全文获取类型
收费全文 | 30054篇 |
免费 | 3557篇 |
国内免费 | 6545篇 |
专业分类
化学 | 33352篇 |
晶体学 | 212篇 |
力学 | 728篇 |
综合类 | 217篇 |
数学 | 1419篇 |
物理学 | 4228篇 |
出版年
2024年 | 39篇 |
2023年 | 489篇 |
2022年 | 736篇 |
2021年 | 1155篇 |
2020年 | 1733篇 |
2019年 | 1366篇 |
2018年 | 1369篇 |
2017年 | 1247篇 |
2016年 | 1441篇 |
2015年 | 1338篇 |
2014年 | 1950篇 |
2013年 | 2988篇 |
2012年 | 1756篇 |
2011年 | 2059篇 |
2010年 | 1576篇 |
2009年 | 1753篇 |
2008年 | 1875篇 |
2007年 | 2005篇 |
2006年 | 1855篇 |
2005年 | 1719篇 |
2004年 | 1631篇 |
2003年 | 1400篇 |
2002年 | 849篇 |
2001年 | 688篇 |
2000年 | 659篇 |
1999年 | 529篇 |
1998年 | 490篇 |
1997年 | 423篇 |
1996年 | 410篇 |
1995年 | 421篇 |
1994年 | 356篇 |
1993年 | 271篇 |
1992年 | 290篇 |
1991年 | 190篇 |
1990年 | 153篇 |
1989年 | 132篇 |
1988年 | 121篇 |
1987年 | 74篇 |
1986年 | 79篇 |
1985年 | 80篇 |
1984年 | 68篇 |
1983年 | 35篇 |
1982年 | 53篇 |
1981年 | 45篇 |
1980年 | 30篇 |
1979年 | 29篇 |
1978年 | 27篇 |
1977年 | 31篇 |
1976年 | 36篇 |
1974年 | 38篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
Prof. Ian J. S. Fairlamb 《Angewandte Chemie (International ed. in English)》2015,54(36):10415-10427
This Minireview highlights the redox and non‐innocent behavior of NOx ligands (x=1, 2, or 3) in selected Pd‐mediated processes, for example, alkene and aromatic oxidation processes. A focus is placed on mechanistic understanding and linking recent transformations, such as C? H bond activation/functionalization and Wacker oxidation, with previous work on the functionalization of aromatics and alkenes by PdII salts. 相似文献
72.
Romain Bénéteau Anne Boussonnière Jean‐Christophe Rouaud Prof. Dr. Jacques Lebreton Dr. Jérôme Graton Prof. Dr. Denis Jacquemin Dr. Muriel Sebban Prof. Dr. Hassan Oulyadi Ghanem Hamdoun Dr. Amber N. Hancock Prof. Dr. Carl H. Schiesser Dr. Fabrice Dénès 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(14):4809-4824
α‐Bromo aluminium acetals are suitable substrates for Ueno–Stork‐like radical cyclisations affording γ‐lactols and acid‐sensitive methylene‐γ‐lactols in high yields. The mechanistic study herein sets the scope and limitation of this reaction. The influence of the halide (or chalcogenide) atom X (X=Cl, Br, I, SPh, SePh) in the precursors α‐haloesters, as well as influence of the solvent and temperature was studied. The structure of the aluminium acetal intermediates resulting from the reduction of the corresponding α‐haloesters has been investigated by low‐temperature 13C‐INEPT diffusion‐ordered NMR spectroscopy (DOSY) experiments and quantum calculations, providing new insights into the structures of these thermally labile intermediates. Oxygen‐bridged dimeric structures with a planar Al2O2 ring are proposed for the least hindered aluminium acetals, while monomeric structures seem to prevail for the most hindered species. A comparison against the radical cyclisation of aluminium acetals derived from allyl and propargyl alcohols with the parent Ueno–Stork has been made at the BHandHLYP/6‐311++G(d,p) level of theory, highlighting mechanistic similarities and differences. 相似文献
73.
Ying Huang Rui Sun Qiaojie Luo Ying Wang Kai Zhang Xuliang Deng Weipu Zhu Xiaodong Li Zhiquan Shen 《Journal of polymer science. Part A, Polymer chemistry》2016,54(1):99-107
In this study, a facile method to fabricate reduction‐responsive core‐crosslinked micelles via in situ thiol‐ene “click” reaction was reported. A series of biodegradable poly(ether‐ester)s with multiple pendent mercapto groups were first synthesized by melt polycondensation of diol poly(ethylene glycol), 1,4‐butanediol, and mercaptosuccinic acid using scandium trifluoromethanesulfonate [Sc(OTf)3] as the catalyst. Then paclitaxel (PTX)‐loaded core‐crosslinked (CCL) micelles were successfully prepared by in situ crosslinking hydrophobic polyester blocks in aqueous media via thiol‐ene “click” chemistry using 2,2′‐dithiodiethanol diacrylate as the crosslinker. These PTX‐loaded CCL micelles with disulfide bonds exhibited reduction‐responsive behaviors in the presence of dithiothreitol (DTT). The drug release profile of the PTX‐loaded CCL micelles revealed that only a small amount of loaded PTX was released slowly in phosphate buffer solution (PBS) without DTT, while quick release was observed in the presence of 10.0 mM DTT. Cell count kit (CCK‐8) assays revealed that the reduction‐sensitive PTX‐loaded CCL micelles showed high antitumor activity toward HeLa cells, which was significantly higher than that of reduction‐insensitive counterparts and free PTX. This kind of biodegradable and biocompatible CCL micelles could serve as a bioreducible nanocarrier for the controlled antitumor drug release. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 99–107 相似文献
74.
A highly active multi‐usable palladium pyridylfluorene film‐based catalyst for C–C cross‐coupling reactions 下载免费PDF全文
The two terminal pyridyl nitrogen atoms of 2,7‐bis(4‐pyridyl)fluorene ( 1 ) were coordinated to Pd(II) ions to give self‐assembled, multilayer films using the layer‐by‐layer (LbL) method. The films were prepared by alternately dipping the substrate, pre‐coated with a polyethyleneimine layer, in aqueous solutions of PdCl2 and ethanol solutions of 1 . The resulting films were characterized using UV–visible absorption spectroscopy, atomic force microscopy (AFM), X‐ray photoelectron spectroscopy, scanning electron microscopy (SEM) and inductively coupled plasma atomic emission spectroscopy (ICP‐AES). UV–visible spectra and SEM images show almost uniform growth of the film in a near ideal LbL manner. AFM images show that nanostructured aggregates of Pd(II) complexes form on the surface. With an increase in the number of Pd(II)/ 1 bilayers, more particulate aggregates are distributed on the surface. When released from the substrate, the Pd(II) complex nanostructure shows high catalytic activity for Suzuki–Miyaura and Mizoroki–Heck cross‐coupling reactions. The catalyst loading is as low as 9.1 × 10?3 mol% Pd, as measured using ICP‐AES, and high turnover numbers of up to 1.08 × 104 are obtained. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
75.
Development of a syn‐Selective Mannich Reaction of Aldehydes with Propargylic Imines by Dual Catalysis: Asymmetric Synthesis of Functionalized Propargylic Amines 下载免费PDF全文
Irati Lapuerta Dr. Silvia Vera Prof. Mikel Oiarbide Prof. Claudio Palomo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(21):7229-7237
Direct coupling of enolizable aldehydes with C‐alkynyl imines is realized affording the corresponding propargylic Mannich adducts of syn configuration, thus complementing previous methods that gave access to the anti‐isomers. The combination of proline and a urea Brønsted base cocatalyst is key for the reactions to proceed under very mild conditions (3–10 mol % catalyst loading, dichloromethane as solvent, ?20 °C, 1.2 molar equivalents of aldehyde) and with virtually total stereocontrol (syn/anti ratio up to 99:1; ee up to 99 %). Some possibilities of further chemical elaboration of adducts are also briefly illustrated. 相似文献
76.
A Supramolecular Chiral Auxiliary Approach: “Remote Control” of Stereochemistry at a Hierarchically Assembled Dimeric Helicate 下载免费PDF全文
David Van Craen Prof. Dr. Markus Albrecht Prof. Dr. Gerhard Raabe Fangfang Pan Prof. Dr. Kari Rissanen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(10):3255-3258
Dimeric hierarchically‐assembled titanium(IV) helicates are in solvent‐dependent equilibrium with the corresponding monomers. Statistically formed mixtures of such complexes bearing chiral stereocontrolling ligands and achiral diene‐substituted ligands show high diastereoselectivity and reasonable enantioselectivity in the Diels–Alder reaction with maleimides if the reaction proceeds with the dimer but not with the monomer. Thus, solvent dependent switching between the monomer and dimer enables on/off switching of the enantioselectivity. 相似文献
77.
《Comptes Rendus Chimie》2015,18(6):614-618
A simple, efficient, and ecofriendly procedure for the aerobic oxidation of alcohols to aldehydes and ketones in the presence of In(NO3)3/[C12mim][FeBr4] in aqueous media has been developed. The oxidation reactions afford the target products in good to high yields and no over-oxidation was observed. The products can be separated by a simple extraction with dichloromethane, and the system can be recycled and reused without loss of activity. 相似文献
78.
Intermolecular Stetter reaction of aromatic aldehydes with (E)-(2-nitrovinyl)cyclohexane catalyzed by thiazolium A has been developed. The reaction rate and efficiency are profoundly impacted by the presence of thiourea B. The reaction affords moderate to good yields of the Stetter product. Some factors influencing yield were discussed. 相似文献
79.
Reaction of an N‐Heterocyclic Carbene‐Stabilized Silicon(II) Monohydride with Alkynes: [2+2+1] Cycloaddition versus Hydrogen Abstraction 下载免费PDF全文
Carsten Eisenhut Tibor Szilvási Dr. Nora C. Breit Prof. Dr. Shigeyoshi Inoue 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(5):1949-1954
An in depth study of the reactivity of an N‐heterocyclic carbene (NHC)‐stabilized silylene monohydride with alkynes is reported. The reaction of silylene monohydride 1 , tBu3Si(H)Si←NHC, with diphenylacetylene afforded silole 2 , tBu3Si(H)Si(C4Ph4). The density functional theory (DFT) calculations for the reaction mechanism of the [2+2+1] cycloaddition revealed that the NHC played a major part stabilizing zwitterionic transition states and intermediates to assist the cyclization pathway. A significantly different outcome was observed, when silylene monohydride 1 was treated with phenylacetylene, which gave rise to supersilyl substituted 1‐alkenyl‐1‐alkynylsilane 3 , tBu3Si(H)Si(CH?CHPh)(C?CPh). Mechanistic investigations using an isotope labelling technique and DFT calculations suggest that this reaction occurs through a similar zwitterionic intermediate and subsequent hydrogen abstraction from a second molecule of phenylacetylene. 相似文献
80.
Hexametaphosphate‐Capped Silica Mesoporous Nanoparticles Containing CuII Complexes for the Selective and Sensitive Optical Detection of Hydrogen Sulfide in Water 下载免费PDF全文
Sameh El Sayed Dr. Michele Milani Prof. Maurizio Licchelli Prof. Ramón Martínez‐Máñez Dr. Félix Sancenón 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(19):7002-7006
CuII‐macrocycle functionalized hexametaphosphate‐capped silica mesoporous nanoparticles have been prepared and used for the selective and sensitive detection of hydrogen sulfide in aqueous environments. The possibility of using different metal complexes combined with different capping anions and choice of different dyes or other sensing molecules as indicators makes this new protocol highly appealing for the preparation of new sensing systems for sulfide detection in different environments. 相似文献