铈离子-氨基复合引发N-异丙基丙烯酰胺表面接枝聚合

将硅片用"Piranha"溶液浸蚀处理,使其表面富含羟基,然后用3-氨基丙基-三乙氧基硅烷（APTES）进行表面修饰,得到硅片表面APTES单分子层,利用APTES分子上的氨基与Ce⁴⁺组成复合引发聚合体系,引发N-异丙基丙烯酰胺（NIPAm）单体进行硅表面接枝聚合。采用表面接触角测定（CA）、X-射线光电子能谱分析（XPS）和原子力显微镜（AFM）分析对产物进行表征,结果表明约50nm厚度的聚N-异丙基丙烯酰胺薄膜能成功地接枝到硅片表面。     

Roughness-enhanced thermal-responsive surfaces by surface-initiated polymerization of polymer on ordered ZnO pore-array films

The correlation between stimuli-responsive wettability switching and surface morphology of poly(N-isopropylacrylamide) (PNIPAm)-modified ZnO pore-array surface is studied. PNIPAm is grafted to the ZnO pore-array surface by surface-initiated polymerization. The effects of thickness of the PNIPAm layer and surface morphology on the thermally responsive switching behavior of the PNIPAm-modified films were studied considering the influences 3D capillary effect (Wenzel's model) and air trapping effect (Cassie's model). The air trapping effect can be controlled by the pore size, amount of grafted PNIPAm polymer, and shape of the pore edge. The surface roughness and expanded pore edge with mushroom-like texture of S2 film amplify the thermally responsive wettability switching between hydrophilicity and hydrophobicity. When the pore structure is completely filled, the switching properties get lower. The thermally responsive switching behavior is enhanced with increasing molecular chain length of the PNIPAm. By controlling the ZnO pore-array structure and the amount of grafted PNIPAm layer, the S2 film shows excellent reversibility for more than 3 cycles and a quick transformation between hydrophilicity and hydrophobicity.     

Preparation and characterization of Mn-Zn ferrite/poly(N,N′-isopropyl acrylamide) core/shell nanocomposites via in-situ polymerization

A kind of thermosensitive core/shell nanoparticles Mn-Zn ferrite/poly N,N′-isopropylacrylamide is designed in this work. By using surface initiated reversible addition-fragmentation chain transfer (RAFT) polymerization, thermoresponsive poly(N,N′-isopropylacrylamide) (PNIPAAm) was successfully covalently grafted from ferrite core. The graft polymerization exhibited the characteristics of a controlled/“living” polymerization which demonstrated a well controlled molecular weight. The nanoparticles obtained were also characterized by FTIR and HRTEM. FTIR results confirmed the successful graft polymerization, whereas HRTEM observation showed clearly a contrast between an ordered crystalline core and a light amorphous polymeric coating. With combined magnetic and thermosensitive properties, it could potentially be used as an anticancer drug carrier in biomedical field.     

One-pot fabrication of magnetic nanocomposite microcapsules

Fe₂O₃ nanoparticles can self-assembly at liquid-liquid interfaces to form stable water-in-oil Pickering emulsions. Novel magnetic and thermo-sensitive microcapsules were one-pot fabricated by radical polymerization of N-isopropylacrylamide (NIPAm) at the aqueous phases of Pickering emulsions at 60 °C. The obtained PNIPAm was deposited from the water phases onto the interfaces of water-in-oil Pickering emulsions to form Fe₂O₃/PNIPAm nanocomposite shells because of its hydrophobicity at this reaction temperature. Pickering emulsion polymerization opens up a new route to fabricate a variety of hollow and hybrid microcapsules.     

Immobilization of chitosan gel with cross-linking reagent on PNIPAAm gel/PP nonwoven composites surface

This study was to immobilize chitosan (CS), which is a biodegradable and antibacterial polymer, on poly(N-isopropylacrylamide) (PNIPAAm) gel/polypropylene (PP) nonwoven composites surface for wound dressing applications. PP nonwoven has been extensively used due to its porosity, allowing ventilation, high surface area and excellent mechanical properties. However, the hydrophobic surface of PP nonwoven limits its applications; in this study, we used the plasma-activation treatment and subsequently UV-light graft polymerization of NIPAAm gel to improve its hydrophilicity. Chitosan was immobilized onto PNIPAAm gel/PP nonwoven composites surface using the cross-linking agent, glutaraldehyde (GA). This complex was characterized by scanning electron microscopy (SEM). The results indicated that the wettability of the composite was improved after plasma treatment and photo-induced graft polymerization and chitosan was successfully immobilized onto the surface of PNIPAAm gel/PP nonwoven composites through cross-linking process. Finally, the preliminary result shows that chitosan hydrogels displayed antibacterial ability to Escherichia coli and Staphylococcus aureus. The (3-(4, 5-dimethylthiazolyl-2)-2, 5-diphenyltetrazolium bromide) (MTT) method indicated that the porous chitosan sponge exhibited good biocompatibility to fibroblast cells.     

An amperometric uric acid biosensor based on Bis[sulfosuccinimidyl] suberate crosslinker/3-aminopropyltriethoxysilane surface modified ITO glass electrode

A label free, amperometric uric acid biosensor is described by immobilizing enzyme uricase through a self assembled monolayer (SAM) of 3-aminopropyltriethoxysilane (APTES) using a crosslinker, Bis[sulfosuccinimidyl]suberate (BS³) on an indium-tin-oxide (ITO) coated glass plate. The biosensor (uricase/BS³/APTES/ITO) was characterized by, scanning electron microscopy (SEM), atomic force microscopy (AFM) and electrochemical techniques. Chronoamperometric response was measured as a function of uric acid concentration in aqueous solution (pH 7.4). The biosensor shows a linear response over a concentration range of 0.05 to 0.58 mM with a sensitivity of 39.35 μA mM ^− 1. The response time is 50 s reaching to a 95% steady state current value and about 90% of enzyme activity is retained for about 7 weeks. These results indicate an efficient binding of enzyme with the crosslinker over the surface of APTES modified ITO glass plates, which leads to an improved sensitivity and shelf life of the biosensor.     

Synthesis and electrochemical characterization of myoglobin-antibody protein immobilized self-assembled gold nanoparticles on ITO-glass plate

We report a protein immobilized self-assembled monolayer (SAM) of gold nanoparticles (GNPs) on indium-tin-oxide (ITO) coated glass plate. The protein-antibody, Mb-Ab, was covalently immobilized over the self-assembly of GNPs through a mixed SAM of 11-mercapto undecanoic acid (MUA) and 3-mercapto propionic acid (MPA) via carbodiimide coupling reaction using N-(3-dimethylaminopropyl)-N′-ethyl carbodiimide (EDC) and N-hydroxy succinimide (NHS). The whole assembly was constructed on 0.25 cm² area of ITO-glass plate (Mb-Ab/MUA-MPA/GNPs/APTES/ITO-glass) and an impedimetric study was carried out for its application in myoglobin detection. This prototype assembly was characterized by scanning electron microscopy, atomic force microscopy and electrochemical techniques. The modified electrode showed an increased electron-transfer resistance on coupling with protein antigen, Mb-Ag, in the presence of a redox probe [Fe(CN)₆]^3−/4−. Its exhibits an electrochemical impedance response to protein myoglobin-antigen, Mb-Ag, concentration in a linear range from 0.01 μg to 1.65 μg mL⁻¹ with a lowest detection limit of 1.4 ng mL⁻¹.     

Preparation of thermosensitive gold nanoparticles by plasma pretreatment and UV grafted polymerization

This work is to develop an easy method of plasma treatment and graft polymerization to prepare thermosensitive gold nanoparticles. Gold nanoparticles (Nano-Au) were reduced by trisodium citrate combined with hydrogen tetrachloroaurate(III) tetrahydrate (chloroauric acid) and modified with 11-mercaptoundecanoic acid (MUA) by the self-assembly monolayers (SAM). The surface graft polymerization of N-isopropylacrylamide (NIPAAm) was carried out by two steps, using O₂ plasma pretreatment of the surface on MUA SAM modified Nano-Au to form the peroxide groups on Nano-Au(MUA), and then subsequently using UV light to induce grafting with thermosensitive polymer. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) were used to direct investigation of the particle size and morphology in situ. The diameters of the gold nanoparticles measured from the TEM images are in good agreement with data measured at room temperature which is about 15 nm. The thermosensitive gold nanoparticles were characterized by chemical structure of surface (ESCA) and Fourier-transform infrared spectroscopy (FTIR). ESCA result suggests that plasma treatments can be employed to generate peroxides on the Nano-Au(MUA) for the subsequent UV graft polymerization of PNIPAAm.     

Cell attachment/detachment behavior on poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide)-based microgel films: the effect of microgel structure and swelling ratio

Microgels are cross-linked soft particles with a three-dimensional network structure that are swollen in a good solvent. Poly(N-isopropylacrylamide) (pNIPAAm)-based microgels have attracted great attentions for their temperature responsive property, particularly in recent years, pNIPAAm-based microgel films were utilized as a new kind of thermoresponsive surface to tune cell attachment/detachment behavior via temperature stimuli. However, some results are not consistent, for example, different polymerization conditions may bring out different results even for pure pNIPAAm microgel. This work aims to find out which factor plays the critical role for successful cell detachment on the pNIPAAm-based microgel films. The results unraveled that the structure and swelling ratio of the microgel rather than the film thickness plays a key role on the successful cells detachment, unlike linear pNIPAAm films in which the cells’ attach/detach property is only determined by the film thickness. For poly(N-isopropylacrylamide–styrene) microgel film, NIH3T3 cells could only detach when the microgel has a uniform structure and the volume dilatation of the microgel (20/38 °C) is larger than 4.     

Fabrication and characterization of thermoresponsive Fe3O4@PNIPAM hybrid nanomaterials by surface-initiated RAFT polymerization

A versatile route applied to the synthesis of thermoresponsive magnetite nanoparticles involved the formation of nanoparticles by coprecipitation of Fe²⁺/Fe³⁺ in the presence of an alkaline solution, followed by attachment of the reversible addition-fragmentation transfer (RAFT) agents onto the surface of the Fe₃O₄ nanoparticles via the electrostatic interactions, subsequent grafting from polymerization of N-isopropylacrylamide (NIPAM) through surface-initiated RAFT polymerization. The surface-initiated RAFT polymerization can be conducted in a well-controlled manner, as revealed by the linear kinetic plot, linear evolution of number-average molecular weights (M _n ) versus monomer conversions, and the relatively narrow molecular weight distributions (M _w /M _n ?相似文献   

Synthesis of thermoresponsive poly(N-isopropylacrylamide) brush on silicon wafer surface via atom transfer radical polymerization

Thermoresponsive poly(N-isopropylacrylamide) [poly(NIPAM)] brush on silicon wafer surface was prepared by combining the self-assembled monolayer of initiator and atom transfer radical polymerization (ATRP). The resulting polymer brush was characterized by in situ reflectance Fourier transform infrared spectroscopy, atomic force microscopy and ellipsometry techniques. Gel permeation chromatography determination of the number-average molecular weight and polydispersity index of the brush detached from the silicon wafer surface suggested that the surface-initiated ATRP method can provide relatively homogeneous polymer brush. Contact angle measurements exhibited a two-stage increase upon heating over the board temperature range 25-45 °C, which is in contrast to the fact that free poly(NIPAM) homopolymer in aqueous solution exhibits a phase transition at ca. 34 °C within a narrow temperature range. The first de-wetting transition takes place at 27 °C, which can be tentatively attributed to the n-cluster induced collapse of the inner region of poly(NIPAM) brush close to the silicon surface; the second de-wetting transition occurs at 38 °C, which can be attributed to the outer region of poly(NIPAM) brush, possessing much lower chain density compared to that of the inner part.     

The pH-induced thermosensitive poly (NIPAAm-<Emphasis Type="Italic">co</Emphasis>-AAc-<Emphasis Type="Italic">co</Emphasis>-HEMA)-<Emphasis Type="Italic">g</Emphasis>-PCL micelles used as a drug carrier

The macromonomer of 2-hydroxyethyl methyacrylate-caprolactone (HPCL) was synthesized by the ring-opening polymerization (ROP) of ε-caprolactone, which was initiated by 2-hydroxyethyl methyacrylate (HEMA). Then, the graft terpolymers of NIPAAm-co-AAc-co-HEMA-g-PCL (PHNA-CL) with varying mole ratios were subsequently synthesized by free radical polymerization of HEMA-PCL, N-isopropylacrylamide (NIPAAm) and acrylic acid (AAc). PHNA-CL was further self-assembled in different types of solvent. All the as-prepared copolymers were characterized by ¹H NMR, FT-IR and GPC. Micellization behaviors of micelles were studied by TEM and DLS. The micelles exhibited a phase transition temperature which can be readily adjusted by changing pH value of the micellization system. Micelle loaded with doxorubicin (DOX) was used to evaluate the drug release behavior. The release of DOX from micelles could be controlled by changing pH value and temperature in buffer solutions. The micelles are potentially to be used as a new anticancer drug carrier for intracellular delivery.     

Characterization of the substructure and properties of immobilized peptides on silicon surface

Immobilization of biomaterials onto solid supports is a means of functionalizing materials for applications such as biosensing. Biologically active peptide (A-A-A-A-G-G-G-E-R-G-D)¹ films were attached to N-hydroxy succinimide ester terminated self-assembled monolayers (SAM) which were covalently linked to a smooth silicon surface via Si–C bonds. The peptide films were characterized using electrical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy. The film structures were determined from examination of the capacitance and conductance dispersions with frequency. Analysis of XPS, EIS and FTIR after immobilization of the peptide film at pH 4 and 7 provided information on the extent of the activation and overall coupling efficiencies of the peptides to the N-hydroxy succinimide ester surface. The resulting film structure was markedly altered by attachment of the peptide at pH 4.     

Interfacial construction of gold nanoshells on 3-aminopropyl triethoxysilane modified ITO electrode surface for studying cytochrome b562 electrochemistry

An interface of gold nanoshells (GNSs) was constructed on the surface of the 3-aminopropyl triethoxysilane (APTES) modified ITO glass substrates by a simple self-assemble method to form the GNSs-coated ITO electrode. UV-vis spectroscopy, scanning electron microscopy (SEM), and cyclic voltammetry were used to characterize the GNSs interface architectures. SEM and UV-vis spectroscopy showed that an interconnected and stable GNSs interface was formed on the APTES modified ITO glass substrate. The cytochrome b562 (Cyt b562) was selected to observe electron transfer reactions of redox protein at the GNSs-coated ITO electrodes. Quasi-reversible electrochemistry of Cyt b562 was obtained and its electrochemical behaviors were discussed.     

Formation of Ag nanoparticles within the thermosensitive hairy hybrid particles

Herein we report on the production of composite core-shell particles, which are actually self-assembly of poly (N-isopropylacrylamide)-based amphiphilic block copolymers as a template for metal-block copolymer nanocomposites formation. Organic-inorganic composites were prepared with Ag nanoparticles embedded within colloidal particles of an amphiphilic, thermally responsive polymer. To promote the incorporation of unaggregated Ag nanoparticles, temperature responsive microspheres of poly (N-isopropylacrylamide) (NIPAM) block with polystyrene were synthesized. Polyethyleneimine (PEI) could act as the linker between Ag ions (Ag nanoparticles) and poly (styrene-b-N-isopropylacrylamide) (PS-b-PNIPAM) colloids and the reducing agent in the formation of Ag nanoparticles. Transmission electron microscopy (TEM) measurements confirmed the nanostructures, ¹HNMR and FTIR characterized the components of the resulting nanoobjects. These stimuli-responsive hybrid microspheres will have potential applications in biomedical areas, such as tissue engineering and drug delivery.     

Effect of sublayer surface treatments on ZnO transparent conductive oxides using dc magnetron sputtering

Novel sublayer surface treatments were investigated to improve the conductivity of aluminum-doped zinc oxide (ZnO:Al) fabricated by using dc magnetron sputtering on a glass substrate. Introducing artificial minute flaws on the surface of glass substrates enhanced the crystallinity of ZnO:Al films and decreased the resistivity accompanying the increase of electron mobility. Combination of the surface treatment and sputter beam control, i.e., interruption of high-energy oxygen with shadow masks, further reduced the resistivity of the film to 3.7 × 10^− 4 Ω cm (thickness 70 nm).     

Fabrication of low resistivity tin-doped indium oxide films with high electron carrier densities by a plasma sputtering method

Tin-doped indium oxide (ITO) films fabricated on glass substrates using a hot-cathode plasma sputtering method exhibited low resistivity of 9.7 × 10⁻⁵ Ω cm, which is due to a high carrier density of 2.1 × 10²¹ cm⁻³. The change in the number of carriers, N, as a function of film thickness d, strongly suggests that oxygen extraction in the initial stages of ITO film growth on the glass substrate surface, creates oxygen vacancies as an electron carrier source for improvement in the resistivity of the films.     

Characterization of temperature-sensitive membranes prepared from poly(vinylidene fluoride)-graft-poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide) copolymers obtained by atom transfer radical polymerization

In this paper, poly(vinylidene fluoride)-graft-poly(N-isopropylacrylamide) (PVDF-g-PNIPAAm) copolymers were synthesized directly via grafting temperature-sensitive material NIPAAm on PVDF by atom transfer radical polymerization (ATRP). The chemical structure of the graft copolymers was characterized by Fourier transform infrared (FTIR) and ¹H-NMR spectroscopy. The temperature-sensitive membranes were prepared from the PVDF-g-PNIPAAm copolymers by the immersion precipitation process of the phase inversion method. The chemical composition and pore structure of the PVDF-g-PNIPAAm membranes were studied by X-ray photoelectron spectroscopy (XPS) and an automatic mercury porosimeter, respectively. The effects of temperature on pure water flux and bovine serum albumen (BSA) rejection ratio of the membranes were also investigated. The results showed that the grafted PNIPAAm chains tended to enrich on the surfaces of the membranes or the membrane pores during the membrane-forming process. Pore diameter and porosity of the copolymer membranes were larger than those of the pristine PVDF membranes. Also, the PVDF-g-PNIPAAm membranes could exhibit temperature-sensitive performance in water flux and BSA rejection measurements.     

Adsorption and electropolymerization of toluidine blue on the nanostructured octakis(hydridodimethylsiloxy)octasilsesquioxane surface

Toluidine blue O (TBO) was adsorbed on the octakis(hydridodimethylsiloxy)octasilsesquioxane (Q₈M₈^H) surface. The characterization of the precursor (Q₈M₈^H) and resulting materials obtained by the reaction of Q₈M₈^H and toluidine blue (CTBO) were defined using Fourier transform infrared spectra, nuclear magnetic resonance solid-state ¹³C and Si²⁹ magic angle spinning. The electrochemical polymerization in a glassy carbon electrode was verified by means of a film silsesquioxane formation (FCTBO) using cyclic voltammetry in a potential range of −0.5 to 1.3 V (vs. saturated calomel electrode (SCE)) in a Britton Robinson (B-R) buffer solution (pH 2.0). The cyclic voltammogram of the film exhibits two redox couples with a formal potential of −0.15 and −0.02 V (B-R buffer pH 5). The formal potential shifts linearly in the cathodic direction by increasing the pH solution with a slope of 71 and 57 mV per unit for the first and second couple, respectively. The film was electrochemically very stable.     

Synthesis and catalysis of Ag nanoparticles trapped into temperature-sensitive and conductive polymers

Poly(styrene-co-N-isopropylacrylamide)/poly(N-isopropylacrylamide-co-methacrylic acid)/polypyrrole-silver [P(St-NIPAM)/P(NIPAM-co-MAA)/PPy-Ag] composite microgels were synthesized via a one-step redox polymerization of silver ammonia ions and pyrrole monomer at room temperature, using the core–shell P(St-NIPAM)/P(NIPAM-co-MAA) thermo-sensitive polymer microgels as templates. The structure, component, and properties of the as-prepared composite microgels have been characterized by transmission electron microscope, Fourier-transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, and UV–Vis spectrophotometer. The results indicate that the size and the dispersity of the formed PPy-Ag nanocomposite particles can be regulated by adjusting the initial concentration of the precursors. The catalytic activity for the reduction of 4-nitrophenol was regulated by varying the environment temperature. Meanwhile, the higher catalytic activity is contributed to the electron transfer from the conductive polymer PPy to the Ag nanoparticles in the polymer material matrix.