Proton diffusion in γ-manganese dioxide

Deconvolution of the electrolytic manganese dioxide (EMD) discharge curve has indicated the presence of a number of energetically different reduction processes. This has been used to determine the contribution of each reduction process to the total discharge. Using step potential electrochemical spectroscopy (SPECS), the i-t data were modelled as the sum of the discharge of the individual reduction processes. From this, A√ D for each reduction process as a function of degree of discharge was determined. The maximum A√ D values for each process ranged from 2.3×10⁻² to 4.0×10⁻⁴ cm³ s^−1/2 g⁻¹ values are consistent with previously reported values for A√ D, although in this case we have determined values for the entire compositional range.     

Fabrication and optical characterization of poly(2,5‐di‐n‐butoxyphenylene) nanofibril arrays

Anodic aluminum oxide (AAO) membrane can be used as template for the synthesized nanostructures. In this article, we have prepared the AAO membrane by using electrooxidation of aluminum substrate in phosphoric acid, and fabricated poly(2,5‐di‐n‐butoxyphenylene) (BuO–PPP) nanofibril arrays by oxidative coupling polymerization of 1,4‐di‐n‐butoxybenzene (DBB) within the pores of the AAO template membrane. The detailed molecular structure of the polymer nanofibrils was characterized by using infrared and ¹H nuclear magnetic resonance spectra, and estimated to consist of almost equal fractions of 1,4‐ and 1,3‐ linkages. We have used transmission electron microscopy, scanning electron microscopy, and atom force microscopy to confirm the morphologies and images of the AAO template membrane and the fabricated nanometer scale of BuO–PPP nanofibril arrays. The experimental results demonstrated that the pores of the AAO membrane were regular and uniform, and parallel each other, and the BuO–PPP chains in the narrowest template‐synthesized nanofibrils were oriented parallel to the porous axes of the AAO membrane and perpendicular to the surface of the aluminum substrate. The polymer chain orientation was partially responsible for the enhanced conductivity. The ultraviolet absorption spectrum of the BuO–PPP nanofibril arrays shown that the polymer contains a better extended π‐conjugation system along poly‐(p‐phenylene) backbone, which resulted in longer wavelength shift of the absorption band, the absorption maxima were located at 258 nm (E₁ absorption band) and 332 nm (E₂ absorption band), respectively. Photoluminescence spectrum of the BuO–PPP nanofibril arrays exhibited a blue emission. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 425–430, 2004     

碱体系中系列羟基苯基卟啉红外光谱和拉曼光谱性质研究

本文继续深入研究该体系中相关物质的红外光谱和拉曼光谱的性质.论文结果说明,在碱体系中,NaOH只与羟基苯基卟啉周边meso-位的羟基反应形成盐,这个性质与紫外可见光谱性质是一致的.同时这一结果也为研究卟啉与金属的相互作用提供了有益的理论支持.     

Characterization of self-assembled monolayers of iron and cobalt octaalkylthiosubstituted phthalocyanines and their use in nitrite electrocatalytic oxidation

Cobalt and iron phenylthiosubstituted phthalocyanines have been deposited on Au electrode surfaces through the self-assembled monolayer (SAM) technique. The so formed layers were studied using voltammetric and impedance techniques. These SAMs blocked a number of Faradic processes and electrocatalyzed the oxidation of nitrite. The electrocatalytic parameters of the cobalt and iron phenylthiosubstituted phthalocyanines deposited on Au electrodes in nitrite solution were studied. Nitrite overpotentials which are lower than ever reported were obtained in this work for the iron phenylthiosubstituted phthalocyanines with very high stability.     

Impedance spectroscopy study of hardened Portland cement paste

In this paper, the differential impedance analysis (DIA) has been applied to the study of the dielectric properties of hardened Portland cement paste. Two time constants are found in the impedance spectra obtained in the frequency region form 100 kHz to 15 MHz. One time constant has been attributed to the solid matrix and the other one to the liquid phase filling the pores. The effect of the cement paste-electrodes interface has been quantified using two different experimental set-ups. Measurements using direct contact between electrodes and cement paste have been compared with measurements using an air gap technique in which the specimen “floats” between the electrodes. The two referred time constants have been found in both types of measurements. The influence of drying on the dielectric parameters is also studied.     

Ion-dipole interactions between adsorbed CO and support cations in Pt/K-LTL

The adsorption of carbon monoxide on a non-acidic Pt/K-LTL catalyst has been studied by diffuse reflectance and transmission IR spectroscopy. The CO spectrum is strongly dependent on the experimental conditions. Adsorption on the small Pt clusters in the presence of water gives linear-CO bands between 2060 and 1990 cm^–1 and a bridging-CO band around 1800 cm^–1. In the absence of water, the linear bands are red shifted to about 1940 and 1720 cm^–1, respectively. The frequency shift is attributed to an ion-dipole interaction between adsorbed CO and support cations. The ion-dipole interaction is screened by the adsorbed water leading to a smaller red shift in the CO stretching frequency.     

Structural characterization of 1,2-polybutadiene by 13C-n.m.r. spectroscopy: 2. Sequence distribution of 1,2-unit in hydrogenated polybutadienes

The configurational sequences of 1,2-unit in a series of hydrogenated syndiotactic 1,2-polybutadienes were determined in relation to the sequence distribution of 1,2- and 1,4-units on the basis of the ¹³C-n.m.r. signal assignment of the methyl carbons. The observed triad distributions of 1,2- and 1,4-units and configurational distributions of the 1,2-unit are in good agreement with the calculated distributions from transition probabilities. The number average sequence lengths of the 1,2-unit and the 1,2-unit in the racemic addition are 5.7 to 8.0 and 4.1 to 5.4, respectively. From the extrapolation of the plot of the number average sequence length against the crystallinity of the starting 1,2-polybutadienes, the minimum sequence length for crystallization is estimated to be 3.7 for the 1,2-unit in the racemic addition.     

Thermal spraying of biomaterials

Osteoconductive hydroxyapatite coatings for metallic endoprostheses for hip and knee joint replacement provide a state-of-the-art template for enhanced in-growth of bone cells. However, the high temperature of the plasma jet leads to large scale dehydroxylation and decomposition of the starting powder. A model is being developed to explain the formation of chemically and mechanically inhomogeneous porous calcium phosphate coatings deposited by atmospheric plasma spraying onto titanium alloy substrates. In addition the biofunctionality is being discussed of titania bond coats and their influence on the in vivo performance of hydroxyapatite-titania duplex coating systems.