全文获取类型
收费全文 | 16599篇 |
免费 | 503篇 |
国内免费 | 38篇 |
专业分类
化学 | 8763篇 |
晶体学 | 139篇 |
力学 | 421篇 |
数学 | 3352篇 |
物理学 | 4465篇 |
出版年
2022年 | 114篇 |
2021年 | 211篇 |
2020年 | 239篇 |
2019年 | 257篇 |
2018年 | 296篇 |
2017年 | 304篇 |
2016年 | 595篇 |
2015年 | 541篇 |
2014年 | 637篇 |
2013年 | 1150篇 |
2012年 | 858篇 |
2011年 | 995篇 |
2010年 | 670篇 |
2009年 | 554篇 |
2008年 | 697篇 |
2007年 | 586篇 |
2006年 | 548篇 |
2005年 | 343篇 |
2004年 | 383篇 |
2003年 | 323篇 |
2002年 | 323篇 |
2001年 | 222篇 |
2000年 | 265篇 |
1999年 | 192篇 |
1998年 | 200篇 |
1997年 | 177篇 |
1996年 | 184篇 |
1995年 | 170篇 |
1994年 | 151篇 |
1993年 | 167篇 |
1992年 | 155篇 |
1991年 | 131篇 |
1990年 | 146篇 |
1989年 | 125篇 |
1988年 | 139篇 |
1987年 | 142篇 |
1986年 | 127篇 |
1985年 | 176篇 |
1984年 | 189篇 |
1983年 | 128篇 |
1982年 | 146篇 |
1981年 | 164篇 |
1980年 | 154篇 |
1979年 | 155篇 |
1978年 | 153篇 |
1977年 | 148篇 |
1976年 | 164篇 |
1975年 | 164篇 |
1974年 | 157篇 |
1973年 | 120篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
981.
982.
Dr. Liping Cao Dr. Marina Šekutor Dr. Peter Y. Zavalij Prof. Dr. Kata Mlinarić‐Majerski Prof. Dr. Robert Glaser Prof. Dr. Lyle Isaacs 《Angewandte Chemie (International ed. in English)》2014,53(4):988-993
Host?guest complexes between cucurbit[7] (CB[7]) or CB[8] and diamantane diammonium ion guests 3 or 6 were studied by 1H NMR spectroscopy and X‐ray crystallography. 1H NMR competition experiments revealed that CB[7]? 6 is among the tightest monovalent non‐covalent complexes ever reported in water with Ka=7.2×1017 M ?1 in pure D2O and 1.9×1015 M ?1 in D2O buffered with NaO2CCD3 (50 mM ). The crystal structure of CB[7]? 6 allowed us to identify some of the structural features responsible for the ultratight binding, including the distance between the NMe3+ groups of 6 (7.78 Å), which allows it to establish 14 optimal ion‐dipole interactions with CB[7], the complementarity of the convex van der Waals surface contours of 6 with the corresponding concave surfaces of CB[7], desolvation of the C?O portals within the CB[7]? 6 complex, and the co‐linearity of the C7 axis of CB[7] with the N+???N+ line in 6 . This work further blurs the lines of distinction between natural and synthetic receptors. 相似文献
983.
The Origin of the Selectivity and Activity of Ruthenium‐Cluster Catalysts for Fuel‐Cell Feed‐Gas Purification: A Gas‐Phase Approach
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Sandra M. Lang Prof. Dr. Thorsten M. Bernhardt Marjan Krstić Prof. Dr. Vlasta Bonačić‐Koutecký 《Angewandte Chemie (International ed. in English)》2014,53(21):5467-5471
Gas‐phase ruthenium clusters Run+ (n=2–6) are employed as model systems to discover the origin of the outstanding performance of supported sub‐nanometer ruthenium particles in the catalytic CO methanation reaction with relevance to the hydrogen feed‐gas purification for advanced fuel‐cell applications. Using ion‐trap mass spectrometry in conjunction with first‐principles density functional theory calculations three fundamental properties of these clusters are identified which determine the selectivity and catalytic activity: high reactivity toward CO in contrast to inertness in the reaction with CO2; promotion of cooperatively enhanced H2 coadsorption and dissociation on pre‐formed ruthenium carbonyl clusters, that is, no CO poisoning occurs; and the presence of Ru‐atom sites with a low number of metal–metal bonds, which are particularly active for H2 coadsorption and activation. Furthermore, comprehensive theoretical investigations provide mechanistic insight into the CO methanation reaction and discover a reaction route involving the formation of a formyl‐type intermediate. 相似文献
984.
Palladium‐Catalyzed Stereoselective Intramolecular Oxidative Amidation of Alkenes in the Synthesis of 1,3‐ and 1,4‐Amino Alcohols and 1,3‐Diamines
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Prof. Dr. Andrei V. Malkov Dr. Darren S. Lee Dr. Maciej Barłóg Dr. Mark R. J. Elsegood Prof. Dr. Pavel Kočovský 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(17):4901-4905
An efficient and practical Pd‐catalyzed intramolecular oxidative allylic amidation provides facile access to derivatives of 1,3‐ and 1,4‐amino alcohols and 1,3‐diamines. The method operates under mild reaction conditions (RT) with molecular oxygen (1 atm) as the sole reoxidant of Pd. Excellent diastereoselectivities were attained with substrates bearing a secondary stereogenic center 相似文献
985.
Superbasic Alkyl‐Substituted Bisphosphazene Proton Sponges: Synthesis,Structural Features,Thermodynamic and Kinetic Basicity,Nucleophilicity and Coordination Chemistry
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
986.
Iron Dicarbonyl Complexes Featuring Bipyridine‐Based PNN Pincer Ligands with Short Interpyridine CC Bond Lengths: Innocent or Non‐Innocent Ligand?
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
987.
Damien Hueber Marie Hoffmann Dr. Benoît Louis Prof. Dr. Patrick Pale Dr. Aurélien Blanc 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(14):3903-3907
Gold(I)‐polyoxometalate hybrid complexes 1 – 4 ([PPh3AuMeCN]xH4?xSiW12O40, x=1–4) were synthesized and characterized. The structure of the primary gold(I)–polyoxometalate 1 (x=1) was fully ascertained by XRD, FTIR, 31P and 29Si magic‐angle spinning (MAS) NMR, mass spectroscopy, and SEM–energy dispersive X‐ray spectroscopy (EDX) techniques. Moreover, this complex exhibited better catalytic activity and selectivity compared with standard, homogeneous, gold catalysts in the new rearrangement of propargylic gem‐diesters. 相似文献
988.
Redox‐Induced Spin‐State Switching and Mixed Valency in Quinonoid‐Bridged Dicobalt Complexes
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
David Schweinfurth Yvonne Rechkemmer Stephan Hohloch Naina Deibel Irina Peremykin Jan Fiedler Raphael Marx Dr. Petr Neugebauer Prof. Dr. Joris van Slageren Prof. Dr. Biprajit Sarkar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(12):3475-3486
The complexes [{(tmpa)CoII}2(μ‐L1)2?]2+ ( 12+ ) and [{(tmpa)CoII}2(μ‐L2)2?]2+ ( 22+ ), with tmpa=tris(2‐pyridylmethyl)amine, H2L1=2,5‐di‐[2‐(methoxy)‐anilino]‐1,4‐benzoquinone, and H2L2=2,5‐di‐[2‐(trifluoromethyl)‐anilino]‐1,4‐benzoquinone, were synthesized and characterized. Structural analysis of 22+ revealed a distorted octahedral coordination around the cobalt centers, and cobalt–ligand bond lengths that match with high‐spin CoII centers. Superconducting quantum interference device (SQUID) magnetometric studies on 12+ and 22+ are consistent with the presence of two weakly exchange‐coupled high‐spin cobalt(II) ions, for which the nature of the coupling appears to depend on the substituents on the bridging ligand, being antiferromagnetic for 12+ and ferromagnetic for 22+ . Both complexes exhibit several one‐electron redox steps, and these were investigated with cyclic voltammetry and UV/Vis/near‐IR spectroelectrochemistry. For 12+ , it was possible to chemically isolate the pure forms of both the one‐electron oxidized mixed‐valent 13+ and the two‐electron oxidized isovalent 14+ forms, and characterize them structurally as well as magnetically. This series thus provided an opportunity to investigate the effect of reversible electron transfers on the total spin‐state of the molecule. In contrast to 22+ , for 14+ the metal–ligand distances and the distances within the quinonoid ligand point to the existence of two low‐spin CoIII centers, thus showing the innocence of the quintessential non‐innocent ligands L. Magnetic data corroborate these observations by showing the decrease of the magnetic moment by roughly half (neglecting spin exchange effects) on oxidizing the molecules with one electron, and the disappearance of a paramagnetic response upon two‐electron oxidation, which confirms the change in spin state associated with the electron‐transfer steps. 相似文献
989.
A Bis(pyridine N‐oxide) Analogue of DOTA: Relaxometric Properties of the GdIII Complex and Efficient Sensitization of Visible and NIR‐Emitting Lanthanide(III) Cations Including PrIII and HoIII
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Henrique F. Carvalho Dr. João M. C. Teixeira Carlos T. B. Paula Prof. Petr Hermann Dr. Carlos Platas‐Iglesias Prof. Stephane Petoud Prof. Éva Tóth Prof. Carlos F. G. C. Geraldes 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(45):14834-14845
We report the synthesis of a cyclen‐based ligand (4,10‐bis[(1‐oxidopyridin‐2‐yl)methyl]‐1,4,7,10‐tetraazacyclododecane‐1,7‐diacetic acid= L1 ) containing two acetate and two 2‐methylpyridine N‐oxide arms anchored on the nitrogen atoms of the cyclen platform, which has been designed for stable complexation of lanthanide(III) ions in aqueous solution. Relaxometric studies suggest that the thermodynamic stability and kinetic inertness of the GdIII complex may be sufficient for biological applications. A detailed structural study of the complexes by 1H NMR spectroscopy and DFT calculations indicates that they adopt an anti‐Δ(λλλλ) conformation in aqueous solution, that is, an anti‐square antiprismatic (anti‐SAP) isomeric form, as demonstrated by analysis of the 1H NMR paramagnetic shifts induced by YbIII. The water‐exchange rate of the GdIII complex is ${k{{298\hfill \atop {\rm ex}\hfill}}}$ =6.7×106 s?1, about a quarter of that for the mono‐oxidopyridine analogue, but still about 50 % higher than the ${k{{298\hfill \atop {\rm ex}\hfill}}}$ of GdDOTA (DOTA=1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid). The 2‐methylpyridine N‐oxide chromophores can be used to sensitize a wide range of LnIII ions emitting in both the visible (EuIII and TbIII) and NIR (PrIII, NdIII, HoIII, YbIII) spectral regions. The emission quantum yield determined for the YbIII complex (${Q{{{\rm L}\hfill \atop {\rm Yb}\hfill}}}$ =7.3(1)×10?3) is among the highest ever reported for complexes of this metal ion in aqueous solution. The sensitization ability of the ligand, together with the spectroscopic and relaxometric properties of its complexes, constitute a useful step forward on the way to efficient dual probes for optical imaging (OI) and MRI. 相似文献
990.
A General Method for Preparing Bridged Organosilanes with Pendant Functional Groups and Functional Mesoporous Organosilicas
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Prof. Jana Hodačová Dr. Guillaume Toquer Dr. Xavier Cattoën Dr. Michel Wong Chi Man 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10371-10382
New organosilica precursors containing two triethoxysilyl groups suitable for the organosilica material formation through the sol‐gel process were designed and synthesised. These precursors display alkyne or azide groups for attaching targeted functional groups by copper‐catalysed azide–alkyne cycloaddition (CuAAC) and can be used for the preparation of functional organosilicas following two strategies: 1) the functional group is first appended by CuAAC under anhydrous conditions, then the functional material is prepared by the sol‐gel process; 2) the precursor is first subjected to the sol‐gel process, producing porous, clickable bridged silsesquioxanes or periodic mesoporous organosilicas (PMOs), then the desired functional groups are attached by means of CuAAC. Herein, we show the feasibility of both approaches. A series of bridged bis(triethoxysilane)s with different pending organic moieties was prepared, demonstrating the compatibility of the first approach with many functional groups. In particular, we demonstrate that organic functional molecules bearing only one derivatisation site can be used to produce bridged organosilanes and bridged silsesquioxanes. In the second approach, clickable PMOs and porous bridged silsesquioxanes were prepared from the alkyne‐ or azide‐containing precursors, and thereafter, functionalised with complementary model azide‐ or alkyne‐containing molecules. These results confirmed the potential of this approach as a general methodology for preparing functional organosilicas with high loadings of functional groups. Both approaches give rise to a wide range of new functional organosilica materials. 相似文献