全文获取类型
收费全文 | 3223篇 |
免费 | 483篇 |
国内免费 | 435篇 |
专业分类
化学 | 2357篇 |
晶体学 | 30篇 |
力学 | 232篇 |
综合类 | 45篇 |
数学 | 314篇 |
物理学 | 1163篇 |
出版年
2024年 | 8篇 |
2023年 | 57篇 |
2022年 | 112篇 |
2021年 | 113篇 |
2020年 | 137篇 |
2019年 | 105篇 |
2018年 | 119篇 |
2017年 | 118篇 |
2016年 | 152篇 |
2015年 | 132篇 |
2014年 | 180篇 |
2013年 | 220篇 |
2012年 | 221篇 |
2011年 | 299篇 |
2010年 | 207篇 |
2009年 | 198篇 |
2008年 | 210篇 |
2007年 | 197篇 |
2006年 | 162篇 |
2005年 | 125篇 |
2004年 | 95篇 |
2003年 | 76篇 |
2002年 | 75篇 |
2001年 | 69篇 |
2000年 | 60篇 |
1999年 | 73篇 |
1998年 | 60篇 |
1997年 | 50篇 |
1996年 | 48篇 |
1995年 | 51篇 |
1994年 | 52篇 |
1993年 | 48篇 |
1992年 | 47篇 |
1991年 | 37篇 |
1990年 | 40篇 |
1989年 | 32篇 |
1988年 | 25篇 |
1987年 | 31篇 |
1986年 | 23篇 |
1985年 | 13篇 |
1984年 | 8篇 |
1983年 | 11篇 |
1982年 | 12篇 |
1981年 | 5篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1957年 | 4篇 |
排序方式: 共有4141条查询结果,搜索用时 15 毫秒
161.
Junkai Guo Cuiwen Kuang Jian Rong Dr. Lingchun Li Dr. Chuanfa Ni Prof. Dr. Jinbo Hu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(30):7259-7264
The deoxyfluorination of alcohols is a fundamentally important approach to access alkyl fluorides, and thus the development of shelf-stable, easy-to-handle, fluorine-economical, and highly selective deoxyfluorination reagents is highly desired. This work describes the development of a crystalline compound, N-tosyl-4-chlorobenzenesulfonimidoyl fluoride (SulfoxFluor), as a novel deoxyfluorination reagent that possesses all of the aforementioned merits, which is rare in the arena of deoxyfluorination. Endowed by the multi-dimensional modulating ability of the sulfonimidoyl group, SulfoxFluor is superior to 2-pyridinesulfonyl fluoride (PyFluor) in fluorination rate, and is also superior to perfluorobutanesulfonyl fluoride (PBSF) in fluorine-economy. Its reaction with alcohols not only tolerates a wide range of functionalities including the more sterically hindered alcoholic hydroxyl groups, but also exhibits high fluorination/elimination selectivity. Because SulfoxFluor can be easily prepared from inexpensive materials and can be safely handled without special techniques, it promises to serve as a practical deoxyfluorination reagent for the synthesis of various alkyl fluorides. 相似文献
162.
Mengyuan Ge Guangwen Li Zibo Ni Ning Liu Yushan Liu Yuzhou Liu 《Journal of polymer science. Part A, Polymer chemistry》2020,58(21):3009-3017
Utilizing collective forces between reactant and multiple catalyst molecules has been unprecedented due to the difficulty in realizing high order catalysis. Inspired by the power of collective forces in enzymes and organic catalysts, herein we report a rare example of high order catalysis for ring opening reaction (ROR) of strained rings by methanol. ROR is an important way to produce various polysiloxanes, but usually suffers from serious side reactions especially at high conversion, and currently there is a need to design new reaction pathway to achieve low molecular dispersity. In our study, the judiciously designed strained spiral cyclosiloxanes enable a high order catalysis by methanol, and this new methodology leads to a cyclic polysiloxane with high molecular weight and low dispersity even at full conversion of reactants. Kinetic study indicates an extremely unusual high-order reaction involving multiple methanol molecules per reaction, also confirmed by quantum calculation which reveals the presence of zwitterionic ions stabilized by collecting force of hydrogen bonds by methanol molecules. The inherent driving force for this unusual phenomenon is dominated by enthalpy stabilization of the reactive intermediates through hydrogen bonding. The selective formation of Si O Si bonds, instead of silanol products, reflects the power of scientific design. 相似文献
163.
In this paper, we construct a high-order moving mesh method based on total variation diminishing Runge-Kutta and weighted essential nonoscillatory reconstruction for compressible fluid system. Beginning with the integral form of fluid system, we get the semidiscrete system with an arbitrary mesh velocity. We use weighted essential nonoscillatory reconstruction to get the space accuracy on moving meshes, and the time accuracy is obtained by modified Runge-Kutta method; the mesh velocity is determined by moving mesh method. One- and two-dimensional numerical examples are presented to demonstrate the efficient and accurate performance of the scheme. 相似文献
164.
165.
Yi Han Zibo Xue Dr. Guangwu Li Dr. Yanwei Gu Dr. Yong Ni Dr. Shaoqiang Dong Prof. Chunyan Chi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):9111-9116
Incorporation of a non-hexagonal ring into a nanographene framework can lead to new electronic properties. During the attempted synthesis of naphthalene-bridged double [6]helicene and heptagon-containing nanographene by the Scholl reaction, an unexpected azulene-embedded nanographene and its triflyloxylated product were obtained, as confirmed by X-ray crystallographic analysis and 2D NMR spectroscopy. A 5/7/7/5 ring-fused substructure containing two formal azulene units is formed, but only one of them shows an azulene-like electronic structure. The formation of this unique structure is explained by arenium ion mediated 1,2-phenyl migration and a naphthalene to azulene rearrangement reaction according to an in-silico study. This report represents the first experimental example of the thermodynamically unfavorable naphthalene to azulene rearrangement and may lead to new azulene-based molecular materials. 相似文献
166.
Prof. Jen-Shyang Ni Tianliang Min Yaxi Li Menglei Zha Dr. Pengfei Zhang Prof. Chun Loong Ho Prof. Kai Li 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(25):10265-10271
Planar luminogens have encountered difficulties in overcoming intrinsic aggregation-caused emission quenching by intermolecular π-π stacking interactions. Although excited-state double-bond reorganization (ESDBR) can guide us on designing planar aggregation-induced emission (AIE) luminogens (AIEgens), its mechanism has yet been elucidated. Major challenges in the field include methods to efficiently restrict ESDBR and enhance AIE performance without using bulky substituents (e.g., tetraphenylethylene and triphenylamine). In this study, we rationally developed fluoro-substituent AIEgens with stronger intermolecular H-bonding interaction for restricted molecular motions and increased crystal density, leading to decreased nonradiative decay rate by one order of magnitude. The adjusted ESDBR properties also show a corresponding response to variation in viscosity. Furthermore, their aggregation-induced reactive oxygen species (ROS) generations have been discovered. The application of such planar AIEgen in treating multidrug-resistant bacteria has been demonstrated in a mouse model. The relationship between ROS generation and distinct E/Z-configurational stacking behaviors have been further understood, providing a design principle for synthesizing planar AIEgen-based photosensitizers. 相似文献
167.
Dongshun Ni Brittany P. Witherspoon Hong Zhang Chen Zhou Prof. K. N. Houk Prof. M. Kevin Brown 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(28):11529-11536
A method for the stereoselective [4+2]-cycloaddition of alkenylboranes and dienes is presented. This transformation was accomplished through the introduction of a new strategy that involves the use of chiral N-protonated alkenyl oxazaborolidines as dieneophiles. The reaction leads to the formation of products that can be readily derivatized to more complex structural motifs through stereospecific transformations of the C−B bond such as oxidation and homologation. Detailed computation evaluation of the reaction has uncovered a surprising role of the counterion on stereoselectivity. 相似文献
168.
Martien A. Würdemann Cristina Niţu Dr. Stefaan M. A. De Wildeman Dr. Katrien V. Bernaerts Prof. Dr. Romano V. A. Orru 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(36):8090-8100
Pyrazines are an underreported class of N-heterocycles available from nitrogen-rich biomass presenting an interesting functional alternative for current aromatics. In this work, access to pyrazines obtained from amino acids by using the 90 year old Dakin–West reaction was explored. After a qualitative screening several functional proteinogenic amino acids proved good substrates for this reaction, which were successfully scaled to multigram scale synthesis of the corresponding intermediate α-acetamido ketones. Subsequently, the conditions towards pyrazine formation using δ-amino-levulinic acid were optimized, and these were employed to synthesize a relevant set of five functional dimethylpyrazines in high purity. These pyrazines can be considered a versatile toolbox of aromatic building blocks for a wide range of applications, such as in the synthesis of polymers or metal–organic frameworks. 相似文献
169.
For B2 NiAl and NiTi intermetallic compounds, the ideal stress–strain image is lack from the perspective of elastic constants. We use first-principles calculation to investigate the ideal strength and elastic behavior under the tensile and shear loads. The relation between the ideal strength and elastic constants is found. The uniaxial tension of NiAl and NiTi along <001> crystal direction leads to the change from tetragonal path to orthogonal path, which is driven by the vanishing of the shear constant C(66). The shear failure under {110}{111} shear deformation occurring in process of tension may result in a small ideal tensile strength(~ 2 GPa) for NiTi. The unlikeness in the ideal strength of Ni Al and Ni Ti alloys is discussed based on the charge density difference. 相似文献
170.
We present a new methodology for solving large-scale employee tour scheduling problems. An integer programming model is proposed
where tours are decomposed into shifts and start times. This formulation can model complex shift and start time rules for
both continuous and discontinuous scheduling problems. A branch-and-price approach is devised to solve this model efficiently.
The methodology was tested on the largest tour scheduling problems found in the open literature. In comparison with an alternative
implicit model, our approach showed superior computational performance. 相似文献