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61.
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Summary The complexestrans-[Ru(NH3)4(H2O)PPh3](PF6)2 and [Ru(NH3)5L](PF6)2, (L=AsPh3 or SbPh3) have been isolated and characterized by microanalysis, cyclic voltammetry and ultraviolet-visible spectroscopy. The specific rate constants for the aquation of [Ru(NH3)5L]2+ totrans-[Ru(NH3)4L(H2O)]2+ are (2.5±0.1)×10–5s–1 and (1.8±0.1)×10–5s–1 for L=AsPh3 and SbPh3, respectively, at 25.0±0.1°C; =0.10 mol dm–3, NaO2CCF3. Under the same conditions, the second-order rate constants for the substitution of water intrans-[Ru(NH3)4(H2O)L]2+ by isonicotinamide (isn) are 1.2±0.1, (6.3±0.3)×10–2 and (3.8±0.2)×10–2
m
–1s–1 for L=PPh3, AsPh3, and SbPh3, respectively, suggesting that the order of decreasingtrans-effect is: PPh3AsPh3>SbPh3. The formation constants for thetrans-[Ru(NH3)4L(isn)]2+ complexes are 75±3, (1.40±0.01)×103 and (1.80±0.02)×103M–1 for L=PPh3, AsPh3, and SbPh3, respectively, suggesting that the order of increasingtrans-influence is: SbPh33PPh3. 相似文献
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65.
Comparison of different fibers for the solid-phase microextraction of phthalate esters from water 总被引:3,自引:0,他引:3
Solid-phase microextraction (SPME) coupled to gas chromatography-mass spectrometry (GC-MS) has been applied to determine six phthalate esters and one adipate ester in water. The SPME parameters were optimized for several commercially available fibers. A 65-microm polydimethylsiloxane-divinylbenzene (PDMS-DVB) was the fiber selected and was applied to analysis of water from the Ebro river and the industrial port of Tarragona. The studied compounds were found at concentrations ranging from 0.4 microg l(-1) for di-n-butyl phthalate ester (DnBP) to 3.2 microg l(-1) for bis(2-ethylhexyl) phthalate ester (DEHP). The linear range for real samples was from 0.1 to 10 microg l(-1) for most phthalates, and the limits of detection of the method were between 3 and 30 ng l(-1). Repeatability and reproducibility between days (n = 5) for 1 microg l(-1) samples were below 13 and 18%, respectively. 相似文献
66.
A study of the viability of three derivatizing reagents for obtaining amino acid profiles in honey through high performance liquid chromatography (HPLC) is presented. A method using diode array detection based on a reaction with diethyl ethoxymethylene malonate (DEMM) and two other methods using fluorescence detection based on derivatization with fluorenylmethyl chloroformate (FMOC-Cl) and 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) have been developed. The three methods yield detection limits close to the ppb level, but vary in relation to other analytical characteristics. The use of methyl chloroformate derivatives allows the profile to be obtained with the greatest sensitivity within a short time frame. On applying such methods to honey samples of diverse botanical origin, we observe that the proline values obtained are always lower than those found using the official spectrophotometric method, thereby underlining the advisability of using HPLC methods to reduce uncertainty in these results. 相似文献
67.
Biswas I Peisert H Schwieger T Dini D Hanack M Knupfer M Schmidt T Chassé T 《The Journal of chemical physics》2005,122(6):064710
In this work we have investigated the electronic structure and the molecular orientation of (t-Bu)(4)PcMg (tetra-t-butyl magnesium phthalocyanine) on polycrystalline and single crystalline gold substrates using photoemission spectroscopy and x-ray absorption spectroscopy, and we compare the results to the unsubstituted PcCu (copper phthalocyanine). The C 1s photoemission spectrum is described similar to unsubstituted relatives with an additional component for the aliphatic substituents. The variation of the excitation energy causes distinct differences in the shape of the C 1s spectrum, which is very useful for the analysis of the molecular orientation in the uppermost layer. It is shown that despite of the sterically demanding substituents, ordered sublimed films of (t-Bu)(4)PcMg are accessible, the orientation of the molecules, however, is different from the orientation of the unsubstituted relatives. 相似文献
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A polyclonal, multispecific antiserum was raised against a whole 3[(3-cholamidopropyl)-dimethylammonio]-1-propanesulfonate-extract of nonirradiated Blepharisma japonicum cells. It was used to reveal the composition of solutions that were hypothesized to contain the photoreceptor of the ciliate. A Bio-Gel A 1.5 m fine column chromatography of the extract allowed recovery of a single elution peak isolated by recording the 580 nm light absorbance. Fused-rocket immunoelectrophoresis of this material revealed a large number of > 300 kDa coeluted proteins. Blepharismin-rich material with a molecular mass of approximately 50 kDa, consisting of at least nine proteins was obtained when the same extract underwent preparative isoelectric focusing before column chromatography separation. Purification of the pigment obtained from light-exposed cells gave blepharismin-rich material with a molecular weight of approximately 200 kDa. Comparison of the materials obtained under the same conditions, either from the dark-kept or light-irradiated cells, by means of pore-gradient electrophoresis confirmed that proteins present in the two preparations were different. It revealed only a very small amount, if any, of proteins in the chromatography fractions with the highest absorbance at 600 nm. Results are discussed on the basis of the hypothesis that a specific blepharismin-binding protein does not exist in the protozoan. 相似文献
70.
Henriques ES Floriano WB Reuter N Melo A Brown D Gomes JA Maigret B Nascimento MA Ramos MJ 《Journal of computer-aided molecular design》2001,15(4):309-322
We present the search for a new model of -factor XIIa, a blood coagulation enzyme, with an unknown experimental 3D-structure. We decided to build not one but three different models using different homologous proteins as well as different techniques and different modellers. Additional studies, including extensive molecular dynamics simulations on the solvated state, allowed us to draw several conclusions concerning homology modelling, in general, and -factor XIIa, in particular. 相似文献