全文获取类型
收费全文 | 999篇 |
免费 | 30篇 |
国内免费 | 9篇 |
专业分类
化学 | 387篇 |
晶体学 | 4篇 |
力学 | 22篇 |
数学 | 349篇 |
物理学 | 276篇 |
出版年
2021年 | 4篇 |
2020年 | 13篇 |
2019年 | 12篇 |
2018年 | 15篇 |
2017年 | 14篇 |
2016年 | 28篇 |
2015年 | 13篇 |
2014年 | 24篇 |
2013年 | 54篇 |
2012年 | 47篇 |
2011年 | 55篇 |
2010年 | 23篇 |
2009年 | 25篇 |
2008年 | 51篇 |
2007年 | 54篇 |
2006年 | 56篇 |
2005年 | 54篇 |
2004年 | 37篇 |
2003年 | 27篇 |
2002年 | 28篇 |
2001年 | 14篇 |
2000年 | 25篇 |
1999年 | 11篇 |
1998年 | 11篇 |
1997年 | 12篇 |
1996年 | 19篇 |
1995年 | 12篇 |
1994年 | 21篇 |
1993年 | 17篇 |
1992年 | 20篇 |
1991年 | 12篇 |
1990年 | 12篇 |
1989年 | 7篇 |
1988年 | 6篇 |
1987年 | 10篇 |
1986年 | 5篇 |
1985年 | 19篇 |
1984年 | 21篇 |
1983年 | 14篇 |
1982年 | 15篇 |
1981年 | 17篇 |
1980年 | 11篇 |
1979年 | 14篇 |
1978年 | 9篇 |
1977年 | 11篇 |
1976年 | 7篇 |
1975年 | 17篇 |
1974年 | 9篇 |
1973年 | 6篇 |
1967年 | 3篇 |
排序方式: 共有1038条查询结果,搜索用时 31 毫秒
51.
Comstock MJ Levy N Kirakosian A Cho J Lauterwasser F Harvey JH Strubbe DA Fréchet JM Trauner D Louie SG Crommie MF 《Physical review letters》2007,99(3):038301
We have observed reversible light-induced mechanical switching for individual organic molecules bound to a metal surface. Scanning tunneling microscopy (STM) was used to image the features of individual azobenzene molecules on Au(111) before and after reversibly cycling their mechanical structure between trans and cis states using light. Azobenzene molecules were engineered to increase their surface photomechanical activity by attaching varying numbers of tert-butyl (TB) ligands ("legs") to the azobenzene phenyl rings. STM images show that increasing the number of TB legs "lifts" the azobenzene molecules from the substrate, thereby increasing molecular photomechanical activity by decreasing molecule-surface coupling. 相似文献
52.
Koranit Shlosman Ran Y. Suckeveriene Jasmine Rosen‐Kligvasser Roza Tchoudakov Evgeni Zelikman Raphael Semiat Moshe Narkis 《先进技术聚合物》2014,25(12):1484-1491
This paper summarizes a study of controlled migration of an antifog (AF) additive; sorbitan monooleate (SMO), from linear low density polyethylene (LLDPE) films containing a compatibilizer, LLDPE grafted maleic anhydride (LLDPE‐g‐MA). LLDPE/LLDPE‐g‐MA/SMO blends were prepared by melt compounding. Bulk and surface properties of compression molded LLDPE films containing SMO and LLDPE‐g‐MA were characterized using Fourier transform infrared spectroscopy and contact angle measurements. Thermal properties were investigated using a thermal gravimetric analyzer. Diffusion coefficient (D) was calculated, and AF properties were characterized using a “hot fog” test. Compression molded films were characterized for their morphology using high‐resolution scanning electron microscopy, and rheological properties were measured using a parallel‐plate rotational rheometer. It was found that the LLDPE/LLDPE‐g‐MA/SMO systems are characterized by a slower SMO migration rate, a lower diffusion coefficient, and lower contact angle values compared with LLDPE/SMO blends. These results are well correlated with results of a hot fog test. Morphological studies revealed a very fine dispersion of SMO in the LLDPE films, when 3 phr LLDPE‐g‐MA was combined with 1 phr SMO. Thermal analysis results show that the incorporation of 3 phr LLDPE‐g‐MA and 1 phr SMO significantly increases the decomposition temperature of the blend at T > 400°C. At high shear rates, the LLDPE blends show that the AF and the compatibilizer have a lubrication effect on LLDPE. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
53.
Palladium‐Catalyzed Stereoselective Intramolecular Oxidative Amidation of Alkenes in the Synthesis of 1,3‐ and 1,4‐Amino Alcohols and 1,3‐Diamines
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Prof. Dr. Andrei V. Malkov Dr. Darren S. Lee Dr. Maciej Barłóg Dr. Mark R. J. Elsegood Prof. Dr. Pavel Kočovský 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(17):4901-4905
An efficient and practical Pd‐catalyzed intramolecular oxidative allylic amidation provides facile access to derivatives of 1,3‐ and 1,4‐amino alcohols and 1,3‐diamines. The method operates under mild reaction conditions (RT) with molecular oxygen (1 atm) as the sole reoxidant of Pd. Excellent diastereoselectivities were attained with substrates bearing a secondary stereogenic center 相似文献
54.
Modification of Extended Open Frameworks with Fluorescent Tags for Sensing Explosives: Competition between Size Selectivity and Electron Deficiency
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Bappaditya Gole Dr. Arun Kumar Bar Prof. Partha Sarathi Mukherjee 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(8):2276-2291
Three new electron‐rich metal–organic frameworks ( MOF‐1 – MOF‐3 ) have been synthesized by employing ligands bearing aromatic tags. The key role of the chosen aromatic tags is to enhance the π‐electron density of the luminescent MOFs. Single‐crystal X‐ray structures have revealed that these MOFs form three‐dimensional porous networks with the aromatic tags projecting inwardly into the pores. These highly luminescent electron‐rich MOFs have been successfully utilized for the detection of explosive nitroaromatic compounds (NACs) on the basis of fluorescence quenching. Although all of the prepared MOFs can serve as sensors for NACs, MOF‐1 and MOF‐2 exhibit superior sensitivity towards 4‐nitrotoluene (4‐NT) and 2,4‐dinitrotoluene (DNT) compared to 2,4,6‐trinitrotoluene (TNT) and 1,3,5‐trinitrobenzene (TNB). MOF‐3 , on the other hand, shows an order of sensitivity in accordance with the electron deficiencies of the substrates. To understand such anomalous behavior, we have thoroughly analyzed both the steady‐state and time‐resolved fluorescence quenching associated with these interactions. Determination of static Stern–Volmer constants (KS) as well as collisional constants (KC) has revealed that MOF‐1 and MOF‐2 have higher KS values with 4‐NT than with TNT, whereas for MOF‐3 the reverse order is observed. This apparently anomalous phenomenon was well corroborated by theoretical calculations. Moreover, recyclability and sensitivity studies have revealed that these MOFs can be reused several times and that their sensitivities towards TNT solution are at the parts per billion (ppb) level. 相似文献
55.
Carlos Eduardo Barão Leandro Daniel de Paris João Henrique Dantas Matheus Mendonça Pereira Lucio Cardozo Filho Heizir Ferreira de Castro Gisella Maria Zanin Flavio Faria de Moraes Cleide Mara Faria Soares 《Applied biochemistry and biotechnology》2014,172(1):263-274
The use of lipases in industrial processes can result in products with high levels of purity and at the same time reduce pollutant generation and improve both selectivity and yields. In this work, lipase from Thermomyces lanuginosus was immobilized using two different techniques. The first involves the hydrolysis/polycondensation of a silica precursor (tetramethoxysilane (TMOS)) at neutral pH and ambient temperature, and the second one uses tetraethoxysilane (TEOS) as the silica precursor, involving the hydrolysis and polycondensation of the alkoxide in appropriate solvents. After immobilization, the enzymatic preparations were dried using the aerogel and xerogel techniques and then characterized in terms of their hydrolytic activities using a titrimetric method with olive oil and by the formation of 2-phenylethyl acetate in a transesterification reaction. The morphological properties of the materials were characterized using scanning electron microscopy, measurements of the surface area and pore size and volume, thermogravimetric analysis, and exploratory differential calorimetry. The results of the work indicate that the use of different silica precursors (TEOS or TMOS) and different drying techniques (aerogel or xerogel) can significantly affect the properties of the resulting biocatalyst. Drying with supercritical CO2 provided higher enzymatic activities and pore sizes and was therefore preferable to drying, using the xerogel technique. Thermogravimetric analysis and differential scanning calorimetry analyses revealed differences in behavior between the two biocatalyst preparations due to the compounds present. 相似文献
56.
57.
Wan Yong Feng Moshe Goldenberg Chava Lifshitz 《Journal of the American Society for Mass Spectrometry》1994,5(8):695-703
Thermal reactions of proton-bound dimers, (CH3CN)2H +, (CH3OCH3)2H +, and (CH3COCH3)2H+, were studied using a selected ion flow tube. Reactions observed include association, switching, and proton transfer. The association channel was observed only for base molecules that had hydrogen bonding protons such as NH3, CH3NH2, (CH3)2NH, and CH3OH. An association-insertion mechaniSoc was proposed in which the central proton of the symmetrically bound dimers is replaced by a protonated base, for example, NH 4 + . These reactions are relatively slow, which demonstrates a central barrier along the potential energy surface. Ether-containing dimers do not demonstrate this insertion reaction, except for diethers, for example, CH3OCH2CH2OCH3, which can form stable bicyclic structures. Dimers such as (HCOOH)2H+, which possess hydrogen bonding protons in the periphery, undergo switching reactions with ammonia and no insertion. 相似文献
58.
59.
60.
In this paper we study a family of stochastic orders of random variables defined via the comparison of their percentile residual life functions. Some interpretations of these stochastic orders are given, and various properties of them are derived. The relationships to other stochastic orders are also studied. Finally, some applications in reliability theory and finance are described. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献