Effects of polydisperse crowders on aggregation reactions

A molecular thermodynamic analysis

Dhawal Shah, Aik Lee Tan, Vigneshwar Ramakrishnan, Jianwen Jiang, Raj Rajagopalan

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Intracellular crowding in biological systems is usually mimicked in in vitro experiments by adding single crowders at high volume fractions, without taking into consideration the polydispersity of the crowders in the cellular environment. Here, we develop a molecular thermodynamic formalism to examine the effects of size-polydispersity of crowders on aggregation reaction equilibria. Although the predominantly common practice so far has been to appeal to the entropic (excluded-volume) effects in describing crowding effects, we show that the internal energy (hence, the enthalpy) of the system could dramatically alter the effects, even qualitatively, particularly in the case of a mixture of crowders, depending on the changes in the covolume of the products relative to that of the reactants and on the preferential binding or exclusion of the crowders by the reactants and products. We also show that in the case of polydisperse crowders the crowders with the largest size difference dominate the overall changes in the yield of the reaction, depending on the individual concentrations of the crowders.

Original languageEnglish
Article number064704
JournalJournal of Chemical Physics
Volume134
Issue number6
DOIs
Publication statusPublished - Feb 14 2011
Externally publishedYes

Fingerprint

Polydispersity
Thermodynamics
Agglomeration
thermodynamics
crowding
Biological systems
Enthalpy
Volume fraction
products
exclusion
internal energy
enthalpy
Experiments
formalism
In Vitro Techniques

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry
  • Medicine(all)

Cite this

Effects of polydisperse crowders on aggregation reactions : A molecular thermodynamic analysis. / Shah, Dhawal; Tan, Aik Lee; Ramakrishnan, Vigneshwar; Jiang, Jianwen; Rajagopalan, Raj.

In: Journal of Chemical Physics, Vol. 134, No. 6, 064704, 14.02.2011.

Research output: Contribution to journalArticle

Shah, Dhawal ; Tan, Aik Lee ; Ramakrishnan, Vigneshwar ; Jiang, Jianwen ; Rajagopalan, Raj. / Effects of polydisperse crowders on aggregation reactions : A molecular thermodynamic analysis. In: Journal of Chemical Physics. 2011 ; Vol. 134, No. 6.
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