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971.
New alkyl-substituted phosphorus phthalocyanines and triazatetrabenzocorroles were synthesized. The structures of these complexes
were confirmed by 1H, 13C, and 31P NMR spectroscopy, mass spectrometry, and electronic absorption spectroscopy.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1403–1407, July, 2007. 相似文献
972.
B. A. Korolev L. A. Osmolovskaya Yu. V. Kuznetsov L. G. Stolyarova L. D. Smirnov 《Russian Chemical Bulletin》1992,41(2):333-336
Examination of the acid-base properties of 5-hydroxybenzimidazoles has shown them to exist in nitromethane as the 5-hydroxy-tautomers. Substituents in the 2-position have a predominantly inductive effect on the basicity of the 3-nitrogen, rationalized as in other nitrogen heterocycles by the proximity of the substituents to the reaction center.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. The Research Institute for Intermediates and Dyes, 103787 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 421–425, February, 1992. 相似文献
973.
Sample evaporation in splitless injection of large volumes is rapid: depending on the experiment, results indicate that 200 μl of hexane, for instance, evaporates in 2–10 s, producing vapor at a rate of many hundreds of milliliters per minute. A 60 × 4 mm packed bed of 20–35 mesh Tenax TA enabled injection of 200 μl volumes of all solvents tested, and even 1 ml injections were possible provided they were performed over a period of 30 s. Retention of volatile sample components depends on the sample solvent, the injection volume, and the injection speed, but only little on the injector temperature. Losses of n-tridecane varied from hardly 15 % (when dissolved in pentane) to ca 60 % (ethyl acetate); losses of n-heptadecane were usually below 20 %. The column temperature during injection should be at least ca 20–30°C above the standard solvent boiling point. 相似文献
974.
S type Gaussian bond functions are optimized for HF, H2O, NH3, and CH4. The optimization is carried out with respect to the exponent and position in the H-X bond. The position is found to correlate
well with the electronegativity of Pauling and Allred-Rochow. 相似文献
975.
H. Nickel und R. Schaeps 《Fresenius' Journal of Analytical Chemistry》1976,281(3):193-199
Zusammenfassung Es wird über die Beeinflussung spektrochemischer Ergebnisse durch homogene Magnetfelder und Zusatzsubstanzen bei Lichtbogenanregung berichtet. Der Einfluß eines homogenen Magnetfeldes auf die Gesamtintensität der Linien verschiedener Analysenelemente (Hg, Zn, Ga, Tl) in Graphit wurde untersucht. Außerdem wurden die axialen und radialen Verteilungen der Linienintensitäten im Bogenplasma bestimmt. Als Parameter dienten die Magnetfeldstärke (0, 0,01, 0,02, 0,04 T) und die physikalischen Daten der Analysenelemente. Dabei wurde festgestellt, daß die Wirkung des Magnetfeldes vom Ionisationspotential der beteiligten Elemente, von ihrer Atommasse und von der angewendeten Magnetfeldstärke abhängig ist.Weiterhin wurde der Einfluß eines homogenen Magnetfeldes auf die Verdampfungsrate mit Hilfe einer kontinuierlich und zerstörungsfrei arbeitenden Meßmethode untersucht. Es zeigte sich, daß die Verdampfungsrate bei Anwendung eines Magnetfeldes in Abhängigkeit von der Verdampfungswärme der Elemente erhöht wird.Die Auswirkung der Zusatzsubstanz Ga2O3 auf die Linienintensitäten der Verunreinigungen wird von der Ga2O3-Konzentration und vom Ionisationspotential der untersuchten Elemente beeinflußt.
On the influence of additives and homogeneous magnetic fields on the arc as a spectrochemical source of excitationI. Spectrochemical investigations in graphite mixtures
The paper deals with homogeneous magnetic fields and added chemical substances both affecting the spectrochemical results obtained in arc excitation studies. The influence of a homogeneous magnetic field on the total intensity of lines of various analysis elements (Hg, Zn, Ga, Tl) in graphite has been examined. Furthermore, the axial and radial distributions of line intensities in arc plasma were determined. Parameters used were the magnetic field strength (0, 0.01, 0.02, 0.04 T) and the physical data of the analysis elements. It was found that the effect of the magnetic field varies with the ionization potential of the elements involved, their atomic mass and the strength of the magnetic field applied.A non-destructive method of measuring was introduced for studying the effects of a homogeneous magnetic field on the rates of evaporation. The results showed increased evaporation rates in presence of magnetic fields as a function of the evaporation heat of the elements involved.Effects of Ga2O3 additive on the line intensities of impurity elements are governed by the Ga2O3 concentration and the ionization potential of the elements examined.相似文献
976.
Klaus Rakus Sergej P. Verevkin Hans-Dieter Beckhaus Christoph Rüchardt 《欧洲无机化学杂志》1994,127(11):2225-2234
The thermolysis reactions of the tricyanomethyl compounds 10a-c were studied in solution. 2,2-Dicyano-3-methyl-3-phenylbutyronitrile ( 10a ) and 2,2-dicyano-3-methyl-3-(4-nitrophenyl)butyronitrile ( 10b ) decomposed heterolytically into carbenium ions and (CN)3C− anions, while 9-methyl-9-(tricyanomethyl)fluorene ( 10c ) underwent about 11% homolytic C-C bond cleavage into 9-methyl-9-fluorenyl- and tricyanomethyl radicals. The rates of the homolysis were determined by a radical scavenger procedure under conditions of pseudozero order kinetics. From the temperature effect on the rate constants the activation parameters were determined [ΔH ( 10c ) = 155· 2 kJ mol−1, ΔS ( 10c ) = 58· 5 J mol−1 K−1]. Standard enthalpies of formation ΔH (g) were determined for 2,2-dicyanopropionitrile ( 2 ) (422.45 kJ mol−1), 2,2-dicyanohexanenitrile ( 3 ) (349.74 kJ mol−1), 2,2-dicyano-3-phenylpropionitrile ( 4 ) (540.75 kJ mol−1), 2-butyl-2-methylhexanentrile ( 5 ) (-133.20 kJ mol−1), 2,2-dimethylpentanenitrile ( 6 ) (-45.78 kJ mol−1), and 2-methylbutyronitrile ( 7 ) (2.44 kJ mol−1) from the enthalpies of combustion and enthalpies of sublimation/vaporization. From these data and known Δ (g) values for alkanenitriles and -dinitriles, thermochemical increments for ΔH (g) were derived for alkyl groups with one, two, or three cyano groups attached. The comparison of these increments with those of alkanes reveals a strong geminal destabilization, which is interpreted by dipolar repulsions between the cyano groups. - From ΔH (g) of 10c and ΔH of its homolytic decomposition the radical stabilization enthalpy for the tricyanomethyl radical 1 RSE ( 1 ) = -18 kJ mol−1 was determined. Thus, 1 is destabilized, in comparison with the RSEs of tertiary α-cyanalkyl (23 kJ mol−1) and α,α-dicyanoalkyl (27 kJ mol−1) radicals, which were recalculated from bond homolysis measurements[4] and the new thermochemical data. This change of RSE on increasing the number of α-cyano groups is discussed as the result of the additive contributions by resonance stabilization and increasing destabilization by dipolar repulsion. The amount of the dipolar energies was estimated by molecular mechanics (MM2). 相似文献
977.
纳米多孔双金属氧化物在镍钛合金纤维上的原位生长及其对多环芳烃的选择性固相微萃取 总被引:1,自引:0,他引:1
采用阳极氧化法在镍钛合金(NiTi)纤维上原位生长了双金属氧化物纳米孔(NiTiONPs)涂层,通过扫描电镜(SEM)和能谱(EDS)考察了电解质组成和电压对形貌的影响。将NiTiONPs涂层的NiTi纤维与高效液相色谱-紫外检测器联用,研究了4种典型芳香分析物的萃取性能。结果表明,富含TiO2的NiTiONPs涂层对多环芳烃(PAHs)具有良好的萃取效率,尤其对苯并[a]芘的萃取选择性优于市售聚二甲基硅氧烷纤维和聚丙烯酸酯纤维。在优化条件下,PAHs的线性范围为0.05~200μg/L,相关系数均大于0.999,检出限为0.012~0.134μg/L。对单支纤维日内和日间分析的相对标准偏差(RSDs)分别为4.0%~5.5%和6.0%~6.8%,使用分批组装的5支纤维分析的RSDs为6.4%~7.6%。实际水样分析的加标回收率为84.5%~111.5%。所制备NiTi纤维至少可重复使用250次以上,重现性好。 相似文献
978.
979.
Selective detection and identification of Se containing compounds--review and recent developments 总被引:5,自引:0,他引:5
The complexity of selenium (Se) chemistry in the environment and in living organisms presents broad analytical challenges. The selective qualitative and quantitative determination of particular species of this element is vital in order to understand selenium's metabolism and significance in biology, toxicology, clinical chemistry and nutrition. This calls for state-of-the-art analytical techniques such as hyphenated methods that are reviewed with particular emphasis on interfaced separation with element-selective detection and identification of the detected selenium compounds. Atomic spectral element specific detection for monitoring chromatographic eluent enabled quantitative determination of selenium species in selenized yeast and qualitative measurement for breath samples. Gas chromatography with atomic emission detection (AED) of ethylated species and fluoroacid ion pair HPLC applied to the analysis of currently produced or archived selenized yeast and Brassica juncea have revealed the presence of a previously unrecognised Se-S amino acid, S-(methylseleno)cysteine. 相似文献
980.
采用表面改性法制备了负载型Ni2(OEt)2/SiO2双核金属乙氧基配合物催化剂,利用示差量热、红外光谱和微反技术对催化剂的表面结构、热稳定性、化学吸附性质和催化活性进行了研究.结果表明,负载型双核金属乙氧基配合物Ni2(OEt)2/SiO2中的Ni2+与载体SiO2表面的O2-以双齿配位形式键合;二氧化碳在催化剂表面存在桥式吸附态和碳酸单乙酯基物种两种吸附态,丙烯则只有一种分子吸附态;在适宜的反应条件下,二氧化碳和丙烯在Ni2(OEt)2/SiO2催化剂上的反应产物主要是甲基丙烯酸.根据实验结果,提出了二氧化碳和丙烯在Ni2(OEt)2/SiO2催化剂表面的反应机理,反应物分子共吸附于催化剂表面同一活性单元上,羧酸根和丙烯解离吸附态的形成是反应顺利进行的关键步骤. 相似文献