全文获取类型
收费全文 | 2794篇 |
免费 | 553篇 |
国内免费 | 289篇 |
专业分类
化学 | 2218篇 |
晶体学 | 36篇 |
力学 | 154篇 |
综合类 | 13篇 |
数学 | 237篇 |
物理学 | 978篇 |
出版年
2024年 | 5篇 |
2023年 | 62篇 |
2022年 | 71篇 |
2021年 | 109篇 |
2020年 | 158篇 |
2019年 | 155篇 |
2018年 | 137篇 |
2017年 | 116篇 |
2016年 | 168篇 |
2015年 | 175篇 |
2014年 | 173篇 |
2013年 | 255篇 |
2012年 | 273篇 |
2011年 | 283篇 |
2010年 | 173篇 |
2009年 | 144篇 |
2008年 | 206篇 |
2007年 | 146篇 |
2006年 | 141篇 |
2005年 | 102篇 |
2004年 | 90篇 |
2003年 | 76篇 |
2002年 | 58篇 |
2001年 | 48篇 |
2000年 | 38篇 |
1999年 | 45篇 |
1998年 | 27篇 |
1997年 | 22篇 |
1996年 | 30篇 |
1995年 | 23篇 |
1994年 | 25篇 |
1993年 | 18篇 |
1992年 | 14篇 |
1991年 | 10篇 |
1990年 | 20篇 |
1989年 | 10篇 |
1988年 | 10篇 |
1987年 | 4篇 |
1986年 | 5篇 |
1985年 | 2篇 |
1984年 | 4篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1980年 | 1篇 |
排序方式: 共有3636条查询结果,搜索用时 437 毫秒
101.
Yizhao Ouyang Miao Zhan Jing Zhou Jiao Jiao Hao Hu Yoichi M. A. Yamada Pengfei Li 《中国化学》2019,37(8):807-810
A rigid C2‐symmetric chiral bipyridine ligand Z‐bpy with a triptycene‐like backbone was designed and synthesized from simple chemicals in a scalable route. Using this new ligand, copper(I) catalyzed cyclopropanation of styrenes with commercial ethyl diazoacetate produced various corresponding cyclopropanes in high yields, diastereoselectivity and enantioselectivity up to 97% ee. 相似文献
102.
Jiao J Kanellopoulos J Wang W Ray SS Foerster H Freude D Hunger M 《Physical chemistry chemical physics : PCCP》2005,7(17):3221-3226
27Al spin-echo, high-speed MAS (nu(rot) = 30 kHz), and MQMAS NMR spectroscopy in magnetic fields of B0 = 9.4, 14.1, and 17.6 T were applied for the study of aluminum species at framework and extra-framework positions in non-hydrated zeolites Y. Non-hydrated gamma-Al2O3 and non-hydrated aluminum-exchanged zeolite Y (Al,Na-Y) and zeolite H,Na-Y were utilized as reference materials. The solid-state 27Al NMR spectra of steamed zeolite deH,Na-Y/81.5 were found to consist of four signals. The broad low-field signal is caused by a superposition of the signals of framework aluminum atoms in the vicinity of bridging hydroxyl protons and framework aluminum atoms compensated in their negative charge by aluminum cations (delta(iso) = 70 +/- 10 ppm, C(QCC) = 15.0 +/- 1.0 MHz). The second signal is due to a superposition of the signals of framework aluminum atoms compensated by sodium cations and tetrahedrally coordinated aluminum atoms in neutral extra-framework aluminum oxide clusters (delta(iso) = 65 +/- 5 ppm, C(QCC) = 8.0 +/- 0.5 MHz). The residual two signals were attributed to aluminum cations (delta(iso) = 35 +/- 5 ppm, C(QCC) = 7.5 +/- 0.5 MHz) and octahedrally coordinated aluminum atoms in neutral extra-framework aluminum oxide clusters (delta(iso) = 10 +/- 5 ppm, C(QCC) = 5.0 +/- 0.5 MHz). By chemical analysis and evaluating the relative solid-state 27Al NMR intensities of the different signals of aluminum species occurring in zeolite deH,Na-Y/81.5 in the non-hydrated state, the aluminum distribution in this material was determined. 相似文献
103.
We adopt the cluster size distribution model to investigate the effect of temperature on homogeneous nucleation and crystal growth for isothermal polymer crystallization. The model includes the temperature effects of interfacial energy, nucleation rate, growth and dissociation rate coefficients, and equilibrium solubility. The time dependencies of polymer concentration, number and size of crystals, and crystallinity (in Avrami plots) are presented for different temperatures. The denucleation (Ostwald ripening effect) is also investigated by comparing moment and numerical solutions of the population balance equations. Agreement between the model results and temperature-sensitive experimental measurements for different polymer systems required strong temperature dependence for the crystal-melt interfacial energy. 相似文献
104.
105.
Biranje Santosh Shivaji Sun Jianzhong Shi Yifei Yu Sujie Jiao Haixin Zhang Meng Wang Qianqian Wang Jin Liu Jun 《Cellulose (London, England)》2021,28(14):8899-8937
Cellulose - Excessive hemorrhage is a leading cause of death to trauma patients, especially in combat and civilian accidents. The main priority in the medical treatment of trauma patients is to... 相似文献
106.
H. M. Noor ul Huda Khan Asghar Yi Tan Shuang Shi Dachuan Jiang Shiqiang Qin Jiao Liao Shutao Wen Wei Dong Yao Liu 《Applied Physics A: Materials Science & Processing》2014,115(3):753-757
Small amounts of multicrystalline silicon were melted in an electron beam furnace in different experimental conditions in order to investigate the oxygen evaporation behavior during the electron beam melting (EBM) process. The oxygen content level before and after EBM was determined by secondary ion mass spectroscopy. The oxygen content was reduced from 6.177 to 1.629 ppmw when silicon was melted completely at 15 kW with removal efficiency up to 73.6 %. After that, it decreased continually to <0.0517 ppmw when the refining time exceeded 600 s with a removal efficiency of more than 99.08 %. During the melting process, the evaporation rate of silicon is 1.10 × 10?5 kg/s. The loss of silicon could be reduced up to 1.7 % during oxygen removal process to a desirable figure, indicating EBM is an effective method to remove oxygen from silicon and decrease the loss of silicon. 相似文献
107.
108.
Prof. Jiao Jiao Wenzheng Nie Tao Yu Fan Yang Prof. Dr. Qian Zhang Feierdaiweisi Aihemaiti Tingjun Yang Xuanyu Liu Jiachen Wang Prof. Dr. Pengfei Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(15):4817-4838
Continuous-flow multi-step synthesis takes the advantages of microchannel flow chemistry and may transform the conventional multi-step organic synthesis by using integrated synthetic systems. To realize the goal, however, innovative chemical methods and techniques are urgently required to meet the significant remaining challenges. In the past few years, by using green reactions, telescoped chemical design, and/or novel in-line separation techniques, major and rapid advancement has been made in this direction. This minireview summarizes the most recent reports (2017–2020) on continuous-flow synthesis of functional molecules. Notably, several complex active pharmaceutical ingredients (APIs) have been prepared by the continuous-flow approach. Key technologies to the successes and remaining challenges are discussed. These results exemplified the feasibility of using modern continuous-flow chemistry for complex synthetic targets, and bode well for the future development of integrated, automated artificial synthetic systems. 相似文献
109.
110.
Hui Mei Wenjia Han Jianglin Hu Se Xiao Yizhu Lei Rui Zhang Wanlin Mo Guangxing Li 《应用有机金属化学》2013,27(3):177-183
This work describes a highly efficient unstrained C(sp3)―N bond activation approach for synthesis of N,N‐dimethylacetamide (DMAc) via catalytic carbonylation of trimethylamine using a PdCl2/bipy (bipy = 2,2′‐bipyridine)/Me4NI catalyst system. A low Pd catalyst dosage (1.0 mol%) is sufficient for high selectivity (98.1%) and yield (90.8%), with a turnover number (TON) of 90.0 mmol of DMAc obtained per mmol of PdCl2 employed under mild reaction conditions. The influence of reaction parameters such as catalyst precursor dosage, ligand type and promoter on activity is investigated. This work also discusses in detail the halide promoter's role in the reaction, and provides a plausible mechanism based on the intermediates methyl iodide and acetyl iodide. Analyses indicate that the carbonylation of trimethylamine may proceed through an active intermediate acetyl iodide formed by carbonylation of methyl iodide generated from the decomposition of the promoter Me4NI under reaction conditions. The formation of acetyl iodide favors the cleaving efficiency of the inert unstrained C(sp3)―N bond of trimethylamine. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献