR]

Amphiphilic copolymers (AP) represent a class of novel antibiofouling materials whose chemistry and composition can be tuned to optimize their performance. However, the enormous chemistry‐composition design space associated with AP makes their performance optimization laborious; it is not experimentally feasible to assess and validate all possible AP compositions even with the use of rapid screening methodologies. To address this constraint, a robust model development paradigm is reported, yielding a versatile machine learning approach that accurately predicts biofilm formation by Pseudomonas aeruginosa on a library of AP. The model excels in extracting underlying patterns in a "pooled" dataset from various experimental sources, thereby expanding the design space accessible to the model to a much larger selection of AP chemistries and compositions. The model is used to screen virtual libraries of AP for identification of best‐performing candidates for experimental validation. Initiated chemical vapor deposition is used for the precision synthesis of the model‐selected AP chemistries and compositions for validation at solid–liquid interface (often used in conventional antifouling studies) as well as the air–liquid–solid triple interface. Despite the vastly different growth conditions, the model successfully identifies the best‐performing AP for biofilm inhibition at the triple interface. [ABSTRACT FROM AUTHOR]

Polymer micelles represent one of the most attractive drug delivery systems due to their design flexibility based on a variety of macromolecular synthetic methods. The environmentally safe chemistry in which the use or generation of hazardous materials is minimized has an increasing impact on polymer-based drug delivery nanosystems. In this work, a solvent-free green synthetic procedure was applied for the preparation of an amphiphilic diblock copolymer consisting of biodegradable hydrophobic poly(acetylene-functional carbonate) and biocompatible hydrophilic polyethylene glycol (PEG) blocks. The cyclic functional carbonate monomer 5-methyl-5-propargyloxycarbonyl-1,3-dioxane-2-one (MPC) was polymerized in bulk using methoxy PEG-5K as a macroinitiator by applying the metal-free organocatalyzed controlled ring-opening polymerization at a relatively low temperature of 60 °C. The functional amphiphilic block copolymer self-associated in aqueous media into stable micelles with an average diameter of 44 nm. The copolymer micelles were physico-chemically characterized and loaded with the plant-derived anticancer drug curcumin. Preliminary in vitro evaluations indicate that the functional copolymer micelles are non-toxic and promising candidates for further investigation as nanocarriers for biomedical applications. [ABSTRACT FROM AUTHOR]

Polymer compositions of folic acid based on an amphiphilic copolymer of N-vinylpyrrolidone with methacrylic acid, branched with triethylene glycol dimethacrylate, were developed and characterized by DLS, 1H NMR, IR spectroscopy, DSC, and TGA in solutions and in the solid state. Electron absorption spectroscopy was used to determine the effective binding constant of folic acid and the copolymer in isopropanol and in aqueous media. The behavior of nanoscale systems in water depending on the medium temperature and pH was studied, and their hydrodynamic radii were determined. Quantum chemical modeling of the structure of the intermolecular complexes was carried out, and it was shown that the hydrogen bonds formed by oxygen atoms of carboxy groups of either folic acid or methacrylic acid units and hydrogen atoms are weak. The cytotoxicity of polymer compositions with different contents of folic acid (0.5–4 wt.%) was studied on normal (FetMSC, Vero) and tumor cell cultures, namely, HeLa (human cervical adenocarcinoma, clone M-HeLa) and HepG2 (human liver carcinoma), and their high biocompatibility was demonstrated. Fluorescence microscopy was used to study the accumulation dynamics of polymer particles loaded with folic acid and a fluorescent dye, namely, zinc tetraphenylporphyrinate, in Vero and HeLa cells. Inferences were made about the prospects of the obtained compositions as targeted delivery systems. [ABSTRACT FROM AUTHOR]

Mixed micelles from copolymers in aqueous media have emerged as a valuable tool for producing functional polymer nanostructures with applications in nanomedicine, including drug delivery and bioimaging. In this review, we discuss the basics of mixed copolymer micelles' design, structure, and physicochemical properties. We also focus on their utilization in biomedical applications using examples from recent literature. [ABSTRACT FROM AUTHOR]

Water-soluble forms of α-tocopherol (TP) as an effective antioxidant were obtained by encapsulating it into nanoparticles (NPs) of amphiphilic copolymers of N-vinylpyrrolidone with triethylene glycol dimethacrylate (CPL1-TP) and N-vinylpyrrolidone with hexyl methacrylate and triethylene glycol dimethacrylate (CPL2-TP) synthesized by radical copolymerization in toluene. The hydrodynamic radii of NPs loaded with TP (3.7 wt% per copolymers) were typically ca. 50 or 80 nm depending on copolymer composition, media, and temperature. Characterization of NPs was accomplished by transmission electron microscopy (TEM), IR-, and 1H NMR spectroscopy. Quantum chemical modeling showed that TP molecules are capable to form hydrogen bonds with donor groups of the copolymer units. High antioxidant activity of both obtained forms of TP has been found by the thiobarbituric acid reactive species and chemiluminescence assays. CPL1-TP and CPL2-TP effectively inhibited the process of spontaneous lipid peroxidation as well as α-tocopherol itself. The IC50 values of luminol chemiluminescence inhibition were determined. Antiglycation activity against vesperlysine and pentosidine-like AGEs of TP water-soluble forms was shown. The developed NPs of TP are promising as materials with antioxidant and antiglycation activity and can be used in various biomedical applications. [ABSTRACT FROM AUTHOR]

Block copolymers synthesized via Atom Transfer Radical Polymerization from alkyl acrylate and t-butyl acrylate and the subsequent hydrolysis of the t-butyl acrylate to acrylic acid were systematically varied with respect to their hydrophobic part by the variation in the alkyl chain length and the degree of polymerisation in this block. Depending on the architecture of the hydrophobic part, they had a more or less pronounced tendency to form copolymer micelles in an aqueous solution. They were employed for the preparation of IPECs by mixing the copolymer aggregates with the polycations polydiallyldimethylammonium chloride (PDADMAC) or q-chit. The IPEC structure as a function of the composition was investigated by Static Light and Small Angle Neutron Scattering. For weakly-associated block copolymers (short alkyl chain), complexation with polycation led to the formation of globular complexes, while already existing micelles (long alkyl chain) grew further in mass. In general, aggregates became larger upon the addition of further polycation, but this growth was much more pronounced for PDADMAC compared to q-chit, thereby leading to the formation of clusters of aggregates. Accordingly, the structure of such IPECs with a hydrophobic block depended largely on the type of complexing polyelectrolyte, which allowed for controlling the structural organisation via the molecular architecture of the two oppositely charged polyelectrolytes. [ABSTRACT FROM AUTHOR]

The development of effective anti-cancer therapeutics remains one of the current pharmaceutical challenges. The joint delivery of chemotherapeutic agents and biopharmaceuticals is a cutting-edge approach to creating therapeutic agents of enhanced efficacy. In this study, amphiphilic polypeptide delivery systems capable of loading both hydrophobic drug and small interfering RNA (siRNA) were developed. The synthesis of amphiphilic polypeptides included two steps: (i) synthesis of poly-αl-lysine by ring-opening polymerization and (ii) its post-polymerization modification with hydrophobic l-amino acid and l-arginine/l-histidine. The obtained polymers were used for the preparation of single and dual delivery systems of PTX and short double-stranded nucleic acid. The obtained double component systems were quite compact and had a hydrodynamic diameter in the range of 90–200 nm depending on the polypeptide. The release of PTX from the formulations was studied, and the release profiles were approximated using a number of mathematical dissolution models to establish the most probable release mechanism. A determination of the cytotoxicity in normal (HEK 293T) and cancer (HeLa and A549) cells revealed the higher toxicity of the polypeptide particles to cancer cells. The separate evaluation of the biological activity of PTX and anti-GFP siRNA formulations testified the inhibitory efficiency of PTX formulations based on all polypeptides (IC50 4.5–6.2 ng/mL), while gene silencing was effective only for the Tyr-Arg-containing polypeptide (56–70% GFP knockdown). [ABSTRACT FROM AUTHOR]

[Display omitted] • Novel gradient-like copolymers were synthesized by RAFT polymerization. • Copolymerization of N -vinylsuccinimide with O-cholesteryl (meth)acrylate was studied. • Amphiphilic poly(vinylsuccinamic acid-co-cholesteryl (meth)acrylate)s were obtained. • Stable nanoparticles of 100–400 nm were produced by several techniques. • Irinotecan delivery systems with high loading and inhibitory activity were developed. Today, biocompatible and bioinspired well-defined copolymers with the ability to form nanoparticles are of great interest as potential drug delivery systems. In this study, we report the synthesis of novel biocompatible copolymers from monomers with different activity and capable of forming gradient copolymers by RAFT polymerization. In particular, the copolymerization of N -vinylsuccinimide (VSI) and O -cholesteryl (meth)acrylate (Ch(M)A) mediated by S,S' -dibenzyl trithiocarbonate (DBTTC) has been thoroughly studied by varying the monomer ratio and the ratio of monomer to RAFT agent. Important dependencies such as molecular weight and monomer conversion versus time, and molar fraction of monomer units as a function of monomer conversion were investigated. The obtained copolymers were thoroughly characterized using a number of physicochemical methods such as 1H NMR, 1H–13C HSQC and ATR-IR-spectroscopy, size-exclusion chromatography, static and dynamic light-scattering, as well as thermogravimetric analysis. In addition, the reactivity ratios of VSI and ChMA were determined and the dyad and triad compositions of the copolymers were calculated from the obtained values. The synthesized P(VSI- co -Ch(M)A) were subjected to selective hydrolysis of succinimide ring to convert it into succinamic acid. This approach yields a set of bioinspired amphiphilic copolymers based on N -vinylsuccinamic acid (VSAA) and Ch(M)A. The synthesized series of P(VSI- co- Ch(M)A) and P(VSAA- co -Ch(M)A) were used to obtain nanoparticles by nanoprecipitation or self-assembly via direct dissolution in aqueous medium. In addition, the method of surface hydrolysis of VSI units in pre-formed P(VSI- co- Ch(M)A) nanoparticles was applied to produce nanoparticles with hydrophilic negatively charged surface and enhanced stability. All techniques were optimized to prepare nanoparticles with characteristics suitable for systems considered for drug delivery. Successful loading of the antitumor drug irinotecan into nanoparticles was achieved with high encapsulation efficacies. The storage stability of empty and irinotecan loaded nanoparticles were studied in various media (water, saline solution, serum containing cell culture medium) under room and refrigerator conditions. The developed empty nanoparticles exhibited low rate of uptake by macrophages and low cytotoxicity to irinotecan-sensitive colon cancer cells (Caco-2). In turn, the irinotecan-loaded nanoparticles demonstrated inhibitory activity against Caco-2 cells comparable to the free drug. [ABSTRACT FROM AUTHOR]

Small hydrophilic drugs are widely used for systemic administration, but they suffer from poor absorption and fast clearance. Their nanoencapsulation can improve biodistribution, targeted delivery, and pharmaceutical efficacy. Hydrophilics are effectively encapsulated in compartmented particles, such as liposomes or extracellular vesicles, which are biocompatible but poorly customizable. Polymeric vectors can form compartmental structures, also being functionalizable. Here, we report a system composed of polymeric stabilized reversed micelles for hydrophilic drugs encapsulation. We optimized the preparation procedure, and calculated the critical micellar concentration. Then, we developed a strategy for stabilization that improves micelle stability upon dilution. We tested the drug loading and delivery capabilities with creatine as a drug molecule. Prepared stabilized reversed micelles had a size of around 130 nm and a negative z-potential around −16 mV, making them functional as a drug carrier. The creatine cargo increased micelle size and depended on the loading conditions. The higher amount of loaded creatine was around 60 μg/mg of particles. Delivery tests indicated full release within three days in micelles with the lower cargo, while higher loadings can provide a sustained release for longer times. Obtained results are interesting and encouraging to test the same system with different drug cargoes. [ABSTRACT FROM AUTHOR]

In this study, reversible addition-fragmentation chain transfer (RAFT) polymerization is utilized in order to synthesize novel hyperbranched poly(oligoethylene glycol) methyl ether methacrylate-co-tert-butyl methacrylate-co-methacrylic acid) (H-[P(OEGMA-co-tBMA-co-MAA)]) copolymers in combination with selective hydrolysis reactions. The copolymers showing amphiphilicity induced by the polar OEGMA and hydrophobic tBMA monomeric units, and polyelectrolyte character due to MAA units, combined with unique macromolecular architecture were characterized by physicochemical techniques, such as size exclusion chromatography (SEC) and 1H-NMR spectroscopy. The hyperbranched copolymers were investigated in terms of their ability to self-assemble into nanostructures when dissolved in aqueous media. Dynamic light scattering and fluorescence spectroscopy revealed multimolecular aggregates of nanoscale dimensions with low critical aggregation concentration, the size and mass of which depend on copolymer composition and solution conditions, whereas zeta potential measurements indicated pH sensitive features. In addition, aiming to evaluate their potential use as nanocarriers, the copolymers were studied in terms of their drug encapsulation and protein complexation ability utilizing curcumin and lysozyme, as a model hydrophobic drug and a model cationic protein, respectively. [ABSTRACT FROM AUTHOR]

This research concerns the investigation of the preparation of polymeric nanocarriers containing a flavonoid—naringenin, xanthohumol or isoxanthohumol—based on Pluronics by the thin-film formation method. The size of the formed micelles and their stability upon dilution were evaluated using Dynamic light scattering (DLS) analysis; the high values of the drug loading and the encapsulation efficiency confirmed that the proposed systems of flavonoids delivery consisting of Pluronic P123 and F127 nanomicelles could effectively distribute the drug into tumour tissues, which makes these nanocarriers ideal candidates for passive targeting of cancer cells by the enhanced permeation and retention (EPR) effect. The in vitro cytotoxicity of proposed flavonoids in the Pluronic formulations was investigated by the SRB assay with human colon cancer cells. We designed mixed polymeric micelles, which was a successful drug delivery system for the case of naringenin not being able to enhance the bioavailability and cytotoxic activity of xanthohumol and isoxanthohumol. Furthermore, it was observed that the higher amount of polymer in the formulation achieved better cytotoxic activity. [ABSTRACT FROM AUTHOR]

[Display omitted] • Symmetric 14-armed βCD-cored star amphiphilic block copolymers βCD-(PBO-PGL) 14 were obtained with tunable arm block lengths, high purity and low polydispersity. • Star copolymers βCD-(PBO-PGL) 14 have similar self-assembly behavior compared to linear analogues (PGL-PBO-PGL). • Polymersomes made from βCD-(PBO-PGL) 14 have different ion permeability behavior compared to linear analogues (PGL-PBO-PGL). For polymersome-based nanoreactor purposes, we herein present the synthesis and characterization of well-defined star amphiphilic copolymers composed of a beta -cyclodextrin (βCD) core and seven poly(butylene oxide)- block -polyglycidol (PBO-PGL) arms per side (βCD-(PBO-PGL) 14). The self-assembly behavior of 14-armed βCD-(PBO-PGL) 14 and PGL-PBO-PGL (linear analogues without the βCD segment) was investigated using scattering techniques for comparison. The morphologies, including vesicles and micelles, are governed by the hydrophobic-to-hydrophilic (weight) ratio, regardless of the polymer architecture (linear or star). Interestingly, despite notable differences in polymer conformation, the produced supramolecular structures were evidenced to be fairly similar on the structural point of view. We subsequently investigated the ion permeability of the membranes of the self-assemblies focusing on the impact of the presence of βCD. The results demonstrated that the βCD-containing vesicular membranes are less permeable to H+, compared with βCD-free vesicular membranes. The presence of βCD in planar membranes also influences the K+Cl− permeability to some extent. Thus, βCD-containing membranes can be considered as potential candidates in designing nano-containers towards applications where precise changes in environmental pH are required. [ABSTRACT FROM AUTHOR]

By combining oppositely charged polydiallyldimethylammonium chloride (PDADMAC) and sodium polyacrylate (NaPA), interpolyelectrolyte complexes (IPECs) can be formed in aqueous solution. Such IPECs are studied for rather short NaPA and under variation of the Mw of PDADMAC. The focus is on elucidating the effect of having a hydrophobic modification of the NaPA, which is introduced by having 10 mol% of the monomeric units substituted by ones carrying a dodecyl alkyl chain. This modification renders the complexes more hydrophobic, which is seen in the fact that precipitation of the complexes occurs at a lower mixing ratio and the biphasic region is also wider. The structures of the soluble IPECs are studied by a combination of light and neutron scattering (SANS). It is observed that the complexes formed possess typical radii of gyration of ≈30–40 nm, which become somewhat smaller with increasing length of the PDADMAC chain. The SANS data can be described well with the Beaucage model for complexes, where locally small hydrophobic domains of cylindrical shape are formed, whose persistence length decreases with increasing content of NaPA in the complexes. In contrast no such structures are seen for NaPA without the hydrophobic modification. The cylindrical domains are then arranged within larger‐sized clusters of 30–40 nm, which become more compact with reduced length of the PDAMAC chains. The structure of the IPECs is largely determined by the presence of the hydrophobic modification of the NaPA and is further controlled by the length of the hydrophobic modification. Such IPECs of controlled structure, relatively small size, and containing hydrophobic domains are potentially interesting as delivery systems due to having domains of variable polarity. [ABSTRACT FROM AUTHOR]

A series of nanoparticles (NPs) with a hydrodynamic radius from 20 to 100 nm in PBS was developed over the solubilization of hydrophobic dye methyl pheophorbide a (chlorin e6 derivative) by amphiphilic copolymers of N-vinylpyrrolidone with (di)methacrylates. Photophysical properties and biological activity of the NPs aqueous solution were studied. It was found that the dye encapsulated in the copolymers is in an aggregated state. However, its aggregation degree decreases sharply, and singlet oxygen quantum yield and the fluorescence signal increase upon the interaction of these NPs with model biological membranes—liposomes or components of a tissue homogenate. The phototoxic effect of NPs in HeLa cells exceeds by 1.5–2 times that of the reference dye chlorin e6 trisodium salt—one of the most effective photosensitizers used in clinical practice. It could be explained by the effective release of the hydrophobic photosensitizer from the NPs into biological structures. The demonstrated approach can be used not only for the encapsulation of hydrophobic photosensitizers for PDT but also for other drugs, and N-vinylpyrrolidone amphiphilic copolymers show promising potential as a modern platform for the design of targeted delivery vehicles. [ABSTRACT FROM AUTHOR]

This paper provides a review of the literature on the use of Pluronic® triblock copolymers for drug encapsulation over the last 10 years. A special focus is given to the progress of drug delivery systems (e.g. , micelles, liposomes, micro/nanoemulsions, hydrogels and nanogels, and polymersomes and niosomes); the beneficial aspects of Pluronic® triblock copolymers as biological response modifiers and as pharmaceutical additives, adjuvants, and stabilizers, are also discussed. The advantages and limitations encountered in developing site-specific targeting approaches based on Pluronic-based nanostructures in cancer treatment are highlighted, in addition to innovative examples for improving tumor cytotoxicity while reducing side effects. [Display omitted] [ABSTRACT FROM AUTHOR]

Nanosized systems of DOX with antitumor activity on the base of micelle-like particles of amphiphilic thermosensitive copolymers of N-vinylpyrrolidone (VP) with triethylene glycol dimethacrylate (TEGDM), and N-vinylpyrrolidone and methacrylic acid (MAA) with TEGDM were explored. They were investigated in aqueous solutions by electron absorption spectroscopy, dynamic light scattering and cyclic voltammetry. Experimental data and quantum-chemical modeling indicated the formation of a hydrogen bond between oxygen-containing groups of monomer units of the copolymers and H-atoms of OH and NH2 groups of DOX; the energies and H-bond lengths in the considered structures were calculated. A simulation of TDDFT spectra of DOX and its complexes with the VP and TEGDM units was carried out. Electrochemical studies in PBS have demonstrated that the oxidation of encapsulated DOX appeared to be easier than that of the free one, and its reduction was somewhat more difficult. The cytotoxicity of VP-TEGDM copolymer compositions containing 1, 5 and 15 wt% DOX was studied in vitro on HeLa cells, and the values of IC50 doses were determined at 24 and 72 h of exposure. The copolymer compositions containing 5 and 15 wt% DOX accumulated actively in cell nuclei and did not cause visual changes in cell morphology. [ABSTRACT FROM AUTHOR]

The physicochemical properties of "smart" or stimuli-sensitive amphiphilic copolymers can be modeled as a function of their environment. In special, pH-sensitive copolymers have practical applications in the biomedical field as drug delivery systems. Interactions between the structural units of any polymer-drug system imply mutual constraints at various scale resolutions and the nonlinearity is accepted as one of the most fundamental properties. The release kinetics, as a function of pH, of a model active principle, i.e., Curcumin, from nanomicelles obtained from amphiphilic pH-sensitive poly(2-vinylpyridine)-b-poly(ethylene oxide) (P2VP-b-PEO) tailor-made diblock copolymers was firstly studied by using the Rietger-Peppas equation. The value of the exponential coefficient, n, is around 0.5, generally suggesting a diffusion process, slightly disturbed in some cases. Moreover, the evaluation of the polymer-drug system's nonstationary dynamics was caried out through harmonic mapping from the usual space to the hyperbolic one. The kinetic model we developed, based on fractal theory, fits very well with the experimental data obtained for the release of Curcumin from the amphiphilic copolymer micelles in which it was encapsulated. This model is a variant of the classical kinetic models based on the formal kinetics of the process. [ABSTRACT FROM AUTHOR]

Previous studies have demonstrated that films of sequence‐controlled amphiphilic copolymers display contact angles that depend on microblock size. This suggests that microblock length may provide a means of tuning surface and interfacial properties. In this work, the interfacial rheology of a series of sequence‐controlled copolymers, prepared through the addition of bicyclo[4.2.0]oct‐1(8)‐ene‐8‐carboxamide (monomer A) and cyclohexene (monomer B) to generate sequences up to 24 monomeric units composed of (AmBn)i microblocks, where m, n, and i range from 1 to 6. Interfacial rheometry is used to measure the mechanical properties of an air–water interface with these copolymers. As the microblock size increases, the interfacial storage modulus, G′, increases, which may be due to an increase in the size of interfacial hydrophobic domains. Small‐angle X‐ray scattering shows that the copolymers have a similar conformation in solution, suggesting that any variations in the mechanics of the interface are due to assembly at the interface, and not on solution association or bulk rheological properties. This is the first study demonstrating that microblock size can be used to control interfacial rheology of amphiphilic copolymers. Thus, the results provide a new strategy for controlling the dynamics of fluid interfaces through precision sequence‐controlled polymers. [ABSTRACT FROM AUTHOR]

This paper deals with the development of polymeric nanocarriers based on amphiphilic copolymers of N‐vinyl‐2‐pyrrolidone and acrylic acid of various molecular weights synthesized through the AIBN‐initiated radical copolymerization of N‐vinyl‐2‐pyrrolidone and acrylic acid in the presence of n‐octadecyl mercaptan. The structure of the copolymers is characterized by 1Н NMR, 13С NMR, IR and MALDI‐TOF MS spectroscopy. It is shown that the length of the hydrophilic block defines the size of the nanoaggregates while impacting the steric stabilization efficiency and the probability of the interchain hydrogen bond formation. The hydrogen bonds formation between the residues of N‐vinyl‐2‐pyrrolidone and acrylic acid is in agreement with the reduction of the ζ‐potential of the nanoaggregates and the critical aggregation concentrations upon increasing the molecular weight. The presence of acrylic acid residues in the amphiphilic macromolecules leads to a higher affinity for doxorubicin and slow partial release of doxorubicin bonded with the aggregates' corona, which is helpful for reducing its cardiac toxicity. Nanoaggregates with a paclitaxel‐loaded hydrophobic core are obtained, showing the possibility of dual loading. The amphiphilic copolymers of N‐vinyl‐2‐pyrrolidone and acrylic acid containing an n‐octadecyl thio end group are thus promising candidates for combination cancer therapy with immobilized anti‐cancer drugs, paclitaxel, and doxorubicin. [ABSTRACT FROM AUTHOR]

[Display omitted] • Amphiphilic core–shell nanoparticles were self-assembled by emulsion polymerization. • Nanoparticle dispersion was tuned by adjusting hydrogen-donors and hydrogen-acceptors. • Particle size was adjusted by regulating hydrogen-donors and hydrogen-acceptors. • Hydrogen bond interactions were weakened with covalent bonds. • The introduction of hydrogen-acceptors promoted the release of active chlorine. Bacterial contamination in water bodies is potentially transmissible to humans, making water bodies a major pathway of bacterial transmission. However, existing hydantoin copolymer nanoparticles did not achieve the regulation of nanoparticle dispersion and particle size by adjusting the ratio of hydrogen-donors and hydrogen-acceptors. To tackle this issue, amphiphilic hydantoin copolymer nanoparticles (P(VBDH-BA-NVP)NPs) were synthesized by modulating hydrogen-donors and hydrogen-acceptors using emulsion polymerization, and amphiphilic N-halamine copolymer nanoparticles (P(ClV-BA-NVP)NPs) were subsequently prepared via chlorination treatment. Impressively, nanoparticle dispersion and particle size were modulated by adjusting the ratio of hydrogen-donors and hydrogen-acceptors. With the increase of nanoparticle dispersion and the decrease of particle size, the active chlorine content was gradually enlarged, and the antibacterial performance was progressively enhanced against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). More importantly, amphiphilic N-halamine copolymer nanoparticles with two-dimensional dispersing (2DD-P(ClV-BA-NVP)NPs) exhibited excellent antibacterial properties, which benefited from the dual coordination of direct contact killing and indirect release killing in aqueous medium. Through designing P(VBDH-BA-NVP)NPs with hydrogen bond interactions, this approach aims to achieve the constitutive relationship between the effective exposure of active sites and the antibacterial effect. [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. Single-particle cryo-electron microscopy (cryo-EM) studies of membrane proteins have become routine and often yield structures at near-atomic resolution. Cryo-EM structures of membrane proteins in lipid nanodiscs often yield information not seen in structures obtained with detergent-solubilized proteins. Nanodiscs not only provide a native-like lipid environment for membrane proteins, but also make it possible to custom design and modify most aspects of the lipid bilayer. Because of the facility of generating and imaging nanodiscs by cryo-EM and because of the novel mechanistic insights into membrane protein function they can provide, nanodiscs ought to become the standard for membrane protein structure determination by single-particle cryo-EM. [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 13C 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. [ABSTRACT FROM AUTHOR]

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. [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. [ABSTRACT FROM AUTHOR]

This research concerns the investigation of the preparation of polymeric nanocarriers containing a flavonoid—naringenin, xanthohumol or isoxanthohumol—based on Pluronics by the thin-film formation method. The size of the formed micelles and their stability upon dilution were evaluated using Dynamic light scattering (DLS) analysis; the high values of the drug loading and the encapsulation efficiency confirmed that the proposed systems of flavonoids delivery consisting of Pluronic P123 and F127 nanomicelles could effectively distribute the drug into tumour tissues, which makes these nanocarriers ideal candidates for passive targeting of cancer cells by the enhanced permeation and retention (EPR) effect. The in vitro cytotoxicity of proposed flavonoids in the Pluronic formulations was investigated by the SRB assay with human colon cancer cells. We designed mixed polymeric micelles, which was a successful drug delivery system for the case of naringenin not being able to enhance the bioavailability and cytotoxic activity of xanthohumol and isoxanthohumol. Furthermore, it was observed that the higher amount of polymer in the formulation achieved better cytotoxic activity.

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.

The paper describes a comparative study on the effects of the composition of polymers of higher alkyl (meth)acrylates on their dispersion degree in petroleum oil I-20A. The dispersion degree parameter is evaluated in accordance with a modified spectrophotometric method proposed in the study. It was found that increasing the polymer amphiphilicity by introducing nitrogen-based units in an amount of 5–15% dramatically enhances the dispersion properties, and that amide groups have a stronger effect than amine ones. Increasing the polyalkyl methacrylate amphiphilicity by introducing (in an amount of 5–40%) alkoxy oligo(ethylene glycol) methacrylate (AOEGM) units containing 3–7 ethoxy groups does not enhance the polymer's dispersion ability. The only exception was a single case of a fairly high dispersion ability achieved for a copolymer containing 30% of AOEGM units with long hydrophilic chains consisting of ten ethoxy groups. [ABSTRACT FROM AUTHOR]