全文获取类型
收费全文 | 20062篇 |
免费 | 3573篇 |
国内免费 | 2908篇 |
专业分类
化学 | 15204篇 |
晶体学 | 342篇 |
力学 | 1169篇 |
综合类 | 203篇 |
数学 | 2526篇 |
物理学 | 7099篇 |
出版年
2024年 | 54篇 |
2023年 | 500篇 |
2022年 | 595篇 |
2021年 | 729篇 |
2020年 | 947篇 |
2019年 | 918篇 |
2018年 | 736篇 |
2017年 | 611篇 |
2016年 | 960篇 |
2015年 | 993篇 |
2014年 | 1165篇 |
2013年 | 1501篇 |
2012年 | 1815篇 |
2011年 | 1800篇 |
2010年 | 1266篇 |
2009年 | 1139篇 |
2008年 | 1306篇 |
2007年 | 1231篇 |
2006年 | 1094篇 |
2005年 | 995篇 |
2004年 | 709篇 |
2003年 | 651篇 |
2002年 | 674篇 |
2001年 | 590篇 |
2000年 | 443篇 |
1999年 | 413篇 |
1998年 | 353篇 |
1997年 | 313篇 |
1996年 | 343篇 |
1995年 | 275篇 |
1994年 | 252篇 |
1993年 | 214篇 |
1992年 | 174篇 |
1991年 | 148篇 |
1990年 | 119篇 |
1989年 | 112篇 |
1988年 | 78篇 |
1987年 | 54篇 |
1986年 | 44篇 |
1985年 | 55篇 |
1984年 | 53篇 |
1983年 | 33篇 |
1982年 | 25篇 |
1981年 | 14篇 |
1980年 | 14篇 |
1979年 | 6篇 |
1978年 | 5篇 |
1977年 | 4篇 |
1973年 | 4篇 |
1957年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Jun‐Ju Xu Da‐Ke Zhao Hong‐Lian Ai Li‐Mei Zhang Shi‐Qing Xie Shu‐Hui Zi Sheng‐Chao Yang Yong Shen 《Helvetica chimica acta》2013,96(11):2155-2159
A further study of the alkaloid constituents of Aconitum forrestii led to the isolation of three new C19‐diterpenoid alkaloids, named 14‐acetoxy‐8‐O‐methylsachaconitine ( 1 ), 14‐acetoxyscaconine ( 2 ), and 8‐O‐ethylcammaconine ( 3 ). Their structures were determined by UV, IR, and MS, 1D‐ and 2D‐NMR analyses. 相似文献
992.
Hongwei Shi Xiangui Huang Guixia Liu Kunqian Yu Congying Xu Weihua Li Bubing Zeng Yun Tang 《International journal of quantum chemistry》2013,113(9):1339-1348
In asymmetric Michael addition between ketones and nitroolefins catalyzed by L ‐proline, we observed that it was benzoic acid or its derivatives rather than other proton acid that could accelerate the reaction greatly, and different benzoic acid derivatives brought different yields. To explain the experimental phenomena, a density functional theory study was performed to elucidate the mechanism of proline‐catalyzed asymmetric Michael addition with benzoic acid. The results of the theoretical calculation at the level of B3LYP/6‐311+G(2df,p)//B3LYP/6‐31G(d) demonstrated that benzoic acid played two major roles in the formation of nitroalkane: assisting proton transfer and activating the nitro group. In the stage of enamine formation from imine, the energy profiles of benzoic acid derivatives were also calculated to investigate the reasons why different benzoic acid derivatives caused different yields. The results demonstrated that the pKa value was the major factor for p‐substituted benzoic acid derivatives to improve the yields, whereas for m/o‐substituted benzoic acid derivatives, both pKa value and electronic and steric effects could significantly increase the yields. The calculated results would be very helpful for understanding the reaction mechanism of Michael addition and provide some insights into the selection of efficient additives for similar experiments. © 2012 Wiley Periodicals, Inc. 相似文献
993.
A series of new dispiropyrrolidine derivatives were synthesized via the three‐component 1,3‐dipolar cycloaddition reaction of azomethine ylides generated in situ by the decarboxylative condensation of acenaphthenequinone and sarcosine or l ‐thioproline with 5‐benzylidene‐1,3‐dimethylpyrimidine‐2,4,6‐trione. The structures of the products were identified by IR, 1H‐NMR, and HRMS spectra. 相似文献
994.
995.
An efficient one‐pot synthesis of spiro[indoline‐3,1′‐pyrazolo[1,2‐b]phthalazine] derivatives via three‐component reaction of phthalhydrazide, isatin, and malononitrile (cyanoacetic ester) is described. This new protocol has the advantages of high efficiency, mild reaction conditions, one‐pot procedure, and convenient operation. 相似文献
996.
A series of novel 5‐aryl‐1‐(aryloxyacetyl)‐3‐(tert‐butyl or phenyl)‐4‐(1H‐1,2,4‐triazol‐1‐yl)‐4,5‐dihydropyrazole 3a – 3n were synthesized by the annulation of 2‐aryloxyacetohydrazides with 3‐aryl‐1‐t‐butyl (or phenyl)‐2‐(1H‐1,2,4‐triazol‐1‐yl)prop‐2‐en‐1‐ones ( 2 ) in the presence of a catalytic amount of acetic acid. Compounds 2 were obtained by the Knoevenagel reactions of 1‐t‐butyl (or phenyl)‐2‐(1H‐1,2,4‐triazol‐1‐yl)ethanone ( 1 ) with aromatic aldehydes in the presence of piperidine. Their structures were confirmed by IR, 1H‐NMR, ESI‐MS, and elemental analyses. The preliminary bioassay indicated that some compounds displayed moderate to excellent fungicidal activity. For example, compounds 3l , 3m , and 3n possessed 100% inhibition against Cercospora arachidicola Hori at the concentration of 50 mg/L. 相似文献
997.
Hemin was physically adsorbed onto porous carbon felt (CF), a microelectrode ensemble of micro-carbon fiber (ca. 7 μm in diameter) and possessing a three-dimensional random structure. The hemin-CF exhibited a well-defined redox wave that is due to Fe(III)/Fe(II) redox process in hemin, with a formal potential of ?0.32 V (vs. Ag/AgCl) in deoxygenated buffer solution of pH 7.0. The surface coverage of the electroactive hemin molecules on the surface of the CF was calculated to be 5.0?×?10?11 mol cm?2, and the apparent heterogeneous electron transfer rate constant is 3.35 s?1. The hemin-CF electrode displays excellent electrocatalytic activity for the reduction of dissolved oxygen (DO), and the magnitude of the cathodic current increases with increasing concentrations of DO in the sample solution. The electrode was used as a flow-through detector for sensitive and rapid consecutive determination of DO. Deoxygenated pH 7.0 solutions were analyzed at a flow rate of 8.0 mL min?1 at an applied potential of ?0.2 V, and highly reproducible cathodic peak current responses to DO were observed in the 0.72 to 13.3 mg L?1 concentration range. The maximum throughput is 170 samples h?1. The hemin-CF-based amperometric flow-sensor was applied to determine the concentration of DO in environmental water samples. Graphical abstract
Hemin was physically adsorbed onto porous carbon felt (CF), a microelectrode ensemble of micro-carbon fiber (ca. 7 μm in diameter). The hemin-CF electrode was used as a flow-through detector for highly sensitive and rapid determination of dissolved oxygen. 相似文献
998.
Molecularly imprinted films with self-supporting property (SS-MIFs) have been prepared by using the strategy of transition layer construction followed by reversible addition-fragmentation chain transfer (RAFT) polymerization. The structure, composition and selectivity of the SS-MIFs as well as the mechanism of mass transfer were characterized by scanning electron microscopy, X-ray diffraction, Fourier transform IR spectrometry, specific surface area analysis, thermogravimetric analysis, and HPLC. Surface area analysis showed the samples possessed specific surface areas as high as 80.5 m2.g?1. This is almost 9 times more than that of the original porous anodic aluminum oxide substrate. Thermogravimetric analysis also showed the samples to be thermally stable up to 350 °C. The separating power was investigated by HPLC and revealed a selective separation effect for the target molecules theobromine. The separation factor is 5.37. Figure
Self-supporting molecularly imprinted films (SS-MIFs) have been prepared by the strategy of transition layer construction followed by reversible addition-fragmentation chain transfer polymerization. The obtained samples had high specific surface areas and good recognition selectivity. This synthesis method is facile and the obtained samples had excellent self-supporting performance and better potential use in chemical separation. 相似文献
999.
A facile and efficient synthesis of 14-aryl or alkyl-14H-dibenzo[a,j]xanthenes has been accomplished by treatment of β-naphthol with aryl or alkyl aldehydes catalyzed by 2-1′-methylimidazolium-3-yl-1-ethyl sulfate in ionic liquid [BMIM][BF4] at 80°C. The luminescence of products was studied in detail. 相似文献
1000.
One‐pot Wittig reactions of ethyl bromoacetate and bromoacetonitrile with aldehydes in the presence of PPh3 and LiOH in water were investigated. Most of the olefination reactions completed within 5–120 min in refluxing water containing 1.2 M LiCl to afford the olefin products in 71–97% yields with 100:0–55:45 ratios of E:Z isomers. 相似文献