Cationic Amphiphilic Comb-Shaped Polymer Emulsifier for Fabricating Avermectin Nanoemulsion with Exceptional Leaf Behaviors and Multidimensional Controlled Release.

The development of intelligent multifunctional nanopesticides featuring enhanced foliage affinity and hierarchical target release is increasingly pivotal in modern agriculture. In this study, a novel cationic amphiphilic comb-shaped polymer, termed PEI-TA, was prepared via a one-step Michael addition between low-molecular-weight biodegradable polyethylenimine (PEI) and tetradecyl acrylate (TA), followed by neutralization with acetic acid. Using the emulsifier PEI-TA, a positively charged avermectin (AVM) nanoemulsion was prepared via a phase inversion emulsification process. Under optimal formulation, the obtained AVM nanoemulsion (defined as AVM@PEI-TA) demonstrated exceptional properties, including small size (as low as 67.6 nm), high encapsulation efficiency (up to 87.96%), and high stability toward shearing, storage, dilution, and UV irradiation. The emulsifier endowed AVM@PEI-TA with a pronounced thixotropy, so that the droplets exhibited no splash and bounce when they were sprayed on the cabbage leaf. Owing to the electrostatic attraction between the emulsifier and the leaf, AVM@PEI-TA showed improved leaf adhesion, better deposition, and higher washing resistance in contrast to both its negatively charged counterpart and AVM emulsifiable concentrate (AVM-EC). Compared to the large-sized particles, the small-sized particles of the AVM nanoemulsion more effectively traveled long distances through the vascular system of veins after entering the leaf apoplast. Moreover, the nanoparticles lost stability when exposed to multidimensional stimuli, including pH, temperature, esterase, and ursolic acid individually or simultaneously, thereby promoting the release of AVM. The release mechanisms were discussed for understanding the important role of the emulsifier in nanopesticides.

From Cauliflowers to Microspheres: Particle Growth Mechanism in Self-Stabilized Precipitation Polymerization.

Self-stabilized precipitation (2SP) polymerization enables the facile synthesis of uniform polymer spheres with sizes ranging from 100 nm to 3 µm, without the need for stabilizers or cross-linkers, even at high monomer concentrations of up to 30%. While previous studies have extensively explored the influence of reaction conditions on the size and uniformity of microsphere products, their impact on particle morphology has received less attention. In this work, we demonstrate that particle growth in 2SP polymerization primarily occurs via the adsorption of polymers from the solution onto the particle surface, leading to an increase in particle circularity and a smoother surface. The surface roughness of the particles is controlled by the aggregation of primary particles and the subsequent polymer adsorption process during the growth stage. Smooth microspheres are obtained under conditions of moderate monomer concentration, high initiator concentration, and elevated temperature. Our findings highlight the significance of the particle growth process in determining particle morphology in addition to the well-established role of polymer-solvent interactions during precipitation polymerization.

Preparation of multifunctional PET membrane and its application in high-efficiency filtration and separation in complex environment.

Nowadays, effluent treatment is a severe challenge mainly because of its complex composition, which includes oil, heavy metal ions, and dyes. Developing new intelligent membranes is one of the strategies to tackle these significant challenges in wastewater treatment. In this study, we fabricated asymmetric polyethylene glycol terephthalate (PET) membranes by grafting cross-linked poly (itaconic anhydride) (CL-PITA) nanoparticles onto the irradiated face. These nanoparticles were then functionalized with polyethyleneimine (PEI) and protonated with HCl to introduce numerous active electropositive amine groups. The fundamental purpose was to increase surface roughness, introduce numerous hydrophilic groups, and modify it to create a multi-functional PET membrane to separate complex environments. The promising results demonstrated that the protonated PET-g-ITA/DVB(10)-cat membrane exhibited excellent separation efficiencies (SE) for water/light oil, water/heavy oil and oil-in-water (O/W) emulsion. Compared to PET-g-ITA/DVB(0)-cat, it showed superior performance in SE for O/W emulsion and flux decay for water/light oil after 10 cycles. More interestingly, owing to numerous positively charged active amino groups and negativley charged carboxylate groups, the intelligent membrane exhibited a high removal rate of ca. 90 % for anionic dye (congo red) and heavy metals (Cu2+ and Co2+), showing great potential in complex water treatment environments.

Fabrication of Eco-Friendly Hydrolyzed Ethylene-Maleic Anhydride Copolymer-Avermectin Nanoemulsion with High Stability, Adhesion Property, pH, and Temperature-Responsive Releasing Behaviors.

In this study, novel amphiphilic polymer emulsifiers for avermectin (Avm) were synthesized facilely via the hydrolysis of ethylene-maleic anhydride copolymer (EMA) with different agents, and their structures were confirmed by various techniques. Then, water-based Avm-nanoemulsions were fabricated with the emulsifiers via phase inversion emulsification process, and superior emulsifier was selected via the emulsification effects. Using the superior emulsifier, an optimal Avm-nanoemulsion (defined as Avm@HEMA) with satisfying particle size of 156.8 ± 4.9 nm, encapsulation efficiency (EE) of 69.72 ± 4.01% and drug loading capacity (DLC) of 54.93 ± 1.12% was constructed based on response surface methodology (RSM). Owing to the emulsifier, the Avm@HEMA showed a series of advantages, including high stability, ultraviolet resistance, low surface tension, good spreading and high affinity to different leaves. Additionally, compared to pure Avm and Avm-emulsifiable concentrate (Avm-EC), Avm@HEMA displayed a controlled releasing feature. The encapsulated Avm was released quite slowly at normal conditions (pH 7.0, 25 °C or 15 °C) but could be released at an accelerated rate in weak acid (pH 5.5) or weak alkali (pH 8.5) media or at high temperature (40 °C). The drug releasing profiles of Avm@HEMA fit the Korsmeyer-Peppas model quite well at pH 7.0 and 25 °C (controlled by Fickian diffusion) and at pH 7.0 and 10 °C (controlled by non-Fickian diffusion), while it fits the logistic model under other conditions (pH 5.5 and 25 °C, pH 8.5 and 25 °C, pH 7.0 and 40 °C).

Recyclable Solid-Solid Phase Change Materials with Superior Latent Heat via Reversible Anhydride-Alcohol Crosslinking for Efficient Thermal Storage.

Solid-solid phase change materials (SSPCMs) with crosslinked polymer structures have received sustained interest due to their remarkable shape stability, enabling their application independently without the need for encapsulation or supporting materials. However, the crosslinking structure also compromises their latent heat and poses challenges to their recyclability. Herein, a novel strategy harnessing the internal-catalyzed reversible anhydride-alcohol crosslinking reaction to fabricate SSPCMs with superior latent heat and exceptional dual recyclability is presented. Easily accessible anhydride copolymers (e.g., propylene-maleic anhydride alternating copolymers), provide abundant reactive anhydride sites within the polymer matrix; polyethylene glycol serves as both the grafted phase change component and the crosslinker. The resulting SSPCMs attain a peak latent heat value of 156.8 J g-1 which surpasses all other reported recyclable crosslinked SSPCMs. The materials also exhibit certain flexibility and a tunable tensile strength ranging from 6.6 to 11.0 MPa. Beyond that, leveraging the reversible anhydride-alcohol crosslinks, the SSPCMs demonstrate dual recyclability through bond-exchange remolding and reversible-dissociation-enabled dissolving-recrosslinking without any reactive chemicals. Furthermore, by integrating solar-thermal conversion fillers like polydopamine nanoparticles, the potential of the system in efficient conversion, storage, and release of solar energy is highlighted.

Yolk-Shell Encapsulation of Cells by Biomimetic Mineralization and Visible Light-Induced Surface Graft Polymerization.

The pursuit of low-cytotoxicity modification strategies represents a prominent avenue in cell coating research, holding immense significance for the advancement of practical living cell-related technologies. Here, we presented a novel method to fabricate encapsulated yeast cells with a yolk-shell structure by biomimetic mineralization and visible-light-induced surface graft polymerization. In this approach, an amorphous calcium carbonate (ACC) shell was first deposited on the surface of a yeast cell (cell@ACC) modified with 4 layers of self-assembled poly(diallyl dimethylammonium chloride) (PDADMAC)/poly(acrylic acid) (PAA) film using a biomimetic mineralization technique. Subsequently, polyethylenimine (PEI) was absorbed on the surface of cell@ACC by electrostatic interaction. Then, a cross-linked shell was introduced by surface-initiated graft polymerization of poly(ethylene glycol) diacrylate (PEGDA) on cell@ACC under irradiation of visible light using thioxanthone catechol-O,O'-diacetic acid as the photosensitizer. After the removal of the inner ACC shell, the yolk-shell-structured yeast cells (cell@PHS) were obtained. Due to the mild conditions of the strategy, the cell@PHS could retain 98.81% of its original viability. The introduction of the shell layer significantly prolonged the lag phase of yeast cells, which could be tuned between 5 and 25 h by regulating the thickness of the shell. Moreover, the cell@PHS showed improved resistance against lyticase due to the presence of a protective shell. After 30 days of storage, the viability of cell@PHS was 81.09%, which is significantly higher than the 19.89% viability of native yeast cells.

Self-Cross-Linkable Maleic Anhydride Terpolymer Coating with Inherent High Antimicrobial Activity and Low Cytotoxicity.

Developing coating materials with low cytotoxicity and high antimicrobial activity has been recognized as an effective way to prevent medical device-associated infections. In this study, a maleic anhydride terpolymer (PPTM) is synthesized and covalently attached to silicone rubber (SR) surface. The formed coating can be further cross-linked (SPM) through the self-condensation of pendent siloxane groups of terpolymer. No crack or delamination of SPM was observed after 500 cycles of bending and 7 day immersion in deionized water. The sliding friction force of a catheter was reduced by 50% after coating with SPM. The SPM coating without adding any extra antibacterial reagents can kill 99.99% of Staphylococcus aureus and Escherichia coli and also significantly reduce bacterial coverage, while the coating displayed no antimicrobial activity when maleic anhydride groups of SPM were aminated or hydrolyzed. The results of the repeated disinfection tests showed that the SR coated with SPM could maintain 87.3% bactericidal activity within 5 cycles. Furthermore, the SPM coating only imparted slight toxic effect (>85% viability) on L929 cells after 36 h of coculture, which is superior to the coating of aminated SPM conjugated with the antimicrobial peptide E6. The terpolymer containing maleic anhydride units have great potential as a flexible and durable coating against implant infections.

UV-Induced Thiol-Ene "Click" Surface Grafting Polymerization on BOPP Substrate and Its Postmodifying for Hydrophilic and Antibacterial Applications.

This paper proposed a novel and versatile surface modification route by integrating UV light-mediated thiol-ene "click" surface grafting polymerization and postmodification via the reactions of the surface thiol groups. At first, poly(thiol ether) layers with tunable thiol group density, up to 8.2 × 102 ea/nm3 for cross-linked grafting layers, were grafted from biaxially oriented polypropylene (BOPP) film. Then, the surface -SH groups reacted with epoxy compounds to introduce quaternary ammonium salt. With the immobilized quaternary ammonium salt and coordinated Zn2+ ions, the modified film demonstrated 99.98% antibacterial rate against Staphylococcus aureusafter soaking in DI water for 21 days and in a highly alkaline environment (0.1 M NaOH aqueous solution) for 3 days, and the surface water contact angle decreased to 39°. At last, the polymethacrylate chains were also successfully grafted from the surface thiol groups of the cross-linked poly(thiol ether) under visible light irradiation. With 2-(dimethyldodecylammonium) ethyl methacrylate as the grafting monomer, the modified BOPP film had shown a 99.99% antibacterial rate against both Escherichia coliand S. aureus. Meanwhile, with 2-methacryloxyethyl phosphoryl choline as grafting monomer, the modified surface showed an excellent antibioadhesion of living S. aureus, and the surface water contact angle was as low as 48°.

Degradable Supramolecular Eutectogel-Based Ionic Skin with Antibacterial, Adhesive, and Self-Healable Capabilities.

The development of degradable, cost-effective, and eco-friendly ionic conductive gels is highly required to reduce electronic waste originating from flexible electronic devices. However, biocompatible, degradable, tough, and durable conductive gels are challenging to achieve. Herein, we develop a facile strategy for the design and synthesis of degradable tough eutectogels by integrating an electrostatically driven supramolecular network composed of branched polyacrylic acid (PAA) and monoethanolamine (MEA) into a green deep eutectic solvent with chitosan quaternary ammonium salt (CQS). The specially designed PAA/MEA/CQS eutectogels present multiple desired properties, including high transparency, widely adjustable mechanical properties, high resilience, reliable adhesiveness, excellent self-healing ability, good conductivity, remarkable anti-freezing performance, and antibacterial properties. The dynamic and reversible supramolecular interactions not only significantly enhance the mechanical properties of the PAA/MEA/CQS eutectogels but also enable fast degradation, addressing the dilemma between mechanical strength and degradability. More importantly, a biocompatible and degradable multifunctional ionic skin is successfully fabricated based on the PAA/MEA/CQS eutectogel, exhibiting high sensitivity, a wide sensing range, and a rapid response speed toward strain, pressure, and temperature. Thus, this study offers a promising strategy for fabricating degradable tough eutectogels, which show great potential as high-performance ionic skins for next-generation flexible wearable electronic devices.

A Novel Family of Stable Polyelectrolyte Complexes Based on Mixed Olefins-Maleic Anhydride Copolymer.

In the present study, the copolymer of mixed olefins included in unetherified gasoline and maleic anhydride (PUGM) was prepared by self-stabilized precipitation polymerization (2SP) and employed for the synthesis of a new family of stable polyelectrolyte complexes (PECs). Polyanionic saponified PUGM partially grafted with methoxy poly(ethylene glycol) (PUGMS-g-mPEG) and polycationic quaternized PUGM (PUGMQ) were both derived from PUGM via the facile modification of anhydride groups. The particle size, zeta potential, morphology, and stability of self-assembled PEC particles were investigated thoroughly. Strikingly, the introduction of long mPEG side chains (Mn = 4000) had a remarkable effect on the self-assembled particles, which displayed a constant particle size of ∼200 nm regardless of varying n+/n-. Moreover, it also enhanced the salt tolerance and long-term stability of PEC particles significantly. Our work not only provides an effective approach to PECs from petroleum resources with low cost but also deepens the understanding of the relationship between the chain structure of polyelectrolytes and the stability of PECs.

Super-adsorbent microspheres based on a triallyl isocyanurate-maleic anhydride copolymer for the removal of organic pollutants from water.

Owing to the frequent occurrence of diclofenac sodium (DS) in fresh aquatic environments and its potential toxicity towards living organisms, the effective removal of DS has attracted worldwide attention. Herein, a green and efficient strategy to fabricate crosslinked microspheres with interconnected mesoporous structures and abundant adsorption active sites was developed. With this strategy, triallyl isocyanurate (TAIC)-maleic anhydride (MAH) copolymer microspheres (TMs) with a diameter of 1.19-1.35 µm were first prepared by self-stabilized precipitation (2SP) polymerization, and the TMs possess a large amount reactive anhydride groups (62.5-71.8 mol%), a specific surface area of 51.6-182.4 m2 g-1 and a mesoporous structure (average pore size: 3.4-3.8 nm). Then the TMs were further functionalized with polyethylenimine (PEI) to give rise to cationic microspheres (Cat-TMs), which showed excellent adsorption performance to DS with a rapid adsorption rate (reached equilibrium within 30 min), a very high equilibrium adsorption capacity (1421 mg g-1) and excellent recyclability. The pseudo-second-order model and Langmuir model were a good fit for the adsorption kinetic and isotherm process, respectively. Furthermore, due to the high cation density (4.291 mmol g-1) and excellent pH buffer capacity of Cat-TMs, the adsorption capacity can be maintained at a high level within the pH range of 6-10. The regenerated Cat-TMs showed only a slight loss (<5%) in the adsorption capacity even after 5 adsorption-desorption cycles. In short, Cat-TMs can be considered as a highly promising adsorbent for the rapid and ultra-efficient removal of anionic organic contaminants and have significant potential to be applied in wastewater treatment.

Multi Stimuli-Responsive Aggregation-Induced Emission Active Polymer Platform Based on Tetraphenylethylene-Appended Maleic Anhydride Terpolymers.

Multi stimuli-responsive aggregation-induced emission (AIE) active polymers have great application prospects in high-tech innovations. Herein, three types of tetraphenylethylene (TPE)-containing monomers were synthesized and utilized in preparing TPE-appended maleic anhydride terpolymers. After hydrolysis, the produced TPE-appended maleic acid terpolymers have identical linear charge densities but different "primary" structures, which created widely varied microenvironments around the carboxylate and TPE groups. Benefiting from the synergistic interaction of the TPE moiety and the terpolymer conformation change, the TPE-appended maleic acid terpolymers exhibited fluorescence changes in response to multi stimuli, including pH, ionic strength, Ca2+, and bovine serum albumin. On both the "signaling" and the "stimuli acceptor" sides, the multi stimuli-responsive fluorescence behavior was influenced markedly by the terpolymer primary structure. The fundamental insights gained in the present work are important for developing an efficient and versatile stimuli-responsive AIE-active polymer platform for chemo-sensing, bioimaging, and so on.

Interfacial Assembly and Jamming of Soft Nanoparticle Surfactants into Colloidosomes and Structured Liquids.

Nanoparticle surfactant (NPS) offers a powerful strategy to generate all-liquid constructs that integrate the inherent properties of the NPs into 3D architectures. Here, using the co-assembly of fluorescent polymeric nanoparticles and amine-functionalized polyhedral oligomeric silsesquioxane, the assembly and jamming behavior of a new type of NPS at the oil-water interface is uncovered. Unlike "solid" inorganic nanoparticles, "soft" polymeric nanoparticles can reorganize when jammed, leading to a relaxation and deformation of the interfacial assemblies, for example, the 3D printed sugar-coated haw stick-like liquid tubules. With NPS serving as emulsifiers, stable Pickering emulsions are prepared that can be converted into robust colloidosomes with pH responsiveness, showing numerous potential applications for encapsulation and controlled release.

Highly Conductive, Transparent, Adhesive, and Self-Healable Ionogel Based on a Deep Eutectic Solvent with Widely Adjustable Mechanical Strength.

Ionogels have attracted intensive attentions as promising flexible conductive materials. However, simultaneous integration of excellent mechanical properties, high conductivity, outstanding self-healing ability, and strong adhesiveness is still challenging. Here, an ingenious composition design is proposed to address this long-standing challenge of ionogels. High-performance PEI/PAA/CMC ionogels, consist of a loosely cross-linked poly(acrylic acid) (PAA) network, dynamically cross-linked network based on polycationic polyethyleneimine (PEI) and polyanionic PAA, and carboxymethyl cellulose (CMC) reinforcing filler, are formed in a deep eutectic solvent (DES) composed of choline chloride and urea. Benefiting from the loose PAA network and dynamic noncovalent interactions, ionogels with both highly enhanced mechanical robustness and excellent conductivity are obtained at high loading of DES, overcoming the strength-ductility/conductivity trade-off dilemma. By adjusting PEI/PAA mass ratio, the tensile strength and strain of PEI/PAA/CMC ionogels are effectively controlled in a wide range of 0.15-7.9 MPa and 232-1161%, respectively, while maintaining the desirable conductivity of ≈10-4 S cm-1 . Besides, healed tensile strength over 2.1 MPa and adhesion strength up to 0.2 MPa are achieved for the PEI0.06 /PAA0.25 /CMC0.01 ionogel. The delicate design strategy provides a feasible approach to prepare ionogels with outstanding comprehensive performance, which have potential for applications in flexible electronics.

Covalently Attaching Hollow Silica Nanoparticles on a COC Surface for the Fabrication of a Three-Dimensional Protein Microarray.

Compared to traditional two-dimensional (2D) biochips, three-dimensional (3D) biochips exhibit the advantages of higher probe density and detection sensitivity due to their designable surface microstructure as well as enlarged surface area. In the study, we proposed an approach to prepare a 3D protein chip by deposition of a monolayer of functionalized hollow silica nanoparticles (HSNs) on an activated cyclic olefin copolymer (COC) substrate. First, the COC substrate was chemically modified through the photografting technique to tether poly[3-(trimethoxysilyl) propyl methacrylate] (PTMSPMA) brushes on it. Then, a monolayer of HSNs was deposited on the modified COC and covalently attached via a condensation reaction between the hydrolyzed pendant siloxane groups of PTMSPMA and the Si-OH groups of HSNs. The roughness of the COC substrate significantly increased to 50.3 nm after depositing a monolayer of HSNs (ranging from 100 to 700 nm), while it only caused a negligible reduction in the light transmittance of COC. The HSN-modified COC was further functionalized with epoxide groups by a silane coupling agent for binding proteins. Immunoglobulin G could be effectively immobilized on this substrate with the highest immobilization efficiency of 75.2% and a maximum immobilization density of 1.236 µg/cm2, while the highest immobilization efficiency on a 2D epoxide group-modified glass slide was only 57.4%. Moreover, immunoassay results confirmed a competitive limit of detection (LOD) (1.06 ng/mL) and a linear detection range (1-100 ng/mL) of the 3D protein chip. This facile and effective approach for fabricating nanoparticle-based 3D protein microarrays has great potential in the field of biorelated detection.

Three-dimensional protein microarrays fabricated on reactive microsphere modified COC substrates.

Fabrication of three-dimensional (3D) surface structures for the high density immobilization of biomolecules is an effective way to prepare highly sensitive biochips. In this work, a strategy to attach polymeric microspheres on a cyclic olefin copolymer (COC) substrate for the preparation of a 3D protein chip was developed. The COC surface was firstly functionalized by the photograft technique with epoxy groups, which were subsequently converted to amine groups. Then monodisperse poly(styrene-alt-maleic anhydride) (PSM) copolymer microspheres were prepared by self-stabilized precipitation polymerization and deposited as a single layer on a modified COC surface to form a 3D surface texture. The surface roughness of the COC support undergoes a significant increase from 1.4 nm to 37.1 nm after deposition of PSM microspheres with a size of 460 nm, and the modified COC still maintains a transmittance of more than 63% at the fluorescence excitation wavelengths (555 nm and 647 nm). The immobilization efficiency of immunoglobulin G (IgG) on the 3D surface reached 75.6% and the immobilization density was calculated to be 0.255 µg cm-2, at a probe protein concentration of 200 µg mL-1. The 3D protein microarray can be rapidly blocked by gaseous ethylenediamine within 10 minutes due to the high reactivity of anhydride groups in PSM microspheres. Immunoassay results show that the 3D protein microarray achieved specific identification of the target protein with a linear detection range from 6.25 ng mL-1 to 250 ng mL-1 (R2 > 0.99) and a limit of detection of 8.87 ng mL-1. This strategy offers a novel way to develop high performance polymer-based 3D protein chips.

Core-Shell Fluorescent Polymeric Particles with Tunable White Light Emission Based on Aggregation Microenvironment Manipulation.

White-light emitting polymers (WLEPs) based on aggregation microenvironment-sensitive aggregation-induced emission (AIE) and Förster resonance energy transfer (FRET) have aroused great interest in lighting and optoelectronic devices. Herein, we developed a novel strategy to construct WLEP particles via a stepwise self-stabilized precipitation polymerization of two emission-complementary AIEgens under core-shell engineering, where the AIE characteristics and FRET process of core-shell fluorescent polymeric particles (CS-FPPs) could be modulated by altering aggregation microenvironment under swelling and shrinking of polymers, facilitating the tunable white light emission of CS-FPPs. Furthermore, such tuning could be fast realized in the solid state, thus demonstrating the potential in anti-counterfeiting. This work proved the significance of aggregation microenvironment on emission of luminogens, guiding the development of high-efficiency emission-tunable materials.

A Versatile Strategy to Coat Individual Cell with Fully/Partially Covered Shell for Preparation of Self-Propelling Living Cells.

Coating living cells with a functional shell has been regarded as an effective way to protect them against environmental stress, regulate their biological behaviors, or extend their functionalities. Here, we reported a facile method to prepare fully or partially coated shells on an individual yeast cell surface by visible light-induced graft polymerization. In this strategy, yeast cells that were surface-absorbed with polyethylenimine (PEI) were deposited on the negatively charged glass slide to form a single layer by electrostatic interaction. Then, surface-initiated graft polymerization of poly(ethylene glycol) diacrylate (PEGDA) on yeast cells under visible light irradiation was carried out to generate cross-linked shells on the cells. The process of surface modification had negligible influence on the viability of yeast cells due to the mild reaction condition. Additionally, compared to the native yeast cells, a 17.5 h of delay in division was observed when the graft polymerization was performed under 15 mW/cm2 irradiation for 30 min. Introducing artificial shell endowed yeast cells with significant resistance against lyticase, and the protection can be enhanced by increasing the thickness of shell. Moreover, the partially coated yeast cells would be prepared by simply adjusting the reaction condition such as irradiation density and time. By immobilizing urease on the functional patch, the asymmetrically modified yeast cells exhibited self-propelling capability, and the speed of directional movement reached 4 µm/s in the presence of 200 mM urea. This tunable coating individual cell strategy with varying functionality has great potential applications in fields of cell-based drug delivery, cell therapy, biocatalysis, and tissue engineering.

Self-Stable Precipitation Polymerization Molecular Entanglement Effect and Molecular Weight Simulations and Experiments.

In this paper, we developed a reactive molecular dynamics (RMD) scheme to simulate the Self-Stable Precipitation (SP) polymerization of 1-pentene and cyclopentene (C5) with maleic anhydride (MAn) in an all-atom resolution. We studied the chain propagation mechanism by tracking the changes in molecular conformation and analyzing end-to-end distance and radius of gyration. The results show that the main reason of chain termination in the reaction process was due to intramolecular cyclic entanglement, which made the active center wrapped in the center of the globular chain. After conducting the experiment in the same condition with the simulation, we found that the distribution trend and peak value of the molecular-weight-distribution curve in the simulation were consistent with experimental results. The simulated number average molecular weight (Mn) and weight average molecular weight (Mw) were in good agreement with the experiment. Moreover, the simulated molecular polydispersity index (PDI) for cyclopentene reaction with maleic anhydride was accurate, differing by 0.04 from the experimental value. These show that this model is suitable for C5-maleic anhydride self-stable precipitation polymerization and is expected to be used as a molecular weight prediction tool for other maleic anhydride self-stable precipitation polymerization system.

UV-Assisted Li+-Catalyzed Radical Grafting Polymerization of Vinyl Ethers: A New Strategy for Creating Hydrolysis-Resistant and Long-Lived Polymer Brushes as a "Smart" Surface Coating.

A facile synthetic route was developed to prepare a surface-grafted brush layer of poly(vinyl ethers) (PVEs) directly by a radical mechanism, with the "naked" Li+ acting as a catalyst. Density functional theory calculations suggested that complexation of naked Li+ to VEs significantly reduced the highest unoccupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) energy gap from 5.08 to 0.68 eV, providing a better prospect for electron transfer. The structure, morphology, and surface properties of grafted polymer layers were characterized using attenuated total reflection Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, and dynamic water contact angle (DCA). Moreover, ellipsometry data indicated that the thickness of the polymer brushes was in the range of 20-60 nm, which corresponds to the grafting densities of 0.65-1.15 chain/nm2, and DCA decreased from 84.4 to 45.3°. Most importantly, no hydrolysis was observed for the modified surface after 30 days of exposure to phosphate-buffered saline solution, 0.1 mol/L NaOH(eq) and 0.1 mol/L HCl(eq), demonstrating excellent hydrolysis resistance with long service life. In addition, as a proof of concept, the side hydroxyl groups of grafted PVEs provide active sites for efficient fixation of bioactive molecules, e.g., glycosaminoglycan and serum protein.