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251.
Bohumír Grüner Jaroslav Ba?kovský Bohumil Štíbr 《Journal of organometallic chemistry》2005,690(11):2850-2852
The compounds with a single and double -CH2C6H4CH2- spacer, [CpFeC3B8H10-NH-CH2C6H4CH2-NH-C3B8H10FeCp] and [CpFeC3B8H10-N-(CH2C6H4CH2)2-N-C3B8H10FeCp], represent the first example of designed shaping by extremely stable cyclopentadienyl-ferratricarbollide (CpFeTCB) cages into rigid molecular constructions approaching linear arrangement. 相似文献
252.
Marek Da?browski 《Tetrahedron letters》2005,46(24):4175-4178
The metalation of (quasi)alkoxy-substituted dibromobenzenes C6H3(OR)Br2 with lithium diisopropylamide (LDA) has been investigated. For 1-(quasi)alkoxy-3,5-dibromobenzenes (R = Me, TMS), different selectivities were observed depending on reaction conditions and the size of the alkoxy group. The methoxy group was an effective ortho-director whereas this was not the case for the bulky trimethylsilyloxy group. The metalation of related 2,5-dibromoanisole was also examined showing a significant meta-directing effect by the methoxy group. The thermal stability of aryllithium intermediates is significantly lower when lithium is flanked by a bromine and a methoxy group, whereas 4-(quasi)alkoxy-2,6-dibromoaryllithiums are less labile. 相似文献
253.
We calculate energy barriers of atom- and proton-transfer reactions in hydrogen-bonded complexes in the gas phase. Our calculations do not involve adjustable parameters and are based on bond-dissociation energies, ionization potentials, electron affinities, bond lengths, and vibration frequencies of the reactive bonds. The calculated barriers are in agreement with experimental data and high-level ab initio calculations. We relate the height of the barrier with the molecular properties of the reactants and complexes. The structure of complexes with strong hydrogen bonds approaches that of the transition state, and substantially reduces the barrier height. We calculate the hydrogen-abstraction rates in H-bonded systems using the transition-state theory with the semiclassical correction for tunneling, and show that they are in excellent agreement with the experimental data. H-bonding leads to an increase in tunneling corrections at room temperature. 相似文献
254.
Michaud AL Frank AJ Ding C Zhao X Douglas DJ 《Journal of the American Society for Mass Spectrometry》2005,16(6):835-849
Modeling of ion motion and experimental investigations of ion excitation in a linear quadrupole trap with a 4% added octopole field are described. The results are compared with those obtained with a conventional round rod set. Motion in the effective potential of the rod set can explain many of the observed phenomena. The frequencies of ion oscillation in the x and y directions shift with amplitude in opposite directions as the amplitudes of oscillation increase. Excitation profiles for ion fragmentation become asymmetric and in some cases show bistable behavior where the amplitude of oscillation suddenly jumps between high and low values with very small changes in excitation frequency. Experiments show these effects. Ions are injected into a linear trap, stored, isolated, excited for MS/MS, and then mass analyzed in a time-of-flight mass analyzer. Frequency shifts between the x and y motions are observed, and in some cases asymmetric excitation profiles and bistable behavior are observed. Higher MS/MS efficiencies are expected when an octopole field is added. MS/MS efficiencies (N(2) collision gas) have been measured for a conventional quadrupole rod set and a linear ion trap with a 4% added octopole field. Efficiencies are chemical compound dependent, but when an octopole field is added, efficiencies can be substantially higher than with a conventional rod set, particularly at pressures of 1.4 x 10(-4) torr or less. 相似文献
255.
Push-pull 2-alkylidene-4-oxothiazolidine vinyl bromides undergo efficient C(5) functionalization through DMSO-assisted carbon-bromine cleavage, followed by a bromine transfer-substitution (or elimination) sequence. A mechanism for this novel transformation is proposed. 相似文献
256.
Zeisler R 《Analytical and bioanalytical chemistry》2004,378(5):1277-1283
NIST maintains a portfolio of more than 1300 standard reference materials (SRM), more than a third of these relating to measurements in the biological and environmental fields. As part of the continuous renewal and replacement efforts, a set of new marine sediments has been recently developed covering organic and inorganic determinations. This paper describes the steps taken in sample preparation, homogeneity assay, and analytical characterization and certification with specific emphasis on SRM 2702 inorganics in marine sediment. Neutron activation analysis showed the SRM to be highly homogeneous, opening the possibility for use with solid sampling techniques. The certificate provides certified mass fraction values for 25 elements, reference values for eight elements, and information values for 11 elements, covering most of the priority pollutants with small uncertainties of only several percent relative. The values were obtained by combining results from different laboratories and techniques using a Bayesian statistical model. An intercomparison carried out in field laboratories with the material before certification illustrates a high commutability of this SRM.Electronic Supplementary Material Supplementary material is available in the online version of this article at 相似文献
257.
W. Schr?n A. Detcheva B. Dre?ler K. Danzer 《Fresenius' Journal of Analytical Chemistry》1998,361(2):106-109
Direct solid sampling graphite furnace AAS (SS-GF-AAS) provides an advantageous alternative to the conventional AAS which
requires wet digestion of the samples. This method is suitable for trace element determination in calcium fluoride and other
fluoride-containing samples. Matrix effects were studied by using calibration standards, certified reference materials with
different matrices and by means of three-dimensional calibration. 3D calibration is suitable for selection of calibration
samples for more reliable analyses. Cu, Pb, Cd, Zn, and Fe were determined by means of calibration with variation of sample
weight using certified reference materials and suitable fluoride-containing calibration samples.
Received: 25 July 1997 / Revised: 15 December 1997 / Accepted: 20 December 1997 相似文献
258.
Bhagwan?S.?GargEmail author Rakesh?K.?Sharma Ekta?Kundra 《Transition Metal Chemistry》2005,30(5):552-559
Complexes of copper(II), nickel(II), cobalt(II), and zinc(II) with 2-[2-(6-methylbenzothiazolyl)azo]-5-dimethylaminobenzoic acid have been prepared and characterized by elemental analysis, vibrational spectra, magnetic susceptibility measurements, conductance measurements and e.p.r. spectra. Stability constants have been evaluated potentiometrically. Electronic spectra, magnetic susceptibility measurements and molecular modeling studies support a distorted square planar geometry around the metal ions. Vibrational spectra indicate the coordination of the azo group, nitrogen of benzothiazole, the carboxylate anion and the acetate ion on complexation with the metal ion. All complexes are found to be monomers. The stability of the complexes follow the order: copper(II) > nickel(II) > cobalt(II) > zinc(II). 相似文献
259.
A new capillary electrophoresis procedure with field-enhanced stacking concentration for the analysis of strychnine and brucine is established. After optimization of the separation and concentration conditions, the two alkaloids can be separated within 5 min and quantified with high sensitivity (The detection limits were 1.0 ng mL(-1) for strychnine and 1.4 ng mL(-1) for brucine). The method was useful for qualitative and quantitative analysis of strychnine and brucine in Strychnos nux-vomica L with recovery of 105.1% for strychnine and 98.4% for brucine. 相似文献
260.
A new optical CO2 sensor based on the luminescence intensity change of the europium(III) complex tris(thenoyltrifluoroacetonato) europium(III) dihydrate ([Eu(tta)3]) caused by the absorption change of various pH indicators—thymol blue, phenol red, or cresol red—with CO2 was developed and its CO2 sensing properties were investigated. For all the CO2 sensors using pH indicators the observed luminescence intensity from [Eu(tta)3] at 613 nm increased with increasing CO2 concentration. The linear calibration method based on the plot of (I100–I0)/(I–I0) versus the inverse of CO2 concentration was suggested, where I0 and I100 were luminescence intensities at 613 nm of the CO2 sensor film in 100% nitrogen and 100% gaseous CO2. In all cases the plots showed good linearity and the correlation factors of the plots, r2, were 0.991 for thymol blue, 0.990 for phenol red, and 0.998 for cresol red. The slopes of the plots (A/B) for thymol blue, phenol red, and cresol red were 2.2, 5.2, and 9.0%, respectively. The response times of the CO2 sensor film were 4.0 s for thymol blue, 4.4 s for phenol red, and 8.8 s for cresol red for switching from nitrogen to CO2, and the recovery times of films were 36 s for thymol blue, 39.2 s for phenol red, and 56.6 s for cresol red for switching from CO2 to nitrogen. The signal changes were fully reversible and hysteresis was not observed during the measurements. The highly sensitive CO2 sensor was developed using thymol blue as an indicator for the CO2-sensing probe. 相似文献