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131.
Jeanne Brygier Michel Gelbcke Claude Guermant Michelle Nijs Danielle Baeyens-Volant Yvan Looze 《Applied biochemistry and biotechnology》1993,42(2-3):127-135
Carbonylimidazol-l-yl-mPEG is obtained quantitatively by reacting methoxypoly(ethyleneglycol) (mPEG) with 1.1 Eq of N,N′-carbonyldiimidazole
in the presence of a stoechiometric amount of 4-dimethyl-aminopyridine used as hypernucleophilic acylation catalyst. Carbonylimidazol-l-yl-mPEG is quite stable in aqueous solutions with half-lives up to 70 h in pHs ranging from 6.0 to 7.0 at 25‡C. From reactivity
studies toward amines with various nucleophilic strengths, it is suggested that carbonylimidazol-l-yl-mPEG may be best used to modify α-amino terminal function of proteins selectively or to introduce amino function on PEG chains. 相似文献
132.
Emilio Pardo Dr. Danielle Cangussu Dr. Marie-Claire Dul Rodrigue Lescouëzec Dr. Patrick Herson Yves Journaux Dr. Emerson F. Pedroso Dr. Cynthia L. M. Pereira Dr. M. Carmen Muñoz Prof. Dr. Rafael Ruiz-García Dr. Joan Cano Dr. Pedro Amorós Prof. Dr. Miguel Julve Prof. Dr. Francesc Lloret Prof. Dr. 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2008,120(22):4279-4284
133.
The dehydroxy-fluorination of propargylic alcohols occurs with a complete regiocontrol and a good to complete stereocontrol, in contrast to the reactions performed on allylic alcohols. The gem-difluorination of propargylic ketones occurs smoothly in contrast to enones which have a very low reactivity towards DAST or Deoxo-fluor™. It is proposed that the large differences in the stabilization energies of the key carbonium ion intermediates (either propargylic or allylic) could explain these strong differences in reactivity during nucleophilic fluorination. The calculations of isodesmic reactions are in full agreement with this proposal. 相似文献
134.
Eric L. Petersen Danielle M. Kalitan Gilles Bourque John M. Simmie 《Proceedings of the Combustion Institute》2007,31(1):447-454
Shock tube experiments and chemical kinetic modeling were performed to further understand the ignition and oxidation kinetics of various methane-propane fuel blends at gas turbine pressures. Ignition delay times were obtained behind reflected shock waves for fuel mixtures consisting of CH4/C3H8 in ratios ranging from 90/10% to 60/40%. Equivalence ratios varied from lean (? = 0.5), through stoichiometric to rich (? = 3.0) at test pressures from 5.3 to 31.4 atm. These pressures and mixtures, in conjunction with test temperatures as low as 1042 K, cover a critical range of conditions relevant to practical turbines where few, if any, CH4/C3H8 prior data existed. A methane/propane oxidation mechanism was prepared to simulate the experimental results. It was found that the reactions involving CH3O˙, CH3O˙2, and ?H3 + O2/HO˙2 chemistry were very important in reproducing the correct kinetic behavior. 相似文献
135.
Bourgeois ME Wajer FT Roth M Briguet A Décorps M van Ormondt D Segebarth C Graveron-Demilly D 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2003,163(2):277-287
This paper analyzes the effects of intra-scan motion and demonstrates the possibility of correcting them directly in k-space with a new automatic retrospective method. The method is presented for series of 2D acquisitions with Cartesian sampling. Using a reference k-space acquisition (corrected for translations) within the series, intra-scan motion parameters are accurately estimated for each trajectory in k-space of each data set in the series resulting in pseudo-random sample positions. The images are reconstructed with a Bayesian estimator that can handle sparse arbitrary sampling in k-space and reduces intra-scan rotation artefacts to the noise level. The method has been assessed by means of a Monte Carlo study on axial brain images for different signal-to-noise ratios. The accuracy of motion estimates is better than 0.1 degrees for rotation, and 0.1 and 0.05 pixel, respectively, for translation along the read and phase directions for signal-to-noise ratios higher than 6 of the signals on each trajectory. An example of reconstruction from experimental data corrupted by head motion is also given. 相似文献
136.
Two separate liquid-solid phase transitions are detected in the two monolayers of a mica-supported phospholipid bilayer by atomic force microscopy. The phase transitions of the two monolayers are decoupled by the stronger interaction between the lipid headgroups of the proximal monolayer and the mica support. The transition temperature of the proximal monolayer is increased and this transition occurs over a narrower temperature range. Both transitions occur via grain-boundary melting and the variation of the width of the interfacial zone with temperature is consistent with mean-field theory. 相似文献
137.
Extraction of nutraceuticals from milk thistle 总被引:1,自引:0,他引:1
Sunny N. Wallace Danielle Julie Carrier Edgar C. Clausen 《Applied biochemistry and biotechnology》2003,108(1-3):881-889
Milk thistle contains compounds that display hepatoxic protection properties. We examined the batch extraction of silymarin
compounds from milk thistle seed meal in 50, 70, 85, and 100°C water as a function of time. After 210 min of extraction at
100°C, the yield of taxifolin was 1.2 mg/g of seed, a 6.2-fold increase over the results obtained in a Soxhlet extraction
with ethanol on pretreated (defatted) seeds. Similarly, the yield of silychristin was 5.0 mg/g of seed, a 3.8-fold increase.
The yields of silybinin A and silybinin B were 1.8 and 3.3 mg/g of seed, respectively, or roughly 30% of the Soxhlet yield.
The ratios of the extracted compounds, and particularly the ratios at long extraction times, showed that the more polar compounds
(taxifolin and silychristin) were preferentially extracted at 85°C, while the less polar silybinin was favored at 100°C. 相似文献
138.
Several 15N enriched oximes of heterocyclic aldehydes have been prepared in syn and anti forms. The less stable form may be obtained by UV irradiation of the other one. The geminal 15N? H coupling in the R? CH?15N? OH fragment allows an immediate and unambiguous assignment of the configuration to be made, being 13 to 16 Hz and 2 to 3 Hz for the anti and syn forms, respectively. Whereas oximes 1 to 4 are preferentially in the anti form, the N-methylpyridinium aldoxime iodides (2-PAM, 3-PAM, 4-PAM) are found to be syn in the stable form and not anti as previously thought. This reassignment is of special interest, since 2-PAM ( 8 ), which is an excellent antidote against alkyl phosphate nerve poisoning, has been used to study the geometry of the acetylcholinesterase active site of the enzyme. 相似文献
139.
Genevive Delmas Viviane Daviet Danielle Filiatrault 《Journal of Polymer Science.Polymer Physics》1976,14(9):1629-1639
Intrinsic viscosities have been measured at 25° on five ethylene–propylene copolymer samples ranging in composition from 33 to 75 mole-% ethylene. The solvents used were n-C8 and n-C16 linear alkanes and two branched alkanes, 2,2,4-trimethylpentane and 2,2,4,4,6,8,8-heptamethylnonane (br-C16). This choice was based on the supposition that the branched solvent would prefer the propylene segments and the linear solvent the ethylene segments, due to similarity in shape and possibly in orientational order. It was found that [η]n ? [η]br ≡ Δ[η] is indeed negative for propylene-rich copolymers, zero for a 56% ethylene copolymer, and positive for ethylene-rich copolymers. The Stockmayer–Fixman relation was used to obtain from Δ[η] a molecular-weight independent function of composition. The quantities (Δ[η]/[η])(1 + aM?1/2) and Δ[η]/M are linear with the mole percent ethylene in the range investigated with 200 ≤ a ≤ 2000. The possibility of using these results for composition determination in ethylene–propylene copolymers is discussed. Intrinsic viscosities in the same solvents are reported for two samples of a terpolymer with ethylidene norbornene. 相似文献
140.
The cyclization of small peptides which do not incorporate turn inducers is often difficult. We have developed a method involving the use of removable turn inducers, in the form of pseudoprolines, for the cyclization of difficult peptide sequences. The pseudoprolines induce a cisoid amide bond in the peptide backbone which facilitates cyclization. They are then readily removed to yield a cyclic peptide that does not contain any turn inducers. 相似文献