全文获取类型
收费全文 | 42383篇 |
免费 | 2428篇 |
国内免费 | 2724篇 |
专业分类
化学 | 20632篇 |
晶体学 | 555篇 |
力学 | 2284篇 |
综合类 | 228篇 |
数学 | 10567篇 |
物理学 | 13269篇 |
出版年
2023年 | 186篇 |
2022年 | 410篇 |
2021年 | 437篇 |
2020年 | 465篇 |
2019年 | 545篇 |
2018年 | 1649篇 |
2017年 | 1958篇 |
2016年 | 1361篇 |
2015年 | 1266篇 |
2014年 | 1273篇 |
2013年 | 1698篇 |
2012年 | 4333篇 |
2011年 | 3525篇 |
2010年 | 2717篇 |
2009年 | 2517篇 |
2008年 | 1604篇 |
2007年 | 1569篇 |
2006年 | 1531篇 |
2005年 | 5138篇 |
2004年 | 4576篇 |
2003年 | 2849篇 |
2002年 | 1156篇 |
2001年 | 882篇 |
2000年 | 493篇 |
1999年 | 489篇 |
1998年 | 319篇 |
1997年 | 199篇 |
1996年 | 165篇 |
1995年 | 144篇 |
1994年 | 127篇 |
1993年 | 108篇 |
1992年 | 217篇 |
1991年 | 196篇 |
1990年 | 176篇 |
1989年 | 145篇 |
1988年 | 122篇 |
1987年 | 78篇 |
1986年 | 60篇 |
1985年 | 53篇 |
1984年 | 34篇 |
1979年 | 32篇 |
1976年 | 79篇 |
1975年 | 38篇 |
1974年 | 40篇 |
1973年 | 48篇 |
1972年 | 39篇 |
1970年 | 34篇 |
1969年 | 37篇 |
1968年 | 35篇 |
1966年 | 37篇 |
排序方式: 共有10000条查询结果,搜索用时 24 毫秒
981.
The fragmentation reactions of deprotonated N-benzoyl peptides, specifically hippurylglycine, hippurylglyclyclycine, and hippurylphenylalanine (hippuryl = N-benzoylGly) have been studied using MS2 and MS3 experiments as well as deuterium labeling. A major fragment ion is observed at m/z 160 ([C9H6NO2]-) which, upon collisional activation, mainly eliminates CO2 indicating that the two oxygen atoms have become bonded to the same carbon. This observation is rationalized in terms of formation of deprotonated 2-phenyl-5-oxazolone. Various pathways to the deprotonated oxazolone have been elucidated through MS3 experiments. Fragmentation of deprotonated N-acetylalanylalanine gives a relatively weak signal at m/z 112 which, upon collisional activation, fragments, in part, by loss of CO2 leading to the conclusion that the m/z 112 ion is deprotonated 2,4-dimethyl-5-oxazolone. 相似文献
982.
Thermochemical Properties and Decomposition Kinetics of Ammonium Magnesium Phosphate Monohydrate 总被引:1,自引:0,他引:1
Ammonium magnesium phosphate monohydrate NH4MgPO4·H2O was prepared via solid state reaction at room temperature and characterized by XRD, FT-IR and SEM. Thermochemical study was performed by an isoperibol solution calorimeter, non-isothermal measurement was used in a multivariate non-linear regression analysis to determine the kinetic reaction parameters. The results show that the molar enthalpy of reaction above is (28.795 ± 0.182) kJ/mol (298.15 K), and the standard molar enthalpy of formation of the title complex is (-2185.43 ± 13.80) kJ/mol (298.15 K). Kinetics analysis shows that the second decomposition of NH4MgPO4·H2O acts as a double-step reaction: an nth-order reaction (Fn) with n=4.28, E1=147.35 kJ/mol, A1=3.63×10^13 s^-1 is followed by a second-order reaction (F2) with E2=212.71 kJ/mol, A2= 1.82 × 10^18 s^-1. 相似文献
983.
Background
The completion of several genome-sequencing projects has increased our need to assign functions to newly identified genes. The presence of a specific protein domain has been used as the determinant for suggesting a function for these new genes. In the case of proteins that are predicted to interact with mRNA, most RNAs bound by these proteins are still unknown. In yeast, several protocols for the identification of protein-protein interactions in high-throughput analyses have been developed during the last years leading to an increased understanding of cellular proteomics. If any of these protocols or similar approaches shall be used for the identification of mRNA-protein complexes, the integrity of mRNA is a critical factor. 相似文献984.
985.
One common approach for designing protein tyrosine phosphatase (PTPase) inhibitors is to incorporate a nonhydrolyzable phosphotyrosine (pTyr) mimic into a peptide substrate for PTPases. This report describes the synthesis of three such nonhydrolyzable pTyr mimics that contain alpha-ketoacid, alpha-hydroxyacid, and methylenesulfonamide functional groups in place of the phosphate. These pTyr mimics were incorporated into the peptide sequence Ac-Asp-Ala-Asp-Glu-X-Leu-NH(2), where X is the pTyr mimic, and analyzed for activity against the Yersinia PTPase and PTP1B. 相似文献
986.
A rapid and reliable GC/MS (EI and CI) method was developed for the identification of short-chain mono- and dicarboxylic
acids in complex and strongly alkaline residues of municipal waste incineration. Such residues contain organic carboxylic
acids in the mg/kg to μg/kg range, which may contribute to the mobilization of heavy metals. However, the alkalinity and the
high salt loads of the matrix were found to be a serious problem in the analysis of short chain acids. Extraction with water,
solid phase extraction, and derivatization were studied under these conditions. Solid-phase extraction with polymeric sorbents
and derivatization with diazomethane can be combined in a reproducible manner to yield a robust and simple method which can
be applied for screening unknown solids due to its wide applicability and the well identifiable methyl esters. Absolute recovery
rates varied between 20 and 85% depending on the individual acids.
Received: 13 November 1997 / Revised: 17 February 1998 / Accepted: 18 February 1998 相似文献
987.
F M Demotes-Mainaird G A Vin?on C H Jarry H C Albin 《Journal of chromatography. A》1989,490(1):115-123
A simple and sensitive high-performance liquid chromatographic micro-method for the determination of roxithromycin in human plasma and urine is described. A dichloromethane extract of the sample was chromatographed on a C18 reversed-phase column with acetonitrile-83 mM ammonium acetate-methanol (55:23:22, v/v) adjusted to pH 7.5 with acetic acid as the mobile phase. Roxithromycin and the internal standard, erythromycin, were detected by dual coulometric electrodes operated in the oxidative screen mode. The applied cell potential of the screen electrode was set at +0.7 V and the sample electrode at +0.9 V. The intra- and inter-assay coefficients of variation were less than or equal to 7.0%. The detection limit (signal-to-noise ratio = 3) was 0.1 microgram/ml for both plasma and urine. A study of drug stability during sample storage at 4, 20 and 37 degrees C showed no degradation of roxithromycin. The method is convenient for clinical monitoring and pharmacokinetic studies. 相似文献
988.
Bruno Therrien Ludovic Vieille-Petit Petr Štěpni?ka Georg Süss-Fink 《Journal of organometallic chemistry》2004,689(15):2456-2463
A series of arene-ruthenium complexes of the general formula [RuCl2{η6-C6H5(CH2)2R}L] with R=OH, CH2OH, OC(O)Fc, CH2OC(O)Fc (Fc=ferrocenyl) and L=PPh3, (diphenylphosphino)ferrocene, or bridging 1,1′-bis(diphenylphosphino)ferrocene, have been synthesized. Two synthetic pathways have been used for these ferrocene-modified arene-ruthenium complexes: (a) esterification of ferrocene carboxylic acid with 2-(cyclohexa-1,4-dienyl)ethanol, followed by condensation with RuCl3 · nH2O to afford [RuCl2{η6-C6H5(CH2)2OC(O)Fc}]2, and (b) esterification between ferrocene carboxylic acid and [RuCl2{η6-C6H5(CH2)3OH}L] to give [RuCl2{η6-C6H5(CH2)3OC(O)Fc}L]. All new compounds have been characterized by NMR and IR spectroscopy as well as by mass spectrometry. The single-crystal X-ray structure analysis of [RuCl2{η6-C6H5(CH2)3OH}(PPh3)] shows that the presence of a CH2CH2CH2OH side-arm allows [RuCl2{η6-C6H5(CH2)3OH}(PPh3)] to form an intramolecular hydrogen bond with a chlorine atom. The electrochemical behavior of selected representative compounds has been studied. Complexes with ferrocenylated side arms display the expected cyclic voltammograms, two independent reversible one-electron waves of the Ru(II)/Ru(III) and Fe(II)/Fe(III) redox couples. Introduction of a ferrocenylphosphine onto the ruthenium is reflected by an additonal reversible, one-electron wave due to ferrocene/ferrocenium system which is, however, coupled with the Ru(II)/Ru(III) redox system. 相似文献
989.
Two copper complexes [Cu(TTA)2(4,4′‐azpy)] (1) and [Cu‐(TTA)2(3,3′‐azpy)] (2) (HTTA = 1,1,1‐trifluoro‐3‐(2‐thenoyl)‐acetone, 4,4′‐azpy = 4,4′‐azobispyridine, 3,3′‐azpy = 3,3′‐azobispyridine) were synthesized and characterized. The crystal structures were determined by X‐ray diffraction analysis. The crystal 1 belongs to triclinic with space group P1 , a = 0.8515(2) nm, b = 0.9259(2) nm, c = 0.9468(2) nm, a = 66.126(9)°, β = 79.667(9)°, γ = 90.13(1)°, Z = 1, V = 0.6692(2) nm3, Dc = 3.425 g/cm3, γ = 2.113 mm?1, F(000) = 694, R1 = 0.0594, wR2 = 0.1499. The crystal 2 belongs to monoclinic with space group P21/c, a = 1.0661(2) nm, b = 1.4296(3) ran, c = 1.0041(3) nm, β = 114.50(3)°, V = 1.3926(5) nm3, Z = 2, Dc = 1.646 g/ cm3, μ = 1.015 mm?1, F(000) = 694, R1, = 0.0535, wR2 = 0.1113. In the crystals of complexes 1 and 2, the copper atoms have distorted octahedral symmetry. The two compounds possess very similar one‐dimensional linear chains linked through the rodlike 4,4′‐azpy ligands or 3,3′‐azpy ligands. 相似文献
990.
A new model for energy exchange between translational and internal degrees of freedom in atom-molecule collisions has been developed. It is suitable for both steady state conditions (e.g., a large number of collisions with thermal kinetic energies) and non-steady state conditions with an arbitrary distribution of collision energies (e.g., single high-energy collisions). In particular, it does not require that the collision energies be characterized by a quasi-thermal distribution, but nevertheless it is capable of producing a Boltzmann distribution of internal energies with the correct internal temperature under quasi-thermal conditions. The energy exchange is described by a transfer probability density that depends on the initial relative kinetic energy, the internal energy of the molecule, and the amount of energy transferred. The probability density for collisions that lead to excitation is assumed to decrease exponentially with the amount of transferred energy. The probability density for de-excitation is obtained from microscopic reversibility. The model has been implemented in the ion trap simulation program ITSIM and coupled with an Rice-Rampsberger-Kassel-Marcus (RRKM) algorithm to describe the unimolecular dissociation of populations of ions. Monte Carlo simulations of collisional energy transfer are presented. The model is validated for non-steady state conditions and for steady state conditions, and the effect of the kinetic energy dependence of the collision cross-section on internal temperature is discussed. Applications of the model to the problem of chemical mass shifts in RF ion trap mass spectrometry are shown. 相似文献