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21.
Dr. Francesco Rigodanza Prof. Nadia Marino Dr. Alessandro Bonetto Prof. Antonio Marcomini Prof. Marcella Bonchio Prof. Mirco Natali Prof. Andrea Sartorel 《Chemphyschem》2021,22(12):1208-1218
The cobalt substituted polyoxotungstate [Co6(H2O)2(α-B-PW9O34)2(PW6O26)]17− ( Co6 ) displays fast electron transfer (ET) kinetics to photogenerated RuIII(bpy)33+, 4 to 5 orders of magnitude faster than the corresponding ET observed for cobalt oxide nanoparticles. Mechanistic evidence has been acquired indicating that: (i) the one-electron oxidation of Co6 involves Co(II) aquo or Co(II) hydroxo groups (abbreviated as Co6(II) −OH 2 and Co6(II) −OH, respectively, whose speciation in aqueous solution is associated to a pKa of 7.6), and generates a Co(III)−OH moiety ( Co6(III) −OH), as proven by transient absorption spectroscopy; (ii) at pH>pKa, the Co6(II) −OH→RuIII(bpy)33+ ET occurs via bimolecular kinetics, with a rate constant k close to the diffusion limit and dependent on the ionic strength of the medium, consistent with reaction between charged species; (iii) at pH <pKa, the process involves Co6(II) − OH2 → Co6(III)−OH transformation and proceeds via a multiple-site, concerted proton electron transfer (CPET) where water assists the transfer of the proton, as proven by the absence of effect of buffer base concentrations on the rate of the ET and by a H/D kinetic isotope in a range of 1.2–1.4. The reactivity of water is ascribed to its organization on the surface of the polyanionic scaffold through hydrogen bond networking involving the Co(II)−OH2 group. 相似文献
22.
Javier Mateos Francesco Rigodanza Alberto Vega‐Pealoza Andrea Sartorel Mirco Natali Tommaso Bortolato Giorgio Pelosi Xavier Company Marcella Bonchio Luca Dell'Amico 《Angewandte Chemie (International ed. in English)》2020,59(3):1302-1312
Twelve naphthochromenone photocatalysts (PCs) were synthesized on gram scale. They absorb across the UV/Vis range and feature an extremely wide redox window (up to 3.22 eV) that is accessible using simple visible light irradiation sources (CFL or LED). Their excited‐state redox potentials, PC*/PC.? (up to 1.65 V) and PC.+/PC* (up to ?1.77 V vs. SCE), are such that these novel PCs can engage in both oxidative and reductive quenching mechanisms with strong thermodynamic requirements. The potential of these bimodal PCs was benchmarked in synthetically relevant photocatalytic processes with extreme thermodynamic requirements. Their ability to efficiently catalyze mechanistically opposite oxidative/reductive photoreactions is a unique feature of these organic photocatalysts, thus representing a decisive advance towards generality, sustainability, and cost efficiency in photocatalysis. 相似文献
23.
The differences between the molecular structures of the PCP-pincer complex [RuCl{C6H3(CH2P(C6H5)2)2-2,6}(PPh3)] ([RuCl(PCPH)(PPh3)], 1) and its tetrakis-pentafluorophenyl substituted analogue [RuCl{C6H3(CH2P(C6F5)2)2-2,6}(PPh3)] ([RuCl(PCPF20)(PPh3)], 2) have been rationalised by performing calculations on the cations [Ru(PCPH)(PPh3)]+ (1cat) and [Ru(PCPF20)(PPh3)]+ (2cat). The molecular interactions between the chloride ligand and the axial rings, as found in 1 and 2, respectively, have been studied computationally in the model systems [(C6X5PH2)2Cl−] (X = H, F). The calculations on 2cat show that in 2 it is most likely the attractive electrostatic interaction between the chloride ligand and the fluorinated phenyl rings that forces the Cipso atom to occupy an axial position rather than an equatorial one in the observed (X-ray of 2) square pyramidal arrangement. In 1, however, repulsive steric hindrance forces the PPh3 ligand to take the apical position. The applicability of the TD-DFT method for the calculation of the electronic spectra of the PCP-pincer compounds 1 and 2 has been tested. The results indicate that the excitation energies calculated for both complexes are in a reasonable agreement with the experimental absorption maxima. However, for 1, all the calculated transition energies are underestimated. 相似文献
24.
Cucinotta V Giuffrida A Grasso G Maccarrone G Messina M 《Journal of chromatography. A》2002,979(1-2):137-145
Six different racemates of the profen family were used as analytes in order to test the chiral selector properties of three members of a new class of cyclodextrin derivatives, hemispherodextrins (HMs), in capillary electrophoresis. In addition to experiments carried out to separate each enantiomeric pair one by one, other experiments were carried out on samples containing all six enantiomeric pairs. Electropherograms were obtained either by adding a single HM to the background electrolyte (BGE), or a binary mixture of HMs. The results obtained confirm the excellent chiral selector properties of the HMs, and furthermore show that these compounds can also be used for achiral selection. When mixing different HMs, a complementary effect in chiral selectivity is observed, which, in our opinion, deserves further study. 相似文献
25.
Ambrosi G Boggioni A Formica M Fusi V Giorgi L Lucarini S Micheloni M Secco F Venturini M Zappia G 《Dalton transactions (Cambridge, England : 2003)》2005,(3):485-490
The equilibria and kinetics of the binding of gallium(III) to 4-(N),10-(N)-bis[2-(3-hydroxo-2-oxo-2-H-pyridine-1-y1)acetamido]-1,7-dimethyl-1,4,7,10-tetraazacyclododecane (L) were investigated in acidic medium at ionic strength 1 M (NaClO4). Spectrophotometric titrations in the UV region revealed that L is able to bind Ga3+ also at high H+ concentration. The kinetic (stopped-flow) experiments are interpreted on the basis of three parallel reaction paths (i) M3+ + H2L2+ = M(H2L)5+ where M(H2L)5+ is in a steady state, (ii) M(OH)2+ + H2L2+ = M(HL)4+ + H2O and (iii) M(OH)2+ + HL+ = ML3+ + H2O. The first-order rate constants for conversion of the outer-sphere into the inner-sphere complexes are similar to those of the Ga(III)/tropolone system which is known to react according to the dissociative Id mechanism and to the relevant rate constants for water exchange at the metal ion. The effects of pH on the UV-Vis absorption, fluorescence emission properties and NMR spectral features on the Ga(III)/L system were also investigated. Spectrophotometric titrations in the UV region reveal that, in acid medium the prevailing species is M(HL)4+ whereas the chelate ML3+ prevails for [H+] < 0.01 M. The results indicate metal coordination at the oxygen atoms of the 3-hydroxo-2-oxopyridine residues. 相似文献
26.
Bianco A Guiso M Ballero M Foddai S Nicoletti M Piccin A Serafini M Tomassini L 《Natural product research》2004,18(3):241-246
During our systematic study on the species of genus Linaria (Scrophulariaceae) present in Italy, we examined the glycosidic fraction of Linaria capraria Moris et De Not., a species endemic of Tuscany archipelago. This fraction is particularly complex and we considered in this article only the medium polarity components. In accordance with previous studies, L. capraria shows acyl derivatives of antirrhinoside 1 as specific chemotaxonomic iridoidic markers. L. capraria exhibits a complex composition, with regard to iridoidic constituents, with several chromatographic problems to be resolved. We then isolated, besides the known antirrhinoside 1, two acyl derivatives of antirrhinoside, the 6'-O-senecioyl derivative, 2, and the 6'-O-angeloyl derivative, 3. In addition a glucoside of an acyclic monoterpene, 4, was also isolated, which may be correlated to the other monoterpenic glycosides isolated from other species of Scrophulariaceae. 相似文献
27.
Cucinotta V Giuffrida A Grasso G Maccarrone G Mazzaglia A Vecchio G 《Fresenius' Journal of Analytical Chemistry》2001,370(4):363-366
The separation of three pairs of enantiomeric herbicides has been successfully achieved by capillary electrophoresis at two different pH values in the presence of cyclodextrin derivatives previously synthesized in our laboratory. Two of these derivatives constitute a new class of receptor, the hemispherodextrins, in which a trehalose capping moiety is bonded to beta-cyclodextrin. Because of their peculiar structure hemispherodextrins have very promising characteristics and the low receptor concentration required to achieve separation deserves particular interest. 相似文献
28.
Salvatore Giuffrida Guglielmo G. Condorelli Lucia L. Costanzo Giorgio Ventimiglia Raffaella Lo Nigro Maria Favazza Enrico Votrico Corrado Bongiorno Ignazio L. Fragalà 《Journal of nanoparticle research》2007,9(4):611-619
Liquid Phase Photo-Deposition (LPPD) technique has been used to obtain both colloidal particles and thin films of metallic
and chloride nickel from solutions of only precursor Ni(acac)2 (acac=2,4-pentandionato). Metallic nickel was obtained from ethanol solutions by direct nickel(II) photoreduction at 254 nm
and by acetone sensitised reaction at 300 nm. In this latter process the rate was higher than in the first one. NiCl2 was formed from CCl4 solution by a solvent-initiated reaction. TEM analysis, performed on colloidal particles of nickel, showed that their dimensions
are in the range 2–4 nm. The films did not present carbon contamination and were characterized by AFM, XPS and GIXRD. Metallic
films consisted of particles of 20–40 nm that are the result of the aggregation of smaller crystallites (4–5 nm). Larger agglomerations
(around 200 nm) have been observed for NiCl2 films. 相似文献
29.
Small bimetallic Pd-Fe particles supported on a well ordered alumina film grown on NiAl (1 1 0) were studied focusing on the geometric, electronic, adsorption, as well as magnetic properties. The morphology, growth mode and surface composition were investigated by combining scanning tunneling microscopy (STM), temperature-programmed desorption (TPD) and infrared spectroscopy (IRAS) using CO as a probe molecule. Information on the electronic properties of the bimetallic systems was obtained by means of X-ray photoelectron spectroscopy (XPS). These measurements were amended by in situ ferromagnetic resonance spectroscopy to address the magnetic properties of the bimetallic particles. The subsequent deposition of the metals at 300 K varying the order of metal deposition resulted in two distinct bimetallic systems. Pd deposited on existing Fe particles forms a shell, however, FMR and XPS suggest that intermixing of Pd and Fe occurs to some extent. For the reverse order, a larger amount of Fe is required to coat Pd particles, due to the strong tendency of Pd to segregate to the surface of the particles. 相似文献
30.
Giulio Oliviero Paolo Bergese Marcella Chiari Marina Cretich Sonia Fiorilli Carlo Ricciardi Laura E. Depero 《Analytica chimica acta》2008,630(2):161-167
An innovative route to activate silicon microcantilevers (MCs) for label free molecular recognition is presented. The method consists in coating the underivatized MCs with a functional ter-polymer based on N,N-dimethylacrylamide (DMA) bearing N-acryloyloxysuccinimide (NAS) and 3-(trimethoxysilyl)propyl-methacrylate (MAPS), two functional monomers that confer to the polymer the ability to react with nucleophilic species on biomolecules and with glass silanols, respectively. The polymer was deposited onto MCs by dip coating. Polymer coated MCs were tested in both static and dynamic modes of actuation, featuring detection of DNA hybridization as well as protein/protein interaction. In the dynamic experiments, focused on protein detection, the MCs showed an average mass responsivity of 0.4 Hz/pg for the first resonant mode and of 2.5 Hz/pg for the second resonant mode. The results of the static experiments, dedicated to DNA hybridization detection, allowed for direct estimation of the DNA duplex formation energetics, which resulted fully consistent with the nominal expected values. These results, together with easiness and cheapness, high versatility, and excellent stability of the recognition signal, make the presented route a reliable alternative to standard SAM functionalization (for microcantilevers (MCs) and for micro-electro-mechanical systems (MEMS) in general). 相似文献