全文获取类型
收费全文 | 156篇 |
免费 | 5篇 |
国内免费 | 1篇 |
专业分类
化学 | 98篇 |
晶体学 | 5篇 |
力学 | 4篇 |
数学 | 18篇 |
物理学 | 37篇 |
出版年
2023年 | 3篇 |
2022年 | 3篇 |
2021年 | 4篇 |
2020年 | 2篇 |
2019年 | 3篇 |
2018年 | 10篇 |
2017年 | 7篇 |
2016年 | 4篇 |
2015年 | 7篇 |
2014年 | 9篇 |
2013年 | 11篇 |
2012年 | 16篇 |
2011年 | 17篇 |
2010年 | 5篇 |
2009年 | 5篇 |
2008年 | 7篇 |
2007年 | 7篇 |
2006年 | 3篇 |
2005年 | 5篇 |
2004年 | 4篇 |
2003年 | 5篇 |
2002年 | 2篇 |
2000年 | 2篇 |
1997年 | 1篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1985年 | 2篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1978年 | 1篇 |
排序方式: 共有162条查询结果,搜索用时 31 毫秒
1.
Davor Margeti? 《Tetrahedron》2007,63(20):4338-4346
Four new substituted methano-bridged or heteroatom-bridged norbornadienomaleic anhydrides have been prepared and converted to sesquinorbornadiene anhydrides by reaction with cyclic 1,3-dienes. The versatility of parity reversal, in conjunction with N-substituent steric effects, has been used to produce all three possible stereoisomers of the N,O-sesquinorbornadiene anhydrides in separate, stereoselective cycloadditions. The anhydrides have been synthesized by cyclization of their diacids (in situ production) or by flash vacuum pyrolysis of their furan adducts (yielding crystalline products); further fragmentation occurs at these or higher temperatures to produce five-membered carbocyclic or heterocyclic anhydrides. Activation energies have been evaluated for the fragmentation and cycloaddition processes using DFT calculations (B3LYP/6-31G∗) and these calculations correctly predict, which reaction can be intercepted at the norbornadienomaleic anhydride stage and preferred stereochemistry of cycloadducts. 相似文献
2.
We have developed conformational preference functions and a hierarchy of algorithms that can evaluate the success of each hydrophobicity scale in predicting protein secondary conformation. The results of such evaluation are shown for fiftyfive different scales with respect to their ability to predict -helix, -sheet and coil structure in three testing sets of proteins: five integral membrane proteins, twelve -class and sixteen -class soluble proteins. Our scale of conformational parameters is the best predictor of secondary structure segments in membrane proteins and -class proteins. The success rate and correlation coefficient for -helix conformation in membrane proteins are 76% and 0.46 respectively, which is superior to the performance measures attained with other prediction schemes. Evaluation of solution hydrophobicity scales, often used to predict transmembrane segments in membrane proteins, indicated absence of correlation in prediction of helix segments and experimental results for the conformation of membrane proteins. Such scales have better performance (correlation coefficient around 0.30) in predicting sheet conformation in the -class proteins. 相似文献
3.
A. A. Kamnev E. Kuzmann Yu. D. Perfiliev A. Vértes M. Ristić S. Popović S. Musić 《Journal of Radioanalytical and Nuclear Chemistry》2000,246(1):123-129
Mössbauer, FTIR and XRD analyses showed that in aqueous medium in air in the presence of L-tryptophan (Trp) or indole-3-acetic acid (IAA) the ambient-temperature ageing of the precipitates formed from ferrous sulphate at pH7 gave composite phases with varying proportions of -FeOOH (a dominating crystalline phase), -FeOOH (both fine-grained, showing superparamagnetic behaviour at 298 K, and relatively better crystallized) and amorphous ferric hydroxide. The experimental data suggested a competition for adsorption sites at the oxyhydroxide surface in the suspension during phase transformations, as well as the transformation of -FeOOH (and/or amorphous ferric hydroxide) to -FeOOH via the dissolution-reprecipitation mechanism. The formation of certain ferric oxyhydroxide phases in the presence of Trp and IAA — released e.g., in the course of bacterial and plant metabolism — can contribute to the regulation of soil mineral composition. 相似文献
4.
Chiral 2,2′-polyoxaalkano-9,9′-spirobifluorenes From 2,2′-diacetyl-9,9′-spirobifluorene (2) , twelve chiral polyethers have been prepared as potential ion- and enantiomer-selective ionophores. The absolute configuration of the polyethers 15 – 17 , 19 – 22 , and 25 has been determined by chemical correlation with vespirenes [11] [29], by circular dichroism, and by X-ray analysis. The circular dichroism of 15 – 17 , 19 and 21 depends on the size of the macrocycle and indicates that the fluorene chromophores of 19 and 21 with 13- and 16-membered rings respectively deviate considerably from orthogonality. 相似文献
5.
Davor Margetić Ronlad N. Warrener Mirjana Eckert-Maksić Ivana Antol Zoran Glasovac 《Theoretical chemistry accounts》2003,109(4):182-189
DFT calculations of 7′–oxasesquinorbornenes and 7,7′-dioxasesquinorbornenes using the B3LYP/6–31G* method are reported.
All the investigated structures (syn- and anti- derivatives) showed significant non-planarity of the central double bond, with the exception of those anti-derivatives possessing symmetrical structures. The influence of the replacement of the methylene groups at position 7- of
the norbornene fragment with oxygen and the introduction of second and third (peripheral) double bonds and benzene rings on
the molecular and electronic structures of these molecules have also been investigated.
Received: 11 November 2002 / Accepted: 6 June 2002 /
Published online: 29 April 2003 相似文献
6.
The thermal rearrangement of [3]polynorbornane bis-imide rack-mounted 7-oxabenzonorbornadienes has been conducted using flash vacuum pyrolysis (FVP) at 520 °C and is compared with the FVP of similar 7-oxabenzonorbornadienes off the rack. The isomerisation is considered to involve (a) C–O bond cleavage to a vinylogous 1,5-dipole, (b) formation of a benzene epoxide by nucleophilic ring-closure and (c) valence-isomerisation of the benzene epoxide to the oxepine. Competing fragmentation to the isobenzofuran by ejection of acetylene and other rearrangements become prominent pathways off the rack, whereas isomerisation to the oxepine is highly favored on the rack. 相似文献
7.
Thermal electrocyclization reactions of benzooctatetraenes and benzodecapentaenes substituted with R=H, Cl, and methyl were studied experimentally and computationally. Methyl and unsubstituted benzooctatetraenes and benzodecapentaenes give the [4.2.0]bicyclooctadiene products by 8π,6π-electrocyclization. Chlorine substitution led to thermal rearrangement of the initially formed 8π,6π-electrocyclization intermediates to give unprecedented products. 相似文献
8.
Miroslav M. Ristić Muna M. Aoneas Mirjana M. Vojnović Goran B. Poparić 《Plasma Chemistry and Plasma Processing》2017,37(5):1431-1443
Excitation of electronic states of the N2 molecule by electron impact is recognized as an essential process in nitrogen plasmas that strongly impacts their chemical reactivity and other properties. Many surface and coating technologies are based on radio-frequency plasma discharges in nitrogen. In this paper the electron impact excitation rate coefficients for singlet and triplet electronic states of the N2 molecule have been calculated in non-equilibrium conditions in the presence of a radio-frequency electric field. A Monte Carlo simulation has been performed in order to determine non-equilibrium electron energy distribution functions within one period of the electric field. By using these distribution functions, the excitation rate coefficients have been obtained in the frequency range from 13.56 up to 500 MHz, at reduced electric field values from 200 to 700 Td. 相似文献
9.
Pavle Tro?elj Anamarija Bri? Yasujiro Murata Davor Margeti? 《Structural chemistry》2012,23(3):791-799
Two novel polarofacial-[5]-polynorbornanes, O
2
N
2
O
2– and COCOC–, were synthesized by cycloaddition reactions and their molecular and crystal structures were determined. These hetero[5]polynorbornanes
posses heteroatoms at the norbornene bridges located at the outer convex surface, whereas functionalities are positioned on
the inner concave surface. Molecular structures attest the extent of the curvature of their polycyclic backbone, and established
that the COCOC-[5]-polynorbornane possesses more curved topology due to larger steric repulsion of 7-norbornane bridges. These experimental
results are in good agreement with computational predictions of geometry. Quantum chemical study has identified lone pair
repulsive interactions and steric repulsions of bridges as important factors for determining curvature. 相似文献
10.
Stolcic D Fischer M Ganteför G Kim YD Sun Q Jena P 《Journal of the American Chemical Society》2003,125(10):2848-2849
Using ultraviolet photoelectron spectroscopy, we provide direct experimental evidence that di-oxygen species are stable on anionic gold dimer and tetramer clusters at room temperature. The stabilization of molecular oxygen is crucial for the high activities of the low-temperature reactions on gold catalysts. 相似文献