Hydrophilic Segments Research Articles

Hierarchical Structures of Amino Acid Derived Polyhydroxyurethanes: Promising Candidates as Drug Carriers and Cell Adhesive Scaffolds.

In this study, we examined the self-assembly of a series of biodegradable and biocompatible amino acid-based polyhydroxyurethanes (PHUs), investigating the structural influence of these polymers on their self-assembly and the resulting morphological features. The presence of hydrophilic and hydrophobic segments, along with carbonyl urethane, ester, and hydroxyl groups in the PHU backbone, facilitates intermolecular hydrogen bonding, enabling the formation of self-assemblies with hierarchical nanodimensional morphologies. We determined the critical aggregation concentration (CAC) and found that it largely depends on the PHU's structure. In-depth morphological studies demonstrated that the evolution of morphology proceeds in four steps: (1) the initial formation of micelles, which act as seeds at very low concentrations, (2) the elongation of these micelles into nanorod or nanopalette shapes below the CAC range, (3) the epitaxial growth of nanofibers at the CAC, and (4) the complete formation of fibrous mats above the CAC. Additionally, these hierarchical structures were utilized for the encapsulation and release of the drug doxorubicin (DOX). We observed that 75% of the encapsulated DOX was readily released in a mildly acidic environment, similar to the physiological conditions of cancer cells. Cellular uptake studies confirmed the effective uptake of the drug-loaded nanoassemblies into the cytoplasm of cells. Our studies also confirmed that these self-assembled structures can serve as effective cell adhesive scaffolds for tissue engineering applications.

Fluoro-polymer/TiO2 based photocatalysts for hydrogen generation

In view of limited number of studies on photoreforming of synthetic polymers, herein, a series of new glycopolymers are synthesized via RAFT polymerization to obtain diblock copolymers containing fluorinated and non-fluorinated segments in the glucopyranoside. These glycopolymers are used as probes to investigate photocatalytic reactions at different pH values of the modulated TiO2 photocatalyst. Through structural and surface characterizations, photocatalytic activities are investigated. Fluoro-polymers with deacetylated glucose, hydrophilic segment, PGD such as PPFPM-b-PGD and PPFBM-b-PGD could synergistically increase hydrogen generation rate up to 1368 μmol g-1h−1 and 1549 μmol g-1h−1 with quantum yields of 3.34 % and 3.79 % compared to non-fluoro glycopolymers. The presence of both fluorinated and non-fluorinated groups in diblock copolymers enhanced the rate of photocatalytic hydrogen generation compared to the homopolymer. The accelerated photo-reforming is attributed to in-situ fluorine-doped TiO2 along with high affinity and activation of water molecules. These polymers can generate hydrogen via photo-reforming process.

Experimental and Simulation Study of Single-matrix, All-polymeric Thin-film Composite Membranes for CO2 Capture: Block vs Random Copolymers

High-performance, additive-free, all-polymeric thin-film composite (TFC) membranes were developed for CO₂ capture, focusing on a comparison between block and random copolymers (referred to as PTF) composed of hydrophobic poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) and CO2-philic polar poly(oxyethylene methacrylate) (POEM) chains. The PTF random copolymer, synthesized via free-radical polymerization (FRP), exhibited a disordered morphology. In contrast, the PTF block copolymer, synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization, formed a well-ordered hexagonally packed cylindrical structure, creating an amphiphilic, microphase-separated nanostructure. Molecular dynamics (MD) simulations revealed that in both copolymers, there was minimal interaction between the gases (CO₂ and N₂) and the hydrophobic PTFEMA segments, while CO₂ showed strong affinity for the hydrophilic POEM segments. The block and random copolymers demonstrated similar CO₂ permeance, which can be attributed to their comparable CO₂ diffusivity and solubility. However, the block copolymer exhibited significantly lower N₂ permeance than the random copolymer, resulting in nearly quadruple the CO₂/N₂ selectivity. This increase in selectivity was supported by the lower N₂ mean squared displacement (indicating reduced diffusivity) observed in the block copolymer. The PTF block copolymer outperformed the commercial Pebax block copolymer, achieving CO₂ capture efficiencies that surpass industrial standards for CO₂ separation and capture. This positions the single-matrix PTF block copolymer as a promising alternative to mixed-matrix membranes for practical applications in gas separation technologies.

Controlled Distribution of MXene on the Pore Walls of Polyarylene Ether Nitrile Porous Films for Absorption-Dominated Electromagnetic Interference Shielding Materials.

With the increasing application of electronic devices, absorption-dominated electromagnetic interference shielding materials (EMISM) have garnered significant attention for preventing secondary electromagnetic pollution. In this study, polyethyleneimine (PEI)-modified MXene (PEI@MXene) is fabricated and achieved its controlled distribution on the pore walls of polyarylene ether nitrile (PEN) porous films via the phase inversion method (PIM) to obtain a closed porous skeleton of MXene on the pore walls (CPS-MPW). The resulting PEI@MXene/PEN composite film (CFx) exhibited absorption-dominated EMIS efficiency (EMISE). Attributing to the strong interaction between PEI and the hydrophilic segment of amphiphilic Pluronic F127, with its hydrophobic segment anchored by the PEN matrix, PEI@MXene is directionally distributed on the pore walls of CFx. In addition, resulting from the cladding of MXene with PEI and isolating it with closed honeycomb pores, the obtained CFx are insulators without forming aconductive network. As a result, these CFx demonstrate absorption-dominated EMISE with the highest SET of 41.2 dB and coefficient A higher than 0.51. Further continuous hot pressing of CFx results in thinner and denser films with an impressive specific EMISE up to 750 dBcm-1. The successful fabrication of these CPS-MPW-type CFx with absorption-dominated EMISE provides a reference for developing and preparing novel EMISM.

Inertial migration of cylindrical micelles formed by comb-like copolymer in Poiseuille flow

By combining the lattice Boltzmann model of fluid flow with the molecular dynamics model of copolymers, we investigate the inertial migration of cylindrical micelles, which is obtained by controlling the length ratios of hydrophilic and hydrophobic segments in a comb-like copolymer. Our results demonstrate that cylindrical micelles gradually deviate from the center of the nanochannel with increasing Reynolds number (Re). For the same Re, the larger the cylindrical micelle is, the closer it is to the center of the nanochannel. Importantly, we find that the change in the equilibrium position is particularly pronounced at Re less than 0.1, while the trend becomes smoother at Re greater than 0.1, which is because of the transition of micelles from cylindrical to disk-like shapes when Re is smaller than 0.1, and does not change as Re further increases. This work provides an understanding of cylindrical micelles' inertial migration, particularly in identifying the effect of morphological changes on the equilibrium position, which could lead to significant advancements in the inertial migration of polymer micelles.

Probing the inner structure and dynamics of pH-sensitive block copolymer nanoparticles with nitroxide radicals using scattering and EPR techniques

This research emphasizes the crucial role of electron paramagnetic resonance (EPR) spectroscopy in nanoparticle analysis, showcasing its distinctive ability to probe molecular-level details. We demonstrate the synthesis and self-assembly of a new class of pH-responsive amphiphilic diblock copolymers, specifically poly[N-(2-hydroxypropyl)-methacrylamide]-block-poly[2-(diisopropylamino)ethyl methacrylate] (PHPMA-b-PDPA), incorporating 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radicals covalently bound to the hydrophilic PHPMA segment. The copolymer synthesis involved a three-step process, combining reversible addition − fragmentation chain transfer (RAFT) polymerization with carbodiimide (DCC) chemistry. TEMPO radical-containing nanoparticles (RNPs) were created using microfluidic (MF) nanoprecipitation, a technique essential for generating uniform nanoparticles with predictable biodistribution and cellular uptake. Adjusting MF protocol parameters allowed fine-tuning of RNP sizes. EPR spectroscopy confirmed the formation of core–shell RNPs, with features aligning closely with those obtained from scattering techniques like dynamic light scattering (DLS), static light scattering (SLS), small-angle X-ray scattering (SAXS), and cryo-transmission electron microscopy (cryo-TEM). EPR spectroscopy emerges as a potent tool for molecular-level analysis of colloidal polymer systems. This study highlights the EPR-spin label method’s efficacy in probing the internal structural features and dynamics of core–shell nanoparticles, especially their response to pH-triggered disassembly. The findings open new avenues for the use of pH-responsive TEMPO-labeled diblock copolymers in controlled drug delivery applications.

Lifetime evaluation and material failure analysis of a PEMFC prepared using commercial materials

ABSTRACT Hydrogen fuel cells are vital for green energy to replace traditional energy. However, their lifetime is an important factor limiting their development. In this study, commercial materials were used to prepare proton exchange membrane fuel cells (PEMFCs), and pure oxygen was used as the cathode gas to accelerate their lifetime evaluation. The components of the membrane electrode assembly were characterized, and significant thinning was observed in the local proton exchange membrane (PEM). Therefore, the uniformity of the internal conditions of the fuel cell is the key to ensure a long lifetime. The hydrophilicity of the gas diffusion layers increased as the carbon disorder increased via the adsorption of hydrophilic chain segments produced by PEM degradation. The growth of platinum particles in the catalyst layer reduced the electrochemical active area of the catalyst, but the reduction rate slowed and then stabilized. This study of the lifetime of PEMFCs and changing properties of commercial materials clarifies the existing problems of fuel cells and contributes to the development of long-life fuel cells.

Amphiphilic diblock copolymers of polyisobutylene-b-poly(2-ethyl-2-oxazoline) via cationic polymerization

A series of amphiphilic polyisobutylene-b-poly (2-ethyl-2-oxazoline) (PIB-b-PEOX) diblock copolymer/Ag nanoparticle composites were successfully in-situ synthesized via cationic ring-opening polymerization of 2-ethyl-2-oxazoline (EOX) with high initiation efficiency by using allyl bromide end functionalized polyisobutylene (PIB-allylBr) as a macroinitiator and AgClO4 as a coinitiator. The microphase separation formed in the resulting PIB-b-PEOX diblock copolymers due to the thermodynamic imcompability of hydrophilic PEOX segments and hydrophobic PIB segments. The micromorphology of phase separation is dependent on the copolymer composition, in which sea-island micromorphology formed for PIB118-b-PEOX80 and bicontinuous phase micromorphology formed for PIB118-b-PEOX97. The micelles with nano-scale size in the range of 15–80 nm and having high drug loading rate of ca. 48.9 % can be formed by self-assembly of the amphiphilic diblock copolymers in n-hexane. The drug cumulative release rate can be increased with an increase in the proportion of PEOX segments, due to the strong interaction between ibuprofen and the PEOX segments. The hydrophilicity of the PIB-b-PEOX diblock copolymer surfaces can be improved after ethanol vapor induction. The PIB-b-PEOX diblock copolymers behave biocompatibility and good anti-protein adsorption property. The amphiphilic PIB-b-PEOX diblock copolymer/Ag nanoparticle composites exhibit high antibacterial efficiency for Gram-negative bacterium (E. coli) and Gram-positive bacterium (S. aureus). To the best of our knowledge, this is the first example of PIB-b-PEOX diblock copolymer/Ag nanoparticle (6.4 ± 2.6 nm) composites synthesized in-situ with good biocompatibility, anti-protein adsorption, and antibacterial properties, which would have potential applications for drug delivery and anti-protein coating in biomedical areas.

Assembly Regulates Gamma Radiation Polymerization of Polytelluoxane

Regulating chemical drug's responsiveness to gamma radiation is crucial for achieving better therapeutic effects in cancer treatment. Most research focused on thermodynamic chemical structure design, while little attention was paid to kinetic regulate strategy, which possesses greater universality and security. In this study, we achieved a kinetic‐based regulate strategy of gamma radiation reaction, through the construction of microphase environment during polymerization of polytelluoxane (PTeO). We designed hydrophobic segments forming large compound micelles (LCMs) assembly to create kinetically favorable higher concentration for radiation‐induced reaction. It exhibited a > ten times higher responsiveness and, as far as we know, merely required a minimum dosage of 5 Gy for polymerization to occur. What’s more, by taking advantages of the assembly change with Te‐O hydrophilic segments and gamma radiation, polymerization became milder with lower polydispersity than previous methods. Such kinetic‐based regulate strategy could offer a novel perspective on the design of radiation‐responsive chemoradiotherapy and other radiation‐induced chemical process.

Assembly Regulates Gamma Radiation Polymerization of Polytelluoxane.

Regulating chemical drug's responsiveness to gamma radiation is crucial for achieving better therapeutic effects in cancer treatment. Most research focused on thermodynamic chemical structure design, while little attention was paid to kinetic regulate strategy, which possesses greater universality and security. In this study, we achieved a kinetic-based regulate strategy of gamma radiation reaction, through the construction of microphase environment during polymerization of polytelluoxane (PTeO). We designed hydrophobic segments forming large compound micelles (LCMs) assembly to create kinetically favorable higher concentration for radiation-induced reaction. It exhibited a > ten times higher responsiveness and, as far as we know, merely required a minimum dosage of 5 Gy for polymerization to occur. What's more, by taking advantages of the assembly change with Te-O hydrophilic segments and gamma radiation, polymerization became milder with lower polydispersity than previous methods. Such kinetic-based regulate strategy could offer a novel perspective on the design of radiation-responsive chemoradiotherapy and other radiation-induced chemical process.

PH-Induced color changeable AIE-featured polymeric micelles for self-indicating anticancer drug delivery

Multifunctional polymeric micelles, which possess capabilities for tracking, bioimaging, stimuli-responsive drug release and tumor targeting, are essential in facilitating the effective delivery of anticancer drugs. Hence, a novel copolymer (CD-CS-Bio-TPAA, CCBT) was synthesized with biotin and hydroxypropyl-β-cyclodextrin conjugated chitosan as the hydrophilic segment and aggregation-induced emission (AIE) featured tetraphenylethene derivative (TPAA) as the hydrophobic segment. Interestingly, under acidic conditions, CCBT exhibited color-tunable AIE behavior as a result of the cleavage of benzoic imine bonds in TPAA molecules, transitioning from red to yellow. Furthermore, CCBT could also self-assemble into polymeric micelles and be used as drug carriers to encapsulate paclitaxel (PTX) (PTX/CCBT PMs) for self-indicating cancer therapy. In vitro release experiments demonstrated that PTX/CCBT PMs could release drugs specifically under acidic conditions. Fluorescence imaging experiments demonstrated that CCBT PMs exhibited excellent cell imaging capabilities and could be tracked due to their unique color-changing behavior. Moreover, PTX/CCBT PMs exhibited notable cytotoxic effects on MCF-7 cells and showed selective internalization by MCF-7 cells through biotin receptor-mediated active targeting. In vivo antitumor experiments confirmed that PTX/CCBT PMs possessed remarkable tumor-inhibiting effects and low systemic toxicity. This work suggested that PTX/CCBT PMs provided new ideas for self-indicating breast cancer treatment.

One-step fabrication of hetero-structured polyethersulfone hollow fiber membranes through surface segregation for pervaporation desalination

Hollow fiber membranes (HFMs) are an ideal configuration for industrial applications of pervaporation desalination (PV) membranes. Currently, the efficient fabrication of PV HFMs is restricted by multi-step post-treatment processes on their outer surfaces to form the selective layer. Herein, we utilized the surface segregation strategy to fabricate a hetero-structured HFM in one step, simultaneously forming the hydrophilic dense outer layer and the porous support layer. During hollow fiber spinning process, the amphiphilic copolymer polyvinylpyrrolidone-polyvinyl acetate (PVP-PVAc) in polyether sulfone (PES) dope solution migrated towards water contacting interface in the coagulation bath and formed the hydrophilic layer by extending hydrophilic segment outwards. This fast in-situ hydrophilization well matched the spinning efficiency. The optimal PVP-PVAc content and phase inversion temperature were investigated and the spinning parameters on the structure and performance of HFMs were studied. The HFMs prepared realized a flux of 26.70 kg m−2 h−1 and the salt rejection of 99.98 %, along with adaptability to solutions with different salinities and excellent anti-organic fouling property. This study may provide a facile method to fabricate HFMs with desirable PV desalination performance and scaling-up potential.

Waste heat recovery in carbon capture process using a novel amphipathic inorganic membrane

To reduce the CO2 regeneration heat requirement in the CO2 chemical absorption process, a novel amphipathic ceramic membrane-based transport membrane condenser was developed in this study to act as a heat transfer medium in the rich solvent-split mechanism for enhancing the waste heat recovery performance from the stripped gas (i.e., mainly the gas mixture of CO2 and water vapor). Both hydrophobic and hydrophilic segments coexisted on one membrane surface of amphipathic ceramic membrane, while the other surface was totally hydrophilic. The surface characterization and waste heat recovery performance of the flat sheet amphipathic membrane were investigated, and the original hydrophilic ceramic membrane was adopted as the control. Results showed that the water contact angle with 108.9 ± 4° was screened for the hydrophobic surface of the ceramic membrane to achieve the best waste heat recovery performance. Additionally, the waste heat recovery performance of amphipathic membrane firstly increased and then dropped with an increase in the area ratio of hydrophobic surface to the total membrane surface. The maximum waste heat recovery of 13.39 MJ/(m2·h) was achieved at a hydrophobic area ratio of 37.5 % without segmenting by the hydrophilic surface, which was 5.6 % higher than that of the original hydrophilic ceramic membrane. Furthermore, the maximum water recovery of amphipathic membrane was 8.24 % higher than the original hydrophilic ceramic membrane. When the total area of hydrophobic surface was fixed, dividing the hydrophobic surface into two equally sized hydrophobic segments spaced by the hydrophilic segments could further improve the waste heat recovery performance of amphipathic membrane. This study might provide a new insight on improving the waste heat recovery performance of ceramic membrane.

Organic Donor-Acceptor-Donor Trimers Nanoparticles Stabilized by Amphiphilic Block Copolymers for Photocatalytic Generation of H2.

Photocatalytic generation of H2 via water splitting emerges as a promising avenue for the next generation of green hydrogen due to its low carbon footprint. Herein, a versatile platform is designed to the preparation of functional π-conjugated organic nanoparticles dispersed in aqueous phase via mini-emulsification. Such particles are composed of donor-acceptor-donor (DAD) trimers prepared via Stille coupling, stabilized by amphiphilic block copolymers synthesized by reversible addition-fragmentation chain transfer polymerization. The hydrophilic segment of the block copolymers will not only provide colloidal stability, but also allow for precise control over the surface functionalization. Photocatalytic tests of the resulting particles for H2 production resulted in promising photocatalytic activity (≈0.6mmol g-1 h-1). This activity is much enhanced compared to that of DAD trimers dispersed in the water phase without stabilization by the block copolymers.

Barnacle-inspired amphipathic high strength adhesives under-water/oil

Adhesives designed for bonding in liquid environments have a broad application prospect. In general, amphiphilic polymer structures are important research objects for underwater bonding. And in the study of underwater adhesives, it was found that they can quickly dispel or absorb interfacial water and form reliable bulk strength and adhesion strength. However, achieving strong adhesion in both water-based and oily environments poses a significant challenge. In this work, an adhesive inspired by barnacles that can meet the bonding requirements in both water-based and oily environments has been prepared. Hydrophilic (polyethylene glycol (PEG)) main chains and hydrophobic (1-Octadecyl thiol (ODT)) side chains are simultaneously integrated into the polyurethane structure. Different from the past, hydrophobic and hydrophilic segments are included in the hard segment and soft segment microregion, respectively; At the same time, both hydrophilic and hydrophobic chain segments have strong crystallization, which greatly strengthens the driving force of molecular segments migration and phase separation compared with ordinary hydrophilic/hydrophobic structures. Water-based and oil-based solvents drive hydrophilic and hydrophobic molecular chains to diffuse to the surface, respectively, which enhances the adhesive strength to hydrophilic and hydrophilic surfaces, respectively. In comparison to the adhesion strength observed in air, the adhesion strength of the adhesive to polymethyl methacrylate (PMMA) increases by 1.72 times in oil environments (from 1.02 to 1.75 MPa). Similarly, the adhesion strength to aluminum (Al) increases by 2.23 times under water (from 1.82 to 4.04 MPa). These findings suggest that the regulation strategy for polymer chains employed in this study holds great potential for advancing adhesive performance in diverse environments.

Inulin Amphiphilic Copolymer-Based Drug Delivery: Unraveling the Structural Features of Graft Constructs.

In this study, the structural attributes of nanoparticles obtained by a renewable and non-immunogenic "inulinated" analog of the "pegylated" PLA (PEG-PLA) were examined, together with the potential of these novel nanocarriers in delivering poorly water-soluble drugs. Characterization of INU-PLA assemblies, encompassing critical aggregation concentration (CAC), NMR, DLS, LDE, and SEM analyses, was conducted to elucidate the core/shell architecture of the carriers and in vitro cyto- and hemo-compatibility were assayed. The entrapment and in vitro delivery of sorafenib tosylate (ST) were also studied. INU-PLA copolymers exhibit distinctive features: (1) Crew-cut aggregates are formed with coronas of 2-4 nm; (2) a threshold surface density of 1 INU/nm2 triggers a configuration change; (3) INU surface density influences PLA core dynamics, with hydrophilic segment stretching affecting PLA distribution towards the interface. INU-PLA2NPs demonstrated an outstanding loading of ST and excellent biological profile, with effective internalization and ST delivery to HepG2 cells, yielding a comparable IC50.

Tandem one‐pot synthesis of block copolymers for anion exchange membranes

AbstractThe anion exchange membrane (AEM) suffered from poor mechanical properties and low ionic conductivity in fuel cells. Herein, a series of novel block fluorene‐contained poly(arylene ether ketone)s backbones are synthesized by a tandem one‐pot process and then grafted with alkyl chains to form comb‐shaped structure for preparing AEMs. The one‐pot synthesis of block copolymer avoids the multiple purifications of oligomers. The membranes' structure–property relationship is studied by changing the ratios of hydrophilic and hydrophobic segments. The designed comb‐shaped structures grafted on fluorene‐containing block backbones can widen the space between chains and form clear microphase separation patterns, as determined by atomic force microscope (AFM) and small angle x‐ray scattering (SAXS). Hence, resulting AEMs have a high ionic conductivity (117.4 mS cm−1, 80°C). Meanwhile, they also present low swelling rate (SR) from 12.76% to 18.51% at 30°C, 16.84% to 24.36% at 60°C, and 18.33% to 25.81% at 80°C. In addition, excellent mechanical properties, that is, an elongation at break of 29.63% and a tensile strength of 28.72 MPa, are achieved and showed the promise of as‐fabricated AEMs in fuel cell applications.

Effects of a dual functional filler, polyethersulfone-g-carboxymethyl chitosan@MWCNT, for enhanced antifouling and penetration performance of PES composite membranes

Ultrafiltration technology, separating water from impurities by the core membrane, is an effective strategy for treating wastewater to meet the ever-growing requirement of clean and drinking water. However, the similar nature of hydrophobic organic pollutants and the membrane surface leads to severe adsorption and aggregation, resulting unavoidable membrane degradation of penetration and rejection. The present study presents a novel block amphiphilic polymer, polyethersulfone-g-carboxymethyl chitosan@MWCNT (PES-g-CMC@MWCNT), which is synthesized by grafting hydrophobic polyethersulfone to hydrophilic carboxymethyl chitosan in order to suspend CMC in organic solution. A mixture of hydrophilic carboxymethyl chitosan and hydrophobic polymers (polyethersulfone), in which hydrophilic segments are bonded to hydrophobic segments, could provide hydrophilic groups, as well as gather and remain stable on membrane surfaces by their hydrophobic interaction for improved compatibility and durability. The resultant ultrafiltration membranes exhibit high water flux (198.10 L m−2·h−1), suitable hydrophilicity (64.77°), enhanced antifouling property (82.96%), while still maintains excellent rejection of bovine serum albumin (91.75%). There has also been an improvement in membrane cross-sectional morphology, resulting in more regular pores size (47.64 nm) and higher porosity (84.60%). These results indicate that amphiphilic polymer may be able to significantly promote antifouling and permeability of ultrafiltration membranes.

Flash precipitation of random copolymers in a micro-mixer for controlling the size and surface charge of nanoparticles.

Precisely controlling the size and surface chemistry of polymeric nanoparticles (P-NPs) is critical for their versatile engineering and biomedical applications. In this work, various NPs of amphipathic random copolymers were comparatively produced by the flash nanoprecipitation (FNP) method using a tube-in-tube type of micro-mixer up to 330 mg min-1 in production scale in a kinetically controlled manner. The NPs obtained from poly(styrene-co-maleic acid), poly(styrene-co-allyl alcohol), and poly(methyl methacrylate-co-methacrylic acid) were concurrently controlled in the range 51-819 nm in size with narrow polydispersity index (<0.1) and -44 to -16 mV in zeta potential, by depending not only on the polymeric chemistry and the concentration but also the mixing behavior of good solvents (THF, alcohols) and anti-solvent (water) under three flow regimes (laminar, vortex and turbulence, turbulent jet). Moreover, the P(St-MA) derived NPs under turbulent jet flow conditions were post-treated in the initial solution mixture for up to 16 h, resulting in lowering of the zeta potential to -52 mV from the initial -27 mV and decreasing size to 46 nm from 50 nm by further migration of hydrophilic segments with -COOH groups on the outer surface, and the removal of THF trapped in the hydrophobic core.

Poly(Sitosterol)-Based Hydrophobic Blocks in Amphiphilic Block Copolymers for the Assembly of Hybrid Vesicles.

Amphiphilic block copolymer and lipids can be assembled into hybrid vesicles (HVs), which are an alternative to liposomes and polymersomes. Block copolymers that have either poly(sitostryl methacrylate) or statistical copolymers of sitosteryl methacrylate and butyl methacrylate as the hydrophobic part and a poly(carboxyethyl acrylate) hydrophilic segment are synthesized and characterized. These block copolymers assemble into small HVs with soybean L-α-phosphatidylcholine (soyPC), confirmed by electron microscopy and small-angle X-ray scattering. The membrane's hybrid nature is illustrated by fluorescence resonance energy transfer between labeled building blocks. The membrane packing, derived from spectra when using Laurdan as an environmentally sensitive fluorescent probe, is comparable between small HVs and the corresponding liposomes with molecular sitosterol, although the former show indications of transmembrane asymmetry. Giant HVs with homogenous distribution of the block copolymers and soyPC in their membranes are assembled using the electroformation method. The lateral diffusion of both building blocks is slowed down in giant HVs with higher block copolymer content, but their permeability toward (6)-carboxy-X-rhodamine is higher compared to giant vesicles made of soyPC and molecular sitosterol. This fundamental effort contributes to the rapidly expanding understanding of the integration of natural membrane constituents with designed synthetic compounds to form hybrid membranes.