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91.
Carson W. Reed Mark G. Fulton Kellie D. Nance Craig W. Lindsley 《Tetrahedron letters》2019,60(10):743-745
This communication details the first total synthesis of the 13-membered macrolide, (?)-Melearoride A, as well as unnatural (+)-Melearoride A. The synthesis features a concise 13 step synthesis (11 steps longest linear sequence) that offers flexible stereo-control and multiple opportunities for unnatural analog synthesis to delve into antifungal SAR. The route features a cuprate addition, an Evans asymmetric alkylation, and a ring-closing metathesis (RCM) to close the 13-membered macrocyclic core. 相似文献
92.
In this study benzyl and ethyl groups were appended to pyridine and aniline ancillary ligands in diiron(II) complexes of the type [Fe(2)(mu-O(2)CAr(R))(2)(O(2)CAr(R))(2)(L)(2)], where (-)O(2)CAr(R) is a sterically hindered terphenyl carboxylate, 2,6-di(p-tolyl)- or 2,6-di(p-fluorophenyl)benzoate (R = Tol or 4-FPh, respectively). These crystallographically characterized compounds were prepared as analogues of the diiron(II) center in the hydroxylase component of soluble methane monooxygenase (MMOH). The use of 2-benzylpyridine (2-Bnpy) yielded doubly bridged [Fe(2)(mu-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)(2-Bnpy)(2)] (1) and [Fe(2)(mu-O(2)CAr(4)(-)(FPh))(2)(O(2)CAr(4)(-)(FPh))(2)(2-Bnpy)(2)] (4), whereas tetra-bridged [Fe(2)(mu-O(2)CAr(Tol))(4)(4-Bnpy)(2)] (3) resulted when 4-benzylpyridine (4-Bnpy) was employed. Similarly, 2-(4-chlorobenzyl)pyridine (2-(4-ClBn)py) and 2-benzylaniline (2-Bnan) were employed as N-donor ligands to prepare [Fe(2)(mu-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)(2-(4-ClBn)py)(2)] (2) and [Fe(2)(mu-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)(2-Bnan)(2)] (5). The placement of the substituent on the pyridine ring had no effect on the geometry of the diiron(II) compounds isolated when 2-, 3-, or 4-ethylpyridine (2-, 3-, or 4-Etpy) was introduced as the ancillary nitrogen ligand. The isolated [Fe(2)(mu-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)(2-Etpy)] (6), [Fe(2)(mu-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)(3-Etpy)] (7), [Fe(2)(mu-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)(4-Etpy)] (8), and [Fe(2)(mu-O(2)CAr(4)(-FPh))(2)(O(2)CAr(4)(-)(FPh))(2)(2-Etpy)(2)] (9) complexes all contain doubly bridged metal centers. The oxygenation of compounds 1-9 was studied by GC-MS and NMR analysis of the organic fragments following decomposition of the product complexes. Hydrocarbon fragment oxidation occurred for compounds in which the substrate moiety was in close proximity to the diiron center. The extent of oxidation depended upon the exact makeup of the ligand set. 相似文献
93.
Methylcellulose (MC), a thermoreversible polymer, was fabricated as thin films into silicon substrates and characterized by x‐ray reflectivity (XRR) measurements for its stability with time and heating. XRR data from the as‐is thin films showed good agreement with the single‐layer model on top of a substrate from Parratt's formalism. Data fitting showed that the density of the thin films is slightly higher than the reported value by manufacturers. Interface roughness values indicate good wetting of the polymer onto the substrate. Heating the thin films at the phase transition temperatures and quenching them to room temperature showed no significant changes in the thin film parameters before and after heating. This showed the thermal stability and/or thermoreversibility of the film. Diffuse scattering measurements also showed no significant changes in the lateral structure of the film with heating and quenching. XRR measurements done on fabricated thin films stored for a month showed a slight increase in the film thickness which could be due to the hygroscopic nature of the polymer. Vacuum heating of the stored thin films at 100 °C for 1 h slightly decreased the thickness, but it has been found that other parameters such as density and surface/interface roughness show good thermal stability. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
94.
Mészáros Szécsényi K. Wadsten T. Carson B. Bencze É. Liptay G. 《Journal of Thermal Analysis and Calorimetry》2002,68(1):81-90
Compounds obtained by a solid–gas phase reactions between copper(II) chloride and bromide and 2,4-, 2,6- 3,4- and 3,5-lutidines
were studied using thermogravimetry, far-infrared, electronic spectroscopy and X-ray diffraction. The results were compared
with the corresponding data for the similar compounds with methylpyridines and 2,4,6-collidine. A special attention was paid
to the host-guest phenomenon, a new structural feature of transition-metal halide complexes.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
95.
96.
Ion-pair solid-phase extraction 总被引:3,自引:0,他引:3
Carson MC 《Journal of chromatography. A》2000,885(1-2):343-350
Solid-phase extraction (SPE) is a technique widely employed by analytical chemists. SPE cartridges are available in a wide variety of formats containing media with diverse chemistries. This paper will review ion-pair SPE, one of the less frequently applied, and presumably less well-known techniques. Advantages of this technique over more conventional reversed-phase or ion-exchange SPE include selectivity, compatibility with rapid evaporative concentration, and potential application to multiclass multiresidue analysis. 相似文献
97.
We report the direct observation of a tangent bifurcation at the period-five window of a driven nonlinear semiconductor oscillator, by observing the fifth iterate of the dynamical variable of the system in real time. The tangent bifurcation is accompanied by an intermittency as predicted by Manneville and Pomeau. 相似文献
98.
Innis PC Masdarolomoor F Kane-Maguire LA Forster RJ Keyes TE Wallace GG 《The journal of physical chemistry. B》2007,111(44):12738-12747
Both the chemical and the electrochemical synthesis of poly(2-methoxyaniline-5-sulfonate) (PMAS) in aqueous media have been found to give two distinct polymer fractions with molecular weights of approximately 8-10 and 2 kDa, respectively. It is now possible to isolate the pure high molecular weight (HMWT) PMAS and low molecular weight (LMWT) PMAS oligomer and to study their individual and combined photochemistry and redox chemistry. The HMWT PMAS fraction was confirmed to be an emeraldine salt by its characteristic redox and pH switching behavior, in contrast to the oligomeric LMWT PMAS, which was inert under the same conditions. Mixtures of these two fractions exhibit photoluminescence arising from the oligomeric LMWT PMAS fraction. The observed LMWT PMAS emission was modulated by the presence of the conducting HMWT PMAS emeraldine salt via a static resonant energy transfer arising from quenching at 460 nm when excited at 355 nm. The nonlinear fluorophore-quencher behavior suggests that the two PMAS fractions are strongly associated. The behavior fitted the static Perrin quenching model in which the oligomeric LMWT PMAS fluorophore is diffusionally restricted by the presence of HMWT PMAS quencher. 相似文献
99.
Carson Chu Ali Naseri Tirthankar Mitra Mehran Dadsetan Anton Sediako Murray J. Thomson 《Proceedings of the Combustion Institute》2021,38(2):2525-2532
The relationship between soot surface growth, soot nanostructure and reactant temperature (Tr) in a coflow diffusion ethylene flame was investigated with multiple experimental techniques. The Tr was raised by heating the coflow air. Three cases, with 300K, 473K, and 673K Tr, respectively, were studied. Laser-induced Incandescence revealed that increasing Tr promotes soot formation. Although soot primary particle diameter (dp) also increases with Tr, the increase in dp slows down after 473K Tr, suggesting that there is a deceleration in soot surface growth. Transmission Electron Microscopy (TEM) imaging showed that increased Tr promotes soot aggregation and yields larger and more mature primary particles. The assessment of the Selected Area Electron Diffraction (SAED) patterns indicated that, at 673K Tr, there is a growth of lattice planes. Raman spectroscopy revealed further structural details. By assessing the band intensity ratios, soot for the Tr of 673K has more curved nanostructures. The deceleration of soot surface growth may be explained by surface aging, which is characterized by an increase in curved nanostructures. 相似文献
100.
Aluminium (iii) is one of the most abundant metal ions found in soil. Typically, Al(+3) is bound to minerals, but its bioavailability and toxicity toward vascular plants increases with increasing soil acidity. Ectomycorrhizal fungi, which live symbiotically on the roots of numerous woody plants, often confer Al(+3) resistance to host plants by reducing metal availability to the plant by unknown mechanisms. A potential mechanism of detoxification is binding of the Al(+3) by organic compounds that are exuded by the fungi into the surrounding soil and solution. A novel method has been developed to purify and characterize Al(+3) binding ligands from Pisolithus tinctorius exudate solutions using Al(+3) immobilized metal affinity chromatography (IMAC), reversed phase chromatography, and mass spectrometry. Fungal exudates produced by P. tinctorius exhibit a strong binding capacity for Al(+3), allowing their selective enrichment and collection using this IMAC method. Elution of the ligands requires the use of high pH. RP-HPLC separation and elemental analysis of the IMAC elutent indicates that the Al(+3) and the exudate ligands both elute from the column but are not bound in a complex. Thus, reversed phase HPLC at pH 10 is used for separation of the ligands and Al(+3) prior to MS analysis. The strongest binding IMAC fraction is analyzed by electrospray ionization mass spectrometry in positive and negative ion modes. This report provides new methods for the direct purification and analysis of naturally occurring ligands that bind hard metal ions. 相似文献