全文获取类型
收费全文 | 1121篇 |
免费 | 71篇 |
国内免费 | 30篇 |
专业分类
化学 | 781篇 |
晶体学 | 7篇 |
力学 | 73篇 |
数学 | 78篇 |
物理学 | 283篇 |
出版年
2023年 | 3篇 |
2022年 | 3篇 |
2021年 | 22篇 |
2020年 | 20篇 |
2019年 | 19篇 |
2018年 | 21篇 |
2017年 | 14篇 |
2016年 | 28篇 |
2015年 | 41篇 |
2014年 | 44篇 |
2013年 | 60篇 |
2012年 | 62篇 |
2011年 | 80篇 |
2010年 | 63篇 |
2009年 | 46篇 |
2008年 | 73篇 |
2007年 | 65篇 |
2006年 | 65篇 |
2005年 | 56篇 |
2004年 | 79篇 |
2003年 | 47篇 |
2002年 | 38篇 |
2001年 | 27篇 |
2000年 | 29篇 |
1999年 | 18篇 |
1998年 | 9篇 |
1997年 | 13篇 |
1996年 | 14篇 |
1995年 | 13篇 |
1994年 | 9篇 |
1993年 | 10篇 |
1992年 | 19篇 |
1991年 | 11篇 |
1990年 | 8篇 |
1989年 | 8篇 |
1988年 | 8篇 |
1987年 | 11篇 |
1986年 | 5篇 |
1985年 | 8篇 |
1984年 | 10篇 |
1983年 | 10篇 |
1982年 | 9篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 5篇 |
1975年 | 2篇 |
1974年 | 4篇 |
排序方式: 共有1222条查询结果,搜索用时 250 毫秒
61.
Simultaneous determination of nine lignans from Schisandra chinensis extract using ultra‐performance liquid chromatography with tandem mass spectrometry in rat plasma,urine, and gastrointestinal tract samples: Application to the pharmacokinetic study of Schisandra chinensis 下载免费PDF全文
You‐Jin Kim Hee Ju Lee Chul Young Kim Sun‐Young Han Young‐Won Chin Young Hee Choi 《Journal of separation science》2014,37(20):2851-2863
The fruit of Schisandra chinensis is a well‐known herbal medicine and dietary supplement due to a variety of biological activities including antihepatotoxic and antihyperlipidemic activities. However, the simultaneous validation methodology and pharmacokinetic investigation of nine lignans of S. chinensis extract in biological samples have not been proved yet. Thus, the present study was undertaken to develop the proper sample preparation method and simultaneous analytical method of schisandrol A, gomisin J, schisandrol B, tigloylgomisin H, angeloylgomisin H, schisandrin A, schisandrin B, gomisin N, and schisandrin C in the hexane‐soluble extract of S. chinensis to apply for the pharmacokinetic study in rats. All intra‐ and interprecisions of nine lignans were below 13.7% and accuracies were 85.1–115% and it is enough to evaluate the pharmacokinetic parameters after both intravenous and oral administration of hexane‐soluble extract of S. chinensis to rats. 相似文献
62.
Sulfur‐containing molecules such as thioethers are commonly found in chemical biology, organic synthesis, and materials chemistry. While many reliable methods have been developed for preparing these compounds, harsh reaction conditions are usually required in the traditional methods. The transition metals have been applied in this field, and the palladium‐catalyzed coupling of thiols with aryl halides and pseudo halides is one of the most important methods in the synthesis of thioethers. Other metals have also been used for the same purpose. Here, we summarize recent efforts in metal‐catalyzed C? S bond cross‐coupling reactions, focusing especially on the coupling of thiols with aryl‐ and vinyl halides based on different metals. 相似文献
63.
Eeray Kim Young-Mi Kim Jongmin Ahn Hee-Sung Chae Young-Won Chin Jinwoong Kim 《Molecules (Basel, Switzerland)》2021,26(12)
Phytochemical investigation on the n-BuOH-soluble fraction of the aerial parts of Epimedium koreanum using the PCSK9 mRNA monitoring assay led to the identification of four previously undescribed acylated flavonoid glycosides and 18 known compounds. The structures of new compounds were elucidated by NMR, MS, and other chemical methods. All isolated compounds were tested for their inhibitory activity against PCSK9 mRNA expression in HepG2 cells. Of the isolates, compounds 6, 7, 10, 15, and 17–22 were found to significantly inhibit PCSK9 mRNA expression. In particular, compound 7 was shown to increase LDLR mRNA expression. Thus, compound 7 may potentially increase LDL uptake and lower cholesterol levels in the blood. 相似文献
64.
Dan Yuan Sharda Yadav Hang T. Ta Hedieh Fallahi Hongjie An Navid Kashaninejad Chin Hong Ooi Nam-Trung Nguyen Jun Zhang 《Electrophoresis》2021,42(21-22):2230-2237
Microfluidic particle focusing has been a vital prerequisite step in sample preparation for downstream particle separation, counting, detection, or analysis, and has attracted broad applications in biomedical and chemical areas. Besides all the active and passive focusing methods in Newtonian fluids, particle focusing in viscoelastic fluids has been attracting increasing interest because of its advantages induced by intrinsic fluid property. However, to achieve a well-defined focusing position, there is a need to extend channel lengths when focusing micrometer-sized or sub-microsized particles, which would result in the size increase of the microfluidic devices. This work investigated the sheathless viscoelastic focusing of particles and cells in a zigzag microfluidic channel. Benefit from the zigzag structure of the channel, the channel length and the footprint of the device can be reduced without sacrificing the focusing performance. In this work, the viscoelastic focusing, including the focusing of 10 μm polystyrene particles, 5 μm polystyrene particles, 5 μm magnetic particles, white blood cells (WBCs), red blood cells (RBCs), and cancer cells, were all demonstrated. Moreover, magnetophoretic separation of magnetic and nonmagnetic particles after viscoelastic pre-focusing was shown. This focusing technique has the potential to be used in a range of biomedical applications. 相似文献
65.
Relaxations in polymer electrolytes were studied in poly(ethylene oxide) and epoxidized natural rubbers both filled with lithium perchlorate. Impedance relaxation was investigated over a wide range of salt concentration at room temperature. Imaginary part of impedance as a function of frequency exhibits generally one maximum and one minimum. These two extreme values rule properties in the DC limit. They can be related to transport properties and degree of dissociation. It turns out that DC conductivity is dominantly ruled by transport coefficient. 相似文献
66.
Upgrade of beamline BL08B at Taiwan Light Source from a photon‐BPM to a double‐grating SGM beamline 下载免费PDF全文
Jih‐Young Yuh Shan‐Wei Lin Liang‐Jen Huang Hok‐Sum Fung Long‐Life Lee Yu‐Joung Chen Chiu‐Ping Cheng Yi‐Ying Chin Hong‐Ji Lin 《Journal of synchrotron radiation》2015,22(5):1312-1318
During the last 20 years, beamline BL08B has been upgraded step by step from a photon beam‐position monitor (BPM) to a testing beamline and a single‐grating beamline that enables experiments to record X‐ray photo‐emission spectra (XPS) and X‐ray absorption spectra (XAS) for research in solar physics, organic semiconductor materials and spinel oxides, with soft X‐ray photon energies in the range 300–1000 eV. Demands for photon energy to extend to the extreme ultraviolet region for applications in nano‐fabrication and topological thin films are increasing. The basic spherical‐grating monochromator beamline was again upgraded by adding a second grating that delivers photons of energy from 80 to 420 eV. Four end‐stations were designed for experiments with XPS, XAS, interstellar photoprocess systems (IPS) and extreme‐ultraviolet lithography (EUVL) in the scheduled beam time. The data from these experiments show a large count rate in core levels probed and excellent statistics on background normalization in the L‐edge adsorption spectrum. 相似文献
67.
Biosynthesis of Streptolidine Involved Two Unexpected Intermediates Produced by a Dihydroxylase and a Cyclase through Unusual Mechanisms 下载免费PDF全文
Dr. Chin‐Yuan Chang Syue‐Yi Lyu Dr. Yu‐Chen Liu Ning‐Shian Hsu Dr. Chih‐Chung Wu Dr. Cheng‐Fong Tang Kuan‐Hung Lin Dr. Jin‐Yuan Ho Dr. Chang‐Jer Wu Dr. Ming‐Daw Tsai Dr. Tsung‐Lin Li 《Angewandte Chemie (International ed. in English)》2014,53(7):1943-1948
Streptothricin‐F (STT‐F), one of the early‐discovered antibiotics, consists of three components, a β‐lysine homopolymer, an aminosugar D ‐gulosamine, and an unusual bicyclic streptolidine. The biosynthesis of streptolidine is a long‐lasting but unresolved puzzle. Herein, a combination of genetic/biochemical/structural approaches was used to unravel this problem. The STT gene cluster was first sequenced from a Streptomyces variant BCRC 12163, wherein two gene products OrfP and OrfR were characterized in vitro to be a dihydroxylase and a cyclase, respectively. Thirteen high‐resolution crystal structures for both enzymes in different reaction intermediate states were snapshotted to help elucidate their catalytic mechanisms. OrfP catalyzes an FeII‐dependent double hydroxylation reaction converting L ‐Arg into (3R,4R)‐(OH)2‐L ‐Arg via (3S)‐OH‐L ‐Arg, while OrfR catalyzes an unusual PLP‐dependent elimination/addition reaction cyclizing (3R,4R)‐(OH)2‐L ‐Arg to the six‐membered (4R)‐OH‐capreomycidine. The biosynthetic mystery finally comes to light as the latter product was incorporation into STT‐F by a feeding experiment. 相似文献
68.
Back Cover: Synthesis,Characterization, Self‐Assembly,Gelation, Morphology and Computational Studies of Alkynylgold(III) Complexes of 2,6‐Bis(benzimidazol‐2′‐yl)pyridine Derivatives (Chem. Eur. J. 32/2014) 下载免费PDF全文
69.
Hexanuclear Gold(I) Phosphide Complexes as Platforms for Multiple Redox‐Active Ferrocenyl Units 下载免费PDF全文
Dr. Terence Kwok‐Ming Lee Dr. Eddie Chung‐Chin Cheng Dr. Nianyong Zhu Prof. Dr. Vivian Wing‐Wah Yam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(1):304-310
The synthesis, X‐ray crystal structures, electrochemical, and spectroscopic studies of a series of hexanuclear gold(I) μ3‐ferrocenylmethylphosphido complexes stabilized by bridging phosphine ligands, [Au6(P?P)n(Fc‐CH2‐P)2][PF6]2 (n=3, P?P=dppm (bis(diphenylphosphino)methane) ( 1 ), dppe (1,2‐bis(diphenylphosphino)ethane) ( 2 ), dppp (1,3‐bis(diphenylphosphino)propane) ( 3 ), Ph2PN(C3H7)‐PPh2 ( 4 ), Ph2PN(Ph‐CH3‐p)PPh2 ( 5 ), dppf (1,1′‐bis(diphenylphosphino)ferrocene) ( 6 ); n=2, P?P=dpepp (bis(2‐diphenylphosphinoethyl)phenylphosphine) ( 7 )), as platforms for multiple redox‐active ferrocenyl units, are reported. The investigation of the structural changes of the clusters has been probed by introducing different bridging phosphine ligands. This class of gold(I) μ3‐ferrocenylmethylphosphido complexes has been found to exhibit one reversible oxidation couple, suggestive of the absence of electronic communication between the ferrocene units through the Au6P2 cluster core, providing an understanding of the electronic properties of the hexanuclear AuI cluster linkage. The present complexes also serve as an ideal system for the design of multi‐electron reservoir and molecular battery systems. 相似文献
70.
Dr. Hong‐Jay Lo M. Sc. Chin‐Yin Lin Dr. Mei‐Chun Tseng Prof. Rong‐Jie Chein 《Angewandte Chemie (International ed. in English)》2014,53(34):9026-9029
A hydroxy‐directed alkylation of an N,N‐diethylarylamide using CIPE‐assisted α‐silyl carbanions (CIPE=complex‐induced proximity effect) has been developed using a simple reagent combination of LDA (lithium diisopropylamide) and chlorosilane. A study of the mechanism, and the application of the procedure to an anionic Snieckus–Fries rearrangement for a highly efficient synthesis of the potent phosphatidylinositol 3‐kinase (PI3K) inhibitor LY294002, are reported. 相似文献