Search results for "conical"
showing 10 items of 109 documents
Photoreactivity of Furocoumarins and DNA in PUVA Therapy: Formation of Psoralen−Thymine Adducts
2008
The mechanism of the [2 + 2] cycloaddition photoreaction of psoralen and a DNA nucleobase, thymine, cornerstone of the furocoumarin-based PUVA (psoralen + UVA radiation) phototherapy, has been studied by the quantum-chemical multiconfigurational CASPT2 method. Triplet- and singlet-mediated mono- and diadduct formations have been determined to take place via singlet-triplet crossings and conical intersections, correlated with the initially promoted triplet or singlet states in different possible reactive orientations. Pyroneside monoadducts are suggested to be formed in the triplet manifold of the system, and to be less prone to yield diadducts because of the properties of the monoadduct low…
The Role of Adenine Excimers in the Photophysics of Oligonucleotides
2009
Energies and structures of different arrangements of the stacked adenine homodimer have been computed at the ab initio CASPT2 level of theory in isolation and in an aqueous environment. Adenine dimers are shown to form excimer singlet states with different degrees of stacking and interaction. A model for a 2-fold decay dynamics of adenine oligomers can be supported in which, after initial excitation in the middle UV range, unstacked or slightly stacked pairs of nucleobases will relax by an ultrafast internal conversion to the ground state, localizing the excitation in the monomer and through the corresponding conical intersection with the ground state. On the other hand, long-lifetime intra…
Theoretical Insight into the Spectroscopy and Photochemistry of Isoalloxazine, the Flavin Core Ring
2006
The electronic singlet-singlet and singlet-triplet electronic transitions of the isoalloxazine ring of the flavin core are studied using second-order perturbation theory within the framework of the CASPT2//CASSCF protocol. The main features of the absorption spectrum are computed at 3.09, 4.28, 4.69, 5.00, and 5.37 eV. The lowest singlet (S1) and triplet (T1) excited states are found to be both of pi character with a singlet-triplet splitting of 0.57 eV. On the basis of the analysis of the computed spin-orbit couplings and the potential energy hypersurfaces built for the relevant excited states, the intrinsic mechanism for photoinduced population of T1 is discussed. Upon light absorption, e…
Multiple Decay Mechanisms and 2D-UV Spectroscopic Fingerprints of Singlet Excited Solvated Adenine-Uracil Monophosphate
2016
The decay channels of singlet excited adenine uracil monophosphate (ApU) in water are studied with CASPT2//CASSCF:MM potential energy calculations and simulation of the 2D-UV spectroscopic fingerprints with the aim of elucidating the role of the different electronic states of the stacked conformer in the excited state dynamics. The adenine 1La state can decay without a barrier to a conical intersection with the ground state. In contrast, the adenine 1Lb and uracil S(U) states have minima that are separated from the intersections by sizeable barriers. Depending on the backbone conformation, the CT state can undergo inter-base hydrogen transfer and decay to the ground state through a conical …
On the FCNS⇆FC(NS) reaction: A matrix isolation and theoretical study
2015
Abstract The FCNS ⇆ FC(NS) photoisomerization process is a simple model system for molecular switches. Here, we examined the switching processes by experimental and theoretical methods. Prior matrix-isolation IR spectroscopic studies were complemented by matrix-isolation UV spectroscopic measurements to assist the interpretation of the mechanism of the ring closure and opening processes and to verify the accuracy of the computations on the vertical excitation energies. Vertical excitation energies were computed by the EOMEE-CCSD, MCSCF, and MR-CISD methods. Conical intersections were also searched for and three conical intersections along the reaction path FCNS → FC(NS) were located, one co…
Biomolecular conjugation inside synthetic polymer nanopores via glycoprotein-lectin interactions
2011
We demonstrate the supramolecular bioconjugation of concanavalin A (Con A) protein with glycoenzyme horseradish peroxidase (HRP) inside single nanopores, fabricated in heavy ion tracked polymer membranes. Firstly, the HRP-enzyme was covalently immobilized on the inner wall of the pores using carbodiimide coupling chemistry. The immobilized HRP-enzyme molecules bear sugar (mannose) groups available for the binding of Con A protein. Secondly, the bioconjugation of Con A on the pore wall was achieved through its biospecific interactions with the mannose residues of the HRP enzyme. The immobilization of biomolecules inside the nanopore leads to the reduction of the available area for ionic tran…
Modulation of current-time traces by two-pore arrangements of polyimide nanofluidic diodes
2019
Liquid state arrangements of two polymeric membranes with single conical nanopores constitute nanofluidic diodes that allow a rich electrical functionality based on the modulation of individual conductances in aqueous electrolyte solutions. In particular, the prescribed sequences of current-time traces can be obtained by preprogramed switching between series and parallel pore connection arrangements. Hybrid nanopore-solid-state circuits are also possible. The basic applied physics of the nanofluidic diode arrangements can be understood from simple circuit theory concepts and should be of widespread interest to sensing and actuating procedures, controlled release dispensers, and energy conve…
FILTER RESPONSE OF RESONANT WAVEGUIDE DIELECTRIC GRATINGS AT PLANE-WAVE CONICAL INCIDENCE
2009
An accurate and efficient formulation is presented for the electromagnetic analysis of dielectric waveguide gratings under plane-wave conical incidence. An arbitrary number of dielectric bars can be placed inside each one-dimension periodic cell, including the effect of dielectric losses. The reflectance of a dielectric waveguide grating under conical incidence is compared with theoretical results presented by other authors, finding a very good agreement. A single-layer reflection filter has been designed centered at λ0=1.5 μm whose spectral and angular responses are shown. For this structure, the effect of the asymmetry of the distribution of the refraction index in the reflectance has bee…
Acousto-optic interaction in biconical tapered fibers: shaping of the stopbands
2016
The effect of a gradual reduction of the fiber diameter on the acousto-optic (AO) interaction is reported. The experimental and theoretical study of the intermodal coupling induced by a flexural acoustic wave in a biconical tapered fiber shows that it is possible to shape the transmission spectrum, for example, substantially broadening the bandwidth of the resonant couplings. The geometry of the taper transitions can be regarded as an extra degree of freedom to design the AO devices. Optical bandwidths above 45 nm are reported in a tapered fiber with a gradual reduction of the fiber down to 70 μm diameter. The effect of including long taper transition is also reported in a double-tapered st…
Conical connection adjustment in prosthetic abutments obtained by different techniques
2019
Background The goal of this study is to compare the misfit (>150µm) generated once the restoration, made by different techniques, is retained to a single conical implant. Material and methods 15 internal connection implants (MIS C1 4'20x10mm) are embedded each one perpendicularly to an horizontal surface of the 1x1x2cm poliuretan resin model. The 15 samples obtained are divided in 5 groups depending on the framework process (n=3): 1/casting, 2/overcasting, 3/Ti-base, 4/milling and 5/laser sintering. The cobalt-chromium alloy frameworks are screw-retained to their respective implants to a 30-Ncm torque. Once it is retained the framework to the implant, the next step is to section the sample …