全文获取类型
收费全文 | 1239篇 |
免费 | 32篇 |
国内免费 | 8篇 |
专业分类
化学 | 919篇 |
晶体学 | 3篇 |
力学 | 26篇 |
数学 | 177篇 |
物理学 | 154篇 |
出版年
2023年 | 8篇 |
2022年 | 13篇 |
2021年 | 20篇 |
2020年 | 23篇 |
2019年 | 12篇 |
2018年 | 17篇 |
2017年 | 14篇 |
2016年 | 40篇 |
2015年 | 41篇 |
2014年 | 27篇 |
2013年 | 59篇 |
2012年 | 90篇 |
2011年 | 90篇 |
2010年 | 61篇 |
2009年 | 57篇 |
2008年 | 79篇 |
2007年 | 77篇 |
2006年 | 79篇 |
2005年 | 68篇 |
2004年 | 72篇 |
2003年 | 53篇 |
2002年 | 44篇 |
2001年 | 36篇 |
2000年 | 28篇 |
1999年 | 13篇 |
1998年 | 14篇 |
1997年 | 11篇 |
1996年 | 18篇 |
1995年 | 10篇 |
1994年 | 11篇 |
1993年 | 13篇 |
1992年 | 11篇 |
1991年 | 4篇 |
1990年 | 6篇 |
1989年 | 11篇 |
1988年 | 6篇 |
1987年 | 7篇 |
1986年 | 11篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1981年 | 1篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 5篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1959年 | 2篇 |
排序方式: 共有1279条查询结果,搜索用时 15 毫秒
21.
I. Brandariz F. Arce X. L. Armesto F. Penedo M. Sastre de Vicente 《Monatshefte für Chemie / Chemical Monthly》1993,124(3):249-257
Summary A systematic study of the dependence of acid-base stoichiometric constants on the ionic strength has been carried out for the aminoacidL-valine in ClK and BrK solutions. The observed dependence has been interpreted by using Guggenheim, Scatchard and Pitzer models for the activity coefficients of the species involved in the equilibria.
Die Abhängigkeit von Gleichgewichtskonstanten desL-Valin von der Ionenstärke entsprechend den Modellen von Guggenheim, Scatchard und Pitzer
Zusammenfassung Es wurde anL-Valin in KCl- und KBr-Lösungen eine systematische Studie der Abhängigkeit der Säure-Base-Stöchiometrie von der Ionenstärke durchgeführt. Die beobachteten Abhängigkeiten wurden aufgrund der nach den Modellen von Guggenheim, Scatchard und Pitzer erhaltenen Aktivitätskoeffizienten der an den Gleichgewichten beteiligten Spezies interpretiert.相似文献
22.
Glycoproteins from sugarcane stalks have been isolated from plants field-grown by size-exclusion chromatography. Some of these glycoproteins, previously labelled with fluorescein isothiocyanate, are able to bind to the cell wall of the sugarcane endophyte, N2-fixing Gluconacetobacter diazotrophicus, and largely removed after washing the bacterial cells with sucrose. This implies that sugarcane glycoproteins use beta-(1-->2)-fructofuranosyl fructose domains in their glycosidic moiety to bind to specific receptors in the bacterial cell walls. These receptors have been isolated by affinity chromatography on a sugarcane glycoprotein-agarose matrix, desorbed with sucrose and characterized by sodium dodecyl sulfate polyacrylamide gel electrophresisand capillary electrophoresis (CE). 相似文献
23.
When C6Cl5AuAsPh3 reacts with halogens, oxidation of the gold(I) complex and formation of X2Au(C6Cl5)AsPh3 (X = Cl, Br, I) take place. However, when C6F5AuAsPh3 reacts with halogens, oxidation is only observed in the case of Cl2, whilst I2 (totally) and Br2 (partially) split the AuC bond. This behaviour is contrary to that observed with C6F5AuPPh3 and halogens, where the tendency to split the AuC bond decreases in the sequence Cl>B>I. 相似文献
24.
Adsorption of acrolein on vanadia/titania catalysts fits a polymerization kinetics if Na–V compounds are not present or the vanadium content is lower than that corresponding to formation of a monolayer of vanadia on the titania support.
, Na–V .相似文献
25.
Paolesse R Nardis S Venanzi M Mastroianni M Russo M Fronczek FR Vicente MG 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(5):1192-1197
5,10,15-Triphenylcorrole (1) reacts with the Vilsmeier reagent (POCl(3)/DMF) to give the corresponding 3-formyl derivative 3 as the major product. The regioselectivity of the reaction was proven by X-ray crystallography and only traces of the 2-formyl isomer were observed. A more polar product is also observed and this compound becomes the major product when an excess of DMF is used for the preparation of the Vilsmeier reagent, while the formation of the 3-formyl isomer is almost completely suppressed. X-ray crystallography allowed us to identify this compound as the fully substituted N-ethane bridged derivative 4, formed from the attack of the Vilsmeier reagent at the inner core of the macrocycle. This compound is unique among porphyrinoid macrocycles, and further confirms the peculiarity of corrole chemistry. 相似文献
26.
27.
The relaxation behavior of poly(5-acryloxymethyl-5-methyl-1,3-dioxacyclohexane), a polymer containing highly flexible side groups, is studied by broadband dielectric spectroscopy in the frequency and temperature ranges 10(-1)-10(9) Hz and 123-473 K, respectively. Above the glass transition temperature T(g) the dielectric loss in the frequency domain exhibits a prominent alpha absorption, followed in increasing order of frequencies by two secondary absorptions called beta and gamma. At temperatures slightly higher than T(g), the a relaxation is well separated from the beta, but as temperature increases overlapping between both relaxations augments forming an alphabeta absorption in the vicinity of 420 K. This latter absorption displays a shoulder on its high-frequency side corresponding to the y relaxation. The strength of the a relaxation decreases with increasing temperature, eventually vanishing at the temperature at which the alphabeta absorption is formed. The time retardation spectra of the isotherms are calculated and further used to facilitate the deconvolution of the overlapping relaxations. The fact that the temperature dependence of the beta relaxation also describes that of the alphabeta absorption suggests that both relaxations have the same nature. It seems that as temperature increases, the a relaxation feeds on the beta absorption until its complete disappearance. The gamma relaxation, in turn, seems to increase at the expense of the alphabeta process at high temperature. 相似文献
28.
Ignacio Alfonso Covadonga Astorga Vicente Gotor 《Journal of inclusion phenomena and macrocyclic chemistry》2005,53(1-2):131-137
Electrospray ionization mass espectrometry (ESI-MS) has been used for the study of a cyclam derivative noncovalent interactions.
At acidic pH, diprotonated macrocycle bound to different anionic species were observed. The selectivity shown by competitive
experiments is rationalized with the help of semiempirical theoretical calculations. At basic pH, the base peak corresponded
to the macrocycle-alkaline metal complexes, and again competition experiments showed different binding strength. Finally,
experiments carried out in the presence of transition metal salts allowed the detection of the complexes present in the mixture
and revealed their different kinetic behavior. 相似文献
29.
[reaction: see text] A lipase-catalyzed double monoaminolysis of dimethyl malonate by (+/-)-trans-cyclopentane-1,2-diamine allows the sequential resolution of the latter compound, affording an enantiopure bis(amidoester), which is subsequently transformed into an optically active polyamine. As an alternative, both enantiomers of the diamine can be obtained from enantiopure (+)- or (-)-2-aminocyclopentanol, prepared by enzymatic resolution. 相似文献
30.
Andrés J Moliner V Safont VS Domingo LR Picher MT 《The Journal of organic chemistry》1996,61(22):7777-7783
As a model of the chemical reactions that take place in the active site of gluthatione reductase, the nature of the molecular mechanism for the hydride transfer step has been characterized by means of accurate quantum chemical characterizations of transition structures. The calculations have been carried out with analytical gradients at AM1 and PM3 semiempirical procedures, ab initio at HF level with 3-21G, 4-31G, 6-31G, and 6-31G basis sets and BP86 and BLYP as density functional methods. The results of this study suggest that the endo relative orientation on the substrate imposed by the active site is optimal in polarizing the C4-Ht bond and situating the system in the neighborhood of the quadratic region of the transition structure associated to the hydride transfer step on potential energy surface. The endo arrangement of the transition structure results in optimal frontier HOMO orbital interaction between NADH and FAD partners. The geometries of the transition structures and the corresponding transition vectors, that contain the fundamental information relating reactive fluctuation patterns, are model independent and weakly dependent on the level of theory used to determine them. A comparison between simple and complex molecular models shows that there is a minimal set of coordinates describing the essentials of hydride transfer step. The analysis of transition vector components suggests that the primary and secondary kinetic isotope effects can be strongly coupled, and this prompted the calculation of deuterium and tritium primary, secondary, and primary and secondary kinetic isotope effects. The results obtained agree well with experimental data and demonstrate this coupling. 相似文献