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11.
The total syntheses of the ladybug alkaloids (±)-propyleine and (±)-isopropyleine are described. Evidence that the alkaloid propyleine is actually a rapidly interconverting mixture of propyleine and a previously unknown isomer isopropyleine is presented. 相似文献
12.
Okamura WH Zhu GD Hill DK Thomas RJ Ringe K Borchardt DB Norman AW Mueller LJ 《The Journal of organic chemistry》2002,67(5):1637-1650
Isotope-labeled drug molecules may be useful for probing by NMR spectroscopy the conformation of ligand associated with biological hosts such as membranes and proteins. Triple-labeled [7,9,19-(13)C(3)]-vitamin D(3) (56), its 25-hydroxylated and 1 alpha,25-dihydroxylated metabolites (58 and 68, respectively), and other labeled materials have been synthesized via coupling of [9-(13)C]-Grundmann's ketone 39 or its protected 25-hydroxy derivative 43 with labeled A ring enyne fragments 25 or 26. The labeled CD-ring fragment 39 was prepared by a sequence involving Grignard addition of [(13)C]-methylmagnesium iodide to Grundmann's enone 28, oxidative cleavage, functional group modifications leading to seco-iodide 38, and finally a kinetic enolate S(N)2 cycloalkylation. The C-7,19 double labeling of the A-ring enyne was achieved by the Corey-Fuchs/Wittig processes on keto aldehyde 11. By employing these labeled fragments in the Wilson-Mazur route, the C-7,9,19 triple-(13)C-labeled metabolites 56, 58, and 68 as well as other (13)C-labeled metabolites have been prepared. In an initial NMR investigation of one of the labeled metabolites prepared in this study, namely [7,9,19-(13)C(3)]-25-hydroxyvitamin D(3) (58), the three (13)C-labeled carbons of the otherwise water insoluble steroid could be clearly detected by (13)C NMR analysis at 0.1 mM in a mixture of CD(3)OD/D(2)O (60/40) or in aqueous dimethylcyclodextrin solution and at 2 mM in 20 mM sodium dodecyl sulfate (SDS) aqueous micellar solution. In the SDS micellar solution, a double half-filter NOESY experiment revealed that the distance between the H(19Z) and H(7) protons is significantly shorter than that of the corresponding distance calculated from the solid state (X-ray) structure of the free ligand. The NMR data in micelles reveals that 58 exists essentially completely in the alpha-conformer with the 3 beta-hydroxyl equatorially oriented, just as in the solid state. The shortened distance (H(19Z))-H(7)) in micellar solutions as compared to that in the solid state is most easily rationalized on the basis that the 5(10)-torsion angle in 58 is decreased in micellar solutions as compared to that in the solid state. 相似文献
13.
Mueller JA Cowell A Chandler BD Sigman MS 《Journal of the American Chemical Society》2005,127(42):14817-14824
A kinetic investigation into the origin of enantioselectivity for the Pd[(-)-sparteine]Cl(2)-catalyzed aerobic oxidative kinetic resolution (OKR) is reported. A mechanism to account for a newly discovered chloride dissociation from Pd[(-)-sparteine]Cl(2) prior to alcohol binding is proposed. The mechanism includes (1) chloride dissociation from Pd[(-)-sparteine]Cl(2) to form cationic Pd(-)-sparteine]Cl, (2) alcohol binding, (3) deprotonation of Pd-bound alcohol to form a Pd-alkoxide, and (4) beta-hydride elimination of Pd-alkoxide to form ketone product and a Pd-hydride. Utilizing the addition of (-)-sparteine HCl to control the [Cl(-)] and [H(+)] and the resulting derived rate law, the key microscopic kinetic and thermodynamic constants were extracted for each enantiomer of sec-phenethyl alcohol. These constants allow for the successful simulation of the oxidation rate in the presence of exogenous (-)-sparteine HCl. A rate law for oxidation of the racemic alcohol was derived that allows for the successful prediction of the experimentally measured k(rel) values when using the extracted constants. Besides a factor of 10 difference between the relative rates of beta-hydride elimination for the enantiomers, the main enhancement in enantiodetermination results from a concentration effect of (-)-sparteine HCl and the relative rates of reprotonation of the diastereomeric Pd-alkoxides. 相似文献
14.
Taw FL Mueller AH Bergman RG Brookhart M 《Journal of the American Chemical Society》2003,125(32):9808-9813
Cationic Rh(III) complex [Cp(PMe(3))Rh(SiPh(3))(CH(2)Cl(2))]BAr(4)' (1) activates the carbon-carbon bond of aryl and alkyl cyanides (R-CN, where R = Ph, (4-(CF(3))C(6)H(4)), (4-(OMe)C(6)H(4)), Me, (i)Pr, (t)Bu) to produce complexes of the general formula [Cp*(PMe(3))Rh(R)(CNSiPh(3))]BAr(4)'. With the exception of the (t)BuCN case, every reaction proceeds at room temperature (t(1/2) < 1 h for aryl cyanides, t(1/2) < 14 h for alkyl cyanides). A general mechanism is presented on the basis of (1) an X-ray crystal structure determination of an intermediate isolated from the reaction involving 4-methoxybenzonitrile and (2) kinetic studies performed on the C-C bond cleavage of para-substituted aryl cyanides. Initial formation of an eta(1)-nitrile species is observed, followed by conversion to an eta(2)-iminoacyl intermediate, which was observed to undergo migration of R (aryl or alkyl) to rhodium to form the product [Cp*(PMe(3))Rh(R)(CNSiPh(3))]BAr(4)'. 相似文献
15.
Werner Bihlmaier Rolf Huisgen Hans-Ulrich Reissig Sabine Vass 《Tetrahedron letters》1979,20(28):2621-2624
Whereas diazomethane cycloadditions are only accelerated by electron-attracting substituents in the olefinic or acetylenic dipolarophile, the cycloadditions of diazoacetic, diazomalonic and diazo(phenylsulfonyl)acetic ester show in accordance with the PMO treatment U-shaped activity functions when log k2 is plotted versus the lowest IP of the dipolarophiles. 相似文献
16.
17.
Noise radiation from a four bladed, 10 in. diameter propeller operating in air at a rotational speed of 3000 RPM and a freestream velocity of 33 ft/s was experimentally analyzed using hot-wire and microphone measurements in an anechoic wind tunnel. Turbulence levels from 0.2 to 5.5% at the propeller location were generated by square-mesh grids upstream of the propeller. Autobicoherence measurements behind the blade trailing edges near the hub and tip showed regions of high phase-coherence between the blade-passage harmonics and the broadband frequencies. Inflow turbulence reduced this coherence. By relating the fluctuation velocities in the propeller wake to the unsteady blade forces, the primary regions of tonal noise generation have been identified as the hub and tip regions, while the midspan has been identified as a region responsible for broadband noise generation. These measurements were complimented by cross-spectra between the propeller wake-flow and the measured sound. The effect of turbulence on the radiated noise level showed an overall increase of 2 dB in the broadband levels for every 1% increase in turbulence. This effect varied for different frequency bands in the acoustic spectrum.List of Symbols
b
2 (f
k, f
l)
Bicoherence
-
B (k, l)
Bispectrum
-
B
Number of Blades
-
c
Speed of Sound
-
C
T
Thrust coefficient=T/n
2D4
-
D
Propeller diameter
-
E [ ]
Expected value
-
f
Frequency, Hz
-
G
xx
(f)
One sided autospectral density function.
-
G
xy
(f)
One sided cross-spectral density function
-
J
Advance ratio, J=U/nD
-
j, k
Fourier component indices
-
m
Grid mesh length
-
M
o
Rotational mach number at a radial location M
o
=2nr/a
o
-
M
c
Axial convection mach number
-
n
Rotational speed, revolutions per second
-
r
Propeller radial location
-
R
Propeller radius
-
R
e
Reynolds number
-
T
Propeller thrust
-
U
Freestream velocity
-
U
i
Induced axial velocity from propeller
-
u, w
RMS of fluctuating velocity, u=(U–u)2
-
X(f)
Fourier transform of x(t)
Symbols
xy
/2
(f)
Coherence function,
-
Observer angle, measured from propeller thrust direction
-
f
Longitudinal Eulerian dissipation length scale
-
f
Longitudinal Eulerian integral length scale
-
Air density
-
Blade azimuthal location
This research was performed at the Hessert Center for Aerospace Research, Department of Aerospace and Mechanical Engineering, University of Notre Dame, and was sponsored by the U.S. Navy, Office of Naval Research, Arlington, Virginia under Contract No. N00014-89-J-1783. The authors would like to thank the program manager, and technical manager, Dr. E. P. Rood. The authors would also like to thank Dr. William Blake of the David Taylor Research Center and Dr. Flint O. Thomas and Dr. Huang-Chang Chu of Notre Dame for their help and comments at various stages of this research 相似文献
18.
Makins NC Ent R Chapman MS Hansen J Lee K Milner RG Nelson J Arnold RG Bosted PE Keppel CE Lung A Rock SE Spengos M Szalata ZM Tao LH White JL Coulter KP Geesaman DF Holt RJ Jackson HE Papavassiliou V Potterveld DH Zeidman B Arrington J Beise EJ Belz E Filippone BW Gao H Lorenzon W Mueller B McKeown RD O'Neill TG Epstein M Margaziotis DJ Napolitano J Kinney E Anthony PL van Bibber K Dietrich FS Gearhart RA Patratos GG Kuhn SE van den Brand JF Bulten H Jones CE 《Physical review letters》1994,72(13):1986-1989
19.
Flögel O Dash J Brüdgam I Hartl H Reissig HU 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(17):4283-4290
Addition of lithiated methoxyallene to pivalonitrile afforded after aqueous workup the expected iminoallene 1 in excellent yield. Treatment of this intermediate with silver nitrate accomplished the desired cyclization to the electron-rich pyrrole derivative 2 in moderate yield. Surprisingly, trifluoroacetic acid converted iminoallene 1 to a mixture of enamide 3 and trifluoromethyl-substituted pyridinol 4 (together with its tautomer 5). A plausible mechanism proposed for this intriguing transformation involves addition of trifluoroacetate to the central allene carbon atom of an allenyl iminium intermediate as crucial step. Enamide 3 is converted to pyridinol 4 by an intramolecular aldol-type process. A practical direct synthesis of trifluoromethyl-substituted pyridinols 4, 10, 11, and 12 starting from typical nitriles and methoxyallene was established. Pyridinol 10 shows an interesting crystal packing with three molecules in the elementary cell and a remarkable helical supramolecular arrangement. Trifluoromethyl-substituted pyridinol 4 was converted to the corresponding pyridyl nonaflate 13, which is an excellent precursor for palladium-catalyzed reactions leading to pyridine derivatives 14-16 in good to excellent yields. The new synthesis of trifluoromethyl-substituted pyridines disclosed here demonstrates a novel reactivity pattern of lithiated methoxyallene which is incorporated into the products as the unusual tripolar synthon B. 相似文献
20.
Wong KL Bitter M Hammett GW Heidbrink W Hendel H Kaita R Scott S Strachan JD Tait G Bell MG Budny R Bush C Chan A Coonrod J Efthimion PC England AC Eubank HP Fredrickson E Furth HP Goldston RJ Grek B Grisham L Hawryluk RJ Hill KW Johnson D Kamperschroer J Kugel H Ma C Mansfield D Manos D McCune DC McGuire K Medley SS Mueller D Nieschmidt E Owens DK Paré VK Park H Ramsey A Rasmussen D Roquemore AL Schivell J Sesnic S Taylor G Williams MD Zarnstorff MC 《Physical review letters》1985,55(23):2587-2590