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31.
1-Amino-3-methoxypropane (3MPA) and 2-dimethylaminoethanol (DMAE) are potential volatile amines for boiler water treatment and were investigated for their complexation behaviour with copper. Their pKb values were 3.67 and 4.52 at 25°C and they formed coloured complexes with absorption in the region of 644 and 510 nm, respectively. In the pH range 10–11, the Cu-3MPA complex exhibited stepwise reduction and [Cu(3MPA)2]+ was identified, with a stability constant of 109.52. In the pH range 8–10.5, the Cu-DMAE complex exhibited 2e? reduction and the species [Cu(DMAE)2(OH)2] was identified, with a stability constant of 1020.39. A correlation between visible and ESR spectra and reduction behaviour was established. 相似文献
32.
The dipole moments μab of some forty complexes between substituted phenols and substituted pyridines were determined, using the Onsager relation. The dipole increment Δμ, vector difference between μab and the dipole moments μa and μb of the components, show a coherent evolution with the pKa of the donor and of the acceptor and with the complexation enthalpy, when such orientations of the molecules which correspond to a hydrogen bond between the O-H group of the phenol and the lone pair of electrons of the nitrogen atom of the base are chosen. This evolution with respect to the ΔpKa is given by a unique curve for all the complexes. This shows that the difference in pKa between the donor and the acceptor is the main factor determining Δμ for these complexes. This curve presents a sigmoidal aspect in agreement with a model assuming a tautomeric equilibrium between two forms of the hydrogen bond: A-H·B ? A?·H+-B. The corresponding equilibrium constant Ks was computed for the complexes lying in the transition region and obeys the linear relation, log Ks = 0.7pKa-2.25. The data also permit the evaluation of the angle θa between the O-H direction and the dipole moment of the 3,4-dinitrophenol. This angle is of the order of magnitude of 70°, showing the presence of appreciable amounts of different rotamers around the C-O direction in the complexes composed of this acid with pyridines. 相似文献
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34.
Togiti Uday Kumar Yadagiri Thigulla Krishnan Rangan Anupam Bhattacharya 《Journal of heterocyclic chemistry》2019,56(4):1283-1290
A metal‐free approach for the synthesis of 2‐acylpyrroles is reported in this paper. Synthesis of the target molecule started from chalcones and was carried out in two steps. Initial step involved the conversion of chalcones to corresponding 4‐substituted‐3‐acylpyrroles by reaction with TosMIC. In the subsequent step, target molecules were obtained in modest to good yields by polyphosphoric acid‐mediated acyl rearrangement of 3‐acylpyrroles to their 2‐acyl congeners. The crucial final step was amenable to diverse substitutions on pyrrole ring. Preliminary experiment for the determination of mechanism indicated the involvement of acylium ion. 相似文献
35.
Abstract Interest in the intensity of lanthanide f?f spectra have begun nearly forty years ago, but most of the work was done after the publication of the theory of lanthanide intensity by Judd1 and Ofelt2 independently in 1962. Since then a number of lanthanide complexes having O-, N- or mixed donor ligands have been studied for the one reason or the other. Various β-diketone chelates were studied3–7 for the reason that they proved to be good lasing materials. The present communication extends this study further to fluorinated β-diketone chelates of Pr3+ and Nd3+ which gives useful information regarding interelectronic repulsion, spin-orbit interaction, nephelauxetic effect and bonding in these chelates. 相似文献
36.
Jan-Christoph Eichler Robert A. Skutnik Anupam Sengupta Marco G. Mazza Martin Schoen 《Molecular physics》2019,117(23-24):3715-3733
Anisotropic fluids (e.g. liquid crystals) offer a remarkable promise as optofluidic materials owing to the directional, tunable, and coupled interactions between the material, flow, and the optical fields. Here we present a comprehensive in silico treatment of this anisotropic interaction by performing nonequilibrium molecular dynamics simulations. We quantify the response of a nematic liquid crystal (NLC) undergoing a Poiseuille flow in the Stokes regime, while being illuminated by a laser beam incident perpendicular to the flow direction. We adopt a minimalistic model to capture the interactions, accounting for two features: first, the laser heats up the NLC locally; and second, the laser polarises the NLC and exerts an optical torque that tends to reorient molecules of the nematic phase. Because of this reorientation the liquid crystal exhibits small regions of biaxiality, where the nematic director is one symmetry axis and the axis of rotation for the reorientation of the molecules is the other one. We find that the relative strength of the viscous and the optical torques mediates the flow-induced response of the biaxial regions, thereby tuning the emergence, shape and location of the regions of enhanced biaxiality. The mechanistic framework presented here promises experimentally tractable routes toward novel optofluidic applications based on material-flow-light interactions. 相似文献
37.
38.
Anupam Bhim Prof. Jean-Pascal Sutter Prof. Jagannatha Gopalakrishnan Prof. Srinivasan Natarajan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(6):1995-2008
The stuffed tridymite structure Ba(Zn/Co)1−xSi1−xM2xO4 (M=Al3+ and Fe3+) is explored for the possible multiferroic behavior and to develop new inorganic colored materials. The compounds were synthesized by employing conventional solid-state chemistry methods in the temperature range 1100–1175 °C for 24 h. The powder X-ray diffraction (PXRD) and Rietveld refinement studies indicate that the compounds stabilize in the P63 space group (no. 173). The refinement results were also rationalized by employing Raman spectroscopic studies. The compounds were found to be second harmonic generation (SHG) active and show weak ferroelectric behavior. The co-substitution of Co2+ and Fe3+ in the structure gives rise to a weak ferromagnetic behavior to the compound, BaCo0.75Si0.75Fe0.5O4, making it a multiferroic material. The optical studies on the prepared compounds exhibited blue color (Co2+ in Td geometry), purple color (Ni2+ in Td geometry), and simultaneous substitution of Co2+ and Fe3+ gives rise to blue-green color owing to metal-to-metal charge transfer (MMCT) effect. 相似文献
39.
Pradep Mathur Anjan K. Bhunia Ch. Srinivasu Shaikh Md. Mobin 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4-5):899-901
Group 16 elements serve as useful bridging and stabilising single atom ligands in mixed-metal carbonyl complexes and impart unusual reactivity on coordinated acetylenic moieties. Reactions of [Fe 3 (CO) 9 (μ 3 -E) 2 ] (E = S, or Se) with mononuclear acetylide complexes, [CpM(CO)_3-x(CCR)] (M = Mo or W, x = 0, R = Ph; M = Fe, x = 1, R = Ph or ferrocenyl) under facile conditions yield complexes featuring acetylide coupling, acetylide-flip and formation of oxo and acetylide-bridged complexes. In presence of free acetylenes, unusual ligand systems arising from C─S bond formation are observed and under certain conditions, formation of quinones by coupling of acetylenes with carbon monoxide is facilitated. 相似文献
40.
Michael Veith Charu Mathur Volker Hugh 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):489-492
The synthesis of the new heteroleptic heterotrimetallic cluster, [(C5H5)Sn(μ-OBut)2Ge(OBut)Mo(CO)5] (1) has been achieved by a thermally induced CO substitution of the transition metal derivative, Mo(CO)6, by the basic germanium atom of the cyclopentadienyl heterobimetallic alkoxide, [(C5H5)Sn(μ-OBut)2Ge(OBut)]. The microanalysis, molecular weight (monomer in benzene), IR and multinuclear NMR data and X-ray diffraction study is consistent with the formulation of 1. The Sn atom has a trigonal pyramidal coordination environment formed by a aysmmterically π-bonded terminal C5H5 ring and two symmetrically bridged tert-butoxy groups. The four-coordinate Ge atom lies at the centre of a distorted tetrahedron and is terminally attached to a tert-butoxy group and a Mo(CO)55? fragment. 相似文献