全文获取类型
收费全文 | 7418篇 |
免费 | 340篇 |
国内免费 | 27篇 |
专业分类
化学 | 5251篇 |
晶体学 | 55篇 |
力学 | 125篇 |
数学 | 1187篇 |
物理学 | 1167篇 |
出版年
2023年 | 59篇 |
2022年 | 89篇 |
2021年 | 151篇 |
2020年 | 141篇 |
2019年 | 156篇 |
2018年 | 136篇 |
2017年 | 143篇 |
2016年 | 292篇 |
2015年 | 242篇 |
2014年 | 274篇 |
2013年 | 459篇 |
2012年 | 595篇 |
2011年 | 654篇 |
2010年 | 348篇 |
2009年 | 281篇 |
2008年 | 515篇 |
2007年 | 504篇 |
2006年 | 437篇 |
2005年 | 448篇 |
2004年 | 326篇 |
2003年 | 272篇 |
2002年 | 219篇 |
2001年 | 164篇 |
2000年 | 126篇 |
1999年 | 87篇 |
1998年 | 58篇 |
1997年 | 46篇 |
1996年 | 79篇 |
1995年 | 52篇 |
1994年 | 47篇 |
1993年 | 47篇 |
1992年 | 48篇 |
1991年 | 38篇 |
1990年 | 23篇 |
1989年 | 12篇 |
1988年 | 21篇 |
1987年 | 15篇 |
1986年 | 15篇 |
1985年 | 25篇 |
1984年 | 25篇 |
1983年 | 15篇 |
1982年 | 23篇 |
1981年 | 13篇 |
1980年 | 11篇 |
1979年 | 9篇 |
1978年 | 8篇 |
1977年 | 6篇 |
1976年 | 5篇 |
1975年 | 5篇 |
1974年 | 6篇 |
排序方式: 共有7785条查询结果,搜索用时 15 毫秒
91.
Román LU Guerra-Ramírez D Morán G Martínez I Hernández JD Cerda-García-Rojas CM Torres-Valencia JM Joseph-Nathan P 《Organic letters》2004,6(2):173-176
[structure: see text] The triterpenes 8,14-seco-oleana-8(26),13-dien-3beta-ol (1) and its acetyl derivative 2 were isolated from Stevia viscida and Stevia eupatoria, respectively. Their structures were elucidated by 2D NMR, including carbon-carbon connectivity experiments, and confirmed by X-ray diffraction analysis of ketone 3. The absolute configuration was determined by NMR analysis of the Mosher esters of 1. The biogenetic implications of the new substances are discussed. 相似文献
92.
C. Martínez R. Cremer D. Neuschütz J. P. Servais D. Loison 《Surface and interface analysis : SIA》2002,34(1):524-526
The formation of oxides at the surface of Fe–1.5%Mn and Fe–0.6%Mn binary alloys was investigated as a function of the conditions of the heat treatments. Both the influence of temperature and the atmosphere under which the experiments were performed were studied. The range of annealing temperatures was adjusted to 800°C. The atmosphere consisted of a mixture of N2–5%H2 and traces of water vapour, with different fixed dew points ranging from −10°C to −30°C. The state of the annealed surfaces was determined using in situ analytical devices attached to the annealing reactor in order to avoid surface contamination or the formation of native oxides after the experiments due to contact with air. The structure and composition of the surfaces were determined by reflection high-energy electron diffraction (RHEED) and electron spectroscopy (XPS, AES). Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
93.
Tormos JR Wiley KL Seravalli J Nachon F Masson P Nicolet Y Quinn DM 《Journal of the American Chemical Society》2005,127(42):14538-14539
Secondary beta-deuterium kinetic isotope effects have been measured as a function of substrate concentration for recombinant human butyrylcholinesterase-catalyzed hydrolysis of acetyl-L3-thiocholine (L = 1H or 2H). The isotope effect on V/K is inverse, D3V/K = 0.93 +/- 0.03, which is consistent with conversion of the sp2 hybridized carbonyl carbon of the scissile ester bond of the E + A reactant state to a quasi-tetrahedral structure in the acylation transition state. In contrast, the isotope effect on Vmax under conditions of substrate activation is markedly normal, D3(betaVmax) = 1.29 +/- 0.06, an observation that is consistent with accumulation of a tetrahedral intermediate as the reactant state for catalytic turnover. Generally, tetrahedral intermediates for nonenzymatic ester hydrolyses are high-energy steady-state intermediates. Apparently, butyrylcholinesterase displays an unusual ability to stabilize such intermediates. Hence, the catalytic power of cholinesterases can largely be understood in terms of their ability to stabilize tetrahedral intermediates in the multistep reaction mechanism. 相似文献
94.
de Farias Robson Fernandes Martínez Leandro Airoldi Claudio 《Transition Metal Chemistry》2002,27(7):748-750
This paper describes the synthesis, characterization and a thermogravimetric (t.g.) study of 11 adducts of general formula MCl2·nL (M = Cu, Co and Sn; n = 1 and 2 for Sn, and 2 for Cu and Co; L = ethyleneurea eu, ethylenethiourea etu, and propyleneurea pu). The i.r. results shows that the eu and pu adducts are coordinated through oxygen, whereas for etu nitrogen is the coordination site. The (C=O) or (C=S) trend is: Cu > Co > Sn. The t.g. curves show that the adducts release ligand molecules in a single mass loss step. As regards considering adducts with the same stoichiometry, the observed thermal stability trend is: etu > pu > eu. 相似文献
95.
J. L. Martínez-Vidal A. Garrido-Frenich M. A. Escobar-García R. Romero-González 《Chromatographia》2007,65(11-12):695-699
Sterols in olive oils have been analyzed by liquid chromatography coupled to mass spectrometry with atmospheric-pressure chemical ionization in positive-ion mode. A simple procedure based on saponification and extraction of the compounds from olive oils was studied. Validation of the method included calibration and determination of recovery and repeatability was carried out. Good linearity was obtained up to 100 mg kg?1 for all the sterols studied except β-sitosterol, for which linearity was obtained up to 2,000 mg kg?1. Recovery ranged from 88 to 110%, detection limits from 0.9 to 3.1 mg kg?1, and precision was good. The method has been successfully used for analysis of sterols in different types of oil. The predominant sterol was β-sitosterol; other minor components, for example sitostanol and cholesterol, were also detected. Total sterol content depended on the type of oil, and ranged from 687 to 2,479 mg kg?1. Stigmasterol and the amount of erythrodiol plus uvaol can be used to distinguish between olive oil and seed oil. 相似文献
96.
Ana I. Olives Emiliano E. Romero-Ale M. Antonia Martín Benito del Castillo Pilar López-Alvarado J. Carlos Menéndez 《Journal of inclusion phenomena and macrocyclic chemistry》2007,57(1-4):553-559
Carbazole-9-carbonyl chloride (C9CC) and 9-carbazolylacetic acid (9CAA) were selected as model fluorescent reagents. The effect
of different chemically modified cyclodextrins (CDs) added to the aqueous solutions of these reagents was studied in water
and in buffered aqueous solutions at pH 4.5 and 8.8. The CDs employed were 2-hydroxypropyl-β-cyclodextrin (HP-βCD), 2,3-di-O-methyl-β-cyclodextrin (DM-βCD) and 2,3,6-tri-O-methyl-β-cyclodextrin (TM-βCD). The inclusion of these reagents inside the cavities of the CDs was verified and this process
can affect the derivatization reaction because CDs can modify the reactivity of the guest molecules. The basic conditions
necessary for the derivatization reaction between C9CC and amines lead to the formation of carbazole anion through hydrolysis
followed by decarboxylation. In the presence of CDs, the hydrolysis-decarboxylation of carbazole-9-carbonyl chloride is faster
than in buffered aqueous homogeneous solutions. The behaviour observed for these reagents in aqueous solutions of CDs was
compared to the one observed in basic ethanolic solutions. These changes are particularly noticeable in the case of 2,3-di-O-methyl-β-CD and 2-hydroxypropyl-β-CD. The characteristics of the fluorescent reagents are compared to carbazole and 9-methylcarbazole
as model compounds.
This paper was presented at XIIIth International Cyclodextrin Symposium. Torino, Italy, May 14–17, 2006. 相似文献
97.
Monitoring multi-class pesticide residues in fresh fruits and vegetables by liquid chromatography with tandem mass spectrometry 总被引:6,自引:0,他引:6
Frenich AG Vidal JL López TL Aguado SC Salvador IM 《Journal of chromatography. A》2004,1048(2):199-206
A new analytical method was developed using liquid chromatography with tandem mass spectrometry for the routine analysis of 31 multi-class pesticide residues and applied to approximately 50 fresh fruit and vegetable samples (green bean, cucumber, pepper, tomato, eggplant, watermelon, melon and zucchini). Extraction of the pesticides with ethyl acetate was carried out. The optimal ionisation conditions were selected for each pesticide in the same run. The procedure was validated and the values of some merit figures, such as recovery, precision, linear range, detection limit and quantification limit for each pesticide were calculated together with its calculated expanded uncertainty (U). The average recoveries in cucumber obtained for each pesticide ranged between 74 and 105% at two different fortification levels (n = 10 each) that ranged between 9 and 250 ng g(-1) (depending on the pesticide). The uncertainty associated to the analytical method was lower than 23% for all compounds tested. The calculated limits of detection and quantitation were typically <1 ng g(-1) that were much lower than the maximum residue levels established by European legislation. 相似文献
98.
Roca M Martí S Andrés J Moliner V Tuñón I Bertrán J Williams IH 《Journal of the American Chemical Society》2003,125(25):7726-7737
A comparative theoretical study of a bimolecular reaction in aqueous solution and catalyzed by the enzyme catechol O-methyltransferase (COMT) has been carried out by a combination of two hybrid QM/MM techniques: statistical simulation methods and internal energy minimizations. In contrast to previous studies by other workers, we have located and characterized transition structures for the reaction in the enzyme active site, in water and in a vacuum, and our potential of mean force calculations are based upon reaction coordinates obtained from features of the potential energy surfaces in the condensed media, not from the gas phase. The AM1/CHARMM calculated free energy of activation for the reaction of S-adenosyl methionine (SAM) with catecholate catalyzed by COMT is 15 kcal mol(-1) lower the AM1/TIP3P free-energy barrier for the reaction of the trimethylsulfonium cation with the catecholate anion in water at 300 K, in agreement with previous estimates. The thermodynamically preferred form of the reactants in the uncatalyzed model reaction in water is a solvent-separated ion pair (SSIP). Conversion of the SSIP into a contact ion pair, with a structure resembling that of the Michaelis complex (MC) for the reaction in the COMT active site, is unfavorable by 7 kcal mol(-1), largely due to reorganization of the solvent. We have considered alternative ways to estimate the so-called "cratic" free energy for bringing the reactant species together in the correct orientation for reaction but conclude that direct evaluation of the free energy of association by means of molecular dynamics simulation with a simple standard-state correction is probably the best approach. The latter correction allows for the fact that the size of the unit cell employed with the periodic boundary simulations does not correspond to the standard state concentration of 1 M. Consideration of MC-like species allows a helpful decomposition of the catalytic effect into preorganization and reorganization phases. In the preorganization phase, the substrates are brought together into the MC-like species, either in water or in the enzyme active site. In the reorganization phase, the roles of the enzymic and aqueous environments may be compared directly because reorganization of the substrate is about the same in both cases. Analysis of the electric field along the reaction coordinate demonstrates that in water the TS is destabilized with respect to the MC-like species because the polarity of the solute diminishes and consequently the reaction field is also decreased. In the enzyme, the electric field is mainly a permanent field and consequently there is only a small reorganization of the environment. Therefore, destabilization of the TS is lower than in solution, and the activation barrier is smaller. 相似文献
99.
Marcelo O. Santiago Alzir A. Batista Marcio P. de Araújo Claudio L. Donnici Icaro de S. Moreira Eduardo E. Castellano Javier Ellena Sauli dos Santos Jr Salete L. Queiroz 《Transition Metal Chemistry》2005,30(2):170-175
A series of cis-{RuCl2(PPh3)2[4,4-(X)2-2,2-bipy]} [cis-chlorines; X=-H, -Me, -SMe, and (-Cl,-Me)] complexes have had their structures determined by single crystal X-ray diffraction. The geometry of these complexes, also determined in CH2Cl2 solution by 31P{1H}-n.m.r. spectroscopy, showed that the chemical shifts for the phosphorus atoms are slightly dependent on the pKa of the 4,4-(-X)2-2,2-bipy ligands. 相似文献
100.
Limited flexibility of lactose detected from residual dipolar couplings using molecular dynamics simulations and steric alignment methods 总被引:1,自引:0,他引:1
Martín-Pastor M Canales A Corzana F Asensio JL Jiménez-Barbero J 《Journal of the American Chemical Society》2005,127(10):3589-3595
The conformational flexibility of lactose in solution has been investigated by residual dipolar couplings (RDCs). One-bond carbon-proton and proton-proton coupling constants have been measured in two oriented media and interpreted in combination with molecular dynamics simulations (MD). Two different approaches, known as PALES (Zweckstetter et al., J. Am. Chem. Soc. 2000, 122, 3791-3792) and TRAMITE (Azurmendi et al., J. Am. Chem. Soc. 2002, 124, 2426-2427), have been used to determine the alignment tensor from a shape-induced alignment model with the oriented medium. The steric alignment of the structures from several MD trajectories has provided ensemble averaged RDCs that have been compared with the experimental ones. The obtained results reveal the almost exclusive presence of a major low energy region defined as syn-phi/syn-psi (> 97%), for which sampling occurs in a dynamic manner. This result satisfactorily agrees with that determined by standard NOE-based methods. 相似文献