全文获取类型
收费全文 | 112篇 |
免费 | 0篇 |
国内免费 | 1篇 |
专业分类
化学 | 65篇 |
数学 | 27篇 |
物理学 | 21篇 |
出版年
2022年 | 2篇 |
2021年 | 1篇 |
2020年 | 5篇 |
2019年 | 2篇 |
2018年 | 1篇 |
2017年 | 1篇 |
2016年 | 4篇 |
2015年 | 3篇 |
2014年 | 3篇 |
2013年 | 2篇 |
2012年 | 8篇 |
2011年 | 1篇 |
2010年 | 4篇 |
2009年 | 6篇 |
2008年 | 5篇 |
2007年 | 8篇 |
2006年 | 5篇 |
2005年 | 6篇 |
2004年 | 7篇 |
2003年 | 3篇 |
2002年 | 1篇 |
2000年 | 1篇 |
1998年 | 2篇 |
1995年 | 1篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1980年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1973年 | 3篇 |
1972年 | 2篇 |
1935年 | 2篇 |
1933年 | 1篇 |
1927年 | 2篇 |
1924年 | 1篇 |
1919年 | 1篇 |
1917年 | 2篇 |
1908年 | 2篇 |
1898年 | 1篇 |
1892年 | 1篇 |
排序方式: 共有113条查询结果,搜索用时 7 毫秒
1.
Hans-Christian Stolzenberg Gunther Kalnowski Wolfgang Dott 《Photochemistry and photobiology》1995,61(6):627-631
A new integrated system for reproducible, automated mechanical stimulation and measurement of bioluminescence (BL) in multiple samples of marine dinoflagellate cell suspensions is described. The system was designed to allow the application of standardized experimental routines to parallel test vials for the purpose of toxicity testing. A sample tray delivered test vials to the position of mechanical stimulation and BL measurement. Mechanical stimulation of BL was applied as sharp rotation-onset of the test vial about its vertical axis. Thus, any direct chemical or physical perturbation of the cell suspension was avoided. A silicon photovoltaic cell measured the emitted light. Stimulation, measurement and recording of BL were integrated and controlled by specially developed software, which runs on a personal computer in the graphic environment of MS-Windows. Precise scheduling, flexible programming and identical repetition of experimental routines are possible in practice. For Gonyaulax polyedra, details of BL, as stimulated and measured with the new system, are presented and discussed. We conclude that the system exhibits specific features that offer wide potential of application in several fields of research on dinoflagellate BL, particularly for toxicity testing. 相似文献
2.
X-ray structure analysis of the title compound (I) is reported. The results are interpreted to predict formation of anti-tricyclo[4.4.01,6.07,12]-1,4,7,10-tetraethoxycarbonyl-3,6,9,12-tetrahydroxy-dodeca-3,9-diene on UV.-irradiation of solid (I). 相似文献
3.
Siebert HC Born K André S Frank M Kaltner H von der Lieth CW Heck AJ Jiménez-Barbero J Kopitz J Gabius HJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,12(2):388-402
The branched pentasaccharide chain of ganglioside GM1 is a prominent cell surface ligand, for example, for cholera toxin or tumor growth-regulatory homodimeric galectins. This activity profile via protein recognition prompted us to examine the binding properties of peptides with this specificity. Our study provides insights into the mechanism of molecular interaction of this thus far unexplored size limit of the protein part. We used three pentadecapeptides in a combined approach of mass spectrometry, NMR spectroscopy and molecular modelling to analyze the ligand binding in solution. Availability of charged and hydrophobic functionalities affected the intramolecular flexibility of the peptides differently. Backfolding led to restrictions in two cases; the flexibility was not reduced significantly by association of the ligand in its energetically privileged conformations. Major contributions to the interaction energy arise from the sialic acid moiety contacting Arg/Lys residues and the N-terminal charge. Considerable involvement of stacking between the monovalent ligand and aromatic rings could not be detected. This carbohydrate binding strategy is similar to how an adenoviral fiber knob targets sialylated glycans. Rational manipulation for an affinity enhancement can now be directed to reduce the flexibility, exploit the potential for stacking and acquire the cross-linking capacity of the natural lectins by peptide attachment to a suitable scaffold. 相似文献
4.
Hans-Christian Mez Günther Rist Jaroslav Kalvoda Otto Ermer Ljubinka Lorenc Mihailo Lj. Mihailovi 《Helvetica chimica acta》1976,59(4):1273-1293
X-ray structure determination of the p-bromobenzoate 2b of one of the (E/Z)-isomeric 3β-hydroxy-5,10-seco-1(10)-cholesten-5-ones confirmed the (E)-configuration proposed previously and showed the cyclodecenone ring to adopt an extended crown conformation of type A 1 (Fig. 9). Analysis of the 1H- and 13C-NMR. spectra of acetate 2a revealed that in solution the ten-membered ring of this steroid exists in at least two distinct forms, the predominant (about 85%) corresponding to the solid-state conformation of 2b (= A 1), and the minor most likely to B 2 (Fig. 9). From NMR. data the energy difference between the two species and the relevant activation energy were estimated. A number of conformational force field calculations using a simplified partial structural model was performed; but the computed energy differences between the various possible conformations do not reproduce the effective situation, neither in solution nor in the crystal lattice, indicating that additional effects such as the transannular interaction of the double bond with the carbonyl group may strongly influence the thermodynamic stability of the system. The conformations deduced were used to rationalize the stereochemical course of different chemical reactions of 2a . 相似文献
5.
The protonation of [Ru(2)(CO)(4)(mu-H)(mu-PBu(t)()(2))(mu-dppm)(mu-eta(2)-ONNO)] (1) with HBF(4) occurs at the oxygen of the noncoordinating side of the trans-hyponitrite ligand to give [Ru(2)(CO)(4)(mu-H)(mu-PBu(t)()(2))(mu-dppm)(mu-eta(2)-ONNOH)][BF(4)] (2) in good yield. The monoprotonated hyponitrite in 2 is deprotonated easily by strong bases to regenerate 1. Furthermore, 1 reacts with the methylating reagent [Me(3)O][BF(4)] to afford [Ru(2)(CO)(4)(mu-H)(mu-PBu(t)()(2))(mu-dppm)(mu-eta(2)-ONNOMe)][BF(4)] (3). The molecular structures of 2 and 3 have been determined crystallographically, and the structure of 2 is discussed with the results of the DFT/B3LYP calculations on the model complex [Ru(2)(CO)(4)(mu-H)(mu-PH(2))(mu-H(2)PCH(2)PH(2))(mu-eta(2)-ONNOH)](+) (2a). Moreover, the thermolysis of 2 in ethanol affords [Ru(2)(CO)(4)(mu-H)(mu-OH)(mu-PBu(t)()(2))(mu-dppm)][BF(4)] (4) in high yield, and the deprotonation of 4 by DBU in THF yields the novel complex [Ru(2)(CO)(4)(mu-OH)(mu-PBu(t)()(2))(mu-dppm)] (5). 相似文献
6.
7.
The sodium benzophenone ketyl-induced reaction of [Ru3(CO)12] with bis(diphenylphosphanyl)amine Ph2PN(H)PPh2 (dppa) in THF resulted in the formation of the expected metal cluster [Ru3(CO)10(μ-dppa)] ( 1 ) in high yield. 1 was fully characterized by spectroscopic means and crystals of the compound suitable for X-ray diffraction were obtained from dichloromethane/dioxane. The molecular structure of 1 as its dioxane solvate was determined by X-ray crystallography. The compound crystallized in a new crystal structure of [Ru3(CO)10(μ-dppa)] in the triclinic space group P1 , whereas that compound was described in an earlier report crystallizing from chloroform in the monoclinic space group P21/c. 相似文献
8.
Dr. Christin Kirst Jonathan Tietze Dr. Peter Mayer Prof. Dr. Hans-Christian Böttcher Prof. Dr. Konstantin Karaghiosoff 《ChemistryOpen》2022,11(3):e202100224
The different coordination behavior of the flexible yet sterically demanding, hemilabile P,N ligand bis(quinoline-2-ylmethyl)phenylphosphine ( bqmpp ) towards selected CuI, AgI and AuI species is described. The resulting X-ray crystal structures reveal interesting coordination geometries. With [Cu(MeCN)4]BF4, compound 1 [Cu2(bqmpp)2](BF4)2 is obtained, wherein the copper(I) atoms display a distorted square planar and square pyramidal geometry. The steric demand and π-stacking of the ligand allow for a short Cu⋅⋅⋅Cu distance (2.588(9) Å). CuI complex 2 [Cu4Cl3(bqmpp)2]BF4 contains a rarely observed Cu4Cl3 cluster, probably enabled by dichloromethane as the chloride source. In the cluster, even shorter Cu⋅⋅⋅Cu distances (2.447(1) Å) are present. The reaction of Ag[SbF6] with the ligand leads to a dinuclear compound ( 3 ) in solution as confirmed by 31P{1H} NMR spectroscopy. During crystallization, instead of the expected phosphine complex 3 , a tris(quinoline-2-ylmethyl)bisphenyl-phosphine ( tqmbp ) compound [Ag2(tqmbp)2](SbF6)2 4 is formed by elimination of quinaldine. The Au(I) compound [Au2(bqmpp)2]PF6 ( 5 ) is prepared as expected and shows a linear arrangement of two phosphine ligands around AuI. 相似文献
9.
Let B be the Bergman projection associated to a domain Ω on which the -Neumann operator is compact. We show that arbitrary L 2 derivatives of Bf are controlled by derivatives of f taken in a single, distinguished direction. As a consequence, functions not contained in that are mapped by B to are explicitly described. 相似文献
10.
We show that the linear syzygy spaces of elliptic normal curves, their secant varieties and of bielliptic canonical curves are spanned by geometric syzygies. 相似文献