Structure and electronic properties of hydrated mesityl oxide: a sequential quantum mechanics/molecular mechanics approach

The hydration of mesityl oxide (MOx) was investigated through a sequential quantum mechanics/molecular mechanics approach. Emphasis was placed on the analysis of the role played by water in the MOx syn-anti equilibrium and the electronic absorption spectrum. Results for the structure of the MOx-water solution, free energy of solvation and polarization effects are also reported. Our main conclusion was that in gas-phase and in low-polarity solvents, the MOx exists dominantly in syn-form and in aqueous solution in anti-form. This conclusion was supported by Gibbs free energy calculations in gas phase and in-water by quantum mechanical calculations with polarizable continuum model and thermodynamic perturbation theory in Monte Carlo simulations using a polarized MOx model. The consideration of the in-water polarization of the MOx is very important to correctly describe the solute-solvent electrostatic interaction. Our best estimate for the shift of the pi-pi* transition energy of MOx, when it changes from gas-phase to water solvent, shows a red-shift of -2,520 +/- 90 cm(-1), which is only 110 cm(-1) (0.014 eV) below the experimental extrapolation of -2,410 +/- 90 cm(-1). This red-shift of around -2,500 cm(-1) can be divided in two distinct and opposite contributions. One contribution is related to the syn -> anti conformational change leading to a blue-shift of similar to 1,700 cm(-1). Other contribution is the solvent effect on the electronic structure of the MOx leading to a red-shift of around -4,200 cm(-1). Additionally, this red-shift caused by the solvent effect on the electronic structure can by composed by approximately 60 % due to the electrostatic bulk effect, 10 % due to the explicit inclusion of the hydrogen-bonded water molecules and 30 % due to the explicit inclusion of the nearest water molecules.

Polyazomethine with vinylene and phenantridine moieties in the main chain: Synthesis, characterization, opto(electrical) properties and theoretical calculations

The opto(electrical) properties and theoretical calculations of polyazomethine with vinylene and phenantridine moieties in the main chain were investigated in the present study. 2,5-Bis(hexyloxy)-1,4-bis[(2,5-bis(hexyloxy)-4-formyl-phenylenevinylene]benzene was polymerized in solution with 3,8-diamino-6-phenylphenanthridine (PAZ-PV-Ph). The temperatures of 5% weight loss (T-5%) of the polyazomethine was observed at 356 degrees C in nitrogen. Electrochemical properties of thin film of the polymer were studied by differential pulse voltammetry. The HOMO level of the PAZ-PV-Ph was at -4.97 eV. The energy band gap (E-g) was detected of approximately similar to 1.9 eV. Energy band gap (E-gopt) was additionally calculated from absorption spectrum and absorption coefficient alpha. The absorption UV-vis spectra of polyazomethine recorded in solution showed a blue shift in comparison with the solid state. HOMO-LUMO levels and E-g were additionally calculated theoretically by density functional theory and molecular simulations of PAZ-PV-Ph are presented. Current density-voltage (J-U) measurements were performed on ITO/PAZ-PV-Ph/Al, ITO/TiO2/PAZ-PV-Ph/Al and ITO/PEDOT/PAZ-PV-Ph:TiO2/Al devices in the dark and during irradiation with light (under illumination of 1000 W m(-2)). The polymer was tested using AFM technique and roughness (R-a, R-ms) along with skew and kurtosis are presented.

FTIR and SEM analysis of CO2 laser irradiated human enamel

Objectives: Considering the enamel chemical structure, especially carbonate band, which has a major role in the caries prevention, the objective of the present study was to assess the chemical alterations on the enamel irradiated with CO2 laser by means of FTIR spectroscopy and SEM analysis. Design: The enamel surfaces were analysed on a spectrometer for acquisition of the absorption spectrum relative to the chemical composition of the control sample. The irradiation was conducted with a 10.6-mu m CO2 laser (0.55 W, 660 W/cm(2)). The carbonate absorption band at 1600-1291 cm(-1) as well as the water absorption band at 3793-2652 cm(-1) was measured in each sample after the irradiation. The water band was measured again 24-h after the irradiation. The band area of each chemical compound was delimited, the background was subtracted, and the area under each band was integrated. Each area was normalized by the phosphate band (1190-702 cm(-1)). Results: There was a statistically significant decrease (p < 0.05) in the water content after irradiation (control: 0.184 +/- 0.04; irradiated: 0.078 +/- 0.026), which increased again after rehydration (0.145 +/- 0.038). The carbonate/phosphate ratio was measured initially (0.112 +/- 0.029) and its reduction after irradiation indicated the carbonate loss (0.088 +/- 0.014) (p < 0.05). Conclusion: The 10.6-mu m CO2 laser irradiation diminishes the carbonate and water contents in the enamel after irradiation. (C) 2012 Elsevier Ltd. All rights reserved.

Pain in photodynamic therapy: mechanism of action and management strategies

Photodynamic therapy involves administration of a photosensitizing drug and its subsequent activation by irradiation with a light source at wavelengths matching the absorption spectrum of the photosensitizer. In many countries around the world, topical photodynamic therapy has been approved for treatment of cutaneous oncologic conditions such as actinic keratosis, Bowen's disease, and superficial basal cell carcinoma. Multicenter, randomized, controlled studies have confirmed its efficacy and superior cosmetic outcomes compared to conventional therapies. Nevertheless, this therapeutic method presents some adverse effects, such as erythema, edema, pigmentation, pustules, and pain. There is no doubt that pain is the most severe of the adverse effects, being sometimes responsible for definitive treatment interruption. The pain mechanism has not yet been fully understood, which makes complete pain control a challenge to be conquered. In spite of that, this literature review presents some useful pain management strategies as well as the most important pain-related factors in photodynamic therapy.

5-(1-(4-phenyl)-3-(4-nitrophenyl)triazene)-10,15,20-triphenylporphyrin: a new triazene-porphyrin dye and its spectroelectrochemical properties

The new triazene-porphyrin dye 5-(1-(4-phenyl)-3-(4-nitrophenyl)triazene)-10,15,20-triphenylporphyrin, encompassing a reactive protonated triazene moiety, was prepared starting from meso-tetraphenylporphyrin (H2TPP), first converting it to the 5-(4-nitrophenyl)-10,15,20-triphenylporphyrin, then reducing to the 5-(4-aminophenyl)-10,15,20-tri(phenyl) porphyrin intermediate, and reacting with the diazonium salt of 4-nitroaniline; and characterized by spectroscopic and electrochemical methods. The absorption spectrum of the neutral species resembled the sum of H2TPP and of 1,3-bis(4-nitrophenyl) triazene spectrum, but the deprotonated anionic species showed more delocalized frontier orbitals, behaving as a push-pull system exhibiting triazenide-to-porphyrin charge-transfer transitions.

Nonlinear optical characterizations of dibenzoylmethane in solution

This work reports on the two-photon absorption (2PA) cross-section and first hyperpolarizability of dibenzoylmethane solutions using femtosecond Z-scan and hyper-Rayleigh scattering techniques. The 2PA spectrum, spanning the wavelength range from 460 to 740 nm, presents a band centered at 510 nm, with a cross-section value estimated as 37 GM at this wavelength. Owing to the molecular symmetry, this band is not observed in the linear absorption spectrum. The sum-over-state approach was adopted to evaluate various spectroscopic parameters. Experimental and theoretical values of the first hyperpolarizability values were estimated in ethanol and DMSO solutions.

Optische Eigenschaften von Pi-konjugierten Modellsystemen

Der erste Teil der vorliegenden Arbeit beschäftigt sich mit der Modifikation der spontanen Emission im Strong Coupling Regime. Hierzu wurden geeignete optische, organische 'Halbleiter'-Mikroresonatoren präpariert.Zunächst wurde das verwendete optisch aktive Material, das J-Aggregat PIC, spektroskopisch charakterisiert. In Transmissionsmessungen an den Mikroresonatoren wurden Vakuum-Rabi-Splitting-Energien zwischen 26 und 52 meV bestimmt. Es wurde die Abhängigkeit der Vakuum-Rabi-Splitting-Energie von der räumlichen Position der optisch aktiven Schicht innerhalb des Mikroresonators untersucht. Durch eine Simulation konnte nachgewiesen werden, daß der Grund für die Asymmetrie des Rabi-Splittings bei einer Verstimmung von 0 meV durch die Asymmetrie des Absorptionsspektrums des optisch aktiven Materials gegeben ist. Weiterhin wurde die Photolumineszenz der Mikroresonatoren untersucht. Es konnte in temperaturabhängigen Messungen gezeigt werden, daß die hochenergetische Bande gegenüber der niederenergetischen Bande bei steigender Temperatur entsprechend einer Boltzmann-Verteilung stärker besetzt wird.Im zweiten Teil der Arbeit wurden die optischen Eigenschaften von dünnen Filmen N´N´Bis (2,6-xylyl)perylene-3,4:9,10-bis(dicarboximide) (DPP-PTCDI) abhängig von der Schichtdicke untersucht. Die Photolumineszenzspektren der dünnen Filme wurden mit zunehmender Dicke durch eine neue Bande bei kleineren Energien bestimmt. Diese Bande kann mit der Emission aus Fallenzuständen erklärt werden. Durch Photolumineszenz-Anregungsspektroskopie konnte gezeigt werden, daß die Fallenzustände auch im Grundzustand existieren. Exzimere können daher als Ursache ausgeschlossen werden.

Multi-parametric classification of Alzheimer's disease and mild cognitive impairment: the impact of quantitative magnetization transfer MR imaging

Multi-parametric and quantitative magnetic resonance imaging (MRI) techniques have come into the focus of interest, both as a research and diagnostic modality for the evaluation of patients suffering from mild cognitive decline and overt dementia. In this study we address the question, if disease related quantitative magnetization transfer effects (qMT) within the intra- and extracellular matrices of the hippocampus may aid in the differentiation between clinically diagnosed patients with Alzheimer disease (AD), patients with mild cognitive impairment (MCI) and healthy controls. We evaluated 22 patients with AD (n=12) and MCI (n=10) and 22 healthy elderly (n=12) and younger (n=10) controls with multi-parametric MRI. Neuropsychological testing was performed in patients and elderly controls (n=34). In order to quantify the qMT effects, the absorption spectrum was sampled at relevant off-resonance frequencies. The qMT-parameters were calculated according to a two-pool spin-bath model including the T1- and T2 relaxation parameters of the free pool, determined in separate experiments. Histograms (fixed bin-size) of the normalized qMT-parameter values (z-scores) within the anterior and posterior hippocampus (hippocampal head and body) were subjected to a fuzzy-c-means classification algorithm with downstreamed PCA projection. The within-cluster sums of point-to-centroid distances were used to examine the effects of qMT- and diffusion anisotropy parameters on the discrimination of healthy volunteers, patients with Alzheimer and MCIs. The qMT-parameters T2(r) (T2 of the restricted pool) and F (fractional pool size) differentiated between the three groups (control, MCI and AD) in the anterior hippocampus. In our cohort, the MT ratio, as proposed in previous reports, did not differentiate between MCI and AD or healthy controls and MCI, but between healthy controls and AD.

Hydroxylation of naphthalene by aromatic peroxygenase from Agrocybe aegerita proceeds via oxygen transfer from H2O2 and intermediary epoxidation

Agrocybe aegerita peroxidase/peroxygenase (AaP) is an extracellular fungal biocatalyst that selectively hydroxylates the aromatic ring of naphthalene. Under alkaline conditions, the reaction proceeds via the formation of an intermediary product with a molecular mass of 144 and a characteristic UV absorption spectrum (A(max) 210, 267, and 303 nm). The compound was semistable at pH 9 but spontaneously hydrolyzed under acidic conditions (pH<7) into 1-naphthol as major product and traces of 2-naphthol. Based on these findings and literature data, we propose naphthalene 1,2-oxide as the primary product of AaP-catalyzed oxygenation of naphthalene. Using (18)O-labeled hydrogen peroxide, the origin of the oxygen atom transferred to naphthalene was proved to be the peroxide that acts both as oxidant (primary electron acceptor) and oxygen source.

Ultrafast Relaxation Dynamics of Osmium-Polypyridine Complexes in Solution

We present steady-state absorption and emission spectroscopy and femtosecond broadband photoluminescence up-conversion spectroscopy studies of the electronic relaxation of Os(dmbp)3 (Os1) and Os(bpy)2(dpp) (Os2) in ethanol, where dmbp is 4,4′-dimethyl-2,2′-biypridine, bpy is 2,2′-biypridine, and dpp is 2,3-dipyridyl pyrazine. In both cases, the steady-state phosphorescence is due to the lowest 3MLCT state, whose quantum yield we estimate to be ≤5.0 × 10–3. For Os1, the steady-state phosphorescence lifetime is 25 ns. In both complexes, the photoluminescence excitation spectra map the absorption spectrum, pointing to an excitation wavelength-independent quantum yield. The ultrafast studies revealed a short-lived (≤100 fs) fluorescence, which stems from the lowest singlet metal-to-ligand-charge-transfer (1MLCT) state and decays by intersystem crossing to the manifold of 3MLCT states. In addition, Os1 exhibits a 50 ps lived emission from an intermediate triplet state at an energy 2000 cm–1 above that of the long-lived (25 ns) phosphorescence. In Os2, the 1MLCT–3MLCT intersystem crossing is faster than that in Os1, and no emission from triplet states is observed other than the lowest one. These observations are attributed to a higher density of states or a smaller energy spacing between them compared with Os1. They highlight the importance of the energetics on the rate of intersystem crossing.

A Compact Tetrathiafulvalene-Benzothiadiazole Dyad and Its Highly Symmetrical Charge-Transfer Salt: Ordered Donor π-Stacks Closely Bound to Their Acceptors

A compact and planar donor–acceptor molecule 1 comprising tetrathiafulvalene (TTF) and benzothiadiazole (BTD) units has been synthesised and experimentally characterised by structural, optical, and electrochemical methods. Solution-processed and thermally evaporated thin films of 1 have also been explored as active materials in organic field-effect transistors (OFETs). For these devices, hole field-effect mobilities of μFE=(1.3±0.5)×10−3 and (2.7±0.4)×10−3 cm2 V s−1 were determined for the solution-processed and thermally evaporated thin films, respectively. An intense intramolecular charge-transfer (ICT) transition at around 495 nm dominates the optical absorption spectrum of the neutral dyad, which also shows a weak emission from its ICT state. The iodine-induced oxidation of 1 leads to a partially oxidised crystalline charge-transfer (CT) salt {(1)2I3}, and eventually also to a fully oxidised compound {1I3}⋅1/2I2. Single crystals of the former CT compound, exhibiting a highly symmetrical crystal structure, reveal a fairly good room temperature electrical conductivity of the order of 2 S cm−1. The one-dimensional spin system bears compactly bonded BTD acceptors (spatial localisation of the LUMO) along its ridge.

Homology Cloning, Heterologous Expression and Characterization of a New Channelrhodopsin

Channelrhodopsins are phototaxis receptors in the plasma membranes of motile unicellular algae. They function as light-gated cation channels and this channel activity has been exploited to trigger action potentials in neurons with light to control neural circuits (“optogenetics"). Four channelrhodopsins were identified in two algal species, Chlamydomonas reinhardtii and Volvox carteri, with known genome sequences; each species contains 2 channelrhodopsins, one absorbing at longer wavelengths and one at shorter wavelengths, named CrChR1 and CrChR2, respectively. Our goals are to expand knowledge of channelrhodopsin mechanisms and also to identify new channelrhodopsins from various algal species with improved properties for optogenetic use. For these aims we are targeting algae from extreme environments to establish the natural diversity of their properties. We cloned a new channelrhodopsin from the psychrophilic (cold-loving) alga, Chlamydomonas augustae, with degenerate primers based on the 4 known homologs. The new protein is 48% and 52% identical to CrChR1 and CrChR2, respectively. We expressed the channelrhodopsin in HEK293 cells and measured light-induced currents to assess their kinetics and action spectrum. Based on the primary structure, kinetics of light-induced photocurrents in HEK293 cells, and action spectrum maximum of 520 nm near that of the two previously found CrChR1, we named the new channelrhodopsin CaChR1. The properties of robust channel activity at physiological pH, fast on-and-off kinetics, and greatly red-shifted action spectrum maximum from that of CrChR2, make CaChR1 advantageous as an optogenetic tool. To know this new channelrhodopsin better, we expressed His-tagged CaChR1 in Pichia pastoris and the yield is about 6 mg/L. The purified His-tagged CaChR1 exhibited an absorption spectrum identical to the action spectrum of CaChR1-generated photocurrents. The future work will be measurement of the photocycles of CaChR1 by flash photolysis, crystallization of CaChR1 for the structure and mutagenesis of CaChR1 to find the critical amino acids accounting for red-shifted spectra, slow inactivation and rapid on-and-off kinetics. Seven new channelrhodopsins including CaChR1 from different algal species have been cloned in our lab at this time, bringing the total known to 13. The work of cloning of these new channelrhodopsins along with the expression of CaChR1 was published in Photochemistry and Photobiology in January 2012

Desarrollo de estructuras nanofotonicas de campo cercano para intensificacion localizada de luz en celulas solares de banda intermedia - Near-field nanophotonic structures for localized light enhancement in intermediate band solar cells

This doctoral thesis explores some of the possibilities that near-field optics can bring to photovoltaics, and in particular to quantum-dot intermediate band solar cells (QD-IBSCs). Our main focus is the analytical optimization of the electric field distribution produced in the vicinity of single scattering particles, in order to produce the highest possible absorption enhancement in the photovoltaic medium in their surroundings. Near-field scattering structures have also been fabricated in laboratory, allowing the application of the previously studied theoretical concepts to real devices. We start by looking into the electrostatic scattering regime, which is only applicable to sub-wavelength sized particles. In this regime it was found that metallic nano-spheroids can produce absorption enhancements of about two orders of magnitude on the material in their vicinity, due to their strong plasmonic resonance. The frequency of such resonance can be tuned with the shape of the particles, allowing us to match it with the optimal transition energies of the intermediate band material. Since these metallic nanoparticles (MNPs) are to be inserted inside the cell photovoltaic medium, they should be coated by a thin insulating layer to prevent electron-hole recombination at their surface. This analysis is then generalized, using an analytical separation-of-variables method implemented in Mathematica7.0, to compute scattering by spheroids of any size and material. This code allowed the study of the scattering properties of wavelengthsized particles (mesoscopic regime), and it was verified that in this regime dielectric spheroids perform better than metallic. The light intensity scattered from such dielectric spheroids can have more than two orders of magnitude than the incident intensity, and the focal region in front of the particle can be shaped in several ways by changing the particle geometry and/or material. Experimental work was also performed in this PhD to implement in practice the concepts studied in the analysis of sub-wavelength MNPs. A wet-coating method was developed to self-assemble regular arrays of colloidal MNPs on the surface of several materials, such as silicon wafers, amorphous silicon films, gallium arsenide and glass. A series of thermal and chemical tests have been performed showing what treatments the nanoparticles can withstand for their embedment in a photovoltaic medium. MNPs arrays are then inserted in an amorphous silicon medium to study the effect of their plasmonic near-field enhancement on the absorption spectrum of the material. The self-assembled arrays of MNPs constructed in these experiments inspired a new strategy for fabricating IBSCs using colloidal quantum dots (CQDs). Such CQDs can be deposited in self-assembled monolayers, using procedures similar to those developed for the patterning of colloidal MNPs. The use of CQDs to form the intermediate band presents several important practical and physical advantages relative to the conventional dots epitaxially grown by the Stranski-Krastanov method. Besides, this provides a fast and inexpensive method for patterning binary arrays of QDs and MNPs, envisioned in the theoretical part of this thesis, in which the MNPs act as antennas focusing the light in the QDs and therefore boosting their absorption

Four-Band Hamiltonian for fast calculations in intermediate-band solar cells

The 8-dimensional Luttinger–Kohn–Pikus–Bir Hamiltonian matrix may be made up of four 4-dimensional blocks. A 4-band Hamiltonian is presented, obtained from making the non-diagonal blocks zero. The parameters of the new Hamiltonian are adjusted to fit the calculated effective masses and strained QD bandgap with the measured ones. The 4-dimensional Hamiltonian thus obtained agrees well with measured quantum efficiency of a quantum dot intermediate band solar cell and the full absorption spectrum can be calculated in about two hours using Mathematica© and a notebook. This is a hundred times faster than with the commonly-used 8-band Hamiltonian and is considered suitable for helping design engineers in the development of nanostructured solar cells.

Solar driven energy conversion applications based on 3C-SiC

There is a strong and growing worldwide research on exploring renewable energy resources. Solar energy is the most abundant, inexhaustible and clean energy source, but there are profound material challenges to capture, convert and store solar energy. In this work, we explore 3C-SiC as an attractive material towards solar-driven energy conversion applications: (i) Boron doped 3C-SiC as candidate for an intermediate band photovoltaic material, and (ii) 3C-SiC as a photoelectrode for solar-driven water splitting. Absorption spectrum of boron doped 3C-SiC shows a deep energy level at ~0.7 eV above the valence band edge. This indicates that boron doped 3C-SiC may be a good candidate as an intermediate band photovoltaic material, and that bulk like 3C-SiC can have sufficient quality to be a promising electrode for photoelectrochemical water splitting.