Thermal Behavior and Structure of Low-temperature Water Confined in Sephadex G15 Gel by Differential Scanning Calorimetry and X-ray Diffraction Method

Itô, Kiyosi; Yoshida, Kōji; Ujimoto, Kikujiro; Yamaguchi, Toshio

doi:10.2116/analsci.29.353

Cited by 17 publications

(8 citation statements)

References 38 publications

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“…Although water in the XLHEA and HF x hydrogels exhibited a freezing point depression, the melting point of the ice formed ( T m = 273 K) did not, Figure S2. The absence of a melting point depression is in stark contrast with the behavior of supercooled water in nanoporous solids, ,,, where confinement produced a Gibbs–Thomson effect . Those results suggest a fundamental difference in the behavior of water in rigid confinement, such as in pores with hard walls (e.g., in silica, ceramics or carbon nanotubes) and in soft confinement, where the supercooled water exists in the interstitial space between discrete nanodomains in soft matter.…”

Section: Results and Discussionmentioning

confidence: 99%

“…The network chains in the hydrogel are typically mobile, so the effect of confinement is likely negligible for most hydrogels. The hydrophilic chains in the hydrogels can provide opportunities for hydrogen bonding of water to suppress freezing, but the effect is limited to relatively small amounts of water and supercoolings of 10–20 K. , The inclusion of hydrophobic nanodomains through the supramolecular assembly of hydrophobes in hydrogels based on copolymers of N,N-dimethylacrylamide- stat -2-(N-ethylperfluorooctane sulfonamido)ethyl acrylate (DMA/FOSA) provides a more robust soft confining environment, which leads to inhibition of up to 45 wt % of the absorbed water in the hydrogel from freezing . However, irrespective of the hydrogel examined, the maximum nonfrozen water content reported in these hydrogel materials has been quite limited. − ,,,− Concentrated protein and polymer solutions, including coacervates, can also provide environments to produce significant quantities of nonfreezing water. − For the coacervates, the nonfrozen water fraction dramatically increases in comparison to that for analogous concentrated polymer/protein solutions (∼60% vs ∼10%) .…”

Section: Introductionmentioning

confidence: 99%

“…The hydrophilic chains in the hydrogels can provide opportunities for hydrogen bonding of water to suppress freezing, but the effect is limited to relatively small amounts of water and supercoolings of 10–20 K. , The inclusion of hydrophobic nanodomains through the supramolecular assembly of hydrophobes in hydrogels based on copolymers of N,N-dimethylacrylamide- stat -2-(N-ethylperfluorooctane sulfonamido)ethyl acrylate (DMA/FOSA) provides a more robust soft confining environment, which leads to inhibition of up to 45 wt % of the absorbed water in the hydrogel from freezing . However, irrespective of the hydrogel examined, the maximum nonfrozen water content reported in these hydrogel materials has been quite limited. − ,,,− Concentrated protein and polymer solutions, including coacervates, can also provide environments to produce significant quantities of nonfreezing water. − For the coacervates, the nonfrozen water fraction dramatically increases in comparison to that for analogous concentrated polymer/protein solutions (∼60% vs ∼10%) . In this case, the increased nonfrozen water is attributed to increased water–polymer/protein contacts, but the average separation between the polymer and protein was estimated at 1–2 nm.…”

Section: Introductionmentioning

confidence: 99%

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Antifreeze Hydrogels from Amphiphilic Statistical Copolymers

et al. 2018

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Prevention of ice formation is a critical issue for many applications, but routes to overcome the large thermodynamic driving force for crystallization of water at significant supercooling are limited. Here, we demonstrate that supramolecular hydrogels formed from statistical copolymers of 2-hydroxyethyl acrylate (HEA) and 2-(N-ethylperfluorooctane sulfonamido)ethyl methacrylate (FOSM) exhibit a degree of ice formation suppression unprecedented in a synthetic material. The mechanisms of ice prevention by these hydrogels mimic two methods used by nature: (1) hydrogen bonding of water to highly hydrophilic macromolecular chains and (2) nanoconfinement of water between hydrophobic moieties. From systematic variation in the copolymer composition to control the nanoscale (<4 nm) separation of the self-assembled hydrophobic nanodomains, the main mechanism by which these supramolecular hydrogels inhibit large amounts of water from freezing appears to be soft nanoconfinement. Nearly complete ice inhibition was achieved in hydrogels when the nanodomain separation was <3 nm (i.e., confinement volume ∼15 nm3) where <290 water molecules are present. Dielectric spectroscopy is consistent with two primary populations of water: a population of water with a bulk-like dynamics as well as T g (136 K) and a minority population of water with suppressed dynamics and an enhanced T g near 151 K that is attributed to interfacial water. The nanostructured design of these supramolecular hydrogels provides a blueprint concept for controlling and manipulating ice formation in concentrated soft matter using the length scale between hydrophobic domains and the hydrophilicity of the network water-soluble component. These insights have the potential to provide solutions to challenges with ice in engineering applications where confinement of water to nanoscale dimensions is possible.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Antifreeze Hydrogels from Amphiphilic Statistical Copolymers

et al. 2018

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“…DSC is a highly sensitive tool used for the study of the thermal and hydration properties of foods, polymers, and gels. − Figures and show the DSC results of hydrated solids containing MIM-6/PFOA and MIM-6/OA systems. In Figure , the DSC traces for PFOA in the bound and unbound states with MIM-6 are shown, where unbound PFOA reveals an endotherm at lower temperature (∼45 °C), and this is attributed to the melting transition (cf.…”

Section: Resultsmentioning

confidence: 99%

Investigation of the Adsorption Processes of Fluorocarbon and Hydrocarbon Anions at the Solid–Solution Interface of Macromolecular Imprinted Polymer Materials

Karoyo

Wilson

2016

J. Phys. Chem. C

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This study details the isotherm adsorption properties of cross-linked polymers containing β-cyclodextrin (β-CD), hereafter referred to as macromolecular imprinted materials (MIMs). The isotherm sorption parameters of the MIMs are reported with perfluorooctanoic acid (PFOA), octanoic acid (OA), and perfluorooctanesulfonate (PFOS) anions. The Sips and BET models describe variable solid-solution interfacial interactions for the MIMs with perfluorocarbon (PFC) and hydrocarbon (HC) anions, respectively. Typical monolayer adsorption occurs for the MIMs/OA system via the hydrocarbon alkyl tail of OA. Atypical adsorption is observed for PFOA and is driven via interactions between the MIMs surface with the carboxylate headgroup, as evidenced by the formation of multilayer adsorption and aggregation of the PFC alkyl chain at elevated levels. Molecular level support for the unique interfacial adsorption phenomenon is provided by several complementary methods: contact angle, infrared (IR) spectral shifts and intensity variations, differential scanning calorimetry (DSC), and isothermal titration calorimetry (ITC). Isotherm studies reveal the formation of monolayers of a hydrocarbon surfactant anion (OA) vs self-assembled multilayer aggregates for PFC anion species (PFOA and PFOS) at the MIMs solid−solution interface. The surface interactions are interpreted as a balance between headgroup electrostatic interactions and hydrophobic effects of the amphiphile chain at the adsorbent−solution interface.

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“…DSC and X-ray diffraction experiments would be useful for quantitative characterization of the hydration properties. 22…”

Section: Melting Temperature Depression Upon Adsorption Of Mbmentioning

confidence: 99%

Characterization of Myoglobin Adsorption into Mesoporous Silica Pores by Differential Scanning Calorimetry

et al. 2018

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Adsorption of protein molecules into the pores of a porous material is an important process for chromatographic separation of proteins and synthesis of nanoscale biocatalyst systems; however, there are barriers to developing a method for analyzing the process quantitatively. The purpose of this study is to examine the applicability of differential scanning calorimetry (DSC) for quantitative analysis of protein adsorption into silica mesopores. For this purpose myoglobin, a globular protein (diameter: 35.2 Å) was selected, and its adsorption onto mesoporous silica powders with uniform pore diameters (pore diameters: 39 and 64 Å) was measured by adsorption assay and DSC experiments. Our results confirmed that the adsorption of myoglobin into the silica mesopores induced significant changes in the positions and areas of freezing/melting peaks of the pore water. The decrease in heat of fusion of the pore water after myoglobin adsorption could be utilized to quantify the amount of myoglobin inside the silica mesopores. The advantages of DSC include its applicability to small wet mesoporous silica samples.

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Thermal Behavior and Structure of Low-temperature Water Confined in Sephadex G15 Gel by Differential Scanning Calorimetry and X-ray Diffraction Method

Cited by 17 publications

References 38 publications

Antifreeze Hydrogels from Amphiphilic Statistical Copolymers

Antifreeze Hydrogels from Amphiphilic Statistical Copolymers

Investigation of the Adsorption Processes of Fluorocarbon and Hydrocarbon Anions at the Solid–Solution Interface of Macromolecular Imprinted Polymer Materials

Characterization of Myoglobin Adsorption into Mesoporous Silica Pores by Differential Scanning Calorimetry

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