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61.
Casella L Monzani E Fantucci P Gullotti M De Gioia L Strini A Chillemi F 《Inorganic chemistry》1996,35(2):439-444
The effect of strain in the axial coordination of imidazole to the heme has been studied in the chelate complexes deuterohemin-histidine (DH-His) and deuterohemin-alanylhistidine (DH-AlaHis). Molecular mechanics calculations indicate that three types of distortion of the axial ligand occur in DH-His, due to the relatively short length of the arm carrying the donor group: tilting off-axis, tipping, and inclination of the imidazole plane with respect to the axial Fe-N bond. The effects of tilting (Deltagamma approximately 10 degrees ) and inclination of the imidazole ring (Deltadelta approximately 17 degrees ) are dominant, while tipping is small and is probably of little importance here. By contrast, the axial imidazole coordination is normal in DH-AlaHis and other computed deuterohemin-dipeptide or -tripeptide complexes where histidine is the terminal residue, the only exception being DH-ProHis, where the rigidity of the proline ring reduces the flexibility of the chelating arm. The distortion in the axial iron-imidazole bond in DH-His has profound and negative influence on the binding and catalytic properties of this complex compared to DH-AlaHis. The former complex binds more weakly carbon monoxide, in its reduced form, and imidazole, in its oxidized form, than the latter. The catalytic efficiency in peroxidative oxidations is also reduced in DH-His with respect to DH-AlaHis. The activity of the latter complex is similar to that of microperoxidase-11, the peptide fragment incorporating the heme that results from hydrolytic cleavage of cytochrome c. 相似文献
62.
D'Archivio AA Galantini L Panatta A Tettamanti E 《The Journal of chemical physics》2004,120(10):4800-4807
Electron spin resonance (ESR) and quasielastic laser scattering (QELS) measurements have been carried out on sodium taurodeoxycholate (NaTDC) micellar aqueous solutions. Computer simulation of the ESR line shape has been used to quantitatively analyze the rotational dynamics of the cholestan-spin label (CSL) dissolved by the NaTDC micellar aggregates as a function of temperature and NaCl concentration. The local reorientation of CSL has been accounted for motionally-averaged g- and A-tensors assuming fast oscillation around the spin-probe long molecular axis. The overall Brownian tumbling of CSL-micelle complexes has been modeled by an axially symmetric rotational tensor. Good agreement with experimental spectra is obtained. Best-fit rotational parameters and QELS data suggest that, in the circumstance of large aggregation, NaTDC micelles have cylindrical shape and micellar growth occurs along the cylinder axis. 相似文献
63.
Luis Adrio Gemma Alberdi Adriana Amoedo Darío Lata Alberto Fernndez Javier Martínez M. Teresa Pereira Jos M. Vila 《无机化学与普通化学杂志》2005,631(11):2197-2203
Reaction of the thiosemicarbazone ligands C4H4NC(H)=NN(H)C(S)NHR (R = Me, a ; Et, b ) with Li2[PdCl4] gave the dinuclear complexes [Pd{C4H4NC(H)=NNC(S)NHR}(μ‐Cl)]2 (R = Me, 1a ; Et, 1b ) with a central Pd2Cl2 core and with deprotonation of the thiosemicarbazones at the hydrazinic nitrogen atom. Treatment of 1a and 1b with triphenylphosphine gave the mononuclear compounds [Pd{C4H4C(H)=NNC(S)NHR}(Cl)(PPh3)] (R = Me, 2a ; Et, 2b ), whereas reaction of 1a and 1b with tertiary diphosphines gave mono‐ and dinuclear compounds, as appropriate, with the corresponding diphosphine acting as a monodentate ( 6b ), chelating ( 3a ) and bridging ligand ( 4a, 5a , 4b, 5b ). Treatment of 1a and 1b with (Ph2PCH2CH2PPh2)W(CO)5 gave the new heterobimetallic complexes 7a and 7b . The crystal structures of complexes 3a and 4a are described. 相似文献
64.
Jacqueline Grewe Adelheid Hagenbach Brigitte Stromburg Roger Alberto Ezequiel Vazquez‐Lopez Ulrich Abram 《无机化学与普通化学杂志》2003,629(2):303-311
Novel rhenium(I) tricarbonyl complexes have been prepared by reactions of (Et4N)2[Re(CO)3Br3] with acetylpyridine benzoylhydrazone, Hapbhyd, di(2‐pyridyl)ketone benzoylhydrazone, Hpy2bhyd, bis(2‐pyridine)ketone, py2CO, and pyridinealdehyde terephtalaldehydebishydrazone, pytehyd. The ligands remain protonated when no supporting base is added and the following complexes have been isolated: [Re(CO)3Br(Hapbhyd)], [Re(CO)3Br(Hpy2bhyd‐py, hyd)], [Re(CO)3Br(Hpy2bhyd‐py1, py2)], [Re(CO)3Br(py2CO‐N, N)] and [Re(CO)3Br(pytehyd)]. Addition of triethyl amine results in deprotonation of Hapbhyd and the formation of [Re(CO)3(OH2)(apbhyd)], whereas Hpy2bhyd is hydrolysed and a rhenium complex with the monoanionic bis(2‐pyridyl)hydroxymethanolato ligand, {py2C(OH)O}‐, is formed. The same compound, [Re(CO)3{py2C(OH)O}], is obtained when triethyl amine and water are added to a mixture of (Et4N)2[Re(CO)3Br3] and py2CO. The air‐stable products have been studied by spectroscopic methods and X‐ray crystallography. 相似文献
65.
Ana Cristina Gmez-Herrero Carlos Snchez-Snchez Frdric Chrioux Jose Ignacio Martínez Jos Abad Luca Floreano Alberto Verdini Albano Cossaro Estelle Mazaleyrat Valrie Guisset Philippe David Simone Lisi Jos Angel Martín Gago Johann Coraux 《Chemical science》2021,12(6):2257
Catechols are ubiquitous substances often acting as antioxidants, thus of importance in a variety of biological processes. The Fenton and Haber–Weiss processes are thought to transform these molecules into aggressive reactive oxygen species (ROS), a source of oxidative stress and possibly inducing degenerative diseases. Here, using model conditions (ultrahigh vacuum and single crystals), we unveil another process capable of converting catechols into ROSs, namely an intramolecular redox reaction catalysed by a Cu surface. We focus on a tri-catechol, the hexahydroxytriphenylene molecule, and show that this antioxidant is thereby transformed into a semiquinone, as an intermediate product, and then into an even stronger oxidant, a quinone, as final product. We argue that the transformations occur via two intramolecular redox reactions: since the Cu surface cannot oxidise the molecules, the starting catechol and the semiquinone forms each are, at the same time, self-oxidised and self-reduced. Thanks to these reactions, the quinone and semiquinone are able to interact with the substrate by readily accepting electrons donated by the substrate. Our combined experimental surface science and ab initio analysis highlights the key role played by metal nanoparticles in the development of degenerative diseases.An antioxidant catechol transforms following intramolecular redox reactions into highly reactive oxygen species, a semiquinone and a quinone, on copper. 相似文献
66.
Alberto Fernández Jesús J. Fernández Margarita López-Torres José M. Vila 《Journal of organometallic chemistry》2005,690(16):3669-3679
Reaction of the ligand C6H5N(H)NCMe(C5H4N) (a) with palladium(II) acetate in toluene gave the mononuclear cyclometallated complex [Pd{C6H4N(H)NCMe(C5H4N)}(AcO)] (1a). Reaction of 1a with sodium chloride gave the analogous chlorine compound [Pd{C6H4N(H)NCMe(C5H4N)}(Cl)] (3a) which could also be prepared by reaction of a with lithium tetrachloropalladate and sodium acetate in methanol for 48 h; whereas shorter reaction times afforded the non-cyclometallated complex [Pd{C6H5N(H)NCMe(C5H4N)}(Cl)2] (2a). Reaction of the ligand 2-ClC6H4N(H)NCMe(C5H4N) · HCl (b), with palladium(II) acetate, or with lithium tetrachloropalladate and sodium acetate, yielded the cyclometallated complex [Pd2-ClC6H3N(H)NCMe(C5H4N)(Cl)] (1b). Treatment of 3a and 1b with silver trifluoromethanesulphonate (triflate) and triphenylphosphine in acetone gave the mononuclear complexes [Pd{2-RC6HnN(H)NCMe(C5H4N)}(PPh3)][CF3SO3], (R = H, n = 4, 4a; R = Cl, n = 3, 2b) with the ligand as C,N,N′ terdentate and substitution of chlorine by triphenylphosphine. Reaction of 3a and 1b with silver triflate and the tertiary diphosphine Ph2P(CH2)4PPh2 (dppb) in a 2:1 molar ratio gave the dinuclear cyclometallated complexes [{Pd[2-RC6H3N(H)NCMe(C5H4N)]}2(μ-Ph2P(CH2)4PPh2)][CF3SO3]2 (R = H, 5a; R = Cl, 3b) with a μ2-diphosphine bridging ligand. Similarly, treatment of 3a and 1b with silver triflate and the tertiary triphosphines MeC(CH2PPh2)3 (tripod) and (Ph2PCH2CH2)2PPh (triphos), in 3:1 molar ratio, gave the novel trinuclear complexes [{Pd[C6H4N(H)NCMe(C5H4N)]}3{μ3-MeC(CH2Ph2)3}][CF3SO3]3 (6a) and [{Pd[2-ClC6H3N(H)NCMe(C5H4N)]}3{μ3-(PPh2CH2CH2)2PPh}][CF3SO3] 3 (4b) regioselectively, with the phosphine as a μ3-bridging ligand. When the reaction between 3a and triphos was carried out in 1:1 molar ratio the mononuclear complex [Pd{C6H4N(H)NCMe(C5H4N)}{(PPh2CH2CH2)2PPh-P,P,P}][ClO4] (7a) was obtained. The crystal structures of 2b, 3a and 4a have been determined by X-ray crystallography. 相似文献
67.
68.
Otón F Tárraga A Velasco MD Molina P 《Dalton transactions (Cambridge, England : 2003)》2005,(7):1159-1161
A ferrocene-based heteroditopic receptor containing urea and crown ether units shows electrochemical responses to dihydrogenphosphate and fluoride anions. K+ cations can only be detected in the presence of dihydrogenphosphate. 相似文献
69.
Lancelot N Elbayed K Raya J Piotto M Briand JP Formaggio F Toniolo C Bianco A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(6):1317-1323
A tetra- and a hepta-homopeptide from the C(alpha)-tetrasubstituted Aib (alpha-aminoisobutyric acid) residue were covalently linked to the POEPOP resin by the fragment-condensation approach. The conformational preferences of the two model peptides were determined for the first time on a solid support by means of high-resolution magic angle spinning NMR spectroscopy. The results obtained indicate that the Aib homopeptides adopt a regular 3(10)-helical structure even when they are covalently bound to a polymeric matrix, and thus confirm the remarkable conformational stability of the peptides rich in this amino acid. An ATR-FTIR spectroscopic investigation, performed in parallel, also confirmed that these polymer-bound peptides do indeed adopt a helical conformation. The results of this study open the possibility to exploit the peptide-resin conjugates based on C(alpha)-tetrasubstituted alpha-amino acids as helpful, structurally organized templates in molecular recognition studies or as catalysts in asymmetric synthesis. 相似文献
70.
Jos R. Ascenso Maria de Deus Carvalho Alberto R. Dias Carlos C. Romo Maria J. Calhorda Luis F. Veiros 《Journal of organometallic chemistry》1994,470(1-2):147-152
The metallocene thioether derivatives [Cp2M(MeSCH2CH2SMe)][PF6]2 (1, M = MO; 2, M = W), [Cp2Mo(SCH2CH2SMe)][PF6] (3) and [Cp2M(SCH2CH2S)] (4, M = Mo; 5, M = W) exhibit temperature-dependent fluxional behavior in solution, owing to the pyramidal sulfur inversion process. The activation energies for this process were determined from proton band-shape analysis in the cases of 1 (54.9 ± 2 kJ mol−1), 2 (51.2 ± 4.6 kJ mol−1) and 3 (30.0 ± 3.1 kJ mol−1). Extended Hückel calculations on related model complexes suggest that local inversion at the sulfur atoms, rather that an inversion of the complete S---C---C---S chain, is responsible for the observed fluxional behaviour. 相似文献