TY - JOUR
T1 - Hierarchically Structured, All-Aqueous-Coated Hydrophobic Surfaces with pH-Selective Droplet Transfer Capability
AU - Brito, Jordan
AU - Asawa, Kaustubh
AU - Marin, Alexander
AU - Andrianov, Alexander K.
AU - Choi, Chang Hwan
AU - Sukhishvili, Svetlana A.
N1 - Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/6/8
Y1 - 2022/6/8
N2 - Often inspired by nature, techniques for precise droplet manipulation have found applications in microfluidics, microreactors, and water harvesting. However, a widely applicable strategy for surface modification combining simultaneous hydrophobicity and pH-sensitivity has not yet been achieved by employing environmentally friendly assembly conditions. The introduction of pH-responsive groups to an otherwise fluorinated polyphosphazene (PPZ) unlocks pH-selective droplet capture and transfer. Here, an all-aqueous layer-by-layer (LbL) deposition of polyelectrolytes is used to create unique hydrophobic coatings, endowing surfaces with the ability to sense environmental pH. The high hydrophobicity of these coatings (ultimately reaching a contact angle >120° on flat surfaces) is enabled by the formation of hydrophobic nanoscale domains and controllable by the degree of fluorination of PPZs, polyamine-binding partners, deposition pH, and coating thickness. Inspired by the hierarchical structure of rose petals, these versatile coatings reach a contact angle >150° when deposited on structured surfaces while introducing a tunable adhesivity that enables precise droplet manipulation. The films exhibited a strongly pronounced parahydrophobic rose petal behavior characterized through the contact angle hysteresis. Depositing as few as five bilayers (∼25 nm) on microstructured rather than smooth substrates resulted in superhydrophobicity with water contact angles >150° and the attenuation of the contact angle hysteresis, enabling highly controlled transfer of aqueous droplets. The pH-selective droplet transfer was achieved between surfaces with either the same microstructure and LbL film building blocks, which were assembled at different pH, or between surfaces with different microstructures coated with identical films. The demonstrated capability of these hydrophobic LbL films to endow surfaces with controlled hydrophobicity through adsorption from aqueous solutions and control the adhesion and transfer of water droplets between surfaces can be used in droplet-based microfluidics applications and water collection/harvesting.
AB - Often inspired by nature, techniques for precise droplet manipulation have found applications in microfluidics, microreactors, and water harvesting. However, a widely applicable strategy for surface modification combining simultaneous hydrophobicity and pH-sensitivity has not yet been achieved by employing environmentally friendly assembly conditions. The introduction of pH-responsive groups to an otherwise fluorinated polyphosphazene (PPZ) unlocks pH-selective droplet capture and transfer. Here, an all-aqueous layer-by-layer (LbL) deposition of polyelectrolytes is used to create unique hydrophobic coatings, endowing surfaces with the ability to sense environmental pH. The high hydrophobicity of these coatings (ultimately reaching a contact angle >120° on flat surfaces) is enabled by the formation of hydrophobic nanoscale domains and controllable by the degree of fluorination of PPZs, polyamine-binding partners, deposition pH, and coating thickness. Inspired by the hierarchical structure of rose petals, these versatile coatings reach a contact angle >150° when deposited on structured surfaces while introducing a tunable adhesivity that enables precise droplet manipulation. The films exhibited a strongly pronounced parahydrophobic rose petal behavior characterized through the contact angle hysteresis. Depositing as few as five bilayers (∼25 nm) on microstructured rather than smooth substrates resulted in superhydrophobicity with water contact angles >150° and the attenuation of the contact angle hysteresis, enabling highly controlled transfer of aqueous droplets. The pH-selective droplet transfer was achieved between surfaces with either the same microstructure and LbL film building blocks, which were assembled at different pH, or between surfaces with different microstructures coated with identical films. The demonstrated capability of these hydrophobic LbL films to endow surfaces with controlled hydrophobicity through adsorption from aqueous solutions and control the adhesion and transfer of water droplets between surfaces can be used in droplet-based microfluidics applications and water collection/harvesting.
KW - fluorination
KW - hydrophobicity
KW - layer-by-layer
KW - microstructure
KW - self-assembly
KW - surface morphology
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U2 - 10.1021/acsami.2c04499
DO - 10.1021/acsami.2c04499
M3 - Article
C2 - 35611942
AN - SCOPUS:85131735661
SN - 1944-8244
VL - 14
SP - 26225
EP - 26237
JO - ACS Applied Materials and Interfaces
JF - ACS Applied Materials and Interfaces
IS - 22
ER -