全文获取类型
收费全文 | 3096篇 |
免费 | 625篇 |
国内免费 | 263篇 |
专业分类
化学 | 918篇 |
晶体学 | 18篇 |
力学 | 546篇 |
综合类 | 81篇 |
数学 | 1207篇 |
物理学 | 1214篇 |
出版年
2024年 | 6篇 |
2023年 | 50篇 |
2022年 | 126篇 |
2021年 | 146篇 |
2020年 | 149篇 |
2019年 | 105篇 |
2018年 | 107篇 |
2017年 | 144篇 |
2016年 | 141篇 |
2015年 | 132篇 |
2014年 | 178篇 |
2013年 | 283篇 |
2012年 | 158篇 |
2011年 | 199篇 |
2010年 | 154篇 |
2009年 | 155篇 |
2008年 | 199篇 |
2007年 | 177篇 |
2006年 | 190篇 |
2005年 | 153篇 |
2004年 | 130篇 |
2003年 | 113篇 |
2002年 | 115篇 |
2001年 | 76篇 |
2000年 | 93篇 |
1999年 | 71篇 |
1998年 | 56篇 |
1997年 | 57篇 |
1996年 | 48篇 |
1995年 | 41篇 |
1994年 | 29篇 |
1993年 | 33篇 |
1992年 | 18篇 |
1991年 | 16篇 |
1990年 | 15篇 |
1989年 | 13篇 |
1988年 | 19篇 |
1987年 | 13篇 |
1986年 | 13篇 |
1985年 | 11篇 |
1984年 | 10篇 |
1983年 | 3篇 |
1982年 | 11篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1974年 | 4篇 |
1957年 | 2篇 |
排序方式: 共有3984条查询结果,搜索用时 78 毫秒
91.
研究由制造商和品牌商组成的混合渠道贴牌生产供应链渠道结构优化问题,制造商通过直销和贴牌两条渠道销售产品.通过与单一渠道比较,分别推导出制造商和品牌商选择混合渠道的依据和优越性,进而归纳出双方共同接受混合渠道的制造商生产成本和品牌商品牌溢价优化条件,分析了渠道转移系数对双方构建混合渠道结构条件的影响,得出了制造商生产成本和品牌商品牌溢价作为竞争要素的互动决策改进贴牌供应链整体绩效的优化机理. 相似文献
92.
This paper examines the combined effects of a transverse magnetic field and variable viscosity on unsteady flow of a reactive third‐grade electrically conducting fluid and heat transfer in a channel with convective cooling at the surface. It is assumed that the fluid has small electrical conductivity and the electromagnetic force produced is very small. The coupled nonlinear partial differential equations governing the problem are derived and solved numerically using a semi‐implicit finite‐difference scheme. Both numerical and graphical results are presented and physical aspects of the problem are discussed with respect to various parameters embedded in the system. It is in general noted that those parameters that increase/decrase one flow quantity (velocity or temperature) also lead to the increase/decrease respectively of the other quantity. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
93.
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
![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)
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
94.
Dr. Zhen Lei Zong‐Jie Guan Dr. Xiao‐Li Pei Shang‐Fu Yuan Xian‐Kai Wan Jin‐Yuan Zhang Prof.Dr. Quan‐Ming Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(32):11156-11160
A red–near‐IR dual‐emissive nanocluster with the composition [Au10Ag2(2‐py?C≡C)3(dppy)6](BF4)5 ( 1 ; 2‐py?C≡C is 2‐pyridylethynyl, dppy=2‐pyridyldiphenylphosphine) has been synthesized. Single‐crystal X‐ray structural analysis reveals that 1 has a trigonal bipyramidal Au10Ag2 core that contains a planar Au4(2‐py?C≡C)3 unit sandwiched by two Au3Ag(dppy)3 motifs. Cluster 1 shows intense red–NIR dual emission in solution. The visible emission originates from metal‐to‐ligand charge transfer (MLCT) from silver atoms to phosphine ligands in the Au3Ag(dppy)3 motifs, and the intense NIR emission is associated with the participation of 2‐pyridylethynyl in the frontier orbitals of the cluster, which is confirmed by a time‐dependent density functional theory (TD‐DFT) calculation. 相似文献
95.
This paper presents the performance analysis of a two-way relay system with nodes-mobility (NM) and channel estimation errors (CEE) under time-varying Rayleigh fading. Herein, analog network coding protocol is employed at the relay node. All the participating nodes are half-duplex and equipped with single-antenna devices. Specifically, we utilize first-order Markovian model to characterize the impact of NM in the channel. Along with the NM, we also consider that the CEE may exist in practical scenarios, where nodes require to estimate the channel state information. By incorporating these factors, we first derive the instantaneous end-to-end (e2e) signal-to-noise ratios (SNRs) at two source nodes. Then, we obtain the exact closed-form expressions for distribution and density functions of the two e2e SNRs. After that, we derive the accurate expressions of various performance metrics, viz., sum-bit error rate, overall outage probability, and ergodic sum-rate. Further, to attain more insights into the considered system, we deduce the asymptotic behavior of these performance metrics. Finally, numerical and Monte-Carlo simulation results are provided to validate our theoretical analysis and to illustrate the impact of NM and CEE on the performance measures of the considered system. 相似文献
96.
Ruliang Xie Ting Zhang Qianfei Zhao Tao Zhang Xiangdong Mei Huizhu Yuan 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):1095-1103
Abstract A series of novel symmetric S,S′-2,2′-(ethane-1,2-diylbis(azanediyl)) bis(2-oxoethane-2,1-diyl) O,O,O′,O′-tetraethyl diphosphorodithioate derivatives (12) was designed and synthesized based on the cluster effect and the multiple binding sites of acetylcholinesterase (AChE). The structures of all the newly synthesized title compounds were characterized by 1 H and 13 C NMR as well as elemental analyses. Their inhibitory activities against AChE were tested, and compound 12b exhibited the best activity (6.60-fold higher than ethion). The results suggested that the compound would bind to the catalytic center and the narrow gorge of the AChE simultaneously. Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional table. 相似文献
97.
A multi‐channel microchip electrophoresis using a programmed step electric field strength (PSEFS) method was investigated for fast parallel detection of feline panleukopenia virus (FPV) DNA. An expanded laser beam, a 10× objective lens, and a charge‐coupled device camera were used to simultaneously detect the separations in three parallel channels using laser‐induced fluorescence detection. The parallel separations of a 100‐bp DNA ladder were demonstrated on the system using a sieving gel matrix of 0.5% poly(ethylene oxide) (Mr = 8 000 000) in the individual channels. In addition, the PSEFS method was also applied for faster DNA separation without loss of resolving power. A DNA size marker, FPV DNA sample, and a negative control were simultaneously analyzed with single‐run and one‐step detection. The FPV DNA was clearly distinguished within 30 s, which was more than 100 times faster than with conventional slab gel electrophoresis. The proposed multi‐channel microchip electrophoresis with PSEFS was demonstrated to be a simple and powerful diagnostic method to analyze multiple disease‐related DNA fragments in parallel with high speed, throughput, and accuracy. 相似文献
98.
This work concentrates on extending the utilization of multiple dual mode (MDM) counter‐current chromatography in chiral separations. Two aromatic acids, 2‐(6‐methoxy‐2‐naphthyl)propionic acid (NAP) and 2‐phenylpropionic acid (2‐PPA), were enantioseparated by MDM counter‐current chromatography using hydroxypropyl‐β‐cyclodextrin (HP‐β‐CD) as chiral selector. The two‐phase solvent systems consisting of n‐hexane/ethyl acetate 0.1 mol/L phosphate buffer pH 2.67 containing 0.1 mol/L HP‐β‐CD (7.5:2.5:10 for NAP and 7:3:10 for 2‐PPA, v/v/v) were used. Conventional MDM and modified MDM were compared according to peak resolution under current separation mechanism. The influence of elution time after the first‐phase inversion and number of cycles for MDM were investigated. Peak resolution of NAP and 2‐PPA increased from 0.62 to 1.05 and 0.72 to 0.84, respectively, using optimized MDM conditions. Being an alternative elution method for counter‐current chromatography, MDM elution greatly improved peak resolution in chiral separations. 相似文献
99.
Papori Goswami 《合成通讯》2013,43(13):2271-2278
A wide range of substituted coumarin derivatives were synthesized by refluxing in acetonitrile, ethyl acetoacetate, and ethyl benzoyl acetate with a wide range of structurally diverse phenol derivatives within a short reaction time with a catalytic combination of pyridine dicarboxylic acid as organocatalyst and nanocrystalline ZnO. 相似文献
100.
Shu‐Xian Hu Jian‐Guo Yu Eddy Y. Zeng 《International journal of quantum chemistry》2013,113(8):1128-1136
Calculations using density functional theory were performed to explore the mechanisms for atmospheric degradation of isopropyl methyl methylphosphonate (IMMP). The potential energy surface profiles for OH‐initiated reaction of IMMP were constructed, and all possible degradation channels were considered. Rate constants were further calculated using transition state theory. It was established from these calculations that H‐abstractions from alkyl groups have much lower energy barriers than substitutions of alkoxyl groups, and four possible H‐abstraction channels are competitive. Investigations into the secondary reactions under the presence of O2/NO were also performed. It is shown that O2 addition, reaction of peroxide radicals with NO to form RO radicals, and removal of ·RO are the major degradation pathways for alkyl radicals. Four selected products, CH3OP(O)(CH3)OC(O)CH3, CH3OP(O)(O)CH3, (CH3)2CHOP(O)(CH3)OH, and (CH3)2CHOP(O)(CH3)OCH?O, are predicted to be the major products in this study. © 2013 Wiley Periodicals, Inc. 相似文献