Oxidation of Cysteine by Electrogenerated Hexacyanoferrate(III) in Microliter Droplets

Chemical reactivity in droplets is often assumed to mimic reactivity in bulk, continuous water. Here, we study the catalytic oxidation of cysteine by electrogenerated hexacyanoferrate(III) in microliter droplets. These droplets are adsorbed onto glassy carbon macroelectrodes and placed into an immis...

Ausführliche Beschreibung

Bibliographische Detailangaben
Veröffentlicht in:Langmuir : the ACS journal of surfaces and colloids. - 1992. - 38(2022), 39 vom: 04. Okt., Seite 11892-11898
1. Verfasser: Vannoy, Kathryn J (VerfasserIn)
Weitere Verfasser: Dick, Jeffrey E
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2022
Zugriff auf das übergeordnete Werk:Langmuir : the ACS journal of surfaces and colloids
Schlagworte:Journal Article Research Support, N.I.H., Extramural Ferrocyanides ferrocyn Water 059QF0KO0R Carbon 7440-44-0 hexacyanoferrate II FLX0VIC39Y mehr... Cysteine K848JZ4886
LEADER 01000naa a22002652 4500
001 NLM346385121
003 DE-627
005 20231226031320.0
007 cr uuu---uuuuu
008 231226s2022 xx |||||o 00| ||eng c
024 7 |a 10.1021/acs.langmuir.2c01385  |2 doi 
028 5 2 |a pubmed24n1154.xml 
035 |a (DE-627)NLM346385121 
035 |a (NLM)36121813 
040 |a DE-627  |b ger  |c DE-627  |e rakwb 
041 |a eng 
100 1 |a Vannoy, Kathryn J  |e verfasserin  |4 aut 
245 1 0 |a Oxidation of Cysteine by Electrogenerated Hexacyanoferrate(III) in Microliter Droplets 
264 1 |c 2022 
336 |a Text  |b txt  |2 rdacontent 
337 |a ƒaComputermedien  |b c  |2 rdamedia 
338 |a ƒa Online-Ressource  |b cr  |2 rdacarrier 
500 |a Date Completed 05.10.2022 
500 |a Date Revised 02.06.2023 
500 |a published: Print-Electronic 
500 |a Citation Status MEDLINE 
520 |a Chemical reactivity in droplets is often assumed to mimic reactivity in bulk, continuous water. Here, we study the catalytic oxidation of cysteine by electrogenerated hexacyanoferrate(III) in microliter droplets. These droplets are adsorbed onto glassy carbon macroelectrodes and placed into an immiscible 1,2-dichloroethane phase. We combined cyclic voltammetry, optical microscopy, and finite element simulations to quantify the apparent bimolecular rate constant, kc,app, in microdroplets and bulk water. Statistical analyses reveal that the apparent bimolecular rate constant (kc,app) values formicrodroplets are larger than those in the continuous phase. Reactant adsorption to the droplet boundary has previously been implicated as the cause of such rate accelerations. Finite element modeling of this system suggests that molecular adsorption to the liquid|liquid interface cannot alone account for our observations, implicating kinetics of the bimolecular reaction either at the boundary or throughout the microliter volume. Our results indicate that cysteine oxidation by electrogenerated hexacyanoferrate(III) can be accelerated within a microenvironment, which may have profound implications on understanding biological processes within a cell 
650 4 |a Journal Article 
650 4 |a Research Support, N.I.H., Extramural 
650 7 |a Ferrocyanides  |2 NLM 
650 7 |a ferrocyn  |2 NLM 
650 7 |a Water  |2 NLM 
650 7 |a 059QF0KO0R  |2 NLM 
650 7 |a Carbon  |2 NLM 
650 7 |a 7440-44-0  |2 NLM 
650 7 |a hexacyanoferrate II  |2 NLM 
650 7 |a FLX0VIC39Y  |2 NLM 
650 7 |a Cysteine  |2 NLM 
650 7 |a K848JZ4886  |2 NLM 
700 1 |a Dick, Jeffrey E  |e verfasserin  |4 aut 
773 0 8 |i Enthalten in  |t Langmuir : the ACS journal of surfaces and colloids  |d 1992  |g 38(2022), 39 vom: 04. Okt., Seite 11892-11898  |w (DE-627)NLM098181009  |x 1520-5827  |7 nnns 
773 1 8 |g volume:38  |g year:2022  |g number:39  |g day:04  |g month:10  |g pages:11892-11898 
856 4 0 |u http://dx.doi.org/10.1021/acs.langmuir.2c01385  |3 Volltext 
912 |a GBV_USEFLAG_A 
912 |a SYSFLAG_A 
912 |a GBV_NLM 
912 |a GBV_ILN_22 
912 |a GBV_ILN_350 
912 |a GBV_ILN_721 
951 |a AR 
952 |d 38  |j 2022  |e 39  |b 04  |c 10  |h 11892-11898