Following in Emil Fischer's Footsteps: A Site-Selective Probe of Glucose Acid-Base Chemistry

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F21%3A43922496" target="_blank" >RIV/60461373:22340/21:43922496 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/acs.jpca.1c04695" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.jpca.1c04695</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpca.1c04695" target="_blank" >10.1021/acs.jpca.1c04695</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Following in Emil Fischer's Footsteps: A Site-Selective Probe of Glucose Acid-Base Chemistry

Popis výsledku v původním jazyce

Liquid-jet photoelectron spectroscopy was applied to determine the first acid dissociation constant (pKa) of aqueous-phase glucose while simultaneously identifying the spectroscopic signature of the respective deprotonation site. Valence spectra from solutions at pH values below and above the first pKa reveal a change in glucose&apos;s lowest ionization energy upon the deprotonation of neutral glucose and the subsequent emergence of its anionic counterpart. Site-specific insights into the solution-pH-dependent molecular structure changes are also shown to be accessible via C 1s photoelectron spectroscopy. The spectra reveal a considerably lower C 1s binding energy of the carbon site associated with the deprotonated hydroxyl group. The occurrence of photoelectron spectral fingerprints of cyclic and linear glucose prior to and upon deprotonation are also discussed. The experimental data are interpreted with the aid of electronic structure calculations. Our findings highlight the potential of liquid-jet photoelectron spectroscopy to act as a site-selective probe of the molecular structures that underpin the acid-base chemistry of polyprotic systems with relevance to environmental chemistry and biochemistry. © 2021 The Authors. Published by American Chemical Society.

Název v anglickém jazyce

Following in Emil Fischer's Footsteps: A Site-Selective Probe of Glucose Acid-Base Chemistry

Popis výsledku anglicky

Liquid-jet photoelectron spectroscopy was applied to determine the first acid dissociation constant (pKa) of aqueous-phase glucose while simultaneously identifying the spectroscopic signature of the respective deprotonation site. Valence spectra from solutions at pH values below and above the first pKa reveal a change in glucose&apos;s lowest ionization energy upon the deprotonation of neutral glucose and the subsequent emergence of its anionic counterpart. Site-specific insights into the solution-pH-dependent molecular structure changes are also shown to be accessible via C 1s photoelectron spectroscopy. The spectra reveal a considerably lower C 1s binding energy of the carbon site associated with the deprotonated hydroxyl group. The occurrence of photoelectron spectral fingerprints of cyclic and linear glucose prior to and upon deprotonation are also discussed. The experimental data are interpreted with the aid of electronic structure calculations. Our findings highlight the potential of liquid-jet photoelectron spectroscopy to act as a site-selective probe of the molecular structures that underpin the acid-base chemistry of polyprotic systems with relevance to environmental chemistry and biochemistry. © 2021 The Authors. Published by American Chemical Society.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GX21-26601X" target="_blank" >GX21-26601X: Zkoumání a transformace hmoty elektrony v kapalných mikrotryskách</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2021

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

—

Svazek periodika

125

Číslo periodika v rámci svazku

32

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

6881-6892

Kód UT WoS článku

000687711700001

EID výsledku v databázi Scopus

2-s2.0-85113600540