全文获取类型
收费全文 | 7352篇 |
免费 | 981篇 |
国内免费 | 506篇 |
专业分类
化学 | 6834篇 |
晶体学 | 36篇 |
力学 | 160篇 |
综合类 | 110篇 |
数学 | 233篇 |
物理学 | 1466篇 |
出版年
2024年 | 8篇 |
2023年 | 106篇 |
2022年 | 343篇 |
2021年 | 422篇 |
2020年 | 418篇 |
2019年 | 262篇 |
2018年 | 247篇 |
2017年 | 252篇 |
2016年 | 365篇 |
2015年 | 371篇 |
2014年 | 406篇 |
2013年 | 544篇 |
2012年 | 541篇 |
2011年 | 418篇 |
2010年 | 409篇 |
2009年 | 463篇 |
2008年 | 410篇 |
2007年 | 385篇 |
2006年 | 375篇 |
2005年 | 360篇 |
2004年 | 305篇 |
2003年 | 236篇 |
2002年 | 164篇 |
2001年 | 131篇 |
2000年 | 131篇 |
1999年 | 138篇 |
1998年 | 107篇 |
1997年 | 112篇 |
1996年 | 64篇 |
1995年 | 58篇 |
1994年 | 53篇 |
1993年 | 41篇 |
1992年 | 31篇 |
1991年 | 27篇 |
1990年 | 20篇 |
1989年 | 12篇 |
1988年 | 19篇 |
1987年 | 15篇 |
1986年 | 17篇 |
1985年 | 14篇 |
1984年 | 12篇 |
1983年 | 2篇 |
1982年 | 8篇 |
1981年 | 6篇 |
1980年 | 4篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 1篇 |
排序方式: 共有8839条查询结果,搜索用时 184 毫秒
141.
《Analytica chimica acta》2004,512(2):287-295
The potential of non-aqueous capillary electrophoresis (NACE) was investigated for the simultaneous separation of paroxetine, tamoxifen, and their main metabolites. Baseline separation of the studied solutes was obtained on a μm capillary using a non-aqueous buffer composed of 18 mM ammonium acetate and 1.1% acetic acid in 80:20 (v/v) methanol-acetonitrile, with a temperature and voltage of 22 °C and 15 kV, respectively. Clomipramine was used as internal standard. Aspects such as stability of the solutions, linearity, accuracy, precision and ruggedness were examined in order to validate the proposed method. Detection limits obtained for all the studied compounds ranged between 3.0 and 7.1 μg l−1. The developed method is sensitive and robust and was used to determine paroxetine, tamoxifen, and their metabolites at clinically relevant levels in human urine. Before NACE determination, the samples were purified and enriched by means of an extraction-pre-concentration step with a pre-conditioned C18 cartridge. Determination of these analytes in the urine of four females urines was demonstrated. 相似文献
142.
Identification of selenium species in urine by ion-pairing HPLC–ICP–MS using laboratory-synthesized standards 总被引:1,自引:0,他引:1
Wrobel K Wrobel K Kannamkumarath SS Caruso JA 《Analytical and bioanalytical chemistry》2003,377(4):670-674
This study focused on the detection/identification of possible selenium metabolites in human urine. Organoselenium compounds not commercially unavailable were synthesized and characterized by electrospray mass spectrometry. Separation of selenomethionine, methylselenomethionine, trimethylselonium, selenoethionine, and selenoadenosylmethionine was achieved by ion-pairing HPLC with a mobile phase of 2 mmol L–1 hexanesulfonic acid, 0.4% acetic acid, 0.2% triethanolamine (pH 2.5), and 5% methanol. The column effluent was introduced on-line to inductively coupled plasma–mass spectrometry for selenium-specific detection (77Se and 78Se). For selenium speciation in urine, solid-phase extraction was carried out using C18 cartridges modified with hexanesulfonic acid. Selective retention of cationic species was observed from acidified urine (perchloric acid, pH 2.0). After elution with methanol, evaporation, and dissolution in the mobile phase, the sample was introduced to the HPLC–ICP–MS system and the chromatographic peaks were assigned by adding standards. The species identified in urine were selenomethionine, trimethylselonium ion, and selenoadenosylmethionine. The last species was detected for the first time and our results suggest that selenomethionine might enter the metabolic pathway of its sulfur analog in the activated methylation cycle.Kazimierz Wrobel and Katarzyna Wrobel are on the leave from the Institute of Scientific Research, University of Guanajuato, L. de Retana No. 5, 36000 Guanajuato, Gto., Mexico 相似文献
143.
Molecular Replacement Studies of Cucurmosin from Cucurbita Moschata:Structure Homology with Trichosanthin 总被引:2,自引:0,他引:2
1 INTRODUCTION Many plants contain proteins that are capable of inactivating ribosomes and therefore are called ribosome-inactivating proteins or RIPs[1]. RIPs are RNA N-glycosidases that inactivate ribosomes through a site-specific deadenylation of the large ribosomal RNA[2, 3]. RIPs are also capable of inactivating many nonribosomal nucleic acid substrates and can be considered as polynucleotide: adenosine glycosidases[4~6]. There are two types of RIPs: type I, single chain pr… 相似文献
144.
Exact rotamer optimization for protein design 总被引:1,自引:0,他引:1
Computational methods play a central role in the rational design of novel proteins. The present work describes a new hybrid exact rotamer optimization (HERO) method that builds on previous dead-end elimination algorithms to yield dramatic performance enhancements. Measured on experimentally validated physical models, these improvements make it possible to perform previously intractable designs of entire protein core, surface, or boundary regions. Computational demonstrations include a full core design of the variable domains of the light and heavy chains of catalytic antibody 48G7 FAB with 74 residues and 10(128) conformations, a full core/boundary design of the beta1 domain of protein G with 25 residues and 10(53) conformations, and a full surface design of the beta1 domain of protein G with 27 residues and 10(60) conformations. In addition, a full sequence design of the beta1 domain of protein G is used to demonstrate the strong dependence of algorithm performance on the exact form of the potential function and the fidelity of the rotamer library. These results emphasize that search algorithm performance for protein design can only be meaningfully evaluated on physical models that have been subjected to experimental scrutiny. The new algorithm greatly facilitates ongoing efforts to engineer increasingly complex protein features. 相似文献
145.
Glow discharge mass spectrometry 总被引:5,自引:0,他引:5
Hoffmann V Kasik M Robinson PK Venzago C 《Analytical and bioanalytical chemistry》2005,381(1):173-188
Over the past twenty years or so, glow discharge mass spectrometry (GDMS) has become the industry standard for the analysis of trace elements in metals and semiconductors. A review of its history is followed by a picture of the present situation and a look to where the future may lie. Applications are summarised, including the ability of GDMS to offer depth-resolved data and non-conductor analysis, and the well-documented quantitative nature of the results is reviewed. The effects resulting from the physical properties of the analyte material are discussed at length. Finally, recent work such as fast flow sources and pulsed glow discharges is reviewed. 相似文献
146.
The technique of three-phase partitioning (TPP) was used to purify the green fluorescent protein (GFP) in a single step. TPP uses a combination of ammonium sulphate and tert-butanol to precipitate proteins from their crude extracts. In the first round of TPP with 20% ammonium sulphate saturation at the ratio of crude to tert-butanol 1:1 (v/v), most of the GFP remains in the lower aqueous phase. When subjected to a second round of TPP with 60% ammonium sulphate saturation at the ratio of crude to tert-butanol 1:2 (v/v) gives 78% recovery of GFP with a 20-fold purification. The sodium dodecyl sulphate-polyacrylamide gel electrophoretic (SDS-PAGE) analysis of purified preparation shows single band. The fluorescence excitation and emission spectra agreed with values reported in literature. 相似文献
147.
Arsenic Speciation in Urine and Blood Reference Materials 总被引:1,自引:0,他引:1
Todor I. Todorov John W. Ejnik Florabel G. Mullick Jose A. Centeno 《Mikrochimica acta》2005,151(3-4):263-268
Acute and chronic exposure to arsenic is a growing problem in the industrialized world. Arsenic is a potent carcinogen and
toxin in humans. In the body, arsenic is metabolized to produce several species, including inorganic forms, such as trivalent
(AsIII) and pentavalent (AsV), and the methylated metabolites such as monomethylarsonic acid, (MMAV), and dimethylarsinic acid (DMAV), in addition to arsenobetaine (AsB) which is ingested and excreted from the body in the same form. Each of these species
has been reported to possess a specific but different degree of toxicity. Thus, not only is the measurement of total As required,
but also quantification of the individual metabolites is necessary to evaluate the toxicity and risk assessment of this element.
There are a large number of reference materials that are used to validate methodology for the analysis of As in blood and
urine, but they are limited to total As concentrations. In this study, the speciation of five arsenic metabolites is reported
in blood and urine from commercial available control materials certified for total arsenic levels. The separation was performed
with an anion exchange column using inductively coupled plasma mass spectrometry as a detector. Baseline separation was achieved
for AsIII, AsV, MMAV, DMAV, and AsB, allowing us to quantify all five species. Excellent agreement between the total arsenic levels and the sum of the
speciated As levels was obtained. 相似文献
148.
《Surface and interface analysis : SIA》2003,35(11):932-939
Error surfaces are calculated for the fitting of concentration–depth profiles to angle‐resolved x‐ray photoelectron spectroscopy (ARXPS) data. The shapes of the error surfaces indicate that model parameters related to composition (especially at the very surface of the sample) are well constrained by the data, whereas parameters related to depth have a less significant impact on the fit. It is then shown that certain parameters in the different depth profile models employed are highly correlated and that the different models convey essentially the same information in different ways. Finally, a compromise profile definition is proposed for the fitting of constrained but flexible depth profiles to ARXPS data. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
149.
Nevin Çelebi Osamu Shirakura Yoshiharu Machida Tsuneji Nagai 《Journal of inclusion phenomena and macrocyclic chemistry》1987,5(4):407-413
Inclusion complex formation of piromidic acid (PA) with dimethyl--cyclodextrin (DM--CD) in aqueous solution and in the solid state was confirmed by the solubility method, differential scanning calorimetry (DSC) and proton nuclear magnetic resonance (1H-NMR) spectroscopy. The apparent stability constant,K
c
, of the complex was estimated to be 244 M–1. The stoichiometry of the complex was given as the ratio 1:2 of PA to DM--CD. The dissolution rate of the PA/DM--CD complex was much greater than that of intact PA.Presented at the Fourth International Symposium on Inclusion Phenomena and the Third International Symposium on Cyclodextrins, Lancaster, U.K., 20–25 July 1986. 相似文献
150.
Kiyokawa T Kanaori K Tajima K Kawaguchi M Mizuno T Oku J Tanaka T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(14):3548-3554
The alpha-helical coiled coils have a representative amino acid sequence of (abcdefg)(n) heptad repeats. We previously reported that two peptides named IZ-2A and IZ-2W formed an (IZ-2A)(2)/IZ-2W heterotrimer with an Ala-Ala-Trp interaction in the hydrophobic core. In this paper, we describe the selective formation of AAB- and ABC-type heterotrimers. To increase the selectivity of the AAB-type heterotrimeric formation, Lys residues at the f position were mutated to either an Ala or a Gln residue to form IZ-2A(fA) or IZ-2W(fQ). Separately, both IZ-2A(fA) and IZ-2W(fQ) have a random structure at pH 7 and 20 degrees C. However, together IZ-2A(fA) and IZ-2W(fQ) form a 2:1 complex with a thermal transition midpoint (Tm) of 48 degrees C. This procedure was applied to prepare the ABC-type heterotrimer, in which two sets of Ala-Ala-Trp interactions were designed in the hydrophobic core. Interhelical interaction between the e and g positions and the alpha-helical propensity of the amino acid at the f position were also considered in the design. The resultant three peptides selectively formed the ABC-type heterotrimer with a Tm of 51 degrees C. Other peptide combinations had random coil properties. 相似文献