全文获取类型
收费全文 | 1308篇 |
免费 | 86篇 |
国内免费 | 5篇 |
专业分类
化学 | 1010篇 |
晶体学 | 15篇 |
力学 | 29篇 |
数学 | 116篇 |
物理学 | 229篇 |
出版年
2024年 | 3篇 |
2023年 | 32篇 |
2022年 | 28篇 |
2021年 | 40篇 |
2020年 | 60篇 |
2019年 | 48篇 |
2018年 | 46篇 |
2017年 | 30篇 |
2016年 | 71篇 |
2015年 | 50篇 |
2014年 | 57篇 |
2013年 | 116篇 |
2012年 | 102篇 |
2011年 | 104篇 |
2010年 | 74篇 |
2009年 | 53篇 |
2008年 | 71篇 |
2007年 | 64篇 |
2006年 | 66篇 |
2005年 | 29篇 |
2004年 | 29篇 |
2003年 | 47篇 |
2002年 | 32篇 |
2001年 | 23篇 |
2000年 | 10篇 |
1999年 | 10篇 |
1998年 | 6篇 |
1997年 | 3篇 |
1996年 | 5篇 |
1995年 | 10篇 |
1994年 | 8篇 |
1993年 | 7篇 |
1992年 | 7篇 |
1991年 | 3篇 |
1989年 | 5篇 |
1988年 | 4篇 |
1987年 | 7篇 |
1986年 | 5篇 |
1985年 | 2篇 |
1984年 | 4篇 |
1983年 | 2篇 |
1982年 | 9篇 |
1981年 | 3篇 |
1980年 | 5篇 |
1978年 | 2篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1969年 | 1篇 |
1967年 | 1篇 |
1954年 | 1篇 |
排序方式: 共有1399条查询结果,搜索用时 387 毫秒
121.
Angiotensin converting enzyme (ACE) catalyzes the conversion of angiotensin I (Ang I) to angiotensin II (Ang II). ACE also cleaves the terminal dipeptide of vasodilating hormone bradykinin (a nonapeptide) to inactivate this hormone. Therefore, inhibition of ACE is generally used as one of the methods for the treatment of hypertension. 'Oxidative stress' is another disease state caused by an imbalance in the production of oxidants and antioxidants. A number of studies suggest that hypertension and oxidative stress are interdependent. Therefore, ACE inhibitors having antioxidant property are considered beneficial for the treatment of hypertension. As selenium compounds are known to exhibit better antioxidant behavior than their sulfur analogues, we have synthesized a number of selenium analogues of captopril, an ACE inhibitor used as an antihypertensive drug. The selenium analogues of captopril not only inhibit ACE activity but also effectively scavenge peroxynitrite, a strong oxidant found in vivo. 相似文献
122.
We consider the motion of Brownian particles confined in a two-dimensional symmetric bilobal enclosure with uneven cross section. Varying cross section of the confinement results in an effective entropic potential in reduced dimension. By employing two external noise forces, one additive and another multiplicative along x direction, we demonstrate that a correlation between them causes a symmetry breaking of entropic stability, i.e., a difference in relative stability of two lobes. This leads to an asymmetric localization of population in the stationary state. A two-state model is proposed to explain the asymmetric localization of population due to entropic diffusion. 相似文献
123.
Kundu T Sarkar B Mondal TK Mobin SM Urbanos FA Fiedler J Jiménez-Aparicio R Kaim W Lahiri GK 《Inorganic chemistry》2011,50(11):4753-4763
Using the [RuCl(μ-tppz)ClRu](2+) [tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine] platform for bridging two o-quinone/catecholate two-step redox systems (unsubstituted, Q(n), or 3,5- di-tert-butyl-substituted, DTBQ(n)), we have obtained the stable complexes [(Q(?-))Ru(II)Cl(μ-tppz)ClRu(II)(Q(?-))] (1) and the structurally characterized [(DTBQ(?-))Ru(II)Cl(μ-tppz)ClRu(II)(DTBQ(?-))] (2). The compounds exhibit mostly quinone-ligand-based redox activity within a narrow potential range, high-intensity near-IR absorptions (λ(max) ≈ 920 nm; ε > 50,000 M(-1) cm(-1)), and variable intra- and intermolecular spin-spin interactions. Density functional theory calculations, electron paramagnetic resonance (EPR), and spectroelectrochemical results (UV-vis-near-IR region) for three one-electron-reduction and two one-electron-oxidation processes were used to probe the electronic structures of the systems in the various accessible valence states. EPR spectroscopy of the singly charged doublet species showed semiquinone-type response for 1(+), 2(+), and 2(-), while 1 exhibits more metal based spin, a consequence of the easier reduction of Q as compared to DTBQ. Comparison with the analogous redox series involving a more basic N-phenyliminoquinone ligand reveals significant differences related to the shifted redox potentials, different space requirements, and different interactions between the metals and the quinone-type ligands. As a result, the tppz bridge is reduced here only after full reduction of the terminal quinone ligands to their catecholate states. 相似文献
124.
125.
Supramolecular calix[4]arene conjugate (L) has been developed as a sensitive and selective sensor for Zn(2+) in HEPES buffer among the 12 metal ion by using fluorescence, absorption and ESI MS and also by visual fluorescent color. The structural, electronic, and emission properties of the calix[4]arene conjugates L and its zinc complex, [ZnL], have been demonstrated using ab initio density functional theory (DFT) combined with time-dependent density functional theory (TDDFT) calculations. The TDDFT calculations reveal the switch on fluorescence behavior of L is mainly due to the utilization of the lone pair of electrons on imine moiety by the Zn(2+). The resultant fluorescent complex, [ZnL], has been used as a secondary sensing chemo-ensemble for the detection of -SH containing molecules by removing Zn(2+) from [ZnL] and forming {Cys/DTT·Zn} adducts as equivalent to those present in metallothioneins. The displacement followed by the release of the coordinated zinc from its Cys/DTT complex by heavy metal ion (viz. Cd(2+) and Hg(2+)), as in the metal detoxification process or by ROS (such as H(2)O(2)) as in the oxidative stress, has been well demonstrated using the conjugate L through the fluorescence intensity retrieval wherein the fluorescence intensity is the same as that observed with [ZnL], which in turn mimics the zinc sensing element (MTF) in biology. 相似文献
126.
Sahoo T Sardar S Mondal P Sarkar B Adhikari S 《The journal of physical chemistry. A》2011,115(21):5256-5273
We include the phonon modes originating from the three layers of Cu(100)/Cu(111) surface atoms on the dynamics of molecular [H(2)(v,j)/D(2)(v,j)] degrees of freedom (DOFs) through a mean field approach, where the surface temperature is incorporated into the effective Hamiltonian (potential) either by considering Boltzmann probability (BP) or by including the Bose-Einstein probability (BEP) factor for the initial state distribution of the surface modes. The formulation of effective potential has been carried out by invoking the expression of transition probabilities for phonon modes known from the "stochastic" treatment of linearly forced harmonic oscillator (LFHO). We perform four-dimensional (4D?2D) as well as six-dimensional (6D) quantum dynamics on a parametrically time and temperature-dependent effective Hamiltonian to calculate elastic/inelastic scattering cross-section of the scattered molecule for the H(2)(v,j)-Cu(100) system, and dissociative chemisorption-physisorption for both H(2)(v,j)-Cu(100) and D(2)(v,j)-Cu(111) systems. Calculated sticking probabilities by either 4D?2D or 6D quantum dynamics on an effective potential constructed by using BP factor for the initial state distribution of the phonon modes could not show any surface temperature dependence. In the BEP case, (a) both 4D?2D and 6D quantum dynamics demonstrate that the phonon modes of the Cu(100) surface affect the state-to-state transition probabilities of the scattered H(2) molecule substantially, and (b) the sticking probabilities due to the collision of H(2) on Cu(100) and D(2) on Cu(111) surfaces show noticeable and substantial change, respectively, as function of surface temperature only when the quantum dynamics of all six molecular DOFs are treated in a fully correlated manner (6D). 相似文献
127.
Bhattacharjee CR Goswami P Pramanik HA Paul PC Mondal P 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,78(5):1408-1415
Two new mixed-ligand iron(III) complexes, [Fe(L(n))(acac)(C(2)H(5)OH)] incorporating coordinated ethanol from the reaction solvent were accessed from the reaction of [Fe(acac)(3)] with [ONO] donor dibasic tridentate unsymmetrical Schiff base ligands derived from condensation of 2-hydroxy-1-napthaldehyde with 2-aminophenol (H(2)L(1)) or 2-aminobenzoic acid (H(2)L(2)). The thermal study (TGA-DTA) provided evidence for weakly bound ethanol which is readily substituted by neutral N-donor molecule imidazole, benzimidazole or pyridine to produce an array of newer complexes, [Fe(L(n))(acac)X] (n=1, 2; X=Im, Bim, Py). The compounds were characterized by elemental analyses, FT-IR, UV-vis, solution electrical conductivity, FAB mass, (1)H and (13)C NMR spectroscopy. Room temperature magnetic susceptibility measurements (μ(eff)~5.8 B.M.) are consistent with spin-free octahedral iron(III) complexes. Cyclic voltammetry of ethanol complexes revealed a quasi-reversible one electron redox response (ΔE(p)>100 mV) for the Fe(III)/Fe(II) couple. Low half wave redox potential (E(1/2)) values suggested easy redox susceptibility. The ground state geometries of the ethanol and imidazole complexes have been ascertained to be distorted octahedral by density functional theory using DMol3 program at BLYP/DNP level. 相似文献
128.
Fleming FF Liu W Yao L Pitta B Purzycki M Ravikumar PC 《European journal of organic chemistry》2011,2011(34):6843-6846
Grignard reagents trigger an addition-elimination with α'-hydroxy acrylonitriles to selectively generate Z-alkenenitriles. The modular assembly of Z-alkenenitriles from a Grignard reagent, acrylonitrile, and an aldehyde is ideal for stereoselectively synthesizing alkenes as illustrated in the synthesis of the putative lignan "morinol I." 相似文献
129.
Complexes of the general formula [ReIII(L)Cl(PPh3)2] have been synthesised by reacting H2L and [ReOCl3(PPh3)2] in ethanol. Here H2L represents imines of α-amino acids (glycine, l-alanine, l-valine, l-phenylalanine) derived from salicylaldehyde and naphthaldehyde. The crystal structure of one complex has been determined. The complexes are mononuclear, paramagnetic and display paramagnetic 1H NMR in CDCl3 solution. Their spectral and redox properties are scrutinised. 相似文献
130.
C R Mondal 《Proceedings Mathematical Sciences》1995,105(2):227-239
For the problem of waves due to an explosion above the surface of a homogeneous ocean of finite depth, asymptotic expressions of the velocity potential and the surface displacement are determined for large times and distances from the pressure area produced by the incident shock. It is shown that the first item in Sakurai's approximation scheme for the pressure field inside the, blast wave as well as the results of Taylor's point blast theory can be used to yield realistic expressions of surface displacement. Some interesting features of the wave motion in general are described. Finally some numerical calculations for the surface elevation were performed and included as a particular case. 相似文献