Synthesis and micromechanical properties of flexible, self-supporting polymer-SiO2 nanofilms

Large-scale, self-supporting ultrathin films composed of an elastomeric polyacrylate network interpenetrated by a silica (SiO2) network were synthesized and characterized. The organic network was first photopolymerized and the silica structure was subsequently developed in situ in the preformed organic gel. Composition and morphology of the hybrid interpenetrated network (IPN) nanofilms were characterized by infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy and compared with the case of zirconia (ZrO2) hybrid IPN reported earlier. Young modulus, ultimate tensile strength, and ultimate tensile elongation were determined for different organic/inorganic molar ratios and give some insights on how the composition of the nanofilms influence their robustness and self-supporting properties.     

Labeled magnetic nanoparticles assembly on polypyrrole film for biosensor applications

In recent years, conducting polymers combined with metallic nanoparticles have been paid more attention due to their potential applications in microelectronics, microsystems, optical sensors and photoelectronic chemistry. The work presented in this paper describes the preparation and characterization of a nanocomposite composed by a thin polypyrrole (PPy) film covered with an assembly of magnetic nanoparticles (NPs). The magnetic particles were immobilized on PPy films under appropriate magnetic field in order to control their organization on the PPy film and finally to improve the sensitivity of the system in potential sensing applications. The electrical properties and morphology of the resulting PPy film and the PPy film/NPs composite were characterized with cyclic voltammetry, impedance spectroscopy (IS), scanning electron microscopy (SEM), atomic force microscopy (AFM) and infra-red spectroscopy (IR). By using streptavidin labeled magnetic particles it was possible to functionalize the NPs assembly with biotin-Fab fragment K47 antibody. The designed biosensor had been successfully applied in rapid, simple, and accurate measurements of atrazine concentrations, with a significantly low detection limit of 5 ng/ml.     

Supported particle track etched polyimide membranes: a grazing incidence small-angle X-ray scattering study

Particle track etched polyimide membranes on silicon substrates covered with a native oxide layer are investigated. Preparation steps similar to the common classical particle track etched membrane production, giving rise to free-standing membranes, are successfully applied to the supported membranes. Polyimide films are used as a starting material for a template preparation based on high energy ion irradiation. The film/membrane structure is probed at different length scales by grazing incidence small-angle X-ray scattering at each individual preparation step. In addition, characterization with atomic force microscopy, variable-angle spectroscopic ellipsometry, Fourier transform infrared transmission, and attenuated total reflection spectroscopy is performed. An amount of 6 +/- 1 vol % pores inside the polyimide film is detected. The pores are oriented perpendicular to the substrate surface and have a conical shape, yielding a slightly reduced pore size at the substrate/film interface.     

Preparation of chitosan nanoparticles using methacrylic acid

In this work the preparation of chitosan nanoparticle was investigated using methacrylic acid in different conditions and studied by particle size analyzer, zeta-potential, Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR) and transmission electron microscopy (TEM). The particle size was dependent on the chitosan concentration used during the preparation method. Nanoparticles with sizes as small as 60 nm were achieved, that can be extremely important for several applications. The nanoparticles solution was also pH-sensitive, due to swelling and aggregation of the nanoparticles. The nanoparticles obtained presented a very homogeneous morphology showing a quite uniform particles size distribution and a rather spherical shape.     

Surfactant-free miniemulsion polymerization as a simple synthetic route to a successful encapsulation of magnetite nanoparticles

Due to the existing interest in new hybrid particles in the colloidal range based on both magnetic and polymeric materials for applications in biotechnological fields, this work is focused on the preparation of magnetic polymer nanoparticles (MPNPs) by a single-step miniemulsion process developed to achieve better control of the morphology of the magnetic nanocomposite particles. MPNPs are prepared by surfactant-free miniemulsion polymerization using styrene (St) as a monomer, hexadecane (HD) as a hydrophobe, and potassium persulfate (KPS) as an initiator in the presence of oleic acid (OA)-modified magnetite nanoparticles. The effect of the type of cross-linker used [divinylbenzene (DVB) and bis[2-(methacryloyloxy)ethyl] phosphate (BMEP)] together with the effect of the amount of an aid stabilizer (dextran) on size, particle size distribution (PSD), and morphology of the hybrid nanoparticles synthesized is analyzed in detail. The mixture of different surface modifiers produces hybrid nanocolloids with various morphologies: from a typical core-shell composed by a magnetite core surrounded by a polymer shell to a homogeneously distributed morphology where the magnetite is uniformly distributed throughout the entire nanocomposite.     

Direct electrochemistry of hemoglobin and its biosensing for hydrogen peroxide on TiO2–polystyrene nanofilms

Nanofilms of titanium dioxide (TiO₂) nanoparticles that mediate the assembly of polystyrene (PS) nanoparticles for immobilizing hemoglobin (Hb) on carbon ionic liquid electrode have been developed. Fourier transform infrared spectroscopy shows that Hb retains its native structure in TiO₂–PS nanofilms. Scanning electron microscopy reveals that the nanofilms possess uniform morphology and Hb is immobilized on the surface of the nanofilms. Electrochemical investigation of the biosensor indicates that the direct electrochemistry of hemoglobin is realized on the nanofilms, and there is a formal potential of ?0.320 V in deaerated buffer solutions; the biosensor shows good electrocatalytic activity toward the reduction of hydrogen peroxide with a linear range from 0.5 to 640 μM, a detection limit of 0.2 μM (S/N = 3) and a sensitivity of 103 μA mM^?1. Thus, the nanofilms will have potential application in the design of novel electrochemical biosensors.     

Fluorescence-modified superparamagnetic nanoparticles: intracellular uptake and use in cellular imaging

This report describes the preparation and characterization of new magnetic fluorescent nanoparticles and our success in using them to label living cells. The bifunctional nanoparticles possess a magnetic oxide core composed of a dimercaptosuccinic acid (DMSA) ligand at the surface and a covalently attached fluorescent dye. The nanoparticles exhibited a high affinity for cells, which was demonstrated by fluorescence microscopy and magnetophoresis. Fluorescence microscopy was used to monitor the localization patterns of magnetic nanoparticles associated with cells. We observed two types of magnetic labeling: adsorption of the nanoparticles on the cell membrane (membranous fluorescence) and internalization of the nanoparticles inside the cell (intracellular vesicular fluorescence). After internalization, nanoparticles were confined inside endosomes, which are submicrometric vesicles of the endocytotic pathway. We demonstrated that endosome movement could be piloted inside the cell by external magnetic fields such that small fluorescent chains of magnetic endosomes were formed in the cell cytoplasm in the direction of the applied magnetic field. Finally, by measuring the critical cellular magnetic load (quantitated by magnetophoresis), we have demonstrated the potential of this new magneto-fluorescent nanoagent for medical use.     

Sterilizable gels from thermoresponsive block copolymer worms

Biocompatible hydrogels have many applications, ranging from contact lenses to tissue engineering scaffolds. In most cases, rigorous sterilization is essential. Herein we show that a biocompatible diblock copolymer forms wormlike micelles via polymerization-induced self-assembly in aqueous solution. At a copolymer concentration of 10.0 w/w %, interworm entanglements lead to the formation of a free-standing physical hydrogel at 21 °C. Gel dissolution occurs on cooling to 4 °C due to an unusual worm-to-sphere order-order transition, as confirmed by rheology, electron microscopy, variable temperature (1)H NMR spectroscopy, and scattering studies. Moreover, this thermo-reversible behavior allows the facile preparation of sterile gels, since ultrafiltration of the diblock copolymer nanoparticles in their low-viscosity spherical form at 4 °C efficiently removes micrometer-sized bacteria; regelation occurs at 21 °C as the copolymer chains regain their wormlike morphology. Biocompatibility tests indicate good cell viabilities for these worm gels, which suggest potential biomedical applications.     

Flexible free-standing films morphology characterization: PVA/silica polymer network dispersed cholesteric liquid crystals films by sol-gel method

A novel flexible free-standing films of polyvinyl alcohol (PVA)/silica polymer network dispersed cholesteric liquid crystals (CLC) have been prepared by the sol-gel process. In the hydrolysis of silicon alkoxides tetraethoxysilane (TEOS) processes, the silica having -OH with the -OH groups on PVA formed polymer networks with Si-O-C bonds by dehydration. The cholesteric liquid crystals were incorporated into the networks. The free-standing films were obtained by the spin-coating method. In order to improve the compatibility and microstructure of the cholesteric liquid crystals with PVA/silica polymer networks, the amphiphilic compound of hexadecyl trimethyl ammonium bromide (HDTMA) was introduced into the forming film solutions. Effects of the different ratios of raw materials on the structure of films were investigated. The microscopic morphology of free-standing films and the uniform dispersion of CLCs in the films have been characterized by polarizing optical microscopy (POM), the field emission scanning electron microscope (FESEM), Fourier transform infrared (FT-IR) spectrometer and atomic force microscope (AFM). The free-standing films exhibiting excellent CLC droplets dispersion, mechanical stability, and good flexibility could be useful for flexible displays, switchable optical elements and smart windows.     

ELECTROSYNTHESES OF FREE-STANDING POLY(THIOPHENE-3-ACETIC ACID) FILM IN MIXED ELECTROLYTES OF BORON TRIFLUORIDE DIETHYL ETHERATE AND TRIFLUOROACETIC ACID

High quality free-standing poly(thiophene-3-acetic acid)(PTAA),a water-soluble polythiophene derivative,was successfully electrosynthesized in boron trifluoride diethyl etherate(BFEE)+ 25%(by volume)trifluoroacetic acid(TFA)at lower potential(0.38 V versus Pt).The carboxyl group makes PTAA highly soluble in water,facilitating its potential application as a blue-light-emitting material.PTAA films with conductivity of 7 S cm"1 obtained from this medium showed better redox activity and thermal stability.The structure and morphology of the polymer were studied by UV-Vis,FT-IR, ~1H-NMR spectra and scanning electron microscopy,respectively.     

Fluorinating hexagonal boron nitride into diamond-like nanofilms with tunable band gap and ferromagnetism

Cubic boron nitride (c-BN) possesses a number of extreme properties rivaling or surpassing those of diamond. Especially, owing to the high chemical stability, c-BN is desired for fabricating electronic devices that can stand up to harsh environments. However, realization of c-BN-based functional devices is still a challenging task due largely to the subtlety in the preparation of high-quality c-BN films with uniform thickness and controllable properties. Here, we present a simple synthetic strategy by surface fluorination of few-layered hexagonal boron nitride (h-BN) sheets to produce thermodynamically favorable F-terminated c-BN nanofilms with an embedded N-N bond layer and strong inbuilt electric polarization. Due to these specific features, the fluorinated c-BN nanofilms have controllable band gap by thickness or inbuilt and applied electric fields. Especially, the produced nanofilms can be tuned into substantial ferromagnetism through electron doping within a reasonable level. The electron-doping-induced deformation ratio of the c-BN nanofilms is found to be 1 order of magnitude higher than those of carbon nanotubes and graphene. At sufficient high doping levels, the nanofilm can be cleaved peculiarly along the N-N bond layer into diamond-like BN films. As the proposed synthesis strategy of the fluorinated c-BN nanofilms is well within the reach of current technologies, our results represent an extremely cost-effective approach for producing high-quality c-BN nanofilms with tunable electronic, magnetic, and electromechanical properties for versatile applications.     

Microemulsion approach to neodymium, europium, and ytterbium oxide/hydroxide colloids--effects of precursors and preparation parameters on particle size and crystallinity

Colloids based on lanthanides or their oxides have a great potential in the areas of optical and magnetic materials. In this study the confined space of reverse micellar systems formed by water in cyclohexane was used to precipitate particles based on neodymium, europium, and ytterbium. The morphology and structural properties of the prepared colloids were determined by transmission electron microscopy, IR spectroscopy, and X-ray diffraction and absorption measurements. The size of the obtained systems as determined by dynamic light scattering ranged from a few nanometers to several hundreds of nanometers in diameter, depending on the reaction conditions. The employed surfactant was found to have a major influence on the particle size and morphology. In contrast to the ionic surfactants sodium dodecyl sulfate and cetyltrimethylammonium bromide, the nonionic surfactant Triton X-100 generally delivered very small and unagglomerated particles. The precursor counterion had a similar effect, depending on its ability to coordinate to the particle surface, and prevented particle growth and agglomeration. The influence of further parameters such as the pH of the aqueous starting solutions, the mixing methodology, and the preparation temperature was also investigated. Applying increased temperatures the particles exhibited a higher crystallinity, and at the same time the particle size was drastically increased.     

全同立构聚丁烯-1溶液浇铸膜直接生成晶型Ⅰ结构

作为一种半结品性的聚烯烃材料．全同立构聚丁烯-1(iPB-1)的结晶存在Ⅰ,Ⅱ．Ⅲ和Ⅰ’4种品型,其中,晶型Ⅰ和Ⅰ’是由3／1螺旋链堆砌的六方晶胞结构,晶型Ⅱ是由11／3螺旋构象链堆砌的四方晶胞结构,晶型Ⅱ则是由4/1螺旋链堆砌而成的正交品胞结构．通常溶液结晶得到品型Ⅲ和晶型Ⅰ’,在高压条件下从本体结品也可得到晶型．     

Ku-band EMI shielding effectiveness and dielectric properties of Polyaniline-Y2O3 composites

Electromagnetic interference (EMI) shielding has become a phenomenon of great concern and there is growing demand towards the synthesis of materials with better EMI shielding effectiveness (EMI SE). This work highlights the preparation of Polyaniline-Yttrium Oxide (PANI-Y₂O₃) composites for EMI shielding applications in the frequency range from 12.4 to 18 GHz (Ku-band). The structure and morphology of the composites were investigated by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). EMI SE, microwave absorption and reflection, dielectric properties of the composites are discussed in detail. All the computations were based on microwave scattering parameters measured by transmission line waveguide technique. The observed results show absorption dominant EMI shielding in these composites with EMI SE of ?19 to ?20 dB, which mainly depends on the dielectric loss of the composites. Through the results of our observations, we propose these composites to be potential materials for microwave absorption and EMI shielding applications.     

Fabrication and characterization of ultra-thin magnetic films for biomedical applications

Polymeric ultra-thin films, so called nanosheets, show peculiar properties making them potentially useful for several applications in biomedicine. Moreover, the possibility to functionalize these films by using different agents opens new and partially unexplored scenarios, including micro/nano sensing and actuation. This paper compares two different methods for the preparation of free-standing nanosheets, loaded with magnetic particles for no-contact manipulation in liquid environment. Morphology and functionalities of the two types of nanosheets have been characterized and compared. These magnetic nanosheets could find applications as free-standing carriers to be released and controlled in endoluminal surgery or as plasters with nanometric thickness to be delivered in situ on surgical incisions.     

二氧化锡/石墨烯柔性电极的制备及其在锂离子电池中的应用

采用简便的抽滤装置制备了三明治结构的不同粒径大小的二氧化锡(SnO_2)/石墨烯柔性薄膜电极,通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、原子力显微镜(AFM)、比表面积(BET)和电化学等测试技术手段对样品结构、形貌和电化学性能进行表征,研究了二氧化锡颗粒大小对复合电极电化学性能的影响。结果表明,当SnO_2纳米颗粒的粒径为6 nm时柔性复合电极表现出最优的电化学性能,在100 m A/g的电流密度下经过100次循环后,可逆比容量保持在555 m A·h/g,远高于纯SnO_2和粒径过大或过小的SnO_2/石墨烯复合电极。     

Local chemical composition of nanophase-separated polymer brushes

Using scattering scanning nearfield infrared microscopy (s-SNIM), we have imaged the nanoscale phase separation of mixed polystyrene-poly(methyl methacrylate) (PS-PMMA) brushes and investigated changes in the top layer as a function of solvent exposure. We deduce that the top-layer of the mixed brushes is composed primarily of PMMA after exposure to acetone, while after exposure to toluene this changes to PS. Access to simultaneously measured topographic and chemical information allows direct correlation of the chemical morphology of the sample with topographic information. Our results demonstrate the potential of s-SNIM for chemical mapping based on distinct infrared absorption properties of polymers with a high spatial resolution of 80 nm × 80 nm.     

Characterization of the morphology of co-extruded, thermoplastic/rubber multi-layer tapes

Tapes with alternating semi-crystalline thermoplastic/rubber layers with thicknesses varying from 100 nm up to several μm were prepared by multi-layer co-extrusion. The variation in layer thickness was obtained by varying the thermoplastic/rubber feed ratio. A systematic study on the use of various microscopy techniques to visualize the morphology of the layered systems is presented. The relatively large length scales and the sample preparation make optical microscopy (OM) unsuitable to study the morphology of the multi-layer tapes. Although excellent contrast between the thermoplastic and rubber layers can be obtained, the usually applied, relatively large magnifications limit the use of transmission electron microscopy (TEM) and atomic force microscopy (AFM) to small sample areas. The large range of applicable magnifications makes scanning electron microscopy (SEM) the most suitable technique to study the morphology of the multi-layer tapes. The sample preparation for SEM with a secondary electron (SE) detector is often based on the removal of one of the components, which may induce changes in the morphology. SEM with a back-scattered electron (BSE) detector is a very convenient method to study the morphology over a wide range of length scales, where the contrast between the different layers can be enhanced by chemical staining. Finally, the nucleation behavior (homogeneous versus heterogeneous) of the semi-crystalline layers, as probed by differential scanning calorimetry (DSC), provides valuable information on the layered morphology. The use of relatively straightforward DSC measurements shows a clear advantage with respect to the discussed microscopy techniques, since no sample preparation is required and relatively large samples can be studied, which are more representative for the bulk.     

Free-standing mesoporous carbon thin films with highly ordered pore architectures for nanodevices

We report for the first time the synthesis of free-standing mesoporous carbon films with highly ordered pore architecture by a simple coating-etching approach, which have an intact morphology with variable sizes as large as several square centimeters and a controllable thickness of 90 nm to ～3 μm. The mesoporous carbon films were first synthesized by coating a resol precursors/Pluronic copolymer solution on a preoxidized silicon wafer and forming highly ordered polymeric mesostructures based on organic-organic self-assembly, followed by carbonizing at 600 °C and finally etching of the native oxide layer between the carbon film and the silicon substrate. The mesostructure of this free-standing carbon film is confirmed to be an ordered face-centered orthorhombic Fmmm structure, distorted from the (110) oriented body-centered cubic Im3?m symmetry. The mesoporosity of the carbon films has been evaluated by nitrogen sorption, which shows a high specific BET surface area of 700 m(2)/g and large uniform mesopores of ～4.3 nm. Both mesostructures and pore sizes can be tuned by changing the block copolymer templates or the ratio of resol to template. These free-standing mesoporous carbon films with cracking-free uniform morphology can be transferred or bent on different surfaces, especially with the aid of the soft polymer layer transfer technique, thus allowing for a variety of potential applications in electrochemistry and biomolecule separation. As a proof of concept, an electrochemical supercapacitor device directly made by the mesoporous carbon thin films shows a capacitance of 136 F/g at 0.5 A/g. Moreover, a nanofilter based on the carbon films has shown an excellent size-selective filtration of cytochrome c and bovine serum albumin.     

Synthesis and stabilization of Prussian blue nanoparticles and application for sensors

Prussian blue (PB) nanoparticles were synthesized by two methods from FeCl2 and K3Fe(CN)6 and from FeCl3 and K3Fe(CN)6 based on the method published by Fiorito et al., and stabilized by different polymers like polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polyallylamine hydrochloride (PAH), polydiallyl-dimethyldiammonium chloride (PDDA) and polystyrene sulfonate (PSS). The effect of the monomer/Fe3+ ratio was studied regarding the average particle size and zeta-potential. The forming PB structure was checked by X-ray diffraction. The stabilization was successful for every applied polymer, but the average particle size significantly differs. Particle size distributions were determined by Malvern type nanosizer equipment and by transmission electron microscope (TEM) and zeta potential values were determined for the obtained stabile samples. The results revealed that by using FeCl2 and K3Fe(CN)6 for PB preparation particles with narrow size distribution and average diameter of 1.7 nm occurred but stabilization was necessary. By the other method the dispersion was stabile with 182 nm particles but the particle size exponentially decreased to 18 nm with increasing PVP concentration. Ultrathin nanofilms were prepared on glass support by the alternating layer-by-layer (LbL) method from PB particles and PAH. The morphology of the prepared films was investigated also by AFM. The films were immobilized on interdigitated microsensor electrodes (IME) and tested in sensing hydrogen peroxide and different acids like acetic acid, hydrochloric acid vapors.