Improving Channel Hydrate Stability via Localized Chemical Tuning of the Water Environment

Watts, Taylor A.; Niederberger, Sara M.; Swift, Jennifer A.

doi:10.1021/acs.cgd.1c00551

Cited by 6 publications

(5 citation statements)

References 54 publications

(83 reference statements)

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“…Nonetheless, such common sense appears not applicable here. We found that the apparent activation energy of solid-state dehydration ($60 kJ mol À1 ) of the UAD phase is significantly lower than the values reported ($70-170 kJ mol À1 ) in the literature (Watts et al, 2021;Takahashi & Uekusa, 2022), which indicates crystal defects may play an important role in the UAD-to-UAA solid-state phase transition. Such defect may be introduced in the growth of UAD crystals at nearly neutral pH (5-6), wherein monovalent tautomer species were suggested to be significant (Fig.…”

Section: Mechanism Of the Core-shell Phase Transitioncontrasting

confidence: 73%

Unusual shape-preserved pathway of a core-shell phase transition triggered by orientational disorder

Tang

2023

Int Union Crystallogr J

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The ubiquitous presence of crystal defects provides great potential and opportunities to construct the desired structure (hence with the desired properties) and tailor the synthetic process of crystalline materials. However, little is known about their regulation role in phase transition and crystallization pathways. It was generally thought that a phase transition in solution proceeds predominantly via the solvent-mediated phase-transformation pathway due to energetically high-cost solid-state phase transitions (if any). Herein, we report an unprecedented finding that an orientational disorder defect present in the crystal structure triggers an unusual pathway of a core-shell phase transition with apparent shape-preserved evolution. In the pathway, the solid-state dehydration phase transition occurs inside the crystal prior to its competitive transformation approach mediated by solvent, forming an unconventional core-shell structure. Through a series of combined experimental and computational techniques, we revealed that the presence of crystal defects, introduced by urate tautomerism over the course of crystallization, elevates the metastability of uric acid dihydrate (UAD) crystals and triggers UAD dehydration to the uric acid anhydrate (UAA) phase in the crystal core which precedes with surface dissolution of the shell UAD crystal and recrystallization of the core phase. This unique phase transition could also be related to defect density, which appears to be influenced by the thickness of UAD crystals and crystallization driving force. The discovery of an unusual pathway of the core-shell phase transition suggests that the solid-state phase transition is not necessarily slower than the solvent-mediated phase transformation in solution and provides an alternative approach to constructing the core-shell structure. Moreover, the fundamental role of orientational disorder defects on the phase transition identified in this study demonstrates the feasibility to tailor phase transition and crystallization pathways by strategically importing crystal defects, which has broad applications in crystal engineering.

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Section: Mechanism Of the Core-shell Phase Transitioncontrasting

confidence: 73%

Unusual shape-preserved pathway of a core-shell phase transition triggered by orientational disorder

Tang

2023

Int Union Crystallogr J

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“…Along with the aromatic zipper, the ionic backbone channel influences overall crystal stability and orientation. [ 52 ] Therefore, the aromatic stacking in F confers enough stability to prevent complete crystal collapse at low RH (which we observe in HYF) but are not so stiff as to prevent such a translation (as in FF). We also speculate that the different critical RH thresholds for F and HYF relate to both the H‐bonding strength of aqueous channels and aromatic deformability.…”

Section: Resultsmentioning

confidence: 89%

Aromatic Zipper Topology Dictates Water‐Responsive Actuation in Phenylalanine‐Based Crystals

Sheehan

Wang

Podbevsek

et al. 2023

Small

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Water‐responsive (WR) materials that reversibly deform in response to relative humidity (RH) changes are gaining increasing interest for their potential in energy harvesting and soft robotics applications. Despite progress, there are significant gaps in the understanding of how supramolecular structure underpins the reconfiguration and performance of WR materials. Here, three crystals are compared based on the amino acid phenylalanine (F) that contain water channels and F packing domains that are either layered (F), continuously connected (phenylalanyl‐phenylalanine, FF), or isolated (histidyl‐tyrosyl‐phenylalanine, HYF). Hydration‐induced reconfiguration is analyzed through changes in hydrogen‐bond interactions and aromatic zipper topology. F crystals show the greatest WR deformation (WR energy density of 19.8 MJ m−3) followed by HYF (6.5 MJ m−3), while FF exhibits no observable response. The difference in water‐responsiveness strongly correlates to the deformability of aromatic regions, with FF crystals being too stiff to deform, whereas HYF is too soft to efficiently transfer water tension to external loads. These findings reveal aromatic topology design rules for WR crystals and provide insight into general mechanisms of high‐performance WR actuation. Moreover, the best‐performing crystal, F emerges as an efficient WR material for applications at scale and low cost.

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“…The structural bracing effect (reminiscent of the behaviour of bulk water on freezing) that occurs between −60 °C and −70 °C is probably brought about by non-lattice ordering of the water in T1-R on cooling, which also inhibits the transfer of water to the surroundings. Indeed, it is known that the dehydration temperature of a channel hydrate depends on the level of geometric frustration imposed on the included water by the host framework 29 . That water can flow within the crystal at temperatures above −70 °C is probably due to a mismatch between the geometry of the channel (that is, its diameter and the locations of the exposed hydroxyl groups) and a hypothetical long-range ordered ice-like structure 30 .…”

Section: Dehydration At Subglacial Temperaturesmentioning

confidence: 99%

Dehydration of a crystal hydrate at subglacial temperatures

Eaby

Myburgh

Kosimov

et al. 2023

Nature

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Water is one of the most important substances on our planet1. It is ubiquitous in its solid, liquid and vaporous states and all known biological systems depend on its unique chemical and physical properties. Moreover, many materials exist as water adducts, chief among which are crystal hydrates (a specific class of inclusion compound), which usually retain water indefinitely at subambient temperatures2. We describe a porous organic crystal that readily and reversibly adsorbs water into 1-nm-wide channels at more than 55% relative humidity. The water uptake/release is chromogenic, thus providing a convenient visual indication of the hydration state of the crystal over a wide temperature range. The complementary techniques of X-ray diffraction, optical microscopy, differential scanning calorimetry and molecular simulations were used to establish that the nanoconfined water is in a state of flux above −70 °C, thus allowing low-temperature dehydration to occur. We were able to determine the kinetics of dehydration over a wide temperature range, including well below 0 °C which, owing to the presence of atmospheric moisture, is usually challenging to accomplish. This discovery unlocks opportunities for designing materials that capture/release water over a range of temperatures that extend well below the freezing point of bulk water.

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Improving Channel Hydrate Stability via Localized Chemical Tuning of the Water Environment

Cited by 6 publications

References 54 publications

Unusual shape-preserved pathway of a core-shell phase transition triggered by orientational disorder

Unusual shape-preserved pathway of a core-shell phase transition triggered by orientational disorder

Aromatic Zipper Topology Dictates Water‐Responsive Actuation in Phenylalanine‐Based Crystals

Dehydration of a crystal hydrate at subglacial temperatures

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