scholarly journals Exploring the Mechanism of Olfactory Recognition at the Initial Stage by Modeling the Emission Spectrum of Electron Transfer

2019 ◽  
Author(s):  
Shu Liu ◽  
Rao Fu ◽  
Guangwu Li
Keyword(s):  
Electron Transfer ◽  
Emission Spectrum ◽  
Active Sites ◽  
Isotope Effects ◽  
Emission Spectra ◽  
Initial Stage ◽  
Olfactory Sense ◽  
Bitter Almond ◽  
Deuterated Analogue ◽  
Odorant Molecule

AbstractOlfactory sense remains elusive regarding the primary reception mechanism. Some studies suggest that olfaction is a spectral sense, the olfactory event is triggered by electron transfer (ET) across the odorants at the active sites of odorant receptors (ORs). Herein we present a Donor-Bridge-Acceptor model, proposing that the ET process can be viewed as an electron hopping from the donor molecule to the odorant molecule (Bridge), then hopping off to the acceptor molecule, making the electronic state of the odorant molecule change along with vibrations (vibronic transition). The odorant specific parameter, Huang–Rhys factor can be derived from ab initio calculations, which make the simulation of ET spectra achievable. In this study, we revealed that the emission spectra (after Gaussian convolution) can be acted as odor characteristic spectra. Using the emission spectrum of ET, we were able to reasonably interpret the similar bitter-almond odors among hydrogen cyanide, benzaldehyde and nitrobenzene. In terms of isotope effects, we succeeded in explaining why subjects can easily distinguish cyclopentadecanone from its fully deuterated analogue cyclopentadecanone-d28 but not distinguishing acetophenone from acetophenone-d8.

Searching for 3D effects in the optical, high spectral resolution emission spectrum of KELT-9b

2021 ◽  
Author(s):  
Lorenzo Pino ◽  
Matteo Brogi ◽  
Jean-Michel Désert ◽  
Emily Rauscher
Keyword(s):  
Emission Spectrum ◽  
Spectral Resolution ◽  
Planet Formation ◽  
Emission Spectra ◽  
Optical Emission ◽  
High Spectral Resolution ◽  
Optical Emission Spectrum ◽  
Hot Jupiters ◽  
Atmospheric Structure ◽  
3D Effects

<p>Ultra-hot Jupiters (UHJs; T<sub>eq</sub> ≥ 2500 K) are the hottest gaseous giants known. They emerged as ideal laboratories to test theories of atmospheric structure and its link to planet formation. Indeed, because of their high temperatures, (1) they likely host atmospheres in chemical equilibrium and (2) clouds do not form in their day-side. Their continuum, which can be measured with space-facilities, can be mostly attributed to H- opacity, an indicator of metallicity. From the ground, the high spectral resolution emission spectra of UHJs contains thousands of lines of refractory (Fe, Ti, TiO, …) and volatile species (OH, CO, …), whose combined atmospheric abundances could track planet formation history in a unique way. In this talk, we take a deeper look to the optical emission spectrum of KELT-9b covering planetary phases 0.25 - 0.75 (i.e. between secondary eclipse and quadrature), and search for the effect of atmospheric dynamics and three-dimensionality of the planet atmosphere on the resolved line profiles, in the context of a consolidated statistical framework. We discuss the suitability of the traditionally adopted 1D models to interprete phase-resolved observations of ultra-hot Jupiters, and the potential of this kind of observations to probe their 3D atmospheric structure and dynamics. Ultimately, understanding which factors affect the line-shape in UHJs will also lead to more accurate and more precise abundance measurements, opening a new window on exoplanet formation and evolution.</p>

Kinetics and mechanism of oxidation of N,N′-dimethyl-9,9′-biacridanyl by some π acceptors and a one-electron oxidant

1985 ◽  
Vol 63 (2) ◽  
pp. 445-451 ◽  
Author(s):  
Allan K. Colter ◽  
Charles C. Lai ◽  
A. Gregg Parsons ◽  
N. Bruce Ramsey ◽  
Gunzi Saito
Keyword(s):  
Electron Transfer ◽  
Reduction Potential ◽  
Isotope Effects ◽  
Substituent Effects ◽  
Kinetic Isotope Effects ◽  
Spin Trapping ◽  
Single Electron Transfer ◽  
Kinetic Isotope ◽  
The One ◽  
Rule Out

Oxidation of N,N′-dimethyl-9,9′-biacridanyl (DD) has been investigated as a model for single electron transfer (SET)-initiated oxidation of NADH coenzyme models such as N-methylacridan (DH). Oxidants investigated cover a 1010-fold range of reactivity in acetonitrile and include the π acceptors 1,4-benzoquinone (BQ), 2,6-dichloro-1,4-benzoquinone (DCIBQ), p-chloranil (CA), 2,3-dicyanobenzoquinone (DCBQ), 2,3-dicyano-1,4-naphthoquinone (DCNQ), 2,3-dicyano-5-nitro-1,4-naphthoquinone (DCNNQ), 9-dicyanomethylene-2,4,7-trinitrofluorene (DCMTNF), 9-dicyanomethylene-2,4,5,7-tetranitrofluorene (DCMTENF), 7,7,8,8-tetracyanoquinodimethane (TCNQ), and tetracyanoethylene (TCNE), and the one-electron oxidant tris(2,2′-bipyridyl)cobalt(III), [Formula: see text] The oxidation product is, in every case, N-methylacridinium ion (D+). A mechanism involving a rate-determining electron transfer with simultaneous fragmentation to D+ and N-methyl-9-acridanyl radical (D•) is proposed. This mechanism is supported by the observed dependence of the rate on oxidant reduction potential, by spin-trapping experiments, by kinetic isotope effects in oxidation of 9,9′-dideuterio-DD, and by substituent effects in oxidation of 2,2′- and 3,3′-dimethoxy-DD. The rate of oxidation of DD relative to that of DH is 3.4 × 102 with [Formula: see text] and with the π acceptors varies from ea. 0.3 (BQ) to 8.1 × 104 (DCMTENF). The results rule out a SET-initiated mechanism for oxidation of DH by all of the oxidants studied except TCNQ and DCMTENF.

scholarly journals Mechanisms of Two-Electron and Four-Electron Electrochemical Oxygen Reduction Reactions at Nitrogen-Doped Reduced Graphene Oxide

2019 ◽  
Author(s):  
Hyo Won Kim ◽  
Vanessa Jane Bukas ◽  
Hun Park ◽  
Sojung Park ◽  
Kyle M. Diederichsen ◽  
...  
Keyword(s):  
Oxygen Reduction ◽  
Photoelectron Spectroscopy ◽  
Active Sites ◽  
Isotope Effects ◽  
Underlying Mechanism ◽  
Reduction Reaction ◽  
Graphene Oxides ◽  
Nitrogen Doped ◽  
General Chemical ◽  
Reduced Graphene

Doped carbon-based systems have been extensively studied over the past decade as active electrocatalysts for both the two-electron (2e-) and four-electron (4e-) oxygen reduction reaction (ORR). However, the mechanisms for ORR are generally poorly understood. Here we report an extensive experimental and first-principles theoretical study of the ORR at nitrogen-doped reduced graphene oxides (NrGO). We synthesize three distinct NrGO catalysts and investigate their chemical and structural properties in detail via X-ray photoelectron spectroscopy, infrared and Raman spectroscopy, high-resolution transmission electron microscopy and thin-film electrical conductivity. ORR experiments include the pH dependences of 2e- versus 4e- ORR selectivity, ORR onset potentials, Tafel slopes and H/D kinetic isotope effects. These experiments show very different ORR behavior for the three catalysts, both in terms of selectivity and the underlying mechanism which proceeds either via coupled proton-electron transfers (CPETs) or non-CPETs. Reasonable structural models developed from DFT rationalize this behavior. The key determinant between CPET vs. non-CPET mechanisms is the electron density at the Fermi level under operating ORR conditions. Regardless of the reaction mechanism or electrolyte pH, however, we identify the ORR active sites as sp2 carbons that are located next to oxide regions. This assignment highlights the importance of oxygen functional groups, while details of (modest) N-doping may still affect the overall catalytic activity, and likely also the selectivity, by modifying the general chemical environment around the active site.

scholarly journals Reflection of sound pulses from an inhomogeneous bubble medium

2021 ◽  
Vol 2057 (1) ◽  
pp. 012032
Author(s):  
I A Ogorodnikov
Keyword(s):  
Absorption Band ◽  
Emission Spectrum ◽  
Initial Phase ◽  
Volume Concentration ◽  
Transition Radiation ◽  
Spectral Characteristics ◽  
Bubble Medium ◽  
Boundary Zone ◽  
Initial Stage ◽  
Sound Pulses

Abstract The effect of changes in the volume concentration of bubbles in the boundary zone of the bubble medium on the nature of reflection and radiation of the excited bubble medium is studied. The spectral characteristics of the radiation of a bubble medium are obtained at the initial stage of transition radiation and at large times when the radiation is stationary. It is shown that in the initial phase the emission spectrum is broadband and is located in the absorption band of the bubble medium, and at large times the emission spectrum is located outside this band.

scholarly journals Causes of Color in Minerals and Gemstones

2001 ◽  
Vol 9 (2) ◽  
pp. 14-17
Author(s):  
Paul F. Hlava
Keyword(s):  
Emission Spectrum ◽  
White Light ◽  
Emission Spectra ◽  
Light Sources ◽  
Physical Phenomena

The colors that one sees when looking at a mineral or gemstone are due to the response of that person's eye to the energies of the light, the emission spectrum of the illumination, and, most importantly, physical phenomena in the material that cause some colors to be absorbed while others are undisturbed or enhanced. It is beyond the scope of this article to do more than touch on the physiology of the eye that allows us to see colors. Likewise, we will not dwell on the emission spectra of various light sources. Rather, we will concentrate on the various ways in which materials, especially minerals and their heights of perfection, gemstones, produce color from white light.

Oxygen Isotope Effects on Electron Transfer to O2Probed Using Chemically Modified Flavins Bound to Glucose Oxidase

2004 ◽  
Vol 126 (46) ◽  
pp. 15120-15131 ◽  
Author(s):  
Justine P. Roth ◽  
Roseanne Wincek ◽  
Gabrielle Nodet ◽  
Dale E. Edmondson ◽  
William S. McIntire ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Glucose Oxidase ◽  
Oxygen Isotope ◽  
Isotope Effects ◽  
Chemically Modified
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