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91.
This paper proposes a novel wavelet denoising method, which exploits the statistics of individual scans acquired in the course of a coaveraging process. The proposed method consists of shrinking the wavelet coefficients of the noisy signal by a factor that minimizes the expected square error with respect to the true signal. Since the true signal is not known, a sub-optimal estimate of the shrinking factor is calculated by using the sample statistics of the acquired scans. It is shown that such an estimate can be generated as the limit value of a recursive formulation. In a simulated example, the performance of the proposed method is seen to be equivalent to the best choice between hard and soft thresholding for different signal-to-noise ratios. Such a conclusion is also supported by an experimental investigation involving near-infrared (NIR) scans of a diesel sample. It is worth emphasizing that this experimental example concerns the removal of actual instrumental noise, in contrast to other case studies in the denoising literature, which usually present simulations with artificial noise. The simulated and experimental cases indicate that, in classic denoising based on wavelet coefficient thresholding, choosing between the hard and soft options is not straightforward and may lead to considerably different outcomes. By resorting to the proposed method, the analyst is not required to make such a critical decision in order to achieve appropriate results. 相似文献
92.
Soares VA Severino D Junqueira HC Tersariol IL Shida CS Baptista MS Nascimento OR Nantes IL 《Photochemistry and photobiology》2007,83(5):1254-1262
In this work, the regeneration of native horseradish peroxidase (HRP), following the consecutive reduction of oxo-ferryl pi-cation (compound I) and oxo-ferryl (compound II) forms, was observed by UV-visible spectrometry and electron paramagnetic resonance (EPR) in the presence of methylene (MB+), in the dark and under irradiation. In the dark, MB+ did not affect the rate of HRP compound I and II reduction, compatible with hydrogen peroxide as the solely reducing species. Under irradiation, the dye promoted a significant increase in the native HRP regeneration rate in a pH-dependent manner. Flash photolysis measurements revealed significant redshift of the MB+ triplet absorbance spectrum in the presence of native HRP. This result is compatible with the dye binding on the enzyme structure leading to the increase in the photogenerated MB* yield. In the presence of HRP compound II, the lifetime of the dye at 520 nm decreased approximately 75% relative to the presence of native HRP that suggests MB* as the heme iron photochemical reducing agent. In argon and in air-saturated media, photoactivated MB+ led to native HRP regeneration in a time- and concentration-dependent manner. The apparent rate constant for photoactivated MB+-promoted native HRP regeneration, in argon and in air-saturated medium and measured as a function of MB+ concentration, exhibited saturation that is suggestive of dye binding on the HRP structure. The dissociation constant (KMB) observed for the binding of dye to HRP was 5.4+/-0.6 microM and 0.57+/-0.05 microM in argon and air-saturated media, respectively. In argon-saturated medium, the rate of the conversion of HRP compound II to native HRP was significantly higher, k2argon=(2.1+/-0.1)x10(-2) s(-1), than that obtained in air-equilibrated medium, k2air=(0.73+/-0.02)x10(-2) s(-1). Under these conditions the efficiency of photoactivated MB(+)-promoted native HRP regeneration was determined in argon and air-equilibrated media as being, respectively: k2/KMB=3.9x10(3) and 12.8x10(3) M(-1) s(-1). 相似文献
93.
94.
Clarissa O. Da Silva Fbio Eduardo C. Teixeira Jos Andr T. Azevedo Edilson C. Da Silva Marco Antonio Chaer Nascimento 《International journal of quantum chemistry》1996,60(1):433-438
The two lower-lying electronic states (3Σ− and 5Σ−) of the BeC, MgC, and CaC molecules were investigated using restricted Hartree-Fock (RHF), generalized valence bond (GVB), and configuration interaction (CI) calculations to establish the relative ordering of those states as a function of the size of the alkaline-earth element. It is shown that as a result of the competition between bonding effects, which predominate for the 3Σ− states, and exchange effects, which stabilize the 5Σ− states, the ordering of these states can be reversed as we move from the Be to the Ca atom. For both the BeC and MgC molecules, the ground state was found to be a triplet X3Σ− state, but for the CaC molecule, the high-spin X5Σ− becomes more stable. © 1996 John Wiley & Sons, Inc. 相似文献
95.
Eufrânio N. da Silva Júnior Kelly C.G. de Moura Claudia J. Nascimento Antônio V. Pinto 《Tetrahedron letters》2009,50(14):1575-2418
The structure of ‘lapachol peroxide’ was published by Hooker in 1936; however, we recently discovered a mistake in the originally proposed structure; the correct structure, according to X-ray spectroscopy, is given here. 相似文献
96.
Eliana M.A. Valle Benedicto A.V. Lima Antonio G. Ferreira Fbio B. do Nascimento Victor M. Deflon Izaura C.N. Digenes Ulrich Abram Javier Ellena Eduardo E. Castellano Alzir A. Batista 《Polyhedron》2009,28(16):3473-3478
The reaction of cis-[RuCl2(P–P)(N–N)] type complexes (P–P = 1,4-bis(diphenylphosphino)butane or (1,1′-diphenylphosphino)ferrocene; N–N = 2,2′-bipyridine or 1,10-phenantroline) with monodentate ligands (L), such as 4-methylpyridine, 4-phenylpyridine and benzonitrile forms [RuCl(L)(P–P)(N–N)]+ species. Upon characterization of the isolated compounds by elemental analysis, 31P{1H} NMR and X-ray crystallography it was found out that the type of the L ligand determines its position in relation to the phosphorus atom. While pyridine derivatives like 4-methylpyridine and 4-phenylpyridine coordinate trans to the phosphorus atom, the benzonitrile ligand (bzCN), a good π acceptor, coordinates trans to the nitrogen atom. A 31P{1H} NMR experiment following the reaction of the precursor cis-[RuCl2(dppb)(phen)] with the benzonitrile ligand shows that the final position of the entering ligand in the complex is better defined as a consequence of the competitive effect between the phosphorus atom and the cyano-group from the benzonitrile moiety and not by the trans effect. In this case, the benzonitrile group is stabilized trans to one of the nitrogen atoms of the N–N ligand. A differential pulse voltammetry experiment confirms this statement. In both experiments the [RuCl(bzCN)(dppb)(phen)]PF6 species with the bzCN ligand positioned trans to a phosphorus atom of the dppb ligand was detected as an intermediate complex. 相似文献
97.
Vera L. P. Soares Regina S. V. Nascimento Sandra R. Albinante 《Journal of Thermal Analysis and Calorimetry》2009,97(2):621-626
Biodiesel from soybean oil transesterified with methanol (TSO) becomes viscous and gelifies at low storage temperatures which makes it difficult to pump. To inhibit this behaviour bulky esters were added to reduce the crystallization temperature of TSO and to modify the rate of conversion of crystallized mass. This rate was found to follow a JMAK kinetic model. The Avrami’s parameter n was constant for TSO, while two n values were found for TSO-additive solutions, meaning that the additives first slowed down the rate of nucleation and, later on as enough nuclei had been formed, crystal growth rate dominated and the previous crystallization rate was recovered. 相似文献
98.
Eduardo Colli Marcio L. do Nascimento Edson Vargas 《Annales de l'Institut Henri Poincaré (C) Analyse Non Linéaire》2009,26(4):869
We study the growth of Dfn(f(c)) when f is a Fibonacci critical covering map of the circle with negative Schwarzian derivative, degree d2 and critical point c of order ℓ>1. As an application we prove that f exhibits exponential decay of geometry if and only if ℓ2, and in this case it has an absolutely continuous invariant probability measure, although not satisfying the so-called Collet–Eckmann condition. 相似文献
99.
Machulek A Vautier-Giongo C Moraes JE Nascimento CA Quina FH 《Photochemistry and photobiology》2006,82(1):208-212
The photo-Fenton reaction (Fe2+/Fe3+, H2O2, UV light) is strongly inhibited by high concentrations of added chloride ion. In this work, the effect of added chloride ion on the photocatalytic step that converts Fe(III) back to Fe(II) is studied by nanosecond laser flash photolysis over a wide range of pH (1.0-3.3) and concentrations of Fe(III) (0.1-1.0 mM) and chloride ion (0.05-0.75 M). An explicit mechanistic model based on the preferential formation of the less-reactive Cl2*- radical anion via two routes (competitive photolysis of the iron(III)-chloride complex to chlorine atoms instead of the desired hydroxyl radical and pH-dependent scavenging of the hydroxyl radical by chloride ion) is proposed. This model, which fits the laser flash photolysis data for the production and decay of Cl2*- over the entire range of conditions investigated, suggests that inhibition of the photocatalytic step of the photo-Fenton process in the presence of chloride ion can be circumvented by maintaining the pH of the medium at or slightly above 3.0 throughout the reaction. 相似文献
100.
In this paper, we report electronic temperature measurement in a Rb ultracold plasma formed in a magneto-optical trap. We used the ion evaporation rate and the model presented by Comparat et al. [Mon. Not. R. Astron. Soc. 361, 1227 (2005)] to extract the electronic temperature in the plasma as a function of the energy difference between the laser photon and the ionization threshold. The obtained results are similar to those obtained in Cs; however, they do not seem to show any saturation. Comparison with other models may lead to improvements in the experiments and the theoretical models. 相似文献