Glass polymorphism in glycerol–water mixtures: II. Experimental studies

Bachler, Johannes; Fuentes-Landete, Violeta; Jahn, David A.; Wong, Jessina; Giovambattista, Nicolás; Loerting, Thomas

doi:10.1039/c5cp08069j

Cited by 45 publications

(73 citation statements)

References 52 publications

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“…It was for example shown that concentrated water:glycerol mixtures form a homogeneous glass at low temperatures, thus avoiding cell-damaging crystallization. 13 However, the study of ternary mixtures including water, cosolvent and protein is more challenging. Despite recent advances (see e.g.…”

Section: Introductionmentioning

confidence: 99%

Protein Preferential Solvation in Water:Glycerol Mixtures

et al. 2020

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For proteins in solvent mixtures, the relative abundances of each solvent in their solvation shell have a critical impact on their properties. Preferential solvation of a series of proteins in water-glycerol mixtures is studied here over a broad range of solvent compositions via classical molecular dynamics simulations. Our simulation results reveal that the dierences between shell and bulk compositions exhibit dramatic changes with solvent composition, temperature and protein nature. In contrast with the simple and widely used picture where glycerol is completely excluded from the protein interface, we show that for aqueous solutions with less than 50% glycerol in volume, protein solvation shells have approximately the same composition as the bulk solvent and proteins are in direct contact with glycerol. We further demonstrate that at high glycerol concentration, glycerol depletion from the solvation shell is due to an entropic factor arising from the reduced accessibility of bulky glycerol molecules in protein cavities. The resulting molecular picture is important to understand protein activity and cryopreservation in mixed aqueous solvents.

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Section: Introductionmentioning

confidence: 99%

Protein Preferential Solvation in Water:Glycerol Mixtures

et al. 2020

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“…41-44 3 Recent experimental studies suggest that liquid-liquid transition occurs in a hydrazinium trifluoroacetate solution 45 and various aqueous alcohol solutions. [46][47][48][49][50] Most of the experimental studies measured properties of vitrified aqueous solutions at temperatures near or lower than the crystallization temperature, Tx ~ 150 K, at which amorphous ice crystallizes into ice I by heating.…”

Section: Introductionmentioning

confidence: 99%

Liquid-liquid separation of aqueous solutions: A molecular dynamics study

Yagasaki

Matsumoto

Tanaka

2019

The Journal of Chemical Physics

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In the liquid-liquid phase transition scenario, supercooled water separates into the high density liquid (HDL) and low density liquid (LDL) phases at temperatures lower than the second critical point. We investigate the effects of hydrophilic and hydrophobic solutes on the liquid-liquid phase transition using molecular dynamics simulations. It is found that a supercooled aqueous NaCl solution separates into solute-rich HDL and solute-poor LDL parts at low pressures. By contrast, a supercooled aqueous Ne solution separates into solute-rich LDL and solute-poor HDL parts at high pressures. Both the solutes increase the high temperature limit of the liquid-liquid separation. The degree of separation is quantified using the local density of solute particles to determine the liquid-liquid coexistence region in the pressure-temperature phase diagram. The effects of NaCl and Ne on the phase diagram of supercooled water are explained in terms of preferential solvation of ions in HDL and that of small hydrophobic particles in LDL, respectively.

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“…Although there is supporting evidence for polymorphism in water (1)(2)(3)(4)(5)12), the debate is still continuing for LLT in real water because of the experimental difficulty in accessing it in pure water (recent efforts to access LLT of pure water from the low-temperature side) (4,(13)(14)(15)(16)(17). There have also been efforts to access LLT of water by using aqueous solutions (18)(19)(20)(21)(22)(23)), yet which is often controversial. Thus, an unambiguous example of LLT is highly desirable for establishing its presence firmly.…”

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confidence: 99%

Link between molecular mobility and order parameter during liquid–liquid transition of a molecular liquid

Murata

Tanaka

2019

Proc. Natl. Acad. Sci. U.S.A.

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Liquid-liquid transition (LLT) is the transformation of one liquid to another via first-order phase transition. For example, LLT in a molecular liquid, triphenyl phosphite, is macroscopically the transformation from liquid I in a supercooled state to liquid II in a glassy state. Reflecting the transformation from the liquid to glassy state, the LLT is accompanied by considerable slowing down of overall molecular dynamics, but little is known about how this proceeds at a molecular level coupled with the evolution of the order parameter. We report such information by performing time-resolved simultaneous measurements of dielectric spectroscopy and phase contrast microscopy/Raman spectroscopy by using a dielectric cell with transparent electrodes. We find that the temporal change in molecular mobility crucially depends on whether LLT is nucleation growth type occurring in the metastable state or SD type occurring in the unstable state. Furthermore, our results suggest that the molecular mobility is controlled by the local order parameter: more specifically, the local activation energy of molecular rotation is controlled by the local fraction of locally favored structures formed in the liquid. Our study sheds light on the temporal change in the molecular dynamics during LLT and its link to the order parameter evolution.liquid-liquid transition | phase ordering dynamics | order parameter | local molecular dynamics | dielectric relaxation Significance Contrary to a common sense that a liquid state is unique for a pure system, there have been a number of indications for the presence of more than two liquid states. The transition between the liquid states is called "liquid-liquid transition." There has so far been little information on how local molecular dynamics changes during the transformation. Here, we reveal the correlation between the order parameter and molecular dynamics by real-time dielectric spectroscopy measurements during the transformation from liquid I to liquid II in a molecular liquid, triphenyl phosphite. Our results suggest that the local order parameter controls local dynamics. Our finding sheds light on the nature of liquid-liquid transition from a perspective of molecular-level dynamics.

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Glass polymorphism in glycerol–water mixtures: II. Experimental studies

Abstract: We here study pressure-induced amorphization and polyamorphic transitions in frozen bulk glycerol–water solutions experimentally.

Cited by 45 publications

References 52 publications

Protein Preferential Solvation in Water:Glycerol Mixtures

Protein Preferential Solvation in Water:Glycerol Mixtures

Liquid-liquid separation of aqueous solutions: A molecular dynamics study

Link between molecular mobility and order parameter during liquid–liquid transition of a molecular liquid

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