Search results for "Proton transfer"

Hydrogen bonding and proton transfer involving the trihydride complexes Cp*M(dppe)H 3 (M = Mo, W) and fluorinated alcohols: the competitive role of t…

2003

International audience; The protonation of complexes Cp*M(dppe)H3 (dppe is ethylenebis(diphenylphosphine), M = Mo (1), W (2)) by a variety of fluorinated alcohols of different acid strength (FCH2CH2OH, CF3CH2OH, (CF3)2CHOH, and (CF3)3COH) was investigated experimentally by the variable temperature spectroscopic methods (IR, NMR) and stopped-flow technique (UV-Vis). The structures of the hydrogen-bonded and proton transfer products were studied by DFT calculations. In agreement with the calculation results, the IR data suggest that the initial hydrogen bond is established with a hydride site for complex 1 and with the metal site for complex 2. However, no intermediate dihydrogen complex foun…

A novel 2,6-bis(benzoxazolyl)phenol macrocyclic chemosensor with enhanced fluorophore properties by photoinduced intramolecular proton transfer

2023

Macrocyclic ligand L, in which a 2,6-bis(2-benzoxazolyl)phenol (bis-HBO) group is incorporated in triethylenetetramine, was designed and synthesized with the aim of creating a chemosensor with high selectivity and specificity for metal cations in an aqueous environment. The availability of several proton acceptors and donors, and amine and phenol hydroxy groups, respectively, affects the keto-enol equilibrium in both the ground and excited states, and the ligand properties show dependence on the pH of the solution. L is fluorescent in the visible range, through an excited-state intramolecular proton transfer (ESIPT) mechanism. The results of an exhaustive characterization of L by spectrosco…

Advances and challenges for experiment and theory for multi-electron multi-proton transfer at electrified solid-liquid interfaces.

2020

Multi-electron, multi-proton transfer is important in a wide spectrum of processes spanning biological, chemical and physical systems. These reactions have attracted significant interest due to both fundamental curiosity and potential applications in energy technology. In this Perspective Review, we shed light on modern aspects of electrode processes in the 21st century, in particular on the recent advances and challenges in multistep electron/proton transfers at solid–liquid interfaces. Ongoing developments of analytical techniques and operando spectrometry at electrode/electrolyte interfaces and reliable computational approaches to simulate complicated interfacial electrochemical reaction…

Kinetics of proton release and uptake by channelrhodopsin-2

2012

Electrophysiological experiments showed that the light-activated cation channel channelrhodopsin-2 (ChR2) pumps protons in the absence of a membrane potential. We determined here the kinetics of transient pH change using a water-soluble pH-indicator. It is shown that ChR2 released protons prior to uptake with a stoichiometry of 0.3 protons per ChR2. Comparison to the photocycle kinetics revealed that proton release and uptake match rise and decay of the View the MathML sourceP3520 intermediate. As the View the MathML sourceP3520 state also represents the conductive state of cation channeling, the concurrence of proton pumping and channel gating implies an intimate mechanistic link of the tw…

Experimental and Computational Studies of Hydrogen Bonding and Proton Transfer to [Cp*Fe(dppe)H]

2005

The present contribution reports experimental and computational investigations of the interaction between [Cp*Fe(dppe)H] and different proton donors (HA). The focus is on the structure of the proton transfer intermediates and on the potential energy surface of the proton transfer leading to the dihydrogen complex [Cp*Fe(dppe)(H2)]+. With p-nitrophenol (PNP) a UV/Visible study provides evidence of the formation of the ion-pair stabilized by a hydrogen bond between the nonclassical cation [Cp*Fe(dppe)(H2)]+ and the homoconjugated anion ([AHA]-). With trifluoroacetic acid (TFA), the hydrogen-bonded ion pair containing the simple conjugate base (A-) in equilibrium with the free ions is observed…

Gaining deeper insight into aroma perception: An integrative study of the oral processing of breads with different structures

2017

WOS:000394071900015; International audience; The objective of this study was to investigate for the first time the influence of bread structure, volatile compounds, and oral processing on aroma perception. 3 types of French baguette were created using the same raw ingredients but different bread-making processes; they consequently varied in their crumb and crust structures. We characterized the initial volatile profiles of two bread structural subtypes-namely bread crumb and bread crumb with crust-using proton transfer reaction-mass spectrometry (PTR-MS) headspace analysis. Three types of bread were characterized by thirty-nine ion fragments from m/z 45 to 139. We then conducted a study in …

Proton Transfer and Protein Conformation Dynamics in Photosensitive Proteins by Time-resolved Step-scan Fourier-transform Infrared Spectroscopy

2014

Monitoring the dynamics of protonation and protein backbone conformation changes during the function of a protein is an essential step towards understanding its mechanism. Protonation and conformational changes affect the vibration pattern of amino acid side chains and of the peptide bond, respectively, both of which can be probed by infrared (IR) difference spectroscopy. For proteins whose function can be repetitively and reproducibly triggered by light, it is possible to obtain infrared difference spectra with (sub)microsecond resolution over a broad spectral range using the step-scan Fourier transform infrared technique. With -10(2)-10(3) repetitions of the photoreaction, the minimum num…

Molecular mechanisms of aroma persistence: From noncovalent interactions between aroma compounds and the oral mucosa to metabolization of aroma compo…

2021

International audience; The present study aims to reveal the molecular mechanisms underlying aroma persistence, as it plays a major role in food appreciation and quality. A multidisciplinary approach including ex vivo experiments using a novel model of oral mucosa and saliva as well as in vivo dynamic instrumental and sensory experiments was applied. Ex vivo results showed a reduction in aroma release between 7 and 86% in the presence of the thin layer of salivary proteins covering the oral mucosa (mucosal pellicle). This reduction was explained by hydrophobic interactions involving the mucosal pellicle and by the ability of oral cells and saliva to metabolize specific aroma compounds. The …

Proton-Transfer-Reaction Mass-Spectrometry (PTR-MS) for the study of the aromatic potential of bakery starter strains

2016

Guest-to-host proton transfer in melatonin-beta-cyclodextrin inclusion complex by ionspray, fast atom bombardment and tandem mass spectrometry.

2001

Ionspray (IS) and fast atom bombardment (FAB) positive ionization mass spectrometry (MS) of 1:1 β-cyclodextrin (β-CD)-melatonin (MLT) host-guest complex allowed the detection of gaseous protonated 1:1 β-CD-MLT. Tandem MS collision-induced dissociation (CID) of such protonated 1:1 β-CD-MLT species showed the proton (charge) to be retained to a significant extent by the host and by its cage fragmentation products, in spite of the higher proton affinity of MLT with respect to that of β-CD. This requires an endothermic guest-to-host proton transfer to occur within the gaseous association. Collisional activation could be accounted for by the promotion of such an endothermic process; however…