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951.
Jimi SI Rosman KJ Hong S Candelone JP Burn LJ Boutron CF 《Analytical and bioanalytical chemistry》2008,390(2):495-501
A technique has been developed to simultaneously measure picogram per gram concentrations of Ba and Pb by isotope dilution
mass spectrometry, as well as Pb isotopic ratios in polar ice by thermal ionisation mass spectrometry. and Pb+ ions were employed for these determinations. A calibrated mixture of enriched 205Pb and 137Ba was added to the samples providing an accuracy of better than approximately 2% for Pb/Ba element ratio determinations.
Interference by molecular ions in the Pb mass spectrum occurred only at 204Pb and 205Pb, but these contributions were negligible in terms of precisions expected on picogram-sized Pb samples. The technique is
illustrated with measurements on Greenland firn, using a drill-core section that includes the Laki volcanic eruption of 1783–1784.
The data show deviations from the element concentrations indicating volatile metal enrichments, but the Pb isotopic signature
of the Laki lava could not be identified. 相似文献
952.
Dendrimers are hyperbranched nanosized and precisely defined molecules, attracting increasing attention each year due to their numerous properties in catalysis, materials science, and biology. This tutorial review concerns the use of dendrimers as catalysts and focuses more precisely on their properties as enantioselective catalysts. Emphasis is put on chiral phosphine complexes constituting the core or the end groups of various types of dendrimers. The effect of the location of the catalytic entities, the effect of the size (generation) and the nature of the dendritic skeleton on the enantiomeric excesses are discussed. 相似文献
953.
Deloncle R Coppel Y Rebout C Majoral JP Caminade AM 《Magnetic resonance in chemistry : MRC》2008,46(5):493-496
Two series of small generation dendrimers built with phosphorus atoms at each branching point and various types of nitrogen atoms at natural abundance of (15)N within the branches are characterized by a gradient enhanced GHNMQC (gradient hydrogen-nitrogen multiple quantum coherence) (1)H-(15)N NMR technique. The first series contains two types of nitrogen atoms, included in phosphorhydrazone linkages (CH=NNMe-P(S)), whereas the second series contains four types of nitrogen atoms included in azobenzene linkages (Ar-N=N-Ar') in addition to the phosphorhydrazone. The influence of the trans/cis isomerization of the azo bond on the (15)N NMR has also been studied. Despite the low solubility of the azobenzene-containing dendrimers, which renders the detection of some signals difficult, (15)N NMR appears as a very sensitive tool to detect chemical changes in the dendritic structure. 相似文献
954.
Boudalis AK Sanakis Y Clemente-Juan JM Donnadieu B Nastopoulos V Mari A Coppel Y Tuchagues JP Perlepes SP 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(8):2514-2526
Complexes [Fe9(X)2(O2CMe)8{(2‐py)2CO2}4] (X?=OH? ( 1 ), N3? ( 2 ), and NCO? ( 3 )) have been prepared by a route previously employed for the synthesis of analogous Co9 and Ni9 complexes, involving hydroxide substitution by pseudohalides (N3?, NCO?). As indicated by DC magnetic susceptibility measurements, this substitution induced higher ferromagnetic couplings in complexes 2 and 3 , leading to higher ground spin states compared to that of 1 . Variable‐field experiments have shown that the ground state is not well isolated from excited states, as a result of which it cannot be unambiguously determined. AC susceptometry has revealed out‐of‐phase signals, which suggests that these complexes exhibit a slow relaxation of magnetization that follows Arrhenius behavior, as observed in single‐molecule magnets, with energy barriers of 41 K for 2 (τ0=3.4×10?12 s) and 44 K for 3 (τ0=2.0×10?11 s). Slow magnetic relaxation has also been observed by zero‐field 57Fe Mössbauer spectroscopy. Characteristic integer‐spin electron paramagnetic resonance (EPR) signals have been observed at X‐band for 1 , whereas 2 and 3 were found to be EPR‐silent at this frequency. 1H NMR spectrometry in CD3CN has shown that complexes 1 – 3 are stable in solution. 相似文献
955.
956.
Ho R Girault JP Cousteau PY Bianchini JP Raharivelomanana P Lafont R 《Journal of chromatographic science》2008,46(2):102-110
The Polynesian medicinal fern Microsorum membranifolium contains very large amounts of ecdysteroids, including ecdysone, 20-hydroxyecdysone, 2-deoxy-20-hydroxyecdysone, and 2-deoxyecdysone. It also contains large amounts of unusual ecdysteroids which have been unambiguously identified by mass spectrometry and nuclear magnetic resonance. A new class of ecdysteroid conjugates (3-glucosyl-ferulates of 2-deoxyecdysone and 2-deoxy-20-hydroxyecdysone) is isolated, together with a new glycoside (2-deoxyecdysone 25-rhamnoside). The simultaneous presence of a sugar and an aromatic moiety results in a very particular chromatographic behavior of these conjugates. They behave like flavonoids and polyphenols when using the classical purification on polyamide, aimed at removing the latter from crude plant extracts, and would therefore be lost. They elute as non-polar ecdysteroids on reversed-phase high-performance liquid chromatography (RP-HPLC), whereas their behavior on normal-phase (NP) HPLC is strongly dependent on the mobile phase composition. Our data highlight the importance of selectivity in the choice of HPLC methods used for ecdysteroid separations. 相似文献
957.
Seven alpha-aminoalkylperoxyl radicals have been generated by 355 nm laser flash photolysis (LFP) of oxygen-saturated di-tert-butyl peroxide containing mono-, di-, and trialkylamines and a dialkylarylamine. All these peroxyls possess absorptions in the near-UV (strongest for the trialkylamine-derived peroxyls) which permits direct monitoring of the kinetics of their reactions with many substrates. The measured rate constants for hydrogen atom abstraction from some phenols and oxygen atom transfer to triphenylphosphine demonstrated that all seven alpha-aminoalkylperoxyls have similar reactivities toward each specific substrate. More importantly, a comparison with literature data for alkylperoxyls shows that alpha-aminoalkylperoxyls and these alkylperoxyls have essentially the same reactivities. The combination of LFP and alkylamines provides a quick, reliable method for determining absolute rate constants for alkylperoxyl radical reactions, an otherwise laborious task. 相似文献
958.
959.
Imaging in Raman spectroscopy is a valuable tool for analytical chemistry. Although molecular characterization at micron level is achieved for many applications, it usually fails producing chemical images of micron size samples as expected in chemical, environmental and biological analysis. The aim of the work is to introduce the potential of super-resolution in vibrational spectroscopic imaging. This original chemometrics approach uses several low resolution images of the same sample in order to retrieve a higher resolution chemical image. It is thus possible to overcome in a certain way some physical and instrumentals limitations. To illustrate the methodology, sub-micronic details of a Si/Au sample are retrieved from low resolution images with different super-resolution algorithms. The better results are obtained with Iterative L2/Bilateral Total Variation regularization method. The use of a regularization procedure gives also better results since its first property is to preserve edges during the reconstruction of the super-resolved image. This concept of chemical image data processing should open new analytical opportunities. 相似文献
960.
Boris Jaffrennou Françoise Méchin Jean-Pierre Pascault 《European Polymer Journal》2008,44(11):3439-3455
Poly[Styrene-b-Butadiene-b-(Methyl Methacrylate)], SBM triblock copolymers have been incorporated in different polyurethane, PU formulations in order to prepare nanostructured materials. Macrodiols used for PU synthesis were based on a central bis-phenol A, BPA unit with two hydroxyl-terminated oligo(oxypropylene), BPA-POx or oligo(oxyethylene), BPA-EO chains with varying lengths. The initial solubility of the three blocks and the rheological behavior of the solutions in macrodiols and also in two diisocyanates, isophorone diisocyanate, IPDI, and 1,3-xylylene diisocyanate, XDI have been first characterized. The PMMA block is the most soluble and its role during the reaction is to stabilize the initial nanostructure or to control the reaction-induced microphase separation.Block copolymers can be dissolved first in the macrodiol, or preferably in the diisocyanate. With BPA-POx and low SBM content (<10 wt%), transparent linear or crosslinked PU with well dispersed triblock nanoparticles have been prepared, depending on the molar mass of the macrodiol and on the concentration of diblock SB impurities present in the triblock. For high SBM concentrations (>50 wt%), a twin screw extruder had to be used for the blending. Under well-defined conditions, transparent linear PUs and linear segmented polyurethane-ureas have been prepared.This study confirms that for designing a nanostructured material from a reactive mixture with a triblock additive, one block, called “the nanostructuring block” has to remain soluble up to the end of the reaction. 相似文献