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991.
The effect of H2S on the activity and selectivity of catalysts (Ru/Al2O3, Pd/Al2O3 and Ru and Pd promoted molydena-alumina) was different (on differnt catalysts and different conversions of cyclohexene). Ru-containing catalysts showed higher sulfur sensitivities than the Pd-containing ones. The sequence of catalysts by their H2S uptake related to mass of catalyst was PdMo/Al2O3RuMo/Al2O3Mo/Al2O3>Pd/Al2O3Ru/Al2O3. 相似文献
992.
Synthesis and Spectroscopical Characterization of Di(halo)phthalocyaninato(1–)rhodium(III), [RhX2Pc1?] (X = Cl, Br, I) Bronze-coloured di(halo)phthalocyaninato(1–)-rhodium(III), [RhX2Pc1?] (X = Cl, Br) and [RhI2Pc1?] · I2 is prepared by oxidation of (nBu4N)[RhX2Pc2?] with the corresponding halogene. Irrespective of the halo ligands, two irreversible electrode reactions due to the first ringreduction (ER = ?0,90 V) and ringoxidation (EO = 0,82 V) are present in the cyclovoltammogram of (nBu4N)[RhX2Pc2?]. The optical spectra show typical absorptions of the Pc1?-ligand at 14.0 kK and 19.1 kK. Characteristic vibrational bands are at 1 366/1 449 cm?1 (i. r.) and 569/1 132/1 180/1 600 cm?1 (resonance Raman (r. r.)). The antisym. (Rh? X)-stretching vibration is observed at 294 cm?1 (X = Cl), 240 cm?4 (Br) and 200 cm?1 (I). Only the sym. (Rh? I)-stretching vibration at 133 cm?1 is r. r. enhanced together with a strong line at 170 cm?1, which is assigned to the (I? I)-stretching vibration of the incorporated iodine molecule. Both modes show overtones and combinationbands. 相似文献
993.
Herman Gershon Donald D. Clarke Muriel Gershon 《Monatshefte für Chemie / Chemical Monthly》1994,125(1):51-59
Summary A study was made of the fungitoxicity of 2-, 3-, 4-, 5-, 6- and 7-chloro and bromo-8-quinolinols againstAspergillus niger,A. oryzae,Myrothecium verrucaria,Trichoderma viride andTrichophyton mentagrophytes in Sabouraud dextrose broth and in Yeast Nitrogen Base supplemented with 1%D-glucose and 0.088%L-asparagine. Based on the presence or absence of synergism between pairs of substituted 8-quinolinols and reversal or nonreversal of toxicity byL-cysteine or N-acetyl-L-cysteine, the following conclusions were reached: (1) substituents on the quinoline ring change the site(s) of action of the toxicant; (2) the sites of action of the 5-, 6-, and 7-chloro-8-quinolinols are different from each other and from 8-quinolinol and its 2-, 3-, and 4-chloro analogues, and the same is true for the corresponding bromo compounds; (3) 8-quinolinol and its 3- and 4-chloro and bromo analogues appear to share common sites of action; (4) for good antifungal activity the 2 position of the ring must not be substituted by sterically bulky groups; (5) the geometry of the binding sites of action are not so constrained that they cannot accommodate the analogously substituted chloro- and bromo-8-quinolinols.
Nachweis sterischer Faktoren bei der Fungitoxizität von 8-Chinolinol und seinen 2-, 3-, 4-, 5-, 6- und 7-Chlor- und -Brom-Analogen
Zusammenfassung Es wurde eine Studie der Fungitoxizität von 2-, 3-, 4-, 5-, 6- und 7-Chlor- und-Brom-8-chinolinol gegenüberAspergillus niger,A. oryzae,Myrothecium verrucaria,Trichoderma viride undTrichphyton mentagrophytes in Sabouraud Dextrose Nährmedium und in Hefe-N-Base mit 1%D-Glucose und 0.088%L-Asparagin unternommen. Auf der Basis des Zutreffens oder der Abwesenheit eines Synergismus zwischen Paaren von substituierten 8-Chinolinolen und der Umkehrung oder Nichtumkehrung der Toxizität durchL-Cystein oder N-Acetyl-L-cystein wurden folgende Schlußfolgerungen abgeleitet: (1) Substituenten am Chinolin-Ring ändern die Aktionsstelle(n) des Toxikans; (2) Die Angriffsstellen der 5-, 6- und 7-Chlor-8-chinolinole sind untereinander und von 8-Chinolinol und seinen 2-, 3- und 4-Chlor-Analogen verschieden, wobei das auch für die entsprechenden Brom-Verbindungen gilt; (3) 8-Chinolinol und seine 3- und 4-Chlor- und -Brom-Analogen scheinen gemeinsame Aktionsstellen zu teilen; (4) für eine gute antifungale Aktivität darf die 2-Position des Rings nicht mit sterisch anspruchsvollen Gruppen besetzt sein; (5) Die Geometrie des Bindungsstellen der Wirkung ist nicht so gespannt, daß nicht sowohl analoge Chlor- oder Brom-8-chinolinole Platz finden.相似文献
994.
A. A. Trifonov L. N. Zakharov M. N. Bochkarev Yu. T. Struchkov 《Russian Chemical Bulletin》1994,43(1):145-148
Ytterbium complexes, Cp2Yb(-2:2-DAB)Li(DME) (1) and CpYb(DAB)K(THF)2 (2), containing a bridging diazadiene ligand were prepared by the reaction of CpYbCl2(THF)3 with (DAB)Li2 (11) and (DAB)–K+ (12) (DAB = But-N=CH-CH=N-But). The structure of complex1 was established by X-ray diffraction analysis. The complex is binuclear: the Yb atom of the Cp2Yb fragment and the Li atom, which is bonded as well with the chelating DME molecule, are linked by the DAB ligand.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 148–151, January, 1994. 相似文献
995.
Spectroscopical Properties of Di(phthalocyaninato)metalates(III) of the Rare Earth Elements. Part 2: The Multinuclear (1H, 13C, 15N, 17O, and 31P) NMR Spectra and Determination of Complex Bound Water The 1H, 13C, 15N, 17O and 31P NMR spectra of (PNP)[Ln(Pc2?)2] and (TDOA)[Ln(Pc2?)2] (Ln = La …? (—Pm) …? Lu); PNP: di(triphenylphosphine)-iminium; TDOA: Tri(n-dodecyl)n-octylammonium dissolved in CD2Cl2 are reported. With the exception of the nitrogen atoms of the cations all light atoms of both homologues complex salt rows have been detected and assigned. Proof of the presence of additional water contained in the (solid) complex salts has been given unambigously. The otherwise strong Fermi contact interactions diminuish rapidly with growing distance from the paramagnetic centre favouring dipolar (pseudo-contact) interactions. As a consequence the mostly element independent paramagnetic shifts of the atoms situated on the periphery of the anion as well as those of the cations and water are determined by the distance factor. Therefore a first glance of the structure of the ion-pair present in solution emerges, in which the water molecule seems to play an important role. 相似文献
996.
The -ribofuranosylazide1 is transformed after usual derivatization by suitable protecting groups into the P–N-ylid2, which gives the corresponding N-Glykosyl-N-alkylcarbodiimides4 and a small amount of the glykosylisocyanatde-rivative3 by reaction with alkylisocyanates. The carbodiimides4 were reacted with hydrazoic acid to give the alkylaminotetrazolnucleosides5 and finally the free nucleosidanalogs6. In the case of5 c the 5-aziridinyltetrazolnucleosid5 h was formed by an usual neighbouring group reaction. In addition the compound1 is transformed into the 3,5-diprotected anchor derivative7 by reaction withTIPSCl2. The latter could be transformed by usual steps into the alkylaminotetra-zolnucleosides8 with a free 2-OH group. In the next step the 2-p-tolylthiocarbo-nates9 were prepared followed by transformation to the 2-desoxynucleosides10 by means of tributyltinhydride. Finally the free 2-desoxynucleosides11 were prepared. By reacting the carbodiimides4 with phenylisocyanate a mixture of the two possible regiouretidinonnucleosidderivatives12 and13 are formed. In the case of the N-glykosyl-N-allylcarbodiimide4 d only the one isomer13 d arises.
Herrn Prof. Dr.A. Neckel mit den besten Wünschen zum 60. Geburtstag gewidmet. 相似文献
997.
A protocol has been developed for the reliable titration of aqueous sulfite solutions which minimizes photodecomposition effects.
This procedure has been used to measure the protonation constants of the sulfite ion in aqueous solution by glass electrode
potentiometry at 25.0‡C and ionic strengths (I) from 0.1 to 5.0M in NaCI media and atI = 1.0M in KC1 and Me4NCl media. These measurements provided evidence of weak but significant ionpairing between SO2/3 -and Na+ with a formation constant of logK
Na = 0.431 in 1.0M Me4NCl. This was in very good agreement with the value logK
Na = 0.410 measured directly by Na+ ion-selective electrode potentiometry. Evidence is also presented for an extremely weak association of K+ and SO
2
3
-with logK
k
= 0.22 in 1.0M Me4NCl. 相似文献
998.
V. Pichon H. Rogniaux N. Fischer-Durand S. Ben Rejeb F. Le Goffic M. -C. Hennion 《Chromatographia》1997,45(1):289-295
Summary The trace-level determination of organic pollutants in complex matrices is difficult and often not reliable because theccurrent
extraction procedures are non-selective. New extraction sorbents involving antigen-antibody interactions, called immunosorbents
(ISs), have been synthesised in order to trap a group of structurally related pollutants. The IS capacity is always high for
the analyte-antigen used to make the antibodies, but can be low for some related compounds. In this work, we show the relationship
that exists between capacity, break-through volume and recovery of analytes because of the competition between the structurally
related compounds for antibody sites. Breakthrough due to the overloading of the column should be avoided because calibration
curves are no longer linear. The capacity of two ISs, one made for trapping the triazine pesticide group and the second for
the phenylurea, group, have been optimised by selecting silica with 50 nm pore size. Calibration curves are linear for all
the compounds in a mixture of ten phenylureas up to a concentration of 5 to 10 μg L−1 for each compound when handling 50 mL water samples through a precolumn packed with 0.22 g of IS. Under these conditions,
reliable quantitative results are obtained because calibration curves are similar when compounds are alone or in a mixture.
Application to the clean-up of soil extracts illustrates the high selectivity and the high potential of these new sorbents
in environmental analysis.
Presented at the 21st ISC held in Stuttgart, Germany, 15th–20th September, 1996 相似文献
999.
The electrical conductivities of aqueous solutions of NaCF3SO3, KCF3SO3, and Ni(CF3SO3)2 have been measured at 25‡C in the concentration range 1 to 25X 10-3 mol-dm-3 The data approach the Onsager limiting law at low concentrations, leading to a limiting molar ion conductivity for the CF3SO
3
−
ion of 44.5±0.2 S-cm2-mol-1, based on standard values for the cations. Using a simple size parameter for unsymmetrical polyatomic ions, based on the
ion geometry, it is shown that the well known empirical relation between the molar conductivities of symmetrical ions and
their radii can be extended to include certain polyatomic anions including CF3SO
3
−
. The results suggest that the CF3SO
3
−
ion is either a weak structure breaker in aqueous solution or neutral in this respect. 相似文献
1000.