Modifying Surfaces with the Primary and Secondary Faces of Cyclodextrins To Achieve a Distinct Anti-icing Capability

Abstract

Heterogenous ice nucleation (HIN) induced by organic materials is a long-lasting issue in wide-ranging fields from cryobiology to atmospheric physics, but efforts for controlling HIN are still restricted by incomplete understanding of its mechanism. In this work, distinct anti-icing capabilities were achieved by experimentally investigating the HIN behavior on the surfaces modified with the primary face (PF) and secondary face (SF) of cyclodextrins (CDs) (i.e., α-1,4-linked D-(+)-glucopyranose with two relatively flat and hydroxylated faces). To achieve this, CDs were first immobilized to the surfaces through selectively binding the PF and SF of CDs onto the solid surfaces; as such, either PF or SF is exposed to liquid water. Interestingly, HIN temperature and delay time assays indicate that HIN is depressed when the PF of CDs (which matches with the ice lattice) is exposed to liquid water whereas the HIN is facilitated when the SF of CDs (which mismatches with the ice lattice) is exposed to liquid water. This deviates from the common thought that surfaces with a template of ice lattice match facilitate the HIN. Instead, 1 H NMR studies show that the resonances of hydroxyl (OH) in the SF of CDs are most deshielded due to the formation of intramolecular hydrogen bonds, in comparison to that of OH in the PF of CDs, which weakens the interaction between the OH groups on the SF and water molecules. Thus, the distinct anti-icing capabilities of the PF and SF of CDs can be achieved and established by the distinct interactions between OH groups on the two faces and water, which is of great potential for practical applications. The molecular-level interactions between surfaces and water molecules may be a more appropriate criterion for forecasting materials' HIN ability.

Anti-Icing Properties of Vertically Aligned TiO2 Nanopillars

“…3−5 According to reports, annually, ice accretion on power transport lines, roads, and instruments causes extensive damage, and hence a proper and efficient deicing or anti-icing method is extremely necessary. 6−9 In the last few years, because of the low efficiency, high final cost, and environmentally destructive nature of conventional deicing materials and methods, 10 much effort has been put for developing efficient and durable anti-icing materials using polymers, 11 metals, 12 silicon-based materials, 13 fluorinated materials, 14 Janus particles, 15 cross-linked bilayer fluorinated polymers, 16 cyclodextrins, and lubricant infused materials. 17,18 In conventional deicing methods that mainly consist of electrothermal, chemical, and mechanical approaches, which suffer from low durability and harmful environmental effects, 19,20 organic liquids are used as commercially available agents.…”

“…Designing an anti-icing surface with a long delay time, low adhesion, and short droplet bouncing time has remained under debate in recent years. It is expected that Lotus -inspired superhydrophobic surfaces can be a successful candidate to achieve anti-icing properties. , Anti-icing materials and surfaces are one of the fields that have attracted much attention in recent years because of their high application potential in various industries. − According to reports, annually, ice accretion on power transport lines, roads, and instruments causes extensive damage, and hence a proper and efficient deicing or anti-icing method is extremely necessary. − In the last few years, because of the low efficiency, high final cost, and environmentally destructive nature of conventional deicing materials and methods, much effort has been put for developing efficient and durable anti-icing materials using polymers, metals, silicon-based materials, fluorinated materials, Janus particles, cross-linked bilayer fluorinated polymers, cyclodextrins, and lubricant infused materials. , In conventional deicing methods that mainly consist of electrothermal, chemical, and mechanical approaches, which suffer from low durability and harmful environmental effects, , organic liquids are used as commercially available agents. For example, airline transportation industries have been using such materials for deicing aircraft surfaces for many years.…”

“…Their results showed that the secondary face of cyclodextrin molecules did not match with the ice hydrogen bond. This phenomenon not only delays the freezing time but also interrupts the heterogeneous nucleation process . Recently, vertically aligned nanopillars with low thermal conductivity have attracted much attention for thermoelectric applications. , However, their potential application in anti-icing surfaces because of their low thermal conductivity and strong phonon scattering have not been considered yet.…”

Macrocycle molecule-based cryoprotectants for ice recrystallization inhibition and cell cryopreservation

“…Cyclodextrins 10 are a class of cyclic oligosaccharides with six, seven or eight D-glucose units linked by a-1,4-glucose bonds, which are referred to a-, band gcyclodextrin, respectively. Cyclodextrin-based CPAs showed heterogenous ice nucleation behaviors, 11 and have been widely used in anti-freezing hydrogels 12 and various sperm cryosurvival systems. [13][14][15] Based on the ice recrystallization inhibition (IRI) results for acetyl-b-cyclodextrin and alkylated carbohydrate CPAs, we know that hydration was not the only contributor to IRI activity.…”