全文获取类型
收费全文 | 2407篇 |
免费 | 74篇 |
国内免费 | 15篇 |
专业分类
化学 | 1957篇 |
晶体学 | 10篇 |
力学 | 30篇 |
数学 | 235篇 |
物理学 | 264篇 |
出版年
2023年 | 9篇 |
2022年 | 34篇 |
2021年 | 31篇 |
2020年 | 39篇 |
2019年 | 35篇 |
2018年 | 28篇 |
2017年 | 26篇 |
2016年 | 58篇 |
2015年 | 42篇 |
2014年 | 56篇 |
2013年 | 128篇 |
2012年 | 154篇 |
2011年 | 177篇 |
2010年 | 114篇 |
2009年 | 104篇 |
2008年 | 177篇 |
2007年 | 166篇 |
2006年 | 133篇 |
2005年 | 162篇 |
2004年 | 153篇 |
2003年 | 113篇 |
2002年 | 128篇 |
2001年 | 26篇 |
2000年 | 24篇 |
1999年 | 23篇 |
1998年 | 27篇 |
1997年 | 20篇 |
1996年 | 28篇 |
1995年 | 14篇 |
1994年 | 16篇 |
1993年 | 14篇 |
1992年 | 23篇 |
1991年 | 17篇 |
1990年 | 11篇 |
1989年 | 16篇 |
1988年 | 7篇 |
1986年 | 8篇 |
1985年 | 12篇 |
1984年 | 12篇 |
1983年 | 9篇 |
1982年 | 17篇 |
1981年 | 8篇 |
1980年 | 11篇 |
1979年 | 10篇 |
1978年 | 8篇 |
1977年 | 10篇 |
1976年 | 16篇 |
1975年 | 10篇 |
1973年 | 6篇 |
1970年 | 4篇 |
排序方式: 共有2496条查询结果,搜索用时 15 毫秒
111.
Constable EC Figgemeier E Housecroft CE Olsson J Zimmermann YC 《Dalton transactions (Cambridge, England : 2003)》2004,(13):1918-1927
The synthesis and electronic properties of dinuclear ([(bipy)2Ru(I)M(terpy)][PF6]4(bipy = 2,2'-bipyridine, terpy = 2,2':6',2'-terpyridine; M = Ru, Os)) and trinuclear ([[(bipy)2Ru(I)]2M][PF6]6 M = Ru, Os, Fe, Co) complexes bridged by 4'-(2,2'-bipyridin-4-yl)-2,2':6',2'-terpyridine (I) have been investigated and are compared with those of mononuclear model complexes. The electrochemical analysis using cyclic voltammetry and differential pulse voltammetry reveals that there are no interactions in the ground state between adjacent metal centres. However, there is strong electronic communication between the 2,2'-bipyridine and 2,2':6',2'-terpyridine components of the bridging ligand. This conclusion is supported by a step-by-step reduction of the dinuclear and trinuclear complexes and the assignment of each electrochemical process to localised ligand sites within the didentate and terdentate domains. The investigation of the electronic absorption and emission spectra reveals an energy transfer in the excited state from the terminating bipy-bound metal centres to the central terpy-bound metal centre. This indicates that the bridge is able to facilitate energy transfer in the excited state between the metal centres despite the lack of interactions in the ground state. 相似文献
112.
Catherine D. Clark Morton Z. Hoffman D. Paul Rillema Quinto G. Mulazzani 《Journal of photochemistry and photobiology. A, Chemistry》1997,110(3):285-290
The photophysics of three complexes of the form Ru(bpy)3−(pypm)2+ (where bpy2,2′-bipyridine, pypm 2-(2′-pyridyl)pyrimidine and P=1, 2 or 3) was examined in H2O, propylene carbonate, CH3CN and 4:1 (v/v) C2H5OH---CH3OH; comparison was made with the well-known photophysical behavior of Ru(bpy)32+. The lifetimes of the luminescent metal-to-ligand charge transfer (MLCT) excited states were determined as a function of temperature (between −103 and 90 °C, depending on the solvent), from which were extracted the rate constants for radiative and non-radiative decay and ΔE, the energy gap between the MLCT and metal-centered (MC) excited states. The results indicate that *Ru(bpy)2(pypm)2+ decays via a higher lying MLCT state, whereas *Ru(pypm)32+ and *Ru(pypm)2(bpy)2+ decay predominantly via the MC state. 相似文献
113.
Jonathan Pansieri Igor A. Iashchishyn Hussein Fakhouri Lucija Ostoji Mantas Malisauskas Greta Musteikyte Vytautas Smirnovas Matthias M. Schneider Tom Scheidt Catherine K. Xu Georg Meisl Tuomas P. J. Knowles Ehud Gazit Rodolphe Antoine Ludmilla A. Morozova-Roche 《Chemical science》2020,11(27):7031
The mechanism of amyloid co-aggregation and its nucleation process are not fully understood in spite of extensive studies. Deciphering the interactions between proinflammatory S100A9 protein and Aβ42 peptide in Alzheimer''s disease is fundamental since inflammation plays a central role in the disease onset. Here we use innovative charge detection mass spectrometry (CDMS) together with biophysical techniques to provide mechanistic insight into the co-aggregation process and differentiate amyloid complexes at a single particle level. Combination of mass and charge distributions of amyloids together with reconstruction of the differences between them and detailed microscopy reveals that co-aggregation involves templating of S100A9 fibrils on the surface of Aβ42 amyloids. Kinetic analysis further corroborates that the surfaces available for the Aβ42 secondary nucleation are diminished due to the coating by S100A9 amyloids, while the binding of S100A9 to Aβ42 fibrils is validated by a microfluidic assay. We demonstrate that synergy between CDMS, microscopy, kinetic and microfluidic analyses opens new directions in interdisciplinary research.Templating mechanism of S100A9 amyloids on Aβ fibrillar surfaces during amyloid co-aggregation process was revealed by synergy of biophysical methods including charge detection mass spectrometry, microscopy, kinetic and microfluidic analyses. 相似文献
114.
Free radical reactions induced by the photolysis of the lignin model compound α-guaiacoxylacetoveratrone have been studied by conventional and time-resolved ESR spectroscopy. In the presence of efficient hydrogen donors such as aqueous and hydroxylic solvents the primary reaction involves photoreduction of the triplet phenacyl ether to form the ketyl radical followed by rapid cleavage to the phenacyl radical and guaiacol. Subsequent formation of polarized guaiacoxyl radicals is due to secondary photo-oxidation. The cleavage of the ketyl radical is retarded in basic media and accelerated in acetic acid. Minor reaction pathways involving excited singlets cannot be ruled out by the current CIDEP observations. 相似文献
115.
Focant JF Eppe G Scippo ML Massart AC Pirard C Maghuin-Rogister G De Pauw E 《Journal of chromatography. A》2005,1086(1-2):45-60
A comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC x GC-TOF-MS) experimental setup was tested for the measurement of seven 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs), ten 2,3,7,8-substituted polychlorinated dibenzofurans (PCDFs), four non-ortho-polychlorinated biphenyls (PCBs), eight mono-ortho-PCBs, and six indicator PCBs (Aroclor 1260) in foodstuff samples. A 40m RTX-500 (0.18mm I.D., 0.10 microm df) was used as the first dimension (1D) and a 1.5 m BPX-50 (0.10mm I.D., 0.10 microm df) as the second dimension (2D). The GC x GC chromatographic separation was completed in 45 min. Quantification was performed using 13C-label isotope dilution (ID). Isotope ratios of the selected quantification ions were checked against theoretical values prior to peak assignment and quantification. The dynamic working range spanned three orders of magnitude. The lowest detectable amount of 2,3,7,8-TCDD was 0.2 pg. Fish, pork, and milk samples were considered. On a congener basis, the GC x GC-ID-TOF-MS method was compared to the reference GC-ID high resolution mass spectrometry (HRMS) method and to the alternative GC-ID tandem-in-time quadrupole ion storage mass spectrometry (QIST-MS/MS). PCB levels ranged from low picogram (pg) to low nanogram (ng) per gram of sample and data compared very well between the different methods. For all matrices, PCDD/Fs were at a low pg level (0.05-3 pg) on a fresh weight basis. Although congener profiles were accurately described, RSDs of GC x GC-ID-TOF-MS and GC-QIST-MS/MS were much higher than for GC-ID-HRMS, especially for low level pork and milk. On a toxic equivalent (TEQ) basis, all methods, including the dioxin-responsive chemically activated luciferase gene expression (DR-CALUX) assay, produced similar responses. A cost comparison is also presented. 相似文献
116.
Constable EC Housecroft CE Neuburger M Schaffner S Shardlow EJ 《Dalton transactions (Cambridge, England : 2003)》2005,(2):234-235
Reaction of 4'-(2-propyn-1-oxy)-2,2':6',2'-terpyridine (HC triple bond CCH2Oterpy) with trans-[PtI2(PEt3)2] regioselectively metallates the alkyne to give trans-[Pt(C triple bond CCH2Oterpy)2(PEt3)2] which, when treated with Fe(II), gives a [2 + 2]-metallocycle. 相似文献
117.
Bedford RB Cazin CS Hursthouse MB Light ME Scordia VJ 《Dalton transactions (Cambridge, England : 2003)》2004,(22):3864-3868
The reaction of tricyclohexylphosphine with the S-based palladacycle [(Pd(mu-OAc)(kappa2-S,C-C(6)H(4)CH(2)SMe))(2)] gives several products, regardless of stoichiometry, one of which, [Pd(kappa1-OAc)(eta1-C(6)H(4)CH(2)SMe)(PCy3)2], has been characterised crystallographically. Despite this, catalysts formed in situ from di- and tri-alkylphosphines and [(Pd(mu-OAc)(kappa2-S,C-C(6)H(4)CH(2)SMe))2] show excellent activity in the Suzuki coupling of a range of deactivated, non-activated and activated aryl chloride substrates. 相似文献
118.
119.
120.