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81.
Albrecht C Bode M Pérez JM Daniels J Schnakenburg G Streubel R 《Dalton transactions (Cambridge, England : 2003)》2011,40(11):2654-2665
Synthesis of the first oxaphosphirane chromium(0) and molybdenum(0) complexes of the type [{(R(1)PCH(R(2))-O}M(CO)(5)] (R(1) = C(5)Me(5)) (8a-e, 15a-e) and (R(1) = CH(SiMe(3))(2)) (9a-e, 16a-e) via reaction of dichloro(organo)- (1, 2, 10, 11) and chloro(organo)phosphane complexes (3,4,12) with lithium bases and aldehydes 7a-e is reported. Furthermore, bicyclic 1,3-oxaphospholane complexes 17 and 18 have been obtained via O-protonation of oxaphosphirane complexes 8a and 15a with HCl. All complexes were characterized by NMR, IR spectroscopic, mass spectrometric investigations and, in addition, single-crystal X-ray structures of complexes 8a-e, 9a,c, 15a,b,e, 16a-c, 17, 18 are presented and discussed. 相似文献
82.
A simple and sensitive method was developed using hydrophilic interaction liquid chromatography coupled to tandem mass spectrometry
for determination of monosaccharides liberated from marine polysaccharides by acidic hydrolysis. Optimal separation of diastereomeric
monosaccharides including hexoses, pentoses, and deoxyhexoses was achieved using an aminopropyl bonded column with mobile
phase containing ternary solvents (acetonitrile/methanol/water) in conjunction with MS/MS in SRM mode. Mechanisms for fragmentation
of deprotonated monosaccharides with regard to cross-ring cleavage were proposed. Matrix effects from coeluting interferences
were observed and isotopic-labeled internal standard was used to compensate for the signal suppression. The method demonstrated
excellent instrumental limits of detection (LOD), ranging from 0.7 to 4.2 pg. Method LODs range from 0.9 to 5.1 nM. The proposed
method was applied to the analysis of polysaccharides in seawater collected from the open leads of the central Arctic Ocean
in the summer of 2008. 相似文献
83.
Flores JA Andino JG Tsvetkov NP Pink M Wolfe RJ Head AR Lichtenberger DL Massa J Caulton KG 《Inorganic chemistry》2011,50(17):8121-8131
The ligand class 2,2'-pyridylpyrrolide is surveyed, both for its structural features and its electronic structure, when attached to monovalent K, Cu, Ag, Au, and Rh. The influence of pyrrolide ring substituents is studied, as well as the question of push/pull interaction between the pyridyl and pyrrolide halves. The π donor ability of the pyrrolide is found to be less than that of an analogous phenyl. However, in contrast to the phenyl analog, the HOMO is pyrrolide π in character for pyridylpyrrolide complexes of copper and rhodium, while it is conventionally metal localized for planar, d(8) rhodium pyridylphenyl. Monovalent three-coordinate copper complexes show great deviations from Y-shaped toward T-shaped structures, including cases where the pyridyl ligand bonds only weakly. 相似文献
84.
Rajca A Shiraishi K Boratyński PJ Pink M Miyasaka M Rajca S 《The Journal of organic chemistry》2011,76(20):8447-8457
Oxidation of diaryldiamine 2, a tetrahydrodiazapentacene derivative, provides diarylnitroxide diradical 1 accompanied by an intermediate nitroxide monoradical and a multitude of isolable diamagnetic products. DFT-computed tensors for EPR spectra and paramagnetic (1)H NMR isotropic shifts for nitroxide diradical 1 show good agreement with the experimental EPR spectra in rigid matrices and paramagnetic (1)H NMR spectra in solution, respectively. Examination of the diamagnetic products elucidates their formation via distinct pathways involving C-O bond-forming reactions, including Baeyer-Villiger-type oxidations. An unusual diiminoketone structure and two spirocyclic structures of the predominant diamagnetic products are confirmed by either X-ray crystallography or correlations between DFT-computed and experimental spectroscopic data such as (1)H, (13)C, and (15)N NMR chemical shifts and electronic absorption spectra. 相似文献
85.
An intimate interplay of O-H···O/C-H···F hydrogen bonds and π-π stacking interactions allows a phenyleneethynylene-based dendritic molecule to fold and self-assemble into two distinctively different molecular crystals as pseudopolymorphs. 相似文献
86.
Szabó L Herman K Leopold N Buzumurgă C Chiş V 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,79(1):226-231
The surface-enhanced Raman scattering (SERS) spectra of Eriochrome Black T (EBT) and its Cu(II), Fe(III), Mn(II) and Pb(II) complexes were recorded using a hydroxylamine reduced silver colloid. Molecular geometry optimization, molecular electrostatic potential (MEP) distribution and vibrational frequencies calculation were performed at B3LYP/6-31G(d) level of theory for the EBT molecule and its Cu(EBT), Fe(EBT) and Mn(EBT) metal complexes. Differentiation between EBT complexes of Cu(II), Fe(III), Mn(II) and Pb(II) is shown by the SERS spectral features of each complex. 相似文献
87.
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90.
Leopold Halpern 《General Relativity and Gravitation》1977,8(8):623-630
A gravitational law is proposed on a De Sitter covariant space. Dirac's De Sitter covariant spinning electron equation is generalized to the presence of gravitational fields. The resulting equation differs from the generally covariant Dirac equation by a mass renormalization. The last result is a generalization of that of Gürsey and Lee [2] in case of the homogenous De Sitter metric, and it gives a wider outlook on the significance of this result from the point of view of gauge theory.Dedicated to Achille Papapetrou on the occasion of his retirement. 相似文献