Controlled On-Off Switching of Tight-Binding Hydrogen Bonds between Model Cell Membranes and Acetylated Cellulose Surfaces

Andrey A. Gurtovenko, Mikko Karttunen

Research output

Abstract

Controlling interactions between cellulose-based materials and membranes of living cells is critical in medicine and biotechnology in, for example, wound dressing, tissue engineering, hemodialysis membranes, and drug transport. Cellulose acetylation is a widely used approach to tuning those interactions. Surprisingly, however, detailed interactions of acetylated cellulose and membranes have thus far not been characterized. Using atomistic molecular dynamics (MD) simulations, we show that the key to such control is hydrogen bonds: by tuning the number of hydrogen bonds between tissue (cell membranes) and cellulose, binding can be controlled in a precise manner. We demonstrate that the acetylation of each hydroxymethyl group reduces the free energy of cellulose–membrane binding by an order of magnitude as compared to that of pristine cellulose. Remarkably, this acetylation-induced weakening does not occur gradually and is characterized by a sharp threshold in the degree of substitution, beyond which the microscopic character of lipid–cellulose interactions changes drastically. When the degree of substitution does not exceed 0.125, the cellulose–lipid interactions are mainly driven by hydrogen bonding between cellulose’s hydroxyl groups and phosphate groups of lipid molecules. This results in the tight binding of a cellulose crystal and a lipid bilayer. Larger degrees of substitution (here, 0.25 and 0.5) prevent hydrogen bonding, leading to rather weak and unstable cellulose–bilayer binding. In this case, the lipid–cellulose binding is controlled by the interactions of lipid choline groups with hydroxyl(hydroxymethyl) groups and carbonyl groups of acetyl moieties of acetylated cellulose.
Original languageEnglish
Pages (from-to)13753-13760
JournalLangmuir
Volume35
Issue number42
Early online date25 Sep 2019
DOIs
Publication statusPublished - 2019

Fingerprint

Cell membranes
cellulose
Cellulose
Hydrogen bonds
hydrogen bonds
acetylation
Acetylation
lipids
Substitution reactions
interactions
substitutes
membranes
Membranes
Lipids
Tuning
tuning
choline
biotechnology
Lipid bilayers
tissue engineering

Scopus subject areas

  • Condensed Matter Physics
  • Materials Science(all)
  • Spectroscopy
  • Surfaces and Interfaces
  • Electrochemistry

Cite this

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title = "Controlled On-Off Switching of Tight-Binding Hydrogen Bonds between Model Cell Membranes and Acetylated Cellulose Surfaces",
abstract = "Controlling interactions between cellulose-based materials and membranes of living cells is critical in medicine and biotechnology in, for example, wound dressing, tissue engineering, hemodialysis membranes, and drug transport. Cellulose acetylation is a widely used approach to tuning those interactions. Surprisingly, however, detailed interactions of acetylated cellulose and membranes have thus far not been characterized. Using atomistic molecular dynamics (MD) simulations, we show that the key to such control is hydrogen bonds: by tuning the number of hydrogen bonds between tissue (cell membranes) and cellulose, binding can be controlled in a precise manner. We demonstrate that the acetylation of each hydroxymethyl group reduces the free energy of cellulose–membrane binding by an order of magnitude as compared to that of pristine cellulose. Remarkably, this acetylation-induced weakening does not occur gradually and is characterized by a sharp threshold in the degree of substitution, beyond which the microscopic character of lipid–cellulose interactions changes drastically. When the degree of substitution does not exceed 0.125, the cellulose–lipid interactions are mainly driven by hydrogen bonding between cellulose’s hydroxyl groups and phosphate groups of lipid molecules. This results in the tight binding of a cellulose crystal and a lipid bilayer. Larger degrees of substitution (here, 0.25 and 0.5) prevent hydrogen bonding, leading to rather weak and unstable cellulose–bilayer binding. In this case, the lipid–cellulose binding is controlled by the interactions of lipid choline groups with hydroxyl(hydroxymethyl) groups and carbonyl groups of acetyl moieties of acetylated cellulose.",
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