全文获取类型
收费全文 | 594篇 |
免费 | 11篇 |
国内免费 | 5篇 |
专业分类
化学 | 292篇 |
晶体学 | 9篇 |
力学 | 27篇 |
数学 | 192篇 |
物理学 | 90篇 |
出版年
2022年 | 4篇 |
2021年 | 2篇 |
2020年 | 4篇 |
2019年 | 7篇 |
2018年 | 2篇 |
2017年 | 5篇 |
2016年 | 12篇 |
2015年 | 9篇 |
2014年 | 12篇 |
2013年 | 19篇 |
2012年 | 29篇 |
2011年 | 32篇 |
2010年 | 14篇 |
2009年 | 22篇 |
2008年 | 27篇 |
2007年 | 27篇 |
2006年 | 28篇 |
2005年 | 19篇 |
2004年 | 22篇 |
2003年 | 27篇 |
2002年 | 26篇 |
2001年 | 13篇 |
2000年 | 14篇 |
1999年 | 10篇 |
1998年 | 9篇 |
1996年 | 9篇 |
1995年 | 7篇 |
1994年 | 5篇 |
1993年 | 10篇 |
1992年 | 9篇 |
1991年 | 3篇 |
1990年 | 5篇 |
1989年 | 5篇 |
1988年 | 7篇 |
1987年 | 10篇 |
1986年 | 16篇 |
1985年 | 16篇 |
1984年 | 13篇 |
1983年 | 11篇 |
1982年 | 13篇 |
1981年 | 12篇 |
1980年 | 10篇 |
1979年 | 16篇 |
1978年 | 8篇 |
1977年 | 13篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1973年 | 3篇 |
1938年 | 1篇 |
1883年 | 1篇 |
排序方式: 共有610条查询结果,搜索用时 15 毫秒
11.
Carper WR Wahlbeck PG Antony JH Mertens D Dölle A Wasserscheid P 《Analytical and bioanalytical chemistry》2004,378(6):1548-1554
The molecular structure and rotational motion of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) were studied over a wide temperature range using the Bloembergen–Purcell–Pound 13C NMR spin–lattice relaxation method and NOE factors. Examination of the spin–lattice relaxation times (T
1) and the rates (R
1=1/T
1) of the 1-butyl-3-methylimidazolium cation reveals the relative motions of each carbon in the imidazolium cation. The rotational characteristics of the [BMIM] cation are supported by ab-initio molecular structures of [BMIM][PF6] using density functional theory (DFT) and Hartree–Fock (HF) methods. The ab-initio gas phase structures of [BMIM][PF6] indicate that the 1-butyl-3-methylimidazolium C2 hydrogen, the ring methyl group, and the butyl side-chain hydrogen atoms form hydrogen bonds with the hexafluorophosphate anion. 相似文献
12.
David G. Morris Kenneth W. Muir Karl S. Ryder 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(10):o615-o618
Crystals of 9‐methylfluoren‐9‐ol, C14H12O, undergo a reversible phase transition at 176 (2) K. The structure of the high‐temperature α form at 200 K is compared with that of the low‐temperature β form at 100 K. Both polymorphs crystallize in space group P with Z = 4 and contain discrete hydrogen‐bonded R(8) ring tetramers arranged around crystallographic inversion centres. The most obvious changes observed on cooling the crystals to below 176 K are an abrupt increase of ca 0.5 Å in the shortest lattice translation, and a thermal transition with ΔH = 1 kJ mol?1. 相似文献
13.
The structure of [Pt2Cl(CO) (μ-Ph2PCH2PPh2)2] [PF6] was determined by -ray methods and refined to = 0.082, using diffractometric intensities of 5646 independent reflections. The crystals are monoclinic, space group 21/, = 12.919(3), = 15.576(6), = 25.151(5)Å, β = 94.82(3)°, = 4. They are built of octahedral hexafluorophosphate anions and dinuclear platinum(I) cations. The latter contain PtCl and PtCO fragments linked to one another by a PtPt σ-bond and by two bridging bis(diphenylphosphino)methane ligands. The platinum atoms are in square planar environments and the dihedral angle between the two coordination planes is 40.1°. Selected bond lengths are: PtPt 2.620(1), PtCl 2.384(5), PtC 1.89(3) and PtP 2.291(5) – 2.308(5)Å. 相似文献
14.
Protein trans-splicing involving naturally or artificially split inteins results in two polypeptides being linked together by a peptide bond. While this phenomenon has found a variety of applications in chemical biology and biotechnology, precious little is known about the molecular recognition events governing the initial fragment association step. In this study, fluorescence approaches have been used to measure the dissociation constant for the Ssp DnaE split intein interaction and to determine the on and off rates of fragment association. The DnaE fragments bind with low nanomolar affinity, and our data suggest that electrostatics make an important contribution to the very rapid association of the fragments at physiological pH. This information was used to develop a tandem trans-splicing system based on native and engineered split inteins. This novel system allows the one-pot assembly of three polypeptides under native conditions and can be performed in crude cell lysates. The technology should provide a convenient approach to the segmental isotopic or fluorogenic labeling of specific domains within the context of large multidomain proteins. 相似文献
15.
A series of complexes trans-[PdCl(2)L(2)] has been prepared by the reaction of [PdCl(2)(PhCN)(2)] and/or Na(2)[PdCl(4)] with L = pyridine or quinoline ligands having one or two carboxylic acid groups. These complexes can form 1-D polymers through O-H.O hydrogen bonding between the carboxylic acid groups, as demonstrated by structure determinations of [PdCl(2)(NC(5)H(4)-4-COOH)(2)], [PdCl(2)(NC(5)H(4)-3-COOH)(2)], and [PdCl(2)(2-Ph-NC(9)H(5)-4-COOH)(2)]. In some cases, solvation breaks down the O-H.O hydrogen-bonded structures, as in the structures of [PdCl(2)(NC(5)H(4)-3-COOH)(2)].2DMSO and [PdCl(2)(2-Ph-NC(9)H(5)-4-COOH)(2)].4DMF, while pyridine-2-carboxylic acid underwent deprotonation to give the chelate complex [Pd(NC(5)H(4)-2-C(O)O)(2)]. The complexes trans-[PdCl(2)L(2)], L = pyridine-3,5-dicarboxylic acid or 2,6-dimethyl pyridine-3,5-dicarboxylic acid, self-assembled to give 2-D sheet structures, with hydrogen bonding between the carboxylic acid groups mediated by solvate methanol or water molecules. In the cationic complexes [PdL'(2)L(2)](2+) (L'(2) = Ph(2)PCH(2)PPh(2), Ph(2)P(CH(2))(3)PPh(2); L = pyridine carboxylic acid; anions X(-) = CF(3)SO(3)(-)), hydrogen bonding between the carboxylic acid groups and anions or solvate acetone molecules occurred, and only in one case was a polymeric complex formed by self-assembly. 相似文献
16.
Paul W.R. Harris Victoria J. Muir Michelle Y.H. Lai Nicholas S. Trotter David J. Callis 《Tetrahedron》2005,61(42):10018-10035
The synthesis of ten proline-modified analogues of the neuroprotective tripeptide GPE is described. Five of the analogues incorporate a proline residue with a hydrophobic group at C-2 and two further analogues have this side chain locked into a spirolactam ring system. The pyrrolidine ring was also modified by replacing the γ-CH2 group with sulfur and/or incorporation of two methyl groups at C-5. 相似文献
17.
Stuart Lang Neil Muir Franziska Schönebeck Andrew H. Payne 《Tetrahedron letters》2005,46(23):4027-4030
The phosphorus based radical precursors N-ethylpiperidine hypophosphite (EPHP) and diethylphosphine oxide (DEPO) are efficient reagents for carrying out the formation of seven- and eight-membered rings. Esters and amides were successfully converted into the corresponding eight-membered lactones and seven- and eight-membered lactams in good to excellent yields. 相似文献
18.
Volmer DA Brombacher S Whitehead B 《Rapid communications in mass spectrometry : RCM》2002,16(24):2298-2305
In this study, the performance of monolithic columns was evaluated for ultrafast liquid chromatography/mass spectrometry (LC/MS) analyses and for high-resolution separations of several azaspiracid biotoxin analogs. Because of their high permeability, monolithic columns offer a number of advantages over conventional packed columns; viz., very low backpressures and relatively flat van Deemter curves at high flow rates. That is, very high flow rates can be used for ultrafast analyses or, by using longer than normal columns, high-resolution separations are possible. In a series of experiments, we varied the mobile phase flow rates between 1 and 8 mL/min, and studied their impact on chromatographic parameters such as retention time, resolution, number of plates and pressure. The chromatographic run times could be reduced to ca. 30 s without a significant change in the separation efficiency. A signal intensity comparison revealed interesting differences between atmospheric-pressure chemical ionization (APCI) and electrospray ionization (ESI) in their flow-rate dependency. An explanation with respect to the behavior as of a mass-flow or a concentration-dependent device is given in the paper. Additionally, the column length was varied between 10 and 70 cm. As a result, the number of theoretical plates increased substantially. In the example shown in the report, an increase from 13 000 plates for a 10-cm column to 80 000 for a 70-cm column is demonstrated. In addition, the potential of the monolithic columns for high-resolution LC/MS separations is shown for a complex biotoxin mixture, which was separated on a 40-cm-long column. 相似文献
19.
20.
Abstract— Ellipsometric angles and reflectivity of black lipid membranes containing either egg lecithin or chloroplast extracts were measured at a wavelength of 6328 Å. Evidence was found for positive uniaxial anisotropy in membranes of lecithin. If the thickness of those films is assumed to be 62 Å, the refractive index normal to the film surface is 1.471 ± 0.004, and the refractive index parallel to the film surface is 1.454 ± 0.003. The results for membranes of chloroplast extracts also indicate a positive anisotropy in the indices of absorption. 相似文献