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1.
Georgiy B. Shul’pin Camilla C. Golfeto Lidia S. Shul’pina 《Tetrahedron letters》2005,46(27):4563-4567
The H2O2-FeCl3-bipy system in acetonitrile efficiently oxidises alkanes predominantly to alkyl hydroperoxides. Turnover numbers attain 400 after 1 h at 60 °C. It has been assumed that bipy facilitates proton abstraction from a H2O2 molecule coordinated to the iron ion (these reactions are stages in the catalytic cycle generating hydroxyl radicals from the hydrogen peroxide). Hydroxyl radicals then attack alkane molecules finally yielding the alkyl hydroperoxide. 相似文献
2.
3.
A simple new protocol for the high yielding Suzuki-Miyaura cross-couplings of aryl chlorides with aryl boronic acids using a palladium/imidazolium salt catalytic system is presented. The first examples of a palladium/imidazolium salt protocol for sp3-sp3 Suzuki-Miyaura couplings of alkyl halides are also disclosed. 相似文献
4.
Luigi Ambrosone Lucia Costantino Gerardino D'errico Vincenzo Vitagliano 《Journal of colloid and interface science》1997,190(2):286
The densities and viscosities of binary aqueous mixtures of poly(ethylenoxide)hexanols [C6H13(OCH2CH2)mOH, C6Em] (m= 3, 4, and 5) have been studied in the micellar composition range. For the same surfactants the self-diffusion coefficients in mixtures with heavy water have been determined by the spin-echo pulsed field gradient method. The volumetric data are interpreted by means of the phase separation model, and values of the CMC, volume change, and standard free energy change of micellization are obtained. From the viscosity data the hydration numbers of the surfactant hydrophilic head in the micellar state are computed; they are in agreement with those obtained from HDO self-diffusion data. The surfactant self-diffusion data are used to calculate the apparent micelle radius and the aggregation number. The micellization parameters obtained for the different surfactants are compared and discussed. 相似文献
5.
Mohamed R. Mahran Wafaa M. Abdou Maha D. Khidre 《Monatshefte für Chemie / Chemical Monthly》1990,121(1):51-58
Summary The reaction of furil (1) with trialkyl phosphites2 yielded caged phosphorane derivatives of types3a-c. Dry hydrogen chloride gas converted3a-c into the respectivea-hydroxyvinyl-phosphates8a-c which are equally produced by reacting furil with the appropriate dialkyl phosphite7. The reaction of furil with ylide-phosphoranes10 proceeded according to the Wittig reaction mechanism to give the respective ethylenes11a-c. The new compounds have been characterized by their spectroscopic data (IR, PMR,31P-NMR, MS) and elementary analyses.Dedicated to Prof. M. Sidky on the occasion of his 60th birthday 相似文献
6.
Summary A theoretical treatment is presented which considers differences between the composition of the mobile phase and solvents
that are incorporated into the bonded phase via preferential sorption. Equations are derived and used to analyze retention
data for various homologs chromatographed under reversed-phase conditions using alkyl bonded phases and combinations of water-methanol,
water-acetonitrile and watertetrahydrofuran as mobile phases. In the case of water-methanol the surface phase and bulk mobile
phase compositions are similar. However, significant differences in composition between the two phases are observed when binary
combinations of water-acetonitrile and water-tetrahydrofuran are used as the cluents. 相似文献
7.
The reaction of the tetramethylcyclopentadiene-silyl substituted derivative C5Me4(SiMe3)(SiMe2Cl) with MCl4 afforded the trichloro mono-tetramethylcyclopentadienyl complexes M(η5-C5Me4SiMe2Cl)Cl3 [M=Ti (1), Zr (2)] with selective elimination of SiMe3Cl. Compound 1 reacts with deoxygenated water in methylene chloride, with the evolution of HCl, to give the dinuclear titanium compound {Ti[μ-(η5-C5Me4SiMe2O-κO)]Cl2}2 (3), which was converted into the μ-oxo complex {Ti[μ-(η5-C5Me4SiMe2O-κO)]Cl}2(μ-O) (4) by a further hydrolysis reaction which occurred when a solution of 3 in toluene was refluxed for a long period of time in the air. Depending on the size of the alkyl ligand, reactions of the mononuclear compound 1 with an appropriate alkylating reagent rendered the peralkylated Ti(η5-C5Me4SiMe2R)R3 [R=Me (5), CH2Ph (6)] or partially alkylated {Ti[(η5-C5Me4SiMe2(CH2SiMe3)]Cl(CH2SiMe3)2} (7) compounds by a salt metathesis route. Attempts to synthesise a partially methylated or benzylated complex were unsuccessful. Treatment of the dinuclear compound 3 with four equivalents of MgClMe yielded the tetramethyl derivative {Ti[μ-(η5-C5Me4SiMe2O-κO)]Me2}2 (8), while the same reaction carried out with MgCl(CH2Ph) or Mg(CH2Ph)2·2THF gave the chloro-benzyl derivative {Ti[μ-(η5-C5Me4SiMe2O-κO)]Cl(CH2Ph)}2 (9) as an equimolar mixture of diastereomers, regardless of the molar ratio of the alkylating reagent used. All of the new compounds were characterised by elemental analysis and NMR spectroscopy. 相似文献
8.
四核钴羰基簇合物Co4(CO)8(μ-CO)2(μ4-PSR)2的合成和晶体结构 总被引:1,自引:0,他引:1
The title compounds Co4(CO)8(μ-CO)2 (μ4-PSR) [R=-CH3, -C2H5, -C(CH3)3,-(CHa)4CH3] were synthesized by the reaction of Co2(CO)8 with RSPCl2. They were characterized by IR, 1HNMR, elemental analysis. The crystal and molecular structure of Co4(Co)8(μ-CO)2 (μ4-PSC2H5) has been determined by single crystal diffraction method. Crystal data: monoclinic, space group P21 /c, with a=8-445(3), 6=8.562(3), c= 17.125(6)Å, β=104.26 (3)' 9 V=1200.1Å3, Z=2, Dc=1.937gcm-3. Its molecular structure contains an octahedral Co4P2 skeleton which consists of a rectangular four cobalt atoms core and the Co4 core is capped above and below by two quadruply bridging PSR ligands. 相似文献
9.
10.
Surface diffusion in reversed-phase liquid chromatography (RPLC) using silica gels bonded with C1 and C18 alkyl ligands of different densities was studied from the viewpoints of two extrathermodynamic relationships, i.e., enthalpy-entropy compensation (EEC) and linear free energy relationship (LFER). First, according to the four methods proposed by Krug et al., the values of surface diffusion coefficient (Ds) were analyzed to confirm that an actual EEC resulting from substantial physico-chemical effects takes place for surface diffusion. Then, it was also demonstrated that a LFER is observed between surface diffusion and the retention equilibrium. The establishment of EEC and LFER suggests a mechanistic similarity of molecular migration by surface diffusion, irrespective of the alkyl chain length and the densities of C1 and C18 ligands. Finally, a thermodynamic model for the LFER based on the real EEC was used to estimate Ds values under various RPLC conditions. The Ds values can be estimated with a mean square deviation of about 25–30%. The agreement between the Ds values estimated and those experimentally measured suggests that the total mass flux by surface diffusion consists of the two contributions due to C1 and C18 ligands and that the contribution of each ligand is proportional to the ligand density. 相似文献