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SignificanceStep-bunching instability (SBI) is one of the interfacial instabilities driven by self-organization of elementary step flow associated with crystal-growth dynamics, which has been observed in diverse crystalline materials. However, despite theoretical suggestions of its presence, no direct observations of SBI for simple melt growth have been achieved so far. Here, with the aid of a type of optical microscope and its combination with a two-beam interferometer, we realized quantitative in situ observations of the spatiotemporal dynamics of the SBI. This enables us to examine the origin of the SBI at the level of the step-step interaction. We also found that the SBI spontaneously induces a highly stable spiral growth mode, governing the late stage of the growth process.
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We constructed millimeter-wide monolayers consisting of tetragonally ordered BaTiO3 (BT) nanocubes through the liquid film formation caused by the Marangoni flow in a toluene-hexane binary liquid containing oleic acid. A thin liquid film containing BT nanocubes was overspread on a standing silicon substrate through the condensation of toluene at the advancing front after the preferential evaporation of hexane. Then, the oscillatory droplet formation like "wineglass tears" occurred on the substrate. Finally, two-dimensionally ordered BT nanocubes were observed as a stain of "wineglass tears" on the substrate after the liquid film receded through evaporation. The presence of a thin liquid film in the binary system is essential for the production of millimeter-wide monolayers on the substrate because multilayer deposition occurs without the formation of a thin liquid film in monocomponent systems. We improved the regularity of the ordered arrays of nanocubes by adjusting the liquid component and evaporation conditions.
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The spatio-temporal distribution of type-III antifreeze protein (AFP-III) molecules labeled with fluorescent isocyanate (FITC) was visualized at the interfaces between ice and solutions with an FITC-labeled AFP-III (F-AFP-III) concentration of 20-800 µg/mL by fluorescence microscopy. The number density of F-AFP-III on the surface of ice microcrystals was calculated from the calibrated fluorescence intensity. The adsorption of F-AFP-III molecules on the ice crystal surfaces proceeded at a finite rate and then reached the saturation level. The time course of the number density of adsorbed F-AFP-III molecules could be well represented by Langmuir's model. The characteristic adsorption time of F-AFP-III, the adsorption coefficient k1 = (0.5 ± 0.05) × 10-4 (µg/mL)-1 s-1, and the desorption coefficient k2 = 0.005 ± 0.002 s-1 were determined using the Langmuir's model and obtained experimental data. We found that the adsorption of F-AFP-III could have different kinetics depending on the solution conditions and the type of fluorescence molecules conjugated with AFP-III.
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Gelo , alfa-Fetoproteínas , Adsorção , Cinética , Fluoresceína-5-Isotiocianato , Proteínas Anticongelantes/químicaRESUMO
Ice-binding proteins (IBPs) affect ice crystal growth by attaching to crystal faces. We present the effects on the growth of an ice single crystal caused by an ice-binding protein from the sea ice microalga Fragilariopsis cylindrus (fcIBP) that is characterized by the widespread domain of unknown function 3494 (DUF3494) and known to cause a moderate freezing point depression (below 1 °C). By the application of interferometry, bright-field microscopy, and fluorescence microscopy, we observed that the fcIBP attaches to the basal faces of ice crystals, thereby inhibiting their growth in the c direction and resulting in an increase in the effective supercooling with increasing fcIBP concentration. In addition, we observed that the fcIBP attaches to prism faces and inhibits their growth. In the event that the effective supercooling is small and crystals are faceted, this process causes an emergence of prism faces and suppresses crystal growth in the a direction. When the effective supercooling is large and ice crystals have developed into a dendritic shape, the suppression of prism face growth results in thinner dendrite branches, and growth in the a direction is accelerated due to enhanced latent heat dissipation. Our observations clearly indicate that the fcIBP occupies a separate position in the classification of IBPs due to the fact that it suppresses the growth of basal faces, despite its moderate freezing point depression.
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Proteínas de Algas/química , Diatomáceas/química , Congelamento , Gelo , Microalgas/química , Proteínas de Algas/metabolismo , Diatomáceas/metabolismo , Microalgas/metabolismoRESUMO
The ice premelt, often called the quasi-liquid layer (QLL), is key for the lubrication of ice, gas uptake by ice, and growth of aerosols. Despite its apparent importance, in-depth understanding of the ice premelt from the microscopic to the macroscopic scale has not been gained. By reviewing data obtained using molecular dynamics (MD) simulations, sum-frequency generation (SFG) spectroscopy, and laser confocal differential interference contrast microscopy (LCM-DIM), we provide a unified view of the experimentally observed variation in quasi-liquid (QL) states. In particular, we disentangle three distinct types of QL states of disordered layers, QL-droplet, and QL-film and discuss their nature. The topmost ice layer is energetically unstable, as the topmost interfacial H2O molecules lose a hydrogen bonding partner, generating a disordered layer at the ice-air interface. This disordered layer is homogeneously distributed over the ice surface. The nature of the disordered layer changes over a wide temperature range from -90 °C to the bulk melting point. Combined MD simulations and SFG measurements reveal that the topmost ice surface starts to be disordered around -90 °C through a process that the topmost water molecules with three hydrogen bonds convert to a doubly hydrogen-bonded species. When the temperature is further increased, the second layer starts to become disordered at around -16 °C. This disordering occurs not in a gradual manner, but in a bilayer-by-bilayer manner. When the temperature reaches -2 °C, more complicated structures, QL-droplet and QL-film, emerge on the top of the ice surface. These QL-droplets and QL-films are inhomogeneously distributed, in contrast to the disordered layer. We show that these QL-droplet and QL-film emerge only under supersaturated/undersaturated vapor pressure conditions, as partial and pseudopartial wetting states, respectively. Experiments with precisely controlled pressure show that, near the water vapor pressure at the vapor-ice equilibrium condition, no QL-droplet and QL-film can be observed, implying that the QL-droplet and QL-film emerge exclusively under nonequilibrium conditions, as opposed to the disordered layers formed under equilibrium conditions. These findings are connected with many phenomena related to the ice surface. For example, we explain how the disordering of the topmost ice surface governs the slipperiness of the ice surface, allowing for ice skating. Further focus is on the gas uptake mechanism on the ice surface. Finally, we note the unresolved questions and future challenges regarding the ice premelt.
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A microscopic understanding of crystal-melt interfaces, inseparably involved in the dynamics of crystallization, is a long-standing challenge in condensed matter physics. Here, using an advanced optical microscopy, we directly visualize growing interfaces between ice basal faces and quasiliquid layers (QLLs) during ice crystal growth. This system serves as a model for studying the molecular incorporation process of the crystal growth from a supercooled melt (the so-called melt growth), often hidden by inevitable latent heat diffusion and/or the extremely high crystal growth rate. We reveal that the growth of basal faces inside QLLs proceeds layer by layer via two-dimensional nucleation of monomolecular islands. We also find that the lateral growth rate of the islands is well described by the Wilson-Frenkel law, taking into account the slowing down of the dynamics of water molecules interfaced with ice. These results clearly indicate that, after averaging surface molecular fluctuations, the layer by layer stacking still survives even at the topmost layer on basal faces, which supports the kink-step-terrace picture even for the melt growth.
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An impurity effect on ice crystal growth in supercooled water is an important subject in relation to ice crystal formation in various conditions in the Earth's cryosphere regions. In this review, we consider antifreeze glycoprotein molecules as an impurity. These molecules are well known as functional molecules for controlling ice crystal growth by their adsorption on growing ice/water interfaces. Experiments on free growth of ice crystals in supercooled water containing an antifreeze protein were conducted on the ground and in the International Space Station, and the normal growth rates for the main crystallographic faces of ice, namely, basal and prismatic faces, were precisely measured as functions of growth conditions and time. The crystal-plane-dependent functions of AFGP molecules for ice crystal growth were clearly shown. Based on the magnitude relationship for normal growth rates among basal, prismatic and pyramidal faces, we explain the formation of a dodecahedral external shape of an ice crystal in relation to the key principle governing the growth of polyhedral crystals. Finally, we emphasize that the crystal-plane dependence of the function of antifreeze proteins on ice crystal growth relates to the freezing prevention of living organisms in sub-zero temperature conditions. This article is part of the theme issue 'The physics and chemistry of ice: scaffolding across scales, from the viability of life to the formation of planets'.
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Surfaces of ice are covered with thin liquid water layers, called quasi-liquid layers (QLLs), even below their melting point (0 °C), which govern a wide variety of phenomena in nature. We recently found that two types of QLL phases appear that exhibit different morphologies (droplets and thin layers) [Sazaki G. et al. (2012) Proc Natl Acad Sci USA 109(4):1052-1055]. However, revealing the thermodynamic stabilities of QLLs remains a longstanding elusive problem. Here we show that both types of QLLs are metastable phases that appear only if the water vapor pressure is higher than a certain critical supersaturation. We directly visualized the QLLs on ice crystal surfaces by advanced optical microscopy, which can detect 0.37-nm-thick elementary steps on ice crystal surfaces. At a certain fixed temperature, as the water vapor pressure decreased, thin-layer QLLs first disappeared, and then droplet QLLs vanished next, although elementary steps of ice crystals were still growing. These results clearly demonstrate that both types of QLLs are kinetically formed, not by the melting of ice surfaces, but by the deposition of supersaturated water vapor on ice surfaces. To our knowledge, this is the first experimental evidence that supersaturation of water vapor plays a crucially important role in the formation of QLLs.
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Since the pioneering prediction of surface melting by Michael Faraday, it has been widely accepted that thin water layers, called quasi-liquid layers (QLLs), homogeneously and completely wet ice surfaces. Contrary to this conventional wisdom, here we both theoretically and experimentally demonstrate that QLLs have more than two wetting states and that there is a first-order wetting transition between them. Furthermore, we find that QLLs are born not only under supersaturated conditions, as recently reported, but also at undersaturation, but QLLs are absent at equilibrium. This means that QLLs are a metastable transient state formed through vapor growth and sublimation of ice, casting a serious doubt on the conventional understanding presupposing the spontaneous formation of QLLs in ice-vapor equilibrium. We propose a simple but general physical model that consistently explains these aspects of surface melting and QLLs. Our model shows that a unique interfacial potential solely controls both the wetting and thermodynamic behavior of QLLs.
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We have experimentally determined the surface tension-to-shear viscosity ratio (the so-called characteristic velocity) of quasiliquid layers (QLLs) on ice crystal surfaces from their wetting dynamics. Using an advanced optical microscope, whose resolution reaches the molecular level in the height direction, we directly observed the coalescent process of QLLs and followed the relaxation modes of their contact lines. The relaxation dynamics is known to be governed by the characteristic velocity, which allows us to access the physical properties of QLLs in a noninvasive way. Here we quantitatively demonstrate that QLLs, when completely wetting ices, have a thickness of 9±3 nm and an approximately 200 times lower characteristic velocity than bulk water, whereas QLLs, when partially wetting ices, have a velocity that is 20 times lower than the bulk. This indicates that ice crystal surfaces significantly affect the physical properties of QLLs localized near the surfaces at a nanometer scale.
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Ice plays crucially important roles in various phenomena because of its abundance on Earth. However, revealing the dynamic behavior of quasi-liquid layers (QLLs), which governs the surface properties of ice crystals at temperatures near the melting point, remains an experimental challenge. Here we show that two types of QLL phases appear that exhibit different morphologies and dynamics. We directly visualized the two types of QLLs on ice crystal surfaces by advanced optical microscopy, which can visualize the individual 0.37-nm-thick elementary steps on ice crystal surfaces. We found that they had different stabilities and different interactions with ice crystal surfaces. The two immiscible QLL phases appeared heterogeneously, moved around, and coalesced dynamically on ice crystal surfaces. This picture of surface melting is quite different from the conventional picture in which one QLL phase appears uniformly on ice crystal surfaces.
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Gelo/análise , Microscopia Confocal/métodos , Microscopia de Interferência/métodos , Transição de Fase , Água/química , ObservaçãoRESUMO
Dissipative structures often appear as an unstable counterpart of ordered structures owing to fluctuations that do not form a homogeneous phase. Even a multiphase mixture may simultaneously undergo one chemical reaction near equilibrium and another one that is far from equilibrium. Here, we observed in real time crystal seed formation and simultaneous nanocrystal aggregation proceeding from CeIV complexes to CeO2 nanoparticles in an acidic aqueous solution, and investigated the resultant hierarchical nanoarchitecture. The formed particles exhibited two very different size ranges, resulting in further pattern formation with opalescence. The hierarchically assembled structures in solutions were CeO2 colloids, viz. primary core clusters (1-3 nm) of crystalline ceria and secondary clusters (20-30 nm) assembled through surface ions. Such self-assembly is widespread in multi-component complex fluids, paradoxically moderating hierarchical reactions. Stability and instability are not only critical but also complementary for co-optimisation around the nearby free energy landscape prior to bifurcation.
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Due to the abundance of ice on earth, the phase transition of ice plays crucially important roles in various phenomena in nature. Hence, the molecular-level understanding of ice crystal surfaces holds the key to unlocking the secrets of a number of fields. In this study we demonstrate, by laser confocal microscopy combined with differential interference contrast microscopy, that elementary steps (the growing ends of ubiquitous molecular layers with the minimum height) of ice crystals and their dynamic behavior can be visualized directly at air-ice interfaces. We observed the appearance and lateral growth of two-dimensional islands on ice crystal surfaces. When the steps of neighboring two-dimensional islands coalesced, the contrast of the steps always disappeared completely. We were able to discount the occurrence of steps too small to detect directly because we never observed the associated phenomena that would indicate their presence. In addition, classical two-dimensional nucleation theory does not support the appearance of multilayered two-dimensional islands. Hence, we concluded that two-dimensional islands with elementary height (0.37 and 0.39 nm on basal and prism faces, respectively) were visualized by our optical microscopy. On basal and prism faces, we also observed the spiral growth steps generated by screw dislocations. The distance between adjacent spiral steps on a prism face was about 1/20 of that on a basal face. Hence, the step ledge energy of a prism face was 1/20 of that on a basal face, in accord with the known lower-temperature roughening transition of the prism face.
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High-throughput protein X-ray crystallography offers a significant opportunity to facilitate drug discovery. The most reliable approach is to determine the three-dimensional structure of the protein-ligand complex by soaking the ligand in apo crystals. However, protein apo crystals produced by conventional crystallization in a solution are fatally damaged by osmotic shock during soaking. To overcome this difficulty, we present a novel technique for growing protein crystals in a high-concentration hydrogel that is completely gellified and exhibits high strength. This technique allowed us essentially to increase the mechanical stability of the crystals, preventing serious damage to the crystals caused by osmotic shock. Thus, this method may accelerate structure-based drug discoveries.
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Cristalização/métodos , Hidrogéis/química , Muramidase/química , Fenômenos Biomecânicos , Dureza , Pressão Osmótica , Estabilidade ProteicaRESUMO
Hierarchic structure and anomalous diffusion on submicrometer scale were introduced into an artificial cell membrane, and the spatiotemporal dependence of lipid diffusion was visualized on nanostructured oxide surfaces. We observed the lipid diffusion in supported lipid bilayers (SLBs) on step-and-terrace TiO(2)(100) and amorphous SiO(2)/Si surfaces by single molecule tracking (SMT) method. The SMT at the time resolution of 500 µs to 30 ms achieved observation of the lipid diffusion over the spatial and temporal ranges of 100 nm/millisecond to 1 µm/second. The temporal dependence of the diffusion coefficient in the SLB on TiO(2)(100) showed that the crossover from anomalous diffusion to random diffusion occurred around 10 ms. The surface fine architecture on substrates will be applicable to induce hierarchic structures on the order of 100 nm or less, which correspond to the microcompartment size in vivo.
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Bicamadas Lipídicas/química , Nanoestruturas/química , Nanotecnologia , Dióxido de Silício/química , Titânio/químicaRESUMO
In situ X-ray scattering measurements of insect body surface lipids were successfully attempted by using a synchrotron X-ray source. The temperature-dependent structural changes of the cuticular hydrocarbons covering the forewing of an American cockroach were able to be followed, which showed that the majority of the hydrocarbons were in a liquid state even far below the critical temperature of water transpiration through the body surface. The results clearly demonstrated that synchrotron radiation X-ray scattering has the potential to obtain the detailed information about the intact lipid structure and physical properties on insect body surfaces.
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Lipídeos/química , Periplaneta/química , Animais , Hidrocarbonetos/química , Conformação Molecular , Espalhamento de Radiação , Propriedades de Superfície , Temperatura , Água , Difração de Raios XRESUMO
The cuticular lipid covering the integument of insects is exposed to the environment and involved in a variety of functions offered by insect body surfaces, ranging from protection against the environment, such as the control of water transpiration, the reduction of abrasive damage, and the prevention of pathogen intrusion, to the communication between insects from intraspecific to interspecific interactions. In comparison with the importance of their physiological functions, there is remarkably little information on the structure and physical property of cuticular lipids on insect body surfaces. The lipid layer on the outer exoskeleton is very thin, estimated on the order of 0.01-1 µm or less, and this has led to a lack of practical methodologies for detailed structural analyses. To fill this devoid, we have exploited the characteristics of Fourier transform infrared (FTIR) attenuated total reflection (ATR) spectroscopy, which allows us to conduct a chemical analysis on insect body surfaces and also to investigate depth-dependent structural changes. We have applied a combination of FTIR ATR microspectroscopy with IR radiation provided by a synchrotron facility to obtain in situ two-dimensional (2D) information of the cuticular lipid layer on the surface of the integument. The 2D FTIR spectra measured on the two-spotted cricket and the American cockroach show that the IR bands due to the cuticular lipid, such as CH2 symmetric and antisymmetric stretch, νa(CH2) and νs(CH2), change in intensity significantly, depending on the location of measurements. As if to keep pace with this, the bands of the amide group for the underlying cuticular layer also change in intensity significantly, although the changes are in the opposite direction; as the lipid bands increase in intensity, the amide band decreases, and vice versa. The ATR spectral analysis, which takes into account the characteristics of the evanescent wave, points out that the lipid layer would vary tens of times in the range of 0.01-1 µm significantly. The νa(CH2) and νs(CH2) bands show frequency shifts, which correlate to some extent with their intensity changes, suggesting that the drastic uneven distribution of the cuticular lipid would be related to the solid-liquid phase separation and also the coarsening of the solid phase domains. The formation of such topological features, significant heterogeneity in the lipid layer thickness, and solid-liquid phase ratios would be accompanied by the partitioning of lipid components according to molecular structures and physicochemical properties. Considering that each lipid component in insect body surface lipids is involved in various physiological roles, the segregation of lipid components during the formation of such heterogeneous structures is thought to have a significant impact on the functionality of the insect body surface.
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Lipídeos , Síncrotrons , Animais , Análise de Fourier , Insetos , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
To protect themselves, insects cover their bodies with what is called cuticular lipid. The cuticular lipid of an American cockroach has a unique lipid content; the most abundant is a cis-alkadiene, cis, cis-6,9-heptacosadiene, amounting to about 70%, which is followed by a branched alkane 3-methylpentacosane. In order to clarify the structural features of the unique lipid composition below the critical temperature, the cuticular lipid was studied by Fourier transform infrared (FTIR) spectroscopy in combination with an attenuated total reflection (ATR) sampling technique. The infrared spectra measured on an extracted lipid sample at 20 °C suggested that the lipid keeps an appreciable level of conformational and lateral packing regularity, in spite of a high cis-unsaturated lipid content, and also a highly disordered condition around the methyl terminals and cis-olefin groups. The CH2 scissoring and the CH2 rocking regions showed the characteristics of the O⥠subcell. The same characteristics were observed also by in situ measurements on a forewing of the American cockroach. Combining the spectral features of these bands and the physicochemical properties of each component, it can be inferred that saturated lipids form highly ordered domains within the liquid containing the cis, cis-diene as the main component. For comparison, the cuticular lipid of a male cricket, which consisted of many different hydrocarbons, including 15% of unsaturated hydrocarbons, showed a lower regularity both in the conformation and in the lateral packing of hydrocarbon chains. These results imply that not only the degree of cis-unsaturation but also the chemical structure diversity of hydrocarbons are the important factors to determine the physicochemical properties of cuticular lipid.
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Alcadienos/análise , Exoesqueleto/química , Lipídeos/análise , Asas de Animais/química , Alcadienos/química , Animais , Gryllidae/química , Lipídeos/química , Masculino , Periplaneta/química , Espectroscopia de Infravermelho com Transformada de Fourier/métodos , EstereoisomerismoRESUMO
The free growth of ice crystals in supercooled bulk water containing an impurity of glycoprotein, a bio-macromolecule that functions as 'antifreeze' in living organisms in a subzero environment, was observed under microgravity conditions on the International Space Station. We observed the acceleration and oscillation of the normal growth rates as a result of the interfacial adsorption of these protein molecules, which is a newly discovered impurity effect for crystal growth. As the convection caused by gravity may mitigate or modify this effect, secure observations of this effect were first made possible by continuous measurements of normal growth rates under long-term microgravity condition realized only in the spacecraft. Our findings will lead to a better understanding of a novel kinetic process for growth oscillation in relation to growth promotion due to the adsorption of protein molecules and will shed light on the role that crystal growth kinetics has in the onset of the mysterious antifreeze effect in living organisms, namely, how this protein may prevent fish freezing.
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Proteínas Anticongelantes/metabolismo , Cristalização , Gelo , Poluentes Químicos da Água/metabolismo , Ausência de PesoRESUMO
Pressure is expected to be an important parameter to control protein crystallization, since hydrostatic pressure affects the whole system uniformly and can be changed very rapidly. So far, a lot of studies on protein crystallization have been done. Solubility of protein depends on pressure. For instance, the solubility of tetragonal lysozyme crystal increased with increasing pressure, while that of orthorhombic crystal decreased. The solubility of subtilisin increased with increasing pressure. Crystal growth rates of protein also depend on pressure. The growth rate of glucose isomerase was significantly enhanced with increasing pressure. The growth rate of tetragonal lysozyme crystal and subtilisin decreased with increasing pressure. To study the effects of pressure on the crystallization more precisely and systematically, hen egg white lysozyme is the most suitable protein at this stage, since a lot of data can be used. We focused on growth kinetics under high pressure, since extensive studies on growth kinetics have already been done at atmospheric pressure, and almost all of them have explained the growth mechanisms well. The growth rates of tetragonal lysozyme decreased with pressure under the same supersaturation. This means that the surface growth kinetics significantly depends on pressure. By analyzing the dependence of supersaturation on growth rate, it was found that the increase in average ledge surface energy of the two-dimensional nuclei with pressure explained the decrease in growth rate. At this stage, it is not clear whether the increase in surface energy with increasing pressure is the main reason or not. Fundamental studies on protein crystallization under high pressure will be useful for high pressure crystallography and high pressure protein science.