Biguanide, an Efficient Electrofreezing “Ice-maker” Ion of Supercooled Water

Javitt, Leah; Weissbuch, Isabelle; Ehre, David; Lubomirsky, Igor; Lahav, Meir

doi:10.1021/acs.cgd.1c01025

Cited by 4 publications

(22 citation statements)

References 22 publications

(35 reference statements)

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“…Consequently, di- or polyvalent acids and salts, which can result in various associated ionic structures, might not impact electrofreezing. 39 , 40 …”

Section: Introductionmentioning

confidence: 99%

“… Summary of comparative icing experiments with 30 μL drops of (a) guanidinium nitrate and (b) biguanidinium chloride deposited on the positive (001) and negative (00–1) faces of LiTaO 3 in the presence and absence of the insulators. Reproduced with permission from refs ( 4 ) and ( 40 ). Copyright 2021 and 2022 Wiley and American Chemical Society.…”

Section: Introductionmentioning

confidence: 99%

“… Icing temperature as a function of the concentration of (a) guanidinium + and (b) biguanidinium + ions present in solution. Reproduced with permission from refs ( 4 ) and ( 40 ). Copyright 2021 and 2022 Wiley and American Chemical Society.…”

Section: Introductionmentioning

confidence: 99%

“…At these concentrations, Gdm + and Bgdm + , attracted to the negative face, elevate the icing temperatures by ∼5 and ∼8 °C, respectively. 4 , 40 …”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Chemical Nature of Heterogeneous Electrofreezing of Supercooled Water Revealed on Polar (Pyroelectric) Surfaces

et al. 2022

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Conspectus The ability to control the icing temperature of supercooled water (SCW) is of supreme importance in subfields of pure and applied sciences. The ice freezing of SCW can be influenced heterogeneously by electric effects, a process known as electrofreezing. This effect was first discovered during the 19th century; however, its mechanism is still under debate. In this Account we demonstrate, by capitalizing on the properties of polar crystals, that heterogeneous electrofreezing of SCW is a chemical process influenced by an electric field and specific ions. Polar crystals possess a net dipole moment. In addition, they are pyroelectric, displaying short-lived surface charges at their hemihedral faces at the two poles of the crystals as a result of temperature changes. Accordingly, during cooling or heating, an electric field is created, which is negated by the attraction of compensating charges from the environment. This process had an impact in the following experiments. The icing temperatures of SCW within crevices of polar crystals are higher in comparison to icing temperatures within crevices of nonpolar analogs. The role played by the electric effect was extricated from other effects by the performance of icing experiments on the surfaces of pyroelectric quasi-amorphous SrTiO 3 . During those studies it was found that on positively charged surfaces the icing temperature of SCW is elevated, whereas on negatively charged surfaces it is reduced. Following investigations discovered that the icing temperature of SCW is impacted by an ionic current created within a hydrated layer on top of hydrophilic faces residing parallel to the polar axes of the crystals. In the absence of such current on analogous hydrophobic surfaces, the pyroelectric effect does not influence the icing temperature of SCW. Those results implied that electrofreezing of SCW is a process influenced by specific compensating ions attracted by the pyroelectric field from the aqueous solution. When freezing experiments are performed in an open atmosphere, bicarbonate and hydronium ions, created by the dissolution of atmospheric CO 2 in water, influence the icing temperature. The bicarbonate ions, when attracted by positively charged pyroelectric surfaces, elevate the icing temperature, whereas their counterparts, hydronium ions, when attracted by the negatively charged surfaces reduce the icing temperature. Molecular dynamic simulations suggested that bicarbonate ions, concentrated within the near positively charged interfacial layer, self-assemble with water molecules to create stabilized slightly distorted “ice-like” hexagonal assemblies which mimic the hexagons of the crystals of ice. This occurs by replacing, within those ice-like hexagons, two hydrogen bonds of water by C–O bonds of the HCO 3 – ion. On the basis of these simulations, it was predicted and experimentally confirmed that other trigonal planar ions such as NO 3 ...

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“…Consequently, di- or polyvalent acids and salts, which can result in various associated ionic structures, might not impact electrofreezing. 39 , 40 …”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…At these concentrations, Gdm + and Bgdm + , attracted to the negative face, elevate the icing temperatures by ∼5 and ∼8 °C, respectively. 4 , 40 …”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Chemical Nature of Heterogeneous Electrofreezing of Supercooled Water Revealed on Polar (Pyroelectric) Surfaces

et al. 2022

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Professor Roger Davey: Master ofAllCrystal Trades

Cruz‐Cabeza¹,

Sadiq²,

Vetter³

et al. 2022

Crystal Growth & Design

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Electro-Freezing of Supercooled Water Is Induced by Hydrated Al³⁺ and Mg²⁺ Ions: Experimental and Theoretical Studies

Fuhrman Javitt,

Kalita,

Dubey

et al. 2023

J. Am. Chem. Soc.

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This work reports that the octahedral hydrated Al3+ and Mg2+ ions operate within electrolytic cells as kosmotropic (long-range order-making) “ice makers” of supercooled water (SCW). 10–5 M solutions of hydrated Al3+ and Mg2+ ions each trigger, near the cathode (−20 ± 5 V), electro-freezing of SCW at −4 °C. The hydrated Al3+ ions do so with 100% efficiency, whereas the Mg2+ ions induce icing with 40% efficiency. In contrast, hydrated Na+ ions, under the same experimental conditions, do not induce icing differently than pure water. As such, our study shows that the role played by Al3+ and Mg2+ ions in water electro-freezing is impacted by two synchronous effects: (1) a geometric effect due to the octahedral packing of the coordinated water molecules around the metallic ions, and (2) the degree of polarization which these two ions induce and thereby acidify the coordinated water molecules, which in turn imparts them with an ice-like structure. Long-duration molecular dynamics (MD) simulations of the Al3+ and Mg2+ indeed reveal the formation of “ice-like” hexagons in the vicinity of these ions. Furthermore, the MD shows that these hexagons and the electric fields of the coordinate water molecules give rise to ultimate icing. As such, the MD simulations provide a rational explanation for the order-making properties of these ions during electro-freezing.

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Biguanide, an Efficient Electrofreezing “Ice-maker” Ion of Supercooled Water

Cited by 4 publications

References 22 publications

Chemical Nature of Heterogeneous Electrofreezing of Supercooled Water Revealed on Polar (Pyroelectric) Surfaces

Chemical Nature of Heterogeneous Electrofreezing of Supercooled Water Revealed on Polar (Pyroelectric) Surfaces

Professor Roger Davey: Master ofAllCrystal Trades

Electro-Freezing of Supercooled Water Is Induced by Hydrated Al³⁺ and Mg²⁺ Ions: Experimental and Theoretical Studies

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Biguanide, an Efficient Electrofreezing “Ice-maker” Ion of Supercooled Water

Cited by 4 publications

References 22 publications

Chemical Nature of Heterogeneous Electrofreezing of Supercooled Water Revealed on Polar (Pyroelectric) Surfaces

Chemical Nature of Heterogeneous Electrofreezing of Supercooled Water Revealed on Polar (Pyroelectric) Surfaces

Professor Roger Davey: Master ofAllCrystal Trades

Electro-Freezing of Supercooled Water Is Induced by Hydrated Al3+ and Mg2+ Ions: Experimental and Theoretical Studies

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Electro-Freezing of Supercooled Water Is Induced by Hydrated Al³⁺ and Mg²⁺ Ions: Experimental and Theoretical Studies