ANN原子参数法预报合金相晶型及晶格常数

运用人工神经网络方法，以二元合金组成元素的电子结构为基本特征，对二元合金相晶型作了区分，进一步对其晶格常数作了预报，结果令人满意。     

Vibronisches Spektralverhalten von Molekülen: XX. Theoretische Untersuchung der S2←S0-Absorption des Pyrens im Rahmen der Herzberg-Teller-Näherung erster Ordnung

Summary On the basis of the completely-optimized S₀ and S₂ molecular geometries of pyrene the vibrational structure of the electronic S₂S₀ transition was calculated within both the Condon approach and the first-order Herzberg-Teller approach. The theoretical results demonstrate the significant influence of vibronic coupling. An analysis of the active vibrational modes is given. The theory-experiment comparison within the Herzberg-Teller approach is satisfactory.

     

X-ray crystal structure analyses and atomic charges of color former and developer. I. Color developers

The crystal and molecular structures of 2,2-bis(4-hydroxyphenyl)propane (Bisphenol A, BPA) (1), benzyl 4-hydroxybenzoate (2), 1,7-bis(4-hydroxyphenylthio)-3,5-dioxaheptane (3) and 4-hydroxyphenyl 4-isopropoxyphenyl sulfone (4) have been determined by X-ray crystal structure analysis. Theoretical calculations of the steric hindrance and semiempirical quantum chemical calculations to determine the color characteristics have been carried out. It is clear that the energy barriers for the variation of the orientation of phenol group in 1 to 4 are due to steric hindrance caused by the other moiety and the peak profiles are due to repulsive interactions of the other moiety. Net atomic charges on the hydrogen of the OH group are larger than those on the other atoms in the molecules. This high electron charge of the para orientation will cause the different thermosensitivity and stabilization.     

超声雾化进样微波诱导等离子体原子吸收光谱法测定银的某些影响因素研究

本文将超声雾化技术与MIP-AAS联用,以“L”型吸收管代替“T”型吸收管作为AAS测量的吸收池,采用水冷凝和浓H_2SO_4吸收相结合去溶,研究TUSN-MIP-AAS方法测银时的某些影响因素,讨论了微波前向功率,载气流速、去溶系统、溶液酸度、共存离子及易也离元素等对吸收信号的影响,本法所得的测银的特征浓度为0.01μg/ml(328.1nm)和0.03μg/ml(338.3nm),相对标准偏差为7.5％.     

氮化锇配合物离子[OsN(mnt)2]-的电子结构和光谱性质的理论研究

理论研究了离子型配合物[OsN(mnt)2]-[mnt=S2C2(CN)2)]的电子结构和光谱性质, 考察不同配体三价N、二硫氰烯S2C2(CN)2和金属Os的相互作用对光化学性质的影响. 分别在B3LYP/LANL2DZ和CIS/LANL2DZ水平上优化了配合物的基态和激发态结构. 与基态(1A1)相比, 激发态(3A2)的Os≡N 的键长缩短了0.0066 nm, 这与计算得到的频率增大一致, 使用TD-DFT方法计算得到了配合物的吸收和发射光谱. 计算得到的位于300 nm(f=0.1497)和262 nm(f=0.2890)的强吸收都来自1A1→1B1跃迁, 分别指认为SC→Os≡N+CN 和N+SC→Os≡N+CN的电子跃迁. 最低能量的吸收位于446 nm(f=0.0206) 处, 来自1A1→1B2的电子跃迁, 指认为N→Os和 N+SC→CN. 计算得到配合物在气态的磷光发射位于678 nm(A3A2→X1A1)处, 而在丙酮溶液中则蓝移到了625 nm处, 跃迁属性不变, 都是N→Os和S→Os的跃迁.     

AFM of adsorbed polyelectrolytes on cellulose I surfaces spin-coated on silicon wafers

Thin layers of cellulose I nanocrystals were spin-coated onto silicon wafers to give a flat model cellulose surface. A mild heat treatment was required to stabilize the cellulose layer. Interactions of this surface with polyelectrolyte layers and multilayers were probed by atomic force microscopy in water and dilute salt solutions. Deflection–distance curves for standard silicon nitride tips were measured for silicon, cellulose-coated silicon, and for polyelectrolytes adsorbed on the cellulose surface. Transfer of polymer to the tip was checked by running deflection–distance curves against clean silicon. Deflection–distance curves were relatively insensitive to adsorbed polyelectrolyte, but salt addition caused transfer of cationic polyelectrolyte to the tip, and swelling of the polyelectrolyte multilayers.     

Synthesis and Photophysical Properties of Hetero‐Bischelated Complexes of Rhodium(III) Containing Phenyl‐Pyridin‐2‐Ylmethylene‐Amine

Three new hetero‐bischelated rhodium (III) complexes of cis‐[Rh(PA)(L)Cl₂]Cl (where PA = phenylpyridin‐2‐ylmethylene‐amine; L = 2,2′‐bipyridine, 2,2′‐dipyridylamine and 1,10‐phenanthroline) have been successfully prepared and characterized. Each complex shows high intensity bands in the UV region, and these are assigned to spin‐allowed π‐π* transitions. The medium‐intensity absorption band profile in the lower energy region can be explained by convolution of spin‐allowed CT and d‐d* transitions. The emission spectra at low temperature (77 K) of these complexes in EtOH/MeOH (4:1 v/v) are virtually identical. They all exhibit a broad, symmetric, and structureless red emission with a microsecond lifetime and hence are assigned as the d‐d* phosphorescence.     

Synthesis and spectroscopic properties of highly water-soluble perylene derivatives

Most known perylene diimides are lipophilic, with few exceptions of hydrophilic derivatives. Even in the latter case, the compounds have limited water solubility and show a strong tendency to self-aggregation. In this paper we present the synthesis of four new perylene derivatives with three and four basic side chains, obtained by functionalizing the bay-area of perylene. These molecules show great solubility in aqueous media as hydrochlorides and their tendency to self-aggregate is remarkably reduced with respect to the previously synthesized two-chained perylene diimides. Their different spectroscopic properties in various solvents and conditions are reported and discussed.     

Comparison of pre-reducing agents for antimony determination by hydride generation atomic fluorescence spectrometry

A systematic study of antimony reduction prior to its determination by hydride generation atomic fluorescence spectrometry (HG-AFS) was carried out. The efficiency of l-cysteine, potassium iodide and potassium iodide/ascorbic acid was studied for this purpose. The hydride generation step was optimised in the presence of those pre-reductors. From the results, l-cysteine was found to be the most suitable pre-reducing agent. Methodology was validated, obtaining detection limits lower than 90 ng l⁻¹ and repeatability and reproducibility better than 3% R.S.D. and 5% R.S.D., respectively, in all cases. In order to evaluate the methodology developed and the influence of the matrix, recovery from waters from different sources was tested by HG-AFS and also by inductively coupled plasma mass spectrometry (ICP-MS). Accuracy was assessed by analysing three water reference materials at different antimony concentration levels. The high sensitivity of the developed methodology enables it to be applied for monitoring drinking waters according to the maximum admissible concentration of antimony established by the EU Directives.     

Trace elemental determination in alcohol automotive fuel by electrothermal atomic absorption spectrometry

Suitable analytical methodologies were developed allowing direct determination of As, Cu, Fe, Pb, Sb and Sn in alcohol fuel samples by electrothermal atomic absorption spectrometry. Different chemical modification approaches were tested and compared in terms of analytical performance and in practical terms. Experimental conditions were optimized allowing little sample dilution and use of calibration curves prepared with aqueous inorganic analyte standards. Methodologies were tested with analyte spiked alcohol samples. Good analyte recoveries from spiked alcohol samples, precision better than 10% and limits of detection in the sub μg l⁻¹ range were achieved.