全文获取类型
收费全文 | 1450篇 |
免费 | 43篇 |
国内免费 | 11篇 |
专业分类
化学 | 1102篇 |
晶体学 | 2篇 |
力学 | 13篇 |
数学 | 228篇 |
物理学 | 159篇 |
出版年
2023年 | 8篇 |
2022年 | 42篇 |
2021年 | 55篇 |
2020年 | 25篇 |
2019年 | 25篇 |
2018年 | 26篇 |
2017年 | 23篇 |
2016年 | 41篇 |
2015年 | 35篇 |
2014年 | 46篇 |
2013年 | 89篇 |
2012年 | 84篇 |
2011年 | 92篇 |
2010年 | 71篇 |
2009年 | 53篇 |
2008年 | 96篇 |
2007年 | 84篇 |
2006年 | 99篇 |
2005年 | 76篇 |
2004年 | 61篇 |
2003年 | 53篇 |
2002年 | 46篇 |
2001年 | 23篇 |
2000年 | 20篇 |
1999年 | 11篇 |
1998年 | 21篇 |
1997年 | 9篇 |
1996年 | 13篇 |
1995年 | 11篇 |
1994年 | 16篇 |
1993年 | 10篇 |
1992年 | 9篇 |
1991年 | 9篇 |
1990年 | 11篇 |
1989年 | 11篇 |
1988年 | 4篇 |
1987年 | 10篇 |
1985年 | 14篇 |
1984年 | 12篇 |
1983年 | 5篇 |
1982年 | 7篇 |
1981年 | 5篇 |
1980年 | 6篇 |
1978年 | 5篇 |
1977年 | 4篇 |
1976年 | 2篇 |
1975年 | 5篇 |
1973年 | 4篇 |
1971年 | 4篇 |
1943年 | 2篇 |
排序方式: 共有1504条查询结果,搜索用时 281 毫秒
31.
Ewa Machalska Grzegorz Zajac Malgorzata Baranska Dorota Kaczorek Robert Kawcki Piotr F. J. Lipiski Joanna E. Rode Jan Cz. Dobrowolski 《Chemical science》2021,12(3):911
Raman optical activity (ROA) spectra recorded for a chiral naphthalene diimide derivative (nBu-NDI–BINAM) dissolved in a series of solvents exhibit strong solute to solvent induced chirality with: (1) dominating bands of solvents, (2) nBu-NDI–BINAM resonance ROA (RROA) bands which are barely visible, (3) monosignate RROA Solvent spectra with an unexpected sign concordant with that of the ECD band of the resonant electronic state, (4) bisignate RROA bands for a few solvents, and (5) superposition of non-resonant and resonant ROA bands of the chiral solvents. The unusual ROA enhancement was explained in terms of resonance energy transfer with resonant Raman emission. The surprising RROA sign-switching was found to be due to specific conformational equilibria where one solute conformer dominates in the ground and the other in the first excited singlet state, and, the signs of the related ECD bands of these two conformers are opposite.Unusual solute to solvent induced chirality in ROA comes from specific conformer equilibria in the ground and the excited states. 相似文献
32.
Ede Kapuy Ferenc Bartha Ferenc Bogr Zoltn Cspes Cornelia Kozmutza 《International journal of quantum chemistry》1990,38(2):139-147
Diagrammatic formulation of the MBPT is applied when the occupied and the virtual canonical orbitals are separately localized by unitary transformations. In this localized representation, due to the off-diagonal Fock matrix elements, the perturbation operator contains extra terms generating the so-called localization corrections. These corrections enter the perturbation energy in third and higher orders. Their magnitude depends on the type of localization, but they represent only a small fraction of the canonical corrections. The calculation of the localization corrections, however, does not need a significant amount of extra computer time. It is shown that by introducing an “order of neighborhood” local and nonlocal effects of the electron correlation can be separated and the contribution of the nonlocal effects can be neglected to a good approximation. Ab initio calculations have been carried out for the normal saturated hydrocarbons: C2n+1H4n+4 and for the all-trans conjugated polyenes C2n+2H2n+4. As to the ratio of the local and nonlocal corrections, it is shown that there is only a quantitative difference for these two kinds of systems (strongly or weakly localizable). Neglecting nonlocal effects, considerable amount of computer time can be saved. 相似文献
33.
Bla Ivn Joseph P. Kennedy Tibor Kelen Ferenc Tüdos 《Journal of polymer science. Part A, Polymer chemistry》1981,19(3):679-685
Colorless poly(vinyl chloride)s (PVC) containing up to 1.6 allylic chlorines per molecule have been prepared by controlled random dehydrochlorination with a strong base. The effect of temperature in the ?50 to +24°C range on the number of allylic chlorines and color of PVC has been investigated by ozonization experiments and UV–visible spectroscopy. A two-parameter kinetic model has been developed which quantitatively accounts for the observations and points the way for further research. 相似文献
34.
Matthias HeydenreichAndreas Koch László LázárIstván Szatmári Reijo SillanpääErich Kleinpeter Ferenc Fülöp 《Tetrahedron》2003,59(11):1951-1959
Starting from the 1′- or 2′-phenyl-substituted 1-(2′-hydroxyethyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline diastereomers 3 and 6, 4-unsubstituted and 4-(p-nitrophenyl)- and 4-oxo-substituted 1-phenyl- and 2-phenyl-9,10-dimethoxy-2H,4H-1,6,7,11b-tetrahydro-1,3-oxazino[4,3-a]isoquinolines (7-12) were prepared. The relative configurations and the predominant conformations of the products were determined by NMR spectroscopy, by quantum chemical calculations and, for (2R∗,4S∗,11bR∗)-9,10-dimethoxy-4-(p-nitrophenyl)-2-phenyl-2H,4H-1,6,7,11b-tetrahydro-1,3-oxazino[4,3-a]isoquinoline (11), by X-ray diffraction. 相似文献
35.
In contrast with earlier literature data [7], both acrylic esters and acrylonitrile underwent Michael addition to l-methyl-3,4-dihydroisoquinolines 1-4 to yield the diesters 5-9 or the dinitrile 10 , respectively. Compounds 5-10 were converted by Claisen condensation to 1-[(3′-methoxycarbonyl- or 1-[(3′-ethoxycarbonyl-4′-oxo)-l'-cyclohexyl]-3,4-dihydroisoquinoline derivatives 11-16 . Several derivatives of 12 were prepared. The new compounds possess various pharmacological actions. 相似文献
36.
Rebeka Nádasdi István Szilágyi Gergely Kovács Sándor Dóbé Tibor Bérces Ferenc Márta 《Reaction Kinetics and Catalysis Letters》2006,89(1):193-199
Summary The fast flow technique with OH resonance fluorescence detection has been applied at T = 298 ± 2 K to study the kinetics of the overall reaction: H + CH3C(O)Cl → products (1) A rate constant value of k1 = (1.02 ± 0.12) x 1010 cm3 mol-1 s-1 has been determined which is the first direct kinetic parameter reported for reaction (1) in the literature (the error given
refers to 2σ accuracy). 相似文献
37.
38.
Electrochemical studies of famotidine were carried out using voltammetric techniques: cyclic voltammetry, linear sweep and square wave adsorptive stripping voltammetry. The dependence of the current on pH, buffer concentration, nature of the buffer, and scan rate was investigated. The best results for the determination of famotidine were obtained in MOPS buffer solution at pH 6.7. This electroanalytical procedure enabled to determine famotidine in the concentration range 1 × 10−9–4 × 10−8 mol L−1 by linear sweep adsorptive stripping voltammetry (LS AdSV) and 5 × 10−10–6 × 10−8 mol L−1 by square wave adsorptive stripping voltammetry (SW AdSV). Repeatability, precision and accuracy of the developed methods were checked. The detection and quantification limits were found to be 1.8 × 10−10 and 6.2 × 10−10 mol L−1 for LS AdSV and 4.9 × 10−11 and 1.6 × 10−10 mol L−1 for SW AdSV, respectively. The method was applied for the determination of famotidine in urine. 相似文献
39.
The coil/helix transition of a synthetic, branched-chain polymeric polypeptide (poly (Lys(Glu(1)-DL-Ala(3))EAK), 50-Lys residues long in the backbone, as a function of increasing molarities of methanol in solution, is here studied by both, circular dichroism (CD) and capillary zone electrophoresis. CD spectra showed that, at 75% v/v methanol, the transition from random coil to fully helical structure was obtained, in a pH 1.1 HCI solution in the presence of 20 mM NaCI. CZE studies, run in parallel, exhibited the classical unfolding to folding sigmoidal transition, with mid-point at 60% v/v methanol concentration, plateauing at ca. 80% v/v organic solvent. Surprisingly, though, such unfolding to folding transition was accompanied by an expansion, rather than a contraction, of the resulting ordered polypeptide. As the charge of the polypeptide (a pure polycation at a pH of 2.1 in CZE) was kept rigorously constant, a plot of the radius of the polymer along the sigmoidal transition clearly showed that the radius of gyration of the helical, structured polypeptide was in fact larger than that of the random coil. Such results were confirmed by molecular dynamics simulations, which indicated that the dimensions of such polypeptide, in alpha-helix configuration, were 8.5 nm (in length) and 3.2 nm (in diameter), whereas those of the corresponding random coil were 7.2 nm (in length) and 5.1 nm (length of shorter axis). It would thus appear that the randomized structure assumes the shape of a more compact object, roughly resembling a "rugby ball". 相似文献
40.
Ferenc F. Gaál Biljana F. Abramovi Ferenc B. Szebenyi Velimir D. Cani 《Fresenius' Journal of Analytical Chemistry》1977,286(3-4):222-225
Summary Amperometric and potentiometric methods at a small constant current were developed to follow the course of catalytic titrations. In ammoniacal medium EDTA was determined by titration with 0.1 M copper(II) chloride in the presence of hydrogen peroxide as the indicator. Amounts of 42.26–126.87 mg of EDTA were determined with a maximal average deviation of 0.55 %. The results obtained are in good agreement with those of comparable methods.
Bestimmung von ÄDTA mit Hilfe der katalytischen amperometrischen und der katalytischen potentiometrischen Titration bei kleinem konstantem Strom
Zusammenfassung Die amperometrische und die potentiometrische Methode bei kleinem konstantem Strom wurden für die Verfolgung katalytischer Titrationen ausgearbeitet. ÄDTA wurde in Ammoniakmedium mit 0,1 M Kupfer(II)-chlorid in Anwesenheit von Wasserstoffperoxid als Indicator titriert. Mengen von 42,26–126,87 mg ÄDTA wurden mit einer mittleren Abweichung von 0,55% bestimmt. Die Ergebnisse stimmen gut mit denen vergleichbarer Methoden überein.
The authors thank the SIZ for researchs of SAP Vojvodina for the partial financial support of the present work. 相似文献