全文获取类型
收费全文 | 404篇 |
免费 | 17篇 |
国内免费 | 4篇 |
专业分类
化学 | 247篇 |
晶体学 | 23篇 |
力学 | 8篇 |
数学 | 29篇 |
物理学 | 118篇 |
出版年
2024年 | 2篇 |
2023年 | 2篇 |
2022年 | 5篇 |
2021年 | 8篇 |
2020年 | 5篇 |
2019年 | 19篇 |
2018年 | 7篇 |
2017年 | 2篇 |
2016年 | 7篇 |
2015年 | 13篇 |
2014年 | 9篇 |
2013年 | 14篇 |
2012年 | 29篇 |
2011年 | 34篇 |
2010年 | 25篇 |
2009年 | 28篇 |
2008年 | 27篇 |
2007年 | 23篇 |
2006年 | 47篇 |
2005年 | 17篇 |
2004年 | 11篇 |
2003年 | 16篇 |
2002年 | 13篇 |
2001年 | 10篇 |
2000年 | 4篇 |
1999年 | 7篇 |
1998年 | 2篇 |
1997年 | 1篇 |
1996年 | 3篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 1篇 |
1992年 | 2篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 4篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1975年 | 1篇 |
1974年 | 4篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1959年 | 1篇 |
1941年 | 1篇 |
排序方式: 共有425条查询结果,搜索用时 31 毫秒
1.
The periodic precipitation pattern formation in gelatinous media is interpreted as a moving boundary problem. The time law,
spacing law and width law are revisited on the basis of the new scenario. The explicit dependence of the geometric structure
on the initial concentrations of the reactants is derived. Matalon—Packter law, which relates the spacing coefficient with
the initial concentrations is reformulated removing many ambiguities and impractical parameters. Experimental results are
discussed to establish the significance of moving boundary concept in the diffusion controlled pattern forming systems 相似文献
2.
Varghese Mathai 《Annals of Global Analysis and Geometry》1992,10(2):103-123
We study topological obstructions to the existence of Riemannian metrics of non-negative scalar curvature on almost spin manifolds using the Dirac operator, the Bochner technique, C
* algebras and von Neumann algebras. We also derive some obstructions in terms of the eta invariants of Atiyah, Patodi and Singer. Next, we prove vanishing theorems for the Atiyah-Milnor genus. Finally, we derive obstructions to the existence of metrics of non-negative scalar curvature along the leaves of a leafwise non-amenable foliation on a spin manifold. 相似文献
3.
4.
A new class of low melting liquid crystalline octaalkyloxyporphyrins have been synthesised. Their Zn(II)-complexes display an interesting ligation behaviour towards amines (of varying shapes and sizes), ascribed to the steric hindrance or hydrophobic pockets on both the faces of the porphryin as evidenced from the crystal structure of Zn(II)-octabutyloxyporphyrin. 相似文献
5.
Ruan C Paulose M Varghese OK Mor GK Grimes CA 《The journal of physical chemistry. B》2005,109(33):15754-15759
Anodization of titanium in a fluorinated dimethyl sulfoxide (DMSO) and ethanol mixture electrolyte is investigated. The prepared anodic film has a highly ordered nanotube-array surface architecture. Using a 20 V anodization potential (vs Pt) nanotube arrays having an inner diameter of 60 nm and 40 nm wall thickness are formed. The overall length of the nanotube arrays is controlled by the duration of the anodization, with nanotubes appearing only after approximately 48 h; a 72 h anodization results in a nanotube array approximately 2.3 mum in length. The photoelectrochemical response of the nanotube-array photoelectrodes is studied using a 1 M KOH solution under both UV and visible (AM 1.5) illumination. Enhanced photocurrent density is observed for samples obtained in the organic electrolyte, with an UV photoconversion efficiency of 10.7%. 相似文献
6.
[reaction: see text] Secondary alpha-lithiosulfinyl carbanions react either intermolecularly, after transmetalation into an organocopper derivative in an S(N)2-type process with zinc carbenoid, or intramolecularly via higher-order zincate to give, through a tandem zinc homologation-beta-elimination reaction the corresponding alkenes. alpha,alpha-Disubstituted alkenes are only formed from tertiary alpha-lithiosulfinyl carbanions via the 1,2-metalate rearrangement. 相似文献
7.
Zhang G Chen KS Merer AJ Hsu YC Chen WJ Shaji S Liao YA 《The Journal of chemical physics》2005,122(24):244308
Rotational analyses have been carried out at high resolution for the 000-000 and 000-100 bands of the A (1)Pi(u)-X (1)Sigma(g) (+) transition of supersonic jet-cooled C(3). Two different spectra have been recorded for each band, using time gatings of 20-150 and 800-2300 ns. At the shorter time delay the spectra show only the lines observed by many previous workers. At the longer time delay many extra lines appear, some of which have been observed previously by [McCall et al.Chem. Phys. Lett. 374, 583 (2003)] in cavity ring-down spectra of jet-cooled C(3). Detailed analysis of these extra lines shows that at least two long-lived states perturb the A (1)Pi(u), 000 state. One of these appears to be a (3)Sigma(u) (-) vibronic state, which may possibly be a high vibrational level of the b (3)Pi(g) state, and the other appears to be a P = 1 state with a low rotational constant B. Our spectra also confirm the reassignment by McCall et al. of the R(0) line of the 000-000 band, which is consistent with the spectra recorded towards a number of stars that indicate the presence of C(3) in the interstellar medium. Fluorescence lifetimes have been measured for a number of upper-state rotational levels. The rotational levels of the A (1)Pi(u) state have lifetimes in the range of 230-190 ns, decreasing slightly with J; the levels of the perturbing states have much longer lifetimes, with some of them showing biexponential decays. An improved value has been obtained for the nu(1) vibrational frequency of the ground state, nu(1) = 1224.4933 +/- 0.0029 cm(-1). 相似文献
8.
The reaction of gaseous H2S with aqueous ammonium heptamolybdate in the presence of triethylenetetramine (trien) gave a red complex. The complex was recrystallized in hot water and characterized by element analysis and UV, visible, IR, and 1H NMR spectroscopy. PMR has revealed accidental magnetic equivalence, resulting from the proximity of [MoS4]2- species in one complex molecule to the open triethylenetetramine ligand of another molecule. (TrienH2)[MoS4] crystallizes in the orthorhombic crystal system, space group Pca21, a=13.045(2), b=16.461(3), c=13.754(2) , =90, =90, =90°, V=2953.5(9) 3, Z=8, R1=0.0323, wR2=0.0730. The structure consists of the tetrahedral tetrathiomolybdate anions, forming an extended 3D framework in solids due to the interactions with triene cations via Mo-S...H-N hydrogen bonds. 相似文献
9.
Manikandan P Muthukumaran R Thomas KR Varghese B Chandramouli GV Manoharan PT 《Inorganic chemistry》2001,40(10):2378-2389
Copper(II) azide complexes of three tridentate ligands namely 2,6-(3,5-dimethylpyrazol-1-ylmethyl)pyridine (L), 2,6-(pyrazol-1-ylmethyl)pyridine (L'), and dipropylenetriamine (dpt) yield three kinds of complexes with different azide-binding modes. The ligand L forms two end-on-end (mu-1,3) diazido-bridged binuclear complexes, [CuL(mu-N(3))](2)(ClO(4))(2) (1) and [CuL(mu-N(3))(ClO(4))](2).2CH(3)CN (2), and L' forms a perchlorato-bridged quasi-one-dimensional chain complex, [CuL'(N(3))(ClO(4))](n)() (3) with monodentate azide coordination. The ligation of dipropylenetriamine (dpt) gives a end-on (mu-1,1) diazido-bridged binuclear copper complex [Cu(dpt)(mu-N(3))](2)(ClO(4))(2) (4). The crystal and molecular structures of these complexes have been solved. Variable-temperature EPR results of 1 and 2 are identical and indicate the presence of both ferromagnetic and antiferromagnetic interactions within the dimer, the former dominating at low temperatures and the latter at high temperatures. The unusual temperature-dependent magnetic moment and EPR spectra of this dimer reveal the presence of temperature-dependent population of two triplet states, one being caused by antiferromagnetic and the other by ferromagnetic interaction, the former transforming to the latter on cooling. While the interaction of ground spin doublets of the two metal centers gives rise to a ferromagnetic coupling of J(g) = 90.73 cm(-1), the other coupling of J(e) = -185.64 cm(-1) is suggested to be caused by the interaction between an electron in one metal center and an electron from the azide of the other monomer by excitation of a d-electron to the empty ligand orbital. The ferromagnetic state is energetically favored by 104.39 cm(-1). Compound 3 exhibits axial spectra at room temperature and 77 K, and variable-temperature magnetic susceptibility data indicate that the copper centers form a weakly antiferromagnetic one-dimensional chain with J = -0.11 cm(-1). In the case of 4, the unique presence of two nonidentical dimeric units with different bond lengths and bond angles within the unit cell as inferred by crystal structure is proved by single-crystal EPR spectroscopy. 相似文献
10.
Koushik Saha Benson Joseph Rongala Ramalakshmi Dr. R. S. Anju Dr. Babu Varghese Prof. Sundargopal Ghosh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(23):7871-7878
Thermolysis of [Cp*Ru(PPh2(CH2)PPh2)BH2(L2)] 1 (Cp*=η5‐C5Me5; L=C7H4NS2), with terminal alkynes led to the formation of η4‐σ,π‐borataallyl complexes [Cp*Ru(μ‐H)B{R‐C=CH2}(L)2] ( 2 a – c ) and η2‐vinylborane complexes [Cp*Ru(R‐C=CH2)BH(L)2] ( 3 a – c ) ( 2 a , 3 a : R=Ph; 2 b , 3 b : R=COOCH3; 2 c , 3 c : R=p‐CH3‐C6H4; L=C7H4NS2) through hydroboration reaction. Ruthenium and the HBCC unit of the vinylborane moiety in 2 a – c are linked by a unique η4‐interaction. Conversions of 1 into 3 a – c proceed through the formation of intermediates 2 a – c . Furthermore, in an attempt to expand the library of these novel complexes, chemistry of σ‐borane complex [Cp*RuCO(μ‐H)BH2L] 4 (L=C7H4NS2) was investigated with both internal and terminal alkynes. Interestingly, under photolytic conditions, 4 reacts with methyl propiolate to generate the η4‐σ,π‐borataallyl complexes [Cp*Ru(μ‐H)BH{R‐C=CH2}(L)] 5 and [Cp*Ru(μ‐H)BH{HC=CH‐R}(L)] 6 (R=COOCH3; L=C7H4NS2) by Markovnikov and anti‐Markovnikov hydroboration. In an extension, photolysis of 4 in the presence of dimethyl acetylenedicarboxylate yielded η4‐σ,π‐borataallyl complex [Cp*Ru(μ‐H)BH{R‐C=CH‐R}(L)] 7 (R=COOCH3; L=C7H4NS2). An agostic interaction was also found to be present in 2 a – c and 5 – 7 , which is rare among the borataallyl complexes. All the new compounds have been characterized in solution by IR, 1H, 11B, 13C NMR spectroscopy, mass spectrometry and the structural types were unequivocally established by crystallographic analysis of 2 b , 3 a – c and 5 – 7 . DFT calculations were performed to evaluate possible bonding and electronic structures of the new compounds. 相似文献