Structure of polyethylene films containing copper nanoparticles

We have used IR spectroscopy to study the effect of Cu nanoparticles on the degree of crystallinity in nanostructured high-pressure polyethylene (PE) films. We have shown that for ∼1 mass % Cu in the polyethylene films, we observe the maximum degree of crystallinity. This is connected with commensurability between the nanoparticle sizes and the periodicity of the three-dimensional structure of the straightened polyethylene chains in its transitional phase. Dielectric measurements on the nanostructured polyethylene films are support for the features observed in the IR spectra for the systems under study. From the data obtained, we hypothesize that we can control degree of crystallinity of the polymer by varying the sizes of the nanoparticles and the type of polymer. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 408–410, May–June, 2006.     

溶液浇铸法制备氘代聚乙烯薄膜

 采用改进的溶液浇铸法,用氘代聚乙烯为原料,制备了厚度为100, 200, 400 μm的氘代聚乙烯薄膜。研究了溶液温度、干燥温度、真空加热温度及时间等因素对成膜性、薄膜均匀性和透明性的影响,确定了最佳工艺条件：溶液温度120～130 ℃,干燥温度80～100 ℃,加热温度120 ℃,加热时间1 h。3维视频显微镜和原子力显微镜表征结果表明:制备的薄膜透明性较好,厚度较均匀;薄膜表面起伏较小。     

Nanomechanical control of the activity of enzymes immobilized on single-domain magnetic nanoparticles

Analytical and numerical methods are used to analyze the main regularities of deformation of biologically active molecules caused by the nonthermal effect of low-frequency magnetic field on single-domain magnetic nanoparticles to the surfaces of which the macromolecules are chemically bound.     

Photothermally enhanced catalytic activity of partially aggregated gold nanoparticles

In the present study, a facile, rapid, and environmentally friendly method was used for the preparation of metal oxide nanoparticles in an ionic liquid medium. This technique involves mixing and heating the corresponding powder material (cadmium oxide, anatase, and hematite) and the selected ionic liquid (trihexyl(tetradecyl)phosphonium chloride, [P_6,6,6,14]Cl), without any other precursors or solvents. The confirmation of the existence of nanoparticles in the ionic liquid was carried out using UV?CVis absorption spectroscopy, and its concentration was determined by X-ray fluorescence. In order to analyze the shape and size distribution, transmission electron microscopy and a ZetaSizer (DLS technique) were used; finding out that the size of the hematite nanoparticles was 10?C55?nm. Nevertheless, for the cadmium oxide and the anatase nanoparticles, the size was between 2 and 15?nm. The composition of the prepared nanoparticles was studied by Raman spectroscopy. The structure of solids did not suffer any modification in their transformation to the nanoscale, as concluded from the X-ray powder diffraction analysis.     

Metal-polymer composite films based on polyacrylonitrile and silver nanoparticles. Preparation and properties

The structures consisting of silver nanoparticles and polyacrylonitrile (PAN) are synthesized by the photopolymerization method yielding a homogeneous dispersion and a small size spread of nanoinclusions in PAN matrices, which is observed in images of transmission electron microscopy. The optical properties of the nanocomposites are studied to depend upon conditions of their obtaining. The minimum in the transmission spectra in a wavelength region of 430 nm, which is attributed to the surface plasmon resonance of silver nanoparticles, is found. The absorption peaks in the infrared range are observed at ∼820 and ∼1110 cm⁻¹ for the silver nitrate (AgNO₃) and the photoinitiator, respectively.     

Nonrenewal statistics in the catalytic activity of enzyme molecules at mesoscopic concentrations

Recent fluorescence spectroscopy measurements of single-enzyme kinetics have shown that enzymatic turnovers form a renewal stochastic process in which the inverse of the mean waiting time between turnovers follows the Michaelis-Menten equation. We study enzyme kinetics at physiologically relevant mesoscopic concentrations using a master equation. From the exact solution of the master equation we find that the waiting times are neither independent nor identically distributed, implying that enzymatic turnovers form a nonrenewal stochastic process. The inverse of the mean waiting time shows strong departure from the Michaelis-Menten equation. The waiting times between consecutive turnovers are anticorrelated, where short intervals are more likely to be followed by long intervals and vice versa. Correlations persist beyond consecutive turnovers indicating that multiscale fluctuations govern enzyme kinetics.     

Investigation of metal nanoparticles produced by laser ablation and their catalytic activity

Polydiphenylsilylenemethylene (PDPhSM) thin films, which are difficult to fabricate by conventional methods because of their insolubility and high melting point, have been synthesized by using laser-ablated metal nanoparticles for the thermal ring-opening polymerization of 1,1,3,3-tetraphenyl-1,3-disilacyclobutane (TPDC) in this paper. TPDC was first evaporated on silicon substrates and then exposed to metal (Pt, Cu and Ag) nanoparticles deposition by laser ablation prior to heat treatment. The catalytic activity of Pt, Cu and Ag nanoparticles has been studied. The results showed that the mean diameter of Pt nanoparticles was the smallest, Cu nanoparticles the moderate and Ag nanoparticles the biggest, while the polymerization efficiency for Pt nanoparticles was the highest, Cu nanoparticles the moderate and Ag nanoparticles the lowest. In addition, the penetration behaviours of Pt, Cu and Ag nanoparticles into the TPDC monomer films during laser ablation were different due to the particle size or the chemical interaction between metal nanoparticles and TPDC molecules.     

Preparation and magnetic properties of hexagonal barium ferrite films using BaM nanoparticles

Barium ferrite (BaFe₁₂O₁₉—BaM) thick films have been synthesized using a spinning coating sol-gel process. The coating sol was formed from BaM powders dispersed in the BaM raw sol. XRD, SEM, EDX, vibrating sample magnetometer (VSM), and ac susceptometer, were employed to evaluate the structure, composition and magnetic properties of BaM thick films. The results indicated that a uniform and crack-free coating of BaM with ∼15 μm thickness can be produced with good deal of consistency. The perpendicular and in-plane coercivity had the same value of 5 kOe. The high coercivity is attributed to the magnetocrystalline anisotropy and grain size of the sintered BaM layer. Effective magnetic susceptibility in all measurements have linear variation with increasing dc field.     

Preparation and bactericide activity of gallic acid stabilized gold nanoparticles

In this work, gold nanoparticles with three different sizes (13.7, 39.4, and 76.7 nm) were prepared using a simple aqueous method with gallic acid as the reducing and stabilizing agent, the different sizes were obtained varying some experimental parameters as the pH of the reaction and the amount of the gallic acid. The prepared nanoparticles were characterized using X-ray diffraction, transmission electron microscopy, dynamic light scattering, and UV–Vis spectroscopy. Samples were identified as elemental gold and present spherical morphology, a narrow size distribution and good stabilization according to TEM and DLS results. The antibacterial activity of this gallic acid stabilized gold nanoparticles against S. mutans (the etiologic agent of dental caries) was assessed using a microdilution method obtaining a minimum inhibitory concentration of 12.31, 12.31, and 49.25 μg/mL for 13.7, 39.4, and 76.7 nm gold nanoparticles, respectively. The antibacterial assay showed that gold nanoparticles prepared in this work present a bactericide activity by a synergistic action with gallic acid. The MIC found for this nanoparticles are much lower than those reported for mixtures of gold nanoparticles and antibiotics.     

Synthesis and characterization of vanadium nanoparticles on activated carbon and their catalytic activity in thiophene hydrodesulphurization

Vanadium nanoparticles (∼7 nm) stabilized on activated carbon were synthesized by the reduction of VCl₃·3THF with K[BEt₃H]. This material was characterized by inductive coupled plasma-atomic emission spectroscopy (ICP-AES), high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) analyses. The catalytic performance of the carbon-supported vanadium was studied using thiophene hydrodesulfurization (HDS) as model reaction at 300 °C and P = 1 atm. The catalytic activity of the vanadium carbide phase on the activated carbon carrier was more significant than that of the reference catalysts, alumina supported NiMoS. The method proposed for the synthesis of such a catalyst led to an excellent performance of the HDS process.     

Catalytic properties of gold nanoparticles immobilized on the surfaces of nanocarriers

Gold nanoparticles are immobilized in the hydrophilic coronas of spherical micelle carriers for high catalytic activity. The micelle is formed by self-assembly of block copolymer, polystyrene-b-poly (acrylic acid), in basic aqueous solution (pH 10) and has a polystyrene core and a poly (acrylic acid) corona. The gold nanoparticles are anchored into the poly (acrylic acid) corona by in situ reduction of the mixture of HAuCl₄ and micelle with NaBH₄. The sizes of the gold nanoparticles can be adjusted by changing the content of the HAuCl₄. In the process of catalyzing p-nitrophenol to p-aminophenol, the reaction shows one-order kinetics, furthermore, the reaction rate increases with the concentration of composites as well as reaction temperature. Comparing the composites with polystyrene as core and poly (4-vinylpyridine)/Au as corona, the catalytic activity of the present composites is higher, which is ascribed to their hydrophilic corona structure.     

Substrate effect on the melting temperature of thin polyethylene films

Strong dependence of the crystal orientation, morphology, and melting temperature (Tm) on the substrate is observed in the semicrystalline polyethylene thin films. The Tm decreases with the film thickness decrease when the film is thinner than a certain critical thickness, and the magnitude of the depression increases with increasing surface interaction. We attribute the large Tm depression to the decrease in the overall free energy on melting, which is caused by the substrate attraction force to the chains that competes against the interchain force which drives the chains to crystallization.     

表面修饰碳纳米管/二氧化钛复合光催化剂制备及催化活性研究

采用溶胶-凝胶法在聚乙烯吡咯烷酮(PVP)修饰的碳纳米管表面均匀沉积纳米级二氧化钛粒子制得复合光催化剂。采用透射电子显微镜(TEM)、X射线衍射仪(XRD)、紫外-可见吸收光谱仪(UV-Vis)和X射线光电子能谱仪(XPS)等手段对复合光催化剂进行表征。结果表明,二氧化钛粒子是呈球形、团聚,随机沉积在未修饰碳纳米管任意表面,甚至部分碳纳米管表面是完全裸露的。经PVP修饰后的碳纳米管,二氧化钛纳米粒子均匀沉积在碳纳米管表面,二氧化钛为纯锐钛矿晶体结构,没有金红石和板钛矿相。表面修饰碳纳米管/二氧化钛复合光催化剂在紫外光照射下降解亚甲基蓝,相比纯的二氧化钛和碳纳米管/二氧化钛复合光催化剂,具有非常高的催化活性。     

Surface and interface dipoles on catalytic metal films

The work function changes introduced by hydrogen on the surface and at the metal-support interface of a thin Pd-film were studied by simultaneous Kelvin probe and C(V)-measurements. It is demonstrated how these techniques can be used at atmospheric pressures to yield information about catalytic metals and on chemical kinetics on the metal surface. The main purpose of the communication is to point out the correlation between the surface and interface dipoles on catalytic metal films. Furthermore since the interface dipole is only created by hydrogen atoms it is shown how this can be used in a more complex situation to independently monitor the hydrogen content of the metal films.     

Laser-induced fluorescence decays of polyethylene films

The fluorescence lifetime of photo-oxidative emission at 360 nm becomes shorter when stabilizer is added to polyethylene film. A broad emission band at 450 nm is attributed to the emission from a charge transfer complex. The preliminary results show that the quenching of photo-oxidative emission and the fluorescence intensity decay can be used to evaluate the extent of photo-stability of polyethylene films.     

A method for studying catalytic reactions based on chemiemission of electrons

It was found that, if the energy released in the formation of product molecules in a heterogeneous reaction was smaller than the work function of the surface, the current density of the chemiemission of electrons from the surface of any semiconductor satisfied the condition j ≈ Bexp(βE), where B and β are coefficients and E is the electric field in the semiconductor surface plane. A mathematical model describing the transfer of hot metal electrons excited in a catalytic reaction through the metal-gas interphase boundary was studied. The parameters of the system at which a study of the distribution of catalytic centers over the surface of a metal or semiconductor by the scanning tip method on the basis of the chemiemission of electrons stimulated by an electric field was possible (resolution δr ∼ 10⁻⁸–10⁻⁷ m) were determined. Theoretical results corresponded to the experimental data obtained using weak electric fields (0 < E < 5 × 10⁶ V/m) for the heterogeneous recombination of hydrogen atoms on the surface of calcium, titanium, and n-type silicon.     

Study of the composite based on iron-containing nanoparticles dispersed in the polyethylene matrix

A composite representing a system of iron-based nanoparticles about 5 nm in size embedded in a high-pressure polyethylene matrix has been studied. The technology of preparation of this material has been described. The transmission electron microscopy, X-ray powder diffraction, and nuclear gamma-resonance spectroscopy data presented have been used to establish the volumes of the metal and oxide phases of a nanoparticle and the composition of its oxide shell.     

Effect of substrate interactions on the melting behavior of thin polyethylene films

Polymer films have been known to change their physical properties when film thickness is decreased below a certain value. The cause of this phenomenon is still unclear but it has been suggested that interactions and/or chain free-volume changes at the surface of the films are largely responsible for this behavior. In this paper, the effect of substrate interactions on the behavior of polymer thin films is evaluated quantitatively. The infrared spectra of nanothin polyethylene (PE) films were recorded as a function of temperature and amount of substrate covering the surface of the film. The evolution of specific bands in the CH₂ rocking region of the spectra was used to determine the melting temperature (T _m ) of the material. Results show different variations in T _m depending on the nature of the substrate, indicating that interactions dominate free-volume considerations in PE thin films. By varying the amount of surface coverage, a quantitative estimate of the heat of interaction was determined, which confirmed the importance of surface interactions.     

On the molecular structure of thin molten polyethylene films

Observations by transmission electron microscopy and electron diffraction suggesting that thin molten polyethylene films have a smectic liquid crystal structure consisting of layers of folded molecules are reported. The thickness of each layer is observed to be about 400 to 500 Å.