全文获取类型
收费全文 | 1625篇 |
免费 | 29篇 |
国内免费 | 13篇 |
专业分类
化学 | 986篇 |
晶体学 | 3篇 |
力学 | 47篇 |
数学 | 354篇 |
物理学 | 277篇 |
出版年
2023年 | 10篇 |
2022年 | 35篇 |
2021年 | 40篇 |
2020年 | 29篇 |
2019年 | 24篇 |
2018年 | 20篇 |
2017年 | 18篇 |
2016年 | 62篇 |
2015年 | 35篇 |
2014年 | 37篇 |
2013年 | 90篇 |
2012年 | 81篇 |
2011年 | 133篇 |
2010年 | 63篇 |
2009年 | 51篇 |
2008年 | 95篇 |
2007年 | 95篇 |
2006年 | 84篇 |
2005年 | 58篇 |
2004年 | 45篇 |
2003年 | 49篇 |
2002年 | 35篇 |
2001年 | 15篇 |
2000年 | 21篇 |
1999年 | 16篇 |
1998年 | 15篇 |
1997年 | 21篇 |
1996年 | 22篇 |
1995年 | 17篇 |
1994年 | 25篇 |
1993年 | 27篇 |
1992年 | 17篇 |
1991年 | 8篇 |
1990年 | 14篇 |
1988年 | 8篇 |
1986年 | 10篇 |
1985年 | 17篇 |
1984年 | 8篇 |
1983年 | 11篇 |
1982年 | 15篇 |
1981年 | 18篇 |
1980年 | 13篇 |
1979年 | 14篇 |
1978年 | 7篇 |
1977年 | 6篇 |
1976年 | 9篇 |
1975年 | 9篇 |
1974年 | 8篇 |
1973年 | 10篇 |
1858年 | 7篇 |
排序方式: 共有1667条查询结果,搜索用时 15 毫秒
1.
Apparent molal heat capacities
of some piperidine, morpholine, and piperazine derivatives in aqueous solution have been determined by adiabatic calorimetry
in the temperature range 20–55°C and in the molality range 0.2–1m. Comparison of experimental
values with those calculated through group contributions, found for monofunctional compounds, indicates strong interactions
between the hydrophilic centers. An interpretation is given of the possible mechanism of this interaction. Also, values of
ΔC
p
for the addition reaction of proton to nitrogen centers of mono- and bifunctional organic compounds are examined. 相似文献
2.
The mass spectra of fifteen 1,2-benzisothiazoles are reported; their fragmentation patterns have been investigated by labelling experiments, high resolution mass measurements and defocused metastable ion detection. The parent compound of the series, 1,2-benzisothiazole, eliminates HCN after partial inter-ring hydrogen scrambling. The extent of scrambling has been determined for normal daughter ions produced at different electron beam energies and also for metastable daughter ions, and is compared with the data reported for benzothiazole. Some 3-substituted derivatives show unusual fragmentation patterns. The mechanisms of these processes are under further investigation. 相似文献
3.
Kuppuswamy Kalyanasundaram Enrico Borgarello Michael Grutzel 《Helvetica chimica acta》1981,64(1):362-366
Illumination of aqueous CdS dispersions loaded with Pt and RuO2 by visible light produces hydrogen and oxygen in stoichiometric proportion. No degradation of the photocatalyst is noted after 60 h of irradiation time. The RuO2 deposit on the particle surface greatly accelerates the transfer of holes from the semiconductor valence band to the aqueous solution thus inhibiting photocorrosion. 相似文献
4.
Rapid determination of orotic acid in urine by a fast liquid chromatography/tandem mass spectrometric method 总被引:1,自引:0,他引:1
la Marca G Casetta B Zammarchi E 《Rapid communications in mass spectrometry : RCM》2003,17(8):788-793
Quantification of orotic acid (uracil-6-carboxylic acid) in urine is an important tool to diagnose some inherited diseases, such as urea cycle disorder (OTCD) and hereditary orotic aciduria. New rapid analytical methods are necessary to provide high-throughput orotic acid analyses. A new analytical method has been developed for the rapid analysis of orotic acid in urine by liquid chromatography coupled with ion spray tandem mass spectrometry (LC/MS/MS). After a sample dilution 1:20, the analysis was performed in the selected reaction monitoring mode in which orotic acid was detected through the transition m/z 155 to 111. The retention time was 3.9 min in a 4.5-min analysis. Daily calibration between 0.5-5.0 micromol/L of orotic acid, corresponding to 10-100 micromol/L in urine before the 1:20 dilution, offered consistent linearity and reproducibility. Interassay coefficient of variance (c.v.) was 4.97% at a mean concentration of 10.99 micromol/L. The sensitivity and specificity of tandem mass spectrometry permitted a high volume of analyses of orotic acid. The sample preparation is simple, inexpensive and not time demanding. 相似文献
5.
DFT calculations have been carried out for 2-, 3- and 4-methoxybenzyl alcohol radical cations (1+, 3+ and 4+, respectively) and the α-methyl derivatives 2+ and 5+ using the UB3LYP/6-31G(d) method. The theoretical results have been compared with the experimental rate constants for deprotonation of 1+-5+ under acidic and basic conditions. In acidic solution, the decay of 1+-5+ proceeds by cleavage of the C-H bond, while in the presence of −OH all the radical cations undergo deprotonation from the α-OH group. This pH-dependent change in mechanism has been interpreted qualitatively in terms of simple frontier molecular orbital theory. The −OH induced α-O-H deprotonation is consistent with a charge controlled reaction, whereas the C-H deprotonation, observed when the base is H2O, appears to be affected by frontier orbital interactions. 相似文献
6.
The H(2)O(2)-promoted oxidations of the two nonphenolic beta-O-aryl lignin model trimers 1 and 2, catalyzed by lignin peroxidase (LiP) at pH = 3.5, have been studied. The results have been compared with those obtained in the oxidation of 1 and 2 with the genuine one-electron oxidant potassium 12-tungstocobalt(III)ate. These models present a different substitution pattern of the three aromatic rings, and by one-electron oxidation, they form radical cations with the positive charge, which is localized in the dialkoxylated ring as also evidenced by a pulse radiolysis study. Both the oxidations with the enzymatic and with the chemical systems lead to the formation of products deriving from the cleavage of C-C and C-H bonds in a beta position with respect to the radical cation with the charge residing in the dialkoxylated ring (3,4-dimethoxybenzaldehyde (5) and a trimeric ketone 6 in the oxidation of 1 and a dimeric aldehyde 8 and a trimeric ketone 9 in the oxidation of 2). These products are accompanied by a dimeric aldehyde 7 in the oxidation of 1 and 4-methoxybenzaldehyde (10) in the oxidation of 2. The unexpected formation of these two products has been explained by suggesting that 1.+ and 2.+ can also undergo an intramolecular electron transfer leading to the radical cations 1a.+ and 2a.+ with the charge residing in a monoalkoxylated ring. The fast cleavage of a C-C bond beta to this ring, leading to 7 from 1.+ and to 10 from 2.+, is the driving force of the endoergonic electron transfer. A kinetic steady-state investigation of the LiP-catalyzed oxidation of the trimer 2, the dimeric model 1-(3,4-dimethoxyphenyl)-2-phenoxy-1-ethanol (4), and 3,4-dimethoxybenzyl alcohol (3) has indicated that the turnover number (k(cat)) and the affinity for the enzyme decrease significantly by increasing the size of the model compound. In contrast, the three substrates exhibited a very similar reactivity toward a chemical oxidant [Co(III)W]. This suggests a size-dependent interaction of the enzyme with the substrate which may influence the efficiency of the electron transfer. 相似文献
7.
Francielli S. Santana Mauro Perfetti Matteo Briganti Francesca Sacco Giordano Poneti Enrico Ravera Jaísa F. Soares Roberta Sessoli 《Chemical science》2022,13(20):5860
A common criterion for designing performant single molecule magnets and pseudocontact shift tags is a large magnetic anisotropy. In this article we present a dysprosium complex chemically designed to exhibit strong easy-axis type magnetic anisotropy that is preserved in dichloromethane solution at room temperature. Our detailed theoretical and experimental studies on the magnetic properties allowed explaining several features typical of highly performant SMMs. Moreover, the NMR characterization shows remarkably large chemical shifts, outperforming the current state-of-the art PCS tags.A robust dysprosium(iii) single molecule magnet with large uniaxial magnetic anisotropy induces pseudocontact shifts at almost doubled distance compared to standard shift agents. 相似文献
8.
Enrico DRIOLI Enrica FONTANANOVA Marcella BONCHIO Mauro CARRARO Martino GARDAN Gianfranco SCORRANO 《催化学报》2008,29(11):1152-1158
The design of new heterogeneous photooxygenation systems able to employ visible light, oxygen, mild temperatures, and solvent with a low environmental impact has been investigated. In particular, the heterogenization of decatungstate (W10O4-32), a polyoxometalate with photocatalytic activity in oxidation reactions, has been carried out in polymeric membranes of polyvinylidenefluoride. The polymeric catalytic membranes prepared by phase inversion technique have been successfully applied in the aerobic mineralization of phenol in water, which was used as an example of organic pollutant. In order to evaluate the effect of the polymeric environment on the overall catalyst behavior, we have also heterogenized the decatungstate (opportunely functionalized) in perfluorinated membrane made of Hyflon. The photocatalytic composite membranes are characterized by different and tuneable properties depending on the nature of the polymeric micro-environment, in which the catalyst is confined. Moreover, the selective separation function of the membrane results in enhanced performance in comparison with homogeneous reactions. 相似文献
9.
10.
We present an optical setup for generating a sequence of light pulses in which the orbital angular momentum (OAM) degree of freedom is correlated with the temporal one. The setup is based on a single q plate within a ring optical resonator. By this approach, we demonstrate the generation of a train of pulses carrying increasing values of OAM, or, alternatively, of a controlled temporal sequence of pulses having prescribed OAM superposition states. Finally, we exhibit an "OAM-to-time conversion" apparatus that divides different input OAM states into different time bins. The latter application provides a simple approach to digital spiral spectroscopy of pulsed light. 相似文献