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31.
P. Staszczuk M. Błachnio E. Kowalska D. Sternik 《Journal of Thermal Analysis and Calorimetry》2006,86(1):51-56
Calculations based on the fractal geometry in the estimation of surface
heterogeneity are superior compared with conventional calculation methods
(e.g. from the data of gas adsorption or X-ray radiation scattering) as they
can be applied without limitation as far as the range of surface sizes of
the studied structures is concerned. This paper presents structural characteristics
of carbon and carbon- free nanomaterials based on the determined surface and
volumetric fractal coefficients. Fractal coefficients were determined from
the data obtained by means of two independent methods: sorptometry and atomic
force microscopy (AFM). Correlation between porosity parameters and fractal
coefficients is presented. 相似文献
32.
The Na[Cr(PDA)2] · 2H2O complex (PDA1 = dipicolinic acid anion) and its aquation product, [Cr(PDA)(H2O)3]+, were prepared and characterized. The electronic spectra demonstrate that the bis(dipicolinato) complex undergoes very fast partial dechelation during dissolution. In acidic media, pH controlled, rapid protolytic and ring opening processes lead to coexistence of complexes with one tridentate (PDA) and the other bi- or mono-dentate (PDA). The kinetics of PDA ligand liberation were followed spectrophotometrically within the 0.1–2.0 M HClO4 range at I = 2.0 M. The observed first-order rate constant depends on [H+] according to the equation: k
obs = A[H+]/(1 + B[H+] + C[H+]2). A reaction course via the uncharged [Cr(PDA)(HPDA)(H2O)2]0 complex is proposed. The observed rate increase, followed by rate retardation with [H+] increase, is attributed to the unreactive [Cr(PDA)(H2PDA)(H2O)2]+ complex. In terms of the proposed mechanism, A, B, C parameters have been defined as: A = k
1
Q
1, B = Q
1, C = Q
1
Q
2 where k
1 is the rate constant of the CrIII-carboxylato oxygen bond-breaking in the monodentate HPDA ligand, Q
1 is a composite value describing protolytic and dechelation processes and Q
2 is the protonation constant of the uncharged [Cr(PDA)(HPDA)(H2O)2]0 complex. 相似文献
33.
Krzysztof Ejsmont Magorzata Broda Andrzej Domaski Janusz B. Kyzio Jacek Zaleski 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(9):o545-o548
The two isomeric compounds 4‐amino‐ONN‐azoxybenzene [or 1‐(4‐aminophenyl)‐2‐phenyldiazene 2‐oxide], i.e. the α isomer, and 4‐amino‐NNO‐azoxybenzene [or 2‐(4‐aminophenyl)‐1‐phenyldiazene 2‐oxide], i.e. the β isomer, both C12H11N3O, crystallized from a polar solvent in orthorhombic space groups, and their crystal and molecular structures have been determined using X‐ray diffraction. There are no significant differences in the bond lengths and valence angles in the two isomers, in comparison with their monoclinic polymorphs. However, the conformations of the molecules are different due to rotation along the Ar—N bonds. In the α isomer, the benzene rings are twisted by 31.5 (2) and 14.4 (2)° towards the plane of the azoxy group; the torsion angles along the Ar—N bond in the β isomer are 24.3 (3) and 23.5 (3)°. Quantum‐mechanical calculations indicate that planar conformations are energetically favourable for both isomers. The N—H?O hydrogen bonds observed in both networks may be responsible for the deformation of these flexible molecules. 相似文献
34.
Małgorzata Pazderska-Szabłowicz Agnieszka Białkowska Ewa Kita 《Transition Metal Chemistry》2006,31(3):413-420
New chromium(III) complexes, [Cr(C2O4)2(2-hnic)]2− and [Cr(C2O4)2(3-hpic)]2− (where 2-hnic = O,O′-bonded 2-hydroxynicotinic acid and 3-hpic = N,O-bonded 3-hydroxypicolinic acid), were obtained and characterized
in solution. The acid-catalyzed aquation of the both complexes leads to liberation of the appropriate pyridinecarboxylic acid
and formation of cis-[Cr(C2O4)2(H2O)2]−. Kinetics of these reactions were studied spectrophotometrically in the 0.1–1.0 M HClO4 range, at I = 1.0 M. In the case of [Cr(C2O4)2(2-hnic)]2−, a slow chelate-ring opening at the Cr–O (phenolate) bond is followed by a fast Cr–O (carboxylate) bond breaking. The rate
law: kobs = kHQH[H+] was established, where kH is the acid-catalyzed rate constant and QH is the protonation constant of the coordinated phenolate oxygen atom. In the case of [Cr(C2O4)2(3-hpic)]2−, the reversible chelate-ring opening at Cr–N bond is followed by the rate determining step – the one-end bonded ligand liberation.
The rate law for the first step was determined: kobs = k1+k−1/Q1[H+], where k1 and k−1 are the rate constants of the chelate-ring opening and closure and Q1 is the protonation constant of the pyridine nitrogen atom. The aquation mechanisms are proposed and the effect of ligand
coordination mode on complex reactivity is discussed. 相似文献
35.
(Me2NH2)[(Ph3Sn)3(MoO4)2], a Triorganotin Molybdate with Layer Structure The reaction of [(Ph3Sn)2MoO4] with (Me2NH2)Cl in an acetonitrile/water mixture leads to the formation of (Me2NH2)[(Ph3Sn)3(MoO4)2] ( 1 ). ( 1 ) crystallizes in the space group Pca21 with a = 1967.0(4), b = 1353.1(2) and c = 2176.6(5) pm. In the crystal structure of 1 Ph3SnO2 bipyramides and MoO4 tetrahedra are linked by corner sharing to give a layer structure. Additionally the layers are connected by O···H···N hydrogen bridges between MoO4 groups and [Me2NH2]+ ions to give a 3D network structure. 相似文献
36.
37.
38.
Radosław Bonikowski Józef Kula Anna Bujacz Anna Wajs-Bonikowska Małgorzata Zakłos-Szyda Stanisław Wysocki 《Tetrahedron: Asymmetry》2012,23(14):1038-1045
Ten enantiomerically pure hydroindene-derived compounds obtained by the transformation of (+)-carotol, the main constituent of carrot seed essential oil, were examined for their ability to inhibit the growth of myeloid leukaemia (HL-60) cancer cell lines. All compounds showed significant activity, which was comparable to the most active volatile organic compounds, such as trans–trans-farnesol, citral and nerolidol. Based on the bioactivity and molecular modelling, a 3D QSAR pharmacophore model was generated. 相似文献
39.
Dr. Anaïs Depaix Agnieszka Mlynarska-Cieslak Dr. Marcin Warminski Dr. Pawel J. Sikorski Prof. Dr. Jacek Jemielity Dr. Joanna Kowalska 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(47):12190-12197
Labeled RNAs are invaluable probes for investigation of RNA function and localization. However, mRNA labeling remains challenging. Here, we developed an improved method for 3′-end labeling of in vitro transcribed RNAs. We synthesized novel adenosine 3′,5′-bisphosphate analogues modified at the N6 or C2 position of adenosine with an azide-containing linker, fluorescent label, or biotin and assessed these constructs as substrates for RNA labeling directly by T4 ligase or via postenzymatic strain-promoted alkyne-azide cycloaddition (SPAAC). All analogues were substrates for T4 RNA ligase. Analogues containing bulky fluorescent labels or biotin showed better overall labeling yields than postenzymatic SPAAC. We successfully labeled uncapped RNAs, NAD-capped RNAs, and 5′-fluorescently labeled m7Gp3Am-capped mRNAs. The obtained highly homogenous dually labeled mRNA was translationally active and enabled fluorescence-based monitoring of decapping. This method will facilitate the use of various functionalized mRNA-based probes. 相似文献