全文获取类型
收费全文 | 208813篇 |
免费 | 3610篇 |
国内免费 | 1486篇 |
专业分类
化学 | 105570篇 |
晶体学 | 2711篇 |
力学 | 9921篇 |
综合类 | 70篇 |
数学 | 23499篇 |
物理学 | 72138篇 |
出版年
2021年 | 1860篇 |
2020年 | 2128篇 |
2019年 | 2310篇 |
2018年 | 2980篇 |
2017年 | 2875篇 |
2016年 | 4174篇 |
2015年 | 2706篇 |
2014年 | 4057篇 |
2013年 | 9706篇 |
2012年 | 7954篇 |
2011年 | 9534篇 |
2010年 | 6581篇 |
2009年 | 6427篇 |
2008年 | 8512篇 |
2007年 | 8544篇 |
2006年 | 8223篇 |
2005年 | 7253篇 |
2004年 | 6725篇 |
2003年 | 5894篇 |
2002年 | 5422篇 |
2001年 | 6395篇 |
2000年 | 4816篇 |
1999年 | 3697篇 |
1998年 | 2935篇 |
1997年 | 3000篇 |
1996年 | 2720篇 |
1995年 | 2684篇 |
1994年 | 2515篇 |
1993年 | 2372篇 |
1992年 | 2709篇 |
1991年 | 2657篇 |
1990年 | 2594篇 |
1989年 | 2384篇 |
1988年 | 2431篇 |
1987年 | 2417篇 |
1986年 | 2254篇 |
1985年 | 2934篇 |
1984年 | 3196篇 |
1983年 | 2603篇 |
1982年 | 2772篇 |
1981年 | 2718篇 |
1980年 | 2599篇 |
1979年 | 2697篇 |
1978年 | 2787篇 |
1977年 | 2803篇 |
1976年 | 2864篇 |
1975年 | 2650篇 |
1974年 | 2625篇 |
1973年 | 2755篇 |
1972年 | 1743篇 |
排序方式: 共有10000条查询结果,搜索用时 93 毫秒
991.
Vladimir P. Petrović Dušica Simijonović Zorica D. Petrović Svetlana Marković 《Chemical Papers》2015,69(9):1244-1252
One-pot anti-Mannich reaction of vanillin, aniline and cyclohexanone was successfully catalyzed by ionic liquid triethanolammonium chloroacetate, at room temperature. Yield of the obtained Mannich base was very good and excellent diastereoselectivity was achieved. Mechanism of the reaction was investigated using the density functional theory. The reaction started with a nucleophilic attack of aniline nitrogen at the carbonyl group of vanillin. The intermediate α-amino alcohol formed in this way was further subjected to protonation by the triethanolammonium ion yielding the imminium ion. Theoretically, the obtained imminium ion and the enol form of cyclohexanone can build the protonated Mannich base via the anti and syn pathways. The chloroacetic anion spontaneously abstracts the proton yielding the final product of the reaction anti 2-[1-(N-phenylamino)-1-(4-hydroxy-3-methoxyphenyl)]methylcyclohexanone (MB-H). The syn pathway requires lower activation energy but the anti pathway yields a thermodynamically more stable product, which implies that the examined Mannich reaction is thermodynamically controlled. 相似文献
992.
Synthesis,Characterisation and Reactivity of Copper(I) Amide Complexes and Studies on Their Role in the Modified Ullmann Amination Reaction 下载免费PDF全文
Simon Sung Dr. D. Christopher Braddock Prof. Alan Armstrong Dr. Colin Brennan Dr. David Sale Dr. Andrew J. P. White Dr. Robert P. Davies 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(19):7179-7192
A series of copper(I) alkylamide complexes have been synthesised; copper(I) dicyclohexylamide ( 1 ), copper(I) 2,2,6,6‐tetramethylpiperidide ( 2 ), copper(I) pyrrolidide ( 3 ), copper(I) piperidide ( 4 ), and copper(I) benzylamide ( 5 ). Their solid‐state structures and structures in [D6]benzene solution are characterised, with the aggregation state in solution determined by a combination of DOSY NMR spectroscopy and DFT calculations. Complexes 1 , 2 and 4 are shown to exist as tetramers in the solid state by X‐ray crystallography. In [D6]benzene solution, complexes 1 , 2 and 5 were found by using 1H DOSY NMR to exist in rapid equilibrium between aggregates with average aggregation numbers of 2.5, 2.4 and 3.3, respectively, at 0.05 M concentration. Conversely, distinct trimeric, tetrameric and pentameric forms of 3 and 4 were distinguishable by one‐dimensional 1H and 1H DOSY NMR spectroscopy. Complexes 3 – 5 are found to react stoichiometrically with iodobenzene, in the presence or absence of 1,10‐phenanthroline as an ancillary ligand, to give arylamine products indicative of their role as potential intermediates in the modified Ullmann reaction. The role of phenanthroline has also been explored both in the stoichiometric reaction and in the catalytic Ullmann protocol. 相似文献
993.
Triple Emission from p‐Dimethylaminobenzonitrile–Cucurbit[8]uril Triggers the Elusive Excimer Emission 下载免费PDF全文
Dr. Mhejabeen Sayed Dr. Frank Biedermann Dr. Vanya D. Uzunova Khaleel I. Assaf Dr. Achikanath C. Bhasikuttan Dr. Haridas Pal Prof. Werner M. Nau Dr. Jyotirmayee Mohanty 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(2):691-696
The intriguing dual‐emission behavior of p‐ dimethylaminobenzonitrile (DMABN) and the identity of the associated excited states is, arguably, the most extensively investigated and also controversially discussed molecule‐ specific phenomenon of modern photochemistry. We have now found a new, third fluorescence band when DMABN is encapsulated within the water‐soluble molecular container cucurbit[8]uril (CB8). It is centered between the previously observed emissions and assigned to the elusive excimer emission from DMABN through 1:2 CB8:DMABN complex formation. Heating of the CB8 ? (DMABN)2 complex from 0 to 100 °C results in the dissociation of the ternary complex and restoration of the dual‐emission properties of the monomer. Alternatively, monomer emission can be obtained by selecting cucurbit[7]uril (CB7), a host homologue that is too small to accommodate two DMABN molecules, or by introducing ethyl instead of methyl groups at the amino terminus of the aminobenzonitrile guest. 相似文献
994.
High capacity and cycling stability of poly(diaminoanthraquinone) as an organic cathode for rechargeable lithium batteries 下载免费PDF全文
Yi Fei Shen Ding Ding Yuan Xin Ping Ai Han Xi Yang Min Zhou 《Journal of Polymer Science.Polymer Physics》2015,53(4):235-238
Poly(1,5‐diaminoanthraquinone) is synthesized by oxidative polymerization of diaminoanthraquinone monomers and investigated as an organic host for Li‐storage reaction. Benefiting from its high density of redox‐active, Li+‐associable benzoquinone groups attached to conducting polyaniline backbones, this polymer undergoes its cathodic reaction predominately through Li+‐insertion/extraction processes, delivering a very high reversible capacity of 285 mAh g?1. In addition, the PDAQ polymer cathode exhibits an excellent rate capability (125 mAh g?1 at 800 mA g?1) and a considerable cyclability with a capacity retention of ~160 mAh g?1 over 200 cycles, possibly serving as a sustainable, high capacity Li+ host cathode for Li‐ion batteries. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 235–238 相似文献
995.
本文首次将一系列含有不同酸性咪唑阳离子和不同杂多酸阴离子的杂多酸离子液体[C4mim]3PW12O40、[COOH-Cmim] 3PW12O40、[SO3H-C3mim]3PW12O40、[SO3H-C3mim]3PMo12O40和[SO3H-C3mim]4 SiW12O40作为催化剂,乙腈为萃取剂,H2O2为氧化剂,用于催化含二苯并噻吩、苯并噻吩及噻吩模型油的萃取氧化脱硫研究中.实验结果显示,杂多酸离子液体催化燃油脱硫性能不仅与阳离子的酸性强弱有关,而且与阴离子结构密切相关.阳离子的催化活性顺序为:[SO3H-C3mim]+>[COOH-Cmim]+>[C4mim]+;阴离子的催化活性顺序为PW12O403-> PMo12O403-> SiW12O404-.其中[SO3H-C3 mim]3 PW12O40催化活性最高,在60℃反应40min的条件下,二苯并噻吩的转化率约为100%,催化不同硫化物的转化率为:二苯并噻吩>苯并噻吩>噻吩.此外,该杂多酸离子液体循环使用5次催化活性仅略有下降. 相似文献
996.
Luminescent Di‐ and Trinuclear Boron Complexes Based on Aromatic Iminopyrrolyl Spacer Ligands: Synthesis,Characterization, and Application in OLEDs 下载免费PDF全文
Dr. D. Suresh Dr. Clara S. B. Gomes Patrícia S. Lopes Dr. Cláudia A. Figueira Bruno Ferreira Prof. Pedro T. Gomes Dr. Roberto E. Di Paolo Prof. António L. Maçanita Prof. M. Teresa Duarte Dr. Ana Charas Prof. Jorge Morgado Diogo Vila‐Viçosa Prof. Maria José Calhorda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(25):9133-9149
New bis‐ and tris(iminopyrrole)‐functionalized linear (1,2‐(HNC4H3‐C(H)?N)2‐C6H4 ( 2 ), 1,3‐(HNC4H3‐C(H)?N)2‐C6H4 ( 3 ), 1,4‐(HNC4H3‐C(H)?N)2‐C6H4 ( 4 ), 4,4′‐(HNC4H3‐C(H)?N)2‐(C6H4‐C6H4) ( 5 ), 1,5‐(HNC4H3C‐(H)?N)2‐C10H6 ( 6 ), 2,6‐(HNC4H3C‐(H)?N)2‐C10H6 ( 7 ), 2,6‐(HNC4H3C‐(H)?N)2‐C14H8 ( 8 )) and star‐shaped (1,3,5‐(HNC4H3‐C(H)?N‐1,4‐C6H4)3‐C6H3 ( 9 )) π‐conjugated molecules were synthesized by the condensation reactions of 2‐formylpyrrole ( 1 ) with several aromatic di‐ and triamines. The corresponding linear diboron chelate complexes (Ph2B[1,3‐bis(iminopyrrolyl)‐phenyl]BPh2 ( 10 ), Ph2B[1,4‐bis(iminopyrrolyl)‐phenyl]BPh2 ( 11 ), Ph2B[4,4′‐bis(iminopyrrolyl)‐biphenyl]BPh2 ( 12 ), Ph2B[1,5‐bis(iminopyrrolyl)‐naphthyl]BPh2 ( 13 ), Ph2B[2,6‐bis(iminopyrrolyl)‐naphthyl]BPh2 ( 14 ), Ph2B[2,6‐bis(iminopyrrolyl)‐anthracenyl]BPh2 ( 15 )) and the star‐shaped triboron complex ([4′,4′′,4′′′‐tris(iminopyrrolyl)‐1,3,5‐triphenylbenzene](BPh2)3 ( 16 )) were obtained in moderate to good yields, by the treatment of 3 – 9 with B(C6H5)3. The ligand precursors are non‐emissive, whereas most of their boron complexes are highly fluorescent; their emission color depends on the π‐conjugation length. The photophysical properties of the luminescent polyboron compounds were measured, showing good solution fluorescence quantum yields ranging from 0.15 to 0.69. DFT and time‐dependent DFT calculations confirmed that molecules 10 and 16 are blue emitters, because only one of the iminopyrrolyl groups becomes planar in the singlet excited state, whereas the second (and third) keeps the same geometry. Compound 13 , in which planarity is not achieved in any of the groups, is poorly emissive. In the other examples ( 11 , 12 , 14 , and 15 ), the LUMO is stabilized, narrowing the gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO–LUMO), and the two iminopyrrolyl groups become planar, extending the size of the π‐system, to afford green to yellow emissions. Organic light‐emitting diodes (OLEDs) were fabricated by using the new polyboron complexes and their luminance was found to be in the order of 2400 cd m?2, for single layer devices, increasing to 4400 cd m?2 when a hole‐transporting layer is used. 相似文献
997.
Dr. Caroline T. Saouma Wesley D. Morris Julia W. Darcy Prof. James M. Mayer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(25):9256-9260
Biological [Fe‐S] clusters are increasingly recognized to undergo proton‐coupled electron transfer (PCET), but the site of protonation, mechanism, and role for PCET remains largely unknown. Here we explore this reactivity with synthetic model clusters. Protonation of the arylthiolate‐ligated [4Fe‐4S] cluster [Fe4S4(SAr)4]2? ( 1 , SAr=S‐2,4‐6‐(iPr)3C6H2) leads to thiol dissociation, reversibly forming [Fe4S4(SAr)3L]1? ( 2 ) and ArSH (L=solvent, and/or conjugate base). Solutions of 2 +ArSH react with the nitroxyl radical TEMPO to give [Fe4S4(SAr)4]1? ( 1ox ) and TEMPOH. This reaction involves PCET coupled to thiolate association and may proceed via the unobserved protonated cluster [Fe4S4(SAr)3(HSAr)]1? ( 1‐H ). Similar reactions with this and related clusters proceed comparably. An understanding of the PCET thermochemistry of this cluster system has been developed, encompassing three different redox levels and two protonation states. 相似文献
998.
Well‐Defined Palladium Nanoparticles Supported on Siliceous Mesocellular Foam as Heterogeneous Catalysts for the Oxidation of Water 下载免费PDF全文
Dr. Oscar Verho Dr. Torbjörn Åkermark Dr. Eric V. Johnston Karl P. J. Gustafson Dr. Cheuk‐W. Tai Henrik Svengren Dr. Markus D. Kärkäs Prof. Jan‐E. Bäckvall Prof. Björn Åkermark 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5909-5915
Herein, we describe the use of Pd nanoparticles immobilized on an amino‐functionalized siliceous mesocellular foam for the catalytic oxidation of H2O. The Pd nanocatalyst proved to be capable of mediating the four‐electron oxidation of H2O to O2, both chemically and photochemically. The Pd nanocatalyst is easy to prepare and shows high chemical stability, low leaching, and recyclability. Together with its promising catalytic activity, these features make the Pd nanocatalyst of potential interest for future sustainable solar‐fuel production. 相似文献
999.
Comparing Cyclophellitol N‐Alkyl and N‐Acyl Cyclophellitol Aziridines as Activity‐Based Glycosidase Probes 下载免费PDF全文
Jianbing Jiang Thomas J. M. Beenakker Dr. Wouter W. Kallemeijn Prof. Dr. Gijsbert A. van der Marel Hans van den Elst Dr. Jeroen D. C. Codée Prof. Dr. Johannes M. F. G. Aerts Prof. Dr. Herman S. Overkleeft 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(30):10861-10869
The synthesis and evaluation as activity‐based probes (ABPs) of three configurationally distinct, fluorescent N‐alkyl cyclophellitol aziridine isosteres for profiling GH1 β‐glucosidase (GBA), GH27 α‐galactosidase (GLA) and GH29 α‐fucosidase (FUCA) is described. In comparison with the corresponding acyl aziridine ABPs reported previously, the alkyl aziridine ABPs are synthesized easily and are more stable in mild acidic and basic media, and are thus easier to handle. The β‐glucose‐configured alkyl aziridine ABP proves equally effective in labeling GBA as its N‐acyl counterpart, whereas the N‐acyl aziridines targeting GLA and FUCA outperform their N‐alkyl counterparts. Alkyl aziridines can therefore be an attractive alternative in retaining glycosidase ABP design, but in targeting a new retaining glycosidase both N‐alkyl and N‐acyl aziridines are best considered at the onset of a new study. 相似文献
1000.
Graphene Quantum Dots Assembled with Metalloporphyrins for “Turn on” Sensing of Hydrogen Peroxide and Glucose 下载免费PDF全文
Dr. Li Zhang Dong Peng Prof. Ru‐Ping Liang Prof. Jian‐Ding Qiu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(26):9343-9348
Noncovalent and multifunctional hybrids have been generated via π–π stacking and electrostatic interactions by combining the nanometer‐scale graphene structure of graphene quantum dots (GQDs) with FeIII 5,10,15,20‐tetrakis(1‐methyl‐4‐pyridyl)porphine (FeTMPyP). The inner filter effect (IFE) of FeTMPyP on the GQDs results in substantial PL quenching of the GQDs. The quenched PL of GQDs by the FeTMPyP can be switched back “on” in response to the reaction between FeTMPyP and H2O2, which causes rupture of the cyclic tetrapyrrolic nucleus with consequential loss of iron from FeTMPyP, and then proceeds further to produce colorless dipyrroles and monopyrroles. This “turn on” system can be applied for simple and convenient H2O2 sensing and can be further extended to the detection of glucose in combination with the specific catalytic effect of glucose oxidase (GOx) through the oxidation of glucose and formation of H2O2. Because of the inherent synthetic control available for the design of metalloporphyrins, the GQDs‐based optical sensing approach described here has the potential to be highly versatile for other target analytes. 相似文献