RESUMEN
Water freezing, initiated by ice nucleation, occurs widely in nature, ranging from cellular to global phenomena. Ice nucleation has been experimentally proven to require the formation of a critical ice nucleus, consistent with classical nucleation theory (CNT). However, the accuracy of CNT quantitative predictions of critical cluster sizes and nucleation rates has never been verified experimentally. In this study, we circumvent this difficulty by using molecular dynamics (MD) simulation. The physical properties of water/ice for CNT predictions, including density, chemical potential difference, and diffusion coefficient, are independently obtained using MD simulation, whereas the calculation of interfacial free energy is based on thermodynamic assumptions of CNT, including capillarity approximation among others. The CNT predictions are compared to the MD evaluations of brute-force simulations and forward flux sampling methods. We find that the CNT and MD predicted critical cluster sizes are consistent, and the CNT predicted nucleation rates are higher than the MD predicted values within three orders of magnitude. We also find that the ice crystallized from supercooled water is stacking-disordered ice with a stacking of cubic and hexagonal ices in four representative types of stacking. The prediction discrepancies in nucleation rate mainly arise from the stacking-disordered ice structure, the asphericity of ice cluster, the uncertainty of ice-water interfacial free energy, and the kinetic attachment rate. Our study establishes a relation between CNT and MD to predict homogeneous ice nucleation.
RESUMEN
With the advantages of a long lifetime and high reliability, gas gap heat switches (GGHSs) are attractive in many thermal management applications, especially in space-borne cryogenic systems. The performance of a GGHS is significantly affected by the adsorption characteristics of the adsorbent in the sorption pump. Compared with the commonly used adsorbent in the GGHSs (activated carbon), metal-organic frameworks (MOFs) have larger surface areas, higher pore volumes, and exceptional tunability, which motivates this study to explore their potential for application in cryogenic GGHSs. To this end, two performance metrics, the required volume of adsorbent (vsor) and total input heat (qtot), were computed for about 6000 MOFs via molecular simulations and compared with those of activated carbon. It is found that over 2300 MOFs possess a smaller vsor than activated carbon, and the smallest vsor of MOFs is about 12.7% of that of activated carbon. vsor and qtot generally change in the same direction, which implies it is possible to reduce both parameters simultaneously by choosing a suitable MOF. Structure-performance analysis reveals that 1/vsor consistently increases first and then decreases with pore limiting diameter, largest cavity diameter, available pore volume, accessible surface area, helium void fraction, and bulk density. Descriptor ranges corresponding to high-performing MOFs were identified based on Precision-Recall analysis. Notably, Zr-containing MOFs are particularly likely to have smaller vsor values than activated carbon. It is anticipated that the promising MOFs identified by this study will motivate further experimental investigations, and the insights into structure-performance relationships can serve to guide the rational design of novel MOF candidates for GGHSs.
RESUMEN
The cryopreservation of biomaterials is fundamental to modern biotechnology and biomedicine, but the biggest challenge is the formation of ice, resulting in fatal cryoinjury to biomaterials. To date, abundant ice control strategies have been utilized to inhibit ice formation and thus improve cryopreservation efficiency. This review focuses on the mechanisms of existing control strategies regulating ice formation and the corresponding applications to biomaterial cryopreservation, which are of guiding significance for the development of ice control strategies. Herein, basics related to biomaterial cryopreservation are introduced first. Then, the theoretical bases of ice nucleation, growth, and recrystallization are presented, from which the key factors affecting each process are analyzed, respectively. Ice nucleation is mainly affected by melting temperature, interfacial tension, shape factor, and kinetic prefactor, and ice growth is mainly affected by solution viscosity and cooling/warming rate, while ice recrystallization is inhibited by adsorption or diffusion mechanisms. Furthermore, the corresponding research methods and specific control strategies for each process are summarized. The review ends with an outlook of the current challenges and future perspectives in cryopreservation. STATEMENT OF SIGNIFICANCE: Ice formation is the major limitation of cryopreservation, which causes fatal cryoinjury to cryopreserved biomaterials. This review focuses on the three processes related to ice formation, called nucleation, growth, and recrystallization. The theoretical models, key influencing factors, research methods and corresponding ice control strategies of each process are summarized and discussed, respectively. The systematic introduction on mechanisms and control strategies of ice formation is instructive for the cryopreservation development.
Asunto(s)
Crioprotectores , Hielo , Crioprotectores/química , Cristalización , Criopreservación/métodos , CongelaciónRESUMEN
Freezing of natural biomaterials results in the formation of ice crystals and the generation of hypertonicity, both of which are deleterious to biomaterials. Although the cryopreservation of cells, tissues, and even organs has been achieved empirically by vitrification using cryoprotectants, the underlying mechanisms are poorly understood. To better understand the crystallization and vitrification processes of cryoprotected cells, onion epidermal cells immersed in dimethyl sulfoxide (DMSO) solutions with different concentrations were employed as platforms. The crystallization and vitrification dynamic processes of the individual and multiple monolayer cells were recorded using a high-speed microscope camera and the forms of the intracellular and extracellular ices were further confirmed by corresponding Raman spectra. The effects of DMSO concentration and cooling/warming rate on both processes were investigated and the findings were of an important significance to improve the understanding of the mechanisms of intracellular ice formation in individual cells and the ice propagation between adjacent cells. It is expected to provide a theoretical basis for cryopreservation by vitrification and point toward a new pathway for developing cryopreservation protocols.