全文获取类型
收费全文 | 1142篇 |
免费 | 25篇 |
国内免费 | 6篇 |
专业分类
化学 | 930篇 |
晶体学 | 5篇 |
力学 | 7篇 |
数学 | 152篇 |
物理学 | 79篇 |
出版年
2023年 | 15篇 |
2022年 | 40篇 |
2021年 | 41篇 |
2020年 | 34篇 |
2019年 | 27篇 |
2018年 | 18篇 |
2017年 | 17篇 |
2016年 | 37篇 |
2015年 | 30篇 |
2014年 | 35篇 |
2013年 | 62篇 |
2012年 | 66篇 |
2011年 | 91篇 |
2010年 | 55篇 |
2009年 | 50篇 |
2008年 | 65篇 |
2007年 | 88篇 |
2006年 | 65篇 |
2005年 | 86篇 |
2004年 | 51篇 |
2003年 | 32篇 |
2002年 | 27篇 |
2001年 | 9篇 |
2000年 | 8篇 |
1999年 | 12篇 |
1998年 | 9篇 |
1997年 | 6篇 |
1996年 | 8篇 |
1995年 | 6篇 |
1994年 | 4篇 |
1993年 | 4篇 |
1992年 | 6篇 |
1991年 | 7篇 |
1990年 | 7篇 |
1989年 | 3篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 5篇 |
1980年 | 7篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1972年 | 1篇 |
1970年 | 1篇 |
1969年 | 2篇 |
1968年 | 3篇 |
1967年 | 3篇 |
排序方式: 共有1173条查询结果,搜索用时 15 毫秒
131.
Tamba M Dajka K Ferreri C Asmus KD Chatgilialoglu C 《Journal of the American Chemical Society》2007,129(28):8716-8723
The one-electron reduction of methanesulfonyl chloride (MeSO2Cl) leads, in the first instance, to an electron adduct MeSO2Cl(.)(-) which lives long enough for direct detection and decays into sulfonyl radicals MeSO2(.) and Cl(-), with k = 1.5 x 10(6) s(-1). Both, MeSO2Cl(.)(-) and MeSO2(.) showed a similar absorption in the UV with lambdamax of 320 nm. In the presence of oxygen, MeSO2Cl(.)(-) transfers an electron to O(2) and establishes an equilibrium with superoxide. The rate constant for the forward reaction was measured to 4.1 x 10(9) M(-1) s(-1), while for the back reaction only an interval of 1.7 x 10(5) to 1.7 x 10(6) M(-1) s(-1) could be estimated, with a somewhat higher degree of confidence for the lower value. This corresponds to an equilibrium constant in the range of 2.4 x 10(3) to 2.4 x 10(4). With reference to E degrees (O2/O2(.)(-)) = -155 mV, the redox potential of the sulfonyl chloride couple, E degrees (MeSO2Cl/MeSO2Cl(.)(-)), thus results between being equal to -355 and -414 mV (vs NHE). MeSO2Cl(.)(-) reduces (besides O2) 4-nitroacetophenone. The underlying electron transfer took place with k = 1.5 x 10(9) M(-1) s(-1), corroborating an E degrees for the sulfonyl chloride couple significantly exceeding the above listed lower value. The MeSO2(.) radical added to oxygen with a rate constant of 1.1 x 10(9) M(-1) s(-1). Re-dissociation of O2 from MeSO2OO(.) occurred only very slowly, if at all, that is, with k < 10(5) s(-1). MeSO2(.) radicals can act as the catalyst for the cis-trans isomerization of several Z- and E-mono-unsaturated fatty acid methyl esters in homogeneous solution. The effectiveness of the isomerization processes has been addressed, and in the presence of oxygen the isomerization is completely suppressed. 相似文献
132.
Validation of chromatographic methods: evaluation of detection and quantification limits in the determination of impurities in omeprazole 总被引:1,自引:0,他引:1
To guarantee that an analytical procedure gives reliable, exact and interpretable information about a sample, it must be validated. Two ambiguous parameters are detection limit and quantification limit. The determination of these limits is still of great concern and there are still a variety of procedures described in the current literature. The fundamental objective of the present work is to apply the different recommendations suggested by official guidelines for the quantitative determination of omeprazole and its impurities (omeprazole sulphone and 5-hydroxy-omeprazole) in capsules and tablets using high performance liquid chromatography with UV detection. The importance of calibration linearity in the context of the quantification limit is considered, since one of the approaches, the estimated concentrations of this limit, are deduced from the regression line. The values of the detection limit and the quantification limit obtained show that, in chromatographic analyses, the best method is that based on the use of the parameters obtained from the analytical curve, which are statistically reliable. It was shown that smaller values of the detection limit and the quantification limit were obtained by the visual approach and by the method using the signal-to-noise ratio. However, these values may reflect a subjective evaluation, prone to error and large variations. This was confirmed by showing that these methods result in values that fall outside the linear range of the method. 相似文献
133.
Dr. Carla Gasbarri Prof. Fausto Croce Dr. Ida Meschini Christopher H. Bowen Dr. Lisa Marinelli Prof. Antonio Di Stefano Dr. Guido Angelini 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(2):546-549
Dispersions of single‐walled carbon nanotubes (SWNTs) have been prepared by using the room‐temperature ionic liquid [BMIM][BF4] (1‐butyl‐3‐methylimidazolium tetrafluoroborate), the triblock copolymer Pluronic L121 [poly(ethylene oxide)5‐poly(propylene oxide)68‐poly(ethylene oxide)5] and the non‐ionic surfactant Triton X‐100 (TX100) in the pure state. The size of the SWNTs aggregates and the dispersion degree in the three viscous systems depend on the sonication time, as highlighted by UV/Vis/NIR spectroscopy and optical microscopy analysis. A nonlinear increase in conductivity can be observed as a function of the SWNTs loading, as suggested by electrochemical impedance spectroscopy. The generation of a three‐dimensional network of SWNTs showing a viscoelastic gel‐like behavior above a critical percolation concentration has been found at 25 °C in all the investigated systems by oscillatory rheology measurements. 相似文献
134.
Ftima C. Teixeira Carla Lucas M. Joo M. Curto Antnio P. S. Teixeira M. Teresa Duarte Vnia Andr 《Heteroatom Chemistry》2016,27(1):3-11
Novel tetraethyl ethylene‐1,1‐bisphosphonate esters derived from 1H‐indazole, 1H‐pyrazolo[3,4‐b]pyridine, and 1H‐pyrazolo[3,4‐b]quinoline were synthesized by a Michael addition reaction of tetraethyl ethylidene‐1,1‐bisphosphonate with the corresponding heterocycle, using conventional heating and microwave‐assisted methods. The microwave‐assisted method provides shorter reaction times and better yields. The hydrolysis of bisphosphonates afforded the corresponding bisphosphonic acids or salt, using concentrated hydrochloric acid or TMSBr/collidine, respectively. All new compounds were fully characterized, and their structures were assigned using 1H, 31P, and 13C NMR and IR spectroscopies and mass spectrometry. The molecular structure of compound 6 was confirmed by X‐ray diffraction studies. 相似文献
135.
Ahmad Hasan Carla R. Lambert Prem C. Srivastava 《Journal of heterocyclic chemistry》1990,27(7):1877-1883
The imidazole nucleosides, 4(5)-bromo-5(4)-nitro-1-β-D-ribofuranosylimidazoles, have been prepared via glycosylation of the trimethylsilylated aglycone, 4(5)-bromo-5(4)-nitroimidazole, with tetra-O-acetyl-β-D-ribo-furanose followed by removal of the acetyl protecting groups. The 5-bromo-4-nitro-1-β-D-ribofuranosylimidazole nucleoside was acetonated to produce 5-bromo-4-nitro-1-(2,3-O-isopropylidene-β-D-ribofuranosyl)-imidazole which was cyclized to provide the corresponding anhydronucleoside 5,5′-anhydro-4-nitro-5-oxo-1-(2,3-O-isopropylidene-β-D-ribofuranosyl)imidazole. Sodium hydrosulfide treatment of 5-bromo-4-nitroimidazole nucleoside provided 5-mercapto-4-nitro-1-β-D-ribofuranosylimidazole 5-sodium salt which was alkylated with E-1,5-diiodopent-1-ene to yield 5-(E-1-iodo-1-penten-5-yl)thio-4-nitro-1-β-D-ribofuranosylimidazole. The corresponding iodine-125-labeled compound was prepared similarly using radiolabeled diiodopentene. The 5-bromo-4-nitroimidazole, 5-mercapto-4-nitroimidazole, and 5-iodopentenylthio-4-nitroimidazole nucleosides were cytotoxic to Molt-3 cells in vitro at concentrations higher than 10 μg/mL. The radiolabeled 5-iodopentenylthio-4-nitroimidazole nucleoside showed 2-fold higher uptake in a rapidly growing tumor as compared to uptake in a relatively slower growing tumor in mice. 相似文献
136.
Amanda C. Santos Valtencir Zucolotto Carlos J. L. Constantino Helder N. Cunha José R. dos SantosJr. Carla Eiras 《Journal of Solid State Electrochemistry》2007,11(11):1505-1510
Multilayered nanostructured films have been widely investigated for electrochemical applications as modified electrodes, including
the layer-by-layer (LbL) films where properties such as thickness and film architecture can be controlled at the molecular
level. In this study, we investigate the electrochemical features of LbL films of poly(o-methoxyaniline; POMA) and tetrasulfonated phthalocyanines containing nickel (NiTsPc) or copper (CuTsPc). The films displayed
well-defined electroactivity, with redox pairs at 156 and 347 mV vs SCE, characteristic of POMA, which allowed their use as
modified electrodes for detecting dopamine and ascorbic acid at concentrations as low as 10−5 M.
This paper is dedicated to Prof. Francisco Nart, in memoriam. 相似文献
137.
V. Causin Carla Marega Roberta Saini A. Marigo G. Ferrara 《Journal of Thermal Analysis and Calorimetry》2007,90(3):849-857
The effect of clay dispersion on the crystallization behavior of isotactic polypropylene (iPP)-based nanocomposites is reported.
The T
m0 of the materials was calculated by the method proposed by Marand, the kinetics of crystallization was evaluated by the Avrami
analysis and also the Hoffman-Lauritzen theory of crystallization regimes was applied. Montmorillonite was found to depress
T
m0, to enhance the rate of crystallization and to ease the chain folding of macromolecules. These effects were magnified if
clay was exfoliated, rather than intercalated. 相似文献
138.
Neumann MG Schmitt CC Prieto KR Goi BE 《Journal of colloid and interface science》2007,315(2):810-813
A method based on the aggregate to monomol emission ratio, I(aggr)/I(monomol), was used to determine the minimal hydrotropic concentration (MHC) of aromatic hydrotropes. The main advantage of this method is that it does not require the use of probes or other additives, which might disrupt the aggregation process. Also, it relies on spectrophotometric measurements, which are more sensitive and less arduous than others, like conductivity, light scattering and surface tension. 相似文献
139.
Carrera C Digilio G Baroni S Burgio D Consol S Fedeli F Longo D Mortillaro A Aime S 《Dalton transactions (Cambridge, England : 2003)》2007,(43):4980-4987
A novel Gd(III) complex with a modified DO3A-like chelating cage has been synthesized and characterized as a candidate contrast agent responsive to the concentration of free thiols in tissues (essentially represented by reduced glutathione, GSH). The novel compound (called Gd-DO3AS-Act) bears a flexible linker ending with a 2-pyridyl-dithio group, that can promptly react with free thiols (XSH) to form mixed disulfides of the form Gd-DO3AS-SX. Compound Gd-DO3AS-Act is characterized by a millimolar relaxivity as high as 8.1 mM(-1) s(-1) (at 20 MHz, 25 degrees C and pH 7.4). Upon reaction with GSH, the Gd-DO3AS-SG covalent adduct is formed and the millimolar relaxivity drops to 4.1 mM(-1) s(-1). Such a decrease in relaxivity is explained on the basis of the formation of an intramolecular coordinative bond between one of the glutathionyl carboxyl groups and the Gd(III) centre, lowering the hydration state of the paramagnetic centre. (1)H-NMR dispersion profiles together with (17)O-NMR transverse relaxation time versus temperature profiles confirm that the hydration of the Gd(III) centre is strongly reduced ongoing from Gd-DO3AS-Act to the Gd-DO3AS-SG adduct. The relaxivity difference brought about by the reaction of Gd-DO3AS-Act with GSH can be enhanced up to 60% in the presence of poly-beta-cyclodextrin. 相似文献
140.
Boga C Del Vecchio E Forlani L Goumont R Terrier F Tozzi S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(34):9600-9607
Reactions of DNBF with a series of 2-aminothiazoles (1 a-f) to afford thermodynamically stable C-bonded sigma-adducts have been investigated in acetonitrile. A most significant finding emerged on recording NMR spectra immediately after mixing of equimolar amounts of DNBF and the unsubstituted 2-aminothiazole (1 a) in Me2SO: namely, that the formation of 9 a is preceded by that of a short-lived intermediate species X. From the 1H NMR parameters characterizing this intermediate, as well as the dependence of its lifetime on the experimental conditions-the presence of excess DNBF over 1 a increases the lifetime of X while an excess of base (1 a) accelerates its conversion into 9 a--it is convincingly demonstrated that the structure of X combines the presence of a positively charged Wheland complex moiety (with regard to the thiazole ring) with that of a negatively charged Meisenheimer complex moiety (with regard to the benzofuroxan system). So far, only one intermediate of this type (noted WM) has been successfully characterized, in the reactions of DNBF with 1,3,5-tris(N,N-dialkylamino)benzenes. Among the key features supporting the intermediacy of X along the reaction coordinate leading to 9 a is the fact that the reactions of DNBF with 1 a in the presence of an alcohol (MeOH, EtOH, nPrOH) produce new adducts arising from the addition of an alcohol molecule to the thiazole moiety of WM-1 a. Reflecting the presence of three chiral centres, these species are formed as mixtures of several diastereomers that could all be characterized in their racemic forms in ethanol. These findings generalize the previous report on the formation of Wheland-Meisenheimer carbon-carbon complexes in homocyclic series. 相似文献