全文获取类型
收费全文 | 430篇 |
免费 | 16篇 |
国内免费 | 2篇 |
专业分类
化学 | 297篇 |
晶体学 | 1篇 |
力学 | 3篇 |
数学 | 59篇 |
物理学 | 61篇 |
无线电 | 27篇 |
出版年
2023年 | 5篇 |
2022年 | 15篇 |
2021年 | 10篇 |
2020年 | 13篇 |
2019年 | 11篇 |
2018年 | 8篇 |
2017年 | 3篇 |
2016年 | 13篇 |
2015年 | 16篇 |
2014年 | 22篇 |
2013年 | 42篇 |
2012年 | 49篇 |
2011年 | 52篇 |
2010年 | 18篇 |
2009年 | 19篇 |
2008年 | 23篇 |
2007年 | 20篇 |
2006年 | 25篇 |
2005年 | 15篇 |
2004年 | 13篇 |
2003年 | 3篇 |
2002年 | 18篇 |
2000年 | 1篇 |
1997年 | 4篇 |
1996年 | 1篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1992年 | 1篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1971年 | 1篇 |
1956年 | 1篇 |
1935年 | 1篇 |
排序方式: 共有448条查询结果,搜索用时 15 毫秒
141.
Ankur Kanti Guha 《Journal of organometallic chemistry》2011,696(2):586-593
A systematic density functional investigation has been carried out on the structure, stability and reactivity of heterocyclic carbenes of diverse flexibility, i.e., carbenes with different modes of binding specially normal and remote mode of binding. Ligating properties of these carbenes have been assessed by virtue of their HOMO energies and verified further by inspection of the symmetric CO frequencies of their respective palladium carbonyl complexes. All the remote carbenes were found to have higher σ-donating abilities compared to their normal analogs. N-heterocyclic carbenes 1 and 5 are found to be electrophilic in nature while the remote carbene 3 and P-heterocyclic carbene 6 are found to be nucleophilic. Quantum theory of atoms in molecules (QTAIM) reveals significant covalent character in the Ccarbene-Pd bonds. 相似文献
142.
Chakraborty B Halder P Paine TK 《Dalton transactions (Cambridge, England : 2003)》2011,40(14):3647-3654
The isolation and structural characterisation of three isomeric silver(I) complexes, 1a, 1b and 2 with the general formula {[AgL(1)]ClO(4)}(n) (where L(1) is a bis(bidentate) N,N-donor ligand derived from the Schiff-base condensation of α,α'-diamino-p-xylene and pyridine-2-carboxaldehyde) are discussed. Single-crystal X-ray structures reveal the polymeric nature for the complexes where all the silver ions are in pseudotetrahedral geometry with the AgN(4) coordination environment. Isomers 1a (Pc space group) and 1b (Cc space group) were crystallised from acetonitrile whereas 2 (C2/c space group) was crystallised during the synthesis from a solvent mixture of dicholormethane and methanol. The flexible ligand (L(1)) adopts only an anti conformation in 1b and the presence of two different anti conformations in the repeating unit results in the formation of a trapezoidal wave polymeric chain. However, both gauche and anti conformations of the ligand are found to be present in the polymeric chains of 1a. In the polymeric chain of 2, only one anti isomer of the ligand is present in the repeating unit resulting in a triangular wave chain. The structure of isomer 1a is solvent induced and solvent plays a major role in the crystal packing of this isomer. One-dimensional coordination polymers 1a, 1b and 2 are related to each other as conformational supramolecular isomers. Additionally, two independent polymeric chains parallel to each other: one triangular wave consisting of only an anti conformation and a trapezoidal wave chain consisting of alternate gauche and anti conformations of the ligand are observed in 1a. This is a rare example of two supramolecular isomers present in the same crystal. Six different conformers of the flexible ligand are observed in the crystals of coordination polymers. 相似文献
143.
Cationic antimicrobial peptides are potent inhibitors of growth of a broad spectrum of micro-organisms but often have large cytotoxic effects. We prepared some novel sugar amino acid containing cyclic cationic peptides and their Au nanoparticle attached counterparts and studied their antimicrobial activities and cytotoxic behaviour, including an investigation of the mechanism of the cytotoxicity. 相似文献
144.
A new probe (Z)-3-((naphthalen-1-ylmethylene)amino)phenol has been synthesized by condensation reaction between 1-naphthaldehyde and 3-aminophenol for the fluorescent sensing of Ce3+ by “on” mode and dichromate (Cr2O72?) by “off” mode. Metal ions—Ag+, Al3+, As3+, Ba2+, Ca2+, Cd2+, Ce4+, Co2+, Cr3+, Cr6+, Cu2+, Fe2+, Fe3+, Hg2+, K+, La+, Li+, Mg2+, Mn2+, Na+, Ni2+, Pb2+, Zn2+and anions Br?, C2O42?, CH3COO?, Cl?, CO32?, F?, H2PO4?, HCO3?, HF2?, HPO42?, I?, MnO4?, NO3?, OH?, S2?, S2O32?, SCN?, SO42? do not interfere. The limit of detection (LOD) for sensing Ce3+ and Cr2O72? ions are 1.286?×?10–7 M and 6.425?×?10–6 M, respectively.
相似文献145.
Arenes, heteroarenes, 1,3-dicarbonyls and organosilicon nucleophiles undergo highly efficient alkylation with allylic, propargylic and benzylic alcohols in the presence of a new 'Pd-Sn' bimetallic catalyst in nitromethane; water being the sole byproduct. The plausible mechanism of alkylation and the intermediacy of ether has been enumerated. 相似文献
146.
Abhijit Pal Bhaskar Biswas Sunil Kanti MondalChia-Her Lin Rajarshi Ghosh 《Polyhedron》2012,31(1):671-675
The synthesis and X-ray structural characterisation of a new Cu(II) complex, [Cu(L1)Cl](ClO4)·CH3OH (1) [L1 = N,N′-bis((pyridine-2-yl)phenylidene)-1,3-diaminopropan-2-ol], has been described in this work. The structural study reveals that the Cu(II) centre in 1 has a square pyramidal geometry with a trigonality index τ = 0.43, being coordinated by the organic ligand and a chloro group. The interaction of complex 1 and another complex previously reported by our group, [Cu(L2)](ClO4)2 (2) [L2 = N-(1-pyridin-2-yl-phenylidene)-N′-[2-({2-[(1-pyridin-2-ylphenylidene)amino]ethyl}amino)ethyl]ethane-1,2diamine], with calf thymus DNA (CT-DNA) has been investigated using absorption and emission spectral studies. The binding constant (Kb) and the linear Stern-Volmer quenching constant (Ksv) have been determined. 相似文献
147.
We introduce and study a class of non-stationary semi-Markov decision processes on a finite horizon. By constructing an equivalent Markov decision process, we establish the existence of a piecewise open loop relaxed control which is optimal for the finite horizon problem. 相似文献
148.
Sahana A Banerjee A Guha S Lohar S Chattopadhyay A Mukhopadhyay SK Das D 《The Analyst》2012,137(7):1544-1546
An indole based naphthalene derivative is reported as a highly selective fluorescent probe for azide ion in aqueous ethanol. The probe is applied for cell imaging of the N(3)(-) ion in contaminated living cells. Both experimental and theoretical studies have been performed to figure out the plausible mechanism of fluorescence enhancement of the probe upon binding with N(3)(-). 相似文献
149.
A new easy-to-synthesize chemosensor, 3,3'-bis(indolyl)-4-chlorophenylmethane (hereafter S), was designed, synthesized and employed as a selective optical chemosensor for fluoride ions.(1)H NMR and density functional studies on the system have been carried out to determine the nature of the interaction between S and X(-) (X = inorganic anions) responsible for the significant fluoride-induced changes in the absorption properties of S. The experimental results reveal that abstraction of an acidic proton of S by the fluoride ion, leading to the formation of anionic species, is responsible for the spectral changes. These changes allow signaling for the fluoride ion to detect and estimate the concentration of fluoride ion present even at the submicromolar level, accurate up to 2 μM. Calculations of the transition energies of S, S(-), and S···F(-) (hydrogen bonded complex) show that only S(-) is responsible for the long-wavelength absorption band in the presence of F(-). 相似文献
150.
Mrinal Kanti Roychowdhury 《Israel Journal of Mathematics》2012,192(1):473-488
The quantization dimension function for a probability measure supported on the limit set generated by a set of contractive bi-Lipschitz mappings is determined. The relationship between the quantization dimension function and the temperature function of the thermodynamic formalism arising in multifractal analysis is established. 相似文献