全文获取类型
收费全文 | 2805篇 |
免费 | 140篇 |
国内免费 | 8篇 |
专业分类
化学 | 2123篇 |
晶体学 | 15篇 |
力学 | 33篇 |
数学 | 286篇 |
物理学 | 496篇 |
出版年
2023年 | 37篇 |
2022年 | 76篇 |
2021年 | 88篇 |
2020年 | 97篇 |
2019年 | 68篇 |
2018年 | 41篇 |
2017年 | 50篇 |
2016年 | 110篇 |
2015年 | 109篇 |
2014年 | 99篇 |
2013年 | 150篇 |
2012年 | 195篇 |
2011年 | 244篇 |
2010年 | 132篇 |
2009年 | 105篇 |
2008年 | 172篇 |
2007年 | 139篇 |
2006年 | 135篇 |
2005年 | 115篇 |
2004年 | 103篇 |
2003年 | 81篇 |
2002年 | 62篇 |
2001年 | 44篇 |
2000年 | 23篇 |
1999年 | 19篇 |
1998年 | 14篇 |
1997年 | 13篇 |
1996年 | 26篇 |
1995年 | 15篇 |
1994年 | 25篇 |
1993年 | 25篇 |
1992年 | 27篇 |
1991年 | 23篇 |
1990年 | 22篇 |
1989年 | 18篇 |
1988年 | 17篇 |
1987年 | 11篇 |
1986年 | 13篇 |
1985年 | 19篇 |
1984年 | 18篇 |
1982年 | 20篇 |
1981年 | 9篇 |
1980年 | 13篇 |
1979年 | 13篇 |
1978年 | 13篇 |
1977年 | 11篇 |
1976年 | 18篇 |
1975年 | 7篇 |
1974年 | 9篇 |
1973年 | 11篇 |
排序方式: 共有2953条查询结果,搜索用时 0 毫秒
191.
192.
193.
194.
Zhi-Yong Yang Emilio Jimenez-Vicente Hayden Kallas Dmitriy A. Lukoyanov Hao Yang Julia S. Martin del Campo Dennis R. Dean Brian M. Hoffman Lance C. Seefeldt 《Chemical science》2021,12(20):6913
The electronic structure of the active-site metal cofactor (FeV-cofactor) of resting-state V-dependent nitrogenase has been an open question, with earlier studies indicating that it exhibits a broad S = 3/2 EPR signal (Kramers state) having g values of ∼4.3 and 3.8, along with suggestions that it contains metal-ions with valencies [1V3+, 3Fe3+, 4Fe2+]. In the present work, genetic, biochemical, and spectroscopic approaches were combined to reveal that the EPR signals previously assigned to FeV-cofactor do not correlate with active VFe-protein, and thus cannot arise from the resting-state of catalytically relevant FeV-cofactor. It, instead, appears resting-state FeV-cofactor is either diamagnetic, S = 0, or non-Kramers, integer-spin (S = 1, 2 etc.). When VFe-protein is freeze-trapped during high-flux turnover with its natural electron-donating partner Fe protein, conditions which populate reduced states of the FeV-cofactor, a new rhombic S = 1/2 EPR signal from such a reduced state is observed, with g = [2.18, 2.12, 2.09] and showing well-defined 51V (I = 7/2) hyperfine splitting, aiso = 110 MHz. These findings indicate a different assignment for the electronic structure of the resting state of FeV-cofactor: S = 0 (or integer-spin non-Kramers state) with metal-ion valencies, [1V3+, 4Fe3+, 3Fe2+]. Our findings suggest that the V3+ does not change valency throughout the catalytic cycle.Active site FeV-cofactor of the V-nitrogenase and the EPR spectrum of the reduced cofactor showing 51V-hyperfine coupling. 相似文献
195.
196.
Tropylium ion mediated α-cyanation of amines is described. Even in the presence of KCN, tropylium ion is capable of oxidizing various amine substrates, and the resulting iminium ions undergo salt metathesis with cyanide ion to produce aminonitriles. The byproducts of this transformation are simply cycloheptatriene, a volatile hydrocarbon, and water-soluble potassium tetrafluoroborate. Thirteen total substrates are shown for the α-cyanation procedure, including a gram scale synthesis of 17β-cyanosparteine. In addition, a tropylium ion mediated oxidative aza-Cope rearrangement is demonstrated. 相似文献
197.
Ella Kazakova Julia Morozova Diana Mironova Victor Syakaev Liya Muslinkina Alexander Konovalov 《Supramolecular chemistry》2013,25(12):831-841
Here, we report on the study of cationic amidoammonium calix[4]resorcinarenes 1–5 of various lipophilicity capable of binding acid–base indicator methyl orange (MO). We identified the contributions of macrocycle aggregation and conformational mobility in the binding of MO. The effective pKa values of bound MO systematically decrease as the size and the packing density of the aggregates increase with an increase in calixresorcinarene lipophilicity. Consideration of a series of macrocycles clearly shows that large aggregates form most stable complexes, binding guests not on individual level but as aggregates. It was found that the most stable MO complex with 5 is formed due to electrostatic binding with ammonium groups of the macrocycle and incapsulation of MO in a hydrophobic layer of the aggregates. We have shown that competitive binding of MO and cationic surfactants by aggregates of 5 is suitable for visual/spectrophotometric detection of colourless anionic substrates. 相似文献
198.
Matthias Meier Dr. Julia Kennedy‐Darling Se Hoon Choi Eric M. Norstrom Dr. Sangram S. Sisodia Prof. Dr. Rustem F. Ismagilov Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(8):1487-1489
Small with control : For miniaturization of protein aggregation experiments the interfacial chemistry must be controlled to avoid protein aggregation caused by interfacial adsorption. Plug‐based microfluidics with defined surface chemistry (see schematic picture) can then be used to perform hundreds of aggregation experiments with volume‐limited samples, such as cerebrospinal fluid from mice.
199.
Julia Vallejo Alejandro Pascual‐Álvarez Dr. Joan Cano Dr. Isabel Castro Prof. Dr. Miguel Julve Prof. Dr. Francesc Lloret Dr. J. Krzystek Prof. Dr. Giovanni De Munno Dr. Donatella Armentano Prof. Dr. Wolfgang Wernsdorfer Dr. Rafael Ruiz‐García Dr. Emilio Pardo 《Angewandte Chemie (International ed. in English)》2013,52(52):14075-14079
200.
Julie P. Vanegas Lucas E. Peisino Dr. Salvador Pocoví‐Martínez Dr. Ramón J. Zaragozá Dr. Elena Zaballos‐García Dr. Julia Pérez‐Prieto 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(48):16248-16255
Gold nanoparticles capped with simple adenosine derivatives can form colloidal aggregates in nonpolar solvents. Theoretical calculations indicate the formation of organic channels by the supramolecular assembly of the nanoparticles by means of hydrogen bonds between the adenine moieties. The aggregates were only negligibly sensitive to nPrOH, iPrOH, and tBuOH, whereas some showed a similar response to MeOH and EtOH, and others showed high selectivity toward MeOH. DNA nucleoside derivatives (1‐(2‐deoxy‐β‐D ‐ribofuranosyl)‐5‐methyluracil and 2′,3′‐O‐isopropylideneadenosine) as well as thymine and other aromatic compounds such as pyrene derivatives (pyrene, 1‐chloropyrene, 1‐hydroxypyrene, (1‐pyrenyl)methanol, and 2‐hydroxynapthalene) did not induce disassembly of the nanoparticle aggregates. Data suggest that the nucleoside channels allow access to alcohols according to their size, and an efficient interaction between the alcohol and the adenine units destabilizes the hydrogen bonds, which eventually leads to nanoparticle disassembly. 相似文献