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411.
Frøseth M Netland KA Törnroos KW Dhindsa A Tilset M 《Dalton transactions (Cambridge, England : 2003)》2005,(9):1664-1674
The imidazolium salts [3-R1-1-{2-Ar-imino)-2-R2-ethyl}imidazolium] chloride (C-N; Ar = 2,6-iPr2C6H3; R1/R2 = Me/Me (a), Me/Ph (b), Ph/Me (c), 2,4,6-Me3C6H2 (d), 2,6-iPr2C6H3 (e)) react with Ag(2)O to give Ag(I) iminocarbene complexes (C-N)AgCl (4a-e) in which the iminocarbene ligand is bonded to Ag via the imidazoline-2-ylidene carbon atom. The solid-state structures of 4b and 4d were determined by X-ray crystallography and revealed the presence of monomeric (carbene)AgCl units with Z and E configurations at the imine C=N bonds, respectively. Carbene transfer to Pd occurs when compounds 4b-e are treated with (COD)PdCl2 to yield bis(carbene) complexes (C-N)2PdCl2 (6b-e) containing two kappa1-C bonded iminocarbene moieties. NMR spectroscopic data indicated a trans coordination geometry at Pd. This conclusion was supported by an X-ray structure determination of 6b which clearly demonstrated the non-chelating nature of the iminocarbene ligand system. EXSY 1H NMR spectroscopy suggests that the non-chelating structures undergo E/Z isomerization at the imine C[double bond, length as m-dash]N double bonds in solution. The preparative results contrast our earlier report that the reaction between 4a and (COD)PdCl2 results in a chelating kappa2-C,N bonded iminocarbene complex (C-N)PdCl2. The coordination mode and dynamic behavior of the iminocarbene ligand systems have been found to be dramatically affected by changes in the substitution pattern of the ligand system. Sterically unencumbered systems (a) favor the formation of kappa2-C,N chelate structures containing one iminocarbene moiety per metal upon coordination at Pd(II); these complexes were demonstrated to engage in reversible, solvent-mediated chelate ring-opening reactions. Sterically encumbered systems (b-e) form non-chelating kappa1-C iminocarbene Pd(II) complexes containing two iminocarbene ligands per metal. Transannular repulsions across the chelate ring are believed to be the origin of these structural differences. 相似文献
412.
Mats Berglund Carlaxel Andersson Ragnar Larsson 《Journal of organometallic chemistry》1985,292(3):c15-c17
WCl6 has been used as a catalyst for the metathesis of various alkenylsilanes and the degree of conversion found to be dependent on the distance between the olefinic bond and the silyl group. The first observation of metathetical conversion of allyltrimethylsilane in the absence of a co-catalyst is reported 相似文献
413.
Mats Johnsson Helmuth Berger Richard Becker 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(8):i67-i69
Single crystals of tricobalt(II) tellurium(VI) hexaoxide, Co3TeO6, were synthesized via transport reactions using HCl as transporting agent. The compound crystallizes in the monoclinic system (space group C2/c). The Te atoms are positioned in 4b () and 8f positions, while the Co atoms are in 4e (2) and 8f positions. The structure consists of (100) oxygen layers packed in a hhchhc sequence, with TeVI in octahedral coordination and CoII in both octahedral and tetrahedral coordination. The structure contains face‐sharing CoO6 octahedra, as well as edge‐sharing CoO4 tetrahedra. Co3TeO6 is the first oxide that is isostructural with the β‐Li3MF6 family of compounds (M = Al, Cr, Ga, Ti and V). 相似文献
414.
P. Wagner Naumann Kellner Böttcher Max Popp R. Michel F. Westhausser F. Mach A. Bömer R. Kunze W. Simmermacher L. Wuyts Mats Weibull W. Fuchs H. Neubauer F. Haussding W. Holle Celichowski Ferd Pilz Zachariades Czak D. Crispo R. W. Tuinzing Loges V. Schenke Z. Chmielewski Z. Romański Patten Marti Hugo Ditz S. Kohn W. Möller L. Schucht Aumann J. M. Kolthoff C. A. Peters E. Guerry E. Toussaint Hermann Kaserer Ignaz K. Greisenegger A. Stutzer W. Haupt C. E. Millar F. A. Gangler Schreiner Brown Veitch F. Zöhren 《Analytical and bioanalytical chemistry》1916,55(8):404-414
415.
416.
Zhaunerchyk V Ehlerding A Geppert WD Hellberg F Thomas RD Larsson M Viggiano AA Arnold ST Osterdahl F Hlavenka P 《The Journal of chemical physics》2004,121(21):10483-10488
The dissociative recombination of Na(+)(D(2)O) ion has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). The cross section has been measured as a function of center-of-mass energy ranging from 1 meV to 0.1 eV and found to have an E(-1.37) dependence. The rate coefficient has been deduced to be (2.3+/-0.32)x10(-7)(T(e)/300)(-0.95+/-0.01) cm(3) s(-1) for T(e)=50-1000 K. The branching ratios have been measured at 0 eV. Of the four energetically accessible dissociation channels, three channels are found to occur although the channel that breaks the weak Na(+)-D(2)O bond is by far dominant. 相似文献
417.
High prevalence of uterine occlusions and sterility is found among Baltic ringed and grey seal. Polychlorinated biphenyls (CBs) are suspected to be the main cause. The CB concentrations are higher in affected than in healthy animals, but the natural variation is considerable. Thus, it might be possible to assess the health status of seals by CB analysis. The ratios of chiral compounds (enantiomeric fractions (EFs)) such as atropisomeric CBs are of particularinterest, since these may reflect differences in metabolic rates. An analytical procedure was developed and used to determine the levels of atropisomeric CBs, planar-CBs (WHO-PCBs) and total CBs in seals of different health status. Comprehensive 2D gas chromatography (GC x GC) was used to separate the target analytes from other CBs and interferences and a micro electron-capture detector (microECD) was used for detection. EFs of the atropisomeric CBs were difficult to determine as the levels were low and the interferences many. Two column combinations bad to be used to avoid biased results-both had a chiral column as first-dimension column. The second-dimension column was coated with either a high-polarity cyanopropyl or a liquid crystal phase. EFs were determined for five atropisomeric CBs, i.e. CBs 91,95, 132, 149 and 174. The results were verified by GC x GC-time-of-flight mass spectrometry (TOF-MS). Some atropisomeric CBs had EFs that deviated strongly from the racemic-mixture value. The deviations were larger in liver than blubber, which indicates enantioselective metabolism. However, there was no selective passage of the studied atropisomeric CBs across placenta and no selective blood-brain barrier. Similarly, no correlation between EFs and health status was observed, although there was a correlation between the total CB levels and health status. 相似文献
418.
von Schenck H Akermark B Svensson M 《Journal of the American Chemical Society》2003,125(12):3503-3508
The migratory insertion of propene into the Pd-phenyl bond of a set of neutral palladium(II) complexes with N-N, P-O, and N-O chelating ligands has been investigated by using density functional methods. In contrast to cationic palladium(II)-diimine complexes, which favor 1,2-insertion, the more electron-rich neutral complexes lead to 2,1-insertion. Trans influences are substantial in the unsymmetrical ligand systems, primarily affecting the insertion barrier. Introducing steric effects leads toward improving 1,2-selectivity, due to destabilization of the 2,1-transition state. Electronic and steric influences can be systematically combined to control the regiochemistry in the Heck reaction. 相似文献
419.
A potentiometric enzyme electrode is described for monitoring reactions in organic solvents. By use of an enzyme deposited on magnetic particles which are attracted to the tip of the electrode by means of a magnetic field, it is possible to produce an electrode in which the enzyme can easily be exchanged. As an example, studies of the chymotrypsin-catalyzed ester synthesis in diisopropyl ether and in toluene at varying water contents are reported. The results are consistent with those obtained from batch experiments. Operational behaviour and signal stability of the system makes this kind of potentiometric enzyme electrode attractive for monitoring bioorganic processes. 相似文献
420.
This article summarizes findings from our previous investigations and recent studies concerning precipitation in a maraging steel of type 13Cr-9Ni-2Mo-2Cu (at.%) with small additions of Ti (1 at.%) and Al (0.7 at.%). The material was investigated after aging at 475 degrees C up to 400 h using both conventional and three-dimensional atom-probe analyses. The process of phase decomposition in the steel proved to be complicated. It consisted of precipitation of several phases with different chemistry. A Cu-rich phase was first to precipitate and Mo was last in the precipitation sequence. The influence of the complex precipitation path on the material properties is discussed. The investigation clearly demonstrated the usefulness of the applied techniques for investigation of nanoscale precipitation. It is also shown that, complementary methods (such as TEM and EFTEM) giving structural and chemical information on a larger scale must be applied to explain the good properties of the steel after prolonged aging. 相似文献