Ice Chromatography. Characterization of Water−Ice as a Chromatographic Stationary Phase

Tasaki, Yuiko; Okada, Tetsuo

doi:10.1021/ac0602470

Cited by 58 publications

(58 citation statements)

References 34 publications

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“…[7][8][9][10] This process can be classified as adsorption. When a salt, for example, is incorporated in the ice stationary phase, the liquid phase emerges as discussed above.…”

Section: Ice Chromatography With Doped Ice As a Stationary Phasementioning

confidence: 99%

“…We first developed ice chromatography, in which ice is used as a chromatographic stationary phase. [7][8][9][10] Various compounds can be separated by this method though there is a limitation in its separation capability. The optical properties of ice are also remarkable; it is transparent over a wide wavelength range, from UV to visible region, and is a rare solid material that has a lower refractive index than do usual liquids.…”

Section: Introductionmentioning

confidence: 99%

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Design of Analytical Systems Based on Functionality of Doped Ice

Okada

2014

ANAL. SCI.

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43 IntroductionWater has received special attention from researchers in fundamental and practical sciences because it has various unique physicochemical properties, and is indispensable for sustaining terrestrial life.1,2 Although ice is also a material of scientific interest, much less attention has been paid to this solid material than to its liquid counterpart. The same holds true for analytical chemistry. While water has been used as one of the most important solvents, in which a number of analytical reactions occur, 3,4 positive uses of ice for analytical purpose have been few.It has been known that ice is involved in a number of environmental reactions and plays important roles e.g. in the circulation of some molecules of atmospheric importance, such as NO, NO2, and HONO. 5 Ice also adsorbs compounds, such as HCl, and facilitates their reactions on its surface. 6 These roles of ice in the global environment have led to ideas that novel analytical systems can be designed utilizing the chemical properties and functionality of ice. We first developed ice chromatography, in which ice is used as a chromatographic stationary phase.7-10 Various compounds can be separated by this method though there is a limitation in its separation capability. The optical properties of ice are also remarkable; it is transparent over a wide wavelength range, from UV to visible region, and is a rare solid material that has a lower refractive index than do usual liquids. We utilized this useful optical property of ice to fabricate a liquid-core ice-cladding optical waveguide. 11Not only pure ice but also ice involving some impurity is of analytical use. Salt is a common impurity found in natural ice. Such salt-doped ice can be prepared in the laboratory in such a simple way that an aqueous salt solution is frozen. The liquid water phase coexists with ice (WPI) at the temperature higher than the eutectic point of the system. Figure 1 shows a fluorescence micrograph of KCl-doped ice containing fluorescein to visualize the WPI. Interestingly, fluorescent spots are discretely distributed in the ice matrix, suggesting that liquid inclusions are isolated rather than interconnected. We have found that the number density of the liquid inclusions is constant and independent of the type of salt incorporated in ice and its concentration. Ice plays an important role for the circulations of some compounds in the global environment. Both the ice surface and the liquid phase developed in a frozen solution are involved in such reactions of the molecules of environmental importance. This leads to the idea that ice can be used to design novel analytical reaction systems. We devised ice chromatography, in which ice particles are used as the liquid chromatographic stationary phase, and have subsequently developed various analytical systems utilizing the functionality of ice. This review focuses our attention on the analytical facets of ice containing impurities such as salts; hereinafter, we call this "doped ice". The design of novel separation systems...

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“…[7][8][9][10] This process can be classified as adsorption. When a salt, for example, is incorporated in the ice stationary phase, the liquid phase emerges as discussed above.…”

Section: Ice Chromatography With Doped Ice As a Stationary Phasementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Design of Analytical Systems Based on Functionality of Doped Ice

Okada

2014

ANAL. SCI.

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“…Ice chromatography, in which ice particles are used as a liquid chromatographic stationary phase, has been used for separation based on adsorption through hydrogen bonding between solutes and the ice surface, [1][2][3] retention control by adsorption/partition switching, 4,5 and chiral separation. 6,7 This method also provides information on phenomena occurring at the interface between the ice and a mobile phase.…”

Section: Introductionmentioning

confidence: 99%

Shear-Driven Flow Ice Chromatography as a Possible Tool Probing Ice/Water Interface

et al. 2016

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Although ice chromatography is a useful probe of ice interfaces, its low separation efficiency has often made difficult to access the ice/water interface. Coupling of this method with shear-driven flow chromatography, which has high separation potential, solves the problems involved in ice chromatography. This paper reports on shear-driven flow ice chromatographic instrumentation, and discusses the separation performance. Electrostatic separation of positively and negatively charged dyes is demonstrated with an OH --doped ice plate as a stationary phase.Keywords Shear flow, ice chromatography, electrostatic interaction at ice interface, interface between ice and aqueous solution

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“…We have found that reaction enhancement by freezing depends on the volume of the LP. [3] Ice chromatographic measurements [19] have also revealed that the anomalous enhancement of crown-ether complexation occursw hen the volume of the LP is small, for example, in frozen NaCl of c 0 NaCl < 1mm. [8] The size of the LP was estimatedt ob es omeh undreds of nm for such NaCl concentrations.…”

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Ion‐Transfer Voltammetry at the Interface between Organic and Salt‐Doped Ice Phases

Harada

Okada

2015

ChemElectroChem

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Ions play critical roles in reactions of biological, environmental, and industrial importance under frozen conditions. Transfer voltammetry of tetramethylammonium (TMA) and K + ions is measured at the interface between frozen aqueous NaCl and dichloroethane to give an insight into chemistry in frozen aqueous phases. The ion-transfer current of TMA initially increasesa st he temperature becomes lower from the freezing point, but the further decrease in temperature reduces the transfer current. The half-wave potentialo ft he TMA transfer shows anegative shiftwhen the liquid phase volumeiss maller than 10 %o ft he total volume of the frozen phase. Similarly, the half-wave potential of the facilitated transfer of K + by crown ether complexation also becomes negative with decreasingt emperature, due to the freeze concentration of K + in the liquid phase.Freezingi sa ni mportant process widely utilized in agriculture, fishery,t he food industry,m edicine, biological technologies, and so forth. [1,2] Although chemical reactions are usually retarded at lower temperatures,s ome examples have been reported for freeze enhancements of reactionk inetics.[3] Frozen aqueous solutions are therefore systems of scientific and practical interest. Salts are often involved in aqueous frozen mediaa nd play important roles in chemical processes occurring therein. In frozen aqueous solutions, salt crystals and ice are separately formed at the temperature lower than the eutectic point of the system (T eu ). When the temperature of this solid mixture increasesp ast T eu ,t he salt is dissolved in the liquid phase (LP) that coexists with ice below the melting point. [4] One possible reason for the accelerationso fr eactions in the frozen systems is the freeze concentrationo fs olutes. This aspect has been wells tudied from ak inetic viewpoint;t he reactions of order two or highera re accelerated by freeze concentration.[5] Another explanation of the kinetic acceleration is ap Hc hange in the LP upon freezing. As stated above, ions are mostly expelled from the ice phase as salts but are partly entrapped by ice. If an anion is better distributedt ot he ice phase than ac ation,t he negative charge shortage occursi n the LP,w hich is relaxed by the transfer of OH À to the LP.[6] The LP becomes more basic and the ice is acidified as ar esult. The pH shift by freezing explains the acceleration of some reactions quite well. [7] However,an umber of reactions occurring in the LP cannot be explained by theseorigins. [3,4,8] Unusual reactions in the LP possibly come from the properties of water therein,w hicha re different from those in unfrozen aqueous solution. Ar ecent molecular dynamics study has indicated that protont ransfer,a cids olvation, and ionization in aq uasi-liquid layer,w hich is formed on the surface of ice below the melting point, are different from that of bulk water.[9] The structure of liquid water in contact with ice is affected by ice, and as ar esult its properties are also influenced. However, no experimentali nformation is a...

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Ice Chromatography. Characterization of Water−Ice as a Chromatographic Stationary Phase

Cited by 58 publications

References 34 publications

Design of Analytical Systems Based on Functionality of Doped Ice

Design of Analytical Systems Based on Functionality of Doped Ice

Shear-Driven Flow Ice Chromatography as a Possible Tool Probing Ice/Water Interface

Ion‐Transfer Voltammetry at the Interface between Organic and Salt‐Doped Ice Phases

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