全文获取类型
收费全文 | 1314篇 |
免费 | 86篇 |
国内免费 | 5篇 |
专业分类
化学 | 1016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 | 34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1405条查询结果,搜索用时 15 毫秒
121.
Bhaskar Paul Dheeraj Jain S.P. Chakraborty I.G. Sharma C.G.S. Pillai A.K. Suri 《Thermochimica Acta》2011,512(1-2):134-141
The paper details the results of sintering kinetics studies conducted on nanocrystalline Mo–30 wt.% W alloy powders prepared through mechanical alloying route. Both, constant rate of heating method as well as Stepwise Isothermal Dilatometry (SID) technique were used for studying the sintering kinetics. Measured step isothermal shrinkage data were analyzed by Mekipritti-Meng method. The shrinkage data was found to fit well with the rate equation proposed in this method and its validity was established for mechanically alloyed systems. Kinetic parameters were evaluated and sintering was found to occur through two major mechanisms operative successively, which are grain boundary diffusion and lattice diffusion with corresponding energies of activation as 230 kJ/mol and 480 kJ/mol, respectively. The results have been well supported by micro structural evaluation of specimens at different stages of sintering. 相似文献
122.
Manirul?IslamEmail author Dildar?Hossain Paramita?Mondal Kazi?Tuhina Anupam?Singha?Roy Sanchita?Mondal Manir?Mobarak 《Transition Metal Chemistry》2011,36(2):223-230
A thiosemicarbazone Cu(II) complex anchored to a polystyrene framework has been synthesized and characterized by analytical
and spectroscopic techniques. The complex was found to be a highly active catalyst for the oxidation of various organic substrates
including alkenes and alcohols using H2O2 as oxidant. The reaction conditions were optimized with respect to temperature, solvent, oxidant, catalyst amount, and substrate
to peroxide ratio. The heterogeneous catalyst was reused five times without significant loss of activity. A comparison between
the catalytic activities of this polymer-supported Cu(II) complex and its homogeneous analogue was carried out. 相似文献
123.
Polypyrrole nanoparticles of desired structure have been synthesized through simple micelle technique. It is then grafted with functionalized silica gel to develop a novel organic-inorganic hybrid material. The role of dimethyl dichloro silane (coupling agent) in grafting is demonstrated. The nanoparticles are characterized by TEM, SEM and TGA. Grafting reactions are evaluated by spectral (FTIR) analysis and chemical test. The Cr(VI) binding behavior of the composite is studied in various pH of the medium. The selectivity in binding Cr(VI) is monitored. The metal ion adsorption capacity and surface area of the material are found to be 38 mg/g and 235 m2/g, respectively. 相似文献
124.
Heterologous expression characteristics of Trichoderma viride endoglucanase V in the silkworm, Bombyx mori L 总被引:1,自引:0,他引:1
Li XH Wang MX Zhang P Hu JB Sun CG Liu XJ Zhou F Niu YS Malik FA Bhaskar R Yang HJ Miao YG 《Applied biochemistry and biotechnology》2011,165(2):728-736
Efficient degradation of cellulose needs a synergistic reaction of the cellulolytic enzymes, which include exoglucanases, endoglucanases, and β-1,4-glucosidase. In this study, we used an improved Bac-to-Bac/BmNPV baculovirus expression system, which lacks the virus-encoded chitinase cathepsin (v-cath) genes of Bombyx mori nucleopolyhedrovirus (BmNPV), to express the endoglucanase V (EG V) gene from Trichoderma viride in silkworm BmN cells and silkworm larvae, and analyzed the characteristics of the recombinant enzyme in silkworm larvae. The result showed that an around 36-kDa protein was visualized in BmN cells at 48 h after the second-generation recombinant mBacmid/BmNPV/EG V baculovirus infection. The crude enzyme extract from the recombinant baculoviruses-infected silkworms exhibited a significant maximum activity at the environmental condition of pH 5.0 and a temperature of 50 °C, and increased 39.86% and 37.76% compared with that from blank mBacmid/BmNPV baculovirus-infected silkworms and normal silkworms, respectively. It was stable at pH range from 5.0 to 10.0 and at temperature range from 40 to 60 °C. The availability of large quantities of EG V that the silkworm provides might greatly facilitate the future research and the potential application in industries. 相似文献
125.
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
126.
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
127.
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
128.
129.
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
130.
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