Electrochemical detector with a 20 nl volume for micro-columns liquid chromatography

Summary A flow-through two electrode wall-jet cell with a platinum measuring electrode and a cell volume of 20 nl has been designed and evaluated. It has been used to detect phenols by reversed phase liquid chromatography using short micro bore columns. The linear dynamic range between the measured current and the concentration is greater than 10³ (1.5×10^–7–5×10^–4 mol/l) and the minimum analyzable amount was found to be 10 pg for pyrocatechol. A negligible broadening in the detector permits the use of micro columns down to 0.5 mm internal diameter, packed with 5 m particles, without any substantial distortion of eluted zones.Presented at the 14th International Symposium on Chromatography London, September, 1982     

Prediction of interaction between small molecule and enzyme using AdaBoost

The knowledge of whether one enzyme can interact with a small molecule is essential for understanding the molecular and cellular functions of organisms. In this paper, we introduce a classifier to predict the small molecule– enzyme interaction, i.e., whether they can interact with each other. Small molecules are represented by their chemical functional groups, and enzymes are represented by their biochemical and physicochemical properties, resulting in a total of 160 features. These features are input into the AdaBoost classifier, which is known to have good generalization ability to predict interaction. As a result, the overall prediction accuracy, tested by tenfold cross-validation and independent sets, is 81.76% and 83.35%, respectively, suggesting that this strategy is effective. In this research, we typically choose interactions between small molecules and enzymes involved in metabolism to ultimately improve further understanding of metabolic pathways. An online predictor developed by this research is available at . Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Effect of hydrostatic pressure on self-diffusion in metal nanoparticles

The thermodynamics approach has been developed to describe the self-diffusion in nano-sized solids. It has been established that identical homologous temperatures of metal nanoparticles with their fixed characteristic size give the identical coefficients of diffusion under different pressures. The dependence of the activation enthalpy of diffusion on pressure and on the characteristic size of nanoparticles is first obtained.     

Tracks of 18·56 MeV/u 40Ar ions in Lexan polycarbonate detector

Latent damage tracks of energetic⁴⁰Ar ions (18·56 MeV/u) have been recorded in Lexan polycarbonate detector. Bulk and track-etch parameters are evaluated under successive chemical etching. Our results show a linear correlation between the measured track-etch rate along the track and the corresponding total energy-loss rate and predict a threshold value of 5·0 MeV mg⁻¹ cm² for track registration. Maximum etchable track lengths of⁴⁰Ar ions as a function of energies have also been measured and compared with three different sets of theoretical ranges.     

Study of activation parameters and NMR spin-lattice relaxation time in some substituted amines

The present communication reports the experimental values of NMR spin-lattice relaxation time (T₁) and dielectric relaxation time (τ) of piperidine, pyrrole, pyridine, diethylamine, triethylamine and pyrrolidine. The values of activation energy (ΔE_A) obtained using dielectric relaxation time, have been correlated with calculated values of ΔE_A obtained using Arrhenius equation of NMR relaxation time (T₁) for pyridine, diethylamine and pyrrole. Authors have also established a correlation between the experimental values of NMR spin-relaxation time (T₁) with its calculated values obtained using different equations of dielectric relaxation time (τ).     

Ultrasonic characterization of heavy metal TeO2–WO3–PbO glasses below room temperature

The longitudinal ultrasonic attenuation measurements have been made using pulse echo method at fundamental frequencies of 2, 4, 6 and 8 MHz in 20WO₃–(80−x) TeO₂–xPbO ternary tellurite glasses (x=10, 12.5, 15, 17.5 and 20 mol%) in the temperature range 160–280 K. The results showed the presence of a broad peak which shifts to higher temperature with increasing frequency. The ultrasonic attenuation peaks suggest that the experimental behavior is controlled by thermally activated structural relaxations. The internal friction, acoustic activation energy, deformation potential, relaxation strength, number of loss centers and density of state have been calculated both as a function of temperature and PbO content. The acoustic activation energy was found to decrease from 0.156 to 0.135 eV with the increase of PbO content. The results showed that both the number of loss centers and their activation energy decrease with the atomic ring size. An increase in the density of state is observed with addition of PbO content at the same frequency in the whole range of temperature which is associated with structural units formed when PbO is added.     

A multichannel Raman spectrometry study of polyacetylene isomerization induced by laser irradiation

The multichannel Raman spectrometry has been used in the study of the isomerization reaction of an 80% cis PA film into a trans PA, using a laser beam for a double purpose. It is employed simultaneously as an activation agent inducing the isomerization reaction and the Raman diffusion. In each experience, the power of the laser beam Pⁱ(λ) was equivalent to the temperature. Twelve spectra have been recorded at different time periods tj = j·dt. The integrations of the Raman intensities related to two selected bands were numerically calculated.We also proposed an original method for the determination of the isomeric composition. A quantitative relationship between the equilibrium temperature and the laser beam power (in the range of laser power: 30 < Pⁱ(λ) < 300 mW) has been found. An estimate number of isomerized molecules N₀ and then a correction factors f_cis and f_trans were also obtained.     

Structural and electronic properties of V, Nb and Ta nanoclusters by tight-binding molecular dynamics simulations

We present tight-binding molecular dynamics (TBMD) calculations on V, Nb and Ta nanoclusters with N = 15, 65, 175 and 369 atoms. We found that rhombic dodecahedra are energetically favoured over rhombic hexahedra and icosahedra, with V forming the most compact cluster with the gyration radius increasing with the cluster size. In addition, from the calculated electronic density of states we found that the cluster size plays an important role in the HOMO-LUMO gap and that an increase in cluster size results in enhancement of the electronic density around the Fermi level. Furthermore, we found that the small clusters (N = 15, 65) exhibit energy gap that persists even at 900 K. These findings originate from charge transfer occurring between the inner and outer cluster atoms; interestingly, we found that in the small N = 15, 65 clusters electronic charge accumulates at each surface site at the expense of the inner cluster atoms, while in the larger clusters, N = 175 and 369, charge is gathered on the central particles of the cluster, suggesting different sub-surface character of the clusters. These findings are in agreement with available experimental and theoretical data and promise to offer important information for creating nanostructured materials with improved properties suitable for multiple technological applications.     

H2O2氧化苯一步羟基化制备苯酚连续流动反应体系

采用连续流动反应器研究了苯一步羟基化制备苯酚的反应. 利用载铁活性炭为催化剂,H₂O₂为氧化剂,乙腈为溶剂,得到苯酚收率为28.1%,选择为98%,基于铁计算的转化数为3 h^-1. 对催化剂进行N₂吸附、XRD、XPS、FTIR等表征发现,负载的Fe可能与活性炭表面羧基发生作用,形成了化学环境类似于乙酸铁的铁物种,该结构是催化反应的活性中心. 计算得出,反应的阿伦尼乌斯活化能为13.4 kJ/mol,苯和H₂O₂的反应级数分别为0.2和0.7,总反应级数约为1.