全文获取类型
收费全文 | 743篇 |
免费 | 18篇 |
国内免费 | 2篇 |
专业分类
化学 | 456篇 |
晶体学 | 12篇 |
力学 | 14篇 |
数学 | 75篇 |
物理学 | 206篇 |
出版年
2022年 | 11篇 |
2021年 | 6篇 |
2020年 | 12篇 |
2019年 | 12篇 |
2018年 | 19篇 |
2017年 | 13篇 |
2016年 | 18篇 |
2015年 | 16篇 |
2014年 | 22篇 |
2013年 | 43篇 |
2012年 | 27篇 |
2011年 | 36篇 |
2010年 | 22篇 |
2009年 | 26篇 |
2008年 | 25篇 |
2007年 | 32篇 |
2006年 | 34篇 |
2005年 | 21篇 |
2004年 | 23篇 |
2003年 | 13篇 |
2002年 | 17篇 |
2001年 | 7篇 |
2000年 | 8篇 |
1999年 | 12篇 |
1998年 | 9篇 |
1997年 | 14篇 |
1996年 | 13篇 |
1995年 | 8篇 |
1994年 | 16篇 |
1993年 | 12篇 |
1992年 | 11篇 |
1990年 | 7篇 |
1989年 | 8篇 |
1988年 | 14篇 |
1987年 | 13篇 |
1986年 | 6篇 |
1985年 | 10篇 |
1984年 | 13篇 |
1983年 | 11篇 |
1982年 | 8篇 |
1981年 | 9篇 |
1980年 | 7篇 |
1979年 | 6篇 |
1977年 | 9篇 |
1974年 | 5篇 |
1973年 | 7篇 |
1969年 | 7篇 |
1965年 | 4篇 |
1964年 | 6篇 |
1961年 | 5篇 |
排序方式: 共有763条查询结果,搜索用时 31 毫秒
131.
We have investigated rarely observed 77Se J-couplings (spin-spin couplings) in the mixed-metal face-capped octahedral clusters [Re5OsSe8(CN)6]3- and [Re4Os2Se8(CN)6]2- at natural abundance. To the best of our knowledge, these are the first observations of Se-Se spin-spin interactions between mu3-Se sites, important for stereochemical assignments in hexarhenium analogues, Chevrel phase materials, and similar cluster materials. NMR techniques such as COSY, INADEQUATE, and 2D J-resolved spectroscopy have been used in conjunction to study these interactions. The two isomers (cis and trans) of [Re4Os2Se8(CN)6]2- were distinguishable, and selective isotopic labeling of [Re5OsSe8(CN)6]3- with 13CN ligands enabled resonances to be assigned by observing the 2J (Se-M-C) couplings. For [Re5OsSe8(CN)6]3-, two different 2J (Se-M-Se) couplings were measurable on a single cluster, and these are related to one another through spin-spin interactions across a face diagonal or along an edge of the cube of inner selenium ligands. A rigorous analysis based on combinatorial math has been invoked to assign the couplings on the basis of the probability of multiple-spin interactions. The face diagonal association is found to result in a J-coupling interaction larger in magnitude than that from coupling along an edge of the cube-information critical for making stereochemical assignments of selenium sites. 相似文献
132.
Group 2 metal complexes [Ca(SA)2(phen)]n (1), [Sr2(SA)4(phen)4] (2), and [Ba(SA)2(phen)2]n (3) (SA = salicylate) have been obtained by the addition of 1,10-phenanthroline (phen) to the corresponding metal salicylates, while the bipyridine derivatives {[Ca3(SA)6(H2O)4](4bpy)2}n (4), {[Sr(SA)2(H2O)3](4bpy)1.5(H2O)}n (5), and {[Ba(SA)2(H2O)3]-(4bpy)1.5(H2O)}n (6) have been synthesized starting from the respective metal carbonates, salicylic acid (SA-H), and 4,4'-bipyridine (4bpy). The new compounds have been characterized by elemental analysis, pH measurements, thermal analysis, and spectroscopic measurements (IR, NMR, ultraviolet, and fluorescence). Molecular structure determination by single-crystal X-ray diffraction has been carried out for all the compounds. The thermal analysis studies indicate the loss of coordinated and/or lattice water molecules below 200 degrees C in 4-6 and the absence of any coordinated or uncoordinated water molecules in compounds 1-3. Compounds 1 and 3-6 exist as one-dimensional polymers while compound 2 crystallizes as a discrete dimer. Considerable variations have been observed in the molecular structures of 1-6 in terms of the geometry around the metal, the binding mode of salicylate, and the coordination behavior of the pyridine ligand. Calcium ion is hexacoordinated in 1, while in 4 both hexa- and heptacoordinated calcium ions are simultaneously present. Strontium exhibits coordination numbers of nine and eight in 2 and 5, respectively. The barium ions in 3 and 6 assume coordination numbers of eight and seven, respectively. While the OH group of the salicylate ligand does not directly bind the metal in 1-3, it coordinates to the metal ions in complexes in 4-6 in the un-ionized form. The 4bpy molecules show no direct ligation to the metal in 4-6; the phen ligands in 1-3, however, occupy one side of the coordination sphere around the metal. The presence of additional O-H...O, C-H...O, and N-H...O hydrogen bonding and pi-pi stacking in these compounds results in the formation of polymeric structures. The results obtained for the calcium complexes in this study have been compared with the available data in structural calcium chemistry with the aid of a detailed analysis of the Cambridge Structural Database. 相似文献
133.
Rotationally resolved resonant two-photon ionization (R2PI) spectra of ScCo and YCo are reported. The measured spectra reveal that these molecules possess ground electronic states of (1)Sigma(+) symmetry, as previously found in the isoelectronic Cr(2) and CrMo molecules. The ground state rotational constants for ScCo and YCo are B(0)(")=0.201 31(22) cm(-1) and B(0) (")=0.120 96(10) cm(-1), corresponding to ground state bond lengths of r(0) (")=1.812 1(10) A and r(0) (")=1.983 0(8) A, respectively. A single electronic band system, assigned as a (1)Pi<--X (1)Sigma(+) transition, has been identified in both molecules. In ScCo, the (1)Pi state is characterized by T(0)=15,428.8, omega(e)(')=246.7, and omega(e)(')x(e)(')=0.73 cm(-1). In YCo, the (1)Pi state has T(0)=13 951.3, omega(e)(')=231.3, and omega(e)(')x(e) (')=2.27 cm(-1). For YCo, hot bands originating from levels up to v(")=3 are observed, allowing the ground state vibrational constants omega(e)(")=369.8, omega(e)(")x(e)(")=1.47, and Delta G(12)(")=365.7 cm(-1) to be deduced. The bond energy of ScCo has been measured as 2.45 eV from the onset of predissociation in a congested vibronic spectrum. A comparison of the chemical bonding in these molecules to related molecules is presented. 相似文献
134.
A new, efficient, and highly diastereoselective synthesis of polycyclic indole derivatives through intramolecular imino Diels-Alder reaction of aminoanthraquinone with N-prenylated indole-2-carboxaldehydes in the presence of 20 mol % of triphenylphosphonium perchlorate (TPPP) is reported with extremely high cis selectivity in good yield. 相似文献
135.
Dual-phase oscillations are observed in Belousov–Zhabotinsky system with 4-hydroxy-3-methoxybenzaldehyde (vanillin) as the substrate and manganous sulphate or ammonium Ce(IV) sulphate as the catalyst. The nonoscillatory period of time between the two phases decreases with increase in the concentration of the catalyst and the substrate. Under uncatalyzed and ferroin catalyzed conditions the system exhibits single-phase oscillations. The first-phase oscillations are due to vanillin whereas the second-phase oscillations are brought about by 4-hydroxy-3-methoxybenzoic acid (vanillic acid) formed during the course of the first-phase reactions. The reactions are explained with relevant steps of the FKN mechanism. © 1998 John Wiley & Sons, Inc. Int J. Chem. Kinet 30: 201–206, 1998. 相似文献
136.
Charge transfer states in the photophysics and photochemistry of polyimides and related phthalimides
David Creed Charles E. Hoyle John W. Jordan Chandra A. Pandey Rajamani Nagarajan Surapol Pankasem Alline M. Peeler Petharnan Subramanian 《Macromolecular Symposia》1997,116(1):1-13
Polyimides such as 6F-6F and 6F-ODA and model N-arylphthalimides are stabilized against photooxidative degradation by their electron donor (D) – acceptor (A) character. We have investigated the precise origin(s) of this effect using D and A substituents on the N-aryl groups of these compounds. The lowest excited singlet state (S1) of N-arylphthalimides is an intramolecular charge transfer (ICT) state. A nominally twisted compound, N-(2-t-butylphenyl)phthalimide, shows greatly diminished CT absorption and blue-shifted fluorescence with reduced quantum yield when compared to the 4-t-butyl isomer with an identical N-aryl donor group. It therefore seems unnecessary to claim that the ICT state of phthalimides is a so-called TICT state. Quantum yield and fluorescence lifetime measurements lead to the conclusion that enhanced internal conversion from the ICT state (S1) to the ground state makes a significant contribution to photostabilization of these compounds by suppressing formation of the reactive triplet state. Further stabilization of polymer films may be afforded by triplet state self-quenching which is enhanced for 6F-ODA in increasingly poor solvents. N-alkylarylphthalimides in which the aryl and phthalimide groups are not formally conjugated but, rather, joined by flexible methylene ‘spacers’, exhibit a different kind of fluorescent intramolecular CT singlet state whose formation can also stabilize these compounds by suppressing triplet state formation. 相似文献
137.
138.
We report on SSTR5 receptor modeling and its interaction with reported antagonist and agonist molecules. Modeling of the SSTR5 receptor was carried out using multiple templates with the aim of improving the precision of the generated models. The selective SSTR5 antagonists, agonists and native somatostatin SRIF-14 were employed to propose the binding site of SSTR5 and to identify the critical residues involved in the interaction of the receptor with other molecules. Residues Q2.63, D3.32, Q3.36, C186, Y7.34 and Y7.42 were found to be highly significant for their strong interaction with the receptor. SSTR5 antagonists were utilized to perform a 3D quantitative structure–activity relationship study. A comparative molecular field analysis (CoMFA) was conducted using two different alignment schemes, namely the ligand-based and receptor-based alignment methods. The best statistical results were obtained for ligand-based (\({q}^{2} = 0.454\), \({r}^{2}\) = 0.988, noc = 4) and receptor-guided methods (docked mode 1:\({q}^{2} = 0.530\), \({r}^{2} = 0.916\), noc = 5), (docked mode 2:\({q}^{2}\) = 0.555, \({r}^{2 }= 0.957\), noc = 5). Based on CoMFA contour maps, an electropositive substitution at \(\hbox {R}^{1}\), \(\hbox {R}^{2}\) and \(\hbox {R}^{4}\) position and bulky group at \(\hbox {R}^{4}\) position are important in enhancing molecular activity. 相似文献
139.
苝类化合物具有大的共轭体系,易于进行结构修饰,可引入各种功能性基团,这种奇特结构赋予了苝类化合物优良的理化性质和特殊功能,在材料科学、超分子化学、生物、药学、医学等领域具有宽广的应用潜力,尤其在苝类有机光电材料已得到广泛的研究,取得了许多重要成就。尤其是近来越来越多的研究致力于开发苝类化合物其它可能的应用,已延伸到诸多领域,特别是相关生物医药的应用研究已成为近几年来异常活跃的新兴研究领域,引起广泛关注,进展迅速。本文结合课题组的研究工作,参考国内外近五年文献,首次系统地综述了苝类化合物在有机光电材料、纳米材料、生物医药光敏剂、生物荧光标记和成像、药物载体、人工诊断剂、人工离子受体和荧光分子探针等材料、生物、医药领域应用研究新进展。文中注重强化了化合物结构对苝类化合物性质和应用的影响。对未来苝类化合物研究与应用的发展趋势作了展望。 相似文献
140.
Surface characterisation and electrochemical behaviour of porous titanium dioxide coated 316L stainless steel for orthopaedic applications 总被引:1,自引:0,他引:1
S. Nagarajan 《Applied Surface Science》2009,255(7):3927-3932
Porous titanium dioxide was coated on surgical grade 316L stainless steel (SS) and its role on the corrosion protection and enhanced biocompatibility of the materials was studied. X-ray diffraction analysis (XRD), atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX) were carried out to characterise the surface morphology and also to understand the structure of the as synthesised coating on the substrates. The corrosion behaviour of titanium dioxide coated samples in simulated body fluid was evaluated using polarisation and impedance spectroscopy studies. The results reveal that the titanium dioxide coated 316L SS exhibit a higher corrosion resistance than the uncoated 316L SS. The titanium dioxide coated surface is porous, uniform and also it acts as a barrier layer to metallic substrate and the porous titanium dioxide coating induces the formation of hydroxyapatite layer on the metal surface. 相似文献