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41.
On-line preconcentration system for the selective, sensitive and simultaneous determination of chromium species was investigated. Dual mini-columns containing chelating resin were utilized for the speciation and preconcentration of Cr(III) and Cr(VI) in water samples. In this system, Cr(III) was collected on first column packed with iminodiacetate resin. Cr(VI) in the effluent from the first column was reduced to Cr(III), which was collected on the second column packed with iminodiacetate resin. Hydroxyammonium chloride was examined as a potential reducing agent for Cr(VI) to Cr(III).The effects of pH, sample flow rate, column length, and interfering ions on the recoveries of Cr(III) were carefully studied. Five millilitres of a sample solution was introduced into the system. The collected species were then sequentially washed by 1 M ammonium acetate, eluted by 2 M nitric acid and measured by ICP-AES. The detection limit for Cr(III) and Cr(VI) was 0.08 and 0.15 μg l−1, respectively. The total analysis time was about 9.4 min.The developed method was successfully applied to the speciation of chromium in river, tap water and wastewater samples with satisfied results. 相似文献
42.
[reaction: see text] (Z)-2-Fluoro-1-alkenyl(phenyl)iodonium salts were stereoselectively prepared by the reaction of alkynyl(phenyl)iodonium salts with aqueous HF in good yields. The method is applicable to the synthesis of fluoroalkenyliodonium salts having functional groups such as ketone, ester, and chloride. (Z)-2-Fluoro-1-alkene, (Z)-2-fluoro-2-alkenoate, and (Z)-beta-fluoroenyne could be stereoselectively prepared from the fluoroalkenyliodonium salt. 相似文献
43.
A novel and simple flow-based method was developed for the simultaneous determination of As(III) and As(V) in freshwater samples. Two miniature columns with a solid phase anion exchange resin, placed on two 6-way valves were utilized for the solid-phase collection/concentration of arsenic(III) and arsenic(V), respectively. As(III) could be retained on the column after its oxidation to As(V) species with an oxidizing agent. The collected analytes were then sequentially eluted by 2 M nitric acid and introduced into ICP-AES. Potassium permanganate was examined as potential oxidizing agent for conversion of As(III) to As(V). The standard deviation of the analytical signals (peak height) for the replicate analysis (n = 5) of 0.5 μg l−1 solution were 3 and 5% for As(III) and As(V), respectively. The limit of detection (3σ) for both As(III) and As(V) were 0.1 μg l−1. The proposed system produced satisfactory results on the application to the direct analysis of inorganic arsenic species in freshwater samples. 相似文献
44.
Eguchi S Suzuki T Okawa T Matsushita Y Yashima E Okamoto Y 《The Journal of organic chemistry》1996,61(21):7316-7319
Both optical isomers of a quinazoline alkaloid, vasicinone, were synthesized by two different methods. The first method used (3S)-3-hydroxy-gamma-lactam as a chiral synthon, which was, after O-TBDMS protection, o-azidobenzoylated followed by treatment with tri-n-butylphosphine to afford (S)-(-)-vasicinone via the tandem Staudinger/intramolecualr aza-Wittig reaction. The second method utilized asymmetric oxygenation of deoxyvasicinone with (1S)-(+)- or (1R)-(-)-(10-camphorsulfonyl)oxaziridine (the Davis reagent), respectively. The aza-enolate anion of deoxyvasicinone was treated with (S)-(+)-reagent to afford (R)-(+)-vasicinone in 71% ee, while the reaction with (R)-(-)-reagent gave (S)-(-)-vasicinone in 62% ee. The optical purity was analyzed by HPLC on specially modified cellulose as a stationary phase. These results provided a facile method to prepare both optical isomers of vasicinone and confirmed the recently reversed stereochemistry of natural (-)-vasicinone. 相似文献
45.
Konoike T Matsumura K Yorifuji T Shinomoto S Ide Y Ohya T 《The Journal of organic chemistry》2002,67(22):7741-7749
A practical multikilogram-scale synthesis of enantiomerically pure S-1255 (1), a potent and orally active ET(A) receptor antagonist, is described. Utilizing readily available starting materials and reagents, the entire sequence of reactions starting from 2,5-dihydroxyacetophenone 8 proceeded under mild conditions to give 1 in an excellent chemical yield (8 steps, 41% overall yield) and in a high enantiopurity (98% ee). The crucial step of the synthesis is a dynamic resolution of key intermediate 16. (R)-Methoxy acid (R)-16 having 97-99% ee was obtained in 83-84% yield from racemic 16 as a crystalline (1S,2R)-(+)-norephedrine or (+)-cinchonine salt by the dynamic resolution comprising concurrent crystallization and in situ racemization. A mechanism of the dynamic resolution through a ring-opened zwitterionic intermediate is discussed. In the final synthetic step, an effective carbon-carbon bond formation between the C4 carbon and the p-anisyl group was accomplished by a conjugate addition-elimination reaction of Grignard reagent 3 to (R)-16 to give 1 having 98% ee. Owing to high efficiencies of functional group transformations, carbon-carbon bond formations, and the dynamic resolution, the synthesis required no chromatographic purification and was amenable to a multikilogram-scale preparation. Several kilograms of 1 for clinical trials were successfully prepared by this process. 相似文献
46.
Koji Oshita Mitsuko Oshima Yunhua Gao Kyue-Hyung Lee Shoji Motomizu 《Analytica chimica acta》2003,480(2):239-249
A chitosan resin derivatized with serine moiety (serine-type chitosan) was newly developed by using the cross-linked chitosan as a base material. The adsorption behavior of trace amounts of metal ions on the serine-type chitosan resin was systematically examined by packing it in a mini-column, passing a metal solution through it and measuring metal ions in the effluent by ICP-MS. The resin could adsorb a number of metal cations at pH from neutral to alkaline region, and several oxoanionic metals at acidic pH region by an anion exchange mechanism. Uranium and Cu could be adsorbed selectively at pH from acidic to alkaline region by a chelating mechanism; U could be adsorbed quantitatively even at pH 3–4. Uranium adsorbed on the resin was easily eluted with 1 M nitric acid: the preconcentration (5-, 10-, 50- and 100-fold) of U was possible. The column treatment method was used prior to the ICP-MS measurement of U in natural river, sea and tap waters; R.S.D. were 2.63, 1.13 and 1.37%, respectively. Uranium in tap water could be determined by 10-fold preconcentration: analytical result was 1.46±0.02 ppt. The resin also was applied to the recovery of U in sea water: the recovery tests for artificial and natural sea water were 97.1 and 93.0%, respectively. 相似文献
47.
Monitoring the removal of carbonate from alkali metal hydroxide (MOH, M = K, Na) solutions with calcium oxide (CaO) was studied using a newly developed method for the determination of trace amounts of total carbonate (TC) in alkaline solutions based on a flow injection (FI) technique coupled with a gas diffusion system. The optimized conditions of the FI system were as follows: the flow rate of each carrier, reaction solution (H2SO4) and receptor solution (Cresol Red, pH 8.9) was 0.25 ml min(-1), the sample size was 0.1 ml and the concentration of H2SO4 in the reaction solution was 0.09 M. The limit of detection of TC by the proposed method was 4 x 10(-7) M. The removal efficiency of carbonate was affected by the amount of CaO added, the shaking time of the solutions and the concentration of MOH. For 1 M NaOH and KOH solution, the removal efficiency of carbonate was about 99% and the concentration of residual carbonate was 4 x 10(-5) and 1.2 X 10(-4) M, respectively, when the amount of CaO added was 2 g l(-1) and the shaking time was 16 h. 相似文献
48.
Inumaru K Kasahara T Yasui M Yamanaka S 《Chemical communications (Cambridge, England)》2005,(16):2131-2133
Well-crystallised TiO2 particles (P-25, 20-30 nm in diameter) were directly incorporated into surfactant-templated mesoporous silica particles (pore diameter: 2.7 nm), and the composite material with a high TiO2 content (60 wt%) showed molecular selective and enhanced photocatalysis for decomposition of 4-nonylphenol. 相似文献
49.
Ken-ichi Sato Shoji AkaiToshiyuki Hiroshima Hidenori AokiMayumi Sakuma Ken-ju Suzuki 《Tetrahedron letters》2003,44(17):3513-3516
The chemoenzymatic synthesis of 13C-labeled sialic acid (NeuAc) and 3-deoxy-d-glycero-d-galacto-2-nonulosonic acid (KDN) as useful molecular probes for studying the conformation of sialyl or KDN oligosaccharides attached to proteins was performed by using [6-13C]-ManNAc, [6-13C]-Man and [3-13C]-pyruvic acid sodium salt. In the synthesis of the compounds, 5,6-anhydro intermediates were found to easily provide not only 6-13C-labeled but also 5-, and 6-modified NeuAc and KDN analogs. Furthermore, it was demonstrated that identical results are obtained by NMR for both [3,9-13C]-NeuAc and 1:1 mixtures of [3-13C]- and [9-13C]-NeuAc. 相似文献
50.
Electron beam treatment of lignite-burning flue gas with high concentrations of sulfur dioxide and water 总被引:5,自引:0,他引:5
Hideki Namba Shoji Hashimoto Okihiro Tokunaga Ryoji Suzuki 《Radiation Physics and Chemistry》1998,53(6):673-681
Experiments were carried out to investigate the removals of SO2 and NOx from simulated lignite-burning flue gas containing SO2 (4800 ppm), NO (320 ppm) and H2O (22%) by electron beam irradiation. Removal efficiencies of SO2 and NOx were achieved to reach 97 and 88% at 70°C, and 74 and 85% at 80°C, respectively, with the dose of 10.3 kGy without NH3 leakage. The higher removal efficiencies of SO2 and NOx were observed in simulated lignite-burning flue gas than in coal-fired flue gas containing 800 ppm of SO2, 225 ppm of NO and 7.5% H2O at the same treatment condition. The higher removal efficiencies were attributed to the higher concentrations of SO2, H2O, and added NH3. Simulation calculations indicated that the higher concentrations of these components enhance the effective radical reactions to oxidize NO to form NO2 with HO2 radical, and to oxidize SO2 to form SO3 with OH radical and O2. The reactions of NOx with N and NH2 radicals to produce N2 and N2O also promote the NOx removal. By-product was determined to be the mixture of (NH4)2SO4 and NH4NO3 containing a small amount of H2SO4. 相似文献