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41.
Dash AK Jensen TR Stern CL Marks TJ 《Journal of the American Chemical Society》2004,126(39):12528-12540
Single-site polymerization catalysts generated in situ via activation of Cp*MMe(3) (Cp* = C(5)Me(5); M = Ti, Zr), (CGC)MMe(2) (CGC = C(5)Me(4)SiMe(2)NBu(t)(); M = Ti, Zr), and Cp(2)ZrMe(2) with Ph(3)C(+)B(C(6)F(5))(4)(-) catalyze alkylation of aromatic molecules (benzene, toluene) with alpha-chloronorbornene at room temperature, to regioselectively afford the 1:1 addition products exo-1-chloro-2-arylnorbornane (aryl = C(6)H(5) (1a), C(6)H(4)CH(3) (1b)) in good yields. Analogous deuterium-labeled products exo-1-chloro-2-aryl-d(n)-norbornane-7-d(1) (aryl-d(n) = C(6)D(5) (1a-d(6)), C(6)D(4)CD(3) (1b-d(8))) are obtained via catalytic arylation of alpha-chloronorbornene in either benzene-d(6) or toluene-d(8). Isolated ion-pair complexes such as (CGC)ZrMe(toluene)(+)B(C(6)F(5))(4)(-) and Cp(2)ThMe(+)B(C(6)F(5))(4)(-) also catalyze the reaction of alpha-chloronorbornene in toluene-d(8) to give 1b-d(8) in good yields, respectively. Small quantities of the corresponding bis(1-chloronorbornyl)aromatics 2 are also obtained from preparative-scale reactions. These reactions exhibit turnover frequencies exceeding 120 h(-1) (for the Cp*TiMe(3)/Ph(3)C(+)B(C(6)F(5))(4)(-)-catalyzed system), and chlorine-free products are not observed. Compounds 1 and 2 were characterized by (1)H, (2)H, (13)C, and 2D NMR, GC-MS, and elemental analysis. The aryl group exo-stereochemistry in 1a and 1b is established using (1)H-(1)H COSY, (1)H-(13)C HMBC, and (1)H-(1)H NOESY NMR, and is further corroborated by X-ray analysis of the product 1,4-bis(exo-1-chloro-2-norbornyl)benzene (2a). Control experiments and reactivity studies on each component step suggest a mechanism involving participitation of the metal electrophiles in the catalytic cycle. 相似文献
42.
The MnIV complex of tetra-deprotonated 1,8-bis(2-hydroxybenzamide)-3,6-diazaoctane (MnIVL) engrossed in phenolate-amido-amine coordination is reduced by HSO3− and SO32− in the pH range 3.15–7.3 displaying biphasic kinetics, the MnIIIL− being the reactive intermediate. The MnIIIL− species has been characterized by u.v.–vis. spectra {λ max, (ε, dm3 mol−1 cm−1): 285(15 570), 330 sh (7570), 469(6472), 520 sh (5665), pH=5.42}. SO42− was the major oxidation product of SIV; dithionate is also formed (18 ± 2% of [MnIV]T) which suggests that dimerisation of SO3−• is competitive with its fast oxidation by MnIV/III. The rates and activation parameters for MnIVL + HSO3− (SO32−) → MnIIIL−; MnIIIL− + HSO3− (SO32−) → MnIIL2− are reported at 28.5–45.0 °C (I=0.3 mol dm−3, 10% (v/v) MeOH + H2O). Reduction by SO32− is ca. eight times faster than by HSO3− both for MnIVL and MnIIIL−. There was no evidence of HSO3−/SO32− coordination to the Mn centre indicating an outer sphere (ET) mechanism which is further supported by an isokinetic relationship. The self exchange rate constant (k22) for the redox couple, MnIIIL−/MnIVL (1.5 × 106 dm3 mol−1 s−1 at 25 °C) is reported. 相似文献
43.
Rakesh Paul Dr. Debasish Dutta Raj Paul Prof. Jyotirmayee Dash 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(30):12507-12511
The highly conserved HIV-1 transactivation response element (TAR) binds to the trans-activator protein Tat and facilitates viral replication in its latent state. The inhibition of Tat–TAR interactions by selectively targeting TAR RNA has been used as a strategy to develop potent antiviral agents. Therefore, HIV-1 TAR RNA represents a paradigmatic system for therapeutic intervention. Herein, we have employed biotin-tagged TAR RNA to assemble its own ligands from a pool of reactive azide and alkyne building blocks. To identify the binding sites and selectivity of the ligands, the in situ cycloaddition has been further performed using control nucleotide (TAR DNA and TAR RNA without bulge) templates. The hit triazole-linked thiazole peptidomimetic products have been isolated from the biotin-tagged target templates using streptavidin beads. The major triazole lead generated by the TAR RNA presumably binds in the bulge region, shows specificity for TAR RNA over TAR DNA, and inhibits Tat–TAR interactions. 相似文献
44.
A method for determination of anions and cations in boric acid is proposed by matrix volatilization. The boric acid matrix was eliminated as trimethyl borate ester in a vapour phase matrix elimination (VPME) system using a mixture of glycerol-methanol. In this VPME system, in situ reagent purification, sample decomposition and digest evaporation were achieved in a single step. Trace anions were separated on anion-exchange column (IonPac AS17) by an isocratic elution with 15 mM sodium hydroxide and the cations on a cation-exchange column (IonPac CS12) by 20 mM hydrochloric acid as eluents. Method detection limits (3sigma) for most ions ranged from 0.3 to 8 ng/g (ppb). Recovery experiments combined with comparison of data obtained by other methods were employed to verify the accuracy of the proposed method. Application of the method to determine trace levels of anions like acetate, oxalate, sulfate, phosphate and cations such as lithium, sodium, potassium, magnesium and calcium in two highly pure grades of boric acid using ion chromatography is demonstrated. 相似文献
45.
Strong Stokes and Upconversion Luminescence from Ultrasmall Ln3+‐Doped BiF3 (Ln=Eu3+, Yb3+/Er3+) Nanoparticles Confined in a Polymer Matrix 下载免费PDF全文
Heavy metal fluorides like BiF3 as a host for lanthanide ions are of interest as bismuth is the only heavy metal that is nontoxic. In this work, we report the synthesis of highly water‐dispersible ultrasmall BiF3 nanoparticles about 6 nm in size within a poly(vinyl pyrrolidone) matrix by a hydrothermal method. Microscopy analysis reveals that the nanoparticles are well separated and confined within the polymer network. These nanoparticles were found to be excellent hosts for lanthanide (Ln3+) ions. Through suitable Ln3+ doping, BiF3 exhibits strong emissions in the visible region upon both UV and near infrared (NIR) excitations. The non‐toxicity of both bismuth and PVP can be advantageous for the potential use of BiF3 nanoparticles in drug delivery and bioimaging. 相似文献
46.
Conservation equations for mass, momentum and energy have been solved numerically for a cylindrical funnel with louvers (lateral openings on the side wall of the cylindrical funnel through which air can come into it) to compute the suction rate of air into the funnel. The nozzle placed centrally at the bottom of the cylinder ejects high‐velocity hot gaseous products so that atmospheric air gets sucked into the funnel. The objective of the work is to compute the ratio of the rate of mass suction to that of the mass ejected by the nozzle for different operating conditions and geometrical size of the funnel. From the computation it has been found that there exists optimum funnel diameter and optimum funnel height for which the mass suction is the highest. The protruding length of the nozzle into the funnel has almost no effect on the mass suction rate after a certain funnel height. The louvers opening area has a very high impact on the mass suction rate. The entrance length for such a sucking funnel is strikingly much lower compared with a simple cylindrical pipe having uniform flow at the inlet at same Reynolds number. A new correlation has been developed to propose the entrance length for a sucking pipe, the rate of mass suction into it and the exhaust plume temperature over a wide range of operating parameters that are normally encountered in a general funnel operations of naval or merchant ship. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
47.
J. Satyanarayana V. N. Reddy G. S. Murty A. Dash 《Journal of Radioanalytical and Nuclear Chemistry》1994,188(5):323-330
Zirconium molybdoarsenate (ZrMAs), an inorganic ion exchanger, has been synthesized and the suitable conditions to separate cesium-137 from fission products waste solution are suggested. 相似文献
48.
49.
Majumder G Abe K Abe K Adachi I Aihara H Asano Y Aulchenko V Aushev T Bahinipati S Bakich AM Banerjee S Bedny I Bitenc U Bizjak I Blyth S Bondar A Bozek A Bracko M Brodzicka J Browder TE Chang MC Chang P Chao Y Chen A Chen KF Chen WT Cheon BG Chistov R Choi Y Chuvikov A Cole S Dalseno J Danilov M Dash M Drutskoy A Eidelman S Enari Y Fratina S Gabyshev N Gershon T Go A Gokhroo G Golob B Gorisek A Haba J Hara T Hastings NC Hayasaka K Hayashii H Hazumi M Hinz L Hokuue T Hoshi Y Hou S Hou WS 《Physical review letters》2005,95(4):041803
We report evidence for B(0) --> D(0)D(-) and the first observation of the decay modes B(-) --> D(0)D(-) and B(-) --> D(0)D(*-) based on a sample of 152 x 10(6) BB events collected by the Belle detector at KEKB. The branching fractions for B(0) --> D(+) D(-), B--->D(0)D(-), and B--> D(0)D(*-) are found to be (1.91 +/- 0.51 +/- 0.30) x10(-4), (4.83 +/- 0.78 +/- 0.58) x 10(-4), and (4.57 +/- 0.71 +/- 0.56) x 10(-4), respectively. Charge asymmetries in the B---> D(0)D(-) and B(-) --> D(0)D(*-) channels are consistent with zero. 相似文献
50.
Sumisawa K Ushiroda Y Hazumi M Abe K Abe K Adachi I Aihara H Asano Y Aulchenko V Aushev T Bakich AM Bitenc U Bizjak I Blyth S Bondar A Bozek A Bracko M Brodzicka J Browder TE Chao Y Chen A Chen KF Chen WT Cheon BG Chistov R Choi Y Chuvikov A Cole S Dalseno J Danilov M Dash M Drutskoy A Eidelman S Enari Y Fang F Fratina S Gabyshev N Garmash A Gershon T Gokhroo G Golob B Gorisek A Haba J Hara K Hara T Hayashii H Higuchi T Hokuue T Hoshi Y Hou S Hou WS Hsiung YB Iijima T Imoto A Inami K Ishikawa A 《Physical review letters》2005,95(6):061801
We present a measurement of CP-violation parameters in the B0 --> K(s)0K(s)0K(s)0 decay based on a sample of 275 x 10(6) BB pairs collected at the upsilon(4S) resonance with the Belle detector at the KEKB energy-asymmetric e+e- collider. One neutral B meson is fully reconstructed in the decay B0 --> K(s)0K(s)0K(s)0, and the flavor of the accompanying B meson is identified from its decay products. CP-violation parameters are obtained from the asymmetry in the distributions of the proper-time interval between the two B decays: S = +1.26 +/- 0.68(stat) +/- 0.20(syst) and [symbol: see text] = +0.54 +/- 0.34(stat) +/- 0.09(syst). 相似文献