全文获取类型
收费全文 | 1298篇 |
免费 | 22篇 |
国内免费 | 6篇 |
专业分类
化学 | 1057篇 |
晶体学 | 9篇 |
力学 | 8篇 |
数学 | 144篇 |
物理学 | 108篇 |
出版年
2023年 | 16篇 |
2022年 | 50篇 |
2021年 | 59篇 |
2020年 | 33篇 |
2019年 | 23篇 |
2018年 | 26篇 |
2017年 | 19篇 |
2016年 | 22篇 |
2015年 | 36篇 |
2014年 | 31篇 |
2013年 | 71篇 |
2012年 | 65篇 |
2011年 | 76篇 |
2010年 | 55篇 |
2009年 | 41篇 |
2008年 | 78篇 |
2007年 | 74篇 |
2006年 | 83篇 |
2005年 | 65篇 |
2004年 | 56篇 |
2003年 | 60篇 |
2002年 | 51篇 |
2001年 | 10篇 |
2000年 | 13篇 |
1999年 | 12篇 |
1998年 | 10篇 |
1997年 | 10篇 |
1996年 | 14篇 |
1995年 | 12篇 |
1994年 | 7篇 |
1993年 | 5篇 |
1992年 | 10篇 |
1991年 | 14篇 |
1990年 | 7篇 |
1989年 | 9篇 |
1988年 | 3篇 |
1987年 | 4篇 |
1985年 | 9篇 |
1984年 | 9篇 |
1983年 | 5篇 |
1982年 | 11篇 |
1981年 | 8篇 |
1980年 | 7篇 |
1979年 | 7篇 |
1978年 | 5篇 |
1975年 | 3篇 |
1974年 | 4篇 |
1972年 | 4篇 |
1959年 | 2篇 |
1940年 | 2篇 |
排序方式: 共有1326条查询结果,搜索用时 15 毫秒
31.
32.
Boris S. Krumgalz Rita Pogorelsky Kenneth S. Pitzer 《Journal of solution chemistry》1995,24(10):1025-1038
The ion interaction approach developed by Pitzer was used for the prediction of volumetric properties of mixed electrolyte solutions at 25°C based on parameters calculated from experimental data for single-solute electrolyte solutions. Such an approach was shown to be especially effective for application to the calculation of volumetric properties of natural hypersaline brines and of industrial electrolyte solutions of large complexity. The use of the latest recommended sets of volumetric ion interaction parameters for single electrolyte solutions and symmetrical mixing parameters for Na–K–Cl ion combinations considerably improved the precision of the density calculations of highly concentrated mixed electrolyte solutions and of various natural waters. 相似文献
33.
Studies aimed at a comparison of chemical, biomimetic (Gif system GoAgg(III))and enzymatic (CHMO) transformations of natural (+)-10beta,14-dihydroxy-allo-aromadendrane have led to preparation of an eight-member sesquiterpene lactone. 相似文献
34.
Fundueanu G Constantin M Bortolotti F Ascenzi P Cortesi R Menegatti E 《Macromolecular bioscience》2005,5(10):955-964
Despite the large number of publications and patents concerning pH/thermoresponsive polymers, few data are available concerning the preparation of thermoresponsive cross-linked microspheres from preformed polymers. Therefore, N-isopropylacrylamide-co-acrylamide-co-(2-hydroxyethyl acrylate) copolymers were obtained as a new thermoresponsive material with a lower critical solution temperature (LCST) around 36 degrees C, in phosphate buffer at pH 7.4, and with a cross-linkable OH group in their structure. The LCST value was determined both by UV spectroscopy and microcalorimetric analysis. These copolymers were solubilised in acidified aqueous solution below their LCST, dispersed in mineral oil, and transformed into stable microspheres by cross-linking with glutaraldehyde. The thermoresponsive microspheres were characterised by optical and scanning electron microscopy, degree of swelling, and water retention. The pore dimensions of the microspheres and the retention volumes of some drugs and typical compounds were evaluated at different temperatures by liquid chromatography. Indomethacin, as a model drug, was included in the microspheres by the solvent evaporation method. Finally, the influence of temperature and of temperature cycling on drug release was investigated. 相似文献
35.
Some laws in physics describe the change of a flux and are represented by parabolic equations of the form (*) \documentclass{article}\pagestyle{empty}\begin{document}$$\frac{{\partial u}}{{\partial t}}=\frac{\partial}{{\partial x_j }}(\eta \frac{{\partial u}}{{ax_j}}-vju),$$\end{document} j≤m, where η and vj are functions of both space and time. We show under quite general assumptions that the solutions of equation (*) with homogeneous Dirichlet boundary conditions and initial condition u(x, 0) = uo(x) satisfy The decay rate d > 0 only depends on bounds for η, v and G § Rm the spatial domain, while the constant c depends additionally on which norm is considered. For the solutions of equation (*) with homogeneous Neumann boundary conditions and initial condition u0(x) ≥ 0 we derive bounds d1u1 ≤ u(x, t) ≤ d2u2, Where di, i = 1, 2, depend on bounds for η, v and G, and the ui are bounds on the initial condition u0. 相似文献
36.
Die erste Röntgenstrukturanalyse eines 3,7-Dehydrotropon ( 1 )-Derivates, nämlich von 2-Diisopropylammo-3,7-dehydrotropon ( 4 ) zeigt das Ringsystem in 4 als planaren Bicyclus mit nahezu C2V-Symmetrie. Dementsprechend enthalten Dehydrotropone formell zwei trans-konfigurierte Doppelbindungen in einem 7-gliedrigen Ring; auch das O-Atom und das N-Atom mit seinen Ligandatomen liegen in derselben Ebene wie die Ringatome. Die Bindung zwischen den beiden C-Atomen, welche die Heteroatome tragen, (C(1) and C(2)), ist wesentlich langer (1,56 Å) als die anderen Bindungen im Ringsystem (1,37-1,46 Å). Dies impliziert eine ‘push-pull’-π-Elektronen-Delokalisierung, in der auch das O-und das N-Atom involviert sind, und macht eine ‘aromatische’ Ring-Delokalisierung weniger wahr-scheinlich. Im Gegensatz zu 2-(t-Butyl)-3,7-dehydrotropon ( 3 ) existiert das 2-Diiso-propylamino-3,7-dehydrotropon ( 4 ) im Kristall als Monomeres, was dem stabili-sierenden Einfluss der ‘push-pull’-Delokausierung zugeschrieben werden kann. 相似文献
37.
Wolfgang Stadlbauer Rita Laschober Thomas Kappe 《Monatshefte für Chemie / Chemical Monthly》1991,122(10):853-861
Summary 4-Chloro-3-aryl-coumarins and quinolones2 a–e undergo thermolytic ring closure by reaction with sodium azide in refluxing dimethyl formamide to yield indolo[3,2-c]coumarins and indolo[3,2-c]quinolin-6(5H)-ones6 a–e. In the case of the coumarin2 a the azido coumarin5 can be isolated. The mono- and diazacoumestrol-dimethylethers6 a–c are converted into the coumestrol analogues7 a–c and their diacetyl derivatives8 a–c.
Potentielle nichtsteroidale Östrogene und Antiöstrogene, 4. Mitt.: Organische Azide in der Heterocyclensynthese, Teil 13: Synthese von Aza- und Diazacumöstrolen über Azidzwischenstufen
Zusammenfassung 4-Chlor-3-arylcumarine und-chinolone2 a–e reagieren thermolytisch mit Natriumazid in siedendem Dimethylfomamid unter Ringschluß zu Indolo[3,2-c]cumarinen und Indolo[3,2-c]chinolin-6(5H)-onen6 a–e. Nur aus dem Cumarinderivat2 a kann das zwischenzeitlich gebildete Azidocumarin5 isoliert werden. Die so erhaltenen Mono- und Diazacumöstroldimethylether6 a–c werden in die entsprechenden Cumöstrole7 a–c und ihre Diacetylderivate8 a–c umgewandelt.相似文献
38.
Pinto SS Diogo HP Guedes RC Costa Cabral BJ Minas da Piedade ME Martinho Simões JA 《The journal of physical chemistry. A》2005,109(42):9700-9708
The energetics of the phenolic O-H bond in the three hydroxybenzoic acid isomers and of the intramolecular hydrogen O-H- - -O-C bond in 2-hydroxybenzoic acid, 2-OHBA, were investigated by using a combination of experimental and theoretical methods. The standard molar enthalpies of formation of monoclinic 3- and 4-hydroxybenzoic acids, at 298.15 K, were determined as Delta(f)(3-OHBA, cr) = -593.9 +/- 2.0 kJ x mol(-1) and Delta(f)(4-OHBA, cr) = -597.2 +/- 1.4 kJ x mol(-1), by combustion calorimetry. Calvet drop-sublimation calorimetric measurements on monoclinic samples of 2-, 3-, and 4-OHBA, led to the following enthalpy of sublimation values at 298.15 K: Delta(sub)(2-OHBA) = 94.4 +/- 0.4 kJ x mol(-1), Delta(sub)(3-OHBA) = 118.3 +/- 1.1 kJ x mol(-1), and Delta(sub)(4-OHBA) = 117.0 +/- 0.5 kJ x mol(-1). From the obtained Delta(f)(cr) and Delta(sub) values and the previously reported enthalpy of formation of monoclinic 2-OHBA (-591.7 +/- 1.3 kJ x mol(-1)), it was possible to derive Delta(f)(2-OHBA, g) = -497.3 +/- 1.4 kJ x mol(-1), Delta(f)(3-OHBA, g) = -475.6 +/- 2.3 kJ x mol(-1), and Delta(f)(4-OHBA, cr) = -480.2 +/- 1.5 kJ x mol(-1). These values, together with the enthalpies of isodesmic and isogyric gas-phase reactions predicted by density functional theory (B3PW91/aug-cc-pVDZ, MPW1PW91/aug-cc-pVDZ, and MPW1PW91/aug-cc-pVTZ) and the CBS-QMPW1 methods, were used to derive the enthalpies of formation of the gaseous 2-, 3-, and 4-carboxyphenoxyl radicals as (2-HOOCC(6)H(4)O(*), g) = -322.5 +/- 3.0 kJ.mol(-1) Delta(f)(3-HOOCC(6)H(4)O(*), g) = -310.0 +/- 3.0 kJ x mol(-1), and Delta(f)(4-HOOCC(6)H(4)O(*), g) = -318.2 +/- 3.0 kJ x mol(-1). The O-H bond dissociation enthalpies in 2-OHBA, 3-OHBA, and 4-OHBA were 392.8 +/- 3.3, 383.6 +/- 3.8, and 380.0 +/- 3.4 kJ x mol(-1), respectively. Finally, by using the ortho-para method, it was found that the H- - -O intramolecular hydrogen bond in the 2-carboxyphenoxyl radical is 25.7 kJ x mol(-1), which is ca. 6-9 kJ x mol(-1) above the one estimated in its parent (2-OHBA), viz. 20.2 kJ x mol(-1) (theoretical) or 17.1 +/- 2.1 kJ x mol(-1) (experimental). 相似文献
39.
Rita Patakfalvi Albert Oszk Imre D k ny 《Colloids and surfaces. A, Physicochemical and engineering aspects》2003,220(1-3):45-54
Ag nanoparticles were synthetized in the interlamellar space of a layered kaolinite clay mineral. Disaggregation of the lamellae of non-swelling kaolinite was achieved by intercalation of dimethyl sulfoxide. The kaolinite was suspended in aqueous AgNO3 solution and, after adsorption of Ag+, the ions were reduced with NaBH4. The interlamellar space limits particle growth (dave=3.8–4.2 nm); however, larger silver particles may be formed on the exterior surface of kaolinite with dave=5.6–10.5 nm diameter. The diameter of the particles prepared in this way is depending on the initial AgNO3 concentration. The silver nanoparticles prepared were characterized by UV–vis spectroscopy, X-ray diffraction (XRD), Small angle X-ray scattering (SAXS), X-ray photoelectron spectroscopy (XPS) and Transmission electron microscopy (TEM). 相似文献
40.
Estrela Rde C Salvadori MC Raices RS Suarez-Kurtz G 《Journal of mass spectrometry : JMS》2003,38(4):378-385
A method based on solid-phase extraction coupled to liquid chromatography with positive ion electrospray ionization and tandem mass spectrometric detection was developed for the determination of didanosine in human serum, using lamivudine as internal standard. The acquisition was performed in the multiple reaction monitoring mode, monitoring the transitions m/z 237 --> 136.7 for didanosine and m/z 230 --> 111.7 for lamivudine. The method was linear over the range studied (10-1500 ng ml(-1)), with r(2) > 0.98, and the run time was 5 min. The intra- and inter-assay precisions were < or =10% and the intra- and inter-assay accuracies were >95%. The absolute recoveries were 99.8% (10 ng ml(-1)), 98.4% (30 ng ml(-1)), 91.5% (700 ng ml(-1)) and 94.7% (1200 ng ml(-1)). The limits of detection and quantitation were 5 and 10 ng ml(-1), respectively. The method was applied to a bioequivalence study, in which 24 healthy adult volunteers (12 men) received single oral doses (200 mg) of reference and test didanosine formulations (buffered powder for oral solutions), in an open, two-way, randomized, crossover protocol. The 90% confidence interval of the individual ratios (test formulation/reference formulation) for C(max) (peak serum concentration) and AUC(0-inf) (area under the serum concentration versus time curve from time zero to infinity) were within the range 80-125%, which supports the conclusion that the two formulations are bioequivalent regarding the rate and extent of didanosine absorption. 相似文献