Polymer-Metal Bilayer with Alkoxy Groups for Antibacterial Improvement.

Many bio-applicable materials, medical devices, and prosthetics combine both polymer and metal components to benefit from their complementary properties. This goal is normally achieved by their mechanical bonding or casting only. Here, we report an alternative easy method for the chemical grafting of a polymer on the surfaces of a metal or metal alloys using alkoxy amine salt as a coupling agent. The surface morphology of the created composites was studied by various microscopy methods, and their surface area and porosity were determined by adsorption/desorption nitrogen isotherms. The surface chemical composition was also examined by various spectroscopy techniques and electrokinetic analysis. The distribution of elements on the surface was determined, and the successful bonding of the metal/alloys on one side with the polymer on the other by alkoxy amine was confirmed. The composites show significantly increased hydrophilicity, reliable chemical stability of the bonding, even interaction with solvent for thirty cycles, and up to 95% less bacterial adhesion for the modified samples in comparison with pristine samples, i.e., characteristics that are promising for their application in the biomedical field, such as for implants, prosthetics, etc. All this uses universal, two-step procedures with minimal use of energy and the possibility of production on a mass scale.

A Tailored Interface Design for Anode-Free Solid-State Batteries.

Anode-free solid-state batteries (AFSSBs) are considered to be one of the most promising high-safety and high-energy storage systems. However, low Coulombic efficiency stemming from severe deterioration on solid electrolyte/current collector (Cu foil) interface and undesirable Li dendrite growth impede their practical application, especially when rigid garnet electrolyte is used. Here, an interfacial engineering strategy between garnet electrolyte and Cu foil is introduced for stable and highly efficient AFSSBs. By utilizing the high Li ion conductivity of LiC6 layer, interfacial self-adaption ability arising from ductile lithiated polyacrylic acid polymer layer and regulated Li deposition via Li-Ag alloying reaction, the garnet-based AFSSB delivers a stable long-term operation. Additionally, when combined with a commercial LiCoO2 cathode (3.1 mAh cm-2 ), the cell also exhibits an outstanding capacity retention due to the tailored interface design. The strategies for novel AFSSBs architecture thus offer an alternative route to design next-generation batteries with high safety and high density.

Modifying last layer in polyelectrolyte multilayer coatings for capillary electrophoresis of proteins.

Protein adsorption on the inner wall of the fused silica capillary wall is an important concern for capillary electrophoresis (CE) analysis since it is mainly responsible for separation efficiency reduction. Successive Multiple Ionic-polymer Layers (SMIL) are used as capillary coatings to limit protein adsorption, but even low residual adsorption strongly impacts the separation efficiency, especially at high separation voltages. In this work, the influence of the chemical nature and the PEGylation of the polyelectrolyte deposited in the last layer of the SMIL coating was investigated on the separation performances of a mixture of four model intact proteins (myoglobin (Myo), trypsin inhibitor (TI), ribonuclease a (RNAse A) and lysozyme (Lyz)). Poly(allylamine hydrochloride) (PAH), polyethyleneimine (PEI), ε-poly(L-lysine) (εPLL) and α-poly(L-lysine) (αPLL) were compared before and after chemical modification with polyethyleneglycol (PEG) of different chain lengths. The experimental results obtained by performing electrophoretic separations at different separation voltages allowed determining the residual retention factor of the proteins onto the capillary wall via the determination of the plate height at different solute velocities and demonstrated a strong impact of the polycationic last layer on the electroosmotic mobility, the separation efficiency and the overall resolution. Properties of SMIL coatings were also characterized by quartz microbalance and atomic force microscopy, demonstrating a glassy structure of the films.

Influence of the Graft Length on Nanocomposite Structure and Interfacial Dynamics.

Both the dispersion state of nanoparticles (NPs) within polymer nanocomposites (PNCs) and the dynamical state of the polymer altered by the presence of the NP/polymer interfaces have a strong impact on the macroscopic properties of PNCs. In particular, mechanical properties are strongly affected by percolation of hard phases, which may be NP networks, dynamically modified polymer regions, or combinations of both. In this article, the impact on dispersion and dynamics of surface modification of the NPs by short monomethoxysilanes with eight carbons in the alkyl part (C8) is studied. As a function of grafting density and particle content, polymer dynamics is followed by broadband dielectric spectroscopy and analyzed by an interfacial layer model, whereas the particle dispersion is investigated by small-angle X-ray scattering and analyzed by reverse Monte Carlo simulations. NP dispersions are found to be destabilized only at the highest grafting. The interfacial layer formalism allows the clear identification of the volume fraction of interfacial polymer, with its characteristic time. The strongest dynamical slow-down in the polymer is found for unmodified NPs, while grafting weakens this effect progressively. The combination of all three techniques enables a unique measurement of the true thickness of the interfacial layer, which is ca. 5 nm. Finally, the comparison between longer (C18) and shorter (C8) grafts provides unprecedented insight into the efficacy and tunability of surface modification. It is shown that C8-grafting allows for a more progressive tuning, which goes beyond a pure mass effect.

Hypercrosslinking porous polymer layers on TiO2-graphene photocatalyst: Enhanced adsorption of water pollutants for efficient degradation.

Solar-driven photocatalysis offers an environmentally friendly and sustainable approach for the degradation of organic pollutants in water without chemical additives, but the low specific surface area and adsorption capacity of common photocatalysts restricts the surface reactions with the contaminants. Herein, we hypercrosslinked polymer layers on TiO2-graphene surface to enlarge the specific surface area from 136 to 988 m2/g, leading to a high adsorption capacity of sulfadiazine as 54.3 mg/g, which is 15.5 times that of TiO2-graphene (3.5 mg/g). The adsorption kinetics reveals the combination of physical and chemical adsorption by porous benzene-based polymer for sulfadiazine enrichment. Besides, the polymer layers with broad light absorption enable the composite to function efficiently as visible-light-driven photocatalysts. Thus, the as-designed composite exhibits excellent performance for sulfadiazine removal by integrating the adsorptive and photocatalytic processes, especially for the diluted sulfadiazine solution. More importantly, the porous polymer layer can function as a filter for weakening the interference of TiO2 surface with the natural matters from complex water matrices. Based on the identification of dominant reactive species, the possible attacking pathway and the sulfadiazine subsequent degradation are presented. Further, the enhanced adsorption and photodegradation efficiency can also be achieved for the removal of other typical pollutants such as 4-chlorophenol and methylene blue. This study highlights an adsorption-enhanced-degradation mechanism for water pollutants that can direct the design of high-performance photocatalysts under visible light.

Multimode Robust Lasing in a Dye-Doped Polymer Layer Embedded in a Wedge-Shaped Cholesteric.

Cholesteric liquid crystals (CLCs) with induced defects are one of the most prominent materials to realize compact, low-threshold and tunable coherent light sources. In this context, the investigation of optical properties of induced defect modes in such CLCs is of great interest. In particular, many studies have been devoted to the spectral control of the defect modes depending on their thickness, optical properties, distribution along the CLC, etc. In this paper, we investigate the lasing possibilities of a dye-doped polymer layer embedded in a wedge-shaped CLC. We show that multimode laser generation is possible due to the observed multiple defect modes in the PBG that enlarges the application range of the system. Furthermore, our simulations based on a Berreman 4 × 4 matrix approach for a wide range of CLC thickness show both periodic and continuous generation of defect modes along particular spectral lines inside the PBG. Such a robust spectral behaviour of induced defect modes is unique, and, to our knowledge, is not observed in similar CLC-based structures.

Approximate analytic expressions for the electrophoretic mobility of spherical soft particles.

Approximate analytic expressions are derived for the electrophoretic mobility of a weakly charged spherical soft particle consisting of the particle core covered with a surface layer of polymers in an electrolyte solution. The particle core and the surface polymer layer may be charged or uncharged. The obtained electrophoretic mobility expressions, which involve neither numerical integration nor exponential integrals, are found to be in excellent agreement with the exact numerical results. It is also found that the obtained mobility expressions reproduce all the previously derived limiting expressions and approximate analytic expressions for the electrophoretic mobility of a weakly charged spherical soft particle.

Slippery Liquid-Attached Surface for Robust Biofouling Resistance.

Materials for biodevices and bioimplants commonly suffer from unwanted but unavoidable biofouling problems due to the nonspecific adhesion of proteins, cells, or bacteria. Chemical coating or physical strategies for reducing biofouling have been pursued, yet highly robust antibiofouling surfaces that can persistently resist contamination in biological environments are still lacking. In this study, we developed a facile method to fabricate a highly robust slippery and antibiofouling surface by conjugating a liquid-like polymer layer to a substrate. This slippery liquid-attached (SLA) surface was created via a one-step equilibration reaction by tethering methoxy-terminated polydimethylsiloxane (PDMS-OCH3) polymer brushes onto a substrate to form a transparent "liquid-like" layer. The SLA surface exhibited excellent sliding behaviors toward a wide range of liquids and small particles and antibiofouling properties against the long-term adhesion of small biomolecules, proteins, cells, and bacteria. Moreover, in contrast to superomniphobic surfaces and liquid-infused porous surfaces (SLIPS) requiring micro/nanostructures, the SLA layer could be obtained on smooth surfaces and maintain its biofouling resistance under abrasion with persistent stability. Our study offers a simple method to functionalize surfaces with robust slippery and antibiofouling properties, which is promising for potential applications including medical implants and biodevices.

Evaluation of the Water Content and Skin Permeability of Active Pharmaceutical Ingredients in Ketoprofen Poultice Formulations Removed from Their Airtight Containers and Left at Room Temperature.

The poultice formulation is a patch containing a large amount of water. It is known that the water contained in the adhesive polymer layer (ADPL) of poultice affects the cooling sensation and skin permeability of the active pharmaceutical ingredient (API). In this study, we evaluated the relationship between the water content in a ketoprofen poultice formulation and the amount of time the poultice was left out at room temperature after removal from the airtight container, as well as the influence of the decreasing water content on the skin permeability of the API. After removing the poultice from the container for 1 h, the mass of the ADPL decreased by approximately 40%. When the near-infrared (NIR) spectrum of the ADPL of poultice was measured, the peaks reflecting the hydroxyl group were attenuated depending on the time left out at room temperature. It is suggested that the changes in the mass and NIR spectrum of the ADPL are caused by the change in the water content. Moreover, when the permeability of API was evaluated on hairless mouse skin, the cumulative skin permeation amount and flux decreased, while the lag time was prolonged as the time left out increased. These results suggest that the skin permeability of the API is impaired by water evaporation and that maintaining the water in the ADPL in poultice is very important from not only the viewpoint of cooling sensation, tackiness and moisturizing but also the skin permeability of the API.

Dendrite-Free Lithium Deposition via Flexible-Rigid Coupling Composite Network for LiNi0.5 Mn1.5 O4 /Li Metal Batteries.

Notorious lithium dendrite causes severe capacity fade and harsh safety issues of lithium metal batteries, which hinder the practical applications of lithium metal electrodes in higher energy rechargeable batteries. Here, a kind of 3D-cross-linked composite network is successfully employed as a flexible-rigid coupling protective layer on a lithium metal electrode. During the plating/stripping process, the composite protective layer would enable uniform distribution of lithium ions in the adjacent regions of the lithium electrode, resulting in a dendrite-free deposition at a current density of 2 mA cm-2 . The LiNi0.5 Mn1.5 O4 -based lithium metal battery presents an excellent cycling stability at a voltage range of 3.5-5.0 V with the induction of 3D-cross-linked composite protective layer. From an industrial field application of view, thin lithium metal electrodes (40 µm, with 4 times excess lithium) can be used in LiNi0.5 Mn1.5 O4 (with industrially significant loading of 18 mg cm-2 and 2.6 mAh cm-2 )-based lithium metal batteries, which reveals a promising opportunity for practical applicability in high energy lithium metal batteries.

An automated and self-cleaning nano liquid chromatography mass spectrometry platform featuring an open tubular multi-hole crystal fiber solid phase extraction column and an open tubular separation column.

An open tubular (OT) sample preparation/separation platform was developed. A multi-channel polymer layer open tubular (mPLOT) solid phase extraction (SPE) column was prepared by wall-coating the 126 channels (8µm inner diameter (ID) each) of a crystal fiber capillary with an organic polymer, namely poly(styrene-co-octadecene-co-divinylbenzene) (PS-OD-DVB). The mPLOT SPE was coupled on-line with a 10µm×2m poly(styrene-co-divinylbenzene) (PS-DVB) OT liquid chromatography column with nanospray mass spectrometry (OTLC-MS). Compared to using monolithic/particle-packed SPEs, mPLOT-SPE-OTLC allowed both fast loading and sufficient refocusing on the OT analytical column of small model compounds (sulfonamides≈300Da). Using automatic filtration/filter back-flushing (AFFL) plumbing, the mPLOT SPE column gave a constant and low back-pressure ≈35bar at 0.5µL/min. Surprisingly large sample volumes (10µL) were possible to be injected using a 12cm mPLOT.

Titanium alloy modified with anti-biofouling zwitterionic polymer to facilitate formation of bio-mineral layer.

The surface of a titanium (Ti) alloy was modified with a self-assembled monolayer of poly(ethylene glycol) methacrylate phosphate (Phosmer PE). A zwitterionic monomer (carboxymethyl betaine, CMB) could be copolymerized with the surface-bound Phosmer PE due to a flexible linker between the Ti alloy surface and a methacryloyl group of Phosmer PE. The poly(CMB) (PCMB)-modified Ti alloy plate exhibited strong suppression of protein adsorption and cell adhesion, and induced approximately twice the amount of calcium (Ca2+) deposition as compared to the unmodified Ti alloy plate. The zwitterionic polymer-modified surfaces not only showed enhanced mineralization clusters creation and growth, but they were also highly non-responsive to biologically derived materials such as proteins and cells. Therefore, it is possible to easily form highly pure and rigid hydroxyapatite layers on Ti alloy surfaces without the incorporation of organic molecules such as proteins. The present surface modification technique and strategy can be applied to implantable orthopedic materials as a means of encouraging integration with host tissues, such as the thigh bone.

Optimization of the composition of zwitterionic copolymers for the easy-construction of bio-inactive surfaces.

Random copolymers (S-PCMBx) of the zwitterionic monomer carboxymethylbetaine (CMB) and a small percentage of 3-methacryloyloxypropyl trimethoxysilane with various composition ratios were synthesized in ethanol using 2,2'-azobisisobutyronitrile as the initiator. An S-PCMBx layer formed on the glass substrate after soaking in the copolymer solution and had a thickness of 2-3 nm. The S-PCMBx-modified surface was highly hydrophilic and suppressed both the non-specific adsorption of protein (bovine serum albumin) and NIH3T3-fibroblast adhesion. The degree of adsorption suppression increased with increasing copolymer CMB content with a maximum at 90 mol % CMB. In contrast, the modification of the glass substrate with a PCMB homopolymer terminally modified with a trimethoxysilyl group did not effectively suppress protein adsorption and cell adhesion due to the low graft density. The importance of balancing the number of fixation points and the length of the zwitterionic polymer loops to produce bio-inactive metal oxide surfaces is suggested. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 2029-2036, 2016.

Preparation of a thick polymer brush layer composed of poly(2-methacryloyloxyethyl phosphorylcholine) by surface-initiated atom transfer radical polymerization and analysis of protein adsorption resistance.

The purpose of this study was to prepare a thick polymer brush layer composed of poly(2-methacryloyloxyethyl phosphorylcholine (MPC)) and assess its resistance to protein adsorption from the dissolved state of poly(MPC) chains in an aqueous condition. The thick poly(MPC) brush layer was prepared through the surface-initiated atom transfer radical polymerization (SI-ATRP) of MPC with a free initiator from an initiator-immobilized substrate at given [Monomer]/[Free initiator] ratios. The ellipsometric thickness of the poly(MPC) brush layers could be controlled by the polymerization degree of the poly(MPC) chains. The thickness of the poly(MPC) brush layer in an aqueous medium was larger than that in air, and this tendency became clearer when the polymerization degree of the poly(MPC) increased. The maximum thickness of the poly(MPC) brush layer in an aqueous medium was around 110 nm. The static air contact angle of the poly(MPC) brush layer in water indicated a reasonably hydrophilic nature, which was independent of the thickness of the poly(MPC) brush layer at the surface. This result occurred because the hydrated state of the poly(MPC) chains is not influenced by the environment surrounding them. Finally, as measured with a quartz crystal microbalance, the amount of protein adsorbed from a fetal bovine serum solution (10% in phosphate-buffered saline) on the original substrate was 420 ng/cm(2). However, the poly(MPC) brush layer reduced this value dramatically to less than 50 ng/cm(2). This effect was independent of the thickness of the poly(MPC) brush layer for thicknesses between 20 nm and about 110 nm. These results indicated that the surface covered with a poly(MPC) brush layer is a promising platform to avoid biofouling and could also be applied to analyze the reactions of biological molecules with a high signal/noise ratio.

Toxicity of bare and surfaced functionalized iron oxide nanoparticles towards microalgae.

This study investigates the toxicity of bare iron oxide nanoparticles (IONPs) and surface functionalization iron oxide nanoparticles (SF-IONPs) to the growth of freshwater microalgae Chlorella sp. This study is important due to the increased interest on the application of the magnetic responsive IONPs in various fields, such as biomedical, wastewater treatment, and microalgae harvesting. This study demonstrated that the toxicity of IONPs was mainly contributed by the indirect light shading effect from the suspending nanoparticles which is nanoparticles concentration-dependent, direct light shading effect caused by the attachment of IONPs on cell and the cell aggregation, and the oxidative stress from the internalization of IONPs into the cells. The results showed that the layer of poly(diallyldimethylammonium chloride) (PDDA) tended to mask the IONPs and hence eliminated oxidative stress toward the protein yield but it in turn tended to enhance the toxicity of IONPs by enabling the IONPs to attach on cell surfaces and cause cell aggregation. Therefore, the choice of the polymer that used for surface functionalize the IONPs is the key factor to determine the toxicity of the IONPs.

Investigation of poly(styrene-divinylbenzene-vinylsulfonic acid) as retentive and electroosmotic flow generating phase in open-tubular electrochromatography.

In this work, a new sulfonated polystyrene based porous layer was synthesized on the wall of a capillary by a single step in situ polymerization process. To obtain a capillary suited for electrochromatography, vinylsulfonic acid (VSA) was, next to divinylbenzene (DVB), copolymerized to induce charges for the electroosmotic flow (EOF) generation. The VSA ratio in the monomer mixture and the polymerization time were optimized while the chromatographic characteristics of the obtained open tubular columns were investigated in electrochromatography. To allow unambiguous study of only chromatographic processes, evaluations were performed with a mixture of sufficiently retained and electrophoretically neutral parabens. Comparison of SEM pictures and chromatograms revealed that the polymerization time had a great influence on the polymer layer morphology and on the chromatographic performance. An increase in the VSA ratio, led to an increase in the mobile phase velocity but simultaneously lowered paraben retention. The novel optimized stationary phase could generate a stable and significant electro-osmotic flow (EOF) of 1.1mm/s over a wide pH range which could be produced in a reproducible manner. Minimal plate heights of 10µm, equivalent to the capillary internal diameter, were obtained. The open-tubular character of this optimized porous layer column allowed successful analyses at elevated temperature, resulting in a maximum efficiency of 85,500 plates for a 75cm capillary and linear velocities up to 1.4mm/s. Finally, a thermal gradient was successfully applied, leading to artificial sharpened peaks with a peak capacity of 55 in a 20min time span.

Adsorption of cationic polyacrylamide at the cellulose-liquid interface: a neutron reflectometry study.

The layer thickness and density of high molecular weight cationic polyacrylamide (CPAM) adsorbed at the cellulose-water interface was quantified by neutron reflectometry. The thickness of a full monolayer of CPAM of constant molecular weight (13 MD) but different charge densities, adsorbed with or without NaCl (10(-3) M), was studied. Thin cellulose films (40±7 Å) of roughness <10 Å were produced by spin coating a cellulose acetate-acetone solution and regenerating by alkaline hydrolysis. Film smoothness was greatly improved by controlling the concentration of cellulose acetate (0.13 wt%) and the hydrolysis time in sodium methoxide. The adsorption thickness of CPAM (40% charge 13 MD) at the solid-D2O interface was 43±4 Å on cellulose and 13±2 Å on silicon, an order of magnitude smaller than the CPAM radius of gyration. At constant molecular weight, the thickness of the CPAM layer adsorbed on cellulose increases with polymer charge density (10±1 Å at 5%). Addition of 10(-3) M NaCl decreased the thickness of CPAM layer already adsorbed on cellulose. However, the adsorption layer on cellulose of a CPAM solution equilibrated in 10(-3) M NaCl is much thicker (89±11 Å for 40% CPAM). For high molecular weight CPAMs adsorbed from solution under constant conditions, the adsorption layer can be varied by 1 order of magnitude via control of the variables affecting electrostatic intra- and inter-polymer chain interactions.

High-sensitivity analysis of anionic sulfonamides by capillary electrophoresis using a synergistic stacking approach.

A synergistic stacking approach whereby field-enhanced sample injection and micelle-to-solvent stacking in capillary zone electrophoresis are combined has been developed and has been applied to the separation and quantification of anionic sulfonamides. Electrokinetic injection of the sample in a low conductivity alkaline diluent was performed for 90s at -15kV. Micelle-to-solvent stacking was then undertaken by hydrodynamic injection of micellar cetyltrimethylammonium bromide solution prior to the electrokinetic injection of sample that also contained 50% methanol. This combined stacking approach, when compared to a typical hydrostatic injection, provided improvements in peak height and corrected peak area in the range of 397-1024 and 758-1246, respectively. Limits of quantification in the range of 0.01-0.03µg/mL were obtained for sulfamerazine, sulfamethazine and sulfamethizole and were sufficient for the determination of these analytes in river water. The percentage recovery and accuracy values obtained for a fortified river water sample that had been subjected to sample preparation by evaporation and reconstitution with diluent were 74-135%. Intra-day and inter-day repeatabilities for migration time, peak height, and corrected peak area were in the range 0.5-5.0% (percentage relative standard deviation, n=8) and these relatively low values were attributed to the use of a stable capillary coating established by the successive multiple ionic-polymer layer technique.

Stereospecific micellar electrokinetic chromatography assay of methionine sulfoxide reductase activity employing a multiple layer coated capillary.

A micellar electrokinetic chromatography method for the analysis of the l-methionine sulfoxide diastereomers employing a successive multiple ionic-polymer layer coated fused-silica capillary was developed and validated in order to investigate the stereospecificity of methionine sulfoxide reductases. The capillary coating consisted of a first layer of hexadimethrine and a second layer of dextran sulfate providing a stable strong cathodic EOF and consequently highly repeatable analyte migration times. The methionine sulfoxide diastereomers, methionine as product as well as ß-alanine as internal standard were derivatized by dabsyl chloride and separated using a 35 mM sodium phosphate buffer, pH 8.0, containing 25 mM SDS as BGE and a separation voltage of 25 kV. The method was validated in the range of 0.15-2.0 mM with respect to linearity and precision. The LODs of the analytes ranged between 0.04 and 0.10 mM. The assay was subsequently applied to determine the stereospecificity of methionine sulfoxide reductases as well as the enzyme kinetics of human methionine sulfoxide reductase A. Monitoring the decrease of the l-methionine-(S)-sulfoxide Km = 411.8 ± 33.8 µM and Vmax = 307.5 ± 10.8 µM/min were determined.