全文获取类型
收费全文 | 381篇 |
免费 | 34篇 |
专业分类
化学 | 331篇 |
晶体学 | 2篇 |
力学 | 15篇 |
数学 | 10篇 |
物理学 | 57篇 |
出版年
2023年 | 6篇 |
2022年 | 5篇 |
2021年 | 12篇 |
2020年 | 19篇 |
2019年 | 20篇 |
2018年 | 9篇 |
2017年 | 11篇 |
2016年 | 21篇 |
2015年 | 11篇 |
2014年 | 25篇 |
2013年 | 19篇 |
2012年 | 62篇 |
2011年 | 44篇 |
2010年 | 16篇 |
2009年 | 10篇 |
2008年 | 26篇 |
2007年 | 19篇 |
2006年 | 11篇 |
2005年 | 15篇 |
2004年 | 10篇 |
2003年 | 11篇 |
2002年 | 8篇 |
2001年 | 3篇 |
2000年 | 6篇 |
1999年 | 1篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1995年 | 2篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1988年 | 3篇 |
排序方式: 共有415条查询结果,搜索用时 31 毫秒
31.
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
32.
A bimetallic pillared-layer coordination framework {[Mn(3)(bipy)(3)(H(2)O)(4)][Cr(CN)(6)](2)·2(bipy)·4(H(2)O)}(n) has been constructed using a cyanometallate anion ([Cr(CN)(6)](3-)) and an organic linker (4,4'-bipyridyl) that provides high heat of hydrogen adsorption (~11.5 kJ mol(-1)) and shows guest dependent magnetic modulation. 相似文献
33.
Tiwari AD Mishra AK Mishra SB Mamba BB Maji B Bhattacharya S 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,79(5):1050-1056
The thiocarbohydrazone Schiff-base ligand with a nitrogen and sulphur donor was synthesized through condensation of pyridine-2-carbaldehyde and thiocarbohydrazide. Schiff-base ligands have the ability to conjugate with metal salts. A series of metal complexes with a general formula [MCl2(H2L)]·nH2O (MNi, Co, Cu and Zn) were synthesized by forming complexes of the N1,N5-bis[pyridine-2-methylene]-thiocarbohydrazone (H2L) Schiff-base ligand. These metal complexes and ligand were characterized by using ultraviolet-visible (UV-Vis), Fourier Transform Infrared (FT-IR), 1H and 13C NMR spectroscopy and mass spectroscopy, physicochemical characterization, CHNS and conductivity. The biological activity of the synthesized ligand was investigated by using Escherichia coli DNA as target. The DNA interaction of the synthesized ligand and complexes on E. coli plasmid DNA was investigated in the aqueous medium by UV-Vis spectroscopy and the binding constant (Kb) was calculated. The DNA binding studies showed that the metal complexes had an improved interaction due to trans-geometrical isomers of the complexes than ligand isomers in cis-positions. 相似文献
34.
Isidoro Lpez Mehmed Z. Ertem Somnath Maji Jordi Benet‐Buchholz Anke Keidel Uwe Kuhlmann Peter Hildebrandt Christopher J. Cramer Victor S. Batista Antoni Llobet 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(1):209-213
The homogeneous catalysis of water oxidation by transition‐metal complexes has experienced spectacular development over the last five years. Practical energy‐conversion schemes, however, require robust catalysts with large turnover frequencies. Herein we introduce a new oxidatively rugged and powerful dinuclear water‐oxidation catalyst that is generated by self‐assembly from a mononuclear catalyst during the catalytic process. Our kinetic and DFT computational analysis shows that two interconnected catalytic cycles coexist while the mononuclear system is slowly and irreversibly converted into the more stable dinuclear system: an extremely robust water‐oxidation catalyst that does not decompose over extended periods of time. 相似文献
35.
Carbon fiber-reinforced plastic (CFRP) reinforced concrete beams can fail due to interface debonding, due to the high tensile
strength of such rebars. A set of 16 concrete beams reinforced with different amounts of CFRP reinforcement was subject to
static three-point bending. The beam dimensions and CFRP reinforcements used were selected to demonstrate a transition from
compression failure to bond failure with decreasing reinforcement ratio. It is shown that accurate bond strength data to predict
such failures can be obtained from a “hinged-beam” test configuration, rather than the conventional direct “pull-out” tests.
Deflection under service loads can also be predicted more accurately using a proposed equation that includes the reinforcement
ratio and the elastic modulus of the reinforcement. 相似文献
36.
Dipankar Mishra Subhendu Naskar Shyamal K. Chattopadhyay Milan Maji Parbati Sengupta Rupam Dinda Saktiprasad Ghosh Thomas C. W. Mak 《Transition Metal Chemistry》2005,30(3):352-356
The synthesis, crystal structure, redox and spectroscopic properties of trans-[Ru(bbpH2)(PPh3)2Cl]Cl are reported. In the crystalline solvate trans-[Ru(bbpH2)(PPh3)2cCl]Cl CHCl3 H2O, the molecular components are connected by strong intermolecular hydrogen bonding to form an infinite double column. 相似文献
37.
38.
Detection of kissing bonds by Lamb waves 总被引:6,自引:0,他引:6
Closed cracks under compressive normal stresses are difficult to detect by the conventional ultrasonic techniques. When the crack surfaces stay in very close contact with each other then the bond between the two surfaces of the crack is called a ‘kissing bond’. This is a very dangerous bond. Catastrophic failures can result if the system is subjected to crack opening normal stresses or shear stresses. When the crack surfaces are smooth then kissing bonds cannot transmit shear stress very well but can carry compressive normal stress, these bonds are called ‘slip bonds’. Conventional P-wave scans (C-scan or A-scan) are based on the assumptions that P-waves are reflected by the defective interface. However, an interface subjected to a large compressive stress cannot reflect P-waves effectively, hence these bonds remain invisible to the conventional P-wave based C-scan or A-scan techniques. In this paper it is shown that the kissing bonds can be effectively detected by some leaky Lamb mode. Theoretical and experimental results are presented to show that using the Lamb waves is an effective way of detecting kissing bonds. 相似文献
39.
Debasish Manna Basudeb Maji Soumyashree A. Gangopadhyay Kurt J. Cox Qingxuan Zhou Benjamin K. Law Ralph Mazitschek Amit Choudhary 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(19):6351-6355
Several genome engineering applications of CRISPR‐Cas9, an RNA‐guided DNA endonuclease, require precision control of Cas9 activity over dosage, timing, and targeted site in an organism. While some control of Cas9 activity over dose and time have been achieved using small molecules, and spatial control using light, no singular system with control over all the three attributes exists. Furthermore, the reported small‐molecule systems lack wide dynamic range, have background activity in the absence of the small‐molecule controller, and are not biologically inert, while the optogenetic systems require prolonged exposure to high‐intensity light. We previously reported a small‐molecule‐controlled Cas9 system with some dosage and temporal control. By photocaging this Cas9 activator to render it biologically inert and photoactivatable, and employing next‐generation protein engineering approaches, we have built a system with a wide dynamic range, low background, and fast photoactivation using a low‐intensity light while rendering the small‐molecule activator biologically inert. We anticipate these precision controls will propel the development of practical applications of Cas9. 相似文献
40.
Mithilesh Kumar Nayak Jessica Stubbe Dr. Nicolás I. Neuman Dr. Ramakirushnan Suriya Narayanan Sandipan Maji Prof. Dr. Carola Schulzke Prof. Vadapalli Chandrasekhar Prof. Dr. Biprajit Sarkar Dr. Anukul Jana 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(19):4425-4431
This work presents a stepwise reversible two-electron transfer induced hydrogen shift leading to the conversion of a bis-pyrrolinium cation to an E-diaminoalkene and vice versa. Remarkably, the forward and the reverse reaction, which are both reversible, follow two completely different reaction pathways. Establishing such unprecedented property in this type of processes was possible by developing a novel synthetic route towards the starting dication. All intermediates involved in both the forward and the backward reactions were comprehensively characterized by a combination of spectroscopic, crystallographic, electrochemical, spectroelectrochemical, and theoretical methods. The presented synthetic route opens up new possibilities for the generation of multi-pyrrolinium cation scaffold-based organic redox systems, which constitute decidedly sought-after molecules in contemporary chemistry. 相似文献