全文获取类型
收费全文 | 32790篇 |
免费 | 942篇 |
国内免费 | 249篇 |
专业分类
化学 | 22675篇 |
晶体学 | 223篇 |
力学 | 768篇 |
数学 | 5420篇 |
物理学 | 4895篇 |
出版年
2022年 | 283篇 |
2021年 | 421篇 |
2020年 | 516篇 |
2019年 | 485篇 |
2018年 | 376篇 |
2017年 | 372篇 |
2016年 | 835篇 |
2015年 | 737篇 |
2014年 | 807篇 |
2013年 | 1725篇 |
2012年 | 1866篇 |
2011年 | 2353篇 |
2010年 | 1142篇 |
2009年 | 1004篇 |
2008年 | 2009篇 |
2007年 | 2020篇 |
2006年 | 1996篇 |
2005年 | 1862篇 |
2004年 | 1587篇 |
2003年 | 1382篇 |
2002年 | 1282篇 |
2001年 | 402篇 |
2000年 | 388篇 |
1999年 | 358篇 |
1998年 | 335篇 |
1997年 | 357篇 |
1996年 | 486篇 |
1995年 | 343篇 |
1994年 | 298篇 |
1993年 | 270篇 |
1992年 | 267篇 |
1991年 | 237篇 |
1990年 | 202篇 |
1989年 | 203篇 |
1988年 | 232篇 |
1987年 | 198篇 |
1986年 | 180篇 |
1985年 | 347篇 |
1984年 | 339篇 |
1983年 | 242篇 |
1982年 | 313篇 |
1981年 | 323篇 |
1980年 | 298篇 |
1979年 | 281篇 |
1978年 | 257篇 |
1977年 | 227篇 |
1976年 | 206篇 |
1975年 | 208篇 |
1974年 | 210篇 |
1973年 | 209篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Prof. Xiaoguang Bao Dr. David A. Hrovat Prof. Weston Thatcher Borden 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(18):5687-5693
Cyclobutane‐1,2,3,4‐tetraone, (CO)4, was computationally predicted and, subsequently, experimentally confirmed to have a triplet ground state, in which a b2g σ MO and an a2u π MO were each singly occupied. In contrast, the (U)CCSD(T) calculations reported herein found that cyclobutane‐1,2,3,4‐tetrathione, (CS)4, and cyclobutane‐1,2,3,4‐tetraselenone, (CSe)4, both had singlet ground states, in which the b2g σ MO was doubly occupied and the a2u π MO was empty. Our calculations showed that both the longer C?X distances and smaller coefficients on the carbon atoms in the b2g and a2u MOs of (CS)4 and (CSe)4 contributed to the difference between the ground states of these two molecules and the ground state of (CO)4. An experimental test of the prediction of a singlet ground state for (CS)4 is proposed. 相似文献
992.
Dr. Jacorien Coetzee Dr. Deborah L. Dodds Prof. Jürgen Klankermayer Sandra Brosinski Prof. Walter Leitner Prof. Alexandra M. Z. Slawin Prof. David J. Cole‐Hamilton 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(33):11039-11050
Hydrogenation of amides in the presence of [Ru(acac)3] (acacH=2,4‐pentanedione), triphos [1,1,1‐tris‐ (diphenylphosphinomethyl)ethane] and methanesulfonic acid (MSA) produces secondary and tertiary amines with selectivities as high as 93 % provided that there is at least one aromatic ring on N. The system is also active for the synthesis of primary amines. In an attempt to probe the role of MSA and the mechanism of the reaction, a range of methanesulfonato complexes has been prepared from [Ru(acac)3], triphos and MSA, or from reactions of [RuX(OAc)(triphos)] (X=H or OAc) or [RuH2(CO)(triphos)] with MSA. Crystallographically characterised complexes include: [Ru(OAc‐κ1O)2(H2O)(triphos)], [Ru(OAc‐κ2O,O′)(CH3SO3‐κ1O)(triphos)], [Ru(CH3SO3‐κ1O)2(H2O)(triphos)] and [Ru2(μ‐CH3SO3)3(triphos)2][CH3SO3], whereas other complexes, such as [Ru(OAc‐κ1O)(OAc‐κ2O,O′)(triphos)], [Ru(CH3SO3‐κ1O)(CH3SO3‐κ2O,O′)(triphos)], H[Ru(CH3SO3‐κ1O)3(triphos)], [RuH(CH3SO3‐κ1O)(CO)(triphos)] and [RuH(CH3SO3‐κ2O,O′)(triphos)] have been characterised spectroscopically. The interactions between these various complexes and their relevance to the catalytic reactions are discussed. 相似文献
993.
994.
Dr. David E. Herbert Nadia C. Lara Prof. Theodor Agapie 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(48):16453-16460
The meta‐terphenyl diphosphine, m‐P2, 1 , was utilized to support Ni centers in the oxidation states 0, I, and II. A series of complexes bearing different substituents or ligands at Ni was prepared to investigate the dependence of metal–arene interactions on oxidation state and substitution at the metal center. Complex (m‐P2)Ni ( 2 ) shows strong Ni0–arene interactions involving the central arene ring of the terphenyl ligand both in solution and the solid state. These interactions are significantly less pronounced in Ni0 complexes bearing L‐type ligands ( 2‐L : L=CH3CN, CO, Ph2CN2), NiIX complexes ( 3‐X : X=Cl, BF4, N3, N3B(C6F5)3), and [(m‐P2)NiIICl2] ( 4 ). Complex 2 reacts with substrates, such as diphenyldiazoalkane, sulfur ylides (Ph2S?CH2), organoazides (RN3: R=para‐C6H4OMe, para‐C6H4CF3, 1‐adamantyl), and N2O with the locus of observed reactivity dependent on the nature of the substrate. These reactions led to isolation of an η1‐diphenyldiazoalkane adduct ( 2‐Ph2CN2 ), methylidene insertion into a Ni? P bond followed by rearrangement of a nickel‐bound phosphorus ylide ( 5 ) to a benzylphosphine ( 6) , Staudinger oxidation of the phosphine arms, and metal‐mediated nitrene insertion into an arene C? H bond of 1 , all derived from the same compound ( 2 ). Hydrogen‐atom abstraction from a NiI–amide ( 9 ) and the resulting nitrene transfer supports the viability of Ni–imide intermediates in the reaction of 1 with 1‐azido‐arenes. 相似文献
995.
996.
Christopher M. Lee Ashutosh Mittal Anna L. Barnette Kabindra Kafle Yong Bum Park Heenae Shin David K. Johnson Sunkyu Park Seong H. Kim 《Cellulose (London, England)》2013,20(3):991-1000
Sum-frequency-generation (SFG) vibration spectroscopy is a technique only sensitive to functional groups arranged without centrosymmetry. For crystalline cellulose, SFG can detect the C6H2 and intra-chain hydrogen-bonded OH groups in the crystal. The geometries of these groups are sensitive to the hydrogen bonding network that stabilizes each cellulose polymorph. Therefore, SFG can distinguish cellulose polymorphs (Iβ, II, IIII and IIIII) which have different conformations of the exocyclic hydroxymethylene group or directionalities of glucan chains. The C6H2 asymmetric stretching peaks at 2,944 cm?1 for cellulose Iβ and 2,960 cm?1 for cellulose II, IIII and IIIII corresponds to the trans-gauche (tg) and gauche-trans (gt) conformation, respectively. The SFG intensity of the stretch peak of intra-chain hydrogen-bonded O–H group implies that the chain arrangement in cellulose crystal is parallel in Iβ and IIII, and antiparallel in II and IIIII. 相似文献
997.
998.
This study's aim is to analyze heart rate dynamics in subjects with diabetes by measures of heart rate variability (HRV). The correlation of chaotic global parameters in the two cohorts is able to assess the probability of cardiac failure and other dynamical diseases. Adults (46) were divided into two equal groups. The autonomic evaluation consisted of measuring HRV for 30 min in supine position in absence of any physical, sensory, or pharmacological stimuli. Chaotic global parameters are able to statistically determine which series of electrocardiograph interpeak intervals in short time‐series are diabetic and which are not. The chaotic forward parameter that applies all three parameters is suggested to be the most appropriate and robust algorithm. This was decided after tests for normality; followed by one‐way analysis of variance (ANOVA1); (P < 0.09) and Kruskal–Wallis technique (P < 0.03). Principal component analysis implied two components represent 99.8% of total variance. Therefore, diabetes is a disease which reduces the chaotic response and, as such may be termed a dynamical condition such as are cardiac arrest, asthma, and epilepsy. © 2014 Wiley Periodicals, Inc. Complexity 20: 84–92, 2015 相似文献
999.
Raymond J. Huntley Mahender GurramJoel R. Walker David M. JenkinsEmmanuel J. Robé Feryan Ahmed 《Tetrahedron letters》2014
A new synthetic method has been developed for the synthesis of 2,4,5-substituted isoindolinones by means of intramolecular inverse-electron demand Diels–Alder cycloaddition reactions of substituted pyridazines. By taking advantage of the inherent reactivity of an intermediate chloropyridazine, a diverse set of analogues were prepared from common reagents and intermediates. 相似文献
1000.
Karel Lacina Martin Konhefr Jan Novotný David Potěšil Zbyněk Zdráhal Petr Skládal 《Tetrahedron letters》2014
A redox-active affinity ligand suitable for reagentless sensing of cis-diols was synthesised and characterised. 4-[(Ferrocenylamino)methyl]thiophene-3-boronic acid (FcTBA) was allowed to interact with the model cis-diol, sorbitol. A discrete, cathodic shift of the redox potential was observed upon interaction of FcTBA with sorbitol thus providing simultaneous differentiation between the free and bound forms of this sensor molecule. Similar behaviour was observed also for FcTBA co-immobilised with thiophene in a mixed self-assembled monolayer on a gold electrode. 相似文献