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1.
2.
A series of trinuclear metal clusters MS4(M'PPh3)2(M'PPh3) (M = Mo, W; M' = Cu, Ag, Au) have been studied using the density functional theory (DFT) method. The static polarizabilities and hyperpolarizabilities of the model clusters have been calculated using the finite-field (F-F) method. The model clusters, divided into two groups, are alike in the structure of two fragments of rhombic units M-(mu-S)2-M' (M = Mo, W; M' = Cu, Ag, Au), perpendicular to each other, which are joined by sharing the bridge metal M. It is the charge transfer from one of these moieties to the other in these characteristic sulfido-transitional metal cores that is responsible for the polarizabilities and hyperpolarizabilities. This kind of electronic delocalization, different from that of the planar pi-system, is interesting and warrants further investigation. The structural effects on properties are important. In these models, considerable third-order nonlinearities are exhibited. The element substitution effect of Mo and W is weak, while that of Cu and Ag is relatively substantial. An overall order is gamma xxxx(Mo-Ag) > gamma xxxx(W-Ag) > gamma xxxx(Mo-Au) > gamma xxxx(W-Au) > gamma xxxx (Mo-Cu) > gamma xxxx(W-Cu) and gamma av(Mo-Ag) approximately gamma av(W-Ag) > gamma av(Mo-Au) approximately gamma av(W-Au) approximately gamma av (Mo-Cu) approximately gamma av(W-Cu). 相似文献
3.
Arie van Der Kaaden Johan Haverkamp Jaap J. Boon Jan W. De Leeuw 《Journal of Analytical and Applied Pyrolysis》1983,5(3):199-220
Inorganic additives, viz. Na2CO3, NaOH, HCl, ZnC2, NaH2PO4, Na2HPO4, NaCl. MgSO4 and sea salt, to the pyrolysis matrix change the pyrolysis-mass spectrum of amylose significantly. Carbonyl compounds, acids and their lactones, furans, pyranones anhydrosugars and aromatic substances are found in different ratios under the various conditions, as determined by pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS).Carbonyl compounds, acids and lactones are released from alkaline and neutral matrices. Furans and anhydrohexoses are particularly formed under neutral and acidic conditions. Pyranones are specific for phosphate matrices. Unsaturated hydrocarbons and aromatic substances arise from strongly alkaline or dehydrating matrices. Degradation pathways are proposed for various compound categories.The results of pyrolysis-mass spectrometry and Py-GC-MS are highly compatible. 相似文献
4.
Determination of trans-galactooligosaccharides in selected food products by ion-exchange chromatography: collaborative study 总被引:1,自引:0,他引:1
de Slegte J 《Journal of AOAC International》2002,85(2):417-423
Eleven collaborating laboratories assayed 7 blind duplicate pairs of food and feed products for tans-galactooligosaccharides. The 7 laboratory sample pairs ranged from low (2%) to high levels (15%). Following the proposed method, the test samples were treated with beta-galactosidase and the released galactose was determined by ion-exchange chromatography. Repeatability standard deviation ranged from 2.9 to 11.6%; reproducibility standard deviation ranged from 4.6 to 11.6%. 相似文献
5.
The static polarizabilities and the second-order hyperpolarizabilities of a series of tri-nuclear metal cluster models MS4(M′PPh3)2(M′PPh3)(M=Mo,W;M′=Cu,Ag,Au)have been calculated within the first-principle theoretical framework. The model clusters have two fragments of rhombic units and it is the charge ransfer from one of these moieties to the other that is responsible for nonlinear optical property. This kind of electronic delocaization, differentiated from that of planar π-system, is very interesting and is worthy for further investigation. 相似文献
6.
Stassen AF Kooijman H Spek AL de Jongh LJ Haasnoot JG Reedijk J 《Inorganic chemistry》2002,41(24):6468-6473
Two new isostructural compounds, dichlorobis(1-(2-chloroethyl)tetrazole)copper(II) (1) and dibromobis(1-(2-chloroethyl)tetrazole)copper(II) (2), have been prepared. The synthesis, characterization, and spectral and magnetic properties as well as the crystal and molecular structures of 1 and 2 have been studied. Both complexes form two-dimensional, distorted square grid planes of copper and halides, distinctly separated by layers of tetrazole ligands. The differential (ac) magnetic susceptibility, chi = (deltaM/deltaH)(T), and magnetization M(H) of both complexes have been studied as a function of temperature and field. The compounds possess a ferromagnetic interaction within the isolated copper-halide layers (J/k(B) = 8.0 K, J/k(B) = 10.2 K, respectively, for the chloride and the bromide, and T(c) = 4.75 K, T(c) = 8.01 K). The magnetic coupling J'/k(B) between the different layers is found to be very weak (|J'/J| 相似文献
7.
Paramagnetic species are formed when LiBipy is treated with various alkylzinc halides at ?100°C and the ESR spectra are discussed. The observation that the half-life times of the radical species appear to depend only on the nature of the alkyl group bound to zinc proves that monoalkylzinc-2,2′-bipyridine complexes are formed. The nature of the bonding between zinc and 2,2′-bipyridine is discussed. 相似文献
8.
PHOTOSENSITIZING PROPERTIES OF BACTERIOCHLOROPHYLLIN a and BACTERIOCHLORIN a, TWO DERIVATIVES OF BACTERIOCHLOROPHYLL a 总被引:2,自引:0,他引:2
Eva M. Beems Tom M. A. R. Dubbelman Johan Lugtenburg Jaap A. van Best Monique F. M. A. Smeets J. Pierre J. Boegheim 《Photochemistry and photobiology》1987,46(5):639-643
Abstract The photosensitizing properties of two water soluble derivatives of bacteriochlorophyll a , bacteriochlorophyllin a and bacteriochlorin a (lacking the central Mg-ion) were investigated and compared to those of hematoporphyrin derivatives. At physiological pH the oxygen consumption rate of histidine, tryptophan, dithiothreitol and guanosine upon illumination was 3 to 4 times higher when bacteriochlorin a was used as photosensitizer than when hematoporphyrin derivatives were used. Especially bacteriochlorin a proved to be an effective sensitizer for the killing of L929 cells. Because bacteriochlorin a has an absorption maximum at 765 nm in phosphate buffered saline (allowing a light penetration in tissue about ten times larger than at 630 nm) and a high molar absorption coefficient (32 000 M cm−1 ) it has promising possibilities for the application in photodynamic therapy. 相似文献
9.
Search on ruggedness of fast gas chromatography-mass spectrometry in pesticide residues analysis 总被引:1,自引:0,他引:1
Kirchner M Matisová E Otrekal R Hercegová A de Zeeuwb J 《Journal of chromatography. A》2005,1084(1-2):63-70
In this study, suitability of fast gas chromatography-mass spectrometry (GC-MS) on a narrow-bore column with a programmed temperature vaporizer for the analysis of pesticide residues in non-fatty food was evaluated. The main objectives were ruggedness and stability of chromatographic system with regards to co-extractives injected. The chromatographic matrix induced response enhancement was found to be strongly dependent on the concentration of residues and is reaching up to 700% compared to the pesticides solutions in a neat solvent. However, the responses of pesticides in matrix-matched standards at different concentration levels do not significantly change during 130 injections. Response enhancement/or decrease is influenced by the sample preparation technique. External calibration with matrix-matched calibration standards should, therefore, provide results with good precision also at the concentration level of 0.005 mg kg(-1). Special attention is given to the performance of the chromatographic column and retention gap with regards to peak widths, peak tailing and different sample preparation methods. During approximately 460 matrix sample injections, the performance of the analytical column was acceptable. GC-MS set-up with 0.15 mm i.d. column can be successfully utilized for the pesticide residues analysis. 相似文献
10.
Stortelder A Buijs JB Bulthuis J van der Vies SM Gooijer C van der Zwan G 《Journal of photochemistry and photobiology. B, Biology》2005,78(1):53-60
The time-resolved fluorescence properties of the bacteriophage T4 capsid protein gp23 are investigated. The structural characteristics of this protein are largely unknown and can be probed by recording time-resolved and decay-associated fluorescence spectra and intensity decay curves using a 200 ps-gated intensified CCD-camera. Spectral and decay data are recorded simultaneously, which makes data acquisition fast compared to time-correlated single-photon counting. A red-shift of the emission maximum within the first nanosecond of decay is observed, which can be explained by the different decay-associated spectra of fluorescence lifetimes of the protein in combination with dipolar relaxation. In addition, iodide quenching experiments are performed, to study the degree of exposure of the various tryptophan residues. A model for the origin of the observed lifetimes of 0.032 +/- 0.003, 0.39 +/- 0.06, 2.1 +/- 0.1 and 6.8 +/- 0.8 ns is presented: the 32 ps lifetime can be assigned to the emission of a buried tryptophan residue, the 0.4 and 2.1 ns lifetimes to two partly buried residues, and the 6.8 ns lifetime to a single tryptophan outside the bulk of the folded gp23. 相似文献