全文获取类型
收费全文 | 716篇 |
免费 | 31篇 |
国内免费 | 3篇 |
专业分类
化学 | 543篇 |
晶体学 | 3篇 |
力学 | 5篇 |
数学 | 31篇 |
物理学 | 168篇 |
出版年
2023年 | 9篇 |
2022年 | 14篇 |
2021年 | 20篇 |
2020年 | 29篇 |
2019年 | 28篇 |
2018年 | 18篇 |
2017年 | 25篇 |
2016年 | 21篇 |
2015年 | 26篇 |
2014年 | 21篇 |
2013年 | 44篇 |
2012年 | 59篇 |
2011年 | 58篇 |
2010年 | 37篇 |
2009年 | 33篇 |
2008年 | 35篇 |
2007年 | 31篇 |
2006年 | 33篇 |
2005年 | 26篇 |
2004年 | 23篇 |
2003年 | 11篇 |
2002年 | 13篇 |
2001年 | 4篇 |
2000年 | 8篇 |
1999年 | 4篇 |
1998年 | 4篇 |
1997年 | 3篇 |
1996年 | 5篇 |
1995年 | 3篇 |
1994年 | 6篇 |
1992年 | 8篇 |
1991年 | 9篇 |
1990年 | 11篇 |
1989年 | 10篇 |
1986年 | 2篇 |
1985年 | 6篇 |
1984年 | 2篇 |
1983年 | 5篇 |
1982年 | 10篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1972年 | 2篇 |
1970年 | 4篇 |
1969年 | 3篇 |
1966年 | 2篇 |
排序方式: 共有750条查询结果,搜索用时 15 毫秒
81.
Four new neutral copper azido polymers, [Cu(4)(N(3))(8)(L(1))(2)](n) (1), [Cu(4)(N(3))(8)(L(2))(2)](n) (2), [Cu(4)(N(3))(8)(L(3))(2)](n) (3), and [Cu(9)(N(3))(18)(L(4))(4)](n) (4) [L(1-4) are formed in situ by reacting pyridine-2-carboxaldehyde with 2-[2-(methylamino)ethyl]pyridine (mapy, L(1)), N,N-dimethylethylenediamine (N,N-dmen, L(2)), N,N-diethylethylenediamine (N,N-deen, L(3)), and N,N,2,2-tetramethylpropanediamine (N,N,2,2-tmpn, L(4))], have been synthesized by using 0.5 mol equiv of the chelating tridentate ligands with Cu(NO(3))(2)·3H(2)O and an excess of NaN(3). Single-crystal X-ray structures show that the basic unit of these complexes, especially 1-3, contains very similar Cu(II)(4) building blocks. The overall structure of 3 is two-dimensional, while the other three complexes are one-dimensional in nature. Complex 1 represents a unique example containing hemiaminal ether arrested by copper(II). Complexes 1 and 2 have a rare bridging azido pathway: both end-on and end-to-end bridging azides between a pair of Cu(II) centers. Cryomagnetic susceptibility measurements over a wide range of temperature exhibit dominant ferromagnetic behavior in all four complexes. Density functional theory calculations (B3LYP functional) have been performed on complexes 1-3 to provide a qualitative theoretical interpretation of their overall ferromagnetic behavior. 相似文献
82.
Halder A Bhatt S Nayak SK Chattopadhyay S Bhattacharya S 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,84(1):25-31
The present article reports the spectroscopic investigations on non-covalent interaction of fullerenes C(60) and C(70) with a macrocyclic receptor molecule, namely, 1,3,5,7-tetrahomo-p-tert-butylcalix[8]arene (1) in toluene. Jobs method of continuous variation reveals 1:1 stoichiometry for the fullerene complexes of 1. The most fascinating feature of the present study is that 1 binds selectively C(60) compared to C(70) as obtained from binding constant (K) data of C(60)-1 (K(C60-1)) and C(70)-1 (K(C70-1)) complexes which are enumerated to be 265,000 dm(3) mol(-1) and 63,43 dm(3) mol(-1), respectively, and selectivity in binding (K(C60-1)/K(C70-1)) is estimated to be 4.18 as obtained from UV-Vis study. Steady state fluorescence studies reveal quenching of fluorescence of 1 in presence of fullerenes and the K value of the C(60)-1 and C(70)-1 complexes are estimated to be 80,760 and 68,780 dm(3) mol(-1), respectively, with selectivity in binding (K(C60-1)/K(C70-1)) ~1.18. (1)H NMR analysis provides very good support in favor of strong binding between C(60) and 1. The high value of K value for C(60)-1 complex indicates that 1 forms an inclusion complex with C(60). 相似文献
83.
Ribeiro EA Sidooski T Nandi LG Machado VG 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,81(1):745-753
2,6-Diphenyl-4-(2,4,6-triphenylpyridinium-1-yl)phenolate (1a) and 4-[(1-methyl-4(1H)-pyridinylidene)-ethylidene]-2,5-cyclohexadien-1-one (2a) were protonated in organic solvents (dichloromethane, acetonitrile, and DMSO) to form 1b and 2b, respectively. The appearance of the solvatochromic bands of 1a and 2a was studied UV-vis spectrophotometrically by deprotonation of 1b and 2b in solution in the presence of the following amines: aniline (AN), N-methylaniline (NMAN), N,N-dimethylaniline (NDAN), n-butylamine (BA), diethylamine (DEA), and triethylamine (TEA). Titrations of 1b and 2b with the amines were carried out and the binding constants were determined from the titration curves in each solvent, using a mathematical model adapted from the literature which considers the simultaneous participation of two dye: amine stoichiometries, 1:1 and 1:2. The data obtained showed the following base order for the two compounds in DMSO: BA>DEA>TEA, while aromatic amines did not cause any effect. In dichloromethane, the following base order for 1b was verified: TEA>DEA>BA?NDAN, while for 2b the order was: TEA>DEA>BA, suggesting that 1b is more acidic than 2b. The data in acetonitrile indicated for 1b and 2b the following order for the amines: DEA>TEA>BA. The diversity of the experimental data were explained based on a model that considers the level of interaction of the protonated dyes with the amines to be dependent on three aspects: (a) the basicity of the amine, which varies according to their molecular structure and the solvent in which it is dissolved, (b) the molecular structure of the dye, and (c) the solvent used to study the system. 相似文献
84.
Sandip Paul 《Molecular physics》2013,111(13):2098-2107
We report classical molecular dynamics simulation studies of aqueous solution consisting of water, tert-butyl alcohol (TBA) and trimethylamine-N-oxide (TMAO). In spite of the fact that both TBA and TMAO molecules have very similar geometry with hydrophobic and hydrophilic groups, they behave very differently in aqueous solutions. Our aim is to see the role of TMAO on the self-aggregation (or association) of TBA molecules. We observe that, TMAO acts to postpone the aggregation of TBA molecules (takes place via the hydrophobic ends) to some extent. Addition of 0.10 mole fraction of TMAO shifts the aggregation concentration of TBA from xtba = 0.025 to xtba = 0.06. From the excess coordination number, calculation it is noticed that up to xtba = 0.06, TBA molecules are favourably solvated by TMAO by replacing water molecules from TBA solvation shell but above this concentration, TBA–TMAO interaction decreases. This is further confirmed by water–TMAO interactions which shows a shift above xtba = 0.06 indicating more preferred interactions between them. We also observe a noticeable increase in the water–water hydrogen bond life time in presence of TBA molecules indicating more structuring of water molecules. 相似文献
85.
Tapan Nandi V Nanal W A Fernandes C A Desai M B Kurup K G Prasad P M R Rao S Padmanabhan 《Pramana》1995,44(1):67-76
A facility for carrying out beam-foil spectroscopic studies in the UV and visible region using the 400 kV electrostatic ion
accelerator at Tata Institute of Fundamental Research, Bombay is described. 相似文献
86.
Chiral discrimination and recognition is important in peptide biosynthesis, amino acid synthesis and drug designing. Detailed
structural information is available about the peptide synthesis in ribosome. However, no detailed study is available about
the discrimination in peptide synthesis. We study the conformational energy variation of neutral methoxy phenyl alanine molecule
as a function of its different dihedral angle to locate the minimum energy conformation using quantum chemical theory. We
compared the intermolecular energy surfaces of phenyl alanine molecule in its neutral and zwitterionic state using quantum
chemical theory as a function of distance and mutual orientation. The energy surfaces are studied with rigid geometry by varying
the distance and orientation. The potential energy surfaces of L-L and D-L pairs are found to be dissimilar and reflect the underlying chirality of the homochiral pair and racemic nature of the heterochiral
pair. The intermolecular energy surface of homochiral pair is more favourable than the corresponding energy surface of heterochiral
pair. 相似文献
87.
We have treated the Hulthén-modified separable potentials within the framework of the phase-function method and obtained a
closed form expression fors-wave scattering phase shift. Specializing to a rank one separable potential we have found out the limiting conditions in
which the Hulthén-modified phase shift goes over to its Coulomb counterpart. We demonstrate the usefulness of our approach
by means of a model calculation.
Based in part on a Ph.D. thesis to be submitted by one of the authors (AKJ) to Visva-Bharati University. 相似文献
88.
89.
The nature of the interaction between the unsaturated monomer and the chelate, Fe(DPM)3, is studied in detail. The interaction is found to occur only in solution. The stoichiometry of interaction and the equilibrium constant are evaluated. With the help of spectral evidence, attempts are made to point out the specific sites of interaction. 相似文献
90.
Summary Investigations on the aquation of tris-(substituted)malonatochromate(III)ion, between 25°–40° in the presence of acid (I=1.0M) show that the mono- and dimethyl substituted complexes aquate by a two term rate law, only one of which is acid dependent. All other complexes aquate by a one term rate law which is first-order with respect to acid concentration; the unsubstituted malonato complex behaves in this way. Aquation of the first two complexes is dissociative, while for others appreciable associative character has been observed. 相似文献