全文获取类型
收费全文 | 3375篇 |
免费 | 651篇 |
国内免费 | 274篇 |
学科分类
数理化 | 4300篇 |
出版年
2024年 | 8篇 |
2023年 | 38篇 |
2022年 | 109篇 |
2021年 | 105篇 |
2020年 | 163篇 |
2019年 | 106篇 |
2018年 | 113篇 |
2017年 | 110篇 |
2016年 | 204篇 |
2015年 | 200篇 |
2014年 | 245篇 |
2013年 | 285篇 |
2012年 | 252篇 |
2011年 | 241篇 |
2010年 | 177篇 |
2009年 | 210篇 |
2008年 | 211篇 |
2007年 | 260篇 |
2006年 | 188篇 |
2005年 | 188篇 |
2004年 | 158篇 |
2003年 | 143篇 |
2002年 | 89篇 |
2001年 | 82篇 |
2000年 | 68篇 |
1999年 | 53篇 |
1998年 | 46篇 |
1997年 | 50篇 |
1996年 | 38篇 |
1995年 | 31篇 |
1994年 | 18篇 |
1993年 | 13篇 |
1992年 | 8篇 |
1991年 | 17篇 |
1990年 | 8篇 |
1989年 | 7篇 |
1988年 | 12篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1982年 | 5篇 |
1981年 | 1篇 |
1980年 | 6篇 |
1979年 | 9篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1973年 | 2篇 |
排序方式: 共有4300条查询结果,搜索用时 0 毫秒
61.
62.
Dr. Max Bielitza Prof. Dr. Jörg Pietruszka 《Angewandte Chemie (International ed. in English)》2013,52(42):10960-10985
Psymberin is a marine natural product which has attracted a great deal of interest since its isolation: While the highly cytotoxic compound was detected early on as an ingredient in a marine sponge, it took over a decade and 600 additional samples for the structure to eventually be assigned. In the last eight years fascinating synthetic and biosynthetic investigations have led to a more detailed understanding as well as a new starting point for structure–activity studies towards new antitumor compounds. The Review gives an in‐depth insight into the progress in the field of the marine polyketide psymberin and demonstrates how organic synthesis is influencing neighboring scientific subjects. 相似文献
63.
明日叶黄酮类化合物清除羟基自由基活性研究 总被引:1,自引:0,他引:1
为了研究明日叶黄酮类化合物对羟基自由基的清除作用,以明日叶(主要取叶片)为原料,用体积分数为65%乙醇提取明日叶总黄酮,测定其总黄酮含量.通过Fenton反应体系产生羟基自由基,利用明日叶提取液中的功能成分黄酮类化合物对羟基自由基的清除作用进行研究.结果表明:明日叶提取物总黄酮质量分数为10.18%,且黄酮类化合物对羟基自由基有较强清除效力,当提取物总黄酮浓度在0.1~1.0 mg/mL范围内,其与清除率呈正相关.明日叶中黄酮类化合物对羟基自由基有较强清除效力,作为天然抗氧化产品开发具有一定价值. 相似文献
64.
Total synthesis of α-elvucitabine was achieved in 26% overall yield by a concise nine-step procedure starting from L-lyxose, with trimethylsilyl trifluoromethaneoulfonate (TMSOTf)–mediated stereocontrolled α-N-glycosidation and olefination through Barton–McCombie deoxygenation being the key steps, and the stereochemistry of the product was determined by nuclear Overhauser effect spectroscopy. 相似文献
65.
Total synthesis of (Z) pulchellalactam, a CD protein tyrosine phosphatase inhibitor, from commercially available methallyl chloride employing ring‐closure metathesis (RCM) as a key step is described. 相似文献
66.
V. Leoni A. M. Caricchia C. Cremisini S. Chiavarini L. Fabiani R. Morabito 《International journal of environmental analytical chemistry》2013,93(1-4):411-422
Abstract Total Diet Studies on pesticide residues in foods carried out in Italy in the last two decades are briefly summarized and data are discussed. Health risk assessment is expressed by the ratio total intake/ADI (%ADI ingested) for each compound and by the sum of the percentages of ADI for each compound within the same class of pesticides. The total dietary intake of chlorinated pesticides, that was almost 100% of ADI in the years 1970-74, decreased down to 10% in the period 1978-84. This trend was confirmed for DDT in recent years, while data on Lindane and Heptachlor seem to be constant. As regards the organophosphorus pesticides the sum of the percentages of ADI ingested for each compound, extrapolated from recent data (1990-1991) is about 20% and can be regarded as reasonably acceptable because the study included practically all the mainly used compounds. Only few data are available for some pesticides like dithiocarbamates, especially EBDCs and their derivatives (e.g. ETU), other carbamates (e.g. aldicarb), paraquat etc. Moreover, analytical methods for these compounds should be improved. The need for a considerable improvement in the number and organization of monitoring structures, in the use of standardized analytical procedures, in good laboratory practice standards and in the realibility of “monitoring protocols” and their homogeneity is evidenced. 相似文献
67.
68.
Dr. Christoph W. Wullschleger Prof. Dr. Jürg Gertsch Prof. Dr. Karl‐Heinz Altmann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(39):13105-13111
The stereoselective syntheses of 7,8,9‐trideoxypeloruside A ( 4 ) and a monocyclic peloruside A analogue lacking the entire tetrahydropyran moiety ( 3 ) are described. The syntheses proceeded through the PMB‐ether of an ω‐hydroxy β‐keto aldehyde as a common intermediate which was elaborated into a pair of diastereomeric 1,3‐syn and ‐anti diols by stereoselective Duthaler–Hafner allylations and subsequent 1,3‐syn or anti reduction. One of these isomers was further converted into a tetrahydropyran derivative in a high‐yielding Prins reaction, to provide the precursor for bicyclic analogue 4 . Downstream steps for both syntheses included the substrate‐controlled addition of a vinyl lithium intermediate to an aldehyde, thus connecting the peloruside side chain to C15 (C13) of the macrocyclic core structure in a fully stereoselective fashion. In the case of monocyclic 3 macrocyclization was based on ring‐closing olefin metathesis (RCM), while bicyclic 4 was cyclized through Yamaguchi‐type macrolactonization. The macrolactonization step was surprisingly difficult and was accompanied by extensive cyclic dimer formation. Peloruside A analogues 3 and 4 inhibited the proliferation of human cancer cell lines in vitro with micromolar and sub‐micromolar IC50 values, respectively. The higher potency of 4 highlights the importance of the bicyclic core structure of peloruside A for nM biological activity. 相似文献
69.
Stéphanie Miquet Dr. Nicolas Vanthuyne Dr. Paul Brémond Prof. Gérard Audran 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(32):10632-10642
The first total syntheses of the proposed structures of kopeolin ( 1 ) and kopeolone ( 3 ) have been achieved from a common enantiopure chiral building block obtained by a chemoenzymatic enantioconvergent methodology. The syntheses feature two key steps: a one‐pot reduction/diastereoselective protonation followed by a highly diastereoselective addition of an organocerate. The synthetic structures were fully characterized and all stereocenters were confirmed. The results show that the two previously reported structures were not assigned correctly, and suggest an initial structural misassignment during the isolation of the natural products. Thus, two revised structures, 1′ for kopeolin and 3′ for kopeolone, are proposed. 相似文献
70.
Dr. Nina Schützenmeister Dr. Michael Müller Prof. Dr. Uwe M. Reinscheid Prof. Dr. Christian Griesinger Dr. Andrei Leonov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(51):17584-17588
Here we report the synthesis of all four stereoisomers of mefloquine. Mefloquine (Lariam) is an important anti‐malaria drug that is applied as a racemate of the erythro form. However, the (?)‐isomer induces psychosis, while the (+)‐enantiomer does not have this undesired side effect. There are six syntheses of which five lead to the wrong enantiomer without the authors of these syntheses noting that they had synthesized the wrong compound. At the same time physical chemistry investigations had assigned the absolute configuration correctly and the last enantioselective synthesis that took these results into account delivered the correct absolute configuration. Since various synthetic approaches failed to provide the correct stereoisomers in previous syntheses, we submit here a synthetic approach with a domino Sonogashira‐6π‐electrocyclisation as key step that confirmed synthetically the correct absolute configuration of all four isomers. 相似文献