全文获取类型
收费全文 | 474篇 |
免费 | 20篇 |
国内免费 | 1篇 |
专业分类
化学 | 378篇 |
晶体学 | 6篇 |
力学 | 4篇 |
数学 | 36篇 |
物理学 | 71篇 |
出版年
2023年 | 2篇 |
2022年 | 6篇 |
2021年 | 4篇 |
2020年 | 12篇 |
2019年 | 10篇 |
2018年 | 11篇 |
2017年 | 6篇 |
2016年 | 23篇 |
2015年 | 9篇 |
2014年 | 14篇 |
2013年 | 35篇 |
2012年 | 32篇 |
2011年 | 31篇 |
2010年 | 25篇 |
2009年 | 12篇 |
2008年 | 33篇 |
2007年 | 33篇 |
2006年 | 30篇 |
2005年 | 25篇 |
2004年 | 16篇 |
2003年 | 9篇 |
2002年 | 19篇 |
2001年 | 6篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1997年 | 6篇 |
1996年 | 6篇 |
1994年 | 7篇 |
1993年 | 4篇 |
1992年 | 5篇 |
1991年 | 7篇 |
1990年 | 7篇 |
1989年 | 4篇 |
1988年 | 6篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1979年 | 2篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1970年 | 1篇 |
1968年 | 1篇 |
1964年 | 1篇 |
1957年 | 1篇 |
1943年 | 1篇 |
1933年 | 1篇 |
1929年 | 1篇 |
1926年 | 1篇 |
1901年 | 1篇 |
排序方式: 共有495条查询结果,搜索用时 281 毫秒
11.
12.
The thermodynamic and extra-thermodynamic dependencies of five types of cytochrome c in water-acetonitrile mixtures of different composition in the presence of immobilised n-octyl ligands as a function of temperature from 278 K to 338 K have been investigated. The corresponding enthalpic, entropic and heat capacity parameters, deltaHdegrees assoc, deltaS degrees assoc and delta C degrees p, have been evaluated from the observed non-linear Van't Hoff plots of these globular proteins in these heterogeneous systems. The relationships between the free energy dependencies, various molecular parameters and extra-thermodynamic dependencies (empirical correlations) of these protein-non-polar ligand interactions have also been examined. Thus, the involvement of enthalpy-entropy compensation effects has been documented for the binding of these cytochrome cs to solvated n-octyl ligands. Moreover, the results confirm that this experimental approach permits changes in molecular surface area due to the unfolding of these proteins on association with non-polar ligands as a function of temperature to be correlated with other biophysical properties. This study thus provides a general procedure whereby the corresponding free energy dependencies of globular proteins on association with solvated non-polar ligands in heterogeneous two-phase systems can be quantitatively evaluated in terms of fundamental molecular parameters. 相似文献
13.
G. N. Nikonov A. S. Balueva A. A. Karasik I. A. Litvinov O. A. Erastov B. A. Arbuzov V. A. Nauraov 《Russian Chemical Bulletin》1988,37(1):143-147
1. | Reactions of ammonium 2,2,5-triphenyl-1,3,2,5-dioxaborataphosphorinanes with alkyl halides, diphenylchlorophosphine, formaldehyde, and ethylene oxide were carried out. |
2. | The molecular structure of the N--hydroxyethyltriethylammonium salt of 2,2,5-tri-phenyl-4,6-dimethyl-1, 3,2,5-dioxaborataphosphorinane was established. |
14.
A rapid, precise, accurate, and robust method using capillary electrophoresis (CE) with dynamically coated capillaries for the analysis of the major opium alkaloids in opium is presented. Dynamic coating of the capillary surface is accomplished using a commercially available reagent kit (polycation coating followed by polyanion coating). The addition of dual cyclodextrins (hydroxypropyl-beta-cyclodextrin and dimethyl-beta-cyclodextrin) to the run buffer imparts excellent selectivity for the opium alkaloids. For the determination of morphine, papaverine, codeine, noscapine and thebaine in opium gum and opium latex samples (using tetracaine as an internal standard) good agreement with values obtained by gradient high-performance liquid chromatography is obtained. Compared to the latter technique, CE affords better resolution with significantly faster analysis time (12 min versus 29 min). Dynamically coated capillaries, which give rise to a relatively high and robust electroosmotic flow (EOF) at the background electrolyte pH of 2.5, allow for rapid analysis and excellent migration time and peak area precision (RSDs < or = 0.12% and < or = 1.2%, respectively). Reproducible separations (relative migration times) for over 500 samples have been obtained on a single capillary. The nature of the injection solvent, the injection time and the contents of the waste vials have a profound effect on the pressure injection precision of the relatively hydrophobic solutes. The CE conditions reported in this study are also applicable to the analysis of lysergic acid diethylamide (LSD) exhibits. 相似文献
15.
Kuznetsov R. M. Balueva A. S. Litvinov I. A. Gubaidullin A. T. Nikonov G. N. Karasik A. A. Sinyashin O. G. 《Russian Chemical Bulletin》2002,51(1):151-156
The reaction of bis(hydroxymethyl)phenylphosphine with 4,4"-diaminodiphenylmethane in DMF afforded 1,1",5,5"-bis[methylenedi(p-phenylene)]di(3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) (1) whose structure was established by X-ray diffraction analysis. Sulfurization and oxidation of macrocyclic tetraphosphine 1 gave rise to products 2 and 3, respectively, compound 3 being obtained as a stable hexahydrate. The reaction of bis(hydroxymethyl)phenylphosphine with bis(4-N-methylaminophenyl)methane in DMF followed by sulfurization yielded monocyclic bis{methylenedi[p-phenylene(N-methyl)aminomethyl]}di(P-phenyl)phosphine sulfide (4). 相似文献
16.
Kaljurand I Kütt A Sooväli L Rodima T Mäemets V Leito I Koppel IA 《The Journal of organic chemistry》2005,70(3):1019-1028
The earlier compiled self-consistent spectrophotometric basicity scale in acetonitrile (AN) was expanded to range from 3.8 to 32.0 pK(a) units, that is 28 orders of magnitude. Altogether 54 new relative basicity measurements (DeltapK(a) measurements) were carried out and 37 new compounds were introduced to the scale (it now includes altogether 89 bases). The relative basicity of any two bases in the scale can be obtained by combining at least two independent sets of measurements. Multiple overlapping measurements make the results more reliable. The overall consistency (as defined earlier) of the measurements is s = 0.03 pK(a) units. Thorough analysis of all of our experimental data (DeltapK(a) values of this and earlier works) and experimental pK(a) data in AN available in the literature (works from the groups of Coetzee and Padmanabhan, Kolthoff and Chantooni, Jr., the Schwesinger group, Bren' et al. and some others, altogether 19 papers) was carried out. On the basis of this analysis the anchor point of the scale-pyridine-was shifted upward by 0.20 pK(a) units thereby also revising the absolute pK(a) values of all the bases on the scale. This way very good agreement between our relative data and the absolute pK(a) values of the abovementioned authors was obtained. The revised basicity scale was interconnected with the earlier published self-consistent acidity scale by DeltapK(a) measurements between acids and bases. The rms deviation between the directly measured DeltapK(a) values and the absolute pK(a) values of the compounds was 0.10 pK(a) units. 相似文献
17.
Correia I Costa Pessoa J Duarte MT Henriques RT Piedade MF Veiros LF Jakusch T Kiss T Dörnyei A Castro MM Geraldes CF Avecilla F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(9):2301-2317
The Schiff base N,N'-ethylenebis(pyridoxylideneiminato) (H(2)pyr(2)en, 1) was synthesized by reaction of pyridoxal with ethylenediamine; reduction of H(2)pyr(2)en with NaBH(4) yielded the reduced Schiff base N,N'-ethylenebis(pyridoxylaminato) (H(2)Rpyr(2)en, 2); their crystal structures were determined by X-ray diffraction. The totally protonated forms of 1 and 2 correspond to H(6)L(4+), and all protonation constants were determined by pH-potentiometric and (1)H NMR titrations. Several vanadium(IV) and vanadium(V) complexes of these and other related ligands were prepared and characterized in solution and in the solid state. The X-ray crystal structure of [V(V)O(2)(HRpyr(2)en)] shows the metal in a distorted octahedral geometry, with the ligand coordinated through the N-amine and O-phenolato moieties, with one of the pyridine-N atoms protonated. Crystals of [(V(V)O(2))(2)(pyren)(2)].2 H(2)O were obtained from solutions containing H(2)pyr(2)en and oxovanadium(IV), where Hpyren is the "half" Schiff base of pyridoxal and ethylenediamine. The complexation of V(IV)O(2+) and V(V)O(2) (+) with H(2)pyr(2)en, H(2)Rpyr(2)en and pyridoxamine in aqueous solution were studied by pH-potentiometry, UV/Vis absorption spectrophotometry, as well as by EPR spectroscopy for the V(IV)O systems and (1)H and (51)V NMR spectroscopy for the V(V)O(2) systems. Very significant differences in the metal-binding abilities of the ligands were found. Both 1 and 2 act as tetradentate ligands. H(2)Rpyr(2)en is stable to hydrolysis and several isomers form in solution, namely cis-trans type complexes with V(IV)O, and alpha-cis- and beta-cis-type complexes with V(V)O(2). The pyridinium-N atoms of the pyridoxal rings do not take part in the coordination but are involved in acid-base reactions that affect the number, type, and relative amount of the isomers of the V(IV)O-H(2)Rpyr(2)en and V(V)O(2)-H(2)Rpyr(2)en complexes present in solution. DFT calculations were carried out and support the formation and identification of the isomers detected by EPR or NMR spectroscopy, and the strong equatorial and axial binding of the O-phenolato in V(IV)O and V(V)O(2) complexes. Moreover, the DFT calculations done for the [V(IV)O(H(2)Rpyr(2)en)] system indicate that for almost all complexes the presence of a sixth equatorial or axial H(2)O ligand leads to much more stable compounds. 相似文献
18.
Conclusions 1,3,5-Diazaphosphorinanes react with borane yielding, depending on the nature of the substituents at the ring atoms, complexes with two or three borane molecules and the products of ring opening at the C-N bonds of the P-C-N and N-C-N fragments.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1375–1379, June, 1989. 相似文献
19.
Chaudhuri RK Freed KF Hose G Piecuch P Kowalski K Włoch M Chattopadhyay S Mukherjee D Rolik Z Szabados A Tóth G Surján PR 《The Journal of chemical physics》2005,122(13):134105
Tests have been made to benchmark and assess the relative accuracies of low-order multireference perturbation theories as compared to coupled cluster (CC) and full configuration interaction (FCI) methods. Test calculations include the ground and some excited states of the Be, H(2), BeH(2), CH(2), and SiH(2) systems. Comparisons with FCI and CC calculations show that in most cases the effective valence shell Hamiltonian (H(v)) method is more accurate than other low-order multireference perturbation theories, although none of the perturbative methods is as accurate as the CC approximations. We also briefly discuss some of the basic differences among the multireference perturbation theories considered in this work. 相似文献
20.
In an attempt to generate antibodies for the development of an immunoanalysis method for potassium and caesium ions, new 1,3-alternate calix[4]arenes-crown-5 and -6 bearing either carboxylic or hydroxyl functions were synthesized in good yields. Their complexation properties towards potassium and caesium ions were investigated using 1H NMR spectroscopy and the usual properties proved to be preserved in the presence of the anchoring arms. 相似文献