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91.
Germain ObameHélène Pellissier Nicolas VanthuyneJean-Bernard Bongui Gérard Audran 《Tetrahedron letters》2011,52(10):1082-1085
The enzymatic desymmetrization of methylenecyclopropane diol or its corresponding diacetate derivative, generated from a [2+1] cycloaddition between dioxepin and methylchlorocarbene, is described. After screening five commercial lipases, the two enantiomers of acetic acid 2-hydroxymethyl-3-methylene-cyclopropylmethyl ester are obtained in high yields and excellent enantioselectivities by using PFL or LPP in organic solvent. The stereostructure of the desymmetrization products was established by X-ray analysis. We also reported a new example with this non racemic chiral building block where the sign of optical rotation is dramatically solvent dependent and inverted. Using these enantiopure building blocks, a synthesis of novel nucleoside analogs is also presented. 相似文献
92.
93.
94.
Jeffrey M. Spraggins Julie A. Lloyd Murray V. Johnston Julia Laskin Douglas P. Ridge 《Journal of the American Society for Mass Spectrometry》2009,20(9):1579-1592
The gas-phase fragmentation reactions of singly charged angiotensin II (AngII, DR+VYIHPF) and the ozonolysis products AngII+O (DR+VY*IHPF), AngII+3O (DR+VYIH*PF), and AngII+4O (DR+VY*IH*PF) were studied using SID FT-ICR mass spectrometry, RRKM modeling, and molecular dynamics. Oxidation of Tyr (AngII+O)
leads to a low-energy charge-remote selective fragmentation channel resulting in the b
4
+O fragment ion. Modification of His (AngII+3O and AngII+4O) leads to a series of new selective dissociation channels. For
AngII+3O and AngII+4O, the formation of [MH+3O]
+
−45 and [MH+3O]
+
−71 are driven by charge-remote processes while it is suggested that b
5
and [MH+3O]
+
−88 fragments are a result of charge-directed reactions. Energy-resolved SID experiments and RRKM modeling provide threshold
energies and activation entropies for the lowest energy fragmentation channel for each of the parent ions. Fragmentation of
the ozonolysis products was found to be controlled by entropic effects. Mechanisms are proposed for each of the new dissociation
pathways based on the energies and entropies of activation and parent ion conformations sampled using molecular dynamics. 相似文献
95.
Karyne M. Rogers Kerry Somerton Pamela Rogers Julie Cox 《Rapid communications in mass spectrometry : RCM》2010,24(16):2370-2374
Carbon isotope analyses (δ13C) of some New Zealand Manuka honeys show that they often fail the internationally recognised Association of Official Analytical Chemists sugar test (AOAC method 998.12) which detects added C4 sugar, although these honeys are from unadulterated sources. Failure of these high value products is detrimental to the New Zealand honey industry, not only in lost export revenue, but also in brand and market reputation damage. The standard AOAC test compares the carbon isotope value of the whole honey and corresponding protein isolated from the same honey. Differences between whole honey and protein δ13C values should not be greater than +1.0‰, as it indicates the possibility of adulteration with syrups or sugars from C4 plants such as high fructose corn syrup or cane sugar. We have determined that during the standard AOAC method, pollen and other insoluble components are isolated with the flocculated protein. These non‐protein components have isotope values which are considerably different from those of the pure protein, and can shift the apparent δ13C value of protein further away from the δ13C value of the whole honey, giving a false positive result for added C4 sugar. To eliminate a false positive C4 sugar test for Manuka honey, prior removal of pollen and other insoluble material from the honey is necessary to ensure that only the pure protein is isolated. This will enable a true comparison between whole honey and protein δ13C isotopes. Furthermore, we strongly suggest this modification to the AOAC method be universally adopted for all honey C4 sugar tests. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
96.
97.
A simple model is presented which interprets conductivity variations due to crystallization in amorphous layers and allows the determination of the growth rate of crystallization. The validity of this model is demonstrated in the case of germanium. 相似文献
98.
Erwann Guénin Marc Lecouvey Julie Hardouin 《Rapid communications in mass spectrometry : RCM》2009,23(9):1395-1400
1‐Hydroxymethylene‐1,1‐bisphosphonic acids (or bisphosphonates) are compounds that have interesting pharmacological applications. However, few mass spectrometric investigations have been carried out to determine their fragmentation patterns. Herein, we evaluated different matrices for the study by matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOFMS) of the formation and fragmentation of the protonated, the cationized (MNa+ and MK+) and the deprotonated bisphosphonates. Some in‐source fragmentations were observed both in positive and in negative ion modes. The fragmentation patterns obtained in post‐source decay mode are also discussed. In contrast to previous electrospray ionization/multi‐stage mass spectrometry (ESI‐MSn) studies, some new fragmentation pathways were deduced and the effects of alkali ions on the fragmentation patterns were shown. The results summarized here completed the data previously recorded by ESI‐MSn and could be used for the characterization of bisphosphonates as alkali complexes in biological mixtures. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
99.
Jonathan P. Williams Julie Ann Lough Iain Campuzano Keith Richardson Peter J. Sadler 《Rapid communications in mass spectrometry : RCM》2009,23(22):3563-3569
We report the development of an enhanced algorithm for the calculation of collision cross‐sections in combination with Travelling‐Wave ion mobility mass spectrometry technology and its optimisation and evaluation through the analysis of an organoruthenium anticancer complex [(η6‐biphenyl)RuII(en)Cl]+. Excellent agreement was obtained between the experimentally determined and theoretically determined collision cross‐sections of the complex and its major product ion formed via collision‐induced dissociation. Collision cross‐sections were also experimentally determined for adducts of this ruthenium complex with the single‐stranded oligonucleotide hexamer d(CACGTG). Ion mobility tandem mass spectrometry measurements have allowed the binding sites for ruthenium on the oligonucleotide to be determined. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
100.
N. D. Nguyen M. Germain M. Schmeits R. Evrard B. Schineller M. Heuken 《Journal of Crystal Growth》2001,230(3-4):596-601
The ac characteristics of GaN : Mg and undoped GaN layers, grown by MOVPE on sapphire substrates, are measured for a wide range of temperature and bias conditions, in order to investigate the effect of the magnesium-related level on the transport properties. Two peaks, whose height and position depend on the measurement temperature, are observed in the admittance curves (G/ω versus frequency) of the Mg-doped samples, whereas only one peak appears in undoped samples. The study of the frequency dependence of the impedance, with a model including the two metallic Au/GaN junctions, the GaN layer itself, shows that, besides the effect of the differential resistance of the layer which plays a role in both sample types, the presence of a Mg-related deep level contributes to the observed variations of the peaks in the admittance curves of the p-doped samples. Results of a theoretical steady-state and small-signal analysis based on numerical modelling of the Au/GaN/Au heterostructure complete our analysis. 相似文献