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21.
Stefan Müllegger Kathrin H?nel Thomas Strunskus Christof W?ll Adolf Winkler 《Chemphyschem》2006,7(12):2552-2558
Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy has been applied to reveal the molecular arrangement of ultrathin oligophenyl films [p-quaterphenyl (4P) and p-hexaphenyl (6P)] on Au(111). In the half-monolayer films the molecules lie flat on the surface but still have a considerable inter-ring twist of 30 degrees -40 degrees , similar to the gas-phase conformation. In the saturated monolayer film the second half of the molecules is side-tilted by an angle of less than 66 degrees with respect to the surface. This arrangement is already similar to that in bulk net planes of thicker films parallel to the surface, that is, the 4P(211) and 6P(21-3) planes, respectively. 相似文献
22.
Threshold energies Et are determined for photoelectron emission by 20 inorganic anions in aqueous solution (7.1 < Et < 9.1 eV). Calculated values of Et for Cl?, Br?, I? agree with experiment. The Et are correlated with charge-transf absorption spectra. 相似文献
23.
Field SJ Thornton NP Anderson LJ Gates AJ Reilly A Jepson BJ Richardson DJ George SJ Cheesman MR Butt JN 《Dalton transactions (Cambridge, England : 2003)》2005,(21):3580-3586
Protein film voltammetry of Paracoccus pantotrophus respiratory nitrate reductase (NarGH) and Synechococcus elongatus assimilatory nitrate reductase (NarB) shows that reductive activation of these enzymes may be required before steady state catalysis is observed. For NarGH complementary spectroscopic studies suggest a structural context for the activation. Catalytic protein film voltammetry at a range of temperatures has allowed quantitation of the activation energies for nitrate reduction. For NarGH with an operating potential of ca. 0.05 V the activation energy of ca. 35 kJ mol-1 is over twice that measured for NarB whose operating potential is ca. -0.35 V. 相似文献
24.
The impact of spilled explosives, their by-products and degradation products on human beings and the environment has been
recognised as a serious problem at areas of existing and former ammunition plants. In nature, aerobic and anaerobic degradation
processes of explosives and their accompanying compounds yield polar contaminants with relatively high water solubilities.
Most are potentially carcinogenic and mutagenic. An HPLC method applying UV-detection for nitroaromatic compounds and amperometric
detection for aminoaromatic and phenolic compounds was used for monitoring the degradation of explosives in a polluted groundwater
sample under natural conditions. Analysis was performed by direct injection of aliquots of the sample after exposition to
daylight for different periods of time.
Presented as a poster at the Anakon ’95 Conference in Schliersee, April 24–26, 1995 相似文献
25.
Cytotoxicity and Antiproliferative Effect of Hypericin and Derivatives after Photosensitization 总被引:3,自引:1,他引:3
Ann L. Vandenbogaerde Els M. Delaey Annelies M. Vantieghem Bernard E. Himpens Wilfried J. Merlevede Peter A. de Witte 《Photochemistry and photobiology》1998,67(1):119-125
The toxicity on three human tumor cell lines (A431, HeLa and MCF7) of five phenanthroperylenequinones (hypericin and derivatives) and two perylenequinones (cercosporin and calphostin C) was investigated after photosensitization (4 J/cm2 ). Furthermore, the antiproliferative effect on HeLa cells was studied for the phenanthroperylenequinones. Hypericin, 2,5-dibromohypericin, 2,5,9,12-tetrabromohypericin and perylenequinones displayed a potent cytotoxic and antiproliferative effect in the nanomolar range. Hypericin dicarboxylic acid exhibited no photoactivity. In general, the antiproliferative activity correlated well with the photocytotoxicity. However, the nonphotocytotoxic compound hexamethylhypericin showed potent antiproliferative activity in the nanomolar range, probably exerting its action by protein kinase C inhibition. Without light irradiation, no cytotoxic and antiproliferative effect was observed for any photocytotoxic phenanthroperylenequinone compound. Furthermore, confocal laser microscopy revealed that the subcellular localization in A431 cells was similar for the photoactive compounds; the photosensitizers were mainly concentrated in the perinuclear region, probably corresponding with the Golgi apparatus and the endoplasmic reticulum. In addition, the accumulation of the photosensitizers in HeLa cells was investigated. All compounds except hypericin dicarboxylic acid were found to concentrate to a large extent in the cells. The compound 2,5,9,12-tetrabromohypericin seemed intrinsically more effective than hypericin since the intracellular concentration of the bromoderivative was a magnitude of order lower than that of hypericin although both compounds showed similar photobiological activity. 相似文献
26.
Igumenova TI McDermott AE Zilm KW Martin RW Paulson EK Wand AJ 《Journal of the American Chemical Society》2004,126(21):6720-6727
Solid-state NMR 2D spectroscopy was used to correlate carbon backbone and side-chain chemical shifts for uniformly (13)C,(15)N-enriched microcrystalline ubiquitin. High applied field strengths, 800 MHz for protons, moderate proton decoupling fields, 80-100 kHz, and high magic angle sample spinning frequencies, 20 kHz, were used to narrow the most of the carbon line widths to 0.5-0.8 ppm. Homonuclear magnetization transfer was effected by matching the proton RF field to the spinning frequency, the so-called dipolar-assisted rotational resonance (DARR) (Takegoshi, K.; Nakamura, S.; Terao, T. Chem. Phys. Lett. 2001, 344, 631-637), and a mixing time of 20 ms was used to maximize the intensity of one-bond transfers between carbon atoms. This polarization transfer sequence resulted in roughly 14% transfer efficiencies for directly bonded carbon pairs and 4% transfer efficiencies for carbons separated by a third carbon. With this simple procedure, the majority of the one-bond correlations was observed with moderate transfer efficiencies, and many two-bond correlations were also observed with weaker intensities. Spin systems could be identified for more than half of the amino acid side chains, and site-specific assignments were readily possible via comparison with 400 MHz (15)N-(13)C-(13)C correlation spectroscopy (described separately). 相似文献
27.
Gaussian basis sets, consisting of 15 s-type, 11 p-type, and 6 d-type functions, for the fourth-row main group elements, In-Xe, are presented. In order to compare these basis sets with larger ones, calculations have been performed in I2 and TeO2. 相似文献
28.
Natural products have been synthesized for billions of years in animals, plants, and microorganisms. As a rule they occur enantiomerically pure. Their chiral character corroborates their use in metabolism or as biologically active agents. Natural products may be insufficient in quality or quantity. They have recently begun to become accessible, either unchanged or modified, by biological synthesis; here, too, they are obtained enantiomerically pure. In the last twenty years chemical synthesis has become a major concern of organic chemists. Their target compounds are primarily enantiomerically pure natural products or biologically active variants thereof. 相似文献
29.
Johansson A Abrahamsson M Magnuson A Huang P Mårtensson J Styring S Hammarström L Sun L Akermark B 《Inorganic chemistry》2003,42(23):7502-7511
The preparation of donor (D)-photosensitizer (S) arrays, consisting of a manganese complex as D and a ruthenium tris(bipyridyl) complex as S has been pursued. Two new ruthenium complexes containing coordinating sites for one (2a) and two manganese ions (3a) were prepared in order to provide models for the donor side of photosystem II in green plants. The manganese coordinating site consists of bridging and terminal phenolate as well as terminal pyridyl ligands. The corresponding ruthenium-manganese complexes, a manganese monomer 2b and dimer 3b, were obtained. For the dimer 3b, our data suggest that intramolecular electron transfer from manganese to photogenerated ruthenium(III) is fast, k(ET) > 5 x 10(7) s(-)(1). 相似文献
30.
Vacuum ultraviolet natural and magnetic circular dichroism measurements have added significantly to our knowledge of the geometric and electronic structure of molecules and have provided a better understanding of the correct approach for theoretical calculations. In this review, I define natural and magnetic circular dichroism, and discuss information obtained with these techniques. The instrumentation for vacuum ultraviolet natural and magnetic circular dichroism is reviewed, from its beginning with conventional sources to the present time use of synchrotron radiation. The future possibilities and challenges for these measurements are examined with particular reference to making measurements to higher energies. 相似文献