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11.
Mani Ganesan 《Journal of organometallic chemistry》2005,690(23):5145-5149
Treatment of [Cp*CrCl(C6F5)]2 with BnMgCl (Bn = benzyl) in Et2O/THF affords [Cp*Cr(C6F5)(Bn)(THF)] (1) which has been isolated in 72% yield. This compound whose magnetic moment is equal to of 4.037 μB has been characterized by NMR and single crystal X-ray analysis. Compound 1 alone does not polymerize ethylene when dissolved in toluene. However, addition of excess AlEt3 to a solution of 1 in toluene leads to a catalytically active system which readily oligomerizes ethylene under standard conditions. Oligomerization experiments carried out with [1] = 10−3 M and [AlEt3] = 9 × 10−2 M for 15 min lead to the production of ethylene oligomers with an activity of 280 kg mol Cr−1 h−1. The experimental molecular weight distribution observed at intermediate times during the reaction is satisfactorily accounted for by the Poisson distribution formula, which is indicative of a living polymerization system. These observations are in agreement with a catalytic cycle in which the growing alkyl chain is transferred from chromium to aluminum via a bimetallic complex in which the chromium and aluminum centers are bridged by an alkyl group and the growing polymer chain. 相似文献
12.
Parmeswaran D Pushpan SK Srinivasan A Ravi Kumar M Chandrashekar TK Ganesan S 《Photochemistry and photobiology》2003,78(5):487-495
The core modification of expanded porphyrins has been proved to have better photochemical properties, which are favorable for photodynamic therapy (PDT) applications. In this context, this study was aimed to investigate the in vitro and in vivo photodynamic activity of one such core-modified expanded porphyrin, namely, ammonium salt of 5,10,15,20-tetrakis-(meso-p-sulfonato phenyl)-25,27,29-trithia sapphyrin. For the in vitro studies, human erythrocytes were used as a membrane semimodel system to investigate the partitioning ability and drug-uptake characteristics. The partition studies on the membrane semimodel system revealed that maximum partitioning occurs at 12 microgm/mL concentration, and from the drug-uptake studies it is observed that maximum amount of the sensitizer is bound to the erythrocyte membranes during a 45 min incubation period. Photohemolysis studies at different concentrations of the sensitizer and exposure time showed maximum damage at 5 microgm/mL and 30 min exposure time. In vivo studies were performed on 7,12-dimethylbenz(a)nthracene-induced superficial squamous cell carcinoma on mouse skin. The sensitizer at a concentration of 2.5% in 2.0% dimethyl sulfoxide was applied topically on the tumor spot. After 1 h incubation the tumor spot was exposed to laser irradiation from Nd-YAG laser at its second harmonic wavelength of 532 nm. The photodynamic efficacy was estimated by tumor volume measurements at regular intervals after the treatment. One month after PDT exposure a 3.9-fold decrease in the tumor volume was observed with respect to the tumor volume before treatment. The treatment efficacy was further confirmed by histological and fluorescence spectroscopic evaluations of the tissue biopsy sample from the treated area. The results of our study suggest that the ammonium salt of 5,10,15,20-tetrakis-(meso-p-sulfonato phenyl)-25,27,29-trithia sapphyrin may find possible applications in the new modality of cancer treatment. 相似文献
13.
D. Indumathi M. V. N. Murthy V. Ravindran 《Zeitschrift fur Physik C Particles and Fields》1992,56(3):427-436
Following recent interest in the subject of polarisation phenomena, we discuss the cross-sections and polarisation asymmetry in 2-jet production in polarised proton-polarised proton (
) scattering. We set up a complete set of parametrisations for the proton spin-dependent parton densities and use them to demonstrate that this cross-section is dominated by gluonic terms. Hence, a measurement of the asymmetry in such processes will provide information on the gluon spin-dependent density. We further show that a factorisation of the hadronic cross-section a la Combridge and Maxwell's work in unpolarised 2-jet production also applies to the spin-dependent case. Hence, the cross-section can be written in terms of a genericpolarised parton density, which can then be measured in the process. 相似文献
14.
A hydrothermal reaction of a mixture of ZnCO3, phosphoric acid, 1, 10‐phenanthroline in H2O gave rise to large plates of a new zinc phosphate, [(C12H8N2Zn)2(HPO4)(H2PO4)2], I . The structure consists of ZnO3N2 distorted trigonal‐bipyramidal and PO4 tetrahedral units linked through their vertices to give rise to a zero‐dimensional molecular solid (monomer). The structure of the monomer appears to be similar to the secondary building unit (SBU) 4 = 1, commonly found in many fibrous zeolites. To our knowledge, this is the first time this building unit has been isolated. The structure, with a unique composition, is stabilized by hydrogen bond interactions between the terminal —OH groups forms a one‐dimensional molecular wire and also by strong π…π interactions between the 1, 10‐phenanthroline units. Photoluminescence studies show that there is a ligand‐to‐metal charge transfer (LMCT). Crystal data: orthorhombic, space group = Fdd2 (no. 43), a = 40.4669(1), b = 7.4733(2), c = 17.4425(5)Å, V = 5274.9(2)Å3, Z = 8. 相似文献
15.
The triply bonded dirhenium(II) synthons Re(2)X(4)(mu-dppm)(2) (X = Cl, Br; dppm = Ph(2)PCH(2)PPh(2)) react with acetylene at room temperature in CH(2)Cl(2) and acetone to afford the bis(acetylene) complexes Re(2)X(4)(mu-dppm)(2)(mu:eta(2),eta(2)-HCCH)(eta(2)-HCCH) (X = Cl (3), Br(4)). Compound 3 has been derivatized by reaction with RNC ligands in the presence of TlPF(6) to give unsymmetrical complexes of the type [Re(2)Cl(3)(mu-dppm)(2)(mu:eta(2),eta(2)-HCCH)(eta(2)-HCCH)(CNR)]PF(6) (R = Xyl (5), Mes (6), t-Bu (7)), in which the RCN ligand has displaced the chloride ligand cis to the eta(2)-HCCH ligand. The reaction of 3 with an additional 1 equiv of acetylene in the presence of TlPF(6) gives the symmetrical all-cis isomer of [Re(2)Cl(3)(mu-dppm)(2)(mu:eta(2),eta(2)-HCCH)(eta(2)-HCCH)(2)]PF(6) (8). The two terminal eta(2)-HCCH ligands in 8 are very labile and can be displaced by CO and XylNC to give the complexes [Re(2)Cl(3)(mu-dppm)(2)(mu:eta(2),eta(2)-HCCH)(L)(2)]Y (L = CO when Y = PF(6) (9); L = CO when Y = (PF(6))(0.5)/(H(2)PO(4))(0.5) (10); L = XylNC when Y = PF(6) (11)). These substitution reactions proceed with retention of the all-cis stereochemistry. Single-crystal X-ray structure determinations have been carried out on complexes 3, 5, 8, 10, and 11. In no instance have we found that the acetylene ligands undergo reductive coupling reactions. 相似文献
16.
Manimaran Kumar Murugesan Subban Ragavendran Chinnasamy Balasubramani Govindasamy Natarajan Devarajan Ganesan Abirami Seedevi Palaniappan 《Journal of Cluster Science》2021,32(5):1229-1240
Journal of Cluster Science - The titanium dioxide nanoparticles (TiO2NPs) were synthesized by the aqueous extract from P. djamor. The UV–Vis spectrum of TiO2NPs showed maximum absorption at... 相似文献
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19.
Manikandan Chitrarasu Govindaraj Senthilnathan Ganesan Kilivelu 《Journal of heterocyclic chemistry》2021,58(9):1749-1754
We have prepared substituted flexible dimeric pyridinium bromide using conventional and greener approach. Solvent-free solid phase (greener) approach is superior than the conventional owing to nontoxic, easy workup procedure, and 20 times lesser reaction time. Toxic organic solvents and column chromatography are avoided. Aldol condensation reaction is studied with various substituted aromatic aldehyde and compared with available recent literatures. Synthesized substituted flexible dimeric pyridinium salts acted as potential catalysts because of their better performance even in low concentration, recyclability, and activation of two molecules of aldehydes at the same time for aldol condensation reaction. 相似文献
20.
Rimpi Dawar R. Pankajavalli J. Joseph S. Anthonysamy V. Ganesan 《Journal of Thermal Analysis and Calorimetry》2013,112(1):95-102
The standard Gibbs energy of formation of chromium tellurate, Cr2TeO6 was determined from the vapour pressure measurement of TeO2(g) over the phase mixture Cr2TeO6(s) + Cr2O3(s) in the temperature range 1,183–1,293 K. A thermogravimetry (TG)-based transpiration technique was used for the vapour pressure measurement. This technique was validated by measuring the vapour pressure of CdCl2(g) over CdCl2(s). The temperature dependence of the vapour pressure of CdCl2(g) could be represented as logp (Pa) (±0.02) = 12.06 ? 8616.3/T (K) (734 ? 823 K). A ‘third-law’ analysis of the vapour pressure data yielded a mean value of 185.1 ± 0.4 kJ mol?1 for the enthalpy of sublimation of CdCl2(s). The temperature dependence of vapour pressure of TeO2(g) generated by the incongruent vapourisation reaction, $ {\text{Cr}}_{ 2} {\text{TeO}}_{ 6} (\rm s) \to {\text{Cr}}_{ 2} {\text{O}}_{ 3} (\rm s) + {\text{TeO}}_{ 2} (\rm g) + 1/2\,{\text{O}}_{ 2} (\rm g) $ could be represented as logp (Pa) (±0.04) = 18.57 – 21,199/T (K) (1,183 – 1,293 K). The temperature dependence of the Gibbs energy of formation of Cr2TeO6 could be expressed as $ \{ \Updelta G_{\text{f}}^{ \circ } ({\text{Cr}}_{ 2} {\text{TeO}}_{ 6} ,{\text{ s}}){\text{ (kJ}}\,{\text{mol}}^{ - 1} )\pm 4. 0 {\text{\} = }} - 1 6 2 5. 6 { \,+\, 0} . 5 3 3 6\,T({\text{K}}) \, (1{,}183 - 1{,}293\,{\text{K}}). $ A drop calorimeter was used for measuring the enthalpy increments of Cr2TeO6 in the temperature range 373–973 K. Thermodynamic functions viz., heat capacity, entropy and Gibbs energy functions of Cr2TeO6 were derived from the experimentally measured enthalpy increment values. $ \Updelta H_{{{\text{f}},298\,{\text{K}}}}^{ \circ } ({\text{Cr}}_{ 2} {\text{TeO}}_{ 6} ) $ was found to be ?1636.9 ± 0.8 kJ mol?1. 相似文献