全文获取类型
收费全文 | 22406篇 |
免费 | 2198篇 |
国内免费 | 6443篇 |
专业分类
化学 | 28380篇 |
晶体学 | 411篇 |
力学 | 128篇 |
综合类 | 185篇 |
数学 | 101篇 |
物理学 | 1842篇 |
出版年
2024年 | 9篇 |
2023年 | 205篇 |
2022年 | 315篇 |
2021年 | 586篇 |
2020年 | 836篇 |
2019年 | 696篇 |
2018年 | 711篇 |
2017年 | 785篇 |
2016年 | 1110篇 |
2015年 | 1087篇 |
2014年 | 1372篇 |
2013年 | 2326篇 |
2012年 | 1607篇 |
2011年 | 1655篇 |
2010年 | 1394篇 |
2009年 | 1593篇 |
2008年 | 1642篇 |
2007年 | 1735篇 |
2006年 | 1738篇 |
2005年 | 1657篇 |
2004年 | 1585篇 |
2003年 | 1336篇 |
2002年 | 814篇 |
2001年 | 561篇 |
2000年 | 464篇 |
1999年 | 415篇 |
1998年 | 364篇 |
1997年 | 406篇 |
1996年 | 314篇 |
1995年 | 327篇 |
1994年 | 288篇 |
1993年 | 275篇 |
1992年 | 260篇 |
1991年 | 138篇 |
1990年 | 93篇 |
1989年 | 88篇 |
1988年 | 73篇 |
1987年 | 41篇 |
1986年 | 28篇 |
1985年 | 36篇 |
1984年 | 28篇 |
1983年 | 10篇 |
1982年 | 9篇 |
1981年 | 9篇 |
1980年 | 7篇 |
1978年 | 2篇 |
1976年 | 3篇 |
1975年 | 4篇 |
1974年 | 2篇 |
1968年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
11.
Qianqian Fan Zirui Liu Feng Qiu Prof. Yong Mao Prof. Qingju Liu Prof. Longzhou Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(63):e202202700
The artificially accurate design of nonmetal electrocatalysts’ active site has been a huge challenge because no pure active species with the specific structure could be strictly controlled by traditional synthetic methods. Species with a multiconfiguration in the catalyst hinder identification of the active site and the subsequent comprehension of the reaction mechanism. We have developed a novel electro-assisted molecular assembly strategy to obtain a pure pentagon ring on perfect graphene avoiding other reconstructed structures. More importantly, the active atom was confirmed by the subtle passivation process as the topmost carbon atom. Recognition of the carbon-defect electrocatalysis reaction mechanism was first downsized to the single-atom scale from the experimental perspective. It is expected that this innovative electro-assisted molecular assembly strategy could be extensively applied in the active structure-controlled synthesis of nonmetal electrocatalysts and verification of the exact active atom. 相似文献
12.
13.
Kalina Mambourg Laurie Bodart Nikolay Tumanov Steve Lanners Johan Wouters 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(3):205-211
The condensation reaction of 2‐mercapto‐3‐methoxybenzaldehyde with 3‐aminopyridine afforded an unexpected N‐alkylated [1,5]dithiocine instead of the N‐salicylideneaniline. The proposed mechanism for this condensation involves a strong intramolecular hydrogen bond between the thiol and the amine groups, leading to a second condensation. The corresponding product, i.e. 4,10‐dimethoxy‐13‐(pyridin‐3‐yl)‐6H,12H‐6,12‐epiminodibenzo[b,f][1,5]dithiocine methanol 0.463‐solvate, C21H18N2O2S2·0.463CH3OH, was characterized by single‐crystal X‐ray diffraction analysis. The supramolecular structure shows π–π stacking and S…S interactions in the crystal packing. Within the asymmetric unit, two geometries of the N atom are observed. Although a planar geometry should be expected, a pyramidal one is observed due to the crystal packing. The presence of the two geometries was further supported by density functional theory (DFT) calculations that show an electronic energy difference of less than 2 kJ mol?1 between the two conformers. 相似文献
14.
Zhaohui Zhang Hui Liu Qingzhu Sun Feng Shao Qingyan Pan Prof. Tao Zhuang Prof. Yingjie Zhao 《ChemistryOpen》2020,9(3):381-385
A fluorescent monolayered two-dimensional polymer (2DP) containing both tetraphenylethylene (TPE) and imine linkages is synthesized at air-water interface using the Langmuir-Blodgett method. We designed TPE-based monomers with long distances between the TPE and the imine linkages to avoid the charge transfer and therefore keep the fluorescence. A monolayered 2DP provided with more than 104 μm2 in domain size and around 0.8 nm thickness was obtained through a successive Schiff base reaction at air-water interface. The nanostructures and fluorescent property of 2DP films were characterized by optical microscopy, SEM, TEM, AFM and fluorescence spectrum. Most importantly, the tip-enhanced Raman spectroscopy (TERS) was utilized here to confirm the success of the polycondensation of monolayered 2DP. 相似文献
15.
Haruka Takeuchi Prof. Dr. Shinsuke Inuki Kohei Nakagawa Takaaki Kawabe Dr. Atsuhiko Ichimura Prof. Dr. Shinya Oishi Prof. Dr. Hiroaki Ohno 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(47):21396-21401
We report herein a nonbiomimetic strategy for the total synthesis of the plicamine-type alkaloids zephycarinatines C and D. The key feature of the synthesis is a stereoselective reductive radical ipso-cyclization using visible-light-mediated photoredox catalysis. This cyclization enabled the construction of a 6,6-spirocyclic core structure through the addition of a carbon-centered radical onto the aromatic ring. Biological evaluation of zephycarinatines and their derivatives revealed that the synthetic derivative with a keto group displays moderate inhibitory activity against LPS-induced NO production. This approach could offer future opportunities to expand the chemical diversity of plicamine-type alkaloids as well as providing useful intermediates for their syntheses. 相似文献
16.
17.
LI Yuan LI Ruizhe LI Zhenhua WEI Weiqin OUYANG Shuxin YUAN Hong ZHANG Tierui 《高等学校化学研究》2020,36(6):1006-1012
Photothermal Fischer-Tropsch synthesis(FTS) has been extensively studied, but few reports were focused on systematically exploring the influence of support on catalytic performance. Herein, a series of Fe5C2-based catalysts with different supports was fabricated via a one-step wet-chemical method for photothermal conversion of syngas to lower olefins. Under light irradiation, the optimized Fe5C2/α-Al2O3 catalyst demonstrated remarkable photothermal FTS activity, delivering selectivity to lower olefins of 50.3% with a CO conversion rate of 52.5%. Characterization studies using X-ray diffraction and Mössbauer spectroscopy analysis revealed that the active catalyst mainly contained Fe5C2 nanoparticles on α-Al2O3 support. It was found that the weak interaction between active phase and α-Al2O3 could promote the formation of Fe5C2, which contributed to the high selectivity to lower olefins. 相似文献
18.
Ajay Gupta Fillip Kumar Sarkar Rajib Sarkar Ramen Jamatia Chang Yeon Lee Gajendra Gupta Amarta Kumar Pal 《应用有机金属化学》2020,34(9):e5782
Magnetically retrieval CuFe2O4@MIL-101(Cr) metal–organic framework was successfully prepared from easily available starting materials and characterized using various spectroscopic and analytical techniques such as powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray, transmission electron microscopy, elemental mapping, Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller, vibrating sample magnetometer, and inductively coupled plasma optical emission spectroscopy. The catalyst was then used in the synthesis of benzodiazepines containing a triazole moiety in water. The advantages of this protocol include high yields, reusability of the catalyst, and gram-scale synthesis. 相似文献
19.
Immobilization of metal ions onto inorganic supports has very interesting biological, industrial, and catalysis applications. In this study, CoFe2O4@SiO2@PUF@Zn(OAc)2 nanostructure was successfully fabricated by immobilization of zinc acetate on the surface of poly(urea-formaldehyde) supported on magnetic CoFe2O4@SiO2 nanoparticles through a layer-by-layer assembly. The structure of hybrid nanoparticles was characterized by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, energy-dispersive X-ray spectroscopy, inductively coupled plasma atomic emission spectroscopy, vibrating sample magnetometry, Brunauer–Emmett–Teller surface area analysis, scanning electron microscopy, and transmission electron microscopy. Zinc-poly(urea-formaldehyde) supported on magnetic nanoparticles (MNPs@SiO2@PUF@Zn) was successfully used for the synthesis of spirooxindolopyran and spirooxindoloxanthene derivatives in aqueous medium as an environmentally benign condition. High yields, short reaction times, green solvent, reusability without significant reduction in catalytic activity, and simple separation of the catalyst using an external magnet along with environmental compatibility are some benefits of this procedure. 相似文献
20.
Qianwen Deng Zhen Tian Xiaomin Wang Zhewei Yang Yucheng Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(3):650-658
Zinc–cobalt double-metal sulfides (ZCS) as Faradic electrode materials with high energy density have great potential for supercapacitors, but their poor transfer efficiency for electrons and ions hinders their electrochemical response. Herein, ZnCo2(CO3)1.5(OH)3@ZCS microflower hybrid arrays consisting of thin nanolayer petals were anchored on three-dimensional graphene (ZnCo2(CO3)1.5(OH)3@ZCS/3DG) by a simple hydrothermal method and additional ion-exchange process. A ZnCo2(CO3)1.5(OH)3@ZCS/3DG electrode delivered high capacitance (2228 F g−1 at 1 A g−1) and long cycling life (85.7 % retention after 17 000 cycles), which are ascribed to the multicomponent structural design. The 3DG conductive substrate improves the electron-transfer dynamics of the electrode material. Meanwhile, the microflowers consisting of thin nanolayer petals could not only provide many active sites for ions to improve the capacitance, but also alleviate the volume expansion to ensure the structural stability. Furthermore, an all-solid-state asymmetric supercapacitor based on a ZnCo2(CO3)1.5(OH)3@ZCS/3DG electrode achieved a high energy density of 27 W h kg−1 at 528.3 W kg−1 and exhibits exceptional cyclic stability for 23 000 cycles. Its ability to light a blue LED for 9 min verified the feasibility of its application for energy storage devices. 相似文献