全文获取类型
收费全文 | 3309篇 |
免费 | 136篇 |
国内免费 | 16篇 |
专业分类
化学 | 2633篇 |
晶体学 | 44篇 |
力学 | 40篇 |
数学 | 194篇 |
物理学 | 550篇 |
出版年
2023年 | 17篇 |
2022年 | 31篇 |
2021年 | 30篇 |
2020年 | 48篇 |
2019年 | 88篇 |
2018年 | 34篇 |
2017年 | 34篇 |
2016年 | 81篇 |
2015年 | 56篇 |
2014年 | 71篇 |
2013年 | 170篇 |
2012年 | 207篇 |
2011年 | 208篇 |
2010年 | 125篇 |
2009年 | 131篇 |
2008年 | 192篇 |
2007年 | 190篇 |
2006年 | 196篇 |
2005年 | 159篇 |
2004年 | 129篇 |
2003年 | 119篇 |
2002年 | 119篇 |
2001年 | 60篇 |
2000年 | 49篇 |
1999年 | 37篇 |
1998年 | 34篇 |
1997年 | 26篇 |
1996年 | 33篇 |
1995年 | 17篇 |
1993年 | 29篇 |
1992年 | 29篇 |
1991年 | 31篇 |
1990年 | 40篇 |
1989年 | 28篇 |
1988年 | 29篇 |
1987年 | 28篇 |
1986年 | 35篇 |
1985年 | 33篇 |
1984年 | 44篇 |
1983年 | 30篇 |
1982年 | 36篇 |
1981年 | 32篇 |
1980年 | 40篇 |
1979年 | 29篇 |
1978年 | 38篇 |
1977年 | 31篇 |
1976年 | 22篇 |
1975年 | 21篇 |
1974年 | 24篇 |
1973年 | 22篇 |
排序方式: 共有3461条查询结果,搜索用时 15 毫秒
71.
Shoji M Imai H Shiina I Kakeya H Osada H Hayashi Y 《The Journal of organic chemistry》2004,69(5):1548-1556
An oxidative dimerization reaction, involving the three successive steps of oxidation, 6 pi-electrocyclization, and Diels-Alder reaction, has been experimentally and theoretically investigated for the three 2-alkenyl-3-hydroxymethyl-2-cyclohexen-1-one derivatives epoxyquinol 3, epoxyquinone 6, and cyclohexenone 10. Of the sixteen possible modes of the oxidation/6 pi-electrocylization/Diels-Alder reaction cascade for the epoxyquinone 6, and eight for the cyclohexenone 10, only the endo-anti(epoxide)-anti(Me)-hetero and endo-anti(Me)-hetero modes are, respectively, observed, while both endo-anti(epoxide)-anti(Me)-hetero and exo-anti(epoxide)-anti(Me)-homo reaction modes occur with the epoxyquinol 3. Intermolecular hydrogen-bonding is found to be the key cause of formation of both epoxyquinols A and B with 3, although epoxyquinone 6 and cyclohexenone 10 both gave selectively only the epoxyquinol A-type product. In the dimerization of epoxyquinol 3, two monomer 2H-pyrans 5 interact with each other to afford intermediate complex 28 or 29 stabilized by hydrogen-bonding, from which Diels-Alder reaction proceeds. Theoretical calculations have also revealed the differences in the reaction profiles of epoxyquinone 6 and cyclohexenone 10. Namely, the rate-determining step of the former is the Diels-Alder reaction, while that of the latter is the 6 pi-electrocyclization. 相似文献
72.
S. Nakajima H. Hayashi K. OHSHIMA K. Yamazaki Y. Kubo N. Samejima Y. Kakiuchi Y. Shindoh H. Koshimizu I. Sakata H. Yamauchi 《Photochemistry and photobiology》1987,46(5):783-788
Abstract Mono-DPTA-ethyleneglycol-Ga-deuteroporphyrin (MDEGD) was synthesized, by coordinating non-radioactive Ga in the porphyrin ring and connecting DTPA (diethylene-triamine-N,N,N,N,N,-pentaacetic acid) to its side chain. By labeling with 111In , chemicals for scintigraphy were developed. They were applied to Syrian golden hamsters with implanted pancreatic gland cancers and C57-black mice with Lewis lung cancer to enable tumor imaging and biodistribution examination. A comparative study was also conducted with [67 Ga]citrate. In the resultant data, [111 In]MDEGD showed larger tumor/lung, tumor/kidney and tumor/blood ratio with [67 Ga]citrate. The affinity of [n In]MDEGD in inflammatory tissue was much lower than that of 67 Ga citrate. [111 In]MDEGD lost its photosensitivity. 相似文献
73.
A synthesis of the thromboxane A2 analog, -(9,11), (11,12)-dideoxa-(9,11)-epithio-(11,12)-methylene-thromboxane A2 is described. 相似文献
74.
Determination of threo and erythro configurations of both diastereoisomers of 3-fluorophenylalanine on the basis of chemical transformation and X-ray analysis has confirmed that the aziridine ring opening reaction gives the threo isomer stereoselectively, whereas the fluorodehydroxylation reaction affords both isomers nonselectively. 相似文献
75.
An automated direct assay for the simultaneous determination of unconjugated estetrol, estriol, cortisone and cortisol in serum and amniotic fluid, using high-performance liquid chromatography with electrochemical detection and ultraviolet detection, has been developed. The analysis time is ca. 1 h. This system offers good reproducibility with low coefficients of variation (estetrol, 2.3%; estriol, 2.3%; cortisone, 2.6%; cortisol, 1.9%). Detection limits are low enough for routine determinations (estetrol and estriol, 150 pg; cortisone and cortisol, 5 ng). Comparison of the values measured by the present method and by radioimmunoassay revealed significant correlations for estetrol (r = 0.787, p less than 0.01), estriol (r = 0.957, p less than 0.01), cortisone (r = 0.956, p less than 0.01) and cortisol (r = 0.865, p less than 0.01). This system proved to be valuable in monitoring feto-placental function. 相似文献
76.
77.
78.
79.
Akiba Y Beavis D Beery P Britt HC Budick B Chasman C Chen Z Chi CY Chu YY Cianciolo V Cole BA Costales JB Crawford HJ Cumming JB Debbe R Engelage J Fung SY Gonin M Gushue S Hamagaki H Hansen O Hayano RS Hayashi S Homma S Kaneko H Kang J Kaufman S Kehoe WL Kurita K Ledoux RJ Levine MJ Miake Y Morrison DP Morse RJ Moskowitz B Nagamiya S Namboodiri MN Nayak TK Olness J Parsons CG Remsberg LP Roehrich D Rothschild P Sakurai H Sangster TC Seto R Soltz R Stankus P Steadman SG Stephans GS Sung T 《Physical review letters》1996,76(12):2021-2024
80.
Allakhverdiev SI Feyziev YM Ahmed A Hayashi H Aliev JA Klimov VV Murata N Carpentier R 《Journal of photochemistry and photobiology. B, Biology》1996,34(2-3):149-157
The protective action of co-solutes, such as sucrose and glycinebetaine, against the thermal inactivation of photosystem II function was studied in untreated and Mn-depleted photosystem II preparations. It was shown that, in addition to the reactions that depend on the oxygen evolving activity of the photosystem, those that implicate more intimately the reaction center itself are protected by high concentrations of osmolytes. However, the temperature required to inhibit oxygen evolution totally in the presence of osmolytes is lower than that required to eliminate reactions, such as P680 (primary electron donor in photosystem II) photo-oxidation and pheophytin photo reduetion, which only involve charge separation and primary electron transport processes. The energy storage measured from the thermal dissipation yield during photoacoustic experiments and the yield of variable fluorescence are also protected to a significant degree (up to 30%) at temperatures at which oxygen evolution is totally inhibited. It is suggested that a cyclic electron transport reaction around photosystem II may be preserved under these conditions and may be responsible for the energy storage measured at relatively high temperatures. This interpretation is also supported by thermoluminescence data involving the recombination between reduced electron acceptors and oxidized electron donors at - 30 and - 55 °C. The data also imply that a high concentration of osmolyte allows the stabilization of the photosystem core complex together with the oxygen-evolving complex. The stabilization effect is understood in terms of the minimization of protein-water interactions as proposed by the theory of Arakawa and Timasheff (Biophys. J., 47 (1985) 411--414). 相似文献