全文获取类型
收费全文 | 469篇 |
免费 | 7篇 |
国内免费 | 1篇 |
专业分类
化学 | 308篇 |
晶体学 | 4篇 |
力学 | 8篇 |
数学 | 23篇 |
物理学 | 134篇 |
出版年
2023年 | 3篇 |
2022年 | 3篇 |
2021年 | 3篇 |
2020年 | 2篇 |
2019年 | 10篇 |
2018年 | 6篇 |
2017年 | 2篇 |
2016年 | 8篇 |
2015年 | 11篇 |
2014年 | 10篇 |
2013年 | 22篇 |
2012年 | 26篇 |
2011年 | 28篇 |
2010年 | 20篇 |
2009年 | 13篇 |
2008年 | 34篇 |
2007年 | 31篇 |
2006年 | 27篇 |
2005年 | 32篇 |
2004年 | 19篇 |
2003年 | 13篇 |
2002年 | 13篇 |
2001年 | 11篇 |
2000年 | 15篇 |
1999年 | 2篇 |
1997年 | 6篇 |
1996年 | 7篇 |
1995年 | 3篇 |
1993年 | 7篇 |
1987年 | 4篇 |
1986年 | 2篇 |
1985年 | 6篇 |
1984年 | 7篇 |
1983年 | 5篇 |
1982年 | 2篇 |
1981年 | 5篇 |
1979年 | 7篇 |
1978年 | 5篇 |
1977年 | 5篇 |
1976年 | 7篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1973年 | 3篇 |
1972年 | 2篇 |
1969年 | 3篇 |
1968年 | 3篇 |
1967年 | 5篇 |
1965年 | 1篇 |
1961年 | 2篇 |
1928年 | 2篇 |
排序方式: 共有477条查询结果,搜索用时 15 毫秒
21.
The modeling of reactivity in an ionic liquid is examined with DFT and DFT/MM calculations on the S(N)2 intramolecular rearrangement of the Z-phenylhydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole into 4-benzoylamino-2,5-diphenyl-1,2,3-triazole induced by amines. Experimental research has shown that the reaction occurs in 1-butyl-3-methylimidazolium tetrafluoroborate, and in conventional organic solvents such as acetonitrile with comparable rates. The structure for the reactants, transition states and products for the rate-determining step are optimized, and the energy barrier is computed in three different environments: gas phase, water solvent, and ionic liquid. The results are encouraging in describing the energy barrier in the ionic liquid. A simple model is formulated to explain the effect of the solvent in this particular process, and a procedure to study theoretically the reactivity in an ionic liquid is proposed. 相似文献
22.
tert-Butyl 2-hydroxyalkyl sulfides, prepared by reaction of epoxides with 2-methylpropane-2-thiol, are converted directly to 1,3-oxathiolanes upon treatment with pivalaldehyde and boron trifluoride diethyl etherate in the presence of thioanisole. 相似文献
23.
Brizard A Aimé C Labrot T Huc I Berthier D Artzner F Desbat B Oda R 《Journal of the American Chemical Society》2007,129(12):3754-3762
Amphiphile supramolecular assemblies result from the cooperative effects of multiple weak interactions between a large number of subcomponents. As a result, prediction of and control over the morphologies of such assemblies remains difficult to achieve. Here, we described the fine-tuning of the shape, size, and morphology transitions of twisted and helical membranes formed by non-chiral dicationic n-2-n gemini amphiphiles complexed with chiral tartrate anions. We have reported that such systems express the chirality of the tartrate components at a supramolecular level and that the mechanism of the chiral induction by counterions involves specific anion cation recognition and the induction of conformationally labile chirality in the cations. Here, we demonstrate that the morphologies and dimensions of twisted and helical ribbons, as well as tubules, can be controlled and that interconversion between these structures can be induced upon modifying temperature, upon introducing small amounts of additives, or slightly modifying molecular structure. Specifically, electron microscopy, IR spectroscopy, and small-angle X-ray scattering show that (i) varying the hydrophobic chain length or adding gemini having bromide counterions (1%) or the opposite enantiomer (10%) leads to an increase of the diameter of membrane tubules from 33 to 48.5 nm; (ii) further addition (1.5%) of gemini bromide or a slight increase in temperature induces a transition from tubules to twisted ribbons; (iii) the twist pitch of the ribbons can be continuously tuned by varying enantiomeric excess; and (iv) it was also observed that the morphologies of these ribbons much evolve with time. Such unprecedented observations over easy tuning of the chiral supramolecular structures are clearly related to the original feature that the induction of chirality is solely due the counterions, which are much more mobile than the amphiphiles. 相似文献
24.
Petit L Baraige F Bertheau Y Brunschwig P Diolez A Duhem K Duplan MN Fach P Kobilinsky A Lamart S Schattner A Martin P 《Journal of AOAC International》2005,88(2):654-664
The fate of DNA and protein transgenic sequences in products derived from animals fed transgenic crops has recently raised public interest. Sensitive molecular tests targeting the Bt176 genetic construct and the transgenic Cry1Ab protein were developed to determine whether plant sequences, especially transgenic sequences, are present in animal products. A protocol for total DNA extraction and purification from cow whole blood samples was first drawn up and assessed by spiking with known amounts of DNA from Bt176 maize. The limit of detection for transgenic sequences (35S promoter and Bt176-specific junction sequence) was determined by both the polymerase chain reaction-enzyme-linked immunosorbent assay (PCR-ELISA) and the 5'-nuclease PCR assay. Four additional PCR systems were built to substantiate the results. The first detects a mono-copy maize-specific sequence (ADH promoter). Two others target multi-copy sequences from plant nucleus (26S rRNA gene) and chloroplast (psaB gene). The last one, used as a positive control, targets a mono-copy animal sequence (alpha(s1)-casein gene). Both methods detected a minimum spiking at 25 copies of Bt176 maize/mL in 10 mL whole blood samples. The sandwich ELISA kit used detected down to 1 ng transgenic Cry1Ab protein/mL spiked whole blood. 相似文献
25.
Jirí Kozelka Roger Savinelli Gaston Berthier Jean-Pierre Flament Richard Lavery 《Journal of computational chemistry》1993,14(1):45-53
The antitumor drug cis-diamminedichloroplatinum(II) (cisplatin) binds preferentially to GpG and ApG sequences of DNA, forming N7,N7 intrastrand chelates. Molecular modeling of the intrastrand adducts have been handicapped, so far, by the lack of force-field data describing the Pt–guanine and Pt–adenine binding. We used ab initio calculations with relativistic pseudopotentials to evaluate three important parameters for the platinum–adenine model complex [Pt(NH3)3(Ade)]2+: (1) the force constant for the Pt? N7 bond bending out of the adenine plane; (2) the energy profile for the torsion about Pt? N7; (3) a set of fractional atomic charges that reproduce the ab initio potential for a number of space points placed around the adduct. A population analysis and comparative study on the tetrammine complex [Pt(NH3)4]2+ have shown that for platinum adenine is a better σ-donor than NH3, but its capacity as a π-acceptor is weak. © 1993 John Wiley & Sons, Inc. 相似文献
26.
Yves Ellinger André Rassat Robert Subra Gaston Berthier 《Theoretical chemistry accounts》1968,10(4):289-300
Résumé Une méthode de calcul dérivant des théories de champ self-consistant est utilisé pour l'étude des radicaux vinyle et cyclopropyle. L'énergie électronique et les écarts hyperfins dûs aux hydrogènes et au 13C ont été évalués en fonction de la géométrie du carbone radicalaire. L'angle C=-H du radical vinyle a été trouvé de l'ordre de 150°. Il est montré que les radicaux vinyle et cyclopropyle ont une structure électronique similaire qui ne peut être totalement expliquée ni par un modèle ni par un modèle classique, chaque radical présentant à la fois les deux caractères.
A method of calculation derived from self-consistent field theories is used for a study of vinyl and cyclopropyl radicals. Electronic energy, hydrogens and 13C hyperfine splittings are evaluated as a function of the carbon geometry. The C=-H bond angle is found to be about 150°. It is shown that vinyl and cyclopropyl radicals have a similar electronic structure which cannot be completely interpreted neither by a classical model nor by a one, each radical presenting both and character.
Zusammenfassung Nach einer auf dem SCF-Verfahren basierenden Methode werden Elektronenenergie, H- und 13C-Hyperfeinaufspaltung in Vinyl- und Cyclopropylradikalen in Abhängigkeit vom Bindungswinkel am berechnet, der sich im ersten Fall zu 150° ergibt. Es zeigt sich, daß die Elektronenstruktur der beiden behandelten Radikale ähnlich ist und daß sie weder durch ein reines - noch ein reines -Modell zu beschreiben ist.相似文献
27.
Fabienne Barroso-Bujans Ricardo Martínez Mehrdad Yazdani-Pedram Holger Frey 《European Polymer Journal》2007,43(4):1288-1301
Long chain aliphatic alcohols have been used as model compounds to develop a preparative method for a water-soluble material, which could be a carrier for triacontanol, a highly hydrophobic plant growth regulator. New polyesters from long chain aliphatic (C = 12, 18 and 22) mono-1-alkyl citrates and poly(ethylene glycol) were synthesized and characterized by NMR spectroscopy. The polyester containing the triacontyl moiety was obtained from mono-1-triacontyl citrate, which was synthesized from the corresponding alcohol extracted from the Agave fourcroydes. The molecular weight of the polyesters depends on experimental conditions during synthesis such as reaction time, atmosphere, catalyst concentration and temperature. The reaction is second order in the early stage of the polyester synthesis. The reaction rate constant is independent of the length of the aliphatic chain, but it decreases with increasing of the poly(ethylene glycol) employed. Turbidity measurements have been used to study the polyester solubility. Solubility characteristics were found to depend on the of poly(ethylene glycol), the aliphatic-chain length and the value of for the polyester. These preparations could potentially be used to release triacontanol. 相似文献
28.
Pierre L. Huyskens Fabienne van den Broeck Thrse Zeegers-Huyskens 《Journal of Molecular Structure》1997,416(1-3):91-104
CHCl3 solutions containing a few percent polyethylene oxide PEO (MW = 200 000) or the low-molecular model dioxane are stirred at 50°C during more than 100 h in the presence of small amounts of KCl. The specific conductance, the viscosity and the density of the solutions are measured at 25°C as a function of time. Both PEO and dioxane act as ligands improving the solubility of KCl. The relaxation times are of the order of several hours. After 40 h or more the viscosity of the solutions increases in a spectacular way. However, the most striking observation is that the specific conductance of the polymeric solutions at 25°C is systematically 5% higher than the value measured with the same sample at 45°C, just as for metals. The effect of the dilution of the primary stirred solutions either in the pure solvent or in the initial polymer solution is investigated. These results are discussed in terms of a three-step mechanism in the polymer systems: (1) Loading of the coils to polymeric cations with a full elementary charge, as a consequence of charge transfer interactions of the crown-ether type with numerous K+ ions penetrating into the coils; (2) Electron tunnelling conduction of the Hamill—Ceulemans type from one positive coil to the neighbouring one; (3) Alteration of the structure of the coils and of their hydrodynamic radius by the motions of K+ in the coils. These ‘brachiation’ motions by a hopping mechanism result from an increased mobility of the complexed K+ ions, which is also the origin of the Zundel effect. They do not directly contribute to the conductance but are responsible for the delayed increase of the viscosity. 相似文献
29.
Dimur C Pauzat F Ellinger Y Berthier G 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2001,57(4):859-873
This paper looks at the possibility of astronomical detection of molecules of prebiotic interest containing phosphorus. Attention has been focused on the most stable species that can be formed with the four [C,H,O,P] atoms. Ab initio coupled cluster molecular orbital methods and density functional theory have been used. It is found that the best candidate for detection is singlet HPCO (corresponding to singlet HNCO), which lies 23.5 kcal/mol lower than the next isomer (HOCP) and has a non-negligible dipole moment of 0.8 D. Theoretical rotational constants and infrared (IR) spectra have been determined for HPCO and the closely related HPCS. By correcting the known inadequacies in the calculations with the average theoretical to experimental ratio from two benchmark molecules (HOCO+ and HNCO), it is possible to obtain rotational constants and IR frequencies of considerably higher accuracy. The corrected values of B = 5.5322 GHz and C = 5.4071 GHz for HPCO, and B = 3.0416 GHz and C = 3.0014 GHz for HPCS should be accurate to within a few tenths of a percent. It can also be predicted that only the 2000 cm(-1) (HPCO) and 1400 cm(-1) (HPCS) IR bands have sufficient intensity to be searched in the low-abundance conditions prevailing in space. 相似文献
30.