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11.
Haralampus-Grynaviski N Ransom C Ye T Rôzanowska M Wrona M Sarna T Simon JD 《Journal of the American Chemical Society》2002,124(13):3461-3468
Urocanic acid, UCA, is characterized by two electronic transitions in the UV-B (280-320 nm) which comprise its broad absorption spectrum and give rise to wavelength-dependent isomerization quantum yields. The absorption spectrum of UCA extends into the UV-A (320-400 nm). Given the UV-A component of sunlight is significantly greater than the UV-B component it is hypothesized even weak UV-A photochemistry of UCA could be important for in vivo responses to UV radiation. Degenerate pump-probe experiments performed on t-UCA at several wavelengths in the UV-A reveal an excited-state absorption that undergoes a rapid, approximately 1 ps decay. Photoacoustic experiments performed on both the cis and trans isomers reveal the formation of a long-lived intermediate following UV-A excitation. The efficiency and action spectra for this latter photoactive process are presented and are similar for both isomers of UCA. Cholesterol hydroperoxide assays designed to investigate the nature of the UV-A photoreactivity of t-UCA confirm the production of reactive oxygen species. The bimolecular rate constant for the quenching of singlet oxygen by t-UCA is determined to be 3.5 x 10(6) M(-1) s(-1). Taking into consideration recent theoretical calculations and jet expansion studies of the electronic structure of gas-phase t-UCA, a model is proposed to explain the isomerization and photoreactivity of t-UCA in solution over the UV-A region. 相似文献
12.
Two new Schiff base macrocycles - a 4+4 condensation product and a meso-type 2+2 condensation product - were obtained in a reaction of trans-1,2-diaminocyclohexane and 2,6-diformylpyridine. Reduction of these compounds led to the corresponding 4+4 and 2+2 macrocyclic amines. The macrocycles were characterised by NMR spectroscopy and electrospray mass spectrometry. The symmetry and stereochemistry of these macrocycles, as well as of new 3+3 and 4+4 diastereomers identified in solution, has been established. X-Ray structures of the 2+2 and 4+4 Schiff base macrocycles confirm the configurations determined on the basis of spectroscopic investigations. The crystal structures reveal that the centres of the square-shaped 4+4 macrocycles form channels as a result of columnar stacking. 相似文献
13.
Optimized conditions for hydrocarbon group type analysis of base oils by thin-layer chromatography-flame ionisation detection 总被引:1,自引:0,他引:1
The results of research on the optimization of the thin-layer chromatography-flame ionisation detection for the determination of group composition of natural base oils, including separation of the aromatics into subgroups, are presented. Neutral base oils obtained in several steps of refining from vacuum distillation petroleum fractions are the most difficult to analyze by hydrocarbon group type analysis (HGTA) because of the high content of aliphatic fragments in their molecules. Factors affecting the accuracy and precision of the results were identified. The paper presents the analytical procedure, including two different calibration methods, as well as the results of studies on the reproducibility of HGTA of typical base oils of different viscosity classes under the optimized conditions. The same conditions were found suitable for HGTA of other high-boiling petroleum fractions by TLC with flame ionisation detection. The paper also introduces a new procedure for reproducible determination of polar fractions in base oils utilizing solid-phase extraction columns, and presents a corrected procedure for the determination of saturated compounds and aromatics (mono-, bi- and polycyclic) in base oils by column liquid chromatography. 相似文献
14.
Micha? K. Cyrański Paul von Ragué Schleyer Tadeusz M. KrygowskiHaijun Jiao Georg Hohlneicher 《Tetrahedron》2003,59(10):1657-1665
The stability of a set of 105 five-membered π-electron systems (involving aromatic, non-aromatic and anti-aromatic species) was evaluated using six isodesmic reactions of which two belong to the subclass of homodesmotic reactions, which are based on cyclic and acyclic reference systems. We demonstrate that the ‘Resonance Energies’ derived from isodesmotic schemes have obvious flaws and do not correct or cancel other contributions to the energy, such as the changes of hybridization, homoconjugation of heterosubstituted cyclopentadienes, conjugative interactions of CC or CX (X=N or P) with a π or pseudo π orbital at Y (Y=O, S, NH, PH), strain, etc. as effectively as possible. Likewise, ‘aromatic stabilization energies (ASE)’ derived from homodesmotic schemes based on the acyclic reference compounds do not give satisfactory results. We strongly recommend that only cyclic reference compounds should be used for ASE and other aromaticity evaluations. The analysis is based on ab initio optimized geometries at B3LYP/6-311+G∗∗. 相似文献
15.
Przychodzeń P Lewiński K Bałanda M Pełka R Rams M Wasiutyński T Guyard-Duhayon C Sieklucka B 《Inorganic chemistry》2004,43(9):2967-2974
The syntheses, X-ray structures, and magnetic behaviors of two new cyano-bridged assemblies, the molecular [Mn(III)(salen)H2O]3[W(V)(CN)8].H2O (1) and one-dimensional [Mn(salen)(H2O)2]2[[Mn(salen)(H2O)][Mn(salen)]2[Mo(CN)(8)]].0.5ClO4.0.5OH.4.5H2O (2), are presented. Compound 1 crystallizes in the monoclinic system, has space group P2(1)/c, and has unit cell constants a = 13.7210(2) A, b = 20.6840(4) A, c = 20.6370(2) A, and Z = 4. Compound 2 crystallizes in the triclinic system, has space group P, and has unit cell dimensions a = 18.428(4) A, b = 18.521(3) A, c = 18.567(4) A, and Z = 2. The structure of 1 consists of the asymmetric V-shaped Mn-NC-W-NC-Mn-O(phenolate)-Mn molecules, where W(V) coordinates with [Mn(salen)H2O] and singly phenolate-bridged [Mn(salen)H2O]2 moieties through the neighboring cyano bridges. The [W(V)(CN)8]3- ion displays distorted square-antiprism geometry. The structure of 2 consists of the cyano-bridged [Mn3(III)Mo(IV)]n- repeating units linked by double phenolate bridges into one-dimensional zigzag chains. The Mn(III) centers are bound to Mo(IV) of square-antiprism geometry through the neighboring cyano bridges. The magnetic studies of 1 reveal the antiferromagnetic intramolecular interactions through the CN and phenolate bridges and the relatively weak intermolecular interactions. Compound 1 becomes antiferromagnetically ordered below TN = 4.6 K. The presence of the magnetic anisotropy is documented with the MH measurements carried out for both polycrystalline and single-crystal samples. At T = 1.9 K, the spin-flop transition is observed in the field of 18 kOe applied parallel to the bc plane, which is the easy plane of magnetization. Field dependence of magnetization of 1 shows field-induced metamagnetic behavior from the antiferromagnetic ground state of ST = 3/2 to the state of ST = 5/2. The magnetic properties of 2 indicate a weak antiferromagnetic interaction between Mn(III) centers in double-phenolate-bridged [Mn(III)(salen)]2 dinuclear subunits and a very weak ferromagnetic interaction between them through the diamagnetic [Mo(IV)(CN)8]4- spacer. 相似文献
16.
For a technology little over a decade old, comprehensive two-dimensional gas chromatography (GC x GC) has quickly reached the status of one of the most powerful analytical tools for volatile organic compounds. At the heart of any GC x GC system is an interface, which physically connects the primary and the secondary columns and acts to preserve the separation obtained in the first dimension (first column) while allowing additional separation in the second dimension. The paper presents a review of the technology, including fundamental principles of the technique, data processing and interpretation and a timeline of inventive contributions to interface design. In addition, applications of the technique are presented, with a more detailed discussion of selected examples. 相似文献
17.
Five new antifungal bengazoles (C-G) were isolated and fully characterized from a marine sponge of the genus Jaspis sp. Bengazoles C-G, together with the known bengazoles A and B, comprise a homologous series of n, iso, and anteiso fatty acid esters (C(13)-C(16)) of the same heterocyclic bis(oxazolyl)methanol parent. The complete relative and absolute configurations of the bengazoles were determined by application of the modified Mosher method and interpretation of exciton coupling in the CD spectra of the tetra-p-bromobenzoate derivatives of bengazole A and that of a model tetrol synthesized in seven steps from L-fucose. 相似文献
18.
Andrzej Machocki Tadeusz Borowiecki Andrezej Denis 《Reaction Kinetics and Catalysis Letters》1993,51(2):541-545
The studies of the influence of the kind of natural calcium mineral and the kind and amount of sodium promoter on the conversion degree of methane and oxygen, selectivity and yield of the oxidative conversion of methane have shown the usability of limestone as a basic component of the catalyst for this process. 相似文献
19.
A new liquid nitrogen (LN2) jet-based thermal modulator for performing comprehensive two-dimensional (2D) gas chromatographic (GC x GC) separations has been designed and constructed. Temperature measurements of the trapping zone, a segment of uncoated fused silica capillary, show that it can be cooled to -196 degrees C in about 300 ms. A film of liquid nitrogen develops on the outside of the trapping capillary even when the oven temperature is in excess of 200 degrees C. Compounds as volatile as propane can be trapped by the modulator and held for periods of at least 1 min without breakthrough. The peak widths for n-alkanes are on the order of 80 ms at half height after passing through an 80cm second dimension column. Repeated analysis of gasoline demonstrated excellent run-to-run reproducibility of the system. 相似文献
20.
Witold Danikiewicz Tadeusz Jaworski Stefan Kwiatkowski 《Monatshefte für Chemie / Chemical Monthly》1986,117(10):1177-1184
Starting from methyl 7-oxo-7-(1-cyclopentene)-heptanoate, a simple synthesis of the methyl esters of 7-oxo- and 7-hydroxy-9,11-dideoxy-PGF
1 as a model for 7-substituted prostaglandin analogues is described.
7-Substituierte Prostaglandin-Analoge — ein neuer Syntheseweg
Zusammenfassung Ausgehend von Methyl-7-oxo-7-(1-cyclopenten)-heptanoat wird eine einfache Synthese der Methylester von 7-Oxo- und 7-Hydroxy-9,11-dideoxy-PGF 1 als Modellverbindungen für 7-substituierte Prostaglandinanaloge beschrieben.相似文献