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71.
Cofré P  Brinck K 《Talanta》1992,39(2):127-136
Reproducibility for successive determinations with a hanging mercury drop electrode is assessed in relation to solution stirring, drop size and back-diffusion to the mercury thread. The effect of experimental parameters such as drop size, deposition time and gallium concentration on the observed stripping current is investigated. The interference of zinc present in a 0.5M NaSCN + 4.2M NaClO(4) supporting electrolyte on the gallium detection limit and calibration plots is described. Formation of an intermetallic compound with a Zn:Ga ratio of 2:3 and its destruction by co-deposition of zinc with Sb are reported. A detection limit of 10(-8)M gallium was obtained in the presence of 10(-5)M Sb(III).  相似文献   
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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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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   
77.
The investigation of the genetic background and phenotype structures of complex diseases, such as cardiovascular or psychiatric disorders and tumors, is one of the most scrutinized fields of the post genomic era. Besides the multiplex analysis of genetic markers and polymorphisms throughout the whole genome, more and more attention is focused on the interaction between the etiological factors of these traits. Haplotype determination, rather than multiplex genotyping seems to be one of the first building blocks of this endeavor. This review focuses on the importance and theoretical background of haplotyping, and summarizes the recent examples of novel and emerging haplotyping techniques by capillary gel electrophoresis based DNA fragment analysis, a powerful tool for the examination of the inheritance of complex traits.  相似文献   
78.
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   
79.
Adducts of four phosphine chalcogenides with the chiral dirhodium complex ([Rh-Rh]) were investigated by variable-temperature 1H and 31P NMR spectroscopy in order to compare their properties as axial ligands. Whereas the selenide (1) and the sulfide (2) are strong ligands with electrostatic attraction and, in addition, a significant orbital (HOMO-LUMO) interaction, the phosphine oxide compounds (P=O) bind primarily via electrostatic attraction and are relatively weak donors. Moreover, the overall bond strength in these adducts depends on steric congestion around the P=O group.  相似文献   
80.
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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