Thermal decomposition of model compound of algal biomass

This contribution investigates thermal decomposition of leucine, as a representative model compound for amino acids in algal biomass. We map out potential energy surface for a wide array of unimolecular and self-condensation reactions operating in the decomposition of leucine. Decarboxylation and dehydration of leucine ensues by eliminating CO₂ and –OH, respectively, from the –COOH group attached to the α-carbon. The molecular channel for deamination involves cleavage of NH₂ from α-carbon of leucine. The activation energies for direct elimination of CO₂, NH₃, and H₂O from a leucine molecule lie within 20.7 kJ/mol of each other. Activation energies for these decomposition pathways reside below the bond dissociation enthalpy of H–C(α) of 323.1 kJ/mol. The decarboxylation, deamination, and dehydration pathways, via radical-prompted pathways, systematically require lower energy barriers, in reference to closed-shell reaction corridors. Detailed computations at the CBS-QB3 level provide the Arrhenius rate parameters for the unimolecular and bimolecular reactions, and standard enthalpies of formation, standard entropies, and heat capacities for all the products and intermediates. A kinetic analysis of gas-phase reactions, within the context of a plug-flow reactor model, accounts qualitatively for the formation of major products observed experimentally in the thermal degradation of the condensed-phase leucine. Among notable N-containing species, the model predicts the prevailing of NH₃ over HCN and HNCO, in addition to corresponding appreciable concentrations of amines, imines, and nitriles. Our detailed kinetic investigation illustrates a negligible contribution of the self-condensation reactions of leucine in the gas phase.     

Crystal structure,thermal expansion and magnetic properties of Nd2Cu0.8Ge3 compound

A new ternary intermetallic compound, Nd₂Cu_0.8Ge₃, was synthesized and its crystal structure was determined by Rietveld refinement of X-ray powder diffraction data. The Nd₂Cu_0.8Ge₃ compound crystallizes in space group I4₁/amd (No. 141), with a tetragonal a-ThSi₂ structure type, and a=0.41783(2) nm, c=1.43689(9) nm, Z=2 and D_calc=7.466 g/cm³. Using the high temperature powder X-ray diffraction (HTXRD) technique, the lattice thermal expansion behavior of the compound was investigated in the temperature range of 298–648 K, and the result shows that its unit-cell parameters increased anisotropically when temperature increased. The magnetic susceptibility measured in the temperature range of 5–300 K indicated antiferromagnetic order of Nd₂Cu_0.8Ge₃ at low temperatures, and the magnetic susceptibility can be well described over the range of 50–300 K using Curie–Weiss law. The calculated effective magnetic moment (μ_eff) is 3.53 μ_B and dominated by the contribution of the Nd³⁺ ions.     

聚变实验堆真空室壳体成型残余应力分析

为了了解聚变实验堆真空室壳体表面残余应力的分布以及退火工艺对残余应力的影响，通过模拟分析和实验检测两种方式对不锈钢316LN冷压曲面和热压曲面残余应力进行研究，获得退火前后曲面表面残余应力的大小，得到冷压曲面和热压曲面残余应力的分布以及退火工艺对残余应力分布的影响。研究结果为分析成型工艺提供数据支撑，对中国聚变工程实验堆真空室的研究与制造具有重要意义。     

Eigenspace-based minimum variance beamformer combined with Wiener postfilter for medical ultrasound imaging

In this paper, a new beamformer which combines the eigenspace-based minimum variance (ESBMV) beamformer with the Wiener postfilter is proposed for medical ultrasound imaging. The primary goal of this work is to further improve the medical ultrasound imaging quality on the basis of the ESBMV beamformer. In this method, we optimize the ESBMV weights with a Wiener postfilter. With the optimization of the Wiener postfilter, the output power of the new beamformer becomes closer to the actual signal power at the imaging point than the ESBMV beamformer. Different from the ordinary Wiener postfilter, the output signal and noise power needed in calculating the Wiener postfilter are estimated respectively by the orthogonal signal subspace and noise subspace constructed from the eigenstructure of the sample covariance matrix.We demonstrate the performance of the new beamformer when resolving point scatterers and cyst phantom using both simulated data and experimental data and compare it with the delay-and-sum (DAS), the minimum variance (MV) and the ESBMV beamformer. We use the full width at half maximum (FWHM) and the peak-side-lobe level (PSL) to quantify the performance of imaging resolution and the contrast ratio (CR) to quantify the performance of imaging contrast. The FWHM of the new beamformer is only 15%, 50% and 50% of those of the DAS, MV and ESBMV beamformer, while the PSL is 127.2 dB, 115 dB and 60 dB lower. What is more, an improvement of 239.8%, 232.5% and 32.9% in CR using simulated data and an improvement of 814%, 1410.7% and 86.7% in CR using experimental data are achieved compared to the DAS, MV and ESBMV beamformer respectively. In addition, the effect of the sound speed error is investigated by artificially overestimating the speed used in calculating the propagation delay and the results show that the new beamformer provides better robustness against the sound speed errors. Therefore, the proposed beamformer offers a better performance than the DAS, MV and ESBMV beamformer, showing its potential in medical ultrasound imaging.     

Super‐heptazethrene

The challenging synthesis of a laterally extended heptazethrene molecule, the super‐heptazethrene derivative SHZ‐CF3 , is reported. This molecule was prepared using a strategy involving a multiple selective intramolecular Friedel–Crafts alkylation followed by oxidative dehydrogenation. Compound SHZ‐CF3 exhibits an open‐shell singlet diradical ground state with a much larger diradical character compared with the heptazethrene derivatives. An intermediate dibenzo‐terrylene SHZ‐2H was also obtained during the synthesis. This study provides a new synthetic method to access large‐size quinoidal polycyclic hydrocarbons with unique physical properties.     

配位化学课程中研究型教学模式探讨

In this paper, the implementation of research-oriented teaching mode in coordination chemistry was introduced, including the strategies, main contents and evaluation.     

Enantiomeric separation of 2‐arylpropionic acid nonsteroidal anti‐inflammatory drugs by HPLC with hydroxypropyl‐β‐cyclodextrin as chiral mobile phase additive

The enantio‐separations of eight 2‐arylpropionic acid nonsteroidal anti‐inflammatory drugs (2‐APA NSAIDs) were established using reversed‐phase high‐performance liquid chromatography with hydroxypropyl‐β‐cyclodextrin (HP‐β‐CD) as chiral mobile phase additive for studying the stereoselective skin permeation of suprofen, ketoprofen, naproxen, indoprofen, fenoprofen, furbiprofen, ibuprofen and carprofen. The effects of the mobile phase composition, concentration of HP‐β‐CD and column temperature on retention and enantioselective separation were investigated. With 2‐APA NSAIDs as acidic analytes, the retention times and resolutions of the enantiomers were strongly related to the pH of the mobile phase. In addition, both the concentration of HP‐β‐CD and temperature had a great effect on retention time, but only a slight or almost no effect on resolutions of the analytes. Enantioseparations were achieved on a Shimpack CLC‐ODS (150 × 4.6 mm i.d., 5 μm) column. The mobile phase was a mixture of methanol and phosphate buffer (pH 4.0–5.5, 20 mM) containing 25 mM HP‐β‐CD. This method was flexible, simple and economically advantageous over the use of chiral stationary phase, and was successfully applied to the enantioselective determination of the racemic 2‐APA NSAIDs in an enantioselective skin permeation study. Copyright © 2009 John Wiley & Sons, Ltd.