全文获取类型
收费全文 | 498篇 |
免费 | 35篇 |
国内免费 | 39篇 |
专业分类
化学 | 393篇 |
晶体学 | 7篇 |
力学 | 30篇 |
综合类 | 4篇 |
数学 | 20篇 |
物理学 | 118篇 |
出版年
2024年 | 1篇 |
2023年 | 15篇 |
2022年 | 11篇 |
2021年 | 21篇 |
2020年 | 19篇 |
2019年 | 26篇 |
2018年 | 23篇 |
2017年 | 19篇 |
2016年 | 25篇 |
2015年 | 20篇 |
2014年 | 25篇 |
2013年 | 40篇 |
2012年 | 47篇 |
2011年 | 41篇 |
2010年 | 26篇 |
2009年 | 31篇 |
2008年 | 27篇 |
2007年 | 22篇 |
2006年 | 28篇 |
2005年 | 18篇 |
2004年 | 16篇 |
2003年 | 11篇 |
2002年 | 6篇 |
2001年 | 8篇 |
2000年 | 8篇 |
1999年 | 3篇 |
1998年 | 3篇 |
1997年 | 8篇 |
1996年 | 3篇 |
1995年 | 4篇 |
1994年 | 5篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 2篇 |
排序方式: 共有572条查询结果,搜索用时 31 毫秒
11.
Abstract— Several ozone-biomolecule reactions have previously been shown to generate singlet oxygen in high yields. For some of these orone-biomolecule reactions, we now show that the apparent singlet-oxygen yields determined from measurements of 1270 nm chemiluminescence were artifactually elevated by production of gas-phase singlet oxygen. The gas-phase singlet oxygen results from the reaction of gas-phase ozone with biomolecules near the surface of the solution. Through the use of a flow system that excludes air from the reaction chamber, accurate singlet-oxygen yields can be obtained. The revised singlet-oxygen yields (mol 1 O2 per mol O3 ) for the reactions of ozone with cysteine, reduced glutathione, NADH, NADPH, human albumin, methionine, uric acid and oxidized glutathione are 0.23 ± 0.02, 0.26 ± 0.02, 0.48 ± 0.04, 0.41 ± 0.01, 0.53 ± 0.06, 1.11 ± 0.04, 0.73 ± 0.05 and 0.75 ± 0.01, respectively. These revised singlet-oxygen yields are still substantial. 相似文献
12.
Effects of simultaneously doped and deposited Ag on the photocatalytic activity and surface states of TiO2 总被引:8,自引:0,他引:8
Ag-TiO2 catalysts with different Ag contents were prepared via a sol-gel method in the absence of light. Based on the characterizations of XRD, photoluminescence (PL), surface photovoltage spectroscopy (SPS), field-induced surface photovoltage spectroscopy (FISPS), and XPS as well as the evaluation of the photocatalytic activity for degrading rhodamine B(RhB) solutions, it was found that the Ag dopant promoted the phase transformation as well as had an inhibition effect on the growth of anatase crystallite. The PL and SPS intensities were decreased with increasing Ag content, indicating that the Ag dopant could effectively inhibit the recombination of the photoinduced electrons and holes. However, the active sites capturing the photoinduced electrons reduced, while the Ag content exceeded 5 mol %. At rather low Ag dopant concentrations, the migration and diffusion of Ag+ ions were predominant, while at rather high Ag dopant concentrations, the migration, diffusion, and reduction of Ag ions simultaneously occurred. The Ag-TiO2 photocatalysts with appropriate content of Ag (Ag species concentration is from about 3 to 5 mol %) possessed abundant electron traps so as to be favorable for the separation of the photoinduced electron-hole pairs, which could greatly enhance the activity of the photocatalysts. From the results of FISPS measurements, it could be found that the impurity bands and abundant surface states were introduced into the interfacial layer of TiO2 because of Ag simultaneously doping and depositing, which could improve the absorption capability for visible light of the photocatalysts. 相似文献
13.
Silver,iron, and nickel immobilized on hydroxyapatite‐core‐shell γ‐Fe2O3 MNPs catalyzed one‐pot five‐component reactions for the synthesis of tetrahydropyridines by tandem condensation of amines,aldehydes, and methyl acetoacetate
下载免费PDF全文
![点击此处可从《应用有机金属化学》网站下载免费的PDF全文](/ch/ext_images/free.gif)
In this study, Ag, Ni2+, and Fe2+ immobilized on hydroxyapatite‐core‐shell γ‐Fe2O3 nanoparticles (γ‐Fe2O3@HAp‐Ag, γ‐Fe2O3@HAp‐Ni2+, and γ‐Fe2O3@HAp‐Fe2+) as a new and reusable Lewis acid magnetic nanocatalyst was successfully synthesized and reported for an atom economic, extremely facile, and environmentally benign procedure for the synthesis of highly functionalized tetrahydropyridines derivatives 4a‐t is described by one‐pot five‐component reaction of 2 equiv of aldehydes 1 , 2 equiv of amines 2 , and 1 equiv of methyl acetoacetate 3 in EtOH at room temperature in good to high yields and short reaction time. The presented methodology offers several advantages such as easy work‐up procedure, reusability of the magnetic nanocatalyst, operational simplicity, green synthesis avoiding toxic reagents and solvent, mild reaction conditions, and no tedious column chromatographic separation. 相似文献
14.
15.
Weihua Zhou Zoukangning Yu Ming Zhang Lifu Zhang Jingping Yin Qingyun Ai Liqiang Huang Feng Liu Jianrong Zeng Yiwang Chen 《Journal of Polymer Science.Polymer Physics》2019,57(14):941-951
In order to explore the role of fluorine atoms on photostability as well as morphology control of active layer in the presence of 1,4‐butanedithiol (BT), the four polymers with or without fluorine atoms in the backbones including polythieno[3,4‐b]thiophene/benzodithiophene, poly[(4,8‐bis‐(2‐ethylhexyloxy)‐benzo(1,2‐b:4,5‐b9)dithiophene)‐2,6‐diyl‐alt‐(4‐(2‐ethylhexanoyl)‐thieno[3,4‐b]thiophene‐)‐2‐6‐diyl)], poly[4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b;4,5‐b′]dithiophene‐2,6‐diyl‐alt‐(4‐(2‐ethylhexyl)‐3‐fluorothieno[3,4‐b]thiophene‐)‐2‐carboxylate‐2‐6‐diyl)], and poly[4,8‐bis‐(2‐ethyl‐hexyl‐thiophene‐5‐yl)‐benzo[1,2‐b:4,5‐b0]dithiophene‐2,6‐diyl]‐alt‐[2‐(20‐ethyl‐hexanoyl)‐thieno [3,4‐b]thiophen‐4,6‐diyl] were selected for comparison. It is found that the specimens containing fluorine atoms in polymer backbones showed of higher stability after illumination for 1 h in the presence of BT additive, contributing to the higher domain purity. The specific interaction between fluorine atoms and thiol groups was demonstrated by the appearance of novel absorption peak at 2663.1 cm?1, in addition to the broadening of peak at 2556.2 cm?1 ascribing to S? H stretching vibration as confirmed by Fourier transform infrared (FTIR) spectroscopy. The finding may guide the accurate use of thiols as effective solvent additive in morphology and stability optimization. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 941–951 相似文献
16.
Guangzhou Lu Limin Yang Liqiang Wu 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3):403-408
Abstract A simple, inexpensive, and efficient one-pot synthesis of 2-arylthiazoline derivatives under solvent-free conditions using a catalytic amount of 1-butyl-3-methylimidazolium tribromide with excellent product yields is reported. This methodology provides easy, quantitative access to various 2-arylthiazoline derivatives, using environmentally benign 1-butyl-3-methylimidazolium tribromide as a catalyst. 相似文献
17.
We report an original way to prepare luminescent glass–ceramic microrods containing Eu3+ doped BaF2 nanocrystals by sol–gel chemistry within the pores of a polycarbonate template membrane. Structural characterization by scanning
electron microscopy and X-ray diffraction has shown the formation of glass–ceramic microrods with 0.8-m diameter of and 10 μm length in which BaF2 nanocrystals of about 30 nm size are embedded. Photoluminescence measurements have indicated the incorporation of Eu3+ ions inside the BaF2 nanocrystals in a broad range of sites with low coordination symmetry. The comparison made with the bulk glass–ceramic indicated
an influence of the dimensional constraints imposed by the membrane pores during xerogel formation and subsequent glass ceramization. 相似文献
18.
Shyamaprosad Goswami Abhishek Manna Sima Paul Avijit K. Das Prasanta K. Nandi Anup Kumar Maity Partha Saha 《Tetrahedron letters》2014
5(Benzothiazol-2-yl)-4-hydroxyisophthalaldehyde (BHI), an intense ESIPT containing molecule in mixed media loses its properties due to resonance-assisted H-bond (RAHB) in absolute water. Due to resonance-assisted H-bond the o-aldehyde is more reactive than the other one. With addition of cysteine/homocysteine into this solution the o-aldehyde group gets transformed into thiazolidine/thiazine ring, respectively, and the phenolic proton becomes free enough for transfer to nitrogen of the benzothiazole ring in excited state, that is, the ESIPT of BHI is turned on. Thus we can detect cysteine/homocysteine in water as well as in live cells. 相似文献
19.
Liqiang Wu Limin Yang Lizhen Fang Chunguang Yang Fulin Yan 《Phosphorus, sulfur, and silicon and the related elements》2013,188(10):2159-2164
A mild, simple, and efficient method for the synthesis of thiiranes from epoxides using a catalytic amount of silica chloride under solvent-free conditions has been developed. Experimental simplicity, simple work-up procedure, and solvent-free reaction conditions are important features of the present protocol. 相似文献
20.
Xiaojuan Yang Liqiang Wu 《Phosphorus, sulfur, and silicon and the related elements》2013,188(10):1327-1333
Abstract A simple and efficient synthetic protocol has been developed for the synthesis of 3-substituted-2H-1,4-benzothiazines by using bioglycerol-based sulfonic acid-functionalized carbon catalyst, devoid of corrosive acidic and basic reagents. The developed method has the advantages of good to excellent yields, short reaction times, operational simplicity, and a recyclable catalyst. 相似文献