全文获取类型
收费全文 | 716篇 |
免费 | 10篇 |
国内免费 | 1篇 |
专业分类
化学 | 389篇 |
晶体学 | 3篇 |
力学 | 48篇 |
数学 | 156篇 |
物理学 | 131篇 |
出版年
2023年 | 3篇 |
2022年 | 13篇 |
2021年 | 30篇 |
2020年 | 8篇 |
2019年 | 19篇 |
2018年 | 12篇 |
2017年 | 6篇 |
2016年 | 37篇 |
2015年 | 21篇 |
2014年 | 26篇 |
2013年 | 47篇 |
2012年 | 36篇 |
2011年 | 38篇 |
2010年 | 27篇 |
2009年 | 17篇 |
2008年 | 25篇 |
2007年 | 39篇 |
2006年 | 35篇 |
2005年 | 39篇 |
2004年 | 32篇 |
2003年 | 17篇 |
2002年 | 18篇 |
2001年 | 13篇 |
2000年 | 7篇 |
1999年 | 11篇 |
1998年 | 3篇 |
1997年 | 8篇 |
1996年 | 9篇 |
1995年 | 4篇 |
1994年 | 10篇 |
1993年 | 5篇 |
1992年 | 9篇 |
1991年 | 5篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1987年 | 7篇 |
1986年 | 3篇 |
1985年 | 5篇 |
1984年 | 6篇 |
1983年 | 7篇 |
1982年 | 8篇 |
1981年 | 5篇 |
1980年 | 7篇 |
1977年 | 7篇 |
1975年 | 4篇 |
1973年 | 3篇 |
1928年 | 2篇 |
1915年 | 2篇 |
1905年 | 2篇 |
排序方式: 共有727条查询结果,搜索用时 31 毫秒
21.
L. Turrio-Baldassarri A. Carere A. di Domenico S. Fuselli N. Iacovella F. Rodriguez 《Fresenius' Journal of Analytical Chemistry》1994,348(1-2):144-147
Summary The isomer specific determination of PCDD, PCDF and PCB was carried out on samples of air and inhalable particulate from Rome. Samples were taken daily for six months and pooled to yield two samples per month. Normal PCDD+PCDF concentrations expressed in TEQ ranged from 48 to 87 fg/m3, while total PCB ranged from 0.1 to 1.4 ng/m3. The 2, 3, 7, 8-substituted PCDD and PCDF congener pattern is shown together with the PCB congener pattern. 相似文献
22.
We discuss structural and thermodynamical properties of Baxter's adhesive hard sphere model within a class of closures which includes the Percus-Yevick (PY) one. The common feature of all these closures is to have a direct correlation function vanishing beyond a certain range, each closure being identified by a different approximation within the original square-well region. This allows a common analytical solution of the Ornstein-Zernike integral equation, with the cavity function playing a privileged role. A careful analytical treatment of the equation of state is reported. Numerical comparison with Monte Carlo simulations shows that the PY approximation lies between simpler closures, which may yield less accurate predictions but are easily extensible to multicomponent fluids, and more sophisticate closures which give more precise predictions but can hardly be extended to mixtures. In regimes typical for colloidal and protein solutions, however, it is found that the perturbative closures, even when limited to first order, produce satisfactory results. 相似文献
23.
Domenico Osella Mauro Ravera Carlo Floriani Euro Solari 《Journal of organometallic chemistry》1996,510(1-2):45-50
We describe the redox behaviour in non-aqueous solvents of some cyclopentadienyl(oxo)titanium derivatives. The derivative [Ti4{η5-C5H4(SiMe3)}4(μ-O)6] shows an electrochemically and chemically reversible le reduction process, followed by a multi-electron, chemically complicated reduction at a fairly cathodic potential. On the basis of the overall electrochemical features and the comparison with the redox behaviour of the quasi-planar compound [[Ti{η5-C5H4(SiMe3)}Cl(μ-O)]4] we propose an EECCEE mechanism for the first derivative, where the second electron-transfer induces a cascade of chemical reactions giving rise to irreversible cluster breakdown. The electrochemically induced fragmentation can be viewed as a retrosynthetic pathway. The heterometallic derivative [{Ti(η5-C5H4Me)2(μ2-MoO4)2}2] shows two consecutive reduction processes; the first is chemically reversible, and the second quasi-reversible. The molybdate bridges apparently increase the stability of the electrogenerated anions. However none of these poly-oxo clusters can be considered as good models of electron ‘sinks’. 相似文献
24.
The oxidation of some 3-(methoxy- and ethoxycarbonyl)tetrahydro-β-carboline derivatives with sodium periodate led to the formation of 1, 4-benzodiazonine derivatives or fully aromatic β-carbolines depending on both nature and number of substituents at 1-position. 相似文献
25.
NMR spectral data of some (E)-α-phenyl-β-(2-thienyl) acrylic acids indicate that these compounds exist in the preferred s-trans conformation. In the case of (E)-α-phenyl-β-(2-furyl)acrylic acids and their methyl esters the presence of only s-cis rotamer has been established. 相似文献
26.
Marotta E Lapolla A Fedele D Senesi A Reitano R Witt M Seraglia R Traldi P 《Journal of mass spectrometry : JMS》2003,38(2):196-205
The Maillard reaction occurring between sugars and amino groups is important in living systems. When amino groups belonging to protein chains are involved, the Maillard reaction has been invoked as responsible for protein cross-linking and the production of 'toxic' compounds. The reaction leads to the production of a heterogeneous group of substances, usually called advanced glycation end products (AGEs). Classical analytical approaches, such as spectroscopic (ultraviolet, fluorescence) and mass spectrometric (matrix-assisted laser desorption/ionization, liquid chromatography/electrospray ionization mass spectrometry) methods, have shown that the digestion mixture is highly complex. However, there are clear differences between the digestion mixtures of glycated and unglycated human serum albumin (HSA). In the former case, possible glycated peptides belonging to the AGE peptide class may be identified. Tandem mass spectrometric experiments on selected species seemed to be promising as regards structural information, but it was thought of interest to undertake the present investigation, based on liquid chromatography/electrospray ionization Fourier transform mass spectrometry, in order to obtain definitive results on their elemental composition. Using this approach, about 20 glycated peptides were detected and their possible structures were postulated by examining the known sequence of HSA. 相似文献
27.
28.
Alberto Ballistreri Domenico Garozzo Mario Giuffrida Pietro Maravigna Giorgio Montaudo 《Journal of polymer science. Part A, Polymer chemistry》1986,24(2):331-346
The thermal fragmentation processes in poly-Schiff bases have been investigated by direct pyrolysis–mass spectrometry. The mass spectral data show that the thermal fragmentation occurring in the polymers under investigation is characterized by hydrogen transfer reactions. In the case of a totally aromatic poly-Schiff base (polymer I ), the thermal fragmentation process involves hydrogen transfer irom the methyne group with formation of fragments bearing nitrile and/or phenyl end groups. In the case of aromatic-aliphatic poly-Schiff bases (polymers II–IV ), the hydrogen transfer process occurs from the aliphatic methylene groups. The latter process involves a lower energy and therefore occurs at lower temperatures with respect to the totally aromatic polymer I , with formation of thermal fragments bearing olefin and/or imine end groups. Beside these fragments, several thermal fragmentation compounds are also evolved by multiple hydrogen transfer reactions. 相似文献
29.
The oxidation of some tetrahydro-β-carboline derivatives with selenium dioxide led to the formation of 1,4-dihydro or fully aromatic β-carbolines, depending on the nature and the number of substituents at 1 position. The oxidation of 2-acetyl derivatives followed a different course and the products originated by the attack at C-1 of the ring C of the tetrahydro-β-carboline were obtained. 相似文献
30.
Complex formation equilibria between Ag(I) and thiourea or N-alkyl-substituted thioureas have been investigated in n-propanol by potentiometry at 10 °C intervals from 5 to 50 °C. Stepwise formation of tris-coordinated AgLn (n = 1-3) complexes has been found for the majority of the ligands. ΔH and ΔS values for the complex formation reactions have been evaluated from the dependence of ln βn on temperature. The alkyl-substituents affect the ligand affinities in different ways in relation with the coordination level n.The reactions are exothermic with few exceptions. Enthalpy favoured complex formation with negative dependence of ΔG on temperature (ΔS > 0) have been found.The enthalpy and entropy changes for the stepwise complex formation equilibria are correlated by two linear compensative relationships with the same isoequilibrium temperature 50-51 °C. 相似文献