全文获取类型
收费全文 | 658篇 |
免费 | 27篇 |
国内免费 | 3篇 |
专业分类
化学 | 473篇 |
力学 | 25篇 |
数学 | 121篇 |
物理学 | 69篇 |
出版年
2022年 | 2篇 |
2021年 | 6篇 |
2020年 | 7篇 |
2019年 | 12篇 |
2018年 | 10篇 |
2017年 | 8篇 |
2016年 | 10篇 |
2015年 | 13篇 |
2014年 | 29篇 |
2013年 | 32篇 |
2012年 | 47篇 |
2011年 | 67篇 |
2010年 | 32篇 |
2009年 | 36篇 |
2008年 | 51篇 |
2007年 | 42篇 |
2006年 | 44篇 |
2005年 | 42篇 |
2004年 | 40篇 |
2003年 | 15篇 |
2002年 | 19篇 |
2001年 | 8篇 |
2000年 | 4篇 |
1999年 | 6篇 |
1998年 | 3篇 |
1997年 | 3篇 |
1996年 | 6篇 |
1995年 | 8篇 |
1994年 | 6篇 |
1993年 | 5篇 |
1992年 | 2篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1988年 | 1篇 |
1987年 | 3篇 |
1986年 | 12篇 |
1985年 | 13篇 |
1984年 | 9篇 |
1983年 | 1篇 |
1982年 | 7篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1967年 | 1篇 |
1937年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有688条查询结果,搜索用时 15 毫秒
51.
Thi TD Pomponio R Gotti R Saevels J Van Hove B Van Ael W Matthijs N Vander Heyden Y Djan'geing'a RM Chiap P Hubert P Crommen J Fabre H Dehouck P Hoogmartens J Van Schepdael A 《Electrophoresis》2006,27(12):2317-2329
A CE method for metacycline (MTC) determination was investigated in an inter-laboratory experiment. Many problems were encountered in this study, most of which were related to the transfer of the method to different CE equipment. The reported problems could be classified into different categories: problems related to the precision, to the parameters in the protocol, and to the MTC peak shape. As the peak shape problem was partially responsible for the poor precision, a new CE method was developed in order to obtain a good MTC peak shape on all equipment. The precision of this new method for MTC determination was examined in an intermediate precision study, where the influence of the factors "time" and "equipment" was investigated. Although the new method could be transferred to different instruments, the precision remained poor mainly due to the contributions of the between-replicate and the between-injection variances. 相似文献
52.
Rhodopsin is the dim light photosensitive pigment of animals. In this work, we undertook to study the structure of rhodopsin from swine and compare it with bovine and rat rhodopsin. Porcine rhodopsin was analyzed using methodology developed previously for mass spectrometric analysis of integral membrane proteins. Combining efficient protein cleavage and high performance liquid chromatography separation with the sensitivity of mass spectrometry (MS), this technique allows the observation of the full protein map and the posttranslational modifications of the protein in a single experiment. The rhodopsin protein from a single porcine eye was sequenced completely, with the exception of two single-amino acid fragments and one two-amino acid fragment, and the gene sequence reported previously was confirmed. The posttranslational modifications, similar to the ones reported previously for bovine and rat rhodopsin, were also identified. Although porcine rhodopsin has a high degree of homology to bovine and rat rhodopsins and most of their posttranslational modifications are identical, the glycosylation and phosphorylation patterns observed were different. These results show that rhodopsin from a single porcine eye can be characterized completely by MS. This technology opens the possibility of rhodopsin structural and functional studies aided by powerful mass spectrometric analysis, using the fellow eye as an internal control. 相似文献
53.
Laurent Griffe Dr. Mary Poupot Dr. Patrice Marchand Dr. Alexandrine Maraval Dr. Cédric‐Olivier Turrin Dr. Olivier Rolland Pascal Métivier Dr. Gérard Bacquet Dr. Jean‐Jacques Fournié Dr. Anne‐Marie Caminade Dr. Rémy Poupot Dr. Jean‐Pierre Majoral Dr. 《Angewandte Chemie (International ed. in English)》2007,46(14):2334-2334
54.
55.
The reaction of mercuric salts HgY2 or organic mercuric compounds RHHgX with long chain perfluorinated Grignard reagents RFMgBr leads to a series of new perfluoroalkyl mercury derivatives with the general formula RFHgZ (RF=C4F9, C6F13, C8F17 ; Z=RF,RH,Y with Y = I,Br,Cl, NO3,OCOCH3,OCOCF3).The synthesis of these organomercuric compounds is described, and their spectroscopic properties are reported. 相似文献
56.
Goujon F Malfreyt P Simon JM Boutin A Rousseau B Fuchs AH 《The Journal of chemical physics》2004,121(24):12559-12571
The Monte Carlo (MC) and molecular dynamics (MD) methodologies are now well established for computing equilibrium properties in homogeneous fluids. This is not yet the case for the direct simulation of two-phase systems, which exhibit nonuniformity of the density distribution across the interface. We have performed direct MC and MD simulations of the liquid-gas interface of n-pentane using a standard force-field model. We obtained density and pressure components profiles along the direction normal to the interface that can be very different, depending on the truncation and long range correction strategies. We discuss the influence on predicted properties of different potential truncation schemes implemented in both MC and MD simulations. We show that the MD and MC profiles can be made in agreement by using a Lennard-Jones potential truncated via a polynomial function that makes the first and second derivatives of the potential continuous at the cutoff distance. In this case however, the predicted thermodynamic properties (phase envelope, surface tension) deviate from experiments, because of the changes made in the potential. A further readjustment of the potential parameters is needed if one wants to use this method. We conclude that a straightforward use of bulk phase force fields in MD simulations may lead to some physical inconsistencies when computing interfacial properties. 相似文献
57.
Fradi I Servais AC Pedrini M Chiap P Iványi R Crommen J Fillet M 《Electrophoresis》2006,27(17):3434-3442
The enantiomeric separation of a series of acidic pharmaceuticals (mostly nonsteroidal anti-inflammatory drugs) has been investigated in NACE systems using single-isomer amino beta-CD derivatives. The first part of this study consisted of the selection of the basic experimental conditions to separate efficiently the enantiomers of acidic drugs. Several parameters, such as the nature of the ionic BGE components, were studied and a methanolic solution of ammonium acetate containing the cationic CD was selected as BGE. A D-optimal design with 20 experimental points was then applied and the nature and concentration of the CD were found to have a significant effect on the enantiomeric resolution for all studied compounds. Resolution (R(s)) values were always higher with 6-monodeoxy-6-mono(3-hydroxy)propylamino-beta-CD (PA-beta-CD) compared to those obtained with 6-monodeoxy-6-mono(2-hydroxy)propylamino-beta-CD (IPA-beta-CD). However, the latter led to shorter migration times. Generic NACE conditions were then selected by means of the multivariate approach in order to obtain the highest R(s) values in a minimum amount of time. Finally, dependence of separation selectivity, resolution, as well as mobility difference on chiral selector concentration was discussed and binding constants with PA-beta-CD were estimated for the two enantiomers of one of the model compounds, suprofen in these NACE systems. 相似文献
58.
After a review of 1-perfluoroalkene RFCFCF2 synthesis, with RFC4F9, C5F11, C6F13, we have studied their fine structures by 19F N.M.R. This study has led us to first generalize the rules set for the chemical shifts and coupling constants of olefinic fluorine atoms of fluoropropene and their derivatives. Then, we have been able to determinate unambiguously the chemical shifts of the difluoromethylene groups of the perfluorinated chains. We have thus shown, by irradiation, that inversions may take place in the chemical shifts of the CF2 groups at the β and γ position of the double bond. 相似文献
59.
Serge Djekou Armand Gellis Patrice Vanelle Hussein El‐Kashef 《Journal of heterocyclic chemistry》2006,43(5):1225-1229
7‐Chloromethyl‐6‐nitro‐5H‐thiazolo[3,2‐a]pyrimidin‐5‐one ( 2 ) is obtained by cyclocondensation of 2‐aminothiazole with ethyl 4‐chloroacetoacetate. This product was shown to react with various nitronate or malonate anions under microwave irradiation to give potentially bioactive 6‐nitro‐5H‐thiazolo[3,2‐a]pyrimidin‐5‐ones. Extension to other anions centered on S atom allows for the generalization this synthetic procedure. 相似文献
60.
James Elver Johnson Joanne A. Maia Karen Tan Abdolkarim Ghafouripour Patrice De Meester Shirley S. C. Chu 《Journal of heterocyclic chemistry》1986,23(6):1861-1868
O-Methyl-α-ketophenylacetohydroximoyl chloride ( 1 ) was prepared by the reaction of O-methyl-α-methoxyphenylacetohydroximoyl chloride ( 5 ) with N-bromosuccinimide and concentrated hydrobromic acid. Reaction of 1 with ethylenediamine gave 3-phenyl-5,6-dihydro-2(1H)-pyrazinone-O-methyloxime ( 6 ). 3-Phenyl-5,6-cyclohexano-5,6-dihydro-2(1H)-pyrazininone-O-methyloxime ( 7 ) was prepared by reaction of 1 with trans-1,2-diaminocyclohexane. The X-ray structure of 6 has been determined. The crystals are orthorhombic, space group Pbca with a = 10.264(3), b = 18.262(4), c = 23.530(4)Å, V = 4411(2)Å3, and Z = 16. The structure, which was refined to R = 0.038 using 1652 observed reflections, shows the amidoxime moiety to be the Z configuration. Reaction of benzohydroximoyl chloride with aziridine gave (Z)-aziridinylbenzaldoxime ( 16a ). Ultraviolet irradiation of a benzene solution of 16a gave a mixture of the Z and E isomers 16a and 16b . The E isomer 16b underwent thermal isomerization to 16a at 100°. Reaction of 16a with dimethyl sulfate in sodium hydroxide solution gave (Z)-O-methylaziridinylbenzaldoxime ( 17a ). Photoisomerization of a hexane solution of 17a gave a mixture of the Z and E isomers 17a and 17b which were separated by preparative glc. The isomers 17a and 17b are resistant to thermal Z = E isomerization. The mechanisms of thermal isomerization of benzamidoximes are discussed. 相似文献