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21.
The diacetylenic adducts, Fe2(CO)6{-EC(H) = C(C CMe)E} (E = E, E E; E, E = S, Se, Te) (1–8) have been obtained from the room temperature stirring of Fe2(CO)6(-EE) with HC CC CMe in methanol solvent containing sodium acetate. Compounds 1–8 have been characterized by IR and multinuclear NMR (1H, 13C, 77Se, and l25Te) spectroscopy. Trends in the chemical shifts of 77Se and 125Te NMR spectra of Fe2(CO)6{-EC(H) = C(C CMe)E} with a variation of EE are discussed. 相似文献
22.
23.
Rudolph A. Abramovitch Suchet S. Mathur Daniel W. Saunders Danny P. Vanderpool 《Tetrahedron letters》1980,21(8):705-708
Pyridinium -toluenesulfonylmethylide serves as a formyl anion equivalent and, in the presence of an alcohol, undergoes 1,4-addition to -substituted maleimides to give alkoxy- (or aryloxy)-methylene-succinimides. The protected aldehyde group can be liberated readily. 相似文献
24.
The ability of the back-fill and the host rock materials to take up radioisotopes like 241Am, 85,89Sr and 137Cs has been examined as a function of contact time, pH, amount of sorbent, sorbate concentration, and the presence of complementary cations. A batch technique using actual borehole water from the granite formation has been utilized. In general, the uptake of nuclides by bentonite is much higher than that with granite. The sorption order of nuclides on bentonite is Am>Cs>Sr. The presence of complementary cations, Na+, K+, Ca2+ and Mg2+ depresses the sorption of Cs and Sr on bentonite. The sorption data have been interpreted in terms of Freundlich and Langmuir isotherm equations. Utilizing the Langmuir isotherm equation, the monolayer capacity, V
m
,and the binding constant, K, have been evaluated. The change in free energy for the sorption of nuclides on bentonite has also been calculated. 相似文献
25.
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
26.
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
27.
28.
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
29.
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
30.
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