TY - JOUR
T1 - On the hydration of subnanometric antifouling organosilane adlayers
T2 - A molecular dynamics simulation
AU - Sheikh, Sonia
AU - Blaszykowski, Christophe
AU - Nolan, Robert
AU - Thompson, Damien
AU - Thompson, Michael
N1 - Publisher Copyright:
© 2014 Elsevier Inc.
PY - 2015/1/1
Y1 - 2015/1/1
N2 - The connection between antifouling and surface hydration is a fascinating but daunting question to answer. Herein, we use molecular dynamics (MD) computer simulations to gain further insight into the role of surface functionalities in the molecular-level structuration of water (surface kosmotropicity) - within and atop subnanometric organosilane adlayers that were shown in previous experimental work to display varied antifouling behavior. Our simulations support the hypothesized intimate link between surface hydration and antifouling, in particular the importance of both internal and interfacial hydrophilicity and kosmotropicity. The antifouling mechanism is also discussed in terms of surface dehydration energy and water dynamicity (lability and mobility), notably the crucial requirement for clustered water molecules to remain tightly bound for extensive periods of time - i.e. exhibit slow exchange dynamics. A substrate effect on surface hydration, which would also participate in endowing antifouling adlayers with hydrogel-like characteristics, is also proposed. In contrast, the role of adlayer flexibility, if any, is assigned a secondary role in these ultrathin structures made of short building blocks. The conclusions from this work are well in line with those previously drawn in the literature.
AB - The connection between antifouling and surface hydration is a fascinating but daunting question to answer. Herein, we use molecular dynamics (MD) computer simulations to gain further insight into the role of surface functionalities in the molecular-level structuration of water (surface kosmotropicity) - within and atop subnanometric organosilane adlayers that were shown in previous experimental work to display varied antifouling behavior. Our simulations support the hypothesized intimate link between surface hydration and antifouling, in particular the importance of both internal and interfacial hydrophilicity and kosmotropicity. The antifouling mechanism is also discussed in terms of surface dehydration energy and water dynamicity (lability and mobility), notably the crucial requirement for clustered water molecules to remain tightly bound for extensive periods of time - i.e. exhibit slow exchange dynamics. A substrate effect on surface hydration, which would also participate in endowing antifouling adlayers with hydrogel-like characteristics, is also proposed. In contrast, the role of adlayer flexibility, if any, is assigned a secondary role in these ultrathin structures made of short building blocks. The conclusions from this work are well in line with those previously drawn in the literature.
KW - Antifouling
KW - Molecular dynamics simulation
KW - Organosilane adlayer
KW - Surface hydration
KW - Water
UR - http://www.scopus.com/inward/record.url?scp=84908517850&partnerID=8YFLogxK
U2 - 10.1016/j.jcis.2014.09.025
DO - 10.1016/j.jcis.2014.09.025
M3 - Article
C2 - 25313484
AN - SCOPUS:84908517850
SN - 0021-9797
VL - 437
SP - 197
EP - 204
JO - Journal of Colloid and Interface Science
JF - Journal of Colloid and Interface Science
ER -