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61.
The applicability of a previously developed MM2/CNDO model, based on five saturated alcohols, for the calculation of νOH gas frequencies has been tested for the rotamers of several cyclohexanols in both the equatorial and the axial conformation. Experimental νOH values are assigned to the various OH rotamers present. Reasonable agreement is achieved between calculated and experimental data for νOH frequencies and rotamer populations. The decrease of the observed νOH frequencies upon substitution of an -hydrogen vicinal to the OH proton by a methyl group, is properly described in the MM2/CNDO scheme by the implemented electrostatic interactions between calculated CNDO/2 atomic charges. The shifts of νOH observed when the substitution concerns β-hydrogens are in general less well predicted. In order to improve these results an additional interaction is required. 相似文献
62.
Bifunctional Submicron Colloidosomes Coassembled from Fluorescent and Superparamagnetic Nanoparticles 下载免费PDF全文
Tobias Bollhorst Shakiba Shahabi Katharina Wörz Charlotte Petters Prof. Ralf Dringen Dr. Michael Maas Prof. Kurosch Rezwan 《Angewandte Chemie (International ed. in English)》2015,54(1):118-123
Colloidosomes are microcapsules consisting of nanoparticle shells. These microcarriers can be self‐assembled from a wide range of colloidal particles with selective chemical, physical, and morphological properties and show promise for application in the field of theranostic nanomedicine. Previous studies have mainly focused on fairly large colloidosomes (>1 μm) based on a single kind of particle; however, the intrinsic building‐block nature of this microcarrier has not been exploited so far for the introduction of tailored functionality at the nanoscale. We report a synthetic route based on interfacial shear rheology studies that allows the simultaneous incorporation of different nanoparticles with distinct physical properties, that is, superparamagnetic iron oxide and fluorescent silica nanoparticles, in a single submicron colloidosome. These tailor‐made microcapsules can potentially be used in various biomedical applications, including magnetic hyperthermia, magnetic particle imaging, drug targeting, and bioimaging. 相似文献
63.
M Van Puymbroeck M E Kuilman R F Maas R F Witkamp L Leyssens D Vanderzande J Gelan J Raus 《The Analyst》1998,123(12):2681-2686
17 alpha-Boldenone (17 alpha-BOL) and/or 17 beta-boldenone (17 beta-BOL) appear occasionally in fecal matter of cattle. In addition to 17 alpha-BOL, a whole array of boldenone related substances can be found in the same samples. In vitro experiments with microsomal liver preparations and isolated hepatocytes combined with the excretion profiles found in urine and feces samples of in vivo experiments made it possible to identify several metabolites of 17 beta-BOL in 17 beta-BOL positive feces samples. In one animal treated with 17 beta-BOL, no 17 beta-BOL or its metabolites were present before treatment and most of these compounds disappeared gradually in time after the treatment was stopped. It is not clear what the origin is of 17 alpha-BOL and boldenone metabolites in samples screened routinely for the abuse of anabolic steroids and considered to be 'negative' because of the absence of 17 beta-BOL since other workers showed some evidence that 17 alpha-BOL can be of endogenous origin. However, in our hands, most of these 17 alpha-BOL positive samples, obtained during routinely performed screenings of cattle, contained large amounts of delta 4-androstene-3,17-dione (AED), which normally is absent from routinely screened negative samples. Furthermore, AED was absent in all samples obtained from the animals treated with 17 beta-BOL. We have no direct evidence that 17 alpha-BOL or 17 beta-BOL is of endogenous origin. 相似文献
64.
J. Hanuza M. M
czka A. Wa
kowska W. Oganowski H. Ban-Oganowska E. T. G. Lutz J. H. van der Maas 《Journal of Molecular Structure》1998,450(1-3)
The crystal structure of 2,6-dimethyl-4-nitropyridine N-oxide (DMNPO) has been determined at ambient temperature. The compound crystallizes as a monoclinic structure, space group P2/n, with 12 molecules per unit cell. The unit cell contains three non-equivalent formula units. The nitro group is not coplanar with the pyridine ring. Through a system of =C–HO hydrogen bonds the molecules are arranged into a two-dimensional network of layers parallel to the axc plane.The IR and Raman spectra, measured in the 3500–100 cm−1 region at ambient temperature, are correlated with X-ray structural data. The assignment of IR and Raman bands is given. The appearance of characteristic vibrational features in the spectra of this compound and the observed shifts of the =C–H and N–O IR active stretching modes, when the sample is dissolved in CCl4, is discussed in terms of the relatively strong =C–HO hydrogen bonds present in this crystal. 相似文献
65.
Summary Regioselective cleavage of the glycidic ester3 by BF3/ether to pyruvic acid ester4 followed by NaBH4 reduction affords the lactic acid derivative5a which in turn can be acylated by caffeoyl chloride8c to yield the O-protected rosmarinic acid ester9a. Alternatively,9a can be prepared by acylation of5a with diethylphosphono acetyl chloride (6c) thus generating theWadsworth-Emmons reagent7a which is subsequently reacted with the aldehyde1a. The analogous reaction using the silyl protected educts7d and1b failed to give9d. Finally,9a is debenzylated by BCl3 furnishing the title compound10a in fair total yield. 相似文献
66.
67.
68.
s-Triazolo[4,3-b Jpyridazine (I) photochemically reacted with dihydropyran; 2,3-dihydro-p-dioxin; 2,5-dihydrofuran; 2,5-dimethoxy-2,5-dihydrofuran; and 1,3-dioxep-5-ene to give a new series of substituted pyrrolo[1,2-b]-.s-triazoles (II-IX). In most reactions, two or more products were formed. The following compounds have been prepared from I: 9-methylene-4a,5,6,7,8a,9-hexahydropyrano[2,3 :4,5]pyrrolo[1,2-b]-s-triazole (Ha), the corresponding 9-cyanomethyl product (III), and 9-methylene-4a,7,8,8a-tetrahydro-6H,9H-pyrano[3′,2′:4,5]pyrrolo[1,2-b]-s-triazole (IIb) from dihydropyran; 9-methylene-4a,6,7,8a-tetrahydro-9H-p-dioxino[2′,3′:4,5]-pyrrolo[1,2-6]-s-triazole (IV) from 2,3-dihydro-p-dioxin; 8-methylene-4a,5,7a,8-tetrahydro-7H-furo[3′,4′:4,5]pyrrolo[1,2-b]-s-triazole (V) and the corresponding 8-cyanomethyl product (VI) from 2,5-dihydrofuran; 8-cyanomethyl-5,7-dimethoxy-4a,5,7a,8-tetrahydro-7H-furo[3′,4′:4,5]-pyrrolo[1,2-6]-s-lriazole (VII) from 2,5-dimethoxy-2,5-dihydrofuran; and 10-methylene-4a,5,9a,10-tetrahydro-9H-[1,3]dioxepino[5′,6′:4,5]pyrrolo[1,2-b]-s-triazole (VIII) and the corresponding 10-cyanomethyl product (IX) from 1,3-dioxep-5-ene. The addition of several other compounds (1,2,3,6-tetrahydropyridine, 1-acetylimidazole, 3-sulfolene, 2,3-dihydro-p-dithiin, and vinylene carbonate) was attempted, but no reactions were observed. 相似文献
69.
Biomechanical simulation of human locomotion is commonly done via dynamical simulations of multibody systems. The actuation of the system is thereby often represented via muscle models that create a force depending on muscle length and activation level. We show a comparison of such a simulation using a structure preserving integration framework to MATLAB/Simulink results. The conclusion is that structure preservation is important to represent such systems correctly, in particular concerning energy and angular momentum evolutions. We introduce a method for structure preserving simulation of muscle actuated movements. Additionally we show examples of a simple arm movement including only one muscle as well as a finger movement including up to six muscles as an example for more complex biomechanical systems. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
70.
Sierocki P Maas H Dragut P Richardt G Vögtle F Cola LD Brouwer FA Zink JI 《The journal of physical chemistry. B》2006,110(48):24390-24398
A series of derivatized azobenzene molecules are synthesized such that one of the phenyl groups can be chemically bonded to mesostructured silica and the other, derivatized with dendrons, is free to undergo large-amplitude light-driven motion. The silica frameworks on which the motion takes place are either 150 nm thick films containing ordered hexagonal arrays of tubes (inner diameter about 2 nm) containing the bonded azobenzenes, or particles (about 500 nm in diameter) containing the same ordered arrays of functionalized tubes. The photoisomerization yields and the rate constants for the thermal cis to trans back-reaction of the azobenzenes in the tubes are measured and compared to those of the molecules in solution. The rate constants decrease with increasing size of the dendrons. Fluorescence spectra of the cis and trans isomers in the pores show that the photoisomerization in the nanostructured materials is selectively driven by specific wavelengths of light and is reversible. 相似文献