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41.
Inhaltsübersicht. Triorganoantimon- und Triorganobismutdicarboxylate R3M[O2C(CH2)n-2-C4H3X]2 (M = Sb, R = CH3, C6H11, C6H5, 4-CH3OC6H4; M = Bi, R = C6H5, 4-CH3C6H4; n = 0, X = O, S, NH, NCH3. M = Sb, R = CH3, C6H5; M = Bi, R = C6H5; n = 1, X = O, S. M = Sb, R = C6H11, n = 1, X = S; R = 4-FC6H4, n = 0, X = O, S, NCH3; R = 2,4,6-(CH3)3C6H2, n = 0, X = O, S, NH) wurden durch Reaktionen von R3Sb(OH)2 (R = CH3, C6H11, 2,4,6-(CH3)3C6H2), R3SbO (R = C6H5, 4-CH3OC6H4, 4-FC6H4) bzw. R3BiCO3 mit den entsprechenden fünfgliedrigen heterocyclischen Carbonsäuren 2-C4H3X(CH2)nCOOH dargestellt. Auf der Basis schwingungsspektroskopischer Daten wird für alle Verbindungen eine trigonal bipyramidale Umgebung vom M (zwei O-Atome von einzähnigen Carboxylatliganden in den apikalen, drei C-Atome von R in den äquatorialen Positionen) vorgeschlagen, ferner eine schwache Wechselwirkung zwischen O(=C) jeder Carboxylatgruppe und M. Die Kristallstrukturbestimmung von (C6H5)3Sb(O2C–2-C4H3S)3 stützt diesen Vorschlag. Die Verbindung kristallisiert triklin [Raumgruppe P$1; a = 891,8(14), b = 1058,2(12), c = 1435,6(9) pm, α = 68,53(8), β = 85,47(9), γ = 85,99(11)°; Z = 2; d(ber.) = 1,607 Mg m–3; V(Zelle) = 1255,6 Å3; Strukturbestimmung anhand von 3947 unabhängigen Reflexen (Fo > 3σ(F2o)), R(ungewichtet) = 0,037]. Sb bindet drei C6H5-Gruppen in der äquatorialen Ebene [mittlerer Abstand Sb–C: 211,1(5)pm] und zwei einzähnige Carboxylatliganden in den apikalen Positionen einer verzerrten trigonalen Bipyramide [mittlerer Abstand Sb–O: 212,0(4) pm]. Aus den relativ kurzen Sb – O(=C)-Abständen [274,4(4) und 294,9(4) pm] und aus der Aufweitung des dem O(=C)-Atom nächsten äquatorialen C–Sb–C-Winkels auf 145,9(2)° [andere C-Sb-C-Winkel: 104,4(2), 109,5(2)°] wird auf schwache Sb–O(=C)-Koordination geschlossen. Schließlich wird eine Korrelation zwischen dem (+, –)I-Effekt des Organoliganden R an M (M = Sb, Bi) und der Stärke der M–O(=C)-Koordination in den Dicarboxylaten R3M[O2C(CH2)n–2-C4H3X]2 vorgeschlagen. Triorganoanümony and Triorganobismuth Derivatives of Carbonic Acids of Five-membered Heterocycles. Crystal and Molecular Structure of (C6H5)3Sb(O2C–2-C4H3S)2 Triorganoantimony- and triorganobismuth dicarboxylates R3M[O2C(CH2)n–2-C4H3X]2 (M = Sb, R = CH3, C6H11, C6H5, 4-CH3OC6H4; M = Bi, R = C6H5, 4-CH3C6H4; n = 0, X = O, S, NH, NCH3. M = Sb, R = CH3, C6H5; M = Bi, R = C6H5; n = 1, X = O, S. M = Sb, R = C6H11, n = 1, X = S; R = 4-FC6H4, n = 0, X = O, S, NCH3; R = 2,4,6-(CH3)3C6H2, n = 0, X = O, S, NH) have been prepared by reaction of R3Sb(OH)2 (R = CH3, C6H11; 2,4,6-(CH3)3C6H2), R3SbO (R = C6H5, 4-CH3OC6H4, 4-FC6H4) or R3BiCO3 with the appropriate five-membered heterocyclic carboxylic acid. From vibrational data for all compounds a trigonal bipyramidal environment around M (two O atoms of unidendate carboxylate ligands in apical, three C atoms (of R) in equatorial positions) is proposed and also an additional weak interaction of O(=C) of each carboxylate group and M. The crystal structure determination of Ph3Sb(O2C–2-C4H3S)2 gives additional prove to this proposal. It crystallizes triclinic [space group P$1; a = 891.8(14), b = 1058.2(12), c = 1435.6(9) pm, α = 68.53(8), β = 85.47(9), γ = 85.99(11)°; Z = 2; d(calc.) = 1.607 Mg m–3; Vcell = 1255.6 Å3; structure determination from 3 947 independent reflexions (Fo > 3σ(F2o)), R(unweighted) = 0.037]. Sb is bonding to three C6H5 groups in the equatorial plane [mean distance Sb–C: 211.1(5) pm] and two unidentate carboxylate ligands in the apical positions of a distorted trigonal bipyramid [mean distance Sb–O: 212.0(4) pm]. From the relatively short Sb–O(=C) distances [274.4(4) and 294.9(4) pm] and from the enlarged value of the equatorial C–Sb–C angle next to the O(=C) atom [145.9(2)°; other C–Sb–C angles: 104.4(2), 109.5(2)°] additional weak Sb–O(=C) coordination is inferred. Finally a correlation between the (+, –) I-effect of the organic ligands It at M and the strength of the M–O = C interaction is suggested. 相似文献
42.
John M. Kane Christopher R. Dalton Michael A. Staeger Edward W. Huber 《Journal of heterocyclic chemistry》1995,32(1):183-187
Several 1,2,4-triazole derivatives containing a 2-fluorophenyl substituent at either the 3- or 5-position and a methyl group at the 4-position were synthesized. These derivatives exhibit long-range 19F-1H and 19F-13C through-space coupling in their 1H and 13C nmr spectra between the fluorine and the 4-methyl group. The close spatial proximity of these nuclei was confirmed by X-ray analysis and by fluorine irradiated proton observe ({19F}-1H) NOE difference spectroscopy. 相似文献
43.
Ansgar Schäfer Christian Huber Jürgen Gauss Reinhart Ahlrichs 《Theoretical chemistry accounts》1993,87(1-2):29-40
Summary Experimentally known copper selenium clusters show extraordinary geometrical features, especially short Cu-Cu distances. We report the first theoretical investigation of Cu2Se and Cu4Se2. Various quantum chemical methods (SCF, MP2, CPF, CCSD, CCSD(T), LDF) are applied to determine the importance of dynamic electron correlation. We find that inclusion of correlation does not essentially change the electronic structure of the clusters but has a strong influence on geometries. To reduce the computational effort we apply effective core potentials (ECPs) in combination with small, but carefully optimized basis sets. The applicability of simple modellings of correlation energies for approximate inclusion of correlation effects in SCF geometry optimizations is tested. 相似文献
44.
Capillary reversed-phase high-performance liquid chromatography (RP-HPLC) utilizing monolithic poly(styrene-divinylbenzene) columns was optimized for the coupling to electrospray ionization mass spectrometry (ESI-MS) by the application of various temperatures and mobile phase additives during peptide and protein analysis. Peak widths at half height improved significantly upon increasing the temperature and ranged from 2.0 to 5.4 s for peptide and protein separations at 70 degrees. Selectivity of peptide elution was significantly modulated by temperature, whereas the effect on proteins was only minor. A comparison of 0.10% formic acid (FA), 0.050% trifluoroacetic acid (TFA), and 0.050% heptafluorobutyric acid (HFBA) as mobile phase additives revealed that highest chromatographic efficiency but poorest mass spectrometric detectabilities were achieved with HFBA. Clusters of HFBA, water, and acetonitrile were observed in the mass spectra at m/z values >500. Although the signal-to-noise ratios for the individual peptides diverged considerably both in the selected ion chromatograms and extracted mass spectra, the average mass spectrometric detectabilities varied only by a factor of less than 1.7 measured with the different additives. Limits of detection for peptides with 500 nl sample volumes injected onto a 60 mm x 0.20 mm monolithic column were in the 0.2-13 fmol range. In the analysis of hydrophobic membrane proteins, HFBA enabled highest separation selectivity at the cost of lower mass spectral quality. The use of 0.050% TFA as mobile phase additive turned out to be the best compromise between chromatographic and mass spectrometric performance in the analysis of peptides and proteins by RP-HPLC-ESI-MS using monolithic separation columns. 相似文献
45.
A total synthesis of the optically active tetrahydroesterastin β -lactam analogue 2 using Miller's hydroxamate approach is described (Scheme 2). Significant modification of published procedures has resulted in a short and facile stereospecific preparation of the N-[(benzyloxycarbonyl)methyl]-β -lactam 17 starting from the readily available D -serine. This material served as intermediate for the preparation of a variety of N-[(benzyloxycarbonyl)methyl]tetrahydroesterastin β-lactam analogues (Scheme 5). 相似文献
46.
47.
Roland Huber 《Geometriae Dedicata》1995,58(3):291-311
We show some topological properties of semianalytic subsets of rigid analytic varieties: curve selection lemma, the closure
of a semianalytic subsetS is semianalytic,
for every quasi-compact morphismf. As an application we show that a morphismf: X Y of rigid analytic varieties is open at a pointx X if and only if SpecO
X,x SpecO
Y,f(x) is surjective. 相似文献
48.
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