全文获取类型
收费全文 | 38113篇 |
免费 | 1217篇 |
国内免费 | 86篇 |
专业分类
化学 | 25906篇 |
晶体学 | 280篇 |
力学 | 820篇 |
数学 | 5666篇 |
物理学 | 6744篇 |
出版年
2023年 | 295篇 |
2022年 | 366篇 |
2021年 | 547篇 |
2020年 | 671篇 |
2019年 | 638篇 |
2018年 | 789篇 |
2017年 | 709篇 |
2016年 | 1416篇 |
2015年 | 1146篇 |
2014年 | 1177篇 |
2013年 | 2386篇 |
2012年 | 2635篇 |
2011年 | 2896篇 |
2010年 | 1675篇 |
2009年 | 1432篇 |
2008年 | 2447篇 |
2007年 | 2393篇 |
2006年 | 2138篇 |
2005年 | 1901篇 |
2004年 | 1565篇 |
2003年 | 1216篇 |
2002年 | 1126篇 |
2001年 | 765篇 |
2000年 | 638篇 |
1999年 | 495篇 |
1998年 | 377篇 |
1997年 | 305篇 |
1996年 | 440篇 |
1995年 | 283篇 |
1994年 | 293篇 |
1993年 | 321篇 |
1992年 | 289篇 |
1991年 | 197篇 |
1990年 | 199篇 |
1989年 | 169篇 |
1988年 | 162篇 |
1987年 | 163篇 |
1986年 | 145篇 |
1985年 | 221篇 |
1984年 | 209篇 |
1983年 | 162篇 |
1982年 | 150篇 |
1981年 | 130篇 |
1980年 | 117篇 |
1979年 | 123篇 |
1978年 | 108篇 |
1977年 | 100篇 |
1976年 | 89篇 |
1975年 | 82篇 |
1973年 | 95篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
[reaction: see text] Tetrasubstituted pyrazines containing two phosphonate groups 2 in positions 2 and 5 and trisubstituted pyrazines containing a phosphonate 5 or a phosphine oxide group 7 in position 2 are obtained by thermal treatment of 2H-azirine-2-phosphonates 1 and -phosphine oxides 6. These pyrazines can also be prepared from beta-ketoxime tosylates 9 and 10 or from oxime derived from phosphine oxide 11. 相似文献
992.
Sulphophenyl carboxylates (SPC) derived from the biodegradation of commercial blends of linear alkylbenzene sulphonates (LAS), were recorded during OECD-301E screening tests under aerobic conditions. Both HPLC-FL and GC-MS were employed to determine biotransformation products. Two well defined groups of detectable SPC were generated: transient compounds, i.e. SPC which degrade very quickly, and compounds more persistent than the parent LAS which required an acclimatization period before their mineralization could take place. The biodegradation of a C10-C13 LAS commercial mixture and of two individual homologs (C11-LAS and C12-LAS) led to the identification of the most persistent SPC which were C6-SPC, C7-SPC and C8-SPC. The C6-SPC turned out to be the homolog which biodegrades most slowly, this suggests that odd LAS homologs are more easily biodegradable. 相似文献
993.
Rodríguez JL Souto RM Fernández-Mérida L Pastor E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(9):2134-2142
Spectroelectrochemical studies on the reactivity of butanol isomers on Pt electrodes in perchloric acid medium led to the observation of structural effects that result from the different arrangements of atoms in the organic molecules. The use of differential electrochemical mass spectrometry (DEMS) to detect volatile products showed that all four isomers react on the electrode, though different product yields were observed for each compound. In spite of the differences in the electrochemical behaviour of the butanol isomers, a series of general processes accounts for the results obtained. The formation of strongly adsorbed residues by a dehydration process leading to the formation of a C=C bond was proposed for all isomers. Electroreduction of the adsorbates produces C(4) and C(3) alkanes, and the latter reveal the existence of a fragmentation process. The C(4) hydrocarbons can be formed by hydrogenation of these residues and by hydrogenolysis of alcohol molecules in the bulk solution which react at the electrode with adsorbed hydrogen. On the other hand, CO(2) is formed during electrooxidation of the adsorbed species. Partial-oxidation products containing a carbonyl group were detected from 0.2 M solutions of 1-butanol, isobutyl alcohol and sec-butyl alcohol. The tertiary alcohol tert-butyl alcohol only reacts in its adsorbed state. 相似文献
994.
In conformational analysis, the systematic search method completely maps the space but suffers from the combinatorial explosion problem because the number of conformations increases exponentially with the number of free rotation angles. This study introduces a new methodology of conformational analysis that controls the combinatorial explosion. It is based on a dimensional reduction of the system through the use of principal component analysis. The results are exactly the same as those obtained for the complete search but, in this case, the number of conformations increases only quadratically with the number of free rotation angles. The method is applied to a series of three drugs: omeprazole, pantoprazole, lansoprazole-benzimidazoles that suppress gastric-acid secretion by means of H+, K+-ATPase enzyme inhibition. 相似文献
995.
Portilla Y Chávez I Arancibia V Loeb B Manríquez JM Roig A Molins E 《Inorganic chemistry》2002,41(7):1831-1836
In this work, we report the synthesis and a study on the degree of electronic delocalization in the asymmetric mixed valence complexes [CpFe(C(8)H(6))Fe(C(8)H(7))](+), 3a(+), and [CpCo(C(8)H(6))Fe(C(8)H(7))](+), 3b(+), (Cp = C(5)Me(5), C(8)H(6) = pentalenyde, C(8)H(7) = hydropentalenyde, and = ((3,5(CF(3))(2)C(6)H(3))(4)B(-))). Electrochemical methods, (57)Fe M?ssbauer spectroscopy, electronic spectroscopy, and electron paramagnetic resonance were used for this purpose. Although the anti conformation of the complexes precludes any metal-metal interaction, all the techniques employed show that 3a(+) is a electronic delocalized system, while 3b(+) behaves as two individual metallic centers with localized electron density. 相似文献
996.
[reaction: see text] An unprecedented endo-selective and regioselective intermolecular Pauson-Khand reaction takes place when heterobimetallic (Mo-Co) complexes derived from N-(2-alkynoyl)oxazolidinones or sultams are heated in the presence of norbornadiene. 相似文献
997.
Bermejo-Barrera P Barciela-Alonso MC Domínguez-González R Bermejo-Barrera A Cocho De Juan JA Fraga-Bermúdez JM 《Analytical and bioanalytical chemistry》2002,374(7-8):1290-1293
A direct method for silicon determination in milk samples by Electrothermal Atomic Absorption Spectrometry was developed. Palladium was used as chemical modifier at a concentration of 610 mg L(-1); with this modifier, silicon was stable up to 1800 degrees C. The precision and accuracy of the method were investigated. The detection limit was 16.2, 2.7 and 7.2 micro g L(-1) for cows' milk, human milk and infant formula, respectively. The method was applied to silicon determination in 17 infant formula samples, 13 human milk samples and 12 cows' milk samples. 相似文献
998.
Lauceri R Raudino A Scolaro LM Micali N Purrello R 《Journal of the American Chemical Society》2002,124(6):894-895
The presence of 10-13 M of chiral clusters of aromatic amino acids addresses aggregation of opposite-charged achiral porphyrin towards the formation of smart chiral assemblies. The latter supramolecular complexes are able to self-propagate and transfer their chiral information with a 100% yield. The chiral bias occurs through a correlated sequence of induction, memory, and amplification of chirality that strongly recalls possible prebiotic scenarios. 相似文献
999.
Domino metathesis of N-alkylated derivatives of (1S)-2-azanorborn-5-en-3-one allowed for the enantioselective synthesis of pyrrolizidine, quinolizidine, pyrrolidinoazepine, and pyrrolidinoazocine derivatives in a straightforward process. 相似文献
1000.
Ruiz-Angel MJ Caballero RD Simó-Alfonso EF García-Alvarez-Coque MC 《Journal of chromatography. A》2002,947(1):31-45
The screening capability of micellar liquid chromatography (MLC) is discussed using the reported chromatographic data of several sets of compounds (amino acids, beta-blockers, diuretics, phenethylamines, phenols, polynuclear aromatic hydrocarbons, steroids and sulfonamides) and new results (sulfonamides and steroids). The chromatographic data are treated with an interpretive optimisation resolution procedure to obtain the best separation conditions. Usually, the pH and the concentration of surfactant (sodium dodecyl sulfate, SDS, or cetyltrimethylammonium bromide) for the optimal mobile phase were 2.5-3 and < 0.12 M, respectively. The nature and concentration of organic solvent depended on the polarity of the eluted compounds: a low volume fraction of propanol (approximately 1%, v/v) was useful to separate the amino acids, with log P(o/w) < -1 (where P(o/w) is the octanol-water partition coefficient). A greater concentration of this solvent (approximately 5-7%) was needed for compounds in the range -1 < log P(o/w) < 2, as with the studied diuretics and sulfonamides, and a high concentration of propanol (approximately 15%) or a low concentration of butanol (< 10%) had to be used for less polar compounds with 1 < log P(o/w) < 3, such as the beta-blockers. Pentanol (< 6%) was more suitable for the even less polar compounds with log P(o/w) > 3, such as the steroids. For basic drugs such as the phenethylamines (0 < log P(o/w) < 1.7), eluted with a micellar eluent of anionic SDS, propanol was too weak. A study is also shown for mixtures of sulfonamides (log P(o/w) = -1.2 to 1.7) and steroids (log P(o/w) = 3.0-8.1) eluted from conventional C18 columns with SDS mobile phases containing acetonitrile and 1-pentanol, respectively, which are compared with classical acetonitrile-water and methanol-water mixtures. The results complement a previous study on beta-blockers (log P(o/w) = -0.03 to 2.8) and reveal that MLC is a very competitive technique for the screening of compounds against conventional RPLC, due to its peculiar behaviour with regard to the selectivity and elution strength. The concentration of organic solvent needed to obtain sufficiently low retention times (even for highly hydrophobic steroids with log P(o/w) = 7-8) is also appreciably smaller for MLC, which reduces the environmental impact of the mobile phases. 相似文献