Photo-induced electron transfer in supramolecular materials of titania nanostructures and cytochrome c

In the present paper, we report on the molecular interaction and photochemistry of TiO2 nanoparticles (NPs) and cytochrome c systems for understanding the effects of supramolecular organization and electron transfer by using two TiO2 structures: P25 TiO2 NPs and titanate nanotubes. The adsorption and reduction of cytochrome c heme iron promoted by photo-excited TiO2, arranged as P25 TiO2 NPs and as nanotubes, were characterized using electronic absorption spectroscopy, thermogravimetric analysis, and atomic force microscopy. In an aqueous buffered suspension (pH 8.0), the mass of cytochrome c adsorbed on the P25 TiO2 NP surface was 2.3 fold lower (0.75 mu g m(-2)) than that adsorbed on the titanate nanotubes (1.75 mu g m(-2)). Probably due to the high coverage of titanate nanotubes by adsorbed cytochrome c, the low amount of soluble remaining protein was not as efficiently photo-reduced by this nanostructure as it was by the P25 TiO2 NPs. Cytochrome c, which desorbed from both titanium materials, did not exhibit changes in its redox properties. In the presence of the TiO2 NPs, the photo-induced electron transfer from water to soluble cytochrome c heme iron was corroborated by the following findings: (i) identification by EPR of the hydroxyl radical production during the irradiation of an aqueous suspension of TiO2 NPs, (ii) impairment of a cytochrome c reduction by photo-excited TiO2 in the presence of dioxane, which affects the dielectric constant of the water, and (iii) change in the rate of TiO2-promoted cytochrome c reduction when water was replaced with D2O. The TiO2-promoted photo-reduction of cytochrome c was reverted by peroxides. Cytochrome c incorporated in the titanate nanotubes was also reversibly reduced under irradiation, as confirmed by EPR and UV-visible spectroscopy.

Mixed-valence state of symmetric diruthenium complexes: synthesis, characterization, and electron transfer investigation

Complexes of the type {[(pyS)Ru(NH3)(4)](2)-mu-L}(n), where pyS = 4-mercaptopyridine, L = 4,4'-dithiodipyridine (pySSpy), pyrazine (pz) and 1,4-dicyanobenzene (DCB), and n = +4 and +5 for fully reduced and mixed-valence complexes, respectively, were synthesized and characterized. Electrochemical data showed that there is electron communication between the metal centers with comproportionation constants of 33.2, 1.30 x 10(8) and 5.56 x 10(5) for L = pySSpy, pz and DCB, respectively. It was also observed that the electronic coupling between the metal centers is affected by the p-back-bonding interaction toward the pyS ligand. Raman spectroscopy showed a dependence of the intensity of the vibrational modes on the exciting radiations giving support to the assignments of the electronic transitions. The degree of electron communication between the metal centers through the bridging ligands suggests that these systems can be molecular wire materials.

Theoretical study of the absorption and nonradiative deactivation of 1-nitronaphthalene in the low-lying singlet and triplet excited states including methanol and ethanol solvent effects

The photophysics of the 1-nitronaphthalene molecular system, after the absorption transition to the first singlet excited state, is theoretically studied for investigating the ultrafast multiplicity change to the triplet manifold. The consecutive transient absorption spectra experimentally observed in this molecular system are also studied. To identify the electronic states involved in the nonradiative decay, the minimum energy path of the first singlet excited state is obtained using the complete active space self-consistent field//configurational second-order perturbation approach. A near degeneracy region was found between the first singlet and the second triplet excited states with large spin-orbit coupling between them. The intersystem crossing rate was also evaluated. To support the proposed deactivation model the transient absorption spectra observed in the experiments were also considered. For this, computer simulations using sequential quantum mechanic-molecular mechanic methodology was used to consider the solvent effect in the ground and excited states for proper comparison with the experimental results. The absorption transitions from the second triplet excited state in the relaxed geometry permit to describe the transient absorption band experimentally observed around 200 fs after the absorption transition. This indicates that the T-2 electronic state is populated through the intersystem crossing presented here. The two transient absorption bands experimentally observed between 2 and 45 ps after the absorption transition are described here as the T-1 -> T-3 and T-1 -> T-5 transitions, supporting that the intermediate triplet state (T-2) decays by internal conversion to T-1. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4738757]

(18O,16O) Two-neutron transfer reactions for spectroscopic studies.

A systematic study of the response of different nuclei to the (18O, 16O) two-neutron transfer reaction at 84 MeV incident energy was pursued at the INFN-LNS in Catania (Italy). The experiments were performed using several solid targets from light (9Bc, 11 B, 12,13C, 16O, 28Si) to heavier ones (58,64Ni, 120Sn, 208Pb). The 16O ejectiles were detected at forward angles by the MAGNEX magnetic spectrometer and identified without the need of time of flight measurements. Exploiting the large momentum (≈ 25%) and angular (50 msr) acceptance of the spectrometer, energy spectra were obtained with a relevant yield up to about 20 MeV excitation energy. A common feature of the light nuclei spectra is the strong population of states with well known configuration of two-particle over a core and the appearance of unknown resonant structures in the continuum. These latter can reveal the excitation of a collective mode connected with the transfer of a pair. For the heavier nuclei as 66Ni a completely different behaviour is observed indicating the presence of more dissipative processes in the reaction mechanisms that hide the spectroscopic information.

A heat transfer model of the human upper limbs

A steady state multi-segmented heat transfer model of the human upper limbs was developed. The main purpose was to evaluate the impact of blood flow through superficial veins and subcutaneous vascular structures in the palm of the hands over the heat transfer between the limbs and the environment. The distinguishing feature of the model is the inclusion of a detailed circulatory network composed of vessels with diameter larger than 1 mm. The model was validated by comparing its results from exposures to a hot, a neutral, and a cold environment to experimental data presented in the literature. (C) 2011 Elsevier Ltd. All rights reserved.

Effect of some surfactants on the chemiluminescent reactions of bis(2,4,6-trichlorophenyl)oxalate and bis(2-nitrophenyl)oxalate with hydrogen peroxide

The chemiluminescent reactions of bis(2,4,6-trichlorophenyl)oxalate (TCPO) and bis(2-nitrophenyl)oxalate (2-NPO) with hydrogen peroxide in acetonitrile/water micellar systems (anionic, cationic, and non-ionic) and gamma-cyclodextrin were studied in the presence of fluoranthene or 9,10-diphenylanthracene, imidazole, and two buffer solutions, HTRIS+/TRIS and H2PO4-/HPO42-. The relative chemiluminenscence (CL) intensity is higher in the presence of the cationic (DDAB, CTAC, DODAC, and OTAC), anionic (SDS), and non-ionic (Tween 80) surfactants. In the presence of some non-ionic surfactants (Brij 35, Brij 76, and Tween 20), the CL intensity was partially quenched compared with the reaction with no surfactant. The sensitivity for hydrogen peroxide determination in the range 0.01 x 10(-4) to 1.0 x 10(-4) mol L-1, considering the slope of the calibration curves (maximum peak height of CL vs. concentration), improved with the introduction of DDAH, CTAB, and SDS in HTRIS+/TRIS buffer.

Experimental investigations of heat transfer coefficients of cutting fluids in metal cutting processes: analysis of workpiece phenomena in a given case study

This paper reports an experimental method to estimate the convective heat transfer of cutting fluids in a laminar flow regime applied on a thin steel plate. The heat source provided by the metal cutting was simulated by electrical heating of the plate. Three different cooling conditions were evaluated: a dry cooling system, a flooded cooling system and a minimum quantity of lubrication cooling system, as well as two different cutting fluids for the last two systems. The results showed considerable enhancement of convective heat transfer using the flooded system. For the dry and minimum quantity of lubrication systems, the heat conduction inside the body was much faster than the heat convection away from its surface. In addition, using the Biot number, the possible models were analyzed for conduction heat problems for each experimental condition tested.

Radiative transfer analyses of Titan's tropical atmosphere

Titan's optical and near-IR spectra result primarily from the scattering of sunlight by haze and its absorption by methane. With a column abundance of 92 km amagat (11 times that of Earth), Titan's atmosphere is optically thick and only similar to 10% of the incident solar radiation reaches the surface, compared to 57% on Earth. Such a formidable atmosphere obstructs investigations of the moon's lower troposphere and surface, which are highly sensitive to the radiative transfer treatment of methane absorption and haze scattering. The absorption and scattering characteristics of Titan's atmosphere have been constrained by the Huygens Probe Descent Imager/Spectral Radiometer (DISR) experiment for conditions at the probe landing site (Tomasko, M.G., Bezard, B., Doose, L., Engel, S., Karkoschka, E. 120084 Planet. Space Sci. 56, 624-247: Tomasko, M.G. et al. [2008b] Planet. Space Sci. 56, 669-707). Cassini's Visual and Infrared Mapping Spectrometer (VIMS) data indicate that the rest of the atmosphere (except for the polar regions) can be understood with small perturbations in the high haze structure determined at the landing site (Penteado, P.F., Griffith, CA., Tomasko, M.G., Engel, S., See, C., Doose, L, Baines, K.H., Brown, R.H., Buratti, B.J., Clark, R., Nicholson, P., Sotin, C. [2010]. Icarus 206, 352-365). However the in situ measurements were analyzed with a doubling and adding radiative transfer calculation that differs considerably from the discrete ordinates codes used to interpret remote data from Cassini and ground-based measurements. In addition, the calibration of the VIMS data with respect to the DISR data has not yet been tested. Here, VIMS data of the probe landing site are analyzed with the DISR radiative transfer method and the faster discrete ordinates radiative transfer calculation; both models are consistent (to within 0.3%) and reproduce the scattering and absorption characteristics derived from in situ measurements. Constraints on the atmospheric opacity at wavelengths outside those measured by DISR, that is from 1.6 to 5.0 mu m, are derived using clouds as diffuse reflectors in order to derive Titan's surface albedo to within a few percent error and cloud altitudes to within 5 km error. VIMS spectra of Titan at 2.6-3.2 mu m indicate not only spectral features due to CH4 and CH3D (Rannou, P., Cours, T., Le Mouelic, S., Rodriguez, S., Sotin, C., Drossart, P., Brown, R. [2010]. Icarus 208, 850-867), but also a fairly uniform absorption of unknown source, equivalent to the effects of a darkening of the haze to a single scattering albedo of 0.63 +/- 0.05. Titan's 4.8 mu m spectrum point to a haze optical depth of 0.2 at that wavelength. Cloud spectra at 2 mu m indicate that the far wings of the Voigt profile extend 460 cm(-1) from methane line centers. This paper releases the doubling and adding radiative transfer code developed by the DISR team, so that future studies of Titan's atmosphere and surface are consistent with the findings by the Huygens Probe. We derive the surface albedo at eight spectral regions of the 8 x 12 km(2) area surrounding the Huygens landing site. Within the 0.4-1.6 mu m spectral region our surface albedos match DISR measurements, indicating that DISR and VIMS measurements are consistently calibrated. These values together with albedos at longer 1.9-5.0 mu m wavelengths, not sampled by DISR, resemble a dark version of the spectrum of Ganymede's icy leading hemisphere. The eight surface albedos of the landing site are consistent with, but not deterministic of, exposed water ice with dark impurities. (C) 2011 Elsevier Inc. All rights reserved.

Cataract surgery: emotional reactions of patients with monocular versus binocular vision

Purpose: To analyze emotional reactions related to cataract surgery in two groups of patients (monocular vision - Group 1; binocular vision - Group 2). Methods: A transversal comparative study was performed using a structured questionnaire from a previous exploratory study before cataract surgery. Results: 206 patients were enrolled in the study, 96 individuals in Group 1 (69.3 +/- 10.4 years) and 110 in Group 2 (68.2 +/- 10.2 years). Most patients in group 1 (40.6%) and 22.7% of group 2, reported fear of surgery (p<0.001). The most important causes of fear were: possibility of blindness, ocular complications and death during surgery. The most prevalent feelings among the groups were doubts about good results and nervousness. Conclusion: Patients with monocular vision reported more fear and doubts related to surgical outcomes. Thus, it is necessary that phisycians considers such emotional reactions and invest more time than usual explaining the risks and the benefits of cataract surgery. Ouvir

Sequential Methyl-Fluorine Exchange Reactions of Siloxide Ions in the Gas Phase

Air Force Office of Scientific Research (AFOSR)