ABSTRACT
Long-distance proton transfer is a ubiquitous phenomenon in chemical and biological systems. Two mechanisms of proton transfer in solids are well established; the Grotthuss mechanism (proton-relay) and the vehicle mechanism. Previously, intramolecular proton transfer has been extensively studied in the gas phase to understand the proton transfer mechanism microscopically. However, only the Grotthuss mechanism was proposed so far for intramolecular proton transfer. Here we show the first evidence for long-distance proton transfer (ca. 0.7 nm) via the vehicle mechanism in a gas-phase protonated molecule. Using ion mobility mass spectrometry, we observed that intramolecular proton transfer between two structural isomers with different protonation sites of protonated benzocaine (BC; p-NH2C6H4COOC2H5) is induced by a single NH3 molecule. In combination with theoretical calculations of the reaction pathway for the bimolecular reaction of BC·H+ + NH3, it was concluded that intramolecular proton transfer to produce the O-protomer (protonated BC at the C[double bond, length as m-dash]O group) proceeds in the N-protomer (protonated BC at the NH2 group) by NH3 coordination. In the calculated pathway, the NH4+ ion formed by proton transfer from the NH2 group of the N-protomer to NH3 donates a proton to the C[double bond, length as m-dash]O group after hopping on the benzene ring of BC. Our results demonstrate that we can investigate microscopically not only the Grotthuss mechanism but also the vehicle mechanism using gas-phase spectroscopic methods.
ABSTRACT
The Sâ´π hemibond (two-center three-electron, 2c-3e, bond) is an attractive interaction between a sulfur atom and π electrons. The Sâ´π hemibond is of essential importance in understanding chemistry of sulfur radical cations, and its roles in biochemistry have recently attracted much interest. In the present study, we observe the Sâ´π hemibond in the simplest model system in the gas phase. Infrared spectroscopy is applied to the [benzene-(H2S) n ]+ (n = 1-4) radical cation clusters. In n = 1, the CH stretch and SH stretch bands of the benzene and H2S moieties, respectively, are clearly different from those of the neutral molecules but similar to those of the ionic species. These vibrational features show that the positive charge is delocalized over the cluster due to the Sâ´π hemibond formation. In n = 2-4, the Sâ´S hemibond and S-π-S multicenter hemibond (three-center five-electron, 3c-5e, bond) can compete with the Sâ´π hemibond. The observed vibrational features clearly indicate that the Sâ´S hemibond formation is superior to the Sâ´π hemibond and S-π-S multicenter hemibond. Calculations of several dispersion-corrected density functionals are compared with the observations. While all the tested functionals qualitatively catch the feature of the Sâ´π hemibond, the energy order among the isomers of the different hemibond motifs strongly depends on the functionals. These results demonstrate that the [benzene-(H2S) n ]+ clusters can be a benchmark of density functionals to evaluate the sulfur hemibonds.
ABSTRACT
Changes of the excess charge accommodation motif in hemibonded and protonated hydrogen sulfide by microsolvation are studied by infrared spectroscopy of [(H2S)n(X)1]+ and H+(H2S)n(X)1 (n = 1 and 2, X = water, methanol, and ethanol) clusters. While the hemibond in the (H2S)2+ ion core is stable to the microhydration by a single water molecule, the hemibond is broken by the proton transfer with the microsolvation by a single methanol or ethanol molecule. Hetero hemibond formation between hydrogen sulfide and these solvent molecules is not observed. On the other hand, the excess proton in H+(H2S)n can be easily transferred to the solvent molecule, even though the proton affinity of the solvent molecule is lower than that of hydrogen sulfide. Implications of these results to the charge accommodation by sulfur under the biological conditions are discussed.
ABSTRACT
The objective of this study is to develop a device for noninvasive local tissue electrical impedance tomography (EIT) using divided electrodes with guard electrodes and to validate its effectiveness using bioequivalent phantoms. For this purpose, we prepared a measurement device and bioequivalent phantoms, measured the electrical characteristics of the phantoms, and validated the method using the phantoms. Monolayer phantoms mimicking the brain and muscle and bilayer phantoms consisting of muscle and brain layers were prepared. The relative differences between the measured electrical conductivities of the monolayer brain and muscle phantoms and the true values determined by the 4-electrode method were both less than 10%. The relative differences between the measured and true values in the bilayer phantoms were less than 20% in both layers. The biological impedance measurement device that we developed was confirmed to be effective for impedance measurement in bilayer phantoms with different electrical impedances. To develop a device for the early diagnosis of breast diseases, the development of a multi-layer phantom and demonstration of the effectiveness of the device for its examination are necessary. If the device that we developed makes impedance measurement in breast tumors possible, it may be used as a new diagnostic modality for breast diseases.
