全文获取类型
收费全文 | 386篇 |
免费 | 8篇 |
专业分类
化学 | 292篇 |
晶体学 | 19篇 |
力学 | 11篇 |
综合类 | 1篇 |
数学 | 29篇 |
物理学 | 42篇 |
出版年
2022年 | 3篇 |
2021年 | 5篇 |
2020年 | 9篇 |
2019年 | 3篇 |
2018年 | 3篇 |
2017年 | 5篇 |
2016年 | 5篇 |
2015年 | 7篇 |
2014年 | 6篇 |
2013年 | 9篇 |
2012年 | 11篇 |
2011年 | 17篇 |
2010年 | 12篇 |
2009年 | 16篇 |
2008年 | 15篇 |
2007年 | 16篇 |
2006年 | 18篇 |
2005年 | 15篇 |
2004年 | 20篇 |
2003年 | 12篇 |
2002年 | 11篇 |
2001年 | 13篇 |
2000年 | 11篇 |
1999年 | 7篇 |
1998年 | 3篇 |
1997年 | 6篇 |
1996年 | 11篇 |
1995年 | 8篇 |
1994年 | 4篇 |
1993年 | 5篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 5篇 |
1988年 | 3篇 |
1986年 | 4篇 |
1985年 | 6篇 |
1984年 | 8篇 |
1983年 | 5篇 |
1982年 | 5篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 9篇 |
1978年 | 8篇 |
1977年 | 10篇 |
1975年 | 3篇 |
1972年 | 6篇 |
1968年 | 3篇 |
1966年 | 6篇 |
1964年 | 3篇 |
1936年 | 2篇 |
排序方式: 共有394条查询结果,搜索用时 15 毫秒
1.
2.
A study of the viability of three derivatizing reagents for obtaining amino acid profiles in honey through high performance liquid chromatography (HPLC) is presented. A method using diode array detection based on a reaction with diethyl ethoxymethylene malonate (DEMM) and two other methods using fluorescence detection based on derivatization with fluorenylmethyl chloroformate (FMOC-Cl) and 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) have been developed. The three methods yield detection limits close to the ppb level, but vary in relation to other analytical characteristics. The use of methyl chloroformate derivatives allows the profile to be obtained with the greatest sensitivity within a short time frame. On applying such methods to honey samples of diverse botanical origin, we observe that the proline values obtained are always lower than those found using the official spectrophotometric method, thereby underlining the advisability of using HPLC methods to reduce uncertainty in these results. 相似文献
3.
4.
5.
Wolfgang A. Herrmann Carl Krüger Richard Goddard Ivan Bernal 《Journal of organometallic chemistry》1977,140(1):73-89
μ-Carbonylbis(carbonyl-ν5-cycopentadienylrhodium)(Rh—Rh) reacts with N-methyl-and N-ethyl-N-nitrosourea in boiling benzene to yield the dinuclear, diamagnetic, neutral rhodium complexes μ-methylene- (A) and μ-ethylidenebis(carbonyl-η5-cyclopentadienylrhodium)(Rh—Rh) (B), respectively. Deuterium labelled experiments prove the origin of the metal-stabilized methylene ligand to be the alkyl group of the organic precursor. This new method of preparation of transition metal—methylene complexes may be used as an alternative to the commonly used diazo method; the latter method was shown to work with diazodiethylmalonate and dicarbonyl-η5-cyclopentadienylrhodium, the reaction yielding μ-bis(ethoxycarbonyl)methylenebis(carbonyl-η5-cyclopentadienylrhodium)(Rh—Rh).Compound A crystallizes in the triclinic system, P, and with cell constants of a 803.42(5), b 909.98(6), c 938.81(2) pm, α 74.402(3), β81.923(3), and γ 83.685(6)°. The unit cell volume and the calculated density are 651.6 Å3 and 2.069 g cm-3, for one molecule in the asymmetric unit. The molecular geometry of μ-CH2[η5-C5H5Rh(CO)]2 was established from 2718 unique reflections collected with a computer-controlled diffractometer and refined to a final R(F) = 0.0379. The molecular parameters derived from the single-crystal X-ray study conform to a remarkable degree with those found for μ-CO[η5-C5H5Rh(CO)]2. Thus, the bridging ligands CH2 and CO seem to be analogous in their effects on the structural characteristics of the molecular framework of the two molecules. 相似文献
6.
D.C. Lankin G.W. Griffin I. Bernal J. Korp S.F. Watkins T.J. Delord N.S. Bhacca 《Tetrahedron》1984,40(15):2829-2836
Condensation of 2,5,5-trimethylhexa-2,3-dien-6-a1 with malononitrile affords an unexpected product, C15H16N4X, (), the structure of which was partially characterized by spectral (infrared, ultraviolet, 1H, and 13C nmr) methods and fully elucidated by single crystal X-ray analysis. is l-cyano-2-amino-3-(2-propenyl)-5,5-dimethy-6- dicyanomethycycohexa-l,3-diene in a half-chair conformation. Conjugation of the -aminocyanoethenyl moiety leads to intermolecular hydrogen bonding in the crystal. A reaction sequence and its mechanistic implications are proposed. 相似文献
7.
James D. Korp Ivan Bernal Steven F. Watkins F. R. Fronczek 《Journal of heterocyclic chemistry》1982,19(3):459-462
The molecular structure of 10-(1,3-Dithiolan-2-ylidene)-10H-indeno[1,2-f] -1,2,3,4,5-pentathiepin S7C12H89 has been determined by single crystal X-ray diffraction. The crystals are triclinic, space group PI, with two molecules in a unit cell of dimensions α = 8.931(2), b = 9.387(2), c = 10.175(2) Å, α = 75.73(2), β = 73.35(1), γ = 64.37(2)°. The structure was solved by direct methods, and refined to a final R value of 3.3% for 1925 independent reflections. The molecule consists of an indene core with a nearly co-planar dithiolane and a fused pentasulfide chain. The S5C2 ring is in the chair configuration, with an average S? S distance of 2.052 Å. There is no variation of bond lengths as is frequently seen in multi-sulfur chains. The indenone ring shows no evidence of any delocalization, while the dithiolane ring is disordered at the two methylene positions. No attempt was made to resolve the disorder, since it is frequently seen and has been thoroughly investigated previously. 相似文献
8.
Serafin Fraga 《International journal of quantum chemistry》1988,34(6):505-507
The quantity ? = (Φ||(H ? E)Φ|) gives a measure of the error in the approximate solution, Φ (with corresponding energy expectation value E), to an eigenfunction of the Hamiltonian operator H of the system under consideration; this quantity vanishes for the exact function ψ. In a percentage scale (with 0% error for the exact function and 100% for a reference, approximate function), the error of Φ may be expressed as 100(?/?r), where ?r corresponds to the reference function (e.g., obtained with a minimal basis set). This approach eliminates the need of knowing beforehand the exact solution in order to have an estimate of the error of an approximate solution. 相似文献
9.
Single crystals of potassium iron hydrogen phosphate, KFe3(HPO4)2(H2PO4)6 · 4 H2O, were prepared hydrothermally by heating a mixture of Fe2O3, H3PO4 and K2CO3 with a small amount of water. It crystallizes monoclinic, space group C2/c (N° 15 Int. Tab.) with Z = 4 and a = 1701(2), b = 960.4(5), c = 1750(1) pm, β = 90.88(7)°. The crystal structure was solved by using 1716 unique reflections F0 > 4σ(F0) with a final wR2 value of 0.126 (SHELXL-93). The main feature of the crystal structure are layers formed by PO4-tetrahedra around the FeO6-octahedra parallel to (001). K+ and H2O molecules connect these layers. Effective Coordination Numbers (ECoN), Mean Fictive Ionic Radii (MEFIR), Charge Distribution (CHARDI) and the Madelung Part of Lattice Energy (MAPLE) are calculated for the title compound. The existence of hydrogen bonds is confirmed by these calculations. 相似文献