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排序方式: 共有112条查询结果,搜索用时 31 毫秒
31.
Dr. Riccardo Bonsignore Sophie R. Thomas Mathilde Rigoulet Christian Jandl Dr. Alexander Pöthig Dr. Didier Bourissou Prof. Giampaolo Barone Prof. Angela Casini 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(57):14322-14334
In recent years, the reactivity of gold complexes was shown to extend well beyond π-activation and to hold promises to achieve selective cross-couplings in several C−C and C−E (E=heteroatom) bond forming reactions. Here, with the aim of exploiting new organometallic species for cross-coupling reactions, we report on the Au(III)-mediated C(sp2)−C(sp) occurring upon reaction of the cyclometalated complex [Au(CCH2N)Cl2] ( 1 , CCH2N=2-benzylpyridine) with AgPhCC. The reaction progress has been monitored by NMR spectroscopy, demonstrating the involvement of a number of key intermediates, whose structures have been unambiguously ascertained through 1D and 2D NMR analyses (1H, 13C, 1H-1H COSY, 1H-13C HSQC and 1H-13C HMBC) as well as by HR-ESI-MS and X-ray diffraction studies. Furthermore, crystallographic studies have serendipitously resulted in the authentication of zwitterionic Au(I) complexes as side-products arising from cyclization of the coupling product in the coordination sphere of gold. The experimental work has been paralleled and complemented by DFT calculations of the reaction profiles, providing valuable insight into the structure and energetics of the key intermediates and transition states, as well as on the coordination sphere of gold along the whole process. Of note, the broader scope of the cross-coupling at the Au(III) CCH2N centre has also been demonstrated studying the reaction of 1 with C(sp2)-based nucleophiles, namely vinyl and heteroaryl tin and zinc reagents. These reactions stand as rare examples of C(sp2)−C(sp2) cross-couplings at Au(III). 相似文献
32.
Bohn M Leppchen K Katzberg M Lang A Steingroewer J Weber J Bley T Bertau M 《Organic & biomolecular chemistry》2007,5(21):3456-3463
Caffeine affects the stereoselectivity of microbial high cell density reductions with commercial grade Saccharomyces cerevisiae (Baker's yeast). Cyclic beta-keto esters ethyl 2-oxocyclopentanoate (1) and ethyl 2-oxocyclohexanoate (3) were shown to be reduced with increased diastereoselectivity (1: 90.1 --> 92.1% de, 3: 75.0 --> 90.0% de) after addition of caffeine. Effects on enantioselectivity were less pronounced (1: 97.3 --> 98.5% ee, 3: 90.1 --> 92.1% ee). The observations are ascribed to the action of caffeine on cellular calcium homeostasis. These effects are accompanied by caffeine-induced cell-death, which preferably takes effect on pre-stressed cells which were found to decrease diastereoselectivity. 相似文献
33.
Clémens S Monperrus M Donard OF Amouroux D Guérin T 《Analytical and bioanalytical chemistry》2011,401(9):2699-2711
Methylmercury (MeHg) and total mercury (THg) in seafood were determined using species-specific isotope dilution analysis and
gas chromatography combined with inductively coupled plasma mass spectrometry. Sample preparation methods (extraction and
derivation step) were evaluated on certified reference materials using isotopically enriched Hg species. Solid–liquid extraction,
derivation by propylation and automated agitation gave excellent accuracy and precision results. Satisfactory figures of merit
for the selected method were obtained in terms of limit of quantification (1.2 μg Hg kg−1 for MeHg and 1.4 μg Hg kg−1 for THg), repeatability (1.3–1.7%), intermediate precision reproducibility (1.5% for MeHg and 2.2% for THg) and trueness
(bias error less than 7%). By means of a recent strategy based on accuracy profiles (β-expectation tolerance intervals), the
selected method was successfully validated in the range of approximately 0.15–5.1 mg kg−1 for MeHg and 0.27–5.2 mg kg−1 for THg. Probability β was set to 95% and the acceptability limits to ±15%. The method was then applied to 62 seafood samples
representative of consumption in the French population. The MeHg concentrations were generally low (1.9–588 μg kg−1), and the percentage of MeHg varied from 28% to 98% in shellfish and from 84% to 97% in fish. For all real samples tested,
methylation and demethylation reactions were not significant, except in one oyster sample. The method presented here could
be used for monitoring food contamination by MeHg and inorganic Hg in the future to more accurately assess human exposure. 相似文献
34.
Guillaume Picard Dorothée Lebert Mathilde Louwagie Annie Adrait Céline Huillet François Vandenesch Christophe Bruley Jérôme Garin Michel Jaquinod Virginie Brun 《Journal of mass spectrometry : JMS》2012,47(10):1353-1363
Absolute protein quantification, i.e. determining protein concentrations in biological samples, is essential to our understanding of biological and physiopathological phenomena. Protein quantification methods based on the use of antibodies are very effective and widely used. However, over the last ten years, absolute protein quantification by mass spectrometry has attracted considerable interest, particularly for the study of systems biology and as part of biomarker development. This interest is mainly linked to the high multiplexing capacity of MS analysis, and to the availability of stable‐isotope‐labelled standards for quantification. This article describes the details of how to produce, control the quality and use a specific type of standard: Protein Standard Absolute Quantification (PSAQ?) standards. These standards are whole isotopically labelled proteins, analogues of the proteins to be assayed. PSAQ standards can be added early during sample treatment, thus they can correct for protein losses during sample prefractionation and for incomplete sample digestion. Because of this, quantification of target proteins is very accurate and precise using these standards. To illustrate the advantages of the PSAQ method, and to contribute to the increase in its use, selected applications in the biomedical field are detailed here. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
35.
Giffard M Hediger S Lewandowski JR Bardet M Simorre JP Griffin RG De Paëpe G 《Physical chemistry chemical physics : PCCP》2012,14(20):7246-7255
We consider the effect of phase shifts in the context of second-order recoupling techniques in solid-state NMR. Notably we highlight conditions leading to significant improvements for the Third Spin Assisted Recoupling (TSAR) mechanism and demonstrate the benefits of resulting techniques for detecting long-distance transfer in biomolecular systems. The modified pulse sequences of PAR and PAIN-CP, Phase-Shifted Proton Assisted Recoupling (AH-PS-PAR) and Phase-Shifted Proton-Assisted Insensitive Nuclei Cross Polarization (ABH-PS-PAIN-CP), still rely on cross terms between heteronuclear dipolar couplings involving assisting protons that mediate zero-quantum polarization transfer between low-γ nuclei ((13)C-(13)C, (15)N-(15)N, (15)N-(13)C polarization transfer). Using Average Hamiltonian Theory we show that phase inversion compensates off-resonance contributions and yields improved polarization transfer as well as substantial broadening of the matching conditions. PS-TSAR greatly improves on the standard TSAR based methods because it alleviates their sensitivity to precise RF settings which significantly enhances robustness of the experiments. We demonstrate these new methods on a 19.6 kDa protein (U-[(15)N, (13)C]-YajG) at high magnetic fields (up to 900 MHz (1)H frequency) and fast sample spinning (up to 65 kHz MAS frequency). 相似文献
36.
Teodor Stoichev David Amouroux Rosa C. Rodriguez Martin‐Doimeadios Mathilde Monperrus Olivier F. X. Donard Dimiter L. Tsalev 《应用光谱学评论》2013,48(6):591-619
Abstract This review considers methods for mercury speciation with low limits of detection that can be applied to real aquatic environmental samples (waters, sediments, biological tissues). Special attention is given to the necessity of clean sampling procedures and the proper storage of the samples. In this review, different extraction techniques for sediments and biological tissues are considered. The performance of different separation techniques, like liquid chromatography and off‐line and on‐line gas chromatography, are compared for their environmental applications. 相似文献
37.
Magnus Karlsson Pernille R. Jensen Jens ?. Duus Sebastian Meier Mathilde H. Lerche 《Applied magnetic resonance》2012,43(1-2):223-236
Dissolution dynamic nuclear polarization (DNP) provides a broadly applicable and rather simple means of developing probes for the real-time molecular imaging of cellular functions in vivo. The development of novel dissolution DNP substrate formulations is only rewarding for substrates that yield detectable metabolism within few minutes. In addition, in vivo preparations usually require amorphous samples at molar substrate concentrations for an efficient and reproducible DNP step with sufficient material. The composition ranges of novel substrate preparations need to be established experimentally owing to the solute’s impact on vitrification behavior. Here, we describe simple rationales employed in the development of novel substrate preparations for dissolution DNP-magnetic resonance. Solution state substrate polarizations between 10 and 40?% have been obtained for ~40 metabolic substrates in highly concentrated preparations that yield physiologically tolerable solutions with sufficient T 1 for in vivo nuclear magnetic resonance. Substrate metabolism is observed for novel in vivo substrates such as 3-hydroxybutyrate and aspartate. 相似文献
38.
We report the observation of a higher-order frequency shift due to the trapping field in a (87)Sr optical lattice clock. We show that, at the magic wavelength of the lattice, where the first-order term cancels, the higher-order shift will not constitute a limitation to the fractional accuracy of the clock at a level of 10(-18). This result is achieved by operating the clock at very high trapping intensity up to 400 kW/cm(2) and by a specific study of the effect of the two two-photon transitions near the magic wavelength. 相似文献
39.
Frank Hülsemann Karsten Koehler Jürgen Wittsiepe Michael Wilhelm Annett Hilbig Mathilde Kersting 《Isotopes in environmental and health studies》2017,53(4):356-367
Natural stable isotope ratios (δ15N) of humans can be used for nutritional analyses and dietary reconstruction of modern and historic individuals and populations. Information about an individual’s metabolic state can be obtained by comparison of tissue and dietary δ15N. Different methods have been used to estimate dietary δ15N in the past; however, the validity of such predictions has not been compared to experimental values. For a total of 56 meals and 21 samples of 24-h diets, predicted and experimental δ15N values were compared. The δ15N values were predicted from self-recorded food intake and compared with experimental δ15N values. Predicted and experimental δ15N values were in good agreement for meals and preparations (r?=?0.89, p?.001) as well as for the 24-h diets (r?=?0.76, p?.001). Dietary δ15N was mainly determined by the amount of fish, whereas the contribution of meat to dietary δ15N values was less pronounced. Prediction of human dietary δ15N values using standardised food records and representative δ15N data sets yields reliable data for dietary δ15N intake. A differentiated analysis of the primary protein sources is necessary when relating the proportion of animal-derived protein in the diet by δ15N analysis. 相似文献
40.
Atmospheric solid analysis probe mass spectrometry vs electrospray tandem mass spectrometry of polydimethylsiloxanes in positive and negative ionization modes
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