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51.
A series of tetracyanoborate salts M[B(CN)4] with the singly charged cations of Li+, Na+, Rb+, Cs+, [NH4]+, Tl+, and Cu+ as well as the THF solvate tetracyanoborates Na[B(CN)4] x THF and [NH4][B(CN)4] x THF were synthesized and their X-ray structures, vibrational spectra, solubilities in water, and thermal stabilities determined and compared with already known M[B(CN)4] salts. Crystallographic data for these compounds are as follows: Na[B(CN)4], cubic, Fd3m, a = 11.680(1) A, Z= 8; Li[B(CN)4], cubic, P43m, a = 5.4815(1) A, Z= 1; Cu[B(CN)4], cubic, P43m, a = 5.4314(7) A, Z= 1; Rb[B(CN)4], tetragonal, /4(1)/a, a = 7.1354(2) A, c= 14.8197(6) A, Z= 4; Cs[B(CN)4], tetragonal, /4(1)/a, a = 7.300(2) A, c = 15.340(5) A, Z= 4; [NH4][B(CN)4], tetragonal, /4(1)/a, a = 7.132(1) A, c = 14.745(4) A, Z= 4; Tl[B(CN)4], tetragonal, /4(1)/a, a = 7.0655(2) A, c = 14.6791(4) A, Z= 4; Na[B(CN)4] x THF, orthorhombic, Pnma, a = 13.908(3) A, b = 9.288(1) A, c = 8.738(1) A, Z= 4; [NH4][B(CN)4] x THF, orthorhombic, Pnma, a = 8.831(1) A, b = 9.366(2) A, c = 15.061(3) A, Z= 4. The cubic Li+, Na+, and Cu+ salts crystallize in a structure consisting of two interpenetrating independent tetrahedral networks of M cations and [B(CN)4]- ions. The compounds with the larger countercations (Rb+, Cs+, Tl+, and [NH4]+) crystallize as tetragonal, also with a network arrangement. The sodium and ammonium salts with the cocrystallized THF molecules are both orthorhombic but are not isostructural. In the vibrational spectra the two CN stretching modes A1 and T2 coincide in general and the band positions are a measure for the strength of the interionic interaction. An interesting feature in the Raman spectrum of the copper salt is the first appearance of two CN stretching modes. 相似文献
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Dr. Mostakim SK Dr. Soumitra Barman Shounik Paul Ratnadip De Dr. S. S. Sreejith Dr. Helge Reinsch Dr. Maciej Grzywa Dr. Norbert Stock Prof. Dr. Dirk Volkmer Dr. Shyam Biswas Prof. Dr. Soumyajit Roy 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(12):4098-4107
A Zr-based metal-organic framework has been synthesized and employed as a catalyst for photochemical carbon dioxide reduction coupled with water oxidation. The catalyst shows significant carbon dioxide reduction property with concomitant water oxidation. The catalyst has broad visible light as well as UV light absorption property, which is further confirmed from electronic absorption spectroscopy. Formic acid was the only reduced product from carbon dioxide with a turn-over frequency (TOF) of 0.69 h−1 in addition to oxygen, which was produced with a TOF of 0.54 h−1. No external photosensitizer is used and the ligand itself acts as the light harvester. The efficient and selective photochemical carbon dioxide reduction to formic acid with concomitant water oxidation using Zr-based MOF as catalyst is thus demonstrated here. 相似文献
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Short-lived (CF(3))(3)B and (CF(3))(3)BCF(2) are generated as intermediates by thermal dissociation of (CF(3))(3)BCO and F(-) abstraction from the weak coordinating anion [B(CF(3))(4)](-), respectively. Both Lewis acids cannot be detected because of their instability with respect to rearrangement reactions at the B-C-F moiety. A cascade of 1,2-fluorine shifts to boron followed by perfluoroalkyl group migrations and also difluorocarbene transfer reactions occur. In the gas phase, (CF(3))(3)B rearranges to a mixture of linear perfluoroalkyldifluoroboranes C(n)()F(2)(n)()(+1)BF(2) (n = 2-7), while the respective reactions of (CF(3))(3)BCF(2) result in a mixture of linear (n = 2-4) and branched monoperfluoroalkyldifluoroboranes, e.g., (C(2)F(5))(CF(3))FCBF(2). For comparison, the reactions of [CF(3)BF(3)](-) and [C(2)F(5)BF(3)](-) with AsF(5) are studied, and the products in the case of [CF(3)BF(3)](-) are BF(3) and C(2)F(5)BF(2) whereas in the case of [C(2)F(5)BF(3)](-), C(2)F(5)BF(2) is the sole product. In contrast to reports in the literature, it is found that CF(3)BF(2) is too unstable at room temperature to be detected. The decomposition of (CF(3))(3)BCO in anhydrous HF leads to a mixture of the new conjugate Br?nsted-Lewis acids [H(2)F][(CF(3))(3)BF] and [H(2)F][C(2)F(5)BF(3)]. All reactions are modeled by density functional calculations. The energy barriers of the transition states are low in agreement with the experimental results that (CF(3))(3)B and (CF(3))(3)BCF(2) are short-lived intermediates. Since CF(2) complexes are key intermediates in the rearrangement reactions of (CF(3))(3)B and (CF(3))(3)BCF(2), CF(2) affinities of some perfluoroalkylfluoroboranes are presented. CF(2) affinities are compared to CO and F(-) affinities of selected boranes showing a trend in Lewis acidity, and its influence on the stability of the complexes is discussed. Fluoride ion affinities are calculated for a variety of different fluoroboranes, including perfluorocarboranes, and compared to those of the title compounds. 相似文献
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Sarifuddin Santabrata Chakravarty Prashanta Kumar Mandal Helge I. Andersson 《Zeitschrift für Angewandte Mathematik und Physik (ZAMP)》2009,56(Z2):299-323
The present investigation deals with a mathematical model representing the mass transfer to blood streaming through the arteries
under stenotic condition. The mass transport refers to the movement of atherogenic molecules, that is, blood-borne components,
such as oxygen and low-density lipoproteins from flowing blood into the arterial walls or vice versa. The blood flowing through
the artery is treated to be Newtonian and the arterial wall is considered to be rigid having differently shaped stenoses in
its lumen arising from various types of abnormal growth or plaque formation. The nonlinear unsteady pulsatile flow phenomenon
unaffected by concentration-field of the macromolecules is governed by the Navier–Stokes equations together with the equation
of continuity while that of mass transfer is controlled by the convection-diffusion equation. The governing equations of motion
accompanied by appropriate choice of the boundary conditions are solved numerically by MAC(Marker and Cell) method and checked
numerical stability with desired degree of accuracy. The quantitative analysis carried out finally includes the respective
profiles of the flow-field and concentration along with their distributions over the entire arterial segment as well. The
key factors like the wall shear stress and Sherwood number are also examined for further qualitative insight into the flow
and mass transport phenomena through arterial stenosis. The present results show quite consistency with several existing results
in the literature which substantiate sufficiently to validate the applicability of the model under consideration. 相似文献
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Helmut Beckers Dr. Xiaoqing Zeng Dr. Helge Willner Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(5):1506-1520
Pure sym‐N2O4 isolated in solid Ne was obtained by passing cold neon gas over solid N2O4 at ?115 °C and quenching the resulting gaseous mixture at 6.3 K. Filtered UV irradiation (260–400 nm) converts sym‐N2O4 into trans‐ONONO2, a weakly interacting (NO2)2 radical pair, and traces of the cis‐N2O2?O2 complex. Besides the weakly bound ON?O2 complex, cis‐N2O2?O2 was also obtained by co‐deposition of NO and O2 in solid Ne at 6.3 K, and both complexes were characterised by their matrix IR spectra. Concomitantly formed cis‐N2O2 dissociated on exposure to filtered IR irradiation (400–8000 cm?1), and the cis‐N2O2?O2 complex rearranged to sym‐N2O4 and trans‐ONONO2. Experiments using 18O2 in place of 16O2 revealed a non‐concerted conversion of cis‐N2O2?O2 into these species, and gave access to four selectively di‐18O‐substituted trans‐ONONO2 isotopomers. No isotopic scrambling occurred. The IR spectra of sym‐N2O4 and of trans‐ONONO2 in solid Ne were recorded. IR fundamentals of trans‐ONONO2 were assigned based on experimental 16/18O isotopic shifts and guided by DFT calculations. Previously reported contradictory measurements on cis‐ and trans‐ONONO2 are discussed. Dinitroso peroxide, ONOONO, a proposed intermediate in the IR photoinduced rearrangement of cis‐N2O2?O2 to the various N2O4 species, was not detected. Its absence in the photolysis products indicates a low barrier (≤10 kJ mol?1) for its exothermic O? O bond homolysis into a (NO2)2 radical pair. 相似文献