一步法制备PNIPAAm-g-PAN/PSt载银复合微球及其抗菌性能研究

以AgNO3为金属源,通过乙醇将与聚N-异丙基丙烯酰胺接枝聚丙烯腈/聚苯乙烯（PNIPAAm-g-PAN/PSt）聚合物微球表面酰胺基团配位的银离子（Ag+）还原,一步法制备了PNIPAAm-g-PAN/PSt载银复合微球。通过傅立叶变换红外（FTIR）和紫外-可见光光谱表征发现,由Ag+还原所得的Ag纳米颗粒被成功地固载在PNIPAAm-g-PAN/PSt 微球上;用透射电子显微镜（TEM）对载银微球的大小和形态进行了表征;热重分析（TGA）结果表明,固载在微球表面的银纳米颗粒的含量（质量分数）为12%;抗菌实验结果表明,所制备的载银微球具有抗革兰氏阴性菌的活性。     

Reflective and conductive surface‐silvered polyimide films prepared by surface graft copolymerization and electroless plating

Argon plasma‐pretreated polyimide (PI) films were subjected to UV‐induced surface graft copolymerization with 4‐vinylpyridine(4VP) under atmospheric conditions. Electroless plating of silver was carried out effectively on the 4VP graft copolymerized PI (PI‐g‐P4VP) surface after PdCl₂ activation and in the absence of SnCl₂ sensitization (the Sn‐free process). The surface compositions of the modified PI films were studied by X‐ray photoelectron spectroscopy (XPS). XPS results showed that the PI‐g‐P4VP surface is ready for electroless deposition of silver via the Sn‐free process. The grafted 4VP layer with well‐preserved pyridine groups was used not only as the chemisorption sites for the palladium complexes (without the need for prior sensitization by SnCl₂) during the electroless plating of silver, but also as an adhesion promotion layer for the electrolessly deposited silver. The silver metallized PI films show high reflectivity and conductivity with a surface resistance of 1.5 Ω and a reflectivity of 91.3%, respectively. Copyright © 2007 John Wiley & Sons, Ltd.     

Angular-dependent metal-enhanced fluorescence from silver colloid-deposited films: opportunity for angular-ratiometric surface assays

We describe an exciting opportunity for Metal-Enhanced Fluorescence (MEF)-based surface assays using an angular-ratiometric approach to the observed enhanced emission from fluorophores in close proximity to silver colloids deposited on glass substrates. This approach utilizes the radiationless energy transfer (coupling) between the excited states of the fluorophore and the induced surface plasmons of the silver colloids, and the subsequent angular-dependent fluorescence emission from the fluorophore-silver colloid system. Since MEF is related to surface plasmons' ability to scatter light, angular-dependent light scattering from three different silvered surfaces and glass substrates were investigated using two common excitation angles, 45 and 90 degrees . The scattered light from silvered surfaces with a high loading was observed at wider angles on both sides of the glass substrates, while forward scattering (from the back of the glass) was dominant for the silvered surfaces with low loading, as explained by both Mie and Rayleigh theories. When silver colloids were placed between the fluorophore and glass interface, the coupled fluorescence emission through the higher refractive index glass (and in air), increased in an angular-dependent fashion, following closely the angular-dependent light scattering pattern of the silver colloids themselves. Similar observations for fluorescence emission from fluorophores deposited onto glass surfaces alone were made, but at much narrower angles on both sides of the fluorophore-glass interface and were simply explained by Lambert's cosine law. As the loading of silver on glass was increased, the enhanced fluorescence emission was observed at wider angles (towards 0 and 180 degrees ) at both sides of the silvered surfaces. Glass surfaces without silver colloids were used as control samples to demonstrate the benefits of MEF for enhancing fluorescence signatures in an elegant, angular-dependent fashion. Finally, the utility of the angular-dependent MEF phenomenon for intensity-based angular-ratiometric surface assays is demonstrated.     

Electronic and adsorption properties of Ce‐Ag layers

Silver has rarely been considered as the catalyst for CO oxidation, although it has been recognized to be very active in several partial oxidation reactions such as ethylene epoxidation and formaldehyde synthesis. It is generally believed that a metal support interaction plays an important role in catalytic processes. Therefore in our study, we examined electronic and adsorption properties of cerium deposited onto a polycrystalline silver substrate. Layers of approximately one monolayer of cerium deposited on a clean silver substrate were examined in situ using surface‐sensitive techniques—by XPS, ultraviolet photoelectron spectroscopy (UPS) and low energy ion scattering (LEIS). CO molecular adsorption was observed by UPS and LEIS; experimental results exhibited CO adsorption on Ce atoms sites. Oxygen adsorption on deposited layers led to a strong oxidation; stoichiometry of oxidized layers was given by amount of adsorbed oxygen and by temperature. Copyright © 2011 John Wiley & Sons, Ltd.     

Characterization and cytocompatibility of polydopamine on MAO‐HA coating supported on Mg‐Zn‐Ca alloy

Magnesium has been suggested as a potential biodegradable metal for the usage as orthopaedic implants. However, high degradation rate in physiological environment remains the biggest challenge, impeding wide clinical application of magnesium‐based biomaterials. In order to reduce its degradation rate and improve the biocompatibility, micro‐arc oxidation coating doped with HA particles (MAO‐HA) was applied as the inner coating, and polydopamine (PDA) film was synthesized by dopamine self‐polymerization as the outer coating. The microstructure evolution of the coating was characterized using scanning electron microscopy (SEM), atomic force microscope (AFM), X‐ray diffraction analyses (XRD), Fourier transform infrared spectroscopy (FT‐IR), and X‐ray photoelectron spectroscopy (XPS). The results showed that PDA film had covered the entire surface of MAO‐HA coating and the pore size of MAO‐HA coating decreased. The root mean square (RMS) roughness of PDA/MAO‐HA coatings was approximately 106.46 nm, which was closer to the optimum surface roughness for cellular attachment as compared with MAO‐HA coatings. Contact angle measurement indicated that the surface wettability had been transformed from hydrophobic to hydrophilic due to the introduction of PDA. The PDA/MAO‐HA coatings exhibited better corrosion resistance in vitro, with the self‐corrosion potential increasing by 150 mV and the corrosion current density decreasing from 2.09 × 10^?5 A/cm ² to 1.46 × 10^?6 A/cm ² . In hydrogen evolution tests, the corrosion rates of the samples coated with PDA/MAO‐HA and MAO‐HA were 4.40 and 5.95 mm/y, respectively. MTS assay test and cell‐surface interactions experiment demonstrated that PDA/MAO‐HA coatings exhibited good cellular compatibility and could promote the adhesion and proliferation of MC3T3‐E1 cells.     

Direct Ion Exchange Self‐Metallization: A Novel and Efficient Route for the Preparation of Double‐Surface‐Silvered Polyimide Films

Summary: Silvered polyimide films have been fabricated by direct ion exchange of a damp‐dry poly(amic acid) film with an aqueous silver solution such as silver nitrate. Thermal curing of the silver(I )‐containing films under tension leads to cycloimidization of the poly(amic acid) into polyimide with a concomitant silver(I ) reduction and aggregation at both film sides to give reflective and conductive double‐surface‐silvered polyimide films. The metallized films retain the essential properties of the parent polyimide.

Surface morphology of the prepared double‐surface‐silvered polyimide films.     

Grafting of regenerated cellulose membrane by surface‐initiated atom transfer radical polymerization and its pH‐resposive behavior

Regenerated cellulose (RC) membranes which have pH modulated permeability have been prepared by anchoring the hydroxyl groups on the membrane surface with 2‐bromoisobutyryl bromide, followed by grafting with acrylic acid (AA) using atom transfer radical polymerization (ATRP). The obtained membranes were analyzed by X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared attenuated total reflection spectrometer (ATR‐FTIR), scanning electron microscopy (SEM), TGA and the results showed that AA had been grafted onto the membrane surfaces successfully. Then the pH modulated permeability properties were tested by water flux measurement. All results show that the pH modulated permeability properties of a RC membrane can be obtained by surface‐initiated ATRP. Copyright © 2010 John Wiley & Sons, Ltd.     

Surface‐Independent and Oriented Immobilization of Antibody via One‐Step Polydopamine/Protein G Coating: Application to Influenza Virus Immunoassay

For the construction of high‐performance biosensor, it is important to interface bioreceptors with the sensor surface densely and in the optimal orientation. Herein, a simple surface modification method that can optimally immobilize antibodies onto various kinds of surfaces is reported. For the surface modification, a mixture of polydopamine (PDA) and protein G was employed. PDA is a representative mussel‐inspired polymer, and protein G is an immunoglobulin‐binding protein that enables an antibody to have an optimal orientation. The surface characteristics of PDA/Protein G mixture‐coated substrates are analyzed and the PDA/protein G ratio is optimized to maximize the antibody binding efficiency. Moreover, the antibody‐immobilized substrates are applied to the detection of influenza viruses with the naked eye, providing a detection limit of 2.9 × 10³ pfu mL^‐1. Importantly, the several substrates (glass, SiO₂, Si, Al₂O₃, polyethylene terephthalate, polyethylene, polypropylene, and paper) can be modified by simple incubation with the mixture of PDA/protein G, and then the anti‐influenza A H1N1 antibodies can be immobilized on the substrates successfully. Regardless of the substrate, the influenza viruses are detectable after the sandwich immunoreaction and silver enhancement procedure. It is anticipated that the developed PDA/protein G coating method will extend the range of applicable materials for biosensing.     

Functional membranes prepared by layer‐by‐layer assembly and its metal ions adsorption property

PVDF/(PEI‐C/PAA)_n functional membranes were prepared by layer‐by‐layer (LbL) assembly, and their heavy metal ions adsorption capability was investigated. The changes in the chemical compositions of membrane surfaces were determined by X‐ray photoelectron spectroscopy (XPS). XPS results show that the surface of the PVDF membrane can be alternatively functionalized by PEI‐C and PAA. The membrane surface hydrophilicity was evaluated through water contact angle measurement. Contact angle results show that the surface hydrophilicity of the membrane surface depends on the outermost deposited layer. Morphological changes of membrane surfaces were observed by scanning electron microscopy (SEM). The water fluxes for these membranes were elevated after modification. The performances of the PVDF/(PEI‐C/PAA)_n membranes on the adsorption of copper ions (Cu²⁺) from aqueous solutions were investigated by inductively coupled plasma (ICP). The results indicate that the PVDF/(PEI‐C/PAA)_n functional membranes show high copper ions adsorption ability. Copyright © 2010 John Wiley & Sons, Ltd.     

Characteristics of polypyrrole electrodeposited onto roughened substrates composed of gold–silver bimetallic nanoparticles

In this work, the characteristics of polypyrrole (PPy) films electrodeposited onto an electrochemically roughened gold substrate with bimetallic silver and gold nanoparticles were first investigated. First, a silver substrate was roughened by a triangular‐wave oxidation–reduction cycle (ORC) in an aqueous solution containing 0.1 M HCl. Subsequently, a gold substrate was roughened by a similar ORC treatment in this used solution. The results revealed that the surface of the roughened gold substrate demonstrated two different kinds of deposition domains because of the modification of silver nanoparticles. Encouragingly, some novel characteristics of PPy deposited onto this substrate were observed, in comparison with those on the roughened gold substrate without the modification of silver nanoparticles. They included a denser and more compact surface morphology, higher oxidation degree, increased conductivity, and improved surface‐enhanced Raman scattering. Furthermore, the nucleation and growth mechanism for PPy electropolymerization on this silver‐modified roughened gold substrate was distinguishable from that on the unmodified one. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2724–2731, 2006     

Tailoring Size and Coverage Density of Silver Nanoparticles on Monodispersed Polymer Spheres as Highly Sensitive SERS Substrates

Silver nanoparticles (AgNPs) were deposited onto the monodispersed carboxylic polystyrene (CPS) spheres by an improved in situ reduction method. The size and coverage density of the AgNPs on the surface of CPS spheres could be easily tailored by tuning the concentrations of carboxylic functional groups and silver precursor. The morphologies and structures of the resulting CPS/Ag hybrid particles were studied by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD), UV‐Vis‐NIR spectrometer and X‐ray photoelectron spectroscopy (XPS), etc. The surface enhanced Raman scattering (SERS) performances of the resulting uniform CPS/Ag hybrid particles were investigated using 4‐aminobenzenethiol (4‐ABT) as the probe molecule. The optimized CPS/Ag hybrid particles show high enhancement factor (EF) of 2.71×10⁷, low limit of detection (LOD) of 10^?10 m and good reproducibility with relative standard deviation (RSD) of 9.64 %. The good SERS improvement properties demonstrate these hybrid particles could be employed as simple and effective substrates in the SERS spectroscopy.     

Characterization of silver selenide thin films grown on Cr‐covered Si substrates

Thermal stability of silver selenide thin films formed from the solid‐state reaction of Ag‐Se diffusion couples on Si substrates covered with a thin Cr film, is investigated. Glancing angle X‐ray diffraction (GXRD), XPS, atomic force microscopy (AFM) and Rutherford backscattering spectrometry (RBS) are used to characterize the as‐deposited films and those annealed at 100, 200, 300, and 400 °C. The results reveal the formation of polycrystalline orthorhombic silver selenide films that remain stable without compositional change upon thermal annealing, in marked contrast to the agglomeration exhibited by silver selenide films deposited on Si without Cr film. The improvement in the thermal stability is attributed to compressive stress relief by a grainy morphology with large surface area, the formation of which is promoted by partially oxidized Cr adhesion film. Copyright © 2008 John Wiley & Sons, Ltd.     

Surface characterization of electrodeposited silver on activated carbon for bactericidal purposes

The use of an electrochemical reactor operated under different flow conditions to deposit silver from aqueous AgNO(3) solutions and tartaric acid as an organic additive on a commercial activated carbon with ultimate bactericidal applications in water purification processes is presented. The characterization of carbon/silver samples was studied by BET, FTIR, X-ray diffraction, XPS, and SEM techniques. The bactericidal activity of the carbon/silver samples was tested on drinking water samples inoculated with E. coli. A reduction of carbon surface area was detected and was caused by increased amounts of silver deposited on carbon samples. Adherent silver deposits were obtained on the carbon/silver samples. X-ray diffraction studies of carbon with electrodeposited silver showed two different preferential deposition planes, [111] and [220]. The FTIR results confirm the presence of carboxyl, phenolic, quinone, and ether surface groups. The XPS results suggest the formation of Ag(2)O and AgO surface species and confirm the reduction of silver to the metallic form. Antimicrobial activity toward E. coli indicated reductions by up to 7 orders of magnitude in the log CFU/mL in just 10 min contact time and for silver contents of 2.47 wt%.     

Antibacterial effect of silver nanoparticles deposited on corona‐treated polyester and polyamide fabrics

The possibility of using a corona treatment (electrical discharge at atmospheric pressure) for fiber surface activation, which can facilitate the loading of silver nanoparticles (NPs) from colloids onto the polyester (PES) and polyamide (PA) fabrics and thus improve their antibacterial properties, was studied. Bactericidal efficiency and its laundering durability on silver‐loaded fabrics for Gram‐positive bacterium Staphylococcus aureus and Gram‐negative bacterium Escherichia coli were evaluated. The fiber morphology after corona treatment and subsequent loading of silver NPs was followed by SEM. Corona‐treated fabrics loaded with silver NPs exhibited better antibacterial properties in comparison with untreated fabrics. In order to obtain acceptable laundering durability, it is necessary to use highly concentrated silver colloids. Copyright © 2008 John Wiley & Sons, Ltd.     

Nanostructured black cobalt coatings for solar absorbers

Nanocrystalline black cobalt electrically deposited onto a steel substrate from aqueous solution was investigated. The influence of electrolyte composition and operating parameters on the appearance and optical properties of the coat was studied. The deposition conditions that ensure the highest solar absorptance were optimized. The chemical composition of fabricated thin films before and after annealing at 400 °C was determined by energy dispersive X‐ray analysis (EDS) and XPS technique. The crystal structure analysis showed that the bulk composition of the films was mainly cobalt oxide. The surface analysis reveals that the topmost surface layers of the films are made of different cobalt compounds confirming the multivalence state of Co on the surface with an oxidation state of ≥ + 2. Scanning electron microscope (SEM) observation indicated that the surface morphology was changed from dendritic structure to lamellar at higher current density. The black cobalt film showed soft magnetic characteristicsand excellent optical properties to transform solar energy into thermal energy. Copyright © 2008 John Wiley & Sons, Ltd.     

Surface modification of titanium by using plasma‐induced graft‐polymerization

Plasma‐induced graft‐polymerization (PIGP) method was utilized in this study to improve corrosion behavior and biocompatibility of titanium (Ti) surface. Bioactive molecule polyacrylamide (PAM) was immobilized onto Ti surface by introducing silanederivatized spacer arms as an intermediary for the covalent linkage. Ti was firstly activated by O₂ plasma, and oxygen‐containing groups were introduced on its surface consequently. The intermediary mercapto silane spacer molecules were then covalently linked to the oxidated surface, followed by the covalent binding of PAM and the sulfhydryl‐terminal groups via PIGP. Surface analyses following modification process included water contact angles (CA), SEM, attenuated total reflection‐Fourier transform infrared spectroscopy (ATR‐FTIR), XPS and atomic force microscope (AFM). The results revealed the effectiveness of this method on immobilizing PAM to Ti surface, and the hydrophilicity of modified surface improved remarkably. In addition, potentiodynamic polarization and cellular proliferation tests were implemented to validate the enhanced corrosion‐resistance and biocompatibility of modified Ti surface, respectively. Copyright © 2011 John Wiley & Sons, Ltd.     

Polymer brushes grafted from graphene via bioinspired polydopamine chemistry and activators regenerated by electron transfer atom transfer radical polymerization

Polymer brushes decorated reduced GO (rGO) with advanced applications have been prepared by bioinspired polydopamine (PDA) chemistry integrated with activators regenerated by electron transfer atom transfer radical polymerization (ARGET‐ATRP) technique. First, rGO/PDA was obtained by the process for graphene oxide (GO) coated with a homogeneous bio‐adhesive PDA layer. Then the initiator 2‐bromoisobutyryl bromide (BIBB) was immobilized on the surface of PDA functionalized rGO. Finally, rGO/PDA‐Br was polymerized with N, N‐diethylaminoethyl methacrylate (DEAEMA) and glycidyl methacrylate (GMA) to obtain rGO/PDA‐g‐polymer brushes by ARGET‐ATRP process. The prepared rGO/PDA‐g‐PGMA brush would be subjected to further functionalization with ethylenediamine (EDA), which would impart the obtained products (rGO/PDA‐g‐PGMA‐NH₂) with good adsorption ability toward cationic dyes. The chemical structures and morphologies of the functionalized GO products have been characterized in detail by Fourier transform infrared spectroscopy (FTIR), X‐ray photoelectron spectroscopy (XPS), Raman spectroscopy, thermal gravimetric analysis (TGA), scanning electron microscope (SEM), transmission electron microscope(TEM), and atomic force microscopy (AFM). The distinctive pH‐responsive character of rGO/PDA‐g‐PDEAEMA and adsorption ability of rGO/PDA‐g‐PGMA‐NH₂ for cationic dyes have been explored by UV–vis spectrophotometer. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 689–698     

表面引发的原子转移自由基聚合法在聚偏二氟乙烯表面制备可控的聚甲基丙烯酸甲酯刷

采用表面引发的原子转移自由基聚合法(ATRP)在聚偏二氟乙烯(PVDF)表面制备结构可控的聚甲基丙烯酸甲酯刷。通过碱处理和紫外光照溴代的方法,将ATRP引入到PVDF表面; 然后采用ATRP法将甲基丙烯酸甲酯接枝到溴代的PVDF表面。采用傅里叶变换红外光谱和X-射线光电子能谱对改性前后PVDF表面的结构进行了表征。结果表明甲基丙烯酸甲酯成功地接枝到了PVDF表面。     

Characterization of Ce‐rich coating on carbon surface by immersing in an aqueous solution containing Ce ions

Surface modification of carbon fibers with Ce‐rich coating was investigated by scanning electron microscopy (SEM), and it is shown that a Ce‐rich coating can protect carbon fibers. After the carbon surface was scratched crosswise, self‐healing behavior of carbon surface with chemical immersion treatment from Ce salt solution was investigated at various immersion times. The Ce‐rich compounds deposited easily on the scratch sites, filling it with Ce‐rich compounds. Such self‐healing behavior enables the carbon surface to protect itself. X‐ray photoelectron spectroscopy (XPS) results indicate that Ce⁴⁺ was the dominant oxidation state for the Ce‐rich coating on the carbon surface. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis of polydopamine‐coated graphene–polymer nanocomposites via RAFT polymerization

Graphene‐polymer nanocomposites have significant potential in many applications such as photovoltaic devices, fuel cells, and sensors. Functionalization of graphene is an essential step in the synthesis of uniformly distributed graphene‐polymer nanocomposites, but often results in structural defects in the graphitic sp² carbon framework. To address this issue, we synthesized graphene oxide (GO) by oxidative exfoliation of graphite and then reduced it into graphene via self‐polymerization of dopamine (DA). The simultaneous reduction of GO into graphene, and polymerization and coating of polydopamine (PDA) on the reduced graphene oxide (RGO) surface were confirmed with XRD, UV–Vis, XPS, Raman, TGA, and FTIR. The degree of reduction of GO increased with increasing DA/GO ratio from 1/4 to 4/1 and/or with increasing temperature from room temperature to 60 °C. A RAFT agent, 2‐(dodecylthiocarbonothioylthio)?2‐methylpropionic acid, was linked onto the surface of the PDA/RGO, with a higher equivalence of RAFT agent in the reaction leading to a higher concentration of RAFT sites on the surface. Graphene‐poly(methyl methacrylate), graphene‐poly(tert‐butyl acrylate), and graphene‐poly(N‐isopropylacrylamide) nanocomposites were synthesized via RAFT polymerization, showing their characteristic solubility in several different solvents. This novel synthetic route was found facile and can be readily used for the rational design of graphene‐polymer nanocomposites, promoting their applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3941–3949