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51.
Luca Bagnarelli Alessandro Dolmella Carlo Santini Riccardo Vallesi Roberto Giacomantonio Serena Gabrielli Maura Pellei 《Molecules (Basel, Switzerland)》2021,26(20)
A new dimeric copper(II) bromide complex, [Cu(LOHex)Br(μ-Br)]2 (1), was prepared by a reaction of CuBr2 with the hexyl bis(pyrazol-1-yl)acetate ligand (LOHex) in acetonitrile solution and fully characterized in the solid state and in solution. The crystal structure of 1 was also determined: the complex is interlinked by two bridging bromide ligands and possesses terminal bromide ligands on each copper atom. The two pyrazolyl ligands in 1 coordinate with the nitrogen atoms to complete the Cu coordination sphere, resulting in a five-coordinated geometry—away from idealized trigonal bipyramidal and square pyramidal geometries—which can better be described as distorted square pyramidal, as measured by the τ and χ structural parameters. The pendant hexyloxy chain is disordered over two arrangements, with final site occupancies refined to 0.705 and 0.295. The newly synthesized complex was evaluated as a catalyst in copper-catalyzed C–H oxidation for allylic functionalization through a Kharasch–Sosnovsky reaction without any external reducing agent. Using 0.5 mol% of this catalyst, and tert-butyl peroxybenzoate (Luperox) as an oxidant, allylic benzoates were obtained with up to 90% yield. The general reaction time was only slightly decreased to 24 h but a very significant decrease in the alkene:Luperox ratio to 3:1 was achieved. These factors show relevant improvements with respect to classical Kharasch–Sosnovsky reactions in terms of rate and amount of reagents. The present study highlights the potential of copper(II) complexes containing functionalized bis(pyrazol-1-yl)acetate ligands as efficient catalysts for allylic oxidations. 相似文献
52.
Giacomo?Saielli Riccardo?Bini Alessandro?BagnoEmail author 《Theoretical chemistry accounts》2012,131(3):1140
Fluorine-19 NMR chemical shifts have been calculated for a wide variety of fluorine-containing inorganic and organic molecules
by relativistic DFT methods. The agreement with experimental values, spanning the whole range from ClF to FOOF, is satisfactory
but somewhat less accurate than for comparable light nuclei. 19F shifts in uranium chlorofluorides have been analyzed in detail, and the poor agreement with experiment is partly rationalized. 相似文献
53.
Riccardo Zecchina 《Pramana》2005,64(6):1161-1173
The combinatorial problem of satisfying a given set of constraints that depend on N discrete variables is a fundamental one in optimization and coding theory. Even for instances of randomly generated problems, the question “does there exist an assignment to the variables that satisfies all constraints?” may become extraordinarily difficult to solve in some range of parameters where a glass phase sets in. We shall provide a brief review of the recent advances in the statistical mechanics approach to these satisfiability problems and show how the analytic results have helped to design a new class of message-passing algorithms — the survey propagation (SP) algorithms — that can efficiently solve some combinatorial problems considered intractable. As an application, we discuss how the packing properties of clusters of solutions in randomly generated satisfiability problems can be exploited in the design of simple lossy data compression algorithms. 相似文献
54.
Riccardo Rosso André M. Sonnet Epifanio G. Virga 《Continuum Mechanics and Thermodynamics》2002,14(1):127-136
kinks created in a biological membrane by the interaction with a movable bead. We arrive at the evolution equations for both the
bead and the membrane, whence we conclude that the force exerted on the bead by a fixed membrane points in the direction along
which the curvature of the membrane is more concentrated. This is the first step towards understanding the basic mechanism
behind the dynamics of protein aggregation which takes place on biological membranes.
Received November 6, 2001 / Published online February 4, 2002 相似文献
55.
56.
Odendaal AY Fiamengo AL Ferdani R Wadas TJ Hill DC Peng Y Heroux KJ Golen JA Rheingold AL Anderson CJ Weisman GR Wong EH 《Inorganic chemistry》2011,50(7):3078-3086
Ethylene cross-bridged tetraamine macrocycles are useful chelators in coordination, catalytic, medicinal, and radiopharmaceutical chemistry. Springborg and co-workers developed trimethylene cross-bridged analogues, although their pendant-armed derivatives received little attention. We report here the synthesis of a bis-carboxymethyl pendant-armed cyclen with a trimethylene cross-bridge (C3B-DO2A) and its isomeric ethylene-cross-bridged homocyclen ligand (CB-TR2A) as well as their copper(II) complexes. The in vitro and in vivo properties of these complexes are compared with respect to their potential application as (64)Cu-radiopharmaceuticals in positron emission tomography (PET imaging). The inertness of Cu-C3B-DO2A to decomplexation is remarkable, exceeding that of Cu-CB-TE2A. Electrochemical reduction of Cu-CB-TR2A is quasi-reversible, whereas that of Cu-C3B-DO2A is irreversible. The reaction conditions for preparing (64)Cu-C3B-DO2A (microwaving at high temperature) are relatively harsh compared to (64)Cu-CB-TR2A (basic ethanol). The in vivo behavior of the (64)Cu complexes was evaluated in normal rats. Rapid and continual clearance of (64)Cu-CB-TR2A through the blood, liver, and kidneys suggests relatively good in vivo stability, albeit inferior to (64)Cu-CB-TE2A. Although (64)Cu-C3B-DO2A clears continually, the initial uptake is high and only about half is excreted within 22 h, suggesting poor stability and transchelation of (64)Cu to proteins in the blood and/or liver. These data suggest that in vitro inertness of a chelator complex may not always be a good indicator of in vivo stability. 相似文献
57.
Giust D Albasanz JL Martín M Marega R Delforge A Bonifazi D 《Chemical communications (Cambridge, England)》2011,47(38):10617-10619
Here we report on the surface immobilization of redox-active [60]fullerene derivatives and the consequent neuroprotective effects toward l-glutamate induced excitotoxicity in human derived undifferentiated neuroblastoma cells. 相似文献
58.
[structure: see text] The conventional interpretation of proton NMR chemical shifts is supported by large basis set ab initio quantum mechanical calculations. The benzene protons are predicted to lie within the deshielding zone defined in terms of the out-of-plane magnetic shielding domain. However, ring currents by themselves are not sufficient to account quantitatively for the observed benzene proton downfield chemical shift. sigma-Electron contributions must also be taken into account. The conventional explanation for the ethyne proton chemical shift is valid. 相似文献
59.
Pettinari R Pettinari C Marchetti F Gobetto R Nervi C Chierotti MR Chan EJ Skelton BW White AH 《Inorganic chemistry》2010,49(23):11205-11215
Novel [Rh(η-diene)Tp(x)] complexes of sterically encumbered Tp(x) ligands (Tp(x) = Tp(4Bo), diene = cod, 1; nbd, 2; Tp(x) = Tp(4Bo,5Me), diene = cod, 3; nbd, 4; Tp(x) = Tp(a,3Me), diene = cod, 5; nbd, 6; Tp(x) = Tp(a*,3Me), diene = cod, 7; nbd, 8) have been prepared by treatment of [Rh(η-diene)(μ-Cl)](2) with TlTp(x) (Tp(x) in general, in detail: Tp(4Bo) = hydrotris(indazol-1-yl)borate, Tp(4Bo,5Me) = hydrotris(5-methyl-indazol-1-yl)borate, Tp(a,3Me) = hydrotris(3-methyl-2H-benz[g]-4,5-dihydroindazol-2-y1)borate, Tp(a*,3Me) = hydrotris(3-methyl-2H-benz[g]indazol-2-yl)borate), and characterized by analytical and spectral data (IR, (1)H, (11)B, and (13)C NMR solution). The structures adopted by [Rh(nbd)Tp(4Bo)] 2, [Rh(cod)Tp(4Bo,5Me)] 3, [Rh(nbd)Tp(a,3Me)] 6, [Rh(nbd)Tp(a*,3Me)] 8, and [Rh(nbd)Tp(a*,3Me*)] 8* (incorporating a borotropomeric ligand), have been investigated. Low steric hindrance between the ligands in 2 and 3 permits κ(3) coordination of the pyrazolylborate while the high steric encumbrance present in 6, 8, and 8* results in κ(2) ligands. The coordination modes of the ligands to the metal have also been established by (15)N CPMAS studies of selected ligands and their corresponding Rh complexes. These spectroscopic data are in agreement with the (15)N chemical shifts obtained by using quantum-chemical methods to assist reliable assignments of the experimental values, affording new insights into the extraction of structural information concerning the hapticity (κ(2) or κ(3)) of the poly(pyrazolyl)borate ligands to the Rh metal. 相似文献
60.
Wolfgang Bermel Dr. Ivano Bertini Prof. Isabella C. Felli Prof. Riccardo Peruzzini Roberta Pierattelli Prof. 《Chemphyschem》2010,11(3):689-695
Provided that 13C‐detected NMR experiments are either preferable or complementary to 1H detection, we report here tools to determine Cα? C′, C′? N, and Cα? Hα residual dipolar couplings on the basis of the CON experiment. The coupling constants determined on ubiquitin are consistent with the subset measured with the 1H‐detected HNCO sequences. Since the utilization of residual dipolar couplings may depend on the mobility of the involved nuclei, we also provide tools to measure longitudinal and transverse relaxation rates of N and C′. This new set of experiments is a further development of a whole strategy based on 13C direct‐detection NMR spectroscopy for the study of biological macromolecules. 相似文献