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91.
Practical and highly efficient methods for oxidative rearrangement of tertiary allylic alcohols to beta-substituted alpha,beta-unsaturated carbonyl compounds employing oxoammonium salts are described. The methods developed are applicable to acyclic substrates as well as medium membered ring substrates and macrocyclic substrates. The counteranion of the oxoammonium salt plays crucial roles on this oxidative rearrangement. 相似文献
92.
Hayashi M Sasano Y Nagasawa S Shibuya M Iwabuchi Y 《Chemical & pharmaceutical bulletin》2011,59(12):1570-1573
A highly active organocatalyst for alcohol oxidation has been developed. 9-Azanoradamantane N-oxyl (Nor-AZADO 4), constituting an unhindered, stable nitroxyl radical, exhibits superior catalytic activity to 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and AZADOs in the oxidation of alcohols to their corresponding carbonyl compounds. 相似文献
93.
Yatsukawa Y Ito H Matsuda T Nakamura M Watai M Fujita K 《Journal of AOAC International》2011,94(4):1319-1327
A new analytical method for the simultaneous determination of seven fluoroquinolones, namely, norfloxacin, ciprofloxacin, danofloxacin, enrofloxacin, orbifloxacin, sarafloxacin, and difloxacin, especially in dark-colored honey, has been developed. Fluoroquinolone antibiotics were extracted from samples with MacIlvaine buffer solution (pH 4.0) containing EDTA disodium salt dihydrate. The extracts were treated with both a polymeric cartridge and a metal chelate affinity column preloaded with ferric ion (Fe3+). LC separation with fluorescence detection was performed at 40 degrees C using an Inertsil ODS-4 analytical column (150 x 4.6 mm, 3 microm). The mobile phase was composed of 20 mM/L citrate buffer solution (pH 3.1)-acetonitrile mixture (70 + 30, v/v) containing 1 mM/L sodium dodecyl sulfate. Lomefloxacin was used as an internal standard. The developed method was validated according to the criteria of European Commission Decision 2002/657/EC. Decision limits and detection capabilities were below 2.9 and 4.4 microg/kg, respectively. 相似文献
94.
Mg isotope fractionation in biogenic carbonates of deep-sea coral, benthic foraminifera, and hermatypic coral 总被引:1,自引:0,他引:1
Yoshimura T Tanimizu M Inoue M Suzuki A Iwasaki N Kawahata H 《Analytical and bioanalytical chemistry》2011,401(9):2755-2769
High-precision Mg isotope measurements by multiple collector inductively coupled plasma mass spectrometry were applied for
determinations of magnesium isotopic fractionation of biogenic calcium carbonates from seawater with a rapid Mg purification
technique. The mean δ26Mg values of scleractinian corals, giant clam, benthic foraminifera, and calcite deep-sea corals were −0.87‰, −2.57‰, −2.34‰,
and −2.43‰, suggesting preferential precipitation of light Mg isotopes to produce carbonate skeleton in biomineralization.
Mg isotope fractionation in deep-sea coral, which has high Mg calcite skeleton, showed a clear temperature (T) dependence from 2.5 °C to 19.5 °C: 1,000 × ln(α) = −2.63 (±0.076) + 0.0138 (±0.0051) × T(R
2 = 0.82, p < 0.01). The δ26Mg values of large benthic foraminifera, which are also composed of a high-Mg calcite skeleton, can be plotted on the same
regression line as that for deep-sea coral. Since the precipitation rates of deep-sea coral and benthic foraminifera are several
orders of magnitude different, the results suggest that kinetic isotope fractionation may not be a major controlling factor
for high-Mg calcite. The Mg isotope fractionation factors and the slope of temperature dependence from deep-sea corals and
benthic foraminifera are similar to that for an inorganically precipitated calcite speleothem. Taking into account element
partitioning and the calcification rate of biogenic CaCO3, the similarity among inorganic minerals, deep-sea corals, and benthic foraminiferas may indicate a strong mineralogical
control on Mg isotope fractionation for high-Mg calcite. On the other hand, δ26Mg in hermatypic corals composed of aragonite has been comparable with previous data on biogenic aragonite of coral, sclerosponges,
and scaphopad, regardless of species differences of samples. 相似文献
95.
Biosynthesis of a marine ladder-frame polyether yessotoxin (YTX) produced by the dinofalgellate Protoceratium reticulatum was investigated. The 13C-labeling experiments indicated that the carbons in YTX were derived from acetates, a methyl of methionine and glycolate, and six-membered ring tetrads (rings A-D and H-K) were constructed from repetition of C3 units (m-m-c), which consisted of a methyl of acetate and acetate. 相似文献
96.
Miki ItoFujiko Konno Takuya KumamotoNoriyuki Suzuki Masatoshi KawahataKentaro Yamaguchi Tsutomu Ishikawa 《Tetrahedron》2011,67(41):8041-8049
Both enantiomers of chelidonine, a B/C-cis-11-hydroxyhexahydrobenzo[c]phenanthridine alkaloid, were synthesized by manipulation of the B/C-dehydro ring juncture of benzo[c]phenanthridine skeleton using Sharpless asymmetric dihydroxylation and stereospecific catalytic hydrogenation after introduction of oxygen functions on the C ring as key reaction steps for the construction of stereogenic centers. 相似文献
97.
98.
Norio Tsubokawa Masatoshi Inagaki Hidetoshi Kubota Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1993,31(13):3193-3198
The cationic polymerization of vinyl monomers initiated by biosynthesized γ-poly(glutamic acid) (γ-PGA) powder surface was carried out in a heterogeneous system. It was found that the polymerization of N-vinylcarbazole (NVC) and N-vinyl-2-pyrrolidone (NVPD) is initiated by γ-PGA powder. The grafting of polymers onto γ-PGA surface was scarcely observed. The apparent activation energy of the polymerization of NVC and NVPD was estimated to be 20.2 and 24.8 kJ/mol, respectively. The polymerization was totally inhibited by the addition of triethylamine and pyridine, but not hydroquinone. The polymerization rate in nitrobenzene was larger than that in toluene. These results indicated the cationic nature of the polymerization. γ-PGA treated with KOH did not show the initiating activity of the polymerization. Therefore, carboxyl groups on γ-PGA powder surface play an important role in the initiation of the polymerization. It may be suggested that the polymerization is initiated by proton addition to monomer from carboxyl groups on γ-PGA powder surface and the propagation proceeds with carboxylate anion on the surface as counter ion. © 1993 John Wiley & Sons, Inc. 相似文献
99.
Hidenobu Takeyama Masatoshi Kobayashi Hirofumi Yajima Ryuichi Endo Kaoru Kohyama Katsuyoshi Nishinari 《Macromolecular Symposia》1993,76(1):83-88
Amylose gel is obtained by cooling amylose aqueous solution at a certain cooling rate. In order to clarify the gelation process of amylose in the mixed solvent of water and DMSO, the characteristics of turbidity and dynamic viscoelasticity of the solution as a function of temperature have been studied by optical and rheological methods, respectively. Accordingly, cloud temperature (Tc) at which the aggregation of amylose occurs, and gelation temperature (Tgel) at which the elasticity began to appear were obtained. Tc and Tgel were strongly dependent on cooling rate, and these values shifted to higher temperatures with decreasing cooling rate. However, there was difference between Tc and Tgel, and Tc was higher than Tgel, indicating the gelation process occurs in two stages. 相似文献
100.
Kenichiro Todoroki Hidemichi Etoh Hideyuki Yoshida Hitoshi Nohta Masatoshi Yamaguchi 《Analytical and bioanalytical chemistry》2009,394(1):321-327
We have developed a novel pre-column fluorescence derivatization reagent for amines, F-trap pyrene. This reagent comprises
a fluorescent pyrene moiety, an amine-reactive Marshall linker, and a fluorophilic perfluoroalkyl group known as fluorous
tag. When the reagent reacts with aliphatic amines and amino acids to give fluorescent derivatives, the fluorous tag in the
reagent is eliminated simultaneously. Therefore, excess unreacted reagents in the derivatization reaction solution still have
the fluorous tag and could be removed by fluorous solid-phase extraction selectively before high-performance liquid chromatography
(HPLC) analysis. By using this reagent, 13 kinds of aliphatic amine (C2–C16) derivatives can be separated within 40 min by reversed-phase HPLC with gradient elution. In this chromatogram, unreacted
reagents peak at around 28 min, greatly decrease after fluorous solid-phase extraction, and do not interfere with the quantification
of each amine. The detection limits (S/N = 3) for examined aliphatic amines are 3.6–25 fmol per 20 μL injection. We have also applied this reagent successfully to
the amino acid analysis.
相似文献
Kenichiro TodorokiEmail: |