Direct evidence for muonium radicals in water solutions

The precession frequencies of muonium in a molecular radical state have been observed by μSR technique in diluted solutions of 2,6-dihydroxy-5-methyl-pyrimidine (thymine) in water. The conditions for the observation of the radicals are discussed in terms of the interdependent roles played by the chemical reaction time for muonium and by the external magnetic field. A comparison with the known ESR data on solid thymine confirms that the observed product of the muonium's reaction is an adduct radical with an hyperfine interaction reduced to 7% ± 1% of the muonium value     

Exponential self-similar mixing and loss of regularity for continuity equations

We consider the mixing behavior of the solutions to the continuity equation associated with a divergence-free velocity field. In this Note, we sketch two explicit examples of exponential decay of the mixing scale of the solution, in case of Sobolev velocity fields, thus showing the optimality of known lower bounds. We also describe how to use such examples to construct solutions to the continuity equation with Sobolev but non-Lipschitz velocity field exhibiting instantaneous loss of any fractional Sobolev regularity.     

Photogenerated defects in shape-controlled TiO2 anatase nanocrystals: a probe to evaluate the role of crystal facets in photocatalytic processes

The promising properties of anatase TiO(2) nanocrystals exposing specific surfaces have been investigated in depth both theoretically and experimentally. However, a clear assessment of the role of the crystal faces in photocatalytic processes is still under debate. In order to clarify this issue, we have comprehensively explored the properties of the photogenerated defects and in particular their dependence on the exposed crystal faces in shape-controlled anatase. Nanocrystals were synthesized by solvothermal reaction of titanium butoxide in the presence of oleic acid and oleylamine as morphology-directing agents, and their photocatalytic performances were evaluated in the phenol mineralization in aqueous media, using O(2) as the oxidizing agent. The charge-trapping centers, Ti(3+), O(-), and O(2)(-), formed by UV irradiation of the catalyst were detected by electron spin resonance, and their abundance and reactivity were related to the exposed crystal faces and to the photoefficiency of the nanocrystals. In vacuum conditions, the concentration of trapped holes (O(-) centers) increases with increasing {001} surface area and photoactivity, while the amount of Ti(3+) centers increases with the specific surface area of {101} facets, and the highest value occurs for the sample with the worst photooxidative efficacy. These results suggest that {001} surfaces can be considered essentially as oxidation sites with a key role in the photoxidation, while {101} surfaces provide reductive sites which do not directly assist the oxidative processes. Photoexcitation experiments in O(2) atmosphere led to the formation of Ti(4+)-O(2)(-) oxidant species mainly located on {101} faces, confirming the indirect contribution of these surfaces to the photooxidative processes. Although this work focuses on the properties of TiO(2), we expect that the presented quantitative investigation may provide a new methodological tool for a more effective evaluation of the role of metal oxide crystal faces in photocatalytic processes.     

Interaction of muonium with molecules of biological interest in water solution

Muonium's reaction constants with DNA and its constituents in water solutions are reported and compared with the available data for hydrogen. The low frequency spectrum of the resulting muonic radicals in low magnetic fields is recognized.This work was supported by Consiglio Nazionale delle Ricerche, contract n^o 75.00862.02 and by CERN, Experimental Physycs Division. Data analysis performed at CINECA computation facilities.     

Periodic problem for a nonlinear‐damped wave equation on the boundary

In this work we investigate the existence of periodic solutions in t for the following problem: We employ elliptic regularization and monotone method. We consider $\mbox{\boldmath{$\Omega$}}\mbox{\boldmath{$\subset$}}{\mathbb{R}}^{{{n}}} \ (n\geqslant 1)$ an open bounded set that has regular boundary Γ and Q=Ω ×(0,T), T>0, a cylinder of ${\mathbb{R}}^{n+1}$ with lateral boundary Σ = Γ × (0,T). Copyright © 2009 John Wiley & Sons, Ltd.     

Beating untrodden paths: James Gregory and his Italian readers

In this paper, I shall reconstruct the stay in Italy of James Gregory (1638–1675), Regius professor of mathematics at St Andrews. According to a standard account, Gregory spent four years (1664–1668) in Padua, as Stephano degli Angeli's student. However, this claim is problematic. First, Gregory's stay in Padua is confirmed only for the years 1667–1668. Second, the existence of a partial scribal copy of Vera quadratura circuli, ellipseos et hyperbolae in sua propria specie inventa et demonstrata, Gregory's debut work in the domain of quadrature problems, as well as a number of letters preserved at the National Library of Florence, suggest that relations between Gregory and Italian mathematicians were more complex and varied than have been suspected. On the basis of new, albeit scarce, textual evidence, I shall advance a few conjectures regarding scholars and philosophers that Gregory could have met in Padua, Rome and perhaps Florence.     

Theoretical analysis of the adsorption of metal ions to the surface of melanin particles

We have re-examined the problem of the interaction of melanins with metal ions. Metal ions are normal constituents of the pigment, but in some cases they can be related to pathologies, mainly at the level of the skin (Cu²⁺ and Fe³⁺) and of the central nervous system (Fe²⁺ and Mn²⁺). Our approach has been based on the mechanisms of adsorption on the particle surface, by the use of theoretical adsorption isotherms and kinetic models. Although this analysis doesn’t give detailed information on the specific sites involved, it is useful to better characterize the surface behaviour of the colloidal melanin. The results obtained demonstrate that the affinity of melanin for metal ions is very high, comparable to the most efficient materials employed in decontamination and recovery techniques. Moreover, our results demonstrate that three-parameters models, such as Langmuir-Freundlich, Redlich-Peterson and Tóth equations, fit the experimental data with great accuracy and that the adsorption follows pseudo-second-order kinetics.     

Assessment of water-soluble pi-extended squaraines as one- and two-photon singlet oxygen photosensitizers: design, synthesis, and characterization

Singlet oxygen sensitization by organic molecules is a topic of major interest in the development of both efficient photodynamic therapy (PDT) and aerobic oxidations under complete green chemistry conditions. We report on the design, synthesis, biology, and complete spectroscopic characterization (vis-NIR linear and two-photon absorption spectroscopy, singlet oxygen generation efficiencies for both one- and two-photon excitation, electrochemistry, intrinsic dark toxicity, cellular uptake, and subcellular localization) of three classes of innovative singlet oxygen sensitizers pertaining to the family of symmetric squaraine derivatives originating from pi-excessive heterocycles. The main advantage of pi-extended squaraine photosensitizers over the large number of other known photosensitizers is their exceedingly strong two-photon absorption enabling, together with sizable singlet oxygen sensitization capabilities, for their use at the clinical application relevant wavelength of 806 nm. We finally show encouraging results about the dark toxicity and cellular uptake capabilities of water-soluble squaraine photosensitizers, opening the way for clinical small animal PDT trials.     

A model for interfacial electron transfer on colloidal melanin

Though melanins are involved in photochemical reactions (mainly of oxido-reductive type) in vitro and this activity is supposed to have biological implications, no satisfactory model of the reaction kinetics has so far been proposed. The main difficulty arises from the particulate structure of the insoluble melanins and the consequent necessity to describe their reactivity in the framework of heterogeneous chemistry, i.e., at the solid-liquid interface. Our paper presents a simplified model of the monoelectronic reduction reaction of dioxygen, based on well-established experimental facts and some reasonable assumptions: (1) surface adsorption of O₂ on colloidal melanins can be described by a Langmuir isotherm; (2) the kinetics of superoxide formation is photodependent and includes an interfacial electron-transfer process; (3) the photochemical behaviour of the single melanin granule can be described in terms of the electronic properties of amorphous semiconductor particles. Some satisfactory comparisons with experimental data and calculated values of the kinetic constants for the process are presented and discussed.