全文获取类型
收费全文 | 5056篇 |
免费 | 261篇 |
国内免费 | 22篇 |
专业分类
化学 | 3884篇 |
晶体学 | 14篇 |
力学 | 112篇 |
数学 | 665篇 |
物理学 | 664篇 |
出版年
2023年 | 55篇 |
2022年 | 57篇 |
2021年 | 89篇 |
2020年 | 110篇 |
2019年 | 112篇 |
2018年 | 68篇 |
2017年 | 62篇 |
2016年 | 225篇 |
2015年 | 196篇 |
2014年 | 191篇 |
2013年 | 286篇 |
2012年 | 366篇 |
2011年 | 387篇 |
2010年 | 242篇 |
2009年 | 217篇 |
2008年 | 313篇 |
2007年 | 267篇 |
2006年 | 280篇 |
2005年 | 278篇 |
2004年 | 241篇 |
2003年 | 173篇 |
2002年 | 188篇 |
2001年 | 95篇 |
2000年 | 82篇 |
1999年 | 77篇 |
1998年 | 61篇 |
1997年 | 87篇 |
1996年 | 69篇 |
1995年 | 66篇 |
1994年 | 45篇 |
1993年 | 50篇 |
1992年 | 34篇 |
1991年 | 24篇 |
1990年 | 20篇 |
1989年 | 21篇 |
1988年 | 14篇 |
1987年 | 15篇 |
1986年 | 13篇 |
1985年 | 10篇 |
1984年 | 10篇 |
1983年 | 8篇 |
1982年 | 10篇 |
1981年 | 11篇 |
1979年 | 7篇 |
1978年 | 12篇 |
1977年 | 8篇 |
1976年 | 7篇 |
1975年 | 8篇 |
1974年 | 13篇 |
1973年 | 14篇 |
排序方式: 共有5339条查询结果,搜索用时 0 毫秒
91.
Budischowsky David Zwirchmayr Nele Sophie Hosoya Takashi Bacher Markus Hettegger Hubert Potthast Antje Rosenau Thomas 《Cellulose (London, England)》2021,28(10):6051-6071
Cellulose - Chromophores, colored substances of rather high stability that reduce brightness, are present in all kinds of cellulosic products, such as pulp, fibers, aged cellulosic material, and... 相似文献
92.
Loffhagen Detlef Becker Markus M. Czerny Andreas K. Klages Claus-Peter 《Plasma Chemistry and Plasma Processing》2021,41(1):289-334
Plasma Chemistry and Plasma Processing - A time-dependent, spatially one-dimensional fluid-Poisson model is applied to analyze the impact of small amounts of tetramethylsilane (TMS) as precursor on... 相似文献
93.
Markus Bursch Lukas Kunze Dr. Amol M. Vibhute Dr. Andreas Hansen Prof. Dr. Kana M. Sureshan Dr. Peter G. Jones Prof. Dr. Stefan Grimme Prof. Dr. Daniel B. Werz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(14):4627-4639
The noncovalent interactions between azides and oxygen-containing moieties are investigated through a computational study based on experimental findings. The targeted synthesis of organic compounds with close intramolecular azide–oxygen contacts yielded six new representatives, for which X-ray structures were determined. Two of those compounds were investigated with respect to their potential conformations in the gas phase and a possible significantly shorter azide–oxygen contact. Furthermore, a set of 44 high-quality, gas-phase computational model systems with intermolecular azide–pnictogen (N, P, As, Sb), –chalcogen (O, S, Se, Te), and –halogen (F, Cl, Br, I) contacts are compiled and investigated through semiempirical quantum mechanical methods, density functional approximations, and wave function theory. A local energy decomposition (LED) analysis is applied to study the nature of the noncovalent interaction. The special role of electrostatic and London dispersion interactions is discussed in detail. London dispersion is identified as a dominant factor of the azide–donor interaction with mean London dispersion energy-interaction energy ratios of 1.3. Electrostatic contributions enhance the azide–donor coordination motif. The association energies range from −1.00 to −5.5 kcal mol−1. 相似文献
94.
95.
Andrey Shatskiy Anton Axelsson Elena V. Stepanova Jian-Quan Liu Azamat Z. Temerdashev Bhushan P. Kore Bjrn Blomkvist James M. Gardner Peter Dinr Markus D. Krks 《Chemical science》2021,12(15):5430
A protocol for stereoselective C-radical addition to a chiral glyoxylate-derived N-sulfinyl imine was developed through visible light-promoted photoredox catalysis, providing a convenient method for the synthesis of unnatural α-amino acids. The developed protocol allows the use of ubiquitous carboxylic acids as radical precursors without prior derivatization. The protocol utilizes near-stoichiometric amounts of the imine and the acid radical precursor in combination with a catalytic amount of an organic acridinium-based photocatalyst. Alternative mechanisms for the developed transformation are discussed and corroborated by experimental and computational studies.A protocol for stereoselective C-radical addition to a chiral glyoxylate-derived N-sulfinyl imine was developed through visible light-promoted photoredox catalysis, providing a convenient method for the synthesis of unnatural α-amino acids. 相似文献
96.
Omar Sarheed Manar Dibi Kanteti V. R. N. S. Ramesh Markus Drechsler 《Molecules (Basel, Switzerland)》2021,26(9)
Transdermal drug delivery of lidocaine is a good choice for local anesthetic delivery. Microemulsions have shown great effectiveness for the transdermal transport of lidocaine. Oil-in-water nanoemulsions are particularly suitable for encapsulation of lipophilic molecules because of their ability to form stable and transparent delivery systems with good skin permeation. However, fabrication of nanoemulsions containing lidocaine to provide an extended local anesthetic effect is challenging. Hence, the aim of this study was to address this issue by employing alginate-based o/w nanocarriers using nanoemulsion template that is prepared by combined approaches of ultrasound and phase inversion temperature (PIT). In this study, the influence of system composition such as oil type, oil and surfactant concentration on the particle size, in vitro release and skin permeation of lidocaine nanoemulsions was investigated. Structural characterization of lidocaine nanoemulsions as a function of water dilution was done using DSC. Nanoemulsions with small droplet diameters (d < 150 nm) were obtained as demonstrated by dynamic light scattering (DLS) and cryo-TEM. These nanoemulsions were also able to release 90% of their content within 24-h through PDMS and pig skin and able to the drug release over a 48-h. This extended-release profile is highly favorable in transdermal drug delivery and shows the great potential of this nanoemulsion as delivery system. 相似文献
97.
Chiral Bifunctional Phosphine‐Carboxylate Ligands for Palladium(0)‐Catalyzed Enantioselective C−H Arylation 下载免费PDF全文
Dr. Lei Yang Dr. Markus Neuburger Prof. Dr. Olivier Baudoin 《Angewandte Chemie (International ed. in English)》2018,57(5):1394-1398
Previous enantioselective Pd0‐catalyzed C?H activation reactions proceeding via the concerted metalation‐deprotonation mechanism employed either a chiral ancillary ligand, a chiral base, or a bimolecular mixture thereof. This study describes the development of new chiral bifunctional ligands based on a binaphthyl scaffold which incorporates both a phosphine and a carboxylic acid moiety. The optimal ligand provided high yields and enantioselectivities for a desymmetrizing C(sp2)?H arylation leading to 5,6‐dihydrophenanthridines, whereas the corresponding monofunctional ligands showed low enantioselectivities. The bifunctional system proved applicable to a range of substituted dihydrophenanthridines, and allowed the parallel kinetic resolution of racemic substrates. 相似文献
98.
Viktoriia Morad Dr. Michael Wörle Dr. Sergii Yakunin Dr. Gabriele Rainò Olga Nazarenko Markus Fischer Dr. Ivan Infante Prof. Dr. Maksym V. Kovalenko 《Angewandte Chemie (International ed. in English)》2018,57(35):11329-11333
The spatial localization of charge carriers to promote the formation of bound excitons and concomitantly enhance radiative recombination has long been a goal for luminescent semiconductors. Zero‐dimensional materials structurally impose carrier localization and result in the formation of localized Frenkel excitons. Now the fully inorganic, perovskite‐derived zero‐dimensional SnII material Cs4SnBr6 is presented that exhibits room‐temperature broad‐band photoluminescence centered at 540 nm with a quantum yield (QY) of 15±5 %. A series of analogous compositions following the general formula Cs4?xAxSn(Br1?yIy)6 (A=Rb, K; x≤1, y≤1) can be prepared. The emission of these materials ranges from 500 nm to 620 nm with the possibility to compositionally tune the Stokes shift and the self‐trapped exciton emission bands. 相似文献
99.
Fulvene-Dieters: Synthesis, Structure Elucidation and Thermal Behaviour In contrast to earlier assumptions, thermal reaction of pure fulvene ( 1a ), 6-methylfulvene ( lb ) and 6, 6-dimethylfuivene ( 1c ) at 227deg; gives oligomeric mixtures consisting mainly of the endo-[4 + 2]-eycloaddition products 2a , 2b and 2c . Thermal reactivity of the fulvenes decreases strongly in the series 1a > 1b > 1c . While the dimers 2b and 2c equilibrate very easily in solution above room temperature with 1b and 1c , respectively, 2a equilibrates with the isomer 5a (? 1, 6-Dimethyliden3a α, 3bβ, 6a α, 6bβ-tetrahydro-1-H), 6 H-bi (cyclopentadienylen). This surprising rearrangement envolves a formal 1,3-shift of the 1, 2-dihydrofulvene-unit of 2a (s. Scheme 4). 相似文献
100.