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81.
Angelo Sala Kathleen Kayganich Joseph A. Zirrolli Robert C. Murphy 《Journal of the American Society for Mass Spectrometry》1991,2(4):314-321
The sulfidopeptide leukotrienes, leukotriene E4, (LTE4,) and its N-acetyl derivative and several ω? and β-oxidized metabolites of LTE4, have been analyzed by tandem mass spectrometry. [M?H]? ions were produced by continuous flow fast atom bombardment, and collision-induced dissociation of these ions was studied by using a triple quadrupole instrument. The product ion spectra obtained were characteristic of the structure of LTE4, and mechanisms of ion formation were investigated by using deuterated compounds. β-Elimination of the peptide portion of LTE4, by loss of CO2, and ethylene amine leaves the C-l carboxyl group ionized in the most abundant fragment ion for LTE4, and all metabolites. Tandem mass spectrometry of fast atom bombardment-generated anions from ω? and β-oxidized metabolites of LTE4, produced similar ions with only a minor influence of the third carboxyl group at the omega terminus evident. Tandem mass spectrometry was used to identify unequivocally the presence of unmodified LTE4, in a high performance liquid chromatography-purified fraction of urine from a normal healthy volunteer after infusion with LTE4. 相似文献
82.
83.
An ultra-high speed, time-resolved particle image velocimetry (PIV) system is developed to measure velocity fields created
by explosive detonators. When initiated into a gas, the detonators generate blast waves that propagate outwards from the origin
of initiation at supersonic speeds. The PIV system consists of a custom eight-pulse Nd:YAG laser system and an ultra-high
speed camera system comprising four dual-frame CCD cameras optically combined to share a single optic axis. The system is
capable of sampling the flow field four times at up to 333 MHz or eight times at up to 8 MHz. System development is discussed,
and preliminary application to the complex flow behind the blast wave from an exploding bridge wire detonator is demonstrated. 相似文献
84.
Maruthi Kumar Narayanam Yong Liang K. N. Houk Jennifer M. Murphy 《Chemical science》2016,7(2):1257-1261
Density functional theory (DFT) calculations and experiments in tandem led to discoveries of new reactivities and selectivities involving bioorthogonal sydnone cycloadditions. Dibenzocyclooctyne derivatives (DIBAC and BARAC) were identified to be especially reactive dipolarophiles, which undergo the (3 + 2) cycloadditions with N-phenyl sydnone with the rate constant of up to 1.46 M–1 s–1. Most significantly, the sydnone-dibenzocyclooctyne and norbornene-tetrazine cycloadditions were predicted to be mutually orthogonal. This was validated experimentally and used for highly selective fluorescence labeling of two proteins simultaneously. 相似文献
85.
Qingqing Gao Aijun Yang Xiaohua Wang Anthony B. Murphy Yunjia Li Chaojun Zhang Yanhui Lu Li Huan Zhaofang Zhu Mingzhe Rong 《Plasma Chemistry and Plasma Processing》2016,36(5):1301-1323
It has become increasingly clear that deviations from local thermodynamic equilibrium occur in thermal plasmas. This paper is devoted to investigating the non-equilibrium characteristics of CO2 thermal plasmas, which have wide application in industry. A two-temperature chemical kinetic model with a comprehensive chemical system is developed to calculate the non-equilibrium characteristics of CO2 thermal plasmas for a wide temperature range, from 12,000 to 500 K, at atmospheric pressure. The non-equilibrium results are compared to the equilibrium composition obtained by Gibbs free energy minimization, and significant deviations are found at lower temperatures. Based on the dependence of molar fractions on temperature, the dominant species are determined in three temperature ranges. The dominant reactions are then obtained by considering their contribution to the generation and loss of the dominant species. Using the dominant species and reactions, the full model is simplified into three simpler models and the accuracy of the simplified models is evaluated. It is shown that this approach greatly reduces the number of species and reactions considered, while showing good agreement with the full model, with a root-mean-square error of no more than 4 %. Thus, the complicated physicochemical processes in non-equilibrium CO2 thermal plasmas can be characterized by relatively few species and reactions. It is suggested that the two-temperature chemical kinetic model developed in this paper can be applied to the full range of pressures that occur in arc welding, arc quenching and other industrial applications. In addition, the simplified methods can be applied in multi-dimensional models to reduce the chemical complexity and computing time while capturing the main physicochemical processes in non-equilibrium CO2 thermal plasmas. 相似文献
86.
Background
Minichromosome maintenance proteins (Mcm) 2, 3, 4, 5, 6 and 7 are related by sequence and form a variety of complexes that unwind DNA, including Mcm4/6/7. A Mcm4/6/7 trimer forms one half of the Mcm2-7 hexameric ring and can be thought of as the catalytic core of Mcm2-7, the replicative helicase in eukaryotic cells. Oligomeric analysis of Mcm4/6/7 suggests that it forms a hexamer containing two Mcm4/6/7 trimers, however, under certain conditions trimeric Mcm4/6/7 has also been observed. The functional significance of the different Mcm4/6/7 oligomeric states has not been assessed. The results of such an assessment would have implications for studies of both Mcm4/6/7 and Mcm2-7. 相似文献87.
Meier MS Bergosh RG Gallagher ME Spielmann HP Wang Z 《The Journal of organic chemistry》2002,67(17):5946-5952
The fulleride dianions C(60)(2-) and C(70)(2-) were generated by deprotonation of the corresponding hydrogenated fullerenes, 1,2-C(60)H(2) and 1,2-C(70)H(2). These anions were prepared in the presence of a variety of alkylating agents, and mono- or dialkylated products were obtained. Alkylation was not successful with sulfonate ester alkylating agents. Deprotonation of monoalkylated compounds, followed by second alkylation with a different alkylating agent, produced heterodialkylated compounds. The monoalkyated material was invariably the 1,2-isomers, while the dialkylated materials were generally 1,4-isomers, although some 1,2-isomer was observed in the C(70) context. The major product from alkylation of C(70)(2-) was the 7,23-isomer 13a, a structure where the alkylation took place near the equator of the fullerene cage, rather than at the more strained carbons near the poles. 相似文献
88.
High-throughput approaches for the discovery and optimization of new olefin polymerization catalysts
Murphy V Bei X Boussie TR Brümmer O Diamond GM Goh C Hall KA Lapointe AM Leclerc M Longmire JM Shoemaker JA Turner H Weinberg WH 《Chemical record (New York, N.Y.)》2002,2(4):278-289
The discovery of new olefin polymerization catalysts is currently a time-intensive trial-and-error process with no guarantee of success. A fully integrated high-throughput screening workflow for the discovery of new catalysts for polyolefin production has been implemented at Symyx Technologies. The workflow includes the design of the metal-ligand libraries using custom-made computer software, automated delivery of metal precursors and ligands into the reactors using a liquid-handling robot, and a rapid primary screen that serves to assess the potential of each metalligand-activator combination as an olefin polymerization catalyst. "Hits" from the primary screen are subjected to secondary screens using a 48-cell parallel polymerization reactor. Individual polymerization reactions are monitored in real time under conditions that provide meaningful information about the performance capabilities of each catalyst. Rapid polymer characterization techniques support the primary and secondary screens. We have discovered many new and interesting catalyst classes using this technology. 相似文献
89.
Kuehn K Mehta S Fu H Genio E Murphy D Liu F Liu Y Ahlers G 《Physical review letters》2002,88(9):095702
We report new measurements in four cells of the thermal boundary resistance R between copper and (4)He below but near the superfluid-transition temperature T(lambda). For 10(-7)< or =t identical to 1-T/T(lambda))< or =10(-4) fits of R = R(0)t(-x(b))+R(B) to the data yielded x(b) approximately equal to 0.18, whereas a fit to theoretical values based on the renormalization-group theory yielded x(b) = 0.23. Alternatively, a good fit of the theory to the data could be obtained if the amplitude of the prediction was reduced by a factor close to 2. The results raise the question whether the boundary conditions used in the theory should be modified. 相似文献
90.
The preparation and physical properties of the layered VS2, MyV1?yS2 (M = Fe or Cr), and their lithium intercalation adducts are described. These compounds were prepared by oxidative delithiation of LiMyV1?yS2 with iodine. Crystallographic distortions present in LixVS2 (0.25 ? x ? 0.6) are suppressed by Fe or Cr substitution for V. The electrochemical sluggishness of Li/Li+/VS2 cells is reduced by the substitution. 相似文献