Decomposition procedure with aqua regia and hydrofluoric acid at room temperature for the spectrophotometric determination of phosphorus in rocks and minerals

A rapid spectrophotometric method for the determination of phosphorus in rocks and minerals is described. The sample solution is prepared by treatment with hydrofluoric and aqua regia at room temperature. Unreacted fluoride ions are complexed with boric acid. As fluoride ions do not have to be removed by heating, the method is rapid and avoids the use of platinum ware.     

Evaluation of the odd-even effect in limits of detection for electron microprobe analysis of natural minerals

Limit of detection (LOD), being a fundamental quality parameter for analytical techniques, has been recently investigated and a systematic behavior has been observed for most odd-even element pairs for many techniques. However, to the best of our knowledge very few LOD data are available in published literature for electron microprobe analysis; these consist of three papers, two being on rare-earth elements and the third covering a large number of elements of atomic number between 21 and 92. These data confirm the systematic behavior of LODs for many odd-even pairs. To initiate to full this gap, we determined LODs for several major rock-forming chemical elements from Na to Fe with atomic numbers between 11 and 26, during the microprobe analysis of common minerals (olivine, plagioclase, pyroxene, amphibole, quartz, and opaques) in volcanic rocks. The odd-even effect of nuclear stability seems to be present in LOD data for most odd-even pairs investigated. Nevertheless, the experimental strategy concerning the reference materials, calibration procedure, and blank measurements, should be substantially modified to better evaluate the systematic behavior of LOD values in microprobe analysis.     

Studies of the defect structure for V3+ ions in wurtzite structure ZnO

By using crystal field theory, the optical spectra, zero field splitting and g factors have been calculated. The defect structure for V(3+) in ZnO crystal has been studied by using crystal field theory and first-principle calculations. The results show that, the V(3+) ions do not occupy the exact Zn(2+) site, but displaced along C(3) axis.     

The first contribution of capillary electrophoresis to the study of abiotic origins of homochirality: investigation of the enantioselective adsorption of 3-carboxy adipic acid on minerals

CE with UV detection was used for the first time to determine the enantioselective adsorption of the short-chain tricarboxylic acid, 3-carboxy adipic acid, on minerals as a mean of investigating plausible mechanisms for the origin of biochemical homochirality on Earth. The use of vancomycine as chiral selector in the separation buffer using the partial filling technique enabled the separation of the two enantiomers of this organic acid in about 12 min. Taking into account that this compound has a low absorption of the UV light, and in order to achieve the sensitivity needed to determine the enantiomeric excess of samples of 3-carboxy adipic acid adsorbed on minerals, we applied a strategy consisting of a field-amplified sample stacking together with the use of a bubble capillary and detection at low wavelength (192 nm). This combination enabled an LOD of about 10(-7) M and the determination of the enantiomeric excess of 3-carboxy adipic acid adsorbed on calcite and feldspar mineral samples at subnanomol levels of this acid. Results showed that an enantioselective adsorption of the enantiomers of 3-carboxy adipic acid on minerals took place.     

RE2CuO4的热力学稳定性（RE=La,Nd,Sm,Eu）

构筑了ＭｇＯ部分稳定的ＺｒＯ２基固体电解质电化学电池测量ＥＡＦ的实验装置，测定了Ｓｍ２ＣｕＯ４的标准Ｇｉｂｂｓ生成自由能。结果表明化合物ＲＥ２ＣｕＯ２３（ＲＥ＝Ｌａ，Ｎｄ，Ｓｍ，Ｅｕ）随着镧系元素离子半径减小，热力学稳定性下降，并用晶体场理论解释了这一规律。     

The Hydrogen-Bonded Framework of the First Anti-Zeotype: [{(H2NEt2)2}2(CuCl4)][AlCl4]

A two-coordinate cationic link between [CuCl₄]³⁻ tetrahedra by means of two inversion-related dialkylammonium cations yields the hydrogen-bonded A₂X anti-cristobalite framework [{(H₂NEt₂)₂}₂(CuCl₄)]⁺. This novel cationic framework is constructed around space-filling and templating [AlCl₄]⁻ anions resulting in large pores (16.6×6.7 Å).     

Some trends in the development of microplasmas for spectrochemical analysis

The development of microplasmas for spectrochemical analysis by optical methods is discussed. Recent achievements in miniaturization are highlighted, especially for three types of plasmas, namely high-frequency plasmas, dc-discharges and microwave plasmas. The potentials of each of these groups of plasmas as sources for atomic emission spectrometry are discussed. Literature citations and experiments indicate that the plasmas are also very useful as atom reservoirs for atomic absorption spectrometry. Methods of sampling, including feeding with gas chromatography effluents, the use of electrothermal vaporization, and the evolution of gaseous species (as shown for the case of Hg vapor), are discussed as prominent interfaces to make use of these sources for elemental analysis.     

Recent trends in perfluorinated sulfoximines

The search for original perfluorinated moieties is a very modern and attractive challenge. Among the emergent groups, the S-perfluoroalkylated sulfoximines are very peculiar because of their structural diversity and promising properties. A literature survey shows that interest in these molecules is strongly increasing. This short review summarizes the recent works devoted to this topic.     

Some continuous geometry transitions and the consequences for a transition‐metal atom

By considering a transition‐metal ion in the field of some symmetrically placed ions, we illustrate the consequences of a continuous change of the structure of the ligands on the energies of the 3d electrons of the transition‐metal atom. Both a rigorous mathematical derivation and an analysis based on group theory are presented. For six ions surrounding the transition‐metal atom, a continuous D_∞h → D_3d → O_h→ D_3d→ D_6d transition is observed, whereas for four ions, a continuous D_{∞ h}→ D_2d→ T_d→ D_2d→ D_4d transition results. Although the two systems possess many similarities, interesting differences are found as well. Finally, we demonstrate that when including orbital interactions between the ligands and the transition‐metal atom, quantitative differences occur. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

讲授晶体结构的一点体会

简要介绍了晶体结构的各部分内容的特点,重点讨论了点阵和结构基元这一关键点的讲解方法。     

Stability and crystal field splitting of N inf2 sup− in Barium Azide

The crystal field splitting of the ground²_g state and the equilibrium orientation of the N _inf2 ^sup– radical in the monoclinic barium azide are calculated employing a point ion representation of the lattice potential and assuming three different plausible trapping sites for the radical. When the N _inf2 ^– is assumed to replace an azide ion which is parallel to thec axis of the unit cell, the previously suggested trapping site, the calculated crystal field splitting is in order of magnitude agreement with the value deduced from theg shift in the ESR spectrum. The calculated orientational angle of the molecular axis with thec axis of the unit cell is 9.0 degrees which compares favorably with the experimentally determined angle of 5.0 ± 1.5 degrees. Possible reasons why the N _inf2 ^– can not be trapped at the site of an azide ion which is perpendicular to the c axis are suggested from the calculation.     

Quotients of group algebrae in the calculation of intermediate ligand field matrix elements

The structure of the classes of symmetry elements excluded during the subduction of the representations of SU(2) onto the finite group 0* is shown to quantitatively define the relationship of the coupling algebrae of these two groups. This relationship is formalized as a quotient algebra. This quotient algebra is realized as 3-like symbols which exist whether or not the quotient can be defined as a group. These symbols distribute the value of a reduced matrix element of SU(2) onto the subduced reduced matrix elements of O* and are termed Partition Coefficients. Since the structure of the excluded symmetry classes is independent of the quantization of O*, these Partition Coefficients can be used to define the values of the matrix elements of O* without reference to the form of its basis set. Thus, the choice of physical interpretation of the ligand field is unimportant. The strong field, weak field, Russell-Saunders and j-j coupling models are all unified in terms of the Partition Coefficients and the 3 symbols which are appropriate to the quantization.     

Regioselectivity in Reactions of Bis‐Hydrazonoyl Halides with Some Bifunctional Heterocycles

Bis‐hydrazonoyl chloride 1 reacts regioselectively with 3‐mercapto‐1,2,4‐triazole 2a , 2,3‐dihydro‐3‐thioxo‐1,2,4‐triazin‐5(4H)‐one 2b and 2‐mercaptobenzimidazole 2c to give the hitherto unknown annelated 2,3‐bis‐(phenylhydrazono)thiazoles 6a‐c , respectively. Reactions of 1 with the methylthio derivatives of such heterocycles afforded the annelated 3,3′‐bis‐(1,2,4‐triazoles) 11a‐c , respectively. Similar reaction of 1 with 2‐phenylamino‐4(3H)‐pyrimidinones 4 gave 2,3‐bis(phenylhydrazono)imidazo[1,2‐a]pyrimidin‐5(1H)‐ones 16 . Oxidation of 6c yielded the corresponding bis(phenylazo) derivative 15 . The regiochemistry of the studied reactions is discussed.     

多策略可控合成原子精度合金纳米团簇

合金纳米团簇作为一类新兴的多功能纳米材料已被广泛用于催化、光学传感以及生物医学成像等研究领域,而纳米团簇的可控合成和结构特征是调节纳米团簇性质并对其进一步利用的基础。尽管当前有关金属纳米团簇可控合成和结构特征的研究主要集中在单金属纳米团簇中,但有关合金纳米团簇原子精度的可控合成也取得了显著的进展。本文综述了配体保护的合金金属纳米团簇原子精度可控合成策略,包括一步合成法、金属交换、配体交换、化学刻蚀、簇间反应、原位两相配体交换以及最新的表面模体交换反应,并对相关合成策略的优缺点进行了详细的讨论和阐述。     

Design,synthesis and biological evaluation of new rhodacyanine analogues as potential antitumor agents

In an attempt to develop potent antitumor agents,new rhodacyanine analogues containing the pyridinium ring（5a-5h）,the isoquinolinium ring（6a-6c） and the quinolinium ring（7a-7e） linked to the rhodanine ring via N-N covalent bond were designed, synthesized and evaluated for antitumor activity against human lung cancer cell line（H460） by MTT assay in vitro.Most of the tested compounds showed enhanced antitumor activity with IC₅₀ values ranging from 0.006 to 9.2 u,mol/L as compared to the lead compound MKT-077.Among them,the most promising compound 7d(IC₅₀ = 0.006μmol/L) was 216.7 times more active than MKT-077(IC₅₀ = 1.3μmol/L).The preliminary structure-activity relationship of the target compounds was discussed.