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991.
We report results of a systematic investigation of the energies of positive-ion and negative-ion states in alkan-1-ol molecules CnH2n+1 OH (n = 1–5) in low-energy electron impact experiments using a beam of nearly mono-energetic electrons. The measurements have been conducted in a crossed electron-beam/molecular-beam apparatus wherein positive ions are detected using a quadrupole mass spectrometer whereas unstable negative ions are observed as resonance structures in the electron transmission function. Theoretical calculations of anion and cation energies have been carried out using the semi-empirical HAM/3 technique. 相似文献
992.
B. P. Mathur L. E. Abbey E. M. Burgess T. F. Moran 《Journal of mass spectrometry : JMS》1980,15(6):312-316
The doubly charged ion mass spectra for 12 aliphatic nitriles (1–9 carbon atoms) have been obtained using an Hitachi RMU-7L double focusing mass spectrometer. These spectra show some characteristic features such as extensive loss of hydrogen and the grouping of ions in the spectra into n-1 groups where n is the number of carbon atoms in the molecule (n<6). There are no indications of HCN or CN loss in the doubly charged ion spectra of the monosubstituted nitriles. SCF calculations of the energy and structure of doubly charged ions in the propionitrile spectra have been carried out. 相似文献
993.
This paper reports the rotational spectrum and structure of the Ar2-H2S complex and its HDS and D2S isotopomers. The ground state structure has heavy-atom C2v symmetry with the two Ar atoms indistinguishable and H2S freely rotating as evinced by the fact that asymmetric top energy levels with Kp=odd levels are missing. The rotational constants for the parent isotopomer are: A=1733.115(1) MHz, B=1617.6160(5) MHz and C=830.2951(2) MHz. Unlike the Ar-H2S complex, the Ar2-H2S does not show an anomalous isotopic shift in rotational constants on deuterium substitution. However, the intermolecular potential is still quite floppy, leading to very different centrifugal distortion constants for the three isotopomers. The Ar-Ar and Ar-c.m.(H2S) distances are determined to be 3.820 A and 4.105 A, respectively. The A rotational constants for Ar2-H2S/HDS/D2S isotopomers are very close to each other and to the B constant of free Ar2, indicating that H2S does not contribute to the moment of inertia about the a-axis. Ab initio calculations at MP2 level with aug-cc-pVQZ basis set lead to an equilibrium C2v minimum structure with the Ar-Ar line perpendicular to the H-H line and the S away from Ar2. The centrifugal distortion constants, calculated using the ab initio force field, are in reasonable agreement with the experimental values. However, they do not show the variation observed for different isotopmers. The binding energy of Ar2-H2S has been determined to be 507 cm-1(6.0 kJ mol-1) by CBS extrapolation after correcting for basis set superposition error. Potential energy scans point out that the barrier for internal rotation of H2S about its b axis is only 10 cm-1 and it is below the zero point energy (13.5 cm-1) in this torsional degree of freedom. Internal rotation of H2S about its a- and c-axes also have small barriers of about 50 cm-1 only, suggesting that H2S is extremely floppy within the complex. 相似文献
994.
Summary Copper(II) complexes with a tridentate chelating ligand within the general 2N, X (X = O or S) donor class, containing abis(benzimidazolyl) donor set, were prepared and characterized. X-band e.p.r. spectra of the complexes indicateg
>g
and the largeg
and lowA
have been interpreted in terms of a distorted basal plane. Superimposed on theg
component are five SHF lines withA
N = 16±2G, supporting the interaction of two nitrogen atoms with the copper nucleus. Thus, the basal plane of the complex comprises 2N atoms, with the ligand hetero atom being axially coordinated. 相似文献
995.
New N-octylated benzimidazole-based diamide ligands N,N'-bis(N-octylbenzimidazolyl-2-ethyl)hexanediamide (O-ABHA), possessing a chiral center, and N,N'-bis(N-octylbenzimidazolyl-2-methyl)hexanediamide (O-GBHA) have been synthesized and utilized to prepare Cu(II) complexes of general composition [Cu(L)X]X, where L = O-ABHA or O-GBHA and X = Cl(-) or NO(3)(-) . The X-ray structure of one of the complexes, [Cu(O-GBHA)NO(3)]NO(3), has been obtained. The Cu(II) ion is found to possess a distorted octahedral geometry with a highly unsymmetrical bidentate nitrate group. The N(2)O(2) equatorial plane comprises an amide carbonyl O, a nitrate O, and the two benzimidazole imine N atoms while another amide carbonyl O and nitrate O take up the axial positions. The complexes carry out the oxidation of aromatic alcohols to aldehydes in the presence of cumenyl hydroperoxide at 40-45 degrees C and act as catalyst with turnovers varying between 13- and 27-fold. The percentage yields of the respective products have been obtained which vary from 32% to 65% with respect to the catalyst turnover. 相似文献
996.
Both liquid and solid hexahydrocostunolides obtained by the pressure hydrogenation of costunolide (V) and solid dihydrocostunolide (VI) respectively, give the same optically active hexahydrogermacol (IIIa), when subjected to controlled reduction with LiAlH4, followed by Huang-Minlon reduction. The alcohol (IIIa) on oxidation with chromic oxide gives optically active hexahydrogermacrone (IIa). Dehydration of IIIa with KHSO4 followed by catalytic hydrogenation gives the optically inactive saturated hydrocarbon, germacrane (IV). Since the total synthesis of solid dihydrocostunolide (VI) has already been achieved the preparation of IIIa, IIa and IV from VI constitutes a total synthesis of the above three compounds. 相似文献
997.
Pankaj Hazarika Diganta Kalita Swapnalee Sarmah Ruli Borah Nashreen S. Islam 《Polyhedron》2006,25(18):3501-3508
Two new dinuclear oxo-bridged peroxo complexes of tungsten with coordinated dipeptides of the type, Na2[W2O3(O2)4(glycyl-glycine)2] · 3H2O (1) and Na2[W2O3(O2)4(glycyl-leucine)2] · 3H2O (2) have been synthesized from the reaction of H2WO4, 30% H2O2 and the respective dipeptide at pH ca. 2.5. Synthesis of the compounds, in addition to pH, is sensitive to reaction temperature and concentrations of the components. The compounds were characterized by elemental analysis, spectral and physico-chemical methods including thermal analysis. In the dimeric complexes the two W(VI) centres with edge bound peroxo groups are bridged by an oxo group. The dipeptides occurring as zwitterions bind the metal centers through O (carboxylate) atoms leading to hepta co-ordination around each W(VI). Thermal stability of the compounds as well as their stability in solution were determined. The compounds are highly stable toward decomposition in solutions of acidic as well as physiological pH. These compounds, besides another similar dimeric compound Na2[W2O3(O2)4(cystine)] · 4H2O (3) efficiently oxidized bromide to a bromination competent intermediate in phosphate buffer at physiological pH, a reaction in which only two of the peroxide groups of the complex species were found to be active. The complexes could also mediate bromination of organic substrate in aqueous-organic media. 相似文献
998.
A high yield synthesis of the carbonyl dithiocarbamato derivative Fe(CO)2(η2-S2CNMe2)2 and Fe(η2-S2CNMe2)2 by photolysis with visible light of solutions containing Fe2(CO)9 or Fe3(CO)12 and [(η5-C5H5)(CO)3W(η1-SCSNMe2)] is reported. 相似文献
999.
Membranes of dibenzo-24-crown-8 (I) as an ion active material in poly(vinylchloride) (PVC) based matrix have been tried for zinc(II)-selective sensors. The effect of anion excluder, sodium tetraphenylborate (NaTPB) and plasticizers, tris(2-ethylhexyl)phosphate (TEP), tributylphosphate (TBP), dibutylphthalate (DBP), dibutyl(butyl)phosphonate (DBBP), 1-chloronaphthalene (CN) and dioctylphthalate (DOP) on the performance of the membrane electrodes has also been studied. It was observed that the membrane having the composition (I): PVC:NaTPB:DOP in the ratio 10:200:2:100 gave the best results with a wide working concentration range of 9.2 × 10−5 to 1.0 × 10−1 M, Nernstian slope of 29.0 ± 0. 5 mV/decade of activity, fast response time of 12 s and good selectivity over a number of mono-, bi-, and trivalent cations. The sensor works well in a pH range 4.8-6.2 and can be employed for the estimation of zinc ions in partially non-aqueous medium having up to 10% (v/v) methanol, ethanol or acetone content. The practical utility of the sensor has been demonstrated by using it successfully as an indicator electrode in the potentiometric titration of Zn2+ with EDTA and also for the determination of Zn2+ in a real sample analysis of wastewater. 相似文献
1000.
Role of Cyanex-272 as an extractant for uranium in the determination of rare earths by ICP-AES 总被引:2,自引:0,他引:2
B. Rajeswari B. A. Dhawale T. R. Bangia J. N. Mathur A. G. Page 《Journal of Radioanalytical and Nuclear Chemistry》2002,254(3):479-483
A chemical separation procedure has been developed for the extraction of uranium from some of the crucially important rare earths using a novel extractant viz. Cyanex-272 (2,4,4-trimethyl pentyl phosphinic acid). The near total extraction of uranium and quantitative separation of rare earth elements has been validated using inductively coupled argon plasma - atomic emission spectrometry (ICP-AES). The recovery of some of the representative elements has been confirmed by radioactive tracer studies. The back extraction of uranium from the organic phase was carried out using a solution of 0.5M Na2CO3 which resulted in a near total recovery of uranium into the organic phase. These studies have enabled determination of sub ppm amounts of the analyte elements with a precision of 5% RSD utilizing prior chemical separation of rare earths from 1 g uranium samples in just three extractions with Cyanex-272. 相似文献