含CdS的聚碳酸醋薄膜的光电效应

近来有一些学者从理论或实践上探讨了模拟植物光合作用的光电化学膜体系用于太阳能转换的可能性。这种体系的核心是一个具有光活性的膜,把两个含有氧化还原偶的水溶液分隔开;当膜受光照时在膜里产生电荷(电子和空穴)的分离,电子到膜的一侧引起一个还原反应而空穴到膜的另一侧引起一个氧化反应。本文用一种聚碳酸酯的透明薄膜(商品名Nuclepore membrane),膜上已用中子照射的方法打好了大小和分布都很均匀的大量微孔,然后在这些微孔里形成CdS沉淀。这样得到的光活性膜体系,改性后在光照时能     

Heterocyclic diazo compounds as starting materials in organic synthesis (review)

Data on the structures and reactions of heterocyclic diazo compounds that lead to the formation of new heterocyclic systems as a result of intra- or intermolecular cyclization and rearrangements are systematized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 579–603, May, 1980.     

PHOTOSENSITIZATION SYSTEMS OF COVALENTLY LINKED PHTHALOCYANINE COMPLEXES IN BOTH BILAYER LIPID MEMBRANES AND TIN OXIDE PHOTOVOLTAIC CELL

Abstract Zinc phthalolocyanine photosensitized donor-acceptor systems for light energy conversion and for the design of photoelectrochemical molecular devices are presented. Covalently linked phthalocyanine complexes were incorporated in bilayer lipid membranes (BLM) and deposited on SnO₂ transparent electrodes. Their photovoltages were measured and compared. It has been found that a more favorable orientation and closer proximity are attained in the diad compounds between the donor (phthalocyanine)-acceptor (anthraquinone) pair than in the reference compound for efficient light-induced charge separation and transfer. The triad compound is the best among all tested compounds. The decrease in the fluorescence yield and lifetime induced by quinones was examined and the apparent electron-transfer rate constants were calculated.     

Neighbouring group participation in formation of condensed azines. Formation of pyrazolo(3,4-b)pyrazines,isoxazolo(4,5-b)pyrazines and isothiazolo(5,4-b)pyridine

Pyrazine- and pyridinecarboxamidoximes with an amino, potentially tautomeric hydroxy or mercapto group inortho position could be transformed in the appropriate condensed azines. In this manner, representatives of pyrazolo(3,4-b)pyrazine, isoxazolo(4,5-b)pyrazine and isothiazolo(5,4-b)pyridine ring system were synthesized and some transformations investigated.Presented in part at the 8th International Congress of Heterocyclic Chemistry, Graz, 1981.     

Synthesen in der Pyridazin-Reihe, 26. Mitt.:

Zusammenfassung Es wird über die Synthese von verschiedenen methylsubstituiertens-Triazolo[4,3—b]pyridazinen berichtet. Außerdem wurdens-Triazolo[4,3—b]pyridazin und seine 7-Methyl- und 6-Chlor-Derivate der homolytischen Methylierung unterworfen, die Reaktionsgemische gaschromatographisch auf einzelne Methyl-s-triazolo[4,3—b]pyridazine aufgetrennt und die Verbindungen identifiziert.

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Syntheses of pyridazines, XXVI: Synthesis and homolytic methylation of s-triazolo[4.3—b]pyridazines

The syntheses of some methyl substituteds-triazolo[4,3—b]-pyridazines are reported.s-Triazolo[4.3—b]pyridazine and its 7-methyl and 6-chloro analogs were submitted to homolytic methylations and the obtained reaction mixtures were separated by gas chromatography into particular components which were then identified.

     

Effect of vibrational excitation of HBr on the H+HBr abstraction and exchange reactions

The effect of vibrational excitation of HBr on the H+HBrH₂+Br and H+HBrH+HBr reactions has been investigated on the extended LEPS surface (ELEPS) constructed on the basis of quantum chemically calculated points of PES. Together with this surface the LEPS surface of Sudhakaran and Raff [1] was used for comparison at two relative translational energies. A quasiclassical trajectory method was used to study the abstraction and exchange reaction dynamics. The reactive cross section was calculated as a function of the relative collision energy and the vibrational state of HBr. The following conclusions can be drawn from the results of the study: (i) vibrational excitation v=0 v=2 more than doubles the reaction cross section, (ii) the increase in the collision energy is most effectively channelled into the product translational energy.Dedicated to Professor J. Koutecký on the occasion of his 65th birthday     

TheSemmler-Wolff aromatization andSchmidt reaction applied to some pyrido[2′,3′:3,4]pyrazolo[5,1-c][1,2,4]benzotriazines

Pyrido[2,3:3,4]pyrazolo[5,1-c][1,2,4]benzotriazin-4(1H)ones were transformed via their oximes in aSemmler-Wolff aromatization process in the tetracyclic heteroaromatic amines4 or bySchmidt reaction into a mixture of the same amine4 and a ring enlarged lactam3. Syntheses of some halo pyrazolo[3,4-b]pyridines and a photochemical transformation of 3-azidopyrazolo[3,4-b]pyridine are also described.

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Über dieSemmler-Wolff- undSchmidt-Reaktion einiger Pyrido[2,3:3,4]pyrazolo[5,1-c][1,2,4]benzotriazine

Zusammenfassung Pyrido[23:3,4]pyrazolo[5,1-c][1,2,4]benzotriazin-4(1H)one werden über Oxime in einerSemmler-Wolff-Reaktion in die tetracyklischen aromatischen Amine4 umgewandelt. In einerSchmidt-Reaktion wurden dieselben Ketone in ein Gemisch aus Amin4 und Lactam3 übergeführt. Synthesen von halogensubstituierten Pyrazolo[3,4-b]pyridinen und photochemische Umwandlung von 3-Azidopyrazolo[3,4-b]pyridin werden beschrieben.

     

Membrane electrochemistry

Electrochemistry and biomembranes are interface science in that both are concerned with the phenomena at, as well as across, the interfaces. Membrane electrochemistry may be defined as the application of electrochemistry to biomembrane studies. Additionally, transport processes within the membrane are involved in biomembranes. Since biomembranes are diverse and are usually not amenable to probing by electrochemicophysical techniques, model membrane systems have been developed for their investigation.

The introduction of experimental bilayer lipid membranes (BLM) technique and its modifications have been instrumental in the development and testing of membrane transport concepts (carriers vs channels) and electronic processes in membranes. Instead merely viewing a biomembrane as a physical barrier containing carriers or channels to carry out ionic processes, an ultrathin lipid or biological membrane can also be considered as a complete ‘electrochemical cell’ with one membrane/solution interface reducing (as a cathode) and the other membrane/solution interface oxidizing (as an anode). It is now possible to understand energy transduction (charge generation, separation, and redox reactions) in terms of ultrathin lipid membranes separating two aqueous solutions.

In this paper, we shall discuss the basic principles of electrochemistry as they are applied to membrane studies. Emphasis will be on experimental bilayer lipid membranes (BLM) which have been extensively investigated as models of biomembranes.     

Reactions of quaternized imidazo-quinazoline and-pyridopyrimidine with active methylene compounds

Summary Syntheses of 1-methylimidazo[1,2-c]quinazolinium iodide (3) and 1-methylimidazo[2,1-f]pyrido[3,2-d]pyrimidinium iodide (4) are described. These tricyclic compounds react with nucleophiles derived from active methylene compounds to give the corresponding open-chain enamines.

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Reaktionen von quaternisierten Imidazo-Chinazolinen und -Pyridopyrimidinen mit Verbindungen mit reaktiven Methylengruppen

Zusammenfassung Synthesen von 1-Methylimidazo[1,2-c]chinazoliniumjodid (3) und 1-Methylimidazo[2,1-f]pyrido[3,2-d]pyrimidiniumjodid (4) werden beschrieben. Diese tricyclischen Verbindungen reagieren mit einigen Carbanionen aus Verbindungen mit reaktiven Methylengruppen, wobei die offenkettigen Enamine entstehen.