Research output: Contribution to journal › Article › peer-review
Controlled On-Off Switching of Tight-Binding Hydrogen Bonds between Model Cell Membranes and Acetylated Cellulose Surfaces. / Gurtovenko, Andrey A. ; Karttunen, Mikko.
In: Langmuir, Vol. 35, No. 42, 2019, p. 13753-13760.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Controlled On-Off Switching of Tight-Binding Hydrogen Bonds between Model Cell Membranes and Acetylated Cellulose Surfaces
AU - Gurtovenko, Andrey A.
AU - Karttunen, Mikko
PY - 2019
Y1 - 2019
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85073065513&partnerID=8YFLogxK
U2 - 10.1021/acs.langmuir.9b02453
DO - 10.1021/acs.langmuir.9b02453
M3 - Article
VL - 35
SP - 13753
EP - 13760
JO - Langmuir
JF - Langmuir
SN - 0743-7463
IS - 42
ER -
ID: 49261833