Electrogenerated Chemiluminescence Based on Tris(2,2′-bipyridyl) Ruthenium(II) with Hydroxyl Carboxylic Acid

Upon the electrochemical oxidation of tris(2,2′-bipyridyl) ruthenium(II) [Ru(bpy)²⁺₃] and hydroxyl carboxylic acids, for instance, citric acid, tartaric acid, malic acid, and -gluconic acid, bright electrochemiluminescences (ECLs) were observed. Different luminescent reactions were presented depending on the applied potential. The light emission was mainly caused by the reaction between alkoxide radical ion and Ru(bpy)³⁺₃below the potential +1.80 V (vs Ag/AgCl). The luminescence intensity obviously increased because of the more complex reaction process. The luminescence wavelength of 608 nm, which could be found either at higher potential than +1.80 V or in the potential range from +1.30 to +1.80 V, confirmed that ECL was caused by Ru(bpy)²⁺₃*. The factors which affect the determination and HPLC separation of the four acids were also investigated.     

Indirect Determination of Captopril with Sodium Nitrate and Thiocyanate by Floatation Separation of Copper

A new method for indirect determination of captopril (CPT) with NaNO₃ and NH₄SCN by floatation and separation of copper has been studied. In the weak acid, a small amount of Cu(II) can be reduced to Cu(I) by CPT, then Cu(I) reacted with the SCN, which can float on the surface of the liquid phase with NaNO₃. A good linear relationship is observed between the floatation yield (E%) of Cu(II) and the amount of captopril. The linear range is 2?32 mg/L. On the ground, captopril can be indirectly determined by determining E(%) of Cu(II). The method is simple, rapid, reliable and has good selectivity. The developed method can be applied to indirect determination of captopril with satisfactory results.     

Kristallchemische und mikromorphologische Untersuchungen an Carbonat-Apatiten

Zusammenfassung Zwecks Kristallisation von Carbonat-Apatiten wurden Hydrothermalreaktionen sowie Schmelzvorgänge bei Gemischen von Calciumphosphaten und Calcit untersucht. Die vorliegenden Produkte konnten mit analytischen, kristallchemischen und elektronenmikroskopischen Beobachtungen und Messungen als Einkristalle von Hydroxyl- bzw. Fluorapatit identifiziert werden mit einem Carbonatgehalt, der in der Kristallstruktur eingelagert ist.Mit 4 AbbildungenUnter Mitarbeit vonHelga Schmidt. Vortrag auf der Jahrestagung des Vereins Österreichischer Chemiker, Wien 1962.     

Structural and photocatalytic properties of the new solid photocatalyst In2BiTaO7

In₂BiTaO₇ was synthesized using the solid-state reaction method and its photocatalytic properties were investigated. The results of powder X-ray diffraction (XRD) indicated that the compound crystallizes in the pyrochlore-type structure, cubic system with space group Fd-3m. The lattice parameter is 10.6972(1) ?. In addition, the compound shows strong optical absorption in the visible region (λ > 420 nm) and the band gap of In₂BiTaO₇ was estimated to be about 2.47 eV. For the photocatalytic reaction, H₂ or O₂ evolution was observed from CH₃OH/H₂O or AgNO₃ solution respectively with In₂BiTaO₇ as the photocatalyst under visible light irradiation, indicating that In₂BiTaO₇ is responsive to visible light for splitting water. Furthermore, the catalyst remained photoactive in the wavelength range up to 510 nm. Photocatalytic degradation of methylene blue (MB) dye over the compound was further investigated under visible light irradiation. The results showed that complete removal of aqueous MB could be achieved after irradiation for 135 min over In₂BiTaO₇. Furthermore, under visible light irradiation In₂BiTaO₇ showed markedly higher catalytic activity compared to P-25 for MB photocatalytic degradation.     

含多氟烷基侧链的螺环化合物的简易合成及其谱学研究

通过多步反应合成了含有一个长链氟烷基的螺环化合物（2-（5-氯-2，2，3，3，4，4，5，5-八氟-戊烷基）．3-（1-碘-甲基）-8，8-二甲基-7，9-二氧杂-螺[4，5]癸烷-6，10-二酮）。通过对各步产物及最终化合物的^1H NMR、^13C NMR、^1H-^13C COSY和IR、MS谱及X-衍射图的分析，对相关化合物进行了结构确证。     

Confined space-controlled hydroperoxidation of trisubstituted alkenes adsorbed on pentasil zeolites

Photosensitized oxidation of trialkylalkenes 2-methyl-2-pentene (1), 1-methylcyclohexene (2), trans-3-methyl-2-pentene (3), cis-3-methyl-2-pentene (4), and 2-methyl-2-butene (5) included in the internal framework of Na-ZSM-5 zeolites was investigated. The zeolite samples having adsorbed the alkenes were suspended in isooctane, and the sensitizer, tetraphenylporphyrin (TPP), was dissolved in the solution. Singlet oxygen produced in the solution diffused into the internal framework of the zeolites and reacted with alkenes. For all the substrates studied, the ene-type allylic hydroperoxides were obtained in a highly regioselective manner. The regiochemistry for 1-4 in favor of the allylic hydrogen abstraction from the largest substituents is in contrast to their photooxidation within the dye-supported zeolite Na-Y, where the secondary hydroperoxides are preferentially produced. The tight confinement of the alkenes within the narrow channels of the ZSM-5 zeolites is likely to be responsible for this selectivity.     

铜中杂质成分标准物质的研制

介绍铜中9种杂质成分标准物质的研制方法。以1号纯铜为基体，配入硫、铁、铅、锌、镍、铋、锑、磷、砷及锡共10种杂质成分，采用雾化喷粉加工工艺，保证了样品的均匀性。对样品表面作了抗氧化保护处理。采取多家实验室协作定值的方式对除砷外的9种杂质成分进行定值。5年的跟踪检验结果表明，该标准物质稳定性良好。     

Chiral separation of N-(trans-4-isopropylcyclohexylcarbonyl)-D,L-phenylalanine isomers by high performance liquid chromatography

Summary A high-performance liquid chromatographic method was developed for the chiral separation of a new anti-diabetic agent, N-(trans-4-isopropylcyclohexylcarbonyl)-D-phenylalanine, and its L-enantiomer. The separation was performed on a Sumichiral OA-3300 column. Optimized mobile phase was 0.025 mol.L⁻¹ ammonium acetate in methanol solution. UV detection was at 210 nm. Baseline chiral separation was obtained within 12 minutes. The detection limits are 80 pg for the D-enantiomer and 120 pg for the L-enantiomer. RSD of the method was below 1% (n=5).     

Propriétés des copolymères biséquencés polyoxyéthylène-polystyrène

Résumé On a préparé des monocristaux de copolymères biséquencés polyoxyéthylène-polystyrène (POE-PS) à partir de leurs solutions diluées, qui peuvent contenir jusqu'à 55% de PS. Les principales formes de ces cristaux et leurs variantes morphologiques, observées sous microscope optique, sont décrites et rattachées à la maille cristallographique du POE. On présente aussi quelques exemples de monocristaux obtenus par ensemencement, dans lesquels les différentes formes se succèdent par filiation; on discute les transitions des formes et leur dépendance vis à vis des conditions de cristallisation.La cristallisation de ces copolymères provoque généralement un fractionnement en composition, car la proportion de PS dans les cristaux est limitée. On propose deux modèles de structure différents, dans lesquels une ou deux couches cristallines de POE en configuration repliée sont recouvertes par le PS amorphe. Le processus de fractionnement est interprété à partir de ces deux structures en admettant une extension critique pour les séquences de PS, dont l'une des extrémités est ancrée sur la surface des repliements du POE.

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Summary Single crystals of copolymers, composed of one Poly(ethylene-oxide), (POE), and one Polystyrene (PS) block, (which may contain 55% of PS, by weight), have been prepared from dilute solutions. The principal crystal habits and their morphological variations, as observed with an optical microscope, are described and related to the unit cell of POE. Single crystals grown from various types of seeds, in which different external habits succeed one another, are also shown. Transitions of crystal habits and their dependence on crystallisation conditions are discussed in some detail.Generally, crystallisation of these copolymers produces some fractionation with respect to composition, for only a limited fraction of the initial PS can enter into the crystal. Two different crystal structures are proposed in which a single, or a double crystalline layer of folded POE is covered by amorphous PS. The fractionation process is interpreted on the basis of these two structural models, assuming a critical extension of the PS blocks anchored at one end to the fold surface of PEO.

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Zusammenfassung Einkristalle von Copolymeren aus einem Polyäthylenoxyd (PEO) und Polystyrol (PS)-Block, die gewichtsmäßig 55% PS enthalten können, wurden aus verdünnten Lösungen präpariert. Der grundsätzliche Charakter der Kristalle und ihre morphologischen Variationen, wie es in einem optischen Mikroskop beobachtet wird, ist beschrieben und mit der Elementarzelle PEO in Beziehung gebracht. Einkristalle, entstanden aus verschiedenen Typen von Kristallkeimen, in welchen verschiedene äußere Formen auftreten, die aufeinanderfolgen, werden gezeigt. Die übrigen Kristallformen und ihre Abhängigkeit von den Kristallisationsbedingungen werden im einzelnen diskutiert.Im allgemeinen verursacht die Kristallisation dieser Copolymeren gewisse Fraktionierung hinsichtlich der Zusammensetzung, da nur eine begrenzte Menge des ursprünglichen Polystyrols in den Kristall eintreten kann. Zwei verschiedene Kristall-Strukturen werden vorgeschlagen, in denen bzw. eine oder zwei Schichten von gefaltetem PEO mit amorphem Polystyrol bedeckt ist. Der Fraktionierungsprozeß wird auf Grund dieser zwei Struktur-Modelle interpretiert, die eine kritische Größe der PS-Blöcke, verankert an einem Ende der gefalteten Oberfläche von PEO, annehmen.