全文获取类型
收费全文 | 1590篇 |
免费 | 39篇 |
国内免费 | 3篇 |
专业分类
化学 | 1088篇 |
晶体学 | 9篇 |
力学 | 54篇 |
数学 | 289篇 |
物理学 | 192篇 |
出版年
2023年 | 8篇 |
2022年 | 18篇 |
2021年 | 20篇 |
2020年 | 18篇 |
2019年 | 15篇 |
2018年 | 17篇 |
2017年 | 15篇 |
2016年 | 34篇 |
2015年 | 37篇 |
2014年 | 40篇 |
2013年 | 81篇 |
2012年 | 126篇 |
2011年 | 111篇 |
2010年 | 89篇 |
2009年 | 83篇 |
2008年 | 104篇 |
2007年 | 113篇 |
2006年 | 97篇 |
2005年 | 90篇 |
2004年 | 78篇 |
2003年 | 59篇 |
2002年 | 65篇 |
2001年 | 20篇 |
2000年 | 22篇 |
1999年 | 20篇 |
1998年 | 17篇 |
1997年 | 16篇 |
1996年 | 10篇 |
1995年 | 7篇 |
1994年 | 26篇 |
1993年 | 15篇 |
1992年 | 7篇 |
1991年 | 11篇 |
1990年 | 8篇 |
1989年 | 12篇 |
1987年 | 6篇 |
1986年 | 8篇 |
1985年 | 9篇 |
1984年 | 11篇 |
1983年 | 6篇 |
1982年 | 11篇 |
1981年 | 8篇 |
1980年 | 7篇 |
1979年 | 8篇 |
1978年 | 11篇 |
1977年 | 7篇 |
1976年 | 5篇 |
1975年 | 7篇 |
1974年 | 8篇 |
1972年 | 4篇 |
排序方式: 共有1632条查询结果,搜索用时 15 毫秒
111.
112.
Stéphane Laval Wissam Dayoub Leyla Pehlivan Estelle Métay Dominique Delbrayelle Gérard Mignani Marc Lemaire 《Tetrahedron letters》2014
A simple and convenient method for the chemoselective reduction of nitriles into aldehydes using a 1,1,3,3-tetramethyldisiloxane (TMDS)/triisopropoxyvanadium(V) oxide reducing system is described. Aromatic as well as aliphatic nitriles are reduced into the corresponding aldehydes in moderate to good yields. 相似文献
113.
Titanium‐Catalyzed Hydroalumination of Conjugated Dienes: Access to Fulvene‐Derived Allylaluminium Reagents and Their Diastereoselective Reactions with Carbonyl Compounds 下载免费PDF全文
Dr. Jomy Joseph Dr. Florian Jaroschik Dr. Dominique Harakat Dr. K. V. Radhakrishnan Dr. Jean‐Luc Vasse Prof. Jan Szymoniak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(18):5433-5438
The described titanium‐catalyzed hydroalumination of conjugated dienes opens up a new way to allylaluminium reagents. The reaction is carried out by using diisobutylaluminium hydride (DIBAL‐H) and a catalytic amount of [Cp2TiCl2] (Cp=cyclopentadienyl). When applied to mono‐ and disubstitued pentafulvenes, this reaction proceeds in a highly endocyclic manner. The formed allylaluminium compounds react regio‐ and stereoselectively with both aldehydes and ketones to afford homoallylic alcohols that are suitable synthons for functionalized cyclopentanones. An extension of this methodology to simple dienes was also investigated. In the proposed mechanism, the initially formed bimetallic species (Ti/Al) are involved in the two possible catalytic cycles with a direct hydroalumination or/and a hydrotitanation followed by a titanium to aluminium transmetallation. 相似文献
114.
Bénédicte Dayde Claire Pierra Gilles Gosselin Dominique Surleraux Amadou Tidjani Ilagouma Jean-Noël Volle David Virieux Jean-Luc Pirat 《Tetrahedron letters》2014
This Letter describes the synthesis of racemic analogues of unnatural 2′-deoxy nucleoside with a phosphorus atom replacing the carbon atom in the 3′-position. A seven-step sequence was developed in racemic series to afford unnatural 3′-phospha-2′-deoxyfuranose nucleosides. The phospha nucleoside analogues were tested against HCV, but did not show any antiviral activity at a 10 μM maximum concentration used for the inhibition assays of analogues 2-T, 2-C and 4-Tα. 相似文献
115.
5‐O‐Caffeoylshikimic acid from Solanum somalense leaves: Advantage of centrifugal partition chromatography over conventional column chromatography 下载免费PDF全文
Saïda Chideh Serge Pilard Jacques Attoumbré Robert Saguez Alshaimaa Hassan‐Abdallah Dominique Cailleu Anne Wadouachi Sylvie Baltora‐Rosset 《Journal of separation science》2014,37(17):2331-2339
Solanum somalense leaves, used in Djibouti for their medicinal properties, were extracted by MeOH. Because of the high polyphenol and flavonoid contents of the extract, respectively, determined at 80.80 ± 2.13 mg gallic acid equivalent/g dry weight and 24.4 ± 1.01 mg quercetin equivalent/g dry weight, the isolation and purification of the main polyphenols were carried out by silica gel column chromatography and centrifugal partition chromatography. Column chromatography led to 11 enriched fractions requiring further purification, while centrifugal partition chromatography allowed the easy recovery of the main compound of the extract. In a solvent system composed of CHCl3/MeOH/H2O (9.5:10:5), 21.8 mg of this compound at 97% purity was obtained leading to a yield of 2.63%. Its structure was established as 5‐O‐caffeoylshikimic acid by mass spectrometry and NMR spectroscopy. This work shows that S. somalense leaves contain very high level of 5‐O‐caffeoylshikimic acid (0.74% dry weight), making it a potential source of production of this secondary metabolite that is not commonly found in nature but could be partly responsible of the medicinal properties of S. somalense leaves. 相似文献
116.
117.
118.
Karol Kulasinski Sinan Keten Sergey V. Churakov Dominique Derome Jan Carmeliet 《Cellulose (London, England)》2014,21(3):1103-1116
The quintessential form of cellulose in wood consists of microfibrils that have high aspect ratio crystalline domains embedded within an amorphous cellulose domain. In this study, we apply united-atom molecular dynamics simulations to quantify changes in different morphologies of cellulose. We compare the structure of crystalline cellulose with paracrystalline and amorphous phases that are both obtained by high temperature equilibration followed by quenching at room temperature. Our study reveals that the paracrystalline phase may be an intermediate, kinetically arrested phase formed upon amorphisation of crystalline cellulose. The quenched structures yield isotropic amorphous polymer domains consistent with experimental results, thereby validating a new computational protocol for achieving amorphous cellulose structure. The non-crystalline cellulose compared to crystalline structure is characterized by a dramatic decrease in elastic modulus, thermal expansion coefficient, bond energies, and number of hydrogen bonds. Analysis of the lattice parameters shows that Iβ cellulose undergoes a phase transition into high-temperature phase in the range of 450–550 K. The mechanisms of the phase transition elucidated here present an atomistic view of the temperature dependent dynamic structure and mechanical properties of cellulose. The paracrystalline state of cellulose exhibits intermediate mechanical properties, between crystalline and amorphous phases, that can be assigned to the physical properties of the interphase regions between crystalline and amorphous cellulose in wood microfibrils. Our results suggest an atomistic structural view of amorphous cellulose which is consistent with experimental data available up to date and provide a basis for future multi-scale models for wood microfibrils and all-cellulose nanocomposites. 相似文献
119.
Influence of P‐Bonded Bulky Substituents on Electronic Interactions in Ferrocenyl‐Substituted Phospholes 下载免费PDF全文
Dominique Miesel Dr. Alexander Hildebrandt Marcus Korb Prof. Dr. Heinrich Lang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(32):11545-11559
2,5‐Diferrocenyl‐1‐Ar‐1H‐phospholes 3 a – e (Ar=phenyl ( a ), ferrocenyl ( b ), mesityl ( c ), 2,4,6‐triphenylphenyl ( d ), and 2,4,6‐tri‐tert‐butylphenyl ( e )) have been prepared by reactions of ArPH2 ( 1 a – e ) with 1,4‐diferrocenyl butadiyne. Compounds 3 b – e have been structurally characterized by single‐crystal XRD analysis. Application of the sterically demanding 2,4,6‐tri‐tert‐butylphenyl group led to an increased flattening of the pyramidal phosphorus environment. The ferrocenyl units could be oxidized separately, with redox separations of 265 ( 3 b ), 295 ( 3 c ), 340 ( 3 d ), and 315 mV ( 3 e ) in [NnBu4][B(C6F5)4]; these values indicate substantial thermodynamic stability of the mixed‐valence radical cations. Monocationic [ 3 b ]+–[ 3 e ]+ show intervalence charge‐transfer absorptions between 4650 and 5050 cm?1 of moderate intensity and half‐height bandwidth. Compounds 3 c – e with bulky, electron‐rich substituents reveal a significant increase in electronic interactions compared with less demanding groups in 3 a and 3 b . 相似文献
120.
Dr. Dominique T. Thielemann Anna T. Wagner Dr. Yanhua Lan Dr. Pascual Oña‐Burgos Prof. Dr. Ignacio Fernández Prof. Dr. Esther S. Rösch Dr. Dominik K. Kölmel Prof. Dr. Annie K. Powell Prof. Dr. Stefan Bräse Prof. Dr. Peter W. Roesky 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(7):2813-2820
A new family of pentadecanuclear coordination cluster compounds (from now on simply referred to as clusters) [{Ln15(OH)20(PepCO2)10(DBM)10Cl}Cl4] (PepCO2=2‐[{3‐(((tert‐butoxycarbonyl)amino)methyl)benzyl}amino]acetate, DBM=dibenzoylmethanide) with Ln=Y and Dy was obtained by using the cell‐penetrating peptoid (CPPo) monomer PepCO2H and dibenzoylmethane (DBMH) as supporting ligands. The combination of an inorganic cluster core with an organic cell‐penetrating peptoid in the coordination sphere resulted in a core component {Ln15(μ3‐OH)20Cl}24+ (Ln=Y, Dy), which consists of five vertex‐sharing heterocubane {Ln4(μ3‐OH)4}8+ units that assemble to give a pentagonal cyclic structure with one Cl atom located in the middle of the pentagon. The solid‐state structures of both clusters were established by single‐crystal X‐ray crystallography. MS (ESI) experiments suggest that the cluster core is robust and maintained in solution. Pulsed gradient spin echo (PGSE) NMR diffusion measurements were carried out on the diamagnetic yttrium compound and confirmed the stability of the cluster in its dicationic form [{Y15(μ3‐OH)20(PepCO2)10(DBM)10Cl}Cl2]2+. The investigation of both static (dc) and dynamic (ac) magnetic properties in the dysprosium cluster revealed a slow relaxation of magnetization, indicative of single‐molecule magnet (SMM) behavior below 8 K. Furthermore, the χT product as a function of temperature for the dysprosium cluster gave evidence that this is a ferromagnetically coupled compound below 11 K. 相似文献