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81.
Diana Cruz-Garritz Juventino Garcia-Alejandre Hugo Torrens Cecilio Alvarez Raul A. Toscano Rene Poilblanc Alain Thorez 《Transition Metal Chemistry》1991,16(1):130-135
Summary The thiolato-bridged dinuclear compounds [Rh(-SR)-(COD)]2, where R=p-C6HF4 (1),p-C6H4F (2) and CF3 (3), are obtained from the chloro-bridged analogue by ligand exchange.Compound (1) crystallizes in the space group P1 with a=9.740(3)Å, b=11.642(4)Å, c=13.997(6)Å, =103.87(3)°, =106.98(3)° and =105.10(2)°; z=2. In this dinuclear molecule both Rh atoms have a square planar coordination sharing one edge, namely the two sulphur bridging atoms. The Rh—Rh separation of 2.96 Å is consistent with at most a very weak metal-metal interaction. Upon addition of CO the dimeric [Rh(-SR)(CO)2]2 (4), (5) and (6) are obtained, but addition of PPh3 affords the monomeric species [Rh(SR)(PPh3)-(COD)] (7), (8) and (9). Reactions of the dimeric tetracarbonyl derivatives with PPh3 vary with the nature of R; [Rh(-SR)(PPh3)(CO)]2 is obtained when R=p-C6H4F (10) and CF3 (11) but monomeric [Rh(SR)-(PPh3)(CO)2] (12) is produced when R=p-C6HF4. The latter mononuclear compounds, with R=p-C6H4F (13) and CF3 (14), are also formed by reaction of [Rh(SR)-(PPh3)(COD)] with CO. 相似文献
82.
Primary photodamage sites and mitochondrial events after Foscan photosensitization of MCF-7 human breast cancer cells 总被引:4,自引:0,他引:4
Teiten MH Marchal S D'Hallewin MA Guillemin F Bezdetnaya L 《Photochemistry and photobiology》2003,78(1):9-14
To determine the initial photodamage sites of Foscan-mediated photodynamic treatment, we evaluated the enzymatic activities in selected organelles immediately after light exposure of MCF-7 cells. The measurements indicated that the enzymes located in the Golgi apparatus (uridine 5'-diphosphate galactosyl transferase) and in the endoplasmic reticulum (ER) (nicotinamide adenine dinucleotide [reduced] [NADH] cytochrome c [cyt c] reductase) are inactivated by the treatment, whereas mitochondrial marker enzymes (cyt c oxidase and dehydrogenases) were unaffected. This indicates that the ER and the Golgi apparatus are the primary intracellular sites damaged by Foscan-mediated PDT in MCF-7 cells. We further investigated whether the specific mitochondria events could be associated with Foscan photoinduced cell death. The dose response profiles of mitochondrial depolarization and cytochrome c release immediately after Foscan-based PDT were very different from that of overall cell death. By 24 h post-PDT the fluence dependency was strikingly similar for both mitochondrial alterations and cell death. Therefore, although mitochondria are not directly affected by the treatment, they can be strongly implicated in Foscan-mediated MCF-7 cell death by late and indirect mechanism. 相似文献
83.
A commercial cation exchange resin Amberlite 200 has been modified after immersion in solutions of polyethyleneimine (PEI). The kinetic of fixation of the metallic ions have been determined. The modification of the surface of the resin deals with a change in the order of the affinities of the resins towards cations. The retention is the function of the formation and the stability of the complex. The conditions of modification (pH, PEI concentration and time of immersion) have been examined and the modification was confirmed by the determination of the exchange capacities, the distribution coefficient (P) and the selectivity factors (S). The obtained results revealed the effect of PEI on the exchange properties of the resin. The pH range selected (6-8) permitted a good adherence of PEI onto the resin surface. The quantity of the adsorbed PEI was increased by raising the initial concentration and the immersion period. The exchange capacity for copper ion passed from 2.6 mmol g−1, in the case of unmodified resin, to 3.9 mmol g−1 for the modified one. 相似文献
84.
Sulfinyl fluoride and N-(F-isoprophyl)iminosulfur difluoride form the compounds, O(CH3) and i-C3F7N(CH3 with symdimethylethylenediamine (1). In contrast, CF3C(O)NSF2 and (Rf)2SF2 (Rf = CF3, i-C3F7 form only acyclic compounds, CF3C(O)N(CH3)CH2CH2N(CH3)C(O)CF3 and RfSN(CH3)CH2CH2N(CH3)SRf with (1). With PF3, PF5 and OPF3, cyclic compounds F, F3, and -(O)F result. When the latter two compounds are reacted further with LiNC(CF3)2, N(CH3)CH2CH2N(CH3)PF2NC(CF3)2 and (O)NC(CF3)2) form. 相似文献
85.
From the study of the CuCuBrCu2?εSC solid cell in the range of cubic digenite and “high temperature” hexagonal chalcocite we have deduced the laws of variation of the deviation from stoichiometry and the holes concentration with the equilibrium partial pressure of sulfur (δ and p are found to be proportional to ). The electronic model corresponding to the formation of associations (V×CuV′Cu) in the presence of neutral vacancies V×Cu allows one to explain these laws. In the low temperature range (range of “low temperature” hexagonal chalcocite and orthorhombic chalcocite) the study of thermal variations of Hall coefficient permits us to propose the following models: (a) the deviation from stoichiometry of the “low temperature” hexagonal chalcocite is due to the simple ionized vacancies V′Cu; (b) the deviation from stoichiometry of the orthorhombic chalcocite is due to the vacancies V′Cu and to the associations (V×CuV×Cu). 相似文献
86.
Alain Merschaert Laurent DelhayeJean-Paul Kestemont Willy BrionePieter Delbeke Vincent MancusoFreddy Napora Khalid DikerDaniel Giraud Michel Vanmarsenille 《Tetrahedron letters》2003,44(24):4531-4534
A stereoselective approach has been developed for the synthesis of cis- and trans-2-methyl-4-arylpiperidines from a common intermediate. The Ni-catalyzed hydrogenolysis of N-Boc-2-methyl-4-aryl-4-piperidinols, obtained by addition of organometallic reagents on N-Boc-2-methyl-4-piperidone, afforded the trans derivatives with up to 95% selectivity whereas the corresponding cis isomers were obtained in the presence of palladium catalysts. 相似文献
87.
Iványi T Vander Heyden Y Visky D Baten P De Beer J Lázár I Massart DL Roets E Hoogmartens J 《Journal of chromatography. A》2002,954(1-2):99-114
This paper focuses on the classification or differentiation of RP-HPLC columns based on measured chromatographic properties. A chemometric study has been conducted on a published data set consisting of 85 RP-HPLC columns and on a data set consisting of 47 self-tested columns. Principal component analysis enables determination of the number of parameters necessary for a rational differentiation. The results show that reducing the number of parameters for such differentiation still allows classification of the columns just as a higher number did. It is shown that three test parameters produce a classification similar to that obtained with five parameters. 相似文献
88.
In the context of a European project, a new approach of sampling of volatile polycyclic aromatic hydrocarbons (PAHs) from air was developed. In fact, the aim of this project was to test the efficiency of an air cleansing prototype reactor, which was operating by non-thermal plasmolysis. With an eye to model the atmosphere ejected by the prototype, we needed to vaporise the volatile PAHs in an air stream at concentrations as low as those recommended by European Directives (96/62/CE) for PAHs in ambient air (i.e. 1 ng m−3). Our strategy was based on the analysis of PAHs trapped in an aqueous medium, in order to avoid important losses of volatile compounds observed during the delicate desorption-concentration step when classical solid supports are used. Then a study was carried out to determine: the design of the collecting part, the flow-rate of the air sampling, the nature and concentration of chemical additives used to enhance PAH solubility in water. The very highly diluted aqueous media obtained after the bubbling step were concentrated by solid-phase extraction (SPE) on hydrophobic cartridges and analysed on-line by reversed-phase HPLC with UV and fluorimetric detections. Lastly, the sampling technique was directly applied to the outlet of the air cleansing prototype and the analysis after 3-6 h of non-thermal plasmolysis showed that the target volatile PAHs were not present in an air stream initially polluted by volatile organic compounds. 相似文献
89.
Syntheses of new sulfinylcinnolines, quinoxalines, quinazolines and phtalazines have been investigated starting from the appropriate halogenobenzodiazine derivatives. The latter were converted in one step to the corresponding sulfanyl benzodiazines which upon oxidation with m-CPBA led to the corresponding sulfoxide derivatives of benzodiazines in moderate to good yields. In parallel to this study, an improved method for the synthesis of 2-methylsulfinylquinoxaline starting from 2-sulfanylquinoxaline is also described and in the quinazoline series a synthetic route has been developed to prepare 2-tert-butyl-5-phenylsulfinylquinazoline with satisfactory yield as well as 2-tert-butyl-5-tert-butylsulfinyl-4(3H)-quinazolinone and 2-tert-butyl-8-tert-butylsulfinyl-4(3H)-quinazolinone. 相似文献
90.
Sénèque O Rager MN Giorgi M Prangé T Tomas A Reinaud O 《Journal of the American Chemical Society》2005,127(42):14833-14840
The coordination chemistry of Zn in an N(3)ArOH environment has been explored. The ligands are based on calix[6]arenes that present two imidazole arms and an amino phenol moiety at the narrow rim. Three different types of complexes have been characterized. One is dicationic with Zn(2+) coordinated to the three nitrogen atoms and to the oxygen of the phenol group of the calix[6]ligand. This complex is very sensitive to exogenous coordinating molecules and exists as a 5-coordinate species due to the endo-complexation of a guest. The second species is a monocationic complex for which the phenol group has been deprotonated. The resulting N(3)ArOZn complex can also bind a guest ligand albeit with a lower affinity than the dicationic complex. The third species is neutral. It can be obtained upon reaction with a base to yield a hydroxo complex or with an anion such as a chloride that coordinates the metal center from the outside of the calixarene cavity. The simultaneous binding of two anionic donors decreases the Zn Lewis acidity, allowing an impressive conformational reorganization of the system. One imidazole arm is released by the metal center. The other one undergoes self-inclusion into the pi-basic calixarene cavity because the low affinity of the metal center for neutral ligand does not allow the endo-coordination of an exogenous guest. Hence, the calix[6]N(3)ArOH-based Zn complexes act as an acid-base switch for guest binding. Several aspects of this system appear reminiscent of Zn-peptidases of the astacin and serralisin families. 相似文献