全文获取类型
收费全文 | 2286篇 |
免费 | 37篇 |
国内免费 | 16篇 |
专业分类
化学 | 1355篇 |
晶体学 | 14篇 |
力学 | 39篇 |
数学 | 484篇 |
物理学 | 447篇 |
出版年
2021年 | 23篇 |
2020年 | 27篇 |
2019年 | 18篇 |
2018年 | 19篇 |
2017年 | 19篇 |
2016年 | 40篇 |
2015年 | 31篇 |
2014年 | 39篇 |
2013年 | 104篇 |
2012年 | 82篇 |
2011年 | 90篇 |
2010年 | 55篇 |
2009年 | 46篇 |
2008年 | 86篇 |
2007年 | 91篇 |
2006年 | 99篇 |
2005年 | 93篇 |
2004年 | 95篇 |
2003年 | 72篇 |
2002年 | 57篇 |
2001年 | 33篇 |
2000年 | 26篇 |
1998年 | 19篇 |
1997年 | 20篇 |
1996年 | 37篇 |
1995年 | 29篇 |
1994年 | 22篇 |
1993年 | 23篇 |
1992年 | 30篇 |
1991年 | 21篇 |
1990年 | 18篇 |
1989年 | 18篇 |
1988年 | 17篇 |
1987年 | 18篇 |
1986年 | 22篇 |
1985年 | 30篇 |
1984年 | 33篇 |
1983年 | 17篇 |
1982年 | 38篇 |
1981年 | 27篇 |
1980年 | 42篇 |
1979年 | 37篇 |
1978年 | 32篇 |
1977年 | 39篇 |
1976年 | 47篇 |
1975年 | 42篇 |
1974年 | 35篇 |
1973年 | 25篇 |
1972年 | 17篇 |
1971年 | 21篇 |
排序方式: 共有2339条查询结果,搜索用时 15 毫秒
91.
James B. Clark Arthur L. Smirl Eric W. Van Stryland H.J. Mackey B.R. Russell 《Chemical physics letters》1981,78(3):456-460
The population kinetics and the rotational diffusion of the rhodamine B monomer and dimer were measured by using picosecond pulses from a mode-locked Nd : YAG laser to induce and time resolve the concentration-dependent transient absorption saturation of various aqueous solutions of this organic dye. 相似文献
92.
An acyl iminium ion-initiated tandem cyclization gave an unexpected dienone product, a seco-azasteroid (2). The factors governing the formation of 2 were investigated in an attempt to optimize its formation. The reaction was applied to a more elaborate system, resulting in the synthesis of the full steroid skeleton of 13-azaandrosta-1,4-diene-3,17-dione (3), which contains the unusual substitution of a chlorine atom for the axial 19-methyl. 相似文献
93.
Approximate formulas for the transverse-relaxation rate constant and resonance frequency have been derived for nuclear spins subject to two-site chemical exchange. The new results are more accurate than previous approximations when chemical exchange does not approach the fast-exchange limit or when site populations are not highly asymmetric. Results are derived from an effective average evolution operator that contains contributions from both exact eigenvalues of the Bloch-McConnell equations. These expressions are useful for interpretation of chemical exchange processes in NMR spectroscopy. 相似文献
94.
Michael G. Ikonomou Arthur T. Blades Paul Kebarle 《Journal of the American Society for Mass Spectrometry》1991,2(6):497-505
An equation by D. P. H. Smith predicts the capillary voltage required for the onset of electrospray (ES). For different solvents the voltage increases with the square root of the surface tension. Water requires a potential that is 1.8 times higher than that for methanol. This is verified experimentally. The higher potential required for water leads to ES in the presence of corona electric discharge. For low total ES plus corona currents, the electrosprayed analyte ion intensity is not adversely affected by the presence of discharge. At high total currents, there is a large decrease of analyte sensitivity. The sensitivity decrease is probably due to adverse space charge effect at high currents. The discharge can be suppressed by adding sulfur hexafluoride to the ambient gas. Both sensitivity and signal stability are improved. However, the sensitivity still remains lower by a factor of ≈ 4 relative to that observed with methanol. This is attributed to lower efficiency of gas-phase ion formation from charged water, relative to methanol, droplets. 相似文献
95.
Dragana TadicJoannes T.M Linders Judith L Flippen-Anderson Arthur E JacobsonKenner C Rice 《Tetrahedron》2003,59(25):4603-4614
Two of the 12 possible oxide-bridged phenylmorphans, were synthesized, rac-(3R,6aS,11aS)-2-methyl-1,3,4,5,6,11a-hexahydro-2H-3,6a-methanobenzofuro[2,3-c]azocine-10-ol (7) (the ortho-c compound), and rac-(3R,6aS,11aS)-2-methyl-1,3,4,5,6,11a-hexahydro-2H-3,6a-methanobenzofuro[2,3-c]azocine-8-ol (8) (the para-c compound). Single-crystal X-ray diffraction studies indicated that the dihedral angle between the least squares planes through the phenyl ring and the atoms C1, C11a, C12, and C3 in the piperidine ring in both 7·CHCl3 and 8·HBr was 6.9°. The C12-C6a-C6b-C10a torsion angle was found to be 139.3° for both compounds. The angular relationship between the phenolic ring and the piperidine ring in phenylmorphans that interact with specific opioid receptors as agonists or antagonists is of considerable theoretical interest. 相似文献
96.
New quaternary intermetallic phases REMGa(3)Ge (1) (RE = Y, Sm, Tb, Gd, Er, Tm; M = Ni, Co) and RE(3)Ni(3)Ga(8)Ge(3) (2) (RE = Sm, Gd) were obtained from exploratory reactions involving rare-earth elements (RE), transition metal (M), Ge, and excess liquid Ga the reactive solvent. The crystal structures were solved with single-crystal X-ray and electron diffraction. The crystals of 1 and 2 are tetragonal. Single-crystal X-ray data: YNiGa(3)Ge, a = 4.1748(10) A, c = 23.710(8) A, V = 413.24(2) A(3), I4/mmm, Z = 4; Gd(3)Ni(3)Ga(8)Ge(3), a = 4.1809(18) A, c = 17.035(11) A, V = 297.8(3) A(3), P4/mmm, Z = 1. Both compounds feature square nets of Ga atoms. The distribution of Ga and Ge atoms in the REMGa(3)Ge was determined with neutron diffraction. The neutron experiments revealed that in 1 the Ge atoms are specifically located at the 4e crystallographic site, while Ga atoms are at 4d and 8g. The crystal structures of these compounds are related and could be derived from the consecutive stacking of disordered [MGa](2) puckered layers, monatomic RE-Ge planes and [MGa(4)Ge(2)] slabs. Complex superstructures with modulations occurring in the ab-plane and believed to be associated with the square nets of Ga atoms were found by electron diffraction. The magnetic measurements show antiferromagnetic ordering of the moments located on the RE atoms at low temperature, and Curie-Weiss behavior at higher temperatures with the values of mu(eff) close to those expected for RE(3+) free ions. 相似文献
97.
The preparation of some new cationic aryldiazo complexes of platinum of formula trans-[Pt(N2Ar)(PEt3)2L]+, where N2Ar = N2C6H4F-m or -p and L = NH3, Py, Et3P or EtNC, is described. Protonation of these complexes gives the corresponding aryldiimide complexes trans-[Pt(NHNAr)(PEt3)2L]+, and reduction of the protonated complexes with molecular hydrogen in the presence of a catalyst gives the arylhydrazine complexes trans-[Pt(NH2NHAr)(PEt3)2L]+. Some of the spectroscopic properties of these new complexes are reported and discussed. 相似文献
98.
A new series of vanadates with the general formula M Ba2V3O11, where M may be Bi, In, or a rare earth, has been synthesized and structurally characterized by single crystal X-ray diffraction and powder X-ray diffraction. The general formula may be rewritten as M Ba2(VO4)(V2O7) to emphasize that there is one orthovanadate group and one pyrovanadate group in each formula unit. Up to one-third of the vanadium may be replaced by phosphorous, leading to the general formula M Ba2V2PO11. However, phosphorous shows no preference between the ortho and pyro groups. Both M Ba2V3O11 and M Ba2V2PO11 crystallize in the monoclinic system with the space group P21/c and Z = 4. The cell parameters from single crystal X-ray data of BiBa2V3O11 are a = 12.332(4) Å, b = 7.750(4) Å, c = 11.279(4) Å, β = 103.22(3)°, V = 1049(1) Å3; and for BiBa2PO11 are a = 12.266(2) Å, b = 7.615(2) Å, c = 11.312(2) Å, β = 103.32(2)°, V = 1028.2(2) Å3. The Bi atom coordinates to six oxygen atoms forming a distorted octahedron, and the edge sharing of BiO6 octahedra results in a BiO4 chain along the b axis. There are two types of Ba atoms with coordination numbers of 10 and 11. There are three types of tetrahedral (T) atoms in these structures. The nonequivalent T atoms of the pyro group give T-O-T angles of 167 and 171° in BiBa2V3O11 and BiBa2V2PO11, respectively. Isostructural M Ba2V3O11 compounds were prepared in which M is In, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu. 相似文献
99.
An alternative to traditional hydrocarbon bioremediation is to pump air through unsaturated soils to create aerobic conditions
and induce biodegradation. This study examines the effects of moisture and nutrient augmentation on biodegradation of petroleum
hydrocarbons in aerated soils. Findings indicate that forced aeration, coupled with additions of nutrients and moisture, stimulate
hydrocarbon-degrading microorganisms and present a feasible approach to bioremediation management. 相似文献
100.