A Novel Approach for the Surface Modification of Polymeric Membrane with Phospholipid Polymer

A new economic and convenient method to modify the surface of microporous polypropylene (PP) membranes with phospholipid polymer was given. The process included the photo-irradiated graft polymerization of N,N-dimethylaminoethyl methacrylate (DMAEMA) and the ring-opening reaction of the grafted polyDMAEMA with 2-alkyloxy-2-oxide-1,3,2-dioxo-phospholanes (AOP). Four AOPs, whose alkyloxy groups consisted of dodecyl, tetradecyl, hexadecyl and octadecyl moieties, were used to convert the grafted polyDMAEMA to phospholipid polymers. FT-IR spectra confirmed the chemical change of membrane surface. Platelets adhesion experiment indicated that PP membrane with excellent blood compatible surface could be fabricated by this method.

Comparison of Surface Modification of CR-39 Polymer Film Using RF and DC Glow Discharges Plasma

Surfaces of optical elements are deposited by antireflection coatings (ARCs) to decrease the reflection of light. Surface needs treatment before depositing the ARC one of treatment processes by plasma for adhesion improvement and surface hardening. A comparison of RF and DC glow discharges treated CR-39 polymer films gives insight into the mechanism of these surface processes. The surface properties of the plasma-treated samples are examined by microscopy techniques include contact angle measurements, scanning electron microscopy (SEM), atomic force microscopy (AFM), infrared (IR) spectroscopy and refractive index measurements. Results show that the plasma treatment modifies the polymer surface in both composition and morphology. It is found that the surface wettability is enhanced after plasma treatment. It is found that, RF plasma is more effective than DC plasma in CR-39 surface modification, as it implants more oxygen atoms into the surface and makes the contact angle declining to a lower level.

Surface modification of biomaterials by photochemical immobilization and photograft polymerization to improve hemocompatibility

Thrombus formation and blood coagulation are serious problems associated with blood contacting products,such as catheters,vascular grafts,artificial hearts,and heart valves.Recent progresses and strategies to improve the hemocompatibility of biomaterials by surface modification using photochemical immobilization and photograft polymerization are reviewed in this paper.Three approaches to modify biomaterial surfaces for improving the hemocompatibility,i.e.,bioinert surfaces,immobilization of anticoagulative substances and biomimetic surfaces,are introduced.The biomimetic amphiphilic phosphorylcholine and Arg-Gly-Asp(RGD)sequence are the most effective and most often employed biomolecules and peptide sequence for improving hemocompatibility of material surfaces.The RGD sequence can enhance adhesion and growth of endothelial cells(ECs)on material surfaces and increase the retention of ECs under flow shear stress conditions.This surface modification is a promising strategy for biomaterials especially for cardiovascular grafts and functional tissue engineered blood vessels.

PHOTO-INDUCED GRAFT POLYMERIZATION OF ACRYLAMIDE ON POLYPROPYLENE MEMBRANE SURFACE IN THE PRESENCE OF DIBENZYL TRITHIOCARBONATE

Ultraviolet （UV）-induced graft polymerization of acrylamide （AAm） on polypropylene substrates was successfully conducted using dibenzyl trithiocarbonate （DBTTC） as photoinitiator. It was confirmed by chemical analysis and surface morphology observation with attenuated total reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. A possible mechanism for this graft process was presented, which suggested that, under UV irradiation, the C： S bond in DBTTC could split and abstract a hydrogen from the polypropylene surface and a surface free radical was then formed, and initiated the graft polymerization of AAm.

UV-induced Self-initiated Graft Polymerization of Acrylamide onto Poly(ether ether ketone)

Photo-grafting of hydrophilic monomer was used to enhance the hydrophilicity of poly（ether ether ketone） （PEEK） with the aim of extending its applications to biological fields. PEEK sheets were surface modified by grafting of acrylamide（AAm） with ultraviolet（UV） irradiation in the presence or absence of benzophenone（BP）. The effects of BP, irradiation time and monomer concentration on the surface wettability of PEEK were investigated. Characteriza tion of modified PEEK using scanning electron microscopy（SEM）, energy-disperse spectrometer（EDS） and water contact angle measurements shows that AAm was successfully grafted on PEEK surface both in presence and absence of BP. With the increase in irradiation time and monomer concentration, contact angles decrease to as low as 30°, demonstrating a significant improvement of surface hydrophilicity. In agreement with the decrease in contact angle, under identical conditions, the nitrogen concentration increases, suggesting the increase in grafting degree of the grafting polymerization. This investigation demonstrates a self-initiation of PEEK due to its BP-like structure in the backbone of the polymer. Though the graft polymerization proceeds more readily in the presence of BP, the self-initiated graft polymerization is clearly observed.

Model for a UV Laser Based Local Polymer Surface Halogenation Process Using a Gaseous Precursor

An analytical model describing the physical relations of a UV-based process for halogenation of polymeric surfaces is presented. The process allows, depending on the parameters, a local halogenation with sharp edges at the interfaces to areas where no halogenation is desired. This is achieved via a nonreactive halogen-containing gaseous precursor and a UV source providing photons which dissociate the precursor photolytically. Thus, only where the UV photons affect the precursor, halogens are generated and the polymer is being halogenated.

Femtosecond laser-mediated anchoring of polymer layers on the surface of a biodegradable metal

Mg has received much attention as a next-generation implantable material owing to its biocompatibility,bone-like mechanical properties,and biodegradability in physiological environments.The application of various polymer coatings has been conducted in the past to reduce the rapid formation of hydrogen gas and the local change in pH during the initial phase of the chemical reaction with the body fluids.Here,we propose femtosecond(fs)laser-mediated Mg surface patterning for significant enhancement of the binding strength of the coating material,which eventually reduces the corrosion rate.Analyses of the structural,physical,crystallographic,and chemical properties of the Mg surface have been conducted in order to understand the mechanism by which the surface adhesion increases between Mg and the polymer coating layer.Depending on the fs laser conditions,the surface structure becomes rough owing to the presence of several microscaled pits and grooves of nanoporous MgO,resulting in a tightly bonded poly(lactic-co-glycolic acid)(PLGA)layer.The corrosion rate of the PLGA-coated,fs laser-treated Mg is considerably slow compared with the non-treated Mg;the treated Mg is also more biocompatible compared with the non-treated Mg.The fs laser-based surface modification technique offers a simple and quick method for introducing a rough coating on Mg;further,it does not require any chemical treatment,thereby overcoming a potential obstacle for its clinical use.

Ultravilolet-radiation-induced graft polymerization of acrylamide onto the melt-blown polypropylene filter element by dynamic method

By dynamic method under UV irradiation, commercial melt-blown polypropylene （PPMB） filter element was modified with acrylamide （AAm） using benzophenone （BP） as initiator. Attenuated total reflection-Fourier transform infrared spectroscopy and scanning electron microscope verified that polyacrylamide chain was grafted on the fiber surface of PPMB filter element. Elemental content analysis with energy dispersive X-ray of fibers revealed that the polymerization content in the inner part of filter element was relatively higher than that in the outer. Degree of grafting changed with initiator concentration, monomer concentration, reaction temperature and reached 2.6% at the reaction condition： CBp=0.06 mol/L, CAAm=2.0 mol/L, irradiation time： 80 min, temperature： 60℃. Relative water flux altered with the hydrophilicity and pore size of filter element. In the antifouling test, the modified filter gave greater flux recovery （approximately 70%） after filtration of the water extract of Liuweidihuang, suggesting that the fouling layer was more easily reversible due to the hydrophilic nature of the modified filter.

PLASMA MODIFICATION OF POLYPROPYLENE SURFACES AND GRAFTING COPOLYMERIZATION OF STYRENE ONTO POLYPROPYLENE

The surface of polypropylene （iPP） is modified with glow discharge plasma of Ar, so that the modified surfaces of iPP films are obtained. The studies of scanning electron microscopy （SEM） show the surface etching pattern of iPP films. The chemical structures of iPP films are confirmed by X-ray photoelectron spectroscopy （XPS） and Fourier transform infrared （FTIR） spectroscopy. The wetting properties of modified surfaces of iPP films are characterized by contact angle, and the free energy of surfaces is calculated. The free radical of modification surfaces of iPP is measured by chemical method. The surfaces of iPP are achieved with Ar plasma treatment followed by grafting copolymerization with styrene （St） in St. The grafting polymer of St onto iPP is characterized by FTIR. The grafting rate is dependent on plasma exposure time and discharge voltage. The studies show that homopolymerization of St is undergone at the sane time during the graftingcopolymerization of St onto/PP.

Study of Sweet-Sensitive Taste Sensor with Lipid/Polymer Membranes

A sweet-sensitive taste sensor was investigated with potetiometric measurement.The transducer was a lipid/polymer membrane composed of tetradodecylammonium bromide,di-n-octylphenylphosphonate and polyvinyl chloride,which surface was modified with polyphenol and the solvent 30% EtOH,100 mmol/L KC1 and 10 mmol/L KOH.Balancing hydrophobic/ hydrophilic property and charge density on the membrane surface was susceptible to sensitivity for sweetener.Interaction between the membrane and sweet taste substances such as sucrose was detected as membrane potential change.

SYNTHESIS AND CHARACTERIZATION OF STRUCTURALLY WELL-DEFINED POLYMER-INORGANIC HYBRID NANOPARTICLES VIA ATRP

Atom transfer radical polymerization (ATRP) using cuprous chloride/2,2'-bipyridine (bipy) was applied to graft polymerization of styrene on the surface of silica nanoparticles to synthesize polymer-inorganic hybrid nanoparticles, 2-(4Chloromethylphenyl) ethyltriethoxysilane (CTES) was immobilized on the surface of silica nanoparticles through condensation reaction of the silanol groups on silica with triethoxysilane group of CTES. Then ATRP of St was initiated by this surface-modified silica nanoparticles bearing benzyl chloride groups, and formed PSt graft chains on the surface of silica nanoparticles. The thickness of the graft chains increased with reaction time. End group analysis confirmed the occurrence of ATRP. Thermal analysis indicated that thermal stabilization of these resulting hybrid nanoparticles also increases with polymerization conversion. The results above show that this 'grafting from' reaction could be used for the preparation of polymer-inorganic hybrid nanoparticles with controlled structure of the polymer's end groups.

Preparation of Fluoroalkyl End-Capped Oligomer/Cyclodextrin Polymer Composites: Development of Fluorinated Composite Material Having a Higher Adsorption Ability toward Organic Molecules

Fluoroalkyl end-capped vinyltrimethoxysilane oligomer [RF-(CH2CHSi(OMe)3)n-RF;RF = CF(CF3)OCF7, n = 2, 3;RF-(VM)n-RF] was applied to the preparation of fluoroalkyl end-capped vinyltrimethoxysilane oligomer/α-, β-, γ-cyclodextrin polymers (α-, β-, γ-CDPs) composites [RF-(VM-SiO2)n-RF/α-, β-, γ-CDPs] by the sol-gel reaction of the corresponding oligomer in the presence of the α-, β-, γ-CDPs under alkaline conditions. The RF-(VM-SiO2)n-RF/α-, β-, γ-CDPs composites thus obtained were found to give a good dispersibility toward the traditional organic media except for water, and were applied to the surface modification of glass to provide a sueperoleophilic/superhydrophobic characteristic on the modified surface, although the corresponding RF-(VM-SiO2)n-RF nanocomposites can give a usual oleophobic/superhydrophobic property on the surface. These composites powders were also found to be applicable to the packing material for the column chromatography to separate the mixture of oil/water and the water in oil (W/O) emulsions. More interestingly, these composite powders were found to have a higher adsorption ability toward not only low-molecular weight aromatic compounds such as bisphenol A and bisphenol AF but also volatile organic compounds, compared to that of the pristine α-, β-, γ-CDPs.

Osmium-Polymer Modified Carbon Nanotube Paste Electrode for Detection of Sucrose and Fructose

The aim of the work was the modification of a carbon nanotube paste electrode with a highly original osmium-polymer hydrogel for the development of a new amperometric biosensor for detection of sucrose and fructose. The biosensor for sucrose is based on the activity of the enzymes invertase and fructose dehydrogenase (FDH) immobilized into a carbon nanotube paste (CNTP) electrode properly modified with the Os-polymer. A second biosensor, for fructose only, is constructed containing inactive invertase and used for detection of fructose and for signal subtraction. The biosensors exhibit a detection limit for sucrose of 2 mM and for fructose of 1 mM, linearity up to 5 mM for both biosensors, high sensitivity (1.98 mA·cm-2·mM for sucrose and 1.95 mA·cm-2·mM for fructose), a good reproducibility (RSD = 2.5% for sucrose and 2.1% for fructose), fast response time (8 s for sucrose and 4 s for fructose) and a stability of about 4 months for both biosensors when stored under wet conditions at 4°C. Finally, the biosensors were applied for specific determination of sucrose and fructose in several commercial fruit juice samples and validated with a commercial spectrophotometric enzymatic kit.

All-organic modification coating prepared with large-scale atmospheric-pressure plasma for mitigating surface charge accumulation

The surface charge accumulation on polymers often leads to surface flashover.Current solutions are mainly based on the introduction of inorganic fillers.The high-cost process and low compatibility remain formidable challenges.Moreover,existing researches on all-organic insulation focus on capturing electrons,contrary to alleviating charge accumulation.Here,an all-organic modification coating was prepared on polystyrene(PS)with the large-scale atmospheric-pressure plasma,which exhibits outperformed function in mitigating surface charge accumulation.The surface charge dissipation rate and surface conductivity are promoted by about 1.37 and 9.45 times,respectively.Simulation and experimental results show that this all-organic modification coating has a smaller electron affinity potential compared with PS.The decrease of electron affinity potential may result in accelerated surface charge decay of PS,which has never been involved in previous works.Moreover,this coating also has good reliability in a repeated surface flashover.This facile and large-scale approach brings up a novel idea for surface charge regulation and the manufacture of advanced dielectric polymers.

Oil-soluble polymer brushes-functionalized nanoMOFs for highly efficient friction and wear reduction

Nanomaterials as lubricating oil additives have attracted significant attention because of their designable composition and structure,suitable mechanical property,and tunable surface functionalities.However,the poor compatibility between nanomaterials and base oil limits their further applications.In this work,we demonstrated oil-soluble poly(lauryl methacrylate)(PLMA)brushes-grafted metal-organic frameworks nanoparticles(nanoMOFs)as lubricating oil additives that can achieve efficient friction reduction and anti-wear performance.Macroinitiators were synthesized by free-radical polymerization,which was coordinatively grafted onto the surface of the UiO-67 nanoparticles.Then,PLMA brushes were grown on the macroinitiator-modified UiO-67 by surface-initiated atom transfer radical polymerization,which greatly improved the lipophilic property of the UiO-67 nanoparticles and significantly enhanced the colloidal stability and long-term dispersity in both non-polar solvent and base oil.By adding UiO-67@PLMA nanoparticles into the 500 SN base oil,coefficient of friction and wear volume reductions of 45.3%and 75.5%were achieved due to their excellent mechanical properties and oil dispersibility.Moreover,the load-carrying capacity of 500 SN was greatly increased from 100 to 500 N by the UiO-67@PLMA additives,and their excellent tribological performance was demonstrated even at a high friction frequency of 65 Hz and high temperature of 120℃.Our work highlights oil-soluble polymer brushes-functionalized nanoMOFs for highly efficient lubricating additives.

A novel method to prepare SPR sensor chips based on photografting molecularly imprinted polymer

A novel method to prepare surface plasmon resonance（SPR） sensor chips based on grafted imprinted polymer is explored. Benzophenone photografting system is used to grow molecularly imprinted polymer（MIP） films from the modified surface of gold substrate.The surface morphology and thickness of MIP films were investigated by scanning electronic microscope（SEM）.The adsorption properties of sensor chip were studied by SPR spectroscopy.The results demonstrate that nano-MIP films can be constructed on the surface of gold substrate with the good adsorption of template molecules.

Selective modification of two-dimensional MoS_2 nanosheets by polymer grafting

As an emerging two-dimensional (2D) nanomaterial, single layer ora few layers of molybdenum disulfide (MoS_2) has drawn significant attention in the past decade. In the present work, we report a strategy in direct creating polymer brushes on MoS_2 surfaces via S—C bond in the presence of UV light. The modification of MoS_2 nanosheets can be achieved bilaterally or homolaterally by performing the UVgrafting polymerization on exfoliated MoS_2 nanosheets or a single layer of MoS_2 deposited on a silicon substrate. A series of vinyl monomers including methyl methacrylate (MMA), styrene (St) and 2-isopropenyl-2-oxazoline (IPOx) could be applied to this approach, leading to the formation of poly (methyl methacrylate) (PMMA), polystyrene (PS) and poly (2-isopropenyl-2-oxazoline) (PIPOx) brushes.AFM, IR, and XPS characterizations indicate the successful formation of homogeneous brush layers on MoS_2 surfaces. The polymer brushes modified MoS_2 may found potential applications in photo dynamic therapy and sensing technologies.

The Surface Modification of Tourmaline Powder with Triethoxyvinylsilane and Characterization

The surface modification of the tourmaline powder with triethoxyvinylsilane was studied to prepare the polymerizable organic tourmaline.The experimental results showed that the surface of modified tourmaline had the better hydrophobicity compared with unmodified tourmaline,when the mass ratio of triethoxyvinylsilane to tourmaline powder was 1∶5,and reacted at 60 ℃for 1.5hin the mixed-solvent of ethanol and distilled water(1∶5in volume ratio).The structure characterization results indicated that the vinylsiloxane was introduced into the surface of tourmaline powder to generate the polymerizable organic tourmaline,and the crystal structure of tourmaline had no change.

Performances of biological aerated filter employing hollow fiber membrane segments of surface-improved poly(sulfone) as biofilm carriers

Using the surface of poly （sulfone） hollow fiber membrane segments as grafted layer, the hydrophilic acrylamide chain was grafted on by UV-photoinduced grafting polymerization. The gained improvement of surface wettability for the modified membrane was tested by measuring the contact-angle as well as FTIR spectra. Then correlation between the hydrophilic ability of support material and the biofilm adherence ability was demonstrated by comparing the pollutant removal rates from urban wastewater via two identical lab-scale up-flow biological aerated filters, one employed the surface wettability modified poly （sulfone） hollow fiber membrane segment as biofilm carder and the other employed unmodified membrane segment as biofilm carder. The experimental results showed that under the conditions of influent flux 5 L/h, hydraulic retention time 9 h and gas to liquid ratio （G/L） 10： 1, the removal rates of chemical oxygen demand （COD） and ammonium nitrogen （NH4^＋-N） for the modified packing filter and the unmodified packing filter was averaged at 83.64% and 96.25%, respectively, with the former filter being 5%-20% more than the latter. The effluent concentration of COD, NH4^＋-N and turbidity for the modified packing filter was 25.25 mg/L, 2 mg/L and 8 NTU, respectively. Moreover, the ammonium nitrogen removal performance of the filter packing the modified PSF was compared with the other bioreactor packing of an efficient floating medium. The biomass test indicated that the modified membrane matrixes provided better specific adhesion （3310-5653 mg TSS/L support）, which gave a mean of 1000 mg TSS/L more than the unmodified membrane did. In addition, the phenomenon of simultaneous denitrification on the inner surface of the support and nitrification on the outer surface was found in this work.

The past,present,and future of piezoelectric fluoropolymers:Towards efficient and robust wearable nanogenerators

Polyvinylidene difluoride(PVDF)derivatives in metal/PVDF/metal(MPM)sandwich structures have been studied extensively since 1969.Cousin copolymers of the same family have been discovered with fascinating piezoelectric,pyroelectric,electrocaloric,and ferroelectric properties.Solution processing,flexibility,lightweight,and thermal stability make this class of materials complementary to inorganics.Thus,PVDF based polymers potentially compete with inorganic materials for a broad range of technologies such as energy generators,loudspeakers,coolers,and memories.However,the stable non-electroactiveα-phase and hydrophobic nature of PVDF are the main barriers for developoing high performing and robust MPM devices in electronic applications.In this review,we present an up-to-date overview on different methods to induce the electroactiveβ-phase and improve the adhesion strength with metals to ensure robust and durable MPM devices.We go through advantages and disadvantages of several methods and pinpoint future opportunities in this research area.A special attention is paid to wearable piezoelectric nanogenerators for energy harvesting from human body motion,where flexible PVDF derivatives are compared with rigid piezoelectric ceramics.While the piezoelectric coefficient of PVDF(d_(33)~24–34 pm/V)is one order lower than ceramic materials,novel co-polymers of PVDF display d_(33)>1000 pm/V upon bias.This shows promise to bring piezoelectrics to flexible and large-area applications such as smart textiles.We also discussed challenges to improve wearability,such as light weight,breathability,and flexibility.