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Modern research data, where a large number of functional predictors is collected on few subjects are becoming increasingly common. In this paper we propose a variable selection technique, when the predictors are functional and the response is scalar. Our approach is based on adopting a generalized functional linear model framework and using a penalized likelihood method that simultaneously controls the sparsity of the model and the smoothness of the corresponding coefficient functions by adequate penalization. The methodology is characterized by high predictive accuracy, and yields interpretable models, while retaining computational efficiency. The proposed method is investigated numerically in finite samples, and applied to a diffusion tensor imaging tractography data set and a chemometric data set.
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We present a visualization of the predicted instability in ionic conduction from a binary electrolyte into a charge selective solid. This instability develops when a voltage greater than critical is applied to a thin layer of copper sulfate flanked by a copper anode and a cation selective membrane. The current-voltage dependence exhibits a saturation at the limiting current. With a further increase of voltage, the current increases, marking the transition to the overlimiting conductance. This transition is mediated by the appearing vortical flow that increases with the applied voltage.
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The S(1)((1)A('))<--S(0)((1)A(')) absorption spectrum of jet-cooled 2,3-benzofluorene (Bzf) has been measured by cavity ring-down spectroscopy. The potential energy surfaces of the S(n=0,1,2) states of Bzf have been investigated with calculations based on the time-dependent density functional theory (TD-DFT). At the B3LYP/TZ level of theory, TD-DFT does not deliver a realistic difference between the excited S(1) and S(2) potential energy surfaces, a problem which can be avoided by introducing a reference geometry where this difference coincides with the observation. In this geometry, an expression for the Herzberg-Teller corrected intensities of the vibronic bands is proposed, allowing a straightforward assignment of the observed a(') modes below 900 cm(-1), including realistic calculated intensities. For vibronic bands at higher energies, the agreement between calculated and observed modes is deteriorated by substantial Dushinsky rotations and nonparabolicities of the potential energy surface S(1).
Asunto(s)
Frío , Fluorenos/química , Gases/química , Teoría Cuántica , Simulación por Computador , Modelos Químicos , Rotación , Espectrometría de Fluorescencia , Espectrofotometría Ultravioleta , Factores de Tiempo , VibraciónRESUMEN
The study of the S1(1A1)<--S0(1A1) transition of benzo[g,h,i]perylene (BghiP, C22H12) in supersonic jets and solid rare gas matrices is reported. In the jet-cooled spectrum, the origin band position is located at 25,027.1+/-0.2 cm-1, the assignment being supported by the analysis of vibrational shifts and rotational band contours. Except for the origin band, which is weak, all bands are attributed to the fundamental excitation of nontotally symmetric b1 vibrational modes of S1. The intensity pattern is interpreted as a consequence of the weak oscillator strength of the electronic transition combined with intensity-borrowing through vibronic interaction between the S1(1A1) and S2(1B1) states. The spectra of the S1(1A1)<--S0(1A1) and S2(1B1)<--S0(1A1) transitions have also been measured for BghiP in solid neon and argon matrices. The comparison of the redshifts determined for either transition reveals that the polarizability of BghiP is larger in its S2 than in its S1 state. Bandwidths of 2.7 cm-1 measured in supersonic jets, which provide conditions relevant for astrophysics, are similar to those of most diffuse interstellar bands. The electronic transitions of BghiP are found to lie outside the ranges covered by present databases. From the comparison between experimental spectra and theoretical computations, it is concluded that the accuracy of empirical and ab initio approaches in predicting electronic energies is still not sufficient to identify astrophysically interesting candidates for spectroscopic laboratory studies.
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The photodynamic therapy (PDT) became more and more widely used in the treatment of different malignant tumors. For present studies, porphyrins and haematoporphyrin derivatives, in the conditions of N2 laser radiation, were chosen because their strong absorption along a large spectral range; this makes possible the excitation of their fluorescence at 337.1 nm, which is the wavelength of the N2 pulsed laser radiation. The photophysical and photochemical properties depend on the central metal and the peripheral substituents. Trying to find an optimal sensitizer to be used with N2 laser in photodynamic therapy (PDT), a spectroscopic study of these dyes was performed. The obtained data show that the UV radiation emitted by a N2 pulsed laser may be used for PDT application; among other dyes having interesting characteristics, Zn-TSPP and Zn-TNP in DMSO at 0.5% concentration seem to be more relevant.
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Metaloporfirinas/química , Fotoquimioterapia/métodos , Porfirinas/química , Gráficos por Computador , Humanos , Neoplasias/tratamiento farmacológico , Análisis EspectralRESUMEN
The authors present the case of a 48 years old male with lithiasis obstructive icterus who was operated by laparoscopic transcystic approach with choledochoscopy. This minimally invasive technique was very spectacular trough the using of laparoscopic ultrasonography, dissection with Ultra-Shears device and transcystic choledochoscopy. Careful watching of abdominal laparoscopic view and transcystic choledochoscopic view is the particularity of laparoscopic transcystic management of choledocholithiasis. This metod don't let us to explore the biliary tract before the junction between common bile duct and cystic duct.