Freezing of Water Solvation Dynamics in Nanoconfinement by Reverse Micelles at Room Temperature.

Much attention has recently been paid to anomalously low dielectric constants of nanoconfined water between two slabs at room temperature (Fumagalli et al. Science, 2018, 360, 1339). These low values imply that the dipole rotation of the interfacial water on the slab is completely suppressed. Such freezing has so far been observed for water confined between solids. In contrast, it remains unclear whether this holds for water in soft confinement, which is omnipresent naturally and artificially. Here, we address this question using encapsulated reverse micelles with a dye molecule, allowing us to study water sandwiched between the surfactant and dye molecules in solution. Moreover, we examine the solvation related to the dielectric property of water, which is reorientational motion in the hydration layer of the dye molecule, by persistent hole-burning spectroscopy. We first show that the dye molecule is surrounded by water without contact with the surfactant and that the dye molecule has two or three hydration layers on average. We next demonstrate that the solvation dynamics is frozen below the water droplet size of ∼4 nm, whereas they become liquid-like when the RM size is further increased. The average gap distance (∼1.5 nm) for freezing the solvation agrees with the gap distance with no rotational water motions between slabs. Our findings may have biological relevance, providing a new aspect for understanding biological function in cells.

Dielectric relaxation of ice in a partially crystallized poly(N-isopropylacrylamide)microgel suspension compared to other partially crystalized polymer-water mixtures.

A broadband dielectric spectroscopy study was conducted on a partially crystallized 10 wt% poly(N-isopropylacrylamide) [PNIPAM] microgel aqueous suspension to investigate the dielectric relaxation of ice in microgel suspensions. The measurements covered a frequency range of 10 mHz to 10 MHz and at temperatures ranging from 123 K to 273 K. Two distinct relaxation processes were observed at specific frequencies below the melting temperature. One is associated with the combination of the local chain motion of PNIPAM and interfacial polarization in the uncrystallized phase, while another is associated with ice. To understand the temperature-dependent behaviour of the ice relaxation process, the relaxation time of ice was compared with those observed in other frozen polymer water mixtures, including gelatin, poly-vinylpyrrolidone (PVP), and bovine serum albumin (BSA). For concentrations ≥ 10 wt%, the temperature dependence of the relaxation time of ice was found to be independent. Therefore, the study primarily focused on the 10 wt% data for easier comprehension of the ice relaxation process. It was found that the microgel and globular protein BSA had no significant effect on ice crystallization, while gelatin slowed down the crystallization process, and PVP accelerated it. To discuss the mechanism of the dielectric relaxation of ice, the trap-controlled proton transport model developed by Khamzin et al. [Chem. Phys., 2021, 541, 111040.] was employed. The model was used to discuss the dynamic heterogeneity of ice observed in this investigation, distinguishing it from the spatial heterogeneity of ice commonly discussed.

Dielectric relaxations of ice and uncrystallized water in partially crystallized bovine serum albumin-water mixtures.

To investigate the dielectric relaxations of ice in low-concentration protein-water mixtures, broadband dielectric spectroscopy measurements were performed on partially crystallized bovine serum albumin (BSA)-water mixtures with BSA concentrations of 1-10 wt% at temperatures in the range of 123-298 K. The temperature dependence of the relaxation time of ice observed in all these mixtures changes twice at TC1 (∼240 K) and TC2 (200-160 K) (TC1 > TC2), i.e., at which the apparent activation energy, Ea, changes. Below 200 K, the relaxation of ice separates as 3-4 relaxations with different TC2 and Ea values. The presence of the multiple ice relaxations is the same as that observed for the gelatin-water mixtures (T. Yasuda, K. Sasaki, R. Kita, N. Shinyashiki and S. Yagihara, J. Phys. Chem. B, 2017, 121, 2896), but the concentration dependences of TC1 and TC2 are different. The relaxation interpreted to be due to uncrystallized water in 20 wt% and 40 wt% BSA-water mixtures reported (N. Shinyashiki, W. Yamamoto, A. Yokoyama, T. Yoshinari, S. Yagihara, R. Kita, K. L. Ngai and S. Capaccioli, J. Phys. Chem. B, 2009, 113, 14448) was re-examined and concluded to be due to one of the multiple relaxations of ice.

Method for Recognizing Pressing Position and Shear Force Using Active Acoustic Sensing on Gel Plates.

A touch interface is an important technology used in many devices, including touch panels in smartphones. Many touch panels only detect the contact position. If devices can detect shear force in addition to the contact position, various touch interactions are possible. We propose a two-step recognition method for recognizing the pressing position and shear force using active acoustic sensing, which transmits acoustic signals to an object and recognizes the state of the object by analyzing its response. Specifically, we attach a contact speaker transmitting an ultrasonic sweep signal and a contact microphone receiving ultrasonic waves to a plate of gel. The propagation characteristics of ultrasonic waves differ due to changes in the shape of the gel caused by the user's actions on the gel. This system recognizes the pressing position and shear force on the basis of the difference in acoustic characteristics. An evaluation of our method involving a user-independent model confirmed that four pressing positions were recognized with an F1 score of 85.4%, and four shear-force directions were recognized with an F1 score of 69.4%.

Water in the hydrated protein powders: Dynamic and structure.

It is not an understatement to say that the interplay between water and protein is a fundamental aspect of life. The vitality of an organism depends on the functionality of its biological machinery, and this, in turn, is mediated in water. Yet, we understand surprisingly little about the nature of the interface between bulk water and the protein. On the one hand, we know that the nature of the bulk water is dominated by the existence of H-bonding and H-bonded networks. On the other hand, the protein surface, where much of the bioactivity is centered, is a complex landscape of hydrophilic and hydrophobic elements. So how does the interface between these two entities work and how do they influence each other? The question is important because if one understands how a particular protein interface influences the dynamics of the water, it then becomes an easily accessible marker for similar behavior in other protein systems. The dielectric relaxation of hydrated proteins with different structures, lysozyme, collagen, and phycocyanin, has been reviewed in this paper. The dynamics of hydrated water was analyzed in terms of orientation and the ionic defect migration model. This approach enables to characterize the microscopic relaxation mechanism of the dynamics of hydration water on the different structures of the protein. In addition, our model is also capable of characterizing not only hydrated proteins but also polymer-water systems.

Glass transition of partially crystallized gelatin-water mixtures studied by broadband dielectric spectroscopy.

The glass transition of partially crystallized gelatin-water mixtures was investigated for gelatin concentrations of 40 and 20 wt. % by broadband dielectric spectroscopy (BDS) in wide frequency (10 mHz-50 GHz) and temperature (113-298 K) ranges. Three dielectric relaxation processes were clearly observed. The origin of each relaxation process was the same as that observed for partially crystallized bovine serum albumin (BSA)-water mixtures [N. Shinyashiki et al., J. Phys. Chem. B 113, 14448 (2009)]. The relaxation process at the highest frequency is originated from uncrystallized water (UCW) in the hydration shell of gelatin. Its relaxation time is almost the same as that of water in uncrystallized system; water in various binary aqueous mixtures and confined water in nanoscale region. The relaxation process at the intermediate frequency is originated from ice, and its relaxation time and strength were similar to those for the relaxation of pure ice, particularly above 240 K. The glass transition temperature Tg, is defined by BDS measurement as the temperature at which dielectric relaxation time τ, is 100-1000 s. The relaxation process at the lowest frequency, Tg is approximately 200 K, is originated from the cooperative motion of water and gelatin. This relaxation is strong and has a similar relaxation strength to that of hydrated BSA. At Tg for the relaxation process involving the cooperative motion of gelatin and water, the temperature dependence of the relaxation process of UCW crosses over from Vogel-Fulcher behavior to Arrhenius behavior with decreasing temperature. A characteristic property of the gelatin-water mixture is a change in the temperature dependence of the relaxation time of the relaxation processes of hydrated gelatin at approximately 260 K.

A 77-Year-Old Man with a Pulse Granuloma of the Descending Colon Identified by Fluorodeoxyglucose-Positron Emission Tomography (FDG-PET) Imaging 19 Months Following Surgical Resection for Rectal Carcinoma.

BACKGROUND Food particles may sometime lodge in the intestinal wall, resulting in a granuloma. Pulse granuloma is associated with the seed of a legume and has a characteristic appearance on histology. This report describes a case of pulse granuloma of the descending colon identified by fluorodeoxyglucose-positron emission tomography (FDG-PET) imaging. Imaging was done 19 months after surgical resection for rectal carcinoma, and the results of imaging alone suggested a tumor metastasis. CASE REPORT A 77-year-old man underwent sigmoid colostomy for sigmoid colon perforation due to obstruction by rectal cancer affecting the upper rectum approximately 2 years ago. Two months later, after his general condition improved, he underwent laparoscopic low anterior resection. On postoperative pathological examination, the lesion was diagnosed as stage II. Nineteen months later, computed tomography showed an irregular nodule on the dorsolateral side of the descending colon. FDG-PET revealed positive results, and peritoneal dissemination was suspected. Because the lesion was localized and there was no other evidence of metastasis, resection was performed. A pathological examination revealed a pulse granuloma with a central legume seed, and no obvious malignant findings were observed. CONCLUSIONS This report has highlighted the importance of imaging and histopathology in cases in which a solitary nodule is present in the bowel in a patient with previous successful treatment for malignancy. Pulse granuloma, or other types of granuloma associated with impacted food material, may be a cause of a solitary nodule, or pseudotumor, in the bowel wall.

Dynamics of Uncrystallized Water, Ice, and Hydrated Polymer in Partially Crystallized Poly(vinylpyrrolidone)-Water Mixtures.

In this study, we investigated the cooperative molecular dynamics of poly(vinylpyrrolidone) (PVP), ice, and uncrystallized water (UCW) in partially crystallized PVP-water mixtures by means of broadband dielectric spectroscopy. Three relaxation processes, denoted I, II, and III, were observed at temperatures ranging from immediately below the crystallization temperature (Tc) to approximately 200 K. At temperatures of 173-193 K, processes I and II cannot be distinguished. Below 168 K, process II separates into two processes: process IV at higher frequencies and process V at lower frequencies. Process I contributes to process V. In partially crystallized mixtures, process I originates from UCW in an uncrystallized phase with PVP. Process II is attributed to ice in the mixture, with a relaxation time that is 2 orders of magnitude smaller than that of pure ice. The concentration dependence of the strength of process II and the relaxation time relative to that of ice in bovine serum albumin (BSA)-water and gelatin-water mixtures strongly support this conclusion. Observation of processes IV and V indicates the presence of multiple ice relaxation processes. Process III is attributed to the α process of PVP in the uncrystallized phase in 40 and 50 wt % PVP mixtures. For mixtures with 30 wt % PVP or less, process III is attributed not only to the α process of PVP but also to interfacial polarization.

Dielectric Relaxation of Ice in Gelatin-Water Mixtures.

Broadband dielectric spectroscopy measurements were performed on partially crystallized gelatin-water mixtures with gelatin concentrations of 1-5 wt % for temperatures between 123 and 298 K to study the dynamics of ice. These systems contain only hexagonal ice. Nevertheless, four dielectric relaxation processes of ice were observed. At temperatures below the crystallization temperature, a loss peak was observed, and it separated into four loss peaks at around 225 K. Using the temperature and concentration dependencies of these relaxation processes, we confirmed that these four processes originated from ice. For the relaxation time of ice, τice, the deviation of the temperature dependence of τice from the Arrhenius type is larger for the relaxation process at the higher-frequency side. For the temperature dependence of τice for the dominant process, three temperature ranges with different activation energies, Ea, were investigated. The intermediate-temperature range of τice with the smallest Ea decreased as the gelatin concentration increased; therefore, τice of the dominant process changed from the relaxation process with the smaller τice to that with the larger τice as the gelatin concentration increased. In addition, the relaxation process of ice with larger τice values was found to have larger values of Ea. These results suggest that a higher gel network density affects the temperature dependence of τice.

Dynamics of Uncrystallized Water, Ice, and Hydrated Protein in Partially Crystallized Gelatin-Water Mixtures Studied by Broadband Dielectric Spectroscopy.

The glass transition of partially crystallized gelatin-water mixtures was investigated using broadband dielectric spectroscopy (BDS) over a wide range of frequencies (10 mHz to 10 MHz), temperatures (113-298 K), and concentrations (10-45 wt %). Three dielectric relaxation processes (processes I, II, and III) were clearly observed. Processes I, II, and III originate from uncrystallized water (UCW) in the hydration shells of gelatin, ice, and hydrated gelatin, respectively. A dynamic crossover, called the Arrhenius to non-Arrhenius transition of UCW, was observed at the glass transition temperature of the relaxation process of hydrated gelatin for all mixtures. The amount of UCW increases with increasing gelatin content. However, above 35 wt % gelatin, the amount of UCW became more dependent on the gelatin concentration. This increase in UCW causes a decrease in the glass transition temperature of the cooperative motion of gelatin and UCW, which appears to result from a change in the aggregation structure of gelatin in the mixture at a gelatin concentration of approximately 35 wt %. The temperature dependence of the relaxation time of process II has nearly the same activation energy as pure ice made by slow crystallization of ice Ih. This implies that process II originates from the dynamics of slowly crystallized ice Ih.

Dielectric Relaxation Time of Ice-Ih with Different Preparation.

Dielectric relaxation process of ice-Ih has been investigated by many researchers. Pioneering studies focused on the temperature dependence of the dielectric relaxation time, τice, were reported by Auty in 1952 [ Auty, R. P.; Cole, R. H. J. Chem. Phys . 1952 , 120 , 1309 ] and Johari in 1981 [ Johari, G. P.; Whalley, E. J. Chem. Phys. 1981 , 75 , 1333 ]. However, the temperature dependences of τice found in these studies are not in agreement. While Auty et al. reported a single Arrhenius temperature dependence of τice for the entire 207-273 K temperature range, Johari et al. reported changes in the temperature dependence of τice at 230 and 140 K. In this study, the temperature dependence of τice is investigated by broadband dielectric spectroscopy for ice prepared by three different procedures. For all investigated ices, a dielectric relaxation process is observed, and τice decreases with increasing temperature. Temperature dependence of τice with rapid crystallization shows the same properties at temperatures down to 140 K as that reported by Johari et al. On the other hand, ice obtained by slow crystallization exhibits the same temperature dependence of τice as those reported by Auty et al. We suggest that the difference between the temperature dependences of τice found by Auty et al. and Johari et al. can be controlled by preparation conditions. That is, the growth rate of the ice crystal can affect τice because a slow growth speed of the ice crystal induces a smaller impurity content of ice, giving rise to an Arrhenius temperature dependence of τice.

Glass Transition and Dynamics of the Polymer and Water in the Poly(vinylpyrrolidone)-Water Mixtures Studied by Dielectric Relaxation Spectroscopy.

In this study, broadband dielectric spectroscopy and differential scanning calorimetry (DSC) measurements are performed to study the dynamics of water and polymers in an aqueous solution of poly(vinylpyrrolidone) (PVP) with concentrations of 60, 65, and 70 wt % PVP in a temperature range of 123-298 K. Two distinct relaxation processes, l- and h-processes, which originate from the segmental chain motion of PVP and the primary relaxation process of water, respectively, are observed simultaneously. The relationship between l- and h-processes and their temperature dependences mimic those of the α-process and Johari-Goldstein ß-process, which are observed in ordinal glass formers. The relaxation time of the l-process, τl, obeys the Vogel-Fulcher (VF)-type temperature dependence, and the glass-transition temperature of the l-process, Tg,l, which is defined by the temperature that is reached in a τl of 100-1000 s, shows good agreement with the calorimetric Tg obtained by DSC. The temperature dependence of the relaxation time of the h-process, τh, exhibits a crossover from VF to Arrhenius behavior at the so-called fragile-to-strong transition (FST) of water at Tg,l. The temperature dependence of the relaxation strength of the h-process, Δεh, increases with a decrease in temperature from 298 K to Tg,l. Below Tg,l, Δεh is nearly constant or slightly decreases with decreasing temperature. According to previous studies on aqueous solutions of sugars and alcohols, the Δε of the ν-process, which originates from local motion of water, decreases with decreasing temperature above the Tg of the α-process, which originates from the cooperative motion of the solute and water. Therefore, the l-process in the PVP-water mixture is not a result of the cooperative motion of PVP and water but rather a result of the polymer-polymer cooperative motion of PVP. In addition, agreement among Tg,l, the temperature of the FST of water, and calorimetric Tg suggests that the FST of water occurs at Tg.