全文获取类型
收费全文 | 257804篇 |
免费 | 4601篇 |
国内免费 | 1727篇 |
专业分类
化学 | 143272篇 |
晶体学 | 3435篇 |
力学 | 9954篇 |
综合类 | 106篇 |
数学 | 30827篇 |
物理学 | 76538篇 |
出版年
2020年 | 2303篇 |
2019年 | 2345篇 |
2018年 | 3008篇 |
2017年 | 3074篇 |
2016年 | 4704篇 |
2015年 | 3268篇 |
2014年 | 4526篇 |
2013年 | 10815篇 |
2012年 | 9456篇 |
2011年 | 11371篇 |
2010年 | 7926篇 |
2009年 | 7512篇 |
2008年 | 10533篇 |
2007年 | 10535篇 |
2006年 | 9938篇 |
2005年 | 9089篇 |
2004年 | 8073篇 |
2003年 | 7029篇 |
2002年 | 6880篇 |
2001年 | 7498篇 |
2000年 | 5725篇 |
1999年 | 4155篇 |
1998年 | 3467篇 |
1997年 | 3418篇 |
1996年 | 3518篇 |
1995年 | 3084篇 |
1994年 | 3209篇 |
1993年 | 3053篇 |
1992年 | 3354篇 |
1991年 | 3244篇 |
1990年 | 3063篇 |
1989年 | 2936篇 |
1988年 | 2855篇 |
1987年 | 2804篇 |
1986年 | 2804篇 |
1985年 | 3750篇 |
1984年 | 3799篇 |
1983年 | 3170篇 |
1982年 | 3428篇 |
1981年 | 3194篇 |
1980年 | 2967篇 |
1979年 | 3152篇 |
1978年 | 3337篇 |
1977年 | 3369篇 |
1976年 | 3379篇 |
1975年 | 3107篇 |
1974年 | 3202篇 |
1973年 | 3210篇 |
1972年 | 2459篇 |
1971年 | 1998篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
101.
Thomas Wittmann Dr. Renée Siegel Nele Reimer Dr. Wolfgang Milius Prof. Dr. Norbert Stock Prof. Dr. Jürgen Senker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):314-323
The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH2 by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N2 and H2O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m2 g?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with 1H‐27Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking. 相似文献
102.
103.
104.
Journal of Structural Chemistry - An analysis is presented for the results obtained in the studies initiated by A. E. Shvelashivili, Corresponding Member, Academy of Sciences of Georgia, and... 相似文献
105.
106.
Facile non‐lithographic route to highly aligned silica nanopatterns using unidirectionally aligned polystyrene‐block‐polydimethylsiloxane films
下载免费PDF全文
![点击此处可从《Journal of Polymer Science.Polymer Physics》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Zhe Qiang Maurice L. Wadley Bryan D. Vogt Kevin A. Cavicchi 《Journal of Polymer Science.Polymer Physics》2015,53(15):1058-1064
Thin films (monolayer and bilayer) of cylinder forming polystyrene‐block‐polydimethylsiloxane (PS‐b‐PDMS) were shear aligned by the swelling and deswelling of a crosslinked PDMS pad that was physically adhered to the film during solvent vapor annealing. The nanostructures formed by self‐assembly were exposed to ultraviolet‐ozone to partially oxidize the PDMS, followed by calcination in air at 500 °C. In this process, the PS segments were fully decomposed, while the PDMS yielded silica nanostructures. The highly aligned PDMS cylinders were thus deposited as silica nanolines on the silicon substrate. Using a bilayer film, the center‐to‐center distance of these features were effectively halved from 38 to 19 nm. Similarly, by sequential shear‐alignment of two distinct layers, a rhombic array of silica nanolines was fabricated. This methodology provides a facile route to fabricating complex topographically patterned nanostructures. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1058–1064 相似文献
107.
Pan Huang Dawen Xu Robert M. Reich Felix Kaiser Boping Liu Fritz E. Kühn 《Tetrahedron letters》2019,60(24):1574-1577
A first example of an Et2Zn mediated silylation of 1-aklynes is reported. A series of functional groups are tolerated in this reaction. Mechanistic studies support Zn alkynilides as intermediates in the reaction. This reaction protocol provides a practical method for the preparation of alkynylsilanes and expands the application of organometallic zinc in organic synthesis. 相似文献
108.
Guangrui Chen Yuxing Yan Dr. Jie Wang Prof. Yong Sik Ok Guiyuan Zhong Prof. Bu Yuan Guan Prof. Yusuke Yamauchi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(44):19831-19836
Mesoporous core–shell nanostructures with controllable ultra-large open channels in their nanoshells are of great interest. However, soft template-directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored coating of hierarchically macro-/mesoporous polymer and carbon shells, possessing highly accessible radial channels with extremely wide pore size distribution from ca. 10 nm to ca. 200 nm, on diverse functional materials. This strategy creates opportunities to tailor the interfacial assembly of irregular mesostructured nanounits on core materials and generate various core–shell nanomaterials with controllable pore architectures. The obtained Fe,N-doped macro-/mesoporous carbon nanoshells show enhanced electrochemical performance for the oxygen reduction reaction in alkaline condition. 相似文献
109.
Vanessa R. Machado Louis P. Sandjo Giovanni L. Pinheiro Milene H. Moraes Mario Steindel Moacir G. Pizzolatti 《Natural product research》2018,32(3):275-281
The natural product lupeol 1 was isolated from aerial parts of Vernonia scorpioides with satisfactory yield, which made it viable to be used as starting material in semisynthetic approach. Ten lupeol derivatives 2–11 were prepared by classical procedures. Including, five new esters derivatives 7–11, which were obtained by structural modifications in the isopropylidene fragment. All semisynthetic compounds and lupeol 1–11 were confirmed by 1H NMR, 13C NMR and HRMS. Their antiprotozoal activity was evaluated in vitro against L. amazonensis and T. cruzi. Derivative 6 showed the best antitrypanosomal activity (IC50 = 12.48 μg/mL) and the lowest cytotoxic derivative (CC50 = 161.50 μg/mL). The mechanism of action of the most active derivatives (4, 6 and 11) is not dependent from the enzyme trypanothione reductase. 相似文献
110.
In this study, stoichiometric protonation constants of L-tyrosine, L-cysteine, L-tryptophane, L-lysine, and L-histidine, and
their methyl and ethyl esters in water and ethanol–water mixtures of 30, 50, and 70% ethanol (v/v), were determined potentiometrically
using a combined pH electrode system calibrated as the concentration of hydrogen ion. Titrations were performed at 25∘C and the ionic strength of the medium was maintained at 0.10 mol⋅L−1 using sodium chloride. Protonation constants were calculated by using the BEST computer program. The effect of solvent composition
on the protonation constants is discussed. The log10 K2 values of esters generally decreased with increasing ethanol content. However, the log10 K1 values of the esters of L-tyrosine, L-cysteine, and L-tryptophane were found to increase with increasing ethanol content
in contrast those of L-lysine and L-histidine esters. 相似文献