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1.
The ligand‐exchange mechanism of solvated Be2+ cations has been studied by means of DFT calculations (RB3LYP/6‐311+G**). Ligand exchange around [BeL4]2+, where L=H2O, NH3, CO2, formaldehyde (H2CO), HCN, N2, and CO, was found to follow an associative interchange (Ia) process in all cases. The size of the activation barrier is almost independent of the type of donor atom, and depends mainly on the hybridization undergone by the donor atom. This, in turn, suggests that steric effects play a major role in solvent‐ and ligand‐exchange reactions in Be2+ systems. 相似文献
2.
Saalfrank RW Deutscher C Maid H Ako AM Sperner S Nakajima T Bauer W Hampel F Hess BA van Eikema Hommes NJ Puchta R Heinemann FW 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(8):1899-1905
In the reaction of the N-substituted diethanolamines (H(2)L(1-3)) (1-3) with calcium hydride followed by addition of iron(III) or indium(III) chloride, the iron wheels [Fe(6)Cl(6)(L(1))(6)] (4) and [Fe(6)Cl(6)(L(2))(6)] (6) or indium wheels [In(6)Cl(6)(L(1))(6)] (5), [In(6)Cl(6)(L(2))(6)] (8) and [In(6)Cl(6)(L(3))(6)] (9) were formed in excellent yields. Exchange of the chloride ions of 6 by thiocyanate ions afforded [Fe(6)(SCN)(6)(L(2))(6)] (7). Whereas the structures of 4, 5 and 7 were determined unequivocally by single-crystal X-ray analyses, complexes 8 and 9 were characterised by NMR spectroscopy. Contrary to what is normally presumed, the scaffolds of six-membered metallic wheels are not generally rigid, but rather undergo nondissociative topomerisation processes. This was shown by variable temperature (VT) (1)H NMR spectroscopy for the indium wheel [In(6)Cl(6)(L(1))(6)] (5) and is highlighted for the enantiotopomerisation of one indium centre [ 1/6[S(6)-5]<==>[1/6[S(6)-5']]. The self-assembly of metallic wheels, starting from diethanolamine dendrons, is an efficient strategy for the convergent synthesis of metallodendrimers. 相似文献
3.
Snežana Jovanović Ralph Puchta Olivera Klisurić 《Journal of Coordination Chemistry》2016,69(5):735-747
The crystal structure of K[PtCl3(caffeine)] was determined. The coordination geometry around platinum is square-planar formed by N9 of the caffeine ligand and three Cl? ions. The bond lengths and angles of K[PtCl3(caffeine)] were compared with those reported for [PtCl3(caffeine)]? and K[PtCl3(theobromine)]. At the level of the statistical significance of the data we have compared, no differences in the bond distances and angles for any of these compounds were noticed. Weak interactions between K+ and Cl? are responsible for the formation of 1-D polymeric chains in the crystal structure of the complex. The interactions of K[PtCl3(caffeine)] with inosine (Ino) and guanosine-5′-monophosphate (5′-GMP) were studied by 1H NMR spectroscopy at 295 K in D2O in a molar ratio of 1 : 1. The results indicate formation of the reaction product [PtCl3(Nu)] (Nu=Ino or 5′-GMP) with the release of caffeine from the coordination sphere of the starting complex. The higher stability of the bond between the Pt(II) ion and Ino or 5′-GMP compared to the stability of the platinum–caffeine bond is confirmed by density functional theory calculations (B3LYP/LANL2DZp) using as models 9-methylhypoxanthine and 9-methylguanine. 相似文献
4.
5.
Crystal Structure of [BeCl2(15‐Crown‐5)] Single crystals of [BeCl2(15‐crown‐5)] ( 1 ) were obtained from dichloromethane solutions of BeCl2 in the presence of the equivalent amount of 15‐crown‐5 and characterized by IR spectroscopy and X‐ray diffraction. Space group P21/c, Z = 4, lattice dimensions at 100 K: a = 1036.2(1), b = 1071.1(1), c = 1360.1(1) pm, β = 109.86(1)°, R1 = 0.0225. The structure determination shows no disorder, all hydrogen positions were refined isotropically. The results are in contrast to the previously reported crystal structure determination in the space group P21nb. The beryllium atom of 1 forms a BeO2C2 five‐membered heterocycle with terminal chlorine atoms to give a distorted tetrahedral coordination with distances Be–O 166.5(2), 169.9(2) pm, and Be–Cl 195.8(2), 197.8(2) pm. The structural results are in good agreement with DFT calculations on B3LYP/6‐311+G** level. 相似文献
6.
Laura Senft Jamonica L. Moore Alicja Franke Katherine R. Fisher Andreas Scheitler Achim Zahl Ralph Puchta Dominik Fehn Sidney Ison Safaa Sader Ivana Ivanovi-Burmazovi Christian R. Goldsmith 《Chemical science》2021,12(31):10483
Reactivity assays previously suggested that two quinol-containing MRI contrast agent sensors for H2O2, [Mn(H2qp1)(MeCN)]2+ and [Mn(H4qp2)Br2], could also catalytically degrade superoxide. Subsequently, [Zn(H2qp1)(OTf)]+ was found to use the redox activity of the H2qp1 ligand to catalyze the conversion of O2˙− to O2 and H2O2, raising the possibility that the organic ligand, rather than the metal, could serve as the redox partner for O2˙− in the manganese chemistry. Here, we use stopped-flow kinetics and cryospray-ionization mass spectrometry (CSI-MS) analysis of the direct reactions between the manganese-containing contrast agents and O2˙− to confirm the activity and elucidate the catalytic mechanism. The obtained data are consistent with the operation of multiple parallel catalytic cycles, with both the quinol groups and manganese cycling through different oxidation states during the reactions with superoxide. The choice of ligand impacts the overall charges of the intermediates and allows us to visualize complementary sets of intermediates within the catalytic cycles using CSI-MS. With the diquinolic H4qp2, we detect Mn(iii)-superoxo intermediates with both reduced and oxidized forms of the ligand, a Mn(iii)-hydroperoxo compound, and what is formally a Mn(iv)-oxo species with the monoquinolate/mono-para-quinone form of H4qp2. With the monoquinolic H2qp1, we observe a Mn(ii)-superoxo ↔ Mn(iii)-peroxo intermediate with the oxidized para-quinone form of the ligand. The observation of these species suggests inner-sphere mechanisms for O2˙− oxidation and reduction that include both the ligand and manganese as redox partners. The higher positive charges of the complexes with the reduced and oxidized forms of H2qp1 compared to those with related forms of H4qp2 result in higher catalytic activity (kcat ∼ 108 M−1 s−1 at pH 7.4) that rivals those of the most active superoxide dismutase (SOD) mimics. The manganese complex with H2qp1 is markedly more stable in water than other highly active non-porphyrin-based and even some Mn(ii) porphyrin-based SOD mimics.Manganese complexes with polydentate quinol-containing ligands are found to catalyze the degradation of superoxide through inner-sphere mechanisms. The redox activity of the ligand stabilizes higher-valent manganese species. 相似文献
7.
Yrast states in 218Ra up to spin and parity Iπ = 17? were identifíed by means of the 208Pb(13C, 3n) reaction and standard γ-ray spectroscopic techniques. The level scheme is characterized by two bands of opposite parity with nearly constant level spacing. A cascade of strong E1 interband transitions connects both bands.The results are discussed within the systematics of the even Ra isotopes. The negative-parity band which is observed from the Iπ = 5? to the Iπ = 17? state, is interpreted as an octupole vibrational band. The level scheme can be well reproduced in the vibrational limit of the interacting boson approximation (IBA1) which fails, however, to explain the strong E1 feeding of the negative-parity band from the ground-state band 相似文献
8.
H. Auer J. Fernández-Niello H. Puchta F. Riess 《Zeitschrift für Physik A Hadrons and Nuclei》1984,318(3):323-327
Theγ-rays following the radioactive decay of160Lu into160Yb have been studied. The Lu source was produced in the144Sm(19F, 3n) reaction at 85 MeV. Excitation functions, half-lives,γ-γ andγ-X-ray coincidences and conversion electrons were measured. Twoβ + decaying states in160Lu were found with half-lives of 36.2(3) s and 40(1) s.160Yb levels deduced from the decay of160Lu are presented. 相似文献
9.
10.
A. Celler Ch. Briançon J.S. Dionisio A. Lefebvre Ch. Vieu J. Żylicz R. Kulessa C. Mittag J. Fernandez-Niello Ch. Lauterbach H. Puchta F. Riess 《Nuclear Physics A》1985,432(2):421-435
Yrast states in the nucleus 220Ra were studied by means of the 208Pb(14C, 2n) reaction at 61 and 64 MeV. A staggering sequence of levels of positive and negative parity has been observed up to spin and parity Iπ = 16+ (18 +) and from Iπ = 5? to Iπ = 17?, respectively. These states are connected by strong E1 transitions competing with the stretched E2 transitions, the ratio being ~ 10 ?6 fm?2. The ratio of the excitation energy of the 4+ state to that of the 2+ state is close to the vibrational limit. The moment of inertia associated with the negative-parity yrast states is slightly increasing with the rotational frequency ω. It is considerably higher than that of the positive-parity states at lower spins, the difference decreasing monotonically with increasing ω. The data are discussed with reference to the octupole vibrational picture as well as to the results of recent models predicting reflection-asymmetric shapes in the Ra-Th region. 相似文献