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1.
2.
Giancarlo Pelizzi 《Transition Metal Chemistry》1979,4(3):199-204
Summary The structures of the title compounds were both solved from diffractometer data by direct methods and refined by full-matrix least-squares toR=4.63% for 3069 independent reflections for the nickel compound [triclinic,a=10.499(7),b=13.295(8),c=10.182(7) Å, =92.13(8), =103.58(7), =68.79(7)°;Z=2. Space group P1] and toR=7.98% for 772 independent reflections for the copper compound [tetragonal,a=12.939(6),c=14.991(7) Å;Z=4. Space group P4/ncc]. In the first compound two chemically equivalent, crystallographically independent molecules are present, in which each nickel atom attains an octahedral coordination involving four N(ring)-bonded isoxazole molecules and two isothiocyanate groups. In the copper compound, the metal atom shows square-pyramidal fivecoordination with the four symmetry-related organic molecules bondedvia N(ring) in the square plane and one bromide ion (the other is not coordinated) in the apical position. 相似文献
3.
Verardo G Pagani E Geatti P Martinuzzi P 《Analytical and bioanalytical chemistry》2003,376(5):659-667
The composition of the surface waxes of three apple ( Malus domestica L.) cultivars ("Florina", "Golden B" and "Ozark Gold") has been studied by means of spectroscopic and GC–MS analysis of the class-fractionated mixture of components. Odd n -alkanes, mainly C27 and C29 molecules, are prevalent in the saturated fraction. Small concentrations of alkenes were also found; the C28:1 component is strongly (72%) in excess over the other 1-alkenes. Straight-chain esters (mainly of palmitic acid) of saturated primary alcohols (C18–C30) were also detected; whereas the acyl moiety is made up essentially of an even number of carbons, the alcohol counterpart does not exhibit this characteristic. Aldehydes are present (C20–C30) with the homologue patterns C26–C30 most strongly represented. Straight-chain free secondary alcohols characterize the waxes of "Florina" and "Ozark Gold"; the hydroxy function is located far from the extremity of the carbon framework. Outstanding is the presence of three alcohols with 29 carbon centres. These alcohols are accompanied by free straight-chain primary alcohols, mainly with even-numbered carbon chains in the range C26–C30. Free fatty acids are present; all of have a framework of even-numbered carbon chains mainly in the range C16–C20. C18:1 (oleic acid) is well represented. 相似文献
4.
Atmospheric bulk deposition of major and trace elements was measured at Venice from November 1995 to October 1997. Collection was carried out using polyethylene bulk passive samplers, samples being collected bi-weekly. In order to highlight the contribution of the atmosphere to water chemistry and particle budgets in the Lagoon of Venice, the geochemical composition (Si, Al, Ca, Mg, K, Na, Mn, Cr, Zn, Pb, Cd, Cu, As) of dissolved and insoluble bulk fractions was determined by AAS + ICP mass spectrometry. Great sample variability was found, with almost two orders of magnitude between maximum and minimum values for several metals. All fluxes in 1995/96 were 30% lower than in 1996/97, ranging from -3% (Ca) to -57% (Li), except for Zn, Cd and As. On the contrary, the solubility of all elements decreased during 1996/97. Partitioning between soluble and insoluble phases shows that Al, Cr, Fe and Si are mainly in the insoluble form, whereas for As, Ca, Cu, Mg, Na, Ni, K, Pb and Zn the dissolved fraction represents 50-90% of total input. The amount of particle load affects partitioning between dissolved and particulate, especially for Al and Pb. Seasonal variability was evident. The lowest pH values (approximately 5.2) were recorded in winter, causing an increase of solubility for all metals except for As, which showed the highest solubility in summer. 相似文献
5.
Rapid determination of orotic acid in urine by a fast liquid chromatography/tandem mass spectrometric method 总被引:1,自引:0,他引:1
la Marca G Casetta B Zammarchi E 《Rapid communications in mass spectrometry : RCM》2003,17(8):788-793
Quantification of orotic acid (uracil-6-carboxylic acid) in urine is an important tool to diagnose some inherited diseases, such as urea cycle disorder (OTCD) and hereditary orotic aciduria. New rapid analytical methods are necessary to provide high-throughput orotic acid analyses. A new analytical method has been developed for the rapid analysis of orotic acid in urine by liquid chromatography coupled with ion spray tandem mass spectrometry (LC/MS/MS). After a sample dilution 1:20, the analysis was performed in the selected reaction monitoring mode in which orotic acid was detected through the transition m/z 155 to 111. The retention time was 3.9 min in a 4.5-min analysis. Daily calibration between 0.5-5.0 micromol/L of orotic acid, corresponding to 10-100 micromol/L in urine before the 1:20 dilution, offered consistent linearity and reproducibility. Interassay coefficient of variance (c.v.) was 4.97% at a mean concentration of 10.99 micromol/L. The sensitivity and specificity of tandem mass spectrometry permitted a high volume of analyses of orotic acid. The sample preparation is simple, inexpensive and not time demanding. 相似文献
6.
Ternary mixtures of antibiotics, i.e. penicillin-G sodium salt, penicillin-G procain salt and dihydrostreptomycin sulphate salt, are assayed by 'zero-crossing' third-derivative spectrophotometry. Calibration plots follows Beer's law up to 40 mug/ml of penicillin-G sodium at 222.5 nm (r = 0.9997), 46 mug/ml of penicillin-G procain at 217 nm (r = 0.9999) and 36 mug/ml of dihydrostreptomycin sulphate at 211.5 nm (r = 0.9999), in the presence of one another. Detection limits at p = 0.05 level of significance were calculated to be, respectively, 0.66, 0.41 and 0.25 mug/ml. The procedure is rapid, simple, nondestructive and does not require solution of equations. The method was successfully applied for determining laboratory mixtures and commercial injections. 相似文献
7.
We revisit the Landau-Teller heuristic approach to adiabatic invariants and, following Rapp, use it to investigate the energy exchanges between the different degrees of freedom, in simple Hamiltonian systems describing the collision of fast rotating or vibrating molecules with a fixed wall. We critically compare the theoretical results with particularly accurate numerical computations (quite small energy exchanges, namely of one part over 1030, are measured). 相似文献
8.
Silvio Aime Mauro Botta Giancarlo Cravotto Luca Frullano GiovanniB. Giovenzana Simonetta GeninattiCrich Giovanni Palmisano Massimo Sisti 《Helvetica chimica acta》2005,88(3):588-603
Four new ligands for lanthanide ions based on the H3do3a (=1,4,7,10‐tetraazacyclododecane‐1,4,7‐triacetic acid) structure and bearing one N‐sulfonylacetamide arm were synthesized, i.e., H4dota‐NHSO2R=10‐{2‐[(R)sulfonylamino]‐2‐oxoethyl}‐1,4,7,10‐tetraazacyclododecane‐1,4,7‐triacetic acids 1a – e . A 15N‐NMR study of the 15N‐labelled Eu3+ complex of one such ligands, 1d , showed that the coordination of the N‐sulfonylacetamide arm involves the carbonyl O‐atom rather than the N‐atom. The relaxometric properties of the corresponding Gd3+ complexes were investigated as a function of pH and temperature. These complexes have relaxivities in the range 4.5–5.3 mM ?1 s?1, at 20 MHz and 25°, and are characterized by a single H2O molecule in their inner coordination sphere. The mean residence lifetime of this molecule is relatively long (500–700 ns) compared to other anionic complexes. The slow rate of H2O exchange can be justified by the extensive delocalization of the negative charge on the N‐sulfonylacetamide arm. The long residence time of the coordinated H2O allowed the observation of the effect of the prototropic exchange on the relaxivity. The study of the interaction between the complex [Gd( 1e )]‐ and HSA revealed a weak affinity constant highlighting the importance of a localized negative charge on the complex to promote a strong interaction with the protein. 相似文献
9.
The interpretation of the infrared active fundamentals of TCNQ and chloranil monovalent anions is given for the first time. The rationalization of the infrared spectra was made possible by the recently achieved vibrational assignment of the corresponding neutral molecules and is mainly based on a set of judicious adjustments of their empirical valence force fields. 相似文献
10.
P. A. Temussi F. Lelj T. Tancredi M. A. Castiglione Morelli A. Pastore 《International journal of quantum chemistry》1984,26(5):889-906
The structure-activity relationship of sweet molecules is chosen as an example to illustrate a mechanistic approach of soft agonist-receptor interactions. It is shown that an essentially geometric model of the receptor site can explain the activity of most sweet molecules, both rigid and flexible. The relevant conformations of flexible molecules in solution are extracted from a combination of NMR data and of energy calculations. A possible experimental simulation of the receptor environment in solution is illustrated by the complex of a dipeptide sweetener with a crown-ether. 相似文献