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Statements

Subject Item
n2:RIV%2F61388963%3A_____%2F12%3A00376619%21RIV13-AV0-61388963
rdf:type
n8:Vysledek skos:Concept
dcterms:description
We investigated the effect of the background electrolyte (BGE) anions on the electrophoretic mobilities of the cationic amino acids arginine and lysine and the polycationic peptides tetraarginine, tetralysine, nonaarginine, and nonalysine. BGEs composed of sodium chloride, sodium propane-1,3-disulfonate, and sodium sulfate were used. For the amino acids, determination of the limiting mobility by extrapolation, using the OnsagerFuoss (OF) theory expression, yielded consistent estimates. For the peptides, however, the estimates of the limiting mobilities were found to spuriously depend on the BGE salt. This paradox was resolved using molecular modeling. Simulations, on all-atom as well as coarse-grained levels, show that significant counterion condensation, an effect not accounted for in OF theory, occurs for the tetra- and nonapeptides, even for low BGE concentrations. Including this effect in the quantitative estimation of the BGE effect on mobility removed the discrepancy between the estimated limiting mobilities in different salts. The counterion condensation was found to be mainly due to electrostatic interactions, with specific ion effects playing a secondary role. Therefore, the conclusions are likely to be generalizable to other analytes with a similar density of charged groups and OF theory is expected to fail in a predictable way for such analytes. We investigated the effect of the background electrolyte (BGE) anions on the electrophoretic mobilities of the cationic amino acids arginine and lysine and the polycationic peptides tetraarginine, tetralysine, nonaarginine, and nonalysine. BGEs composed of sodium chloride, sodium propane-1,3-disulfonate, and sodium sulfate were used. For the amino acids, determination of the limiting mobility by extrapolation, using the OnsagerFuoss (OF) theory expression, yielded consistent estimates. For the peptides, however, the estimates of the limiting mobilities were found to spuriously depend on the BGE salt. This paradox was resolved using molecular modeling. Simulations, on all-atom as well as coarse-grained levels, show that significant counterion condensation, an effect not accounted for in OF theory, occurs for the tetra- and nonapeptides, even for low BGE concentrations. Including this effect in the quantitative estimation of the BGE effect on mobility removed the discrepancy between the estimated limiting mobilities in different salts. The counterion condensation was found to be mainly due to electrostatic interactions, with specific ion effects playing a secondary role. Therefore, the conclusions are likely to be generalizable to other analytes with a similar density of charged groups and OF theory is expected to fail in a predictable way for such analytes.
dcterms:title
Counterion condensation in short cationic peptides: Limiting mobilities beyond the Onsager–Fuoss theory Counterion condensation in short cationic peptides: Limiting mobilities beyond the Onsager–Fuoss theory
skos:prefLabel
Counterion condensation in short cationic peptides: Limiting mobilities beyond the Onsager–Fuoss theory Counterion condensation in short cationic peptides: Limiting mobilities beyond the Onsager–Fuoss theory
skos:notation
RIV/61388963:_____/12:00376619!RIV13-AV0-61388963
n8:predkladatel
n10:ico%3A61388963
n3:aktivita
n4:S n4:P n4:I n4:Z
n3:aktivity
I, P(GA203/08/0114), S, Z(AV0Z40550506), Z(MSM0021620857)
n3:cisloPeriodika
6
n3:dodaniDat
n13:2013
n3:domaciTvurceVysledku
Wernersson, Erik n17:2793911 n17:8822689
n3:druhVysledku
n9:J
n3:duvernostUdaju
n18:S
n3:entitaPredkladatele
n16:predkladatel
n3:idSjednocenehoVysledku
128929
n3:idVysledku
RIV/61388963:_____/12:00376619
n3:jazykVysledku
n14:eng
n3:klicovaSlova
background electrolyte effects; counterion condensation; ion-pairing; limiting mobility; molecular modeling
n3:klicoveSlovo
n15:molecular%20modeling n15:limiting%20mobility n15:background%20electrolyte%20effects n15:ion-pairing n15:counterion%20condensation
n3:kodStatuVydavatele
DE - Spolková republika Německo
n3:kontrolniKodProRIV
[4270DB74EF5F]
n3:nazevZdroje
Electrophoresis
n3:obor
n11:CF
n3:pocetDomacichTvurcuVysledku
3
n3:pocetTvurcuVysledku
6
n3:projekt
n20:GA203%2F08%2F0114
n3:rokUplatneniVysledku
n13:2012
n3:svazekPeriodika
33
n3:tvurceVysledku
Jungwirth, Pavel Křížek, T. Heyda, Jan Kubíčková, A. Wernersson, Erik Coufal, P.
n3:wos
000303155700012
n3:zamer
n19:AV0Z40550506 n19:MSM0021620857
s:issn
0173-0835
s:numberOfPages
9
n6:doi
10.1002/elps.201100602