全文获取类型
收费全文 | 268篇 |
免费 | 18篇 |
专业分类
化学 | 212篇 |
晶体学 | 11篇 |
力学 | 1篇 |
数学 | 18篇 |
物理学 | 44篇 |
出版年
2023年 | 5篇 |
2022年 | 2篇 |
2021年 | 4篇 |
2020年 | 10篇 |
2019年 | 3篇 |
2018年 | 4篇 |
2017年 | 5篇 |
2016年 | 15篇 |
2015年 | 13篇 |
2014年 | 12篇 |
2013年 | 22篇 |
2012年 | 24篇 |
2011年 | 16篇 |
2010年 | 6篇 |
2009年 | 11篇 |
2008年 | 8篇 |
2007年 | 13篇 |
2006年 | 13篇 |
2005年 | 12篇 |
2004年 | 10篇 |
2003年 | 5篇 |
2002年 | 8篇 |
2001年 | 2篇 |
2000年 | 6篇 |
1999年 | 3篇 |
1998年 | 4篇 |
1997年 | 5篇 |
1996年 | 3篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1988年 | 4篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1982年 | 2篇 |
1980年 | 1篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1975年 | 1篇 |
1967年 | 2篇 |
1966年 | 1篇 |
1965年 | 1篇 |
1962年 | 2篇 |
1934年 | 1篇 |
1931年 | 2篇 |
排序方式: 共有286条查询结果,搜索用时 0 毫秒
1.
The mechanism of degradation of 9-acetoxy-10-arylanthracenes to anthraquinose with the use of HNO3 in AcOH has been reported. This was proved by way of example on 9-acetoxy-10-(4′-acetoxyphenyl )anthracene (1) by means of separation and identification of intermediate products , and . 相似文献
2.
Kabatc J Jedrzejewska B Orliński P Paczkowski J 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(1-3):115-125
The photophysical and photochemical properties of p-substitued 2-styryl-ethylbenzothiazolium iodides, possessing different electron-withdrawing or electron-donating groups are described. The dyes were prepared by the condensation of 3-ethyl-2-methylbenzothiazole salts with p-substituted benzaldehydes. The synthesis of suitable substrates is presented as well. We describe here the absorption, emission spectra and the luminescence quantum yield of hemicyanine dyes (SH) measured in 11 different organic solvents of varying polarity. Molecular structure of the synthesized dyes was established by (1)H NMR, electronic absorption and fluorescence spectrometry. The spectral data confirmed that all the compounds exist in E-configuration of their styryl residues. The planar molecular conformation is typical for the compounds with five-membered side aromatic moieties (for example benzothiazole). The compounds possessing N-alkyl substituent in phenyl ring, in contrast to the compounds with other substituents, exhibit low fluorescence quantum yield in THF solution. This indicates that for N-alkyl derivatives the non-radiative processes are much more effective than the radiative ones. The electronic absorption and fluorescence emission spectra of tested dyes demonstrate high sensitivity to the nature of substituent introduced into the aromatic ring. 相似文献
3.
Strerath M Cramer J Restle T Marx A 《Journal of the American Chemical Society》2002,124(38):11230-11231
DNA polymerase selectivity often varies significantly depending on the DNA polymerase. The origin of this varying error propensity is elusive. It is assumed that DNA polymerases form nucleotide binding pockets that differ in properties such as shape and tightness. We tested this prediction and studied HIV-1 RT by employment of size-augmented nucleotides and site-directed mutagenesis of the enzyme. New valuable insights into the mechanism of DNA polymerase fidelity were obtained. The presented study provides experimental evidence that variations of steric constraints within the nucleotide binding pocket of at least two DNA polymerases cause variations in nucleotide incorporation selectivity. Thus, our results support the concept of active site tightness as a causative in differential fidelity among DNA polymerases. 相似文献
4.
A series of new neutral dicarboxylatoplatinum(II) complexes, containing D(+), L(−) or DL-malate dianion and ethylenediamine,
1-ethylimidazole or 1-propylimidazole as amine ligands, have been synthesized and characterized by elemental analysis, t.l.c.,
conductance, i.r., n.m.r., mass spectra (m/z) and electronic spectra. The new cytotoxic malatoplatinum(II) complexes are very soluble in water and resist hydrolysis.
Their reactivity against glutathione is comparable with the reactivity of carboplatin, which suggests that these new complexes
may be promising candidates in the search for low toxicity platinum cytostatics.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
5.
Jerzy Lange Elzbieta Pytlewska Jan Plenkiewicz Tomasz Kulinski Janina Karolak-Wojciechowska Slawomir Rump 《Journal of heterocyclic chemistry》1997,34(2):389-396
Ethoxycarbonylalkylidene derivatives 2 and 6 of the title hydrazones were obtained in the reaction with ethyl pyruvate or ethyl aroylformate and ethyl acetoacetate, respectively, in methanol. Both compounds were mixtures of geometric isomers with high predominance of one of them. Nmr spectroscopy revealed an unexpected magnetic non-equivalence of the CH2 protons in the ester ethyl group of the major isomer of 6 . On heating (?200°) in an inert medium or on refluxing in ethanolic sodium ethoxide 2 cyclized to the corresponding pyridazino[6,1-c]-triazines 4 , whereas 6 formed pyrazolylpyridazines 7 . The structure of the latter was unambigously established by X-ray analysis. Alkylation of 4a with benzyl bromide in the presence of tetrabutylammonium bromide occurred selectively on the pyridazine N atom. 相似文献
6.
In this paper the thermal energy diffusion for quantum particles is described. The quantum heat transport equation is obtained. It is shown that, for a short-time thermal excitation (of the order of the relaxation time), the excited matter response is quantized on the different levels (atomic, nuclear, quark) with quantum thermal energy equalE
atomic 9 eV,E
nuclear 7 MeV, andE
quark 139 MeV. 相似文献
7.
8.
9.
Abstract The synthesis of nucleoside cyclic 3′,5′-phosphorofluoridates, so far not described compounds in the chemical literature, have been performed. As a key substrate we used 2′-deoxyribonucleoside cyclic 3′,5′-phosphorothioates (1) which have been obtained in this Laboratory several years ago.1 相似文献
10.
Janina Möker Ursula Salge-Bartels Joachim Thiem 《Journal of carbohydrate chemistry》2013,32(9):702-710
Syntheses of carbohydrate-functionalized platinum complexes resembling presently employed cytostatics were performed. Mono-allylated sugar substrates obtained in two steps from glucose and galactose were connected with 2-allyl diethyl malonate by cross-metathesis. Following hydrogenation and acidic cleavage of the ester and alkylidene functionalities gave dicarboxylated glycoconjugates, which were transformed into their diammine platinum complexes. The antitumor activities of these platinum complexes were checked by sensitivity testing with 11 lung cancer cell lines. The novel glucose-platinum complex proved to be comparable to the drug carboplatin. 相似文献