全文获取类型
收费全文 | 466篇 |
免费 | 10篇 |
专业分类
化学 | 335篇 |
晶体学 | 7篇 |
力学 | 2篇 |
数学 | 8篇 |
物理学 | 124篇 |
出版年
2021年 | 6篇 |
2017年 | 4篇 |
2016年 | 8篇 |
2015年 | 8篇 |
2014年 | 6篇 |
2013年 | 9篇 |
2012年 | 16篇 |
2011年 | 24篇 |
2010年 | 10篇 |
2009年 | 8篇 |
2008年 | 15篇 |
2007年 | 18篇 |
2006年 | 18篇 |
2005年 | 21篇 |
2004年 | 31篇 |
2003年 | 21篇 |
2002年 | 22篇 |
2001年 | 14篇 |
2000年 | 10篇 |
1999年 | 10篇 |
1998年 | 7篇 |
1997年 | 4篇 |
1996年 | 5篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 6篇 |
1992年 | 4篇 |
1990年 | 4篇 |
1988年 | 3篇 |
1984年 | 3篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1979年 | 5篇 |
1978年 | 8篇 |
1977年 | 5篇 |
1975年 | 4篇 |
1973年 | 5篇 |
1969年 | 4篇 |
1941年 | 4篇 |
1940年 | 3篇 |
1935年 | 7篇 |
1934年 | 5篇 |
1933年 | 4篇 |
1930年 | 3篇 |
1926年 | 6篇 |
1925年 | 6篇 |
1904年 | 3篇 |
1899年 | 4篇 |
1898年 | 3篇 |
1885年 | 5篇 |
排序方式: 共有476条查询结果,搜索用时 15 毫秒
211.
Jörg Sindlinger Jochen Glaser Helga Bettentrup Thomas Jüstel H.‐Jürgen Meyer Prof. Dr. 《无机化学与普通化学杂志》2007,633(10):1686-1690
Synthesis of Y2O2(CN2) and Luminescence Properties of Y2O2(CN2):Eu Crystalline powders of the new compound Y2O2(CN2) were prepared by solid state reactions from different mixtures of YCl3/YOCl/Y2O3 and Li2(CN2) at temperatures between 620 °C and 650 °C. Structure refinements based on X‐ray powder diffraction revealed that trigonal Y2O2(CN2) crystallizes with a structure that is closely related to that of Y2O2S, whereas linear N‐C‐N units replace sulphur atoms in Y2O2S. In addition, a hexagonal polytype of Y2O2(CN2) was obtained in which a different stacking sequence of yttrium atoms creates a doubling of the c‐axis. Europium‐doped samples of Y2O2(CN2) were prepared and the luminescence properties of Y2O2(CN2):Eu are presented. 相似文献
212.
Novel avilamycin derivatives with improved polarity generated by targeted gene disruption 总被引:3,自引:0,他引:3
Weitnauer G Hauser G Hofmann C Linder U Boll R Pelz K Glaser SJ Bechthold A 《Chemistry & biology》2004,11(10):1403-1411
The oligosaccharide antibiotics avilamycin A and C are produced by Streptomyces viridochromogenes Tu57. Both consist of a heptasaccharide chain, which is attached to a polyketide-derived dichloroisoeverninic acid moiety. They show excellent antibiotic activity against Gram-positive bacteria. Both molecules are modified by O-methylation at different positions, which contributes to poor water solubility and difficulties in galenical drug development. In order to generate novel avilamycin derivatives with improved polarity and improved pharmacokinetic properties, we generated a series of mutants with one, two, or three mutated methyltransferase genes. Based on the structure of the novel avilamycin derivatives, the exact function of three methyltransferases, AviG2, AviG5, and AviG6, involved in avilamycin biosynthesis could be assigned. 相似文献
213.
Anxolabéhère-Mallart E Glaser T Frank P Aliverti A Zanetti G Hedman B Hodgson KO Solomon EI 《Journal of the American Chemical Society》2001,123(23):5444-5452
Ligand K-edge X-ray absorption spectroscopy (XAS) provides a direct experimental probe of ligand-metal bonding. In previous studies, this method has been applied to mononuclear Fe-S and binuclear 2Fe-2S model compounds as well as to rubredoxins and the Rieske protein. These studies are now extended to the oxidized and reduced forms of ferredoxin I from spinach. Because of its high instability, the mixed-valence state was generated electrochemically in the protein matrix, and ligand K-edge absorption spectra were recorded using an XAS spectroelectrochemical cell. The experimental setup is described. The XAS edge data are analyzed to independently determine the covalencies of the iron-sulfide and -thiolate bonds. The results are compared with those obtained previously for the Rieske protein and for 2Fe-2S model compounds. It is found that the sulfide covalency is significantly lower in oxidized FdI compared to that of the oxidized model complex. This decrease is interpreted in terms of H bonding present in the protein, and its contribution to the reduction potential E degrees is estimated. Further, a significant increase in covalency for the Fe(III)-sulfide bond and a decrease of the Fe(II)-sulfide bond are observed in the reduced Fe(III)Fe(II) mixed-valence species compared to those of the Fe(III)Fe(III) homovalent site. This demonstrates that, upon reduction, the sulfide interactions with the ferrous site decrease, allowing greater charge donation to the remaining ferric center. That is the dominant change in electronic structure of the Fe(2)S(2)RS(4) center upon reduction and can contribute to the redox properties of this active site. 相似文献
214.
We analyze the space integralsQ=d
3
x(x) of finitely localized densities . It turns out that the time translated operatorsQ(t) are polynomials int ifQ annihilates the vacuum. In particular,Q(t) =Q in models with short-range forces and complete particle interpretation. These results are valid in the Haag-Araki framework of field theory as well as in the Wightman formalism. Lorentz covariance is not needed in the proofs. 相似文献
215.
Inequalities on eigenvalues of the Schrödinger operator are re-examined in the case of spherically symmetric potentials. In particular, we obtain:
- A connection between the moments of order (n ? 1)/2 of the eigenvalues of a one-dimensional problem and the total number of bound statesN n, inn space dimensions;
- optimal bounds on the total number of bound states below a given energy in one dimension;
- alower bound onN 2;
- a self-contained proof of the inequality for α ≧ 0,n ≧ 3, leading to the optimalC 04,C 3;
- solutions of non-linear variation equations which lead, forn ≧ 7, to counter examples to the conjecture thatC 0n is given either by the one-bound state case or by the classic limit; at the same time a conjecture on the nodal structure of the wave functions is disproved.
216.
217.
Black carbon (BC) is a complex continuum of partly charred organic matter predominantly consisting of condensed aromatic and graphitic moieties and it has high potential for long-term carbon sequestration in soils and sediments. There has been common agreement that BC is exclusively formed by incomplete combustion of organic matter, while non-pyrogenic sources are negligible. In this study, we investigated the stable carbon isotope signature of benzenepolycarboxylic acids (BPCAs) as molecular markers for BC to test if there is also a significant contribution of non-pyrogenic carbon to this fraction in soils. BPCAs were formed by hot nitric acid oxidation of different soils and analyzed by three different procedures: (i) elemental analysis - isotope ratio mass spectrometry (EA-IRMS) of bulk BPCAs and gas chromatography - combustion - isotope ratio mass spectrometry (GC-C-IRMS) of (ii) BPCA trimethylsilyl (TMS) derivatives, and (iii) BPCA methyl derivatives. Best accuracy and precision of isotope measurements were obtained by EA-IRMS of bulk BPCAs although this method has a risk of contamination by non-BC-derived compounds. The accuracy and precision of GC-C-IRMS measurements were superior for methyl derivatives (+/-0.1 per thousand and 0.5 per thousand, respectively) to those for TMS derivatives (+3.5 per thousand and 2.2 per thousand, respectively).Comparison of BPCA delta(13)C values of soil samples prior to and after laboratory and field incubations with both positive and negative (13)C labels at natural and artificial abundances revealed that up to 25% of the isolated BC fraction in soils had been produced in situ, without fire or charring. Commonly applied methods to quantify BC exclusively formed by pyrogenic processes may thus be biased by a significant non-pyrogenic fraction. Further research is encouraged to better define isolated BC fractions and/or understand mechanisms for non-pyrogenic BC production in soils. 相似文献
218.
Strautmann JB George SD Bothe E Bill E Weyhermüller T Stammler A Bögge H Glaser T 《Inorganic chemistry》2008,47(15):6804-6824
The ligand L (2-) (H 2L = N, N'-dimethyl- N, N'-bis(3,5-di- t-butyl-2-hydroxybenzyl)-1,2-diaminoethane) has been employed for the synthesis of two mononuclear Fe (III) complexes, namely, [LFe(eta (2)-NO 3)] and [LFeCl]. L (2-) is comprised of four strongly electron-donating groups (two tert-amines and two phenolates) that increase the electron density at the coordinated ferric ions. This property should facilitate oxidation of the complexes, that is, stabilization of the oxidized species. The molecular structures in the solid state have been established by X-ray diffraction studies. [LFeCl] is five-coordinate in a square-pyramidal coordination environment with the ligand adopting a trans-conformation, while [LFe(eta (2)-NO 3)] is six-coordinate in a distorted octahedral environment with the ligand in a beta-cis conformation. The electronic structures have been studied using magnetization, EPR, Mossbauer (with and without applied field), UV-vis-NIR, and X-ray absorption spectroscopies, which demonstrate highly anisotropic covalency from the strong sigma- and pi-donating phenolates. This analysis is supported by DFT calculations on [LFeCl]. The variations of the well-understood spectroscopic data in the solid state to the spectroscopic data in solution have been used to obtain insight in the molecular structure of the two complexes in solution. While the molecular structures of the solid states are retained in solutions of nonpolar aprotic solvents, there is, however, one common molecular structure in all protic polar solvents. The analysis of the LMCT transitions and the rhombicity E/ D clearly establish that both compounds exhibit a beta-cis conformation in these protic polar solvents. These two open coordination sites, cis to each other, allow access for two potential ligands in close proximity. Electrochemical analysis establishes two reversible oxidation waves for [LFeCl] at +0.55 V and +0.93 V vs Fc (+)/Fc and one reversible oxidation wave at +0.59 V with an irreversible oxidation at +1.07 V vs Fc (+)/Fc for [LFe(eta (2)-NO 3)]. The one- and the two-electron oxidations of [LFeCl] by chronoamperometry have been followed spectroscopically. The increase of a strong band centered at 420 nm indicates the formulation of [LFeCl] (+) as a Fe (III) monophenoxyl radical complex and of [LFeCl] (2+) as a Fe (III) bisphenoxyl radical complex. These studies imply that the ligand L (2-) is capable of providing a flexible coordination geometry with two binding sites for substrates and the allocation of two oxidation equivalents on the ligand. 相似文献
219.
Radicals resulting from one-electron reduction of (N-methylpyridinium-4-yl) methyl esters have been reported to yield (N-methylpyridinium-4-yl) methyl radical, or N-methyl-gamma-picoliniumyl for short, by heterolytic cleavage of carboxylate. This new reaction could provide the foundation for a new structural class of bioreductively activated, hypoxia-selective antitumor agents. N-methyl-gamma-picoliniumyl radicals are likely to damage DNA by way of H-abstraction and it is of paramount significance to assess their H-abstraction capabilities. In this context, the benzylic C-H homolyses were studied of toluene (T), gamma-picoline (P, 4-methylpyridine), and N-methyl-gamma-picolinium (1c, 1,4-dimethylpyridinium). With a view to providing capacity for DNA intercalation the properties also were examined of the annulated derivatives 2c (1,4-dimethylquinolinium), 3c (9,10-dimethylacridinium), and 4c (1,4-dimethylbenzo[g]quinolinium). The benzylic C-H homolyses were studied with density functional theory (DFT), perturbation theory (up to MP4SDTQ), and configuration interaction methods (QCISD(T), CCSD(T)). Although there are many similarities between the results obtained here with DFT and CI theory, a number of significant differences occur and these are shown to be caused by methodological differences in the spin density distributions of the radicals. The quality of the wave functions is established by demonstration of internal consistencies and with reference to a number of observable quantities. The analysis of spin polarization emphasizes the need for a clear distinction between "electron delocalization" and "spin delocalization" in annulated radicals. Aside from their relevance for the rational design of new antitumor drugs, the conceptional insights presented here also will inform the understanding of ferromagnetic materials, of spin-based signaling processes, and of spin topologies in metalloenzymes. 相似文献
220.
The results are presented of a theoretical study of the nitrosation chemistry of pyrroline 1 (X = CH2), imidazoline 2 (X = NH), and 2-oxazoline 3 (X = O). Imines 1-3 are converted to the alpha-hydroxy-N-nitrosamines 7-9 via the N-nitrosoiminium ions 4-6. The NN-cis isomers of 7-9 may undergo retro-ene reactions to the delta-oxoalkyl diazotic acids 10-12. With the opportunity for microsolvation, C-X cleavage becomes possible for 8 and 9 and leads to the formation of N-(2-aminoethyl)- and N-(2-hydroxyethyl)-N-nitrosoformamides 15 and 16, respectively. The NN-isomerization barriers are comparable to the barriers for the ring-opening reactions, and the consideration of two Curtin-Hammett scenarios is required: CH-I for the NN-trans-rotamers of 7-9 to undergo C-X cleavage or NN-isomerization and CH-II for the NN-cis-rotamers to undergo C-X cleavage, C-N cleavage, or NN-isomerization. We determined all stereoisomers of the substrates, the products, and of all transition states structures for the retro-ene reactions of 7-9, the C-X cleavages of microsolvated 8 and 9, and the NN-isomerizations of 8 and 9. The potential energy surfaces were explored at the B3LYP/6-31G level, and the results are discussed with emphasis on the comparison of the kinetics and thermodynamics of C-N versus C-X cleavage. The study shows all decompositions to be very fast with activation barriers below 21 kcal.mol(-1), and the comparative analysis predicts that the chemical toxicologies of 1 and 3 should be similar and remarkably different from that of 2. 相似文献