首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   1259篇
  免费   53篇
  国内免费   8篇
化学   819篇
晶体学   33篇
力学   58篇
综合类   2篇
数学   168篇
物理学   240篇
  2023年   8篇
  2022年   48篇
  2021年   46篇
  2020年   37篇
  2019年   33篇
  2018年   42篇
  2017年   28篇
  2016年   61篇
  2015年   42篇
  2014年   65篇
  2013年   115篇
  2012年   88篇
  2011年   106篇
  2010年   70篇
  2009年   60篇
  2008年   54篇
  2007年   72篇
  2006年   53篇
  2005年   50篇
  2004年   29篇
  2003年   25篇
  2002年   25篇
  2001年   10篇
  2000年   3篇
  1999年   8篇
  1998年   11篇
  1997年   5篇
  1996年   15篇
  1995年   10篇
  1994年   7篇
  1993年   16篇
  1992年   9篇
  1991年   2篇
  1990年   4篇
  1989年   6篇
  1988年   3篇
  1987年   3篇
  1986年   3篇
  1985年   9篇
  1982年   9篇
  1981年   4篇
  1980年   4篇
  1979年   4篇
  1975年   2篇
  1974年   4篇
  1973年   1篇
  1968年   1篇
  1967年   1篇
  1964年   2篇
  1962年   1篇
排序方式: 共有1320条查询结果,搜索用时 0 毫秒
51.
A conformational study of the biomolecules released from submicron- and micron-sized temperature-sensitive composite polymer particles by decreasing the temperature from 40 to 25 °C was done with circular dichroism and the results were compared with those of the native biomolecules. In almost all cases the biomolecules released retained their native conformational states. Received: 10 April 2001 Accepted: 13 June 2001  相似文献   
52.
It is demonstrated that thiols can adsorb to gold without losing hydrogen. Dodecyl sulfide-capped gold clusters have been prepared and subjected to ligand exchange reactions in perdeuterated benzene by addition of dodecanethiol and subsequently dodecyl disulfide. It is shown by 1H NMR spectroscopy that dodecanethiol molecules are readily taken up as ligands producing characteristic broad signals corresponding to the alpha-methylene and S-H protons, with chemical shifts close to those found for thiol in solution; these signals are absent in spectra of thiolate-capped clusters. Addition of excess disulfide to such clusters capped with both dialkyl sulfides and thiols leads to the appearance of sharp signals for free dialkyl sulfide and intact thiol. Amounts of thiols up to 50% of the ligand shell are, however, taken up by the clusters under rapid and irreversible loss of hydrogen.  相似文献   
53.
Journal of Solid State Electrochemistry - The increasing efforts devoted to fabricating electrochromic (EC) devices have motivated a lot of studies to develop new EC materials. Herein, we introduce...  相似文献   
54.
Journal of Thermal Analysis and Calorimetry - TURKSAT-3USAT is the first Turkish communication 3U CubeSat designed and built by the students of the Space Systems Design and Test Laboratory and...  相似文献   
55.
Water structure modification by sugars with a wide difference in stereoregular structures ranging from monosaccharide to trisaccharide and its consequence on the micellization behavior of cetyltrimethylammonium bromide (CTAB) in aqueous medium have been investigated. The characteristic variation in water absorption peaks in the presence of d(?)fructose has been studied by near-infrared spectroscopy. The analyses show that the hydrogen bonding capability of d(+)glucose, d(?)fructose, sucrose, trehalose and raffinose is mainly responsible for the variation in water-additive interactions. The critical micelle concentration determined by specific conductivity measurement and aggregation number determined by steady state fluorescence quenching method show significant variations in presence of additives for CTAB in aqueous solution. The sugars interact with the water structure to varying extents owing to differences in hydrogen bonding capability depending on the stereoregularity of the structure. This induces differences in the microenvironment for competition between the hydrophobic interaction and degree of hydration of the hydrophilic group of the surfactant to ultimately influence the micellization behavior in aqueous solution.  相似文献   
56.
Abstract

The 4-H, 4-methyl and 4-phenyl derivatives of benzo-α-pyrone of 12-crown-4 and 15-crown-5 were synthesised starting from 4-substituted-6,7-dihydroxy- and 7,8-dihydroxybenzo-α-pyrones which reacted with dichloropolyethylene glycols in DMF/water/alkali carbonate. The coumarin-macrocycles were identified by elemental analysis, IR, EI-GC-MS as well as 1H, 13C NMR spectroscopy. The full experimental and spectral data is reported along with ion binding data studied in acetonitrile using fluorescence spectroscopy. The binding of the fluorogenic coumarin-crowns with Li+, Na+ and K+ were recognized as specific alterations on their fluorescence spectra that strongly originated from the structures. The observed CEQFS depending on the bound cation radii and macrocycle size evidenced the rules of cationic recognition of macrocycles. Some 15-crown-5 derivatives exhibited interesting Li+ and Na+ binding selectivities.  相似文献   
57.
A three-channel spectrometer (3CS) based on a commercial digital camera was developed to distinguish among tens of large (>100 nm), anisotropic plasmonic particles with various shapes, orientations, and compositions on a surface simultaneously. Using band pass filters and polarizers, the contrast of 3CS images could be enhanced to identify specific orientation and composition characteristics of gold and gold-silver nanopyramids and as well as the direction of the longest arm of gold nanostars.  相似文献   
58.
Phytochemical investigations on the EtOH extract of Clematis viticella led to the isolation of six flavonoid glycosides, isoorientin (1), isoorientin 3′-O-methyl ether (2), quercetin 7-O-α-L-rhamnopyranoside (3), quercetin 3,7-di-O-α-L-rhamnopyranoside (4), manghaslin (5) and chrysoeriol 7-O-β-D-glucopyranoside (6), one phenylethanol derivative, hydroxytyrosol (7), along with three phenolic acids, caffeic acid (8), (E)-p-coumaric acid (9) and p-hydroxybenzoic acid (10). The structures of the isolates were elucidated on the basis of NMR and HR-MS data. All compounds were isolated from C. viticella for the first time. Compounds 7 and 8 showed significant anti-inflammatory activity at 100 μM by reducing the release of NO in LPS-stimulated macrophages comparable to positive control indomethacin. Compounds 3 and 7 exhibited anti-inflammatory activity through lowering the levels of TNF-α while 1, 3 and 5 decreased the levels of neopterin better than the positive controls.  相似文献   
59.
In the crystal structure of the title compound, [Ni(C6H6N2O)2(H2O)2](C7H4NO3S)2·4H2O or [Ni(pia)2(H2O)2](sac)2·4H2O (pia is picolin­amide or pyridine‐2‐carbox­amide, and sac is the saccharinate anion), the Ni2+ cation, located on a centre of symmetry, is coordinated by two symmetry‐related aqua ligands together with a pair of symmetry‐related bidentate pia mol­ecules and exhibits a distorted octahedral environment. The unique unligated sac anion in the asymmetric unit resides on a general position and has a single negative charge. The coordinated water mol­ecules link the sac ions to the metal complex via O—H⋯O hydrogen bonds. In addition, the sac ions are linked to the metal complex via intermolecular π–π interactions between the benzene ring of the sac ion and the pyridine ring of a pia ligand. Each uncoordinated water mol­ecule is hydrogen bonded to sac moieties through O—H⋯O and O—H⋯N hydrogen bonds.  相似文献   
60.
The crystal structure of the title compound, [Ni(NCS)2(C4H12N2O)2], has two crystallographically independent half‐mol­ecules in the asymmetric unit, with each Ni atom residing on a centre of symmetry. The two mol­ecules exhibit similar coordination geometry but display differences with regard to other structural features. Each NiII centre is octahedrally coordinated by two mutually trans chelating hydroxy­ethyl­ethyl­ene­di­amine ligands and two mutually trans iso­thio­cyanate ions. The two independent mol­ecules form chains through different types of non‐covalent interactions. In the case of one of the mol­ecules, only NCS and free OH groups participate in hydrogen bonding, while in the chain based on the second mol­ecule, the NCS, NH, NH2 and free OH groups are involved in intermolecular hydrogen bonding. The two chains interact with one another through hydrogen bonding, forming planar sheets. The third packing direction is mediated only by van der Waals interactions.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号