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71.
[reaction: see text] On the basis of KIE experiments, the ring opening of cis-bicyclo[4.2.0.]oct-7-ene has been suggested as an anti-Woodward-Hoffmann reaction candidate. We hereby report the results of a high-level computational study of the alternate reaction pathways which proves that the energy profiles show a clear preference for the conrotatory (W-H allowed) ring opening followed by double-bond isomerization. Computed KIE values for the aforementioned mechanism are in good agreement with the experimental values. 相似文献
72.
Capillary Electrophoresis (CE) is becoming an ever more powerful analytical technique for the separation, identification, and quantification of a wide variety of compounds of interest in many application fields. Particularly in food analysis this technique can offer interesting advantages over chromatographic techniques because of its greater simplicity and efficiency. Nevertheless, CE needs to advance with regard to compatibility with sample matrices, sensitivity, and robustness of the methodologies in order to gain even wider acceptance in food analysis laboratories, specially for routine work. This article presents various approaches to expanding the analytical usefulness of CE in food analysis, discussing their advantages over conventional CE. These approaches focus on sample screening, automated sample preparation with on-line CE arrangements, and the automatic integration of calibration in routine analytical work with CE. 相似文献
73.
We apply time-dependent density functional theory to study the valence electron excitations of molecules and generalize the typically used time-propagation scheme and Casida's method to calculate the full wavevector dependent response function. This allows the computational study of dipole-forbidden valence electron transitions and the dispersion of spectral weight as a function of the wavevector. The method provides a novel analysis tool for spectroscopic methods such as inelastic x-ray scattering and electron energy loss spectroscopy. We present results for benzene and CF(3)Cl and make a comparison with experimental results. 相似文献
74.
Netto-Ferreira JC Lhiaubet-Vallet V de Oliveira Bernardes B Ferreira AB Miranda MA 《Photochemistry and photobiology》2009,85(1):153-159
The photochemical reactivity of β-lapachone ( 1 ), nor -β-lapachone ( 2 ) and 1,2-naphthoquinone ( 3 ) towards amino acids and nucleobases or nucleosides has been examined employing the nanosecond laser flash photolysis technique. Excitation (λ = 355 nm) of degassed solutions of 1 – 3 , in acetonitrile, resulted in the formation of their corresponding triplet excited states. These transients were efficiently quenched by l -tryptophan, l -tryptophan methyl ester, l -tyrosine, l -tyrosine methyl ester and l -cysteine ( k q ≈ 109 L mol−1 s−1 ). For l -tryptophan, l -tyrosine and their methyl esters new transients were formed in the quenching process, which were assigned to the corresponding radical pair resulting from an initial electron transfer from the amino acids or their esters to the excited quinone, followed by a fast proton transfer. No measurable quenching rate constants could be observed in the presence of thymine and thymidine. On the other hand, efficient rate constants were obtained when 1 – 3 were quenched by 2'-deoxyguanosine ( k q ≈ 109 L mol−1 s−1 ). The quantum efficiency of singlet oxygen (1 O2 ) formation from 1 to 3 was determined employing time-resolved near-IR emission studies upon laser excitation and showed considerably high values in all cases (ΦΔ = 0.6), which are fully in accord with the ππ* character of these triplets in acetonitrile. 相似文献
75.
San Miguel V Alvarez M Filevich O Etchenique R del Campo A 《Langmuir : the ACS journal of surfaces and colloids》2012,28(2):1217-1221
Photoreactive surfaces derived from a new photocleavable surface modification agent and with photosensitivity in the Vis and IR region are described. A ruthenium(II) caged aminosilane, [Ru(bpy)(2)(PMe(3))(APTS)](PF(6))(2), was synthesized and attached to silica surfaces. Light irradiation removed the cage and generated surface patterns with reactive amine groups. The photosensitivity of this compound under single (460 nm) and two-photon (900) excitation is demonstrated. Functional patterns with site-selective attachment of other molecular species are described. 相似文献
76.
Giuseppe Mele Roberta del Sole Giuseppe Vasapollo Elisa García-López Leonardo Palmisano Li Jun Rudolf Słota Gabriela Dyrda 《Research on Chemical Intermediates》2007,33(3-5):433-448
Photodegradation of organic compounds in water solutions by means of economically advantageous and environment-friendly processes is a topic of growing interest. In recent years a great attention has been devoted to TiO2-based photocatalysts for the oxidative degradation of various organic pollutants. In this context, we have prepared new photo-catalytic polycrystalline TiO2 systems impregnated with sensitizers, i.e., copper, iron or manganese porphyrins, and investigated their photoactivity for 4-nitrophenol oxidation compared with that of bare TiO2. A significant improvement of the photoreactivity was observed in the case of TiO2 impregnated with copper porphyrin, while only a slight beneficial effect was observed in the case of iron porphyrin. In contrast, the presence of manganese porphyrin appeared to be detrimental. 相似文献
77.
Salt effects on the apparent stability of the cucurbit[7]uril-methyl viologen inclusion complex 总被引:1,自引:0,他引:1
The effects of the medium ionic composition on the apparent equilibrium association constant (K) for the formation of a 1:1 inclusion complex between the guest methyl viologen (MV(2+)) and the host cucurbit[7]uril (CB7) were studied in aqueous solutions. The K values were found to decrease with increasing ionic strength, with more pronounced effects for solutions containing divalent Ca(2+) ions than for solutions containing monovalent Na(+) ions. The competing ion-dipole interactions between Ca(2+) or Na(+) and MV(2+) ions appear to be responsible for the remarkable modulation of the K values observed in this work. 相似文献
78.
Calvo del Castillo H Ruvalcaba JL Calderón T 《Analytical and bioanalytical chemistry》2007,387(3):869-878
Ionoluminescence (IL) has mainly been used to detect impurities or defects inside synthetic materials. This paper gives a
summary of new applications of IL to natural minerals that might be found in ancient pieces of jewellery or decorative artefacts
(affreschi, stucchi, mosaics). Some relevant examples of its use for archaeometrical purposes are given to highlight the potential
of the technique. Chemical information can be obtained by luminescent characterization of minerals. IL spectra act as digital
imprint for elements or defects inside each material, enabling differentiation of natural specimens from imitations and/or
synthetic analogues. Crystal field theory indicates it is the coordination number of the emitter inside the crystalline structure
that gives information on its valence. Historical confusion between rubies and red spinel can easily be resolved by analysis
of IL spectra. Modern synthetic diamonds can also be discriminated and blue sapphire can be distinguished from blue kyanite,
a silicate that is currently being sold as its imitation. The technique can also differentiate between the synthetic and the
natural gems. Polymorphs can be identified, and it is possible to recognize minerals from isomorphic series (from the same
chemical group with the same structure) even when they share the same light emitter (e.g. Mn2+, in carbonates). High-quality glasses (e.g. laser glasses) which are normally used for faking gemstones can be also detected.
We fully believe IL will, in the future, be a powerful technique for determining the crystallinity of solids. This paper gives
an overview of possible applications of IL to archaeometry for mineral characterization; this is a new application that still
requires further study. 相似文献
79.
Benito Alcaide Prof. Dr. Pedro Almendros Dr. Rocío Carrascosa Dipl.‐Chem. Teresa Martínez del Campo Dipl.‐Chem. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(11):2496-2499
Positive discrimination : Chemo‐ and regioselective palladium‐catalyzed cycloetherification of allendiols, namely β,γ‐ and γ,δ‐allendiols, may occur by judicious choice of palladium‐catalyzed conditions owing to their potential ability to discriminate between both nucleophilic sites (see scheme).
80.
Alajarin M Bonillo B Ortin MM Orenes RA Vidal A 《Organic & biomolecular chemistry》2011,9(19):6741-6749
N-(2-azidomethyl)phenyl ketenimines and N-(2-azidomethyl)phenyl-N'-alkyl(aryl) carbodiimides undergo, under mild thermal conditions, intramolecular [3 + 2] cycloaddition reactions between the azido group and either the C=C or the distal C=N double bonds of the ketenimine and carbodiimide functions respectively. The reaction products are indolo[1,2-a]quinazolines and/or indolo[2,1-b]quinazolines in the case of azido-ketenimines, and tetrazolo[5,1-b]quinazolines in the case of azido-carbodiimides. The formation of the two classes of indoloquinazolines implies the ulterior dinitrogen extrusion from the non-isolated, putative [3 + 2] cycloadducts between the azide and ketenimine functions, whereas in the case of azido-carbodiimides the initial cycloadducts, tetrazoloquinazolines, were cleanly isolated and further converted into 2-aminoquinazolines by thermally induced dinitrogen extrusion. 相似文献