全文获取类型
收费全文 | 823篇 |
免费 | 27篇 |
国内免费 | 2篇 |
专业分类
化学 | 662篇 |
晶体学 | 5篇 |
力学 | 9篇 |
数学 | 68篇 |
物理学 | 108篇 |
出版年
2023年 | 3篇 |
2022年 | 3篇 |
2021年 | 9篇 |
2020年 | 15篇 |
2019年 | 8篇 |
2018年 | 10篇 |
2017年 | 6篇 |
2016年 | 23篇 |
2015年 | 16篇 |
2014年 | 10篇 |
2013年 | 35篇 |
2012年 | 48篇 |
2011年 | 68篇 |
2010年 | 22篇 |
2009年 | 30篇 |
2008年 | 63篇 |
2007年 | 64篇 |
2006年 | 42篇 |
2005年 | 43篇 |
2004年 | 45篇 |
2003年 | 50篇 |
2002年 | 37篇 |
2001年 | 10篇 |
2000年 | 15篇 |
1999年 | 8篇 |
1998年 | 6篇 |
1997年 | 6篇 |
1996年 | 9篇 |
1995年 | 4篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 14篇 |
1991年 | 14篇 |
1990年 | 9篇 |
1989年 | 9篇 |
1988年 | 6篇 |
1987年 | 9篇 |
1986年 | 4篇 |
1985年 | 13篇 |
1984年 | 10篇 |
1982年 | 7篇 |
1981年 | 5篇 |
1980年 | 4篇 |
1979年 | 6篇 |
1978年 | 6篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1974年 | 4篇 |
1973年 | 2篇 |
1966年 | 2篇 |
排序方式: 共有852条查询结果,搜索用时 15 毫秒
71.
Oishi T Hagiwara K Kinumi T Yamakawa Y Nishijima M Nakamura K Arimoto H 《Organic & biomolecular chemistry》2003,1(15):2626-2629
The effects of Soto's 'beta-sheet breaker peptide' and its polymer on PrPSc formation in ScN2a cells were investigated. Surface plasmon resonance study indicated that direct binding between PrP(81-145) and the 'beta-sheet breaker peptide' is not specific and may not play a major role in the inhibition of PrPSc formation. 相似文献
72.
Otaka A Yukimasa A Watanabe J Sasaki Y Oishi S Tamamura H Fujii N 《Chemical communications (Cambridge, England)》2003,(15):1834-1835
Gamma-acetoxy-alpha,beta-enoates were easily reduced by samarium diiodide (SmI2) in THF to generate samarium dienolates which were kinetically trapped with ease at their alpha-positions by electrophiles (proton, aldehydes or ketones) to yield (E)-alkene dipeptide isosteres or gamma-amino acid derivatives in high chemical yields. 相似文献
73.
[reaction: see text] [60]Fullerenoacetyl chloride, one of the reactive derivatives of [60]fullerenoacetic acid, was isolated and identified for the first time. This acid chloride was easily synthesized in good yield from tert-butyl [60]fullerenoacetate through two steps. In the presence of 4-(dimethylamino)pyridine as a base, the acid chloride smoothly reacted with various alcohols under mild conditions to give the corresponding esters including [60]fullerene-biomolecule hybrids in moderate to high yields. 相似文献
74.
Four new cycloartane glycosides from Aquilegia vulgaris 总被引:2,自引:0,他引:2
Four new cycloartane glycosides, named aquilegiosides G-J, were isolated from the dried aerial parts of Aquilegia vulgaris. Their structures were determined by spectroscopic analysis and chemical evidence. 相似文献
75.
Arakawa Y Ohnishi M Yoshimura N Yoshifuji S 《Chemical & pharmaceutical bulletin》2003,51(8):1015-1020
Synthesis of (1R,2S,5S,6R,8S)-3-azabicyclo[3.3.0]octane-2,6,8-tricarboxylic acid (2) from trans-4-hydroxy-L-proline (5) was attempted. A Diels-Alder reaction of 3,4-dehydroproline derivative 9 and cyclopentadiene afforded a single stereoisomer 11. The Diels-Alder adduct was smoothly converted to the hydrochloride of 2 (24) via RuO(4) oxidation. Although some racemization of the material or product was observed during the synthetic processes, the amino acid 24 proved to be optically pure. 相似文献
76.
Ken-ichi Fujita Shigeru HashimotoAkihiro Oishi Yoichi Taguchi 《Tetrahedron letters》2003,44(19):3793-3795
After immobilizing arylselenenyl bromide on polymer resin, the oxyselenenylation reaction of olefin was carried out in water. An amphiphilic polymer-supported arylselenenyl bromide was employed, and various intramolecular oxyselenenylation and deselenenylation reactions proceeded smoothly in water in fair chemical yields (up to an 83% yield). 相似文献
77.
Single crystals of Rh(Si2O)(PO4)3 and In4(Si2O) · (PO4)6 were prepared by chemical transport reactions in silica tubes and their structures were determined. Crystal data of Rh(Si2O)(PO4)3: trigonal, space group P 3 c1, a = 8.088(3) Å, c = 8.740(2) Å, Z = 2, R(F2) = 0.0379, Rw(F2) = 0.0518 for 601 unique reflections. In4(Si2O)(PO4)6: hexagonal, space group P63/m, a = 8.5149(10) Å, c = 7.7481(12) Å, Z = 1, R(F2) = 0.0436, Rw(F2) = 0.0522 for 509 unique reflections. Both of the compounds have hexagonal close packed array of phosphate groups with metal atoms and SiOSi units in the octahedral interstices, where the SiOSi units show occupational disorder. The structure of the indium compound is considered to be a disordered structure of the reported Mo4Si2P6O13 structure, and contains confacial bioctahedral units. 相似文献
78.
Palladium–N‐Heterocyclic Carbene (NHC)‐Catalyzed Asymmetric Synthesis of Indolines through Regiodivergent C(sp3)H Activation: Scope and DFT Study 下载免费PDF全文
Dmitry Katayev Dr. Evgeny Larionov Dr. Masafumi Nakanishi Dr. Céline Besnard Prof. Dr. E. Peter Kündig 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(46):15021-15030
Two bulky, chiral, monodentate N‐heterocyclic carbene ligands were applied to palladium‐catalyzed asymmetric C?H arylation to incorporate C(sp3)?H bond activation. Racemic mixtures of the carbamate starting materials underwent regiodivergent reactions to afford different trans‐2,3‐substituted indolines. Although this CAr?Calkyl coupling requires high temperatures (140–160 °C), chiral induction is high. This regiodivergent reaction, when carried out with enantiopure starting materials, can lead to single structurally different enantiopure products, depending on the catalyst chirality. The C?H activation at a tertiary center was realized only in the case of a cyclopropyl group. No C?H activation takes place alpha to a tertiary center. A detailed DFT study is included and analyses of methyl versus methylene versus methine C?H activation is used to rationalize experimentally observed regio‐ and enantioselectivities. 相似文献
79.
Folding of Synthetic Homogeneous Glycoproteins in the Presence of a Glycoprotein Folding Sensor Enzyme 下载免费PDF全文
Dr. Simone Dedola Dr. Masayuki Izumi Dr. Yutaka Makimura Dr. Akira Seko Dr. Akiko Kanamori Dr. Masafumi Sakono Prof. Dr. Yukishige Ito Prof. Dr. Yasuhiro Kajihara 《Angewandte Chemie (International ed. in English)》2014,53(11):2883-2887
UDP‐glucose:glycoprotein glucosyltransferase (UGGT) plays a key role in recognizing folded and misfolded glycoproteins in the glycoprotein quality control system of the endoplasmic reticulum. UGGT detects misfolded glycoproteins and re‐glucosylates them as a tag for misfolded glycoproteins. A flexible model to reproduce in vitro folding of a glycoprotein in the presence of UGGT in a mixture containing correctly folded, folding intermediates, and misfolded glycoproteins is described. The data demonstrates that UGGT can re‐glucosylate all intermediates in the in vitro folding experiments, thus indicating that UGGT inspects not only final folded products, but also the glycoprotein folding intermediates. 相似文献
80.
Lifang Chen Yulv Yu Masako Kuwa Tao Cheng Yan Liu Hiroshi Murakami Harada Masafumi Yuan Wang 《物理化学学报》2020,36(1):1907008-0
碱-乙二醇法制备的"非保护型"金属及合金纳米簇由表面吸附的溶剂分子和简单离子实现稳定化,它们被广泛用于制备高性能复相催化剂和研究复相催化剂中的尺寸、组成、载体表面基团以及修饰剂对催化性能的影响。关于此类非保护金属纳米簇的形成过程及机理的认识尚有待进一步深化。本文采用原位快速扫描X射线吸收精细结构谱(QXAFS)、原位紫外-可见(UV-Vis)吸收光谱、透射电子显微镜和动态光散射技术研究了碱-乙二醇法合成中非保护型金属胶体纳米簇的形成过程与机理。结果表明,在碱-乙二醇法合成非保护型Pt金属纳米簇的过程中,室温下即有部分Pt(IV)被还原至Pt(II)。随着反应温度的升高,OH-逐渐取代与Pt离子配位的Cl-,在Pt―Pt键形成之前,反应体系的UV-Vis吸收光谱中可观察到明显的纳米粒子的散射信号,原位QXAFS分析表明Pt纳米簇是由Pt氧化物纳米粒子还原所形成的;在Ru金属纳米簇的形成过程中,OH-首先取代了Ru Cl_3中的Cl~-,形成羟基配合物Ru(OH) _6~(3-),后者进一步缩合形成氧化钌纳米粒子,最终Ru金属纳米簇由乙二醇还原氧化钌纳米粒子形成。由于先形成了氧化物纳米粒子,后续的还原反应被限制在氧化物纳米粒子内,使最终得到的非保护型金属纳米簇具有尺寸小、分布窄的特点。本工作所获得的知识对发展高性能能源转化催化剂、精细化学合成催化剂、传感器等功能体系具有重要意义。 相似文献