全文获取类型
收费全文 | 398篇 |
免费 | 10篇 |
国内免费 | 3篇 |
专业分类
化学 | 290篇 |
晶体学 | 3篇 |
力学 | 1篇 |
数学 | 67篇 |
物理学 | 50篇 |
出版年
2024年 | 1篇 |
2023年 | 2篇 |
2022年 | 2篇 |
2021年 | 3篇 |
2020年 | 4篇 |
2019年 | 5篇 |
2018年 | 3篇 |
2017年 | 9篇 |
2016年 | 6篇 |
2015年 | 3篇 |
2014年 | 8篇 |
2013年 | 15篇 |
2012年 | 30篇 |
2011年 | 19篇 |
2010年 | 12篇 |
2009年 | 13篇 |
2008年 | 18篇 |
2007年 | 26篇 |
2006年 | 19篇 |
2005年 | 29篇 |
2004年 | 28篇 |
2003年 | 13篇 |
2002年 | 15篇 |
2001年 | 3篇 |
2000年 | 4篇 |
1999年 | 3篇 |
1998年 | 8篇 |
1997年 | 4篇 |
1996年 | 10篇 |
1995年 | 8篇 |
1994年 | 8篇 |
1993年 | 6篇 |
1992年 | 8篇 |
1991年 | 3篇 |
1990年 | 12篇 |
1989年 | 14篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1985年 | 3篇 |
1984年 | 4篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1979年 | 4篇 |
1978年 | 6篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1971年 | 2篇 |
1907年 | 2篇 |
排序方式: 共有411条查询结果,搜索用时 15 毫秒
151.
Burlison JA Avila C Vielhauer G Lubbers DJ Holzbeierlein J Blagg BS 《The Journal of organic chemistry》2008,73(6):2130-2137
Recent studies have shown that the DNA gyrase inhibitor, novobiocin, binds to a previously unrecognized ATP-binding site located at the C-terminus of Hsp90 and induces degradation of Hsp90-dependent client proteins at approximately 700 microM. As a result of these studies, several analogues of the coumarin family of antibiotics have been reported and shown to exhibit increased Hsp90 inhibitory activity; however, the monomeric species lacked the ability to manifest anti-proliferative activity against cancer cell lines at concentrations tested. In an effort to develop more efficacious compounds that produce growth inhibitory activity against cancer cell lines, structure-activity relationships were investigated surrounding the prenylated benzamide side chain of the natural product. Results obtained from these studies have produced the first novobiocin analogues that manifest anti-proliferative activity against several cancer cell lines. 相似文献
152.
Dr. Daniele Masseroni Dr. Simone Mosca Matthew P. Mower Prof. Dr. Donna G. Blackmond Prof. Dr. Julius Rebek Jr. 《Angewandte Chemie (International ed. in English)》2016,55(29):8290-8293
The majority of reactions currently performed in the chemical industry take place in organic solvents, compounds that are generally derived from petrochemicals. To promote chemical processes in water, we examined the use of synthetic, deep water‐soluble cavitands in the Staudinger reduction of long‐chain aliphatic diazides (C8, C10, and C12). The diazide substrates are taken up by the cavitand in D2O in folded, dynamic conformations. The reduction of one azide group to an amine gives a complex in which the substrate is fixed in an unsymmetrical conformation, with the amine terminal exposed and the azide terminal deep and inaccessible within the cavitand. Accordingly, the reduction of the second azide group is inhibited, even with excess phosphine, and good yields of the monofunctionalized products are obtained. In contrast, the reduction of the free diazides in bulk solution yields diamine products. 相似文献
153.
Phua PH Mathew SP White AJ de Vries JG Blackmond DG Hii KK 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(16):4602-4613
The mechanism of the palladium-catalysed asymmetric aza-Michael addition of aniline to alpha,beta-unsaturated N-imide was examined from several aspects using a combination of techniques, including X-ray crystallography, mass spectrometry, NMR, UV/Vis spectroscopy, and kinetic studies. The binding of aniline to the dicationic palladium(II) metal centre was found to occur in two consecutive steps: The binding of the first aniline is fast and reversible, whereas the binding of the second aniline is slower and irreversible. This occurs in competition with the binding of the N-imide, which forms a planar six-membered chelate ring with the metal centre; coordinating through the 1,3-dicarbonyl moiety. Isotopic labelling revealed that the addition of N-H occurs in a highly stereoselective manner, allowing the synthesis of optically active beta(2)- and beta(2,3)-amino acid derivatives. The stereochemistry of the addition is postulated to be syn. In situ kinetic studies provided evidence for product inhibition. The binding of the N-imide to the catalyst was found to be the rate-limiting step. Aniline was found to be an inhibitor of the pre-catalyst. The study culminated in the design of a new reaction protocol. By maintaining a low concentration of the aniline substrate during the course of the reaction, significant enhancement of yield and enantioselectivity can be achieved. 相似文献
154.
155.
156.
Pati HN Das U Ramirez-Erosa IJ Dunlop DM Hickie RA Dimmock JR 《Chemical & pharmaceutical bulletin》2007,55(4):511-515
A series of 1-aryl-2-dimethylaminomethyl-2-propenone hydrochlorides 1 were prepared which possessed IC(50) values of less than 10 microM when examined towards human WiDr colon cancer cells. The related 1-aryl-2-dimethylaminomethyl-3-hydroxypropanone hydrochlorides 2, formed by hydration of the analogs in series 1, also had IC(50) values in the low micromolar range. On the other hand, conversion of 2-dimethylaminomethyl-1-(4-nitrophenyl)-2-propenone hydrochloride 1c into the corresponding 2-mercaptoethanol of adduct 3c led to a 37-fold reduction in potency. Two thirds of the compounds prepared in this study were more potent than a reference drug cisplatin while one third of these molecules displayed greater cytotoxicity to the WiDr cells than human CRL-2522 fibroblasts. A stability study of the 4-nitrophenyl analog in each of the series 1-3 in deuterium oxide was undertaken. In the case of 1c, replacement of the dimethylamino hydrochloride group by a hydroxy function was noted while in series 2, the loss of both water and dimethylamine hydrochloride gave rise to a mixture of two enones. The mercaptoethanol adduct 3c underwent deamination. The data obtained provide guidelines for amplifying the project in the future. 相似文献
157.
158.
How Picture Books on the National Science Teacher's Association Recommend List Portray Scientists 下载免费PDF全文
Donna Farland‐Smith Kevin D. Finson Cecile M. Arquette 《School science and mathematics》2017,117(6):250-258
This study utilized the Draw‐A‐Scientist Test Checklist (DAST‐C) to assess the illustrations of scientists in the most recent three years of NSTA Recommends book lists. A total of 15,778 images were contained in the 148 books from those lists, of which 1,676 were of scientists. ANOVA procedures revealed no significant differences in stereotypical elements across the three years of books. However, three notable stereotypical elements were present in large percentages in books from all years: predominance of male images, non‐minority scientists, and scientists who were not youthful. 相似文献
159.
We present the transformation of several sums of positive integer powers of the sine and cosine into non-trigonometric combinatorial forms. The results are applied to the derivation of generating functions and to the number of the closed walks on a path and in a cycle. 相似文献
160.
The observation of single chirality in biological systems has intrigued scientists for more than one hundred years. Here we discuss several recent experimental studies showing amplification of enantiomeric excess based on amino acid phase behavior. Comparing observations of solution-solid and gas-solid phase transitions highlights the underlying fundamental physical chemistry principles that rationalize the observed enantioenrichment in both cases. 相似文献