全文获取类型
收费全文 | 3185篇 |
免费 | 122篇 |
国内免费 | 21篇 |
专业分类
化学 | 2193篇 |
晶体学 | 26篇 |
力学 | 126篇 |
数学 | 526篇 |
物理学 | 457篇 |
出版年
2023年 | 28篇 |
2022年 | 53篇 |
2021年 | 53篇 |
2020年 | 59篇 |
2019年 | 85篇 |
2018年 | 56篇 |
2017年 | 33篇 |
2016年 | 94篇 |
2015年 | 103篇 |
2014年 | 121篇 |
2013年 | 174篇 |
2012年 | 232篇 |
2011年 | 255篇 |
2010年 | 162篇 |
2009年 | 136篇 |
2008年 | 187篇 |
2007年 | 194篇 |
2006年 | 193篇 |
2005年 | 197篇 |
2004年 | 182篇 |
2003年 | 116篇 |
2002年 | 118篇 |
2001年 | 45篇 |
2000年 | 43篇 |
1999年 | 27篇 |
1998年 | 28篇 |
1997年 | 28篇 |
1996年 | 24篇 |
1995年 | 25篇 |
1994年 | 10篇 |
1993年 | 23篇 |
1992年 | 11篇 |
1991年 | 8篇 |
1990年 | 6篇 |
1989年 | 11篇 |
1987年 | 5篇 |
1986年 | 6篇 |
1985年 | 12篇 |
1984年 | 21篇 |
1983年 | 13篇 |
1982年 | 17篇 |
1981年 | 13篇 |
1980年 | 22篇 |
1979年 | 10篇 |
1978年 | 9篇 |
1977年 | 9篇 |
1976年 | 11篇 |
1975年 | 8篇 |
1974年 | 9篇 |
1973年 | 10篇 |
排序方式: 共有3328条查询结果,搜索用时 15 毫秒
991.
Ribot F Escax V Martins JC Biesemans M Ghys L Verbruggen I Willem R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(7):1747-1751
Pulsed field gradient (1)H NMR spectroscopy has been applied to investigate the association behavior of the Sn(12)-oxo cluster macrocation [(BuSn)(12)O(14)(OH)(6)](2+) with two different and smaller anions, p-toluenesulfonate (PTS(-)) and diphenylphosphinate (Ph(2)PO(2) (-)). By monitoring the translational diffusion coefficients of the various species involved, it is shown that the association depends on the anion involved and on the solvent used. Moreover, the possibility to individually monitor the diffusion characteristics of multiple anionic and cationic species in mixtures, by virtue of resolved (1)H resonances available from each species, allows us to evidence the occurrence of ion exchange in such systems. Thus when [(BuSn)(12)O(14)(OH)(6)](PTS)(2) is mixed with two equivalents of Ph(2)PO(2)NMe(4), PTS(-) is displaced by Ph(2)PO(2) (-), highlighting the greater affinity of the organotin macrocation for the diphenylphosphinate. This example clearly illustrates the potential of pulsed field gradient (1)H NMR spectroscopy in inorganic/organometallic chemistry, to follow preferential ion pairing in multi-ion systems at the level of each individually charged species. 相似文献
992.
993.
[reaction: see text] An enantiospecific synthesis of the AB fragment of lactonamycin (5) is achieved in eight steps from dimethyl D-tartrate. Ester enolate chemistry features prominently in the sequence. 相似文献
994.
Porrès L Mongin O Katan C Charlot M Pons T Mertz J Blanchard-Desce M 《Organic letters》2004,6(1):47-50
[structure: see text] Novel octupolar fluorophores derived from the symmetrical functionalization of a triphenylamine core with strong acceptor peripheral groups via phenylene-ethynylene linkers have been synthesized and shown to exhibit high fluorescence quantum yields, very large TPA cross-sections in the red-NIR region, and suitable photostability. 相似文献
995.
New deprotection conditions for the Dde amine protecting group that are fully orthogonal to Fmoc are described and successfully applied to the dual synthesis of PNA-peptide conjugates. 相似文献
996.
Mshvildadze V Elias R Faure R Rondeau D Debrauwer L Dekanosidze G Kemertelidze E Balansard G 《Chemical & pharmaceutical bulletin》2004,52(12):1411-1415
Five new triterpenoid saponins, pastuchoside A (1), B (3), C (5), D (7) and E (9), were isolated from the leaves of Hedera pastuchowii. They have oleanolic acid or hederagenin as aglycone. The structures were established by NMR spectroscopy including gs (gradient selected)-COSY, gs-HSQC, gs-HSQC-TOCSY and gs-HMBC experiments, and mass spectrometry (ESI-HR-MS). Heptaoside saponins, compounds 1 and 3, are described for the first time in the genus Hedera. 相似文献
997.
A mathematical model was proposed to allow the analysis of steady-state and transient behaviors of single-stage continuous aqueous two-phase systems. Since the complete system of simultaneous equations contains more equations than unknown variables, a program based on the method of least squares was developed to solve the problem. The methodology was tested using a system composed of thaumatin, sodium chloride, and a contaminant protein. A poly(ethylene-glycol)/phosphate salt/water system was selected to isolate the thaumatin. For the steady-state and transient operations, a constrained optimization procedure--from the Matlab Optimization Toolbox (MathWork, Inc.)--was implemented after recasting the system of equations as a minimization problem. Euler's method was used in the transient case to discretize the differential equations. The steady-state concentrations agreed with published data. An input-output model based on a 4% step change decrease in the inlet stream flow rate showed that output variables such as concentrations of sodium chloride and phosphate salt settled to their final values in different time periods. The proposed analysis may be helpful in the dynamic control of large-scale commercial extractor units using advanced control schemes. 相似文献
998.
José?Gonzalez-AguilarEmail author Isabel?Dème Laurent?Fulcheri Gilles?Flamant Thomas?M.?Gruenberger Benjamin?Ravary 《Plasma Chemistry and Plasma Processing》2004,24(4):603-623
The effect of soot formation on the radiative heat transfer inside a plasma reactor for carbon black synthesis has been modelled. For this purpose, three methods to quantify the soot volume fraction have been tested and evaluated: (1) Assuming local thermodynamic equilibrium, (2) assuming instantaneous conversion of the hydrocarbon and (3) using a single-step soot model. These approaches have been studied using a two-dimensional axis-symmetric and a three-dimensional steady computational fluid dynamics (CFD) model based on the commercial software FLUENT (v.5.6). The CFD model includes turbulence effects (by standard k– model), an electric arc sub-model to describe the time-average and spatial-average Lorentz forces and ohmic heating generated by the three-phase power-supply, methane transport in a nitrogen plasma and radiation calculations. The calculations show that for the simulated operating conditions the resulting temperature distributions obtained are very similar with the three methods in spite of major differences in the treatment of particle formation in the different methods. 相似文献
999.
A method to characterize the self-association of supramolecular polymers by isothermal titration calorimetry (ITC) has been designed. Association constants in the range 10(4)-10(6) dm(3) mol(-1) have been successfully determined from the heat exchange occurring when a supramolecular polymer solution is injected into a calorimetric cell containing pure solvent. Very good agreement with literature values has been obtained. Compared to other techniques (such as NMR or Fourier transform infrared spectroscopy), the use of ITC presents several advantages: (i) the enthalpy of association is obtained together with the association constant from the same experiment, (ii) the measurements can be performed in almost any solvent, and (iii) systems with higher association constants can be characterized. 相似文献
1000.
de Campo L Yaghmur A Sagalowicz L Leser ME Watzke H Glatter O 《Langmuir : the ACS journal of surfaces and colloids》2004,20(13):5254-5261
Aqueous submicron-sized dispersions of the binary monolinolein/water system, which are stabilized by means of a polymer, internally possess a distinct nanostructure. Taking this as our starting point, we were able to demonstrate for the first time that the internal structure of the dispersed particles can be tuned by temperature in a reversible way. Upon increasing the temperature, the internal structure undergoes a transition from cubic via hexagonal to fluid isotropic, the so-called L2 phase, and vice versa. Intriguingly, in addition to the structural changes in topology, the particles expel (take up) water to (from) the aqueous continuous phase when increasing (decreasing) the temperature in a reversible way. At each temperature, the internal structure of the dispersed particles corresponds very well to the structure observed in nondispersed binary monolinolein with excess water. This agreement is independent of any thermal history (including phase transitions), which proves that the structures in the dispersed particles actually are in thermodynamic equilibrium with the surrounding water phase. 相似文献