Distinct Dynamic Behaviors of Water Molecules in Hydrated Pores

Febles, Martín; Pérez-Hernández, Natalia; Pérez, Cirilo; Rodríguez, Matías L.; Foces‐Foces, Concepción; Roux, Marı́a Victoria; Morales, Ezequiel Q.; Buntkowsky, Gerd; Limbach, Hans−Heinrich; Martı́n, Julio D.

doi:10.1021/ja063223j

Cited by 39 publications

(78 citation statements)

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“…10 Variable temperature powder X-ray diffraction and thermogravimetry 12 confirmed that water can be partially removed from the solids without destroying the crystal structures. These results prompted us to wonder about the mechanism of the diffusion of water in organic crystals which is a prerequisite of the gasÀsolid state deuteration process.…”

Section: ' Introductionmentioning

confidence: 92%

“…10 We were intrigued by The Journal of Physical Chemistry C ARTICLE this finding and thought that knowledge of the individual rates could provide additional information about the mechanism of the gas/solid state deuteration and the diffusion of water through crystals. We thought that the method of choice to solve this problem would be attenuated total reflection infrared (ATR-IR) spectroscopy of the pure polycrystalline powders which would allow us to follow the different OH-stretching bands as a function of the time of exposure to heavy water vapor.…”

Section: ' Introductionmentioning

confidence: 99%

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IR Studies of H/D Exchange of Water, Hydroxyl, and Carboxylic Groups Reveal Slowly Diffusing Lattice Defects in Sub-Nanometer Pores

et al. 2011

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We have studied the properties of a series of solid hydrated organic porous networks with pore diameters ranging from approximately 0.4 to 0.9 nm using the attenuated total reflection infrared (ATR-IR) technique. These subnanometer organic pores are composed of water and of organic racemic bicyclic monomers containing carboxylic, alcoholic, ether functions and different appendices. In particular, the doubly hydrated hydroxyl acids 1 2H 2 O and 2 2H 2 O form cylindrical pores in which half of the water molecules are part of the walls and the other half are located inside the pores. In a first step, by a comparison of the spectra of a family of related compounds, the COOH, COH as well as the wall and pore water stretches were assigned. The COOH bands are broad and red-shifted as compared to carboxylic acid dimers, and exhibit a substructure assigned to Fermi resonances. The OH stretches fulfill well Novak's correlation with the corresponding crystallographic O...O distances. In a second step, we have followed the deuteration of the different functional groups of solid 2 2H 2 O by ATR-IR by heavy water vapor. Surprisingly, we observe that the rates of deuteration are the same for all functional groups although exhibiting biexponential time dependence, in contrast to the liquid state where COOH groups exchange protons with water much faster than with alcohols. This result is rationalized in terms of slowly diffusing lattice defects resembling a local liquid or glass in the subnano scale in which the different exchange reactions take place. The nonexponential deuteration is explained in terms of a faster deuteration of crystal surface layers.

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Section: ' Introductionmentioning

confidence: 92%

Section: ' Introductionmentioning

confidence: 99%

IR Studies of H/D Exchange of Water, Hydroxyl, and Carboxylic Groups Reveal Slowly Diffusing Lattice Defects in Sub-Nanometer Pores

et al. 2011

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“…Various mobility of the water clusters incorporated within the pores and H-bonding waters that structure these pores was demonstrated in Refs. [251,307]. Liu et al demonstrated that anhydrous uric acid and its' dihydrate exhibited various mechanical properties of their single crystals despite the similarity of layered motifs formed by the acid [276].…”

Section: Analysis Of Solvent Associatesmentioning

confidence: 99%

Intermolecular Interactions in Functional Crystalline Materials: From Data to Knowledge

Вологжанина

2019

Crystals

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Intermolecular interactions of organic, inorganic, and organometallic compounds are the key to many composition-structure and structure-property networks. In this review, some of these relations and the tools developed by the Cambridge Crystallographic Data Center (CCDC) to analyze them and design solid forms with desired properties are described. The potential of studies supported by the Cambridge Structural Database (CSD)-Materials tools for investigation of dynamic processes in crystals, for analysis of biologically active, high energy, optical, (electro)conductive, and other functional crystalline materials, and for the prediction of novel solid forms (polymorphs, co-crystals, solvates) are discussed. Besides, some unusual applications, the potential for further development and limitations of the CCDC software are reported. Crystals 2019, 9, 478 2 of 40 these fields, the manuscript cites only (i) recent works devoted to the analysis of correlations between intermolecular interactions and properties of a small molecule (for example its inclination to form polymorphs, solvates, and co-crystals), or a corresponding solid (from a well-known requirement for non-linear optical materials to crystallize in acentric space groups, to recent studies devoted to the effect of solvent presence on mechanical properties), and (ii) the corresponding software developed to investigate these correlations and to design novel solid forms with desired physicochemical properties. As the description of structure-property networks describes mainly the papers published in the last 10 years in the field of organic, organometallic, and coordination crystals, then the software under discussion will be limited with those developed by the Cambridge Crystallographic Data Centre (CCDC) for material chemistry and crystallography. Various examples of applications of the CCDC software to functional materials including their combination with other software, and restrictions found, will be given.First, the Cambridge Structural Database (CSD) and components of the CSD-Enterprise will be described in Section 2. Then, some properties related to the appearance of a given supramolecular associate, and the tools to search for an associate in the CSD will be reported in Section 3. The properties of solids dependent on the crystal morphology, the Bravais, Friedel, Donnay, and Harker (BFDH) tool for crystal morphology prediction and its' application to affect crystal morphology, polymorphism, and solvatomorphism will be reported in Section 4. Knowledge-based predictions of H-bonded polymorphism, co-crystal formation, mapping of likely intermolecular interactions, and conformer generation for the synthesis of novel functional materials will be discussed in Section 5, and the analysis of local connectivity and whole architectures of solvent molecules in Section 6. Finally, Section 7 contains information about Python API algorithms compatible with the CSD-Enterprise and about some examples of the successful combination of the CSD-Enterprise tools with exte...

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“…Additionally, a core-sheath 1D ice structure has been detected in a neutron scattering experiment (5) where the core is a single-file water chain and the sheath is an octagon ice nanotube (provisionally named as 1D ice IVa). Previous classical molecular dynamics simulations (13,14) have suggested that the pentagon and heptagon ice nanotubes are 1D ice with mixed ferroelectric/antiferroelectric domains.Besides the carbon nanotubes, a large number of organic and inorganic species have been successfully synthesized as hosts for confining water on the nanoscale (4,17,(25)(26)(27)(28). Nevertheless, species that can lead to single-phase ferroelectric ice have not been demonstrated experimentally.…”

mentioning

confidence: 99%

“…Besides the carbon nanotubes, a large number of organic and inorganic species have been successfully synthesized as hosts for confining water on the nanoscale (4,17,(25)(26)(27)(28). Nevertheless, species that can lead to single-phase ferroelectric ice have not been demonstrated experimentally.…”

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confidence: 99%

Transition from one-dimensional water to ferroelectric ice within a supramolecular architecture

Zhao

Kong

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

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Ferroelectric materials are characterized by spontaneous electric polarization that can be reversed by inverting an external electric field. Owing to their unique properties, ferroelectric materials have found broad applications in microelectronics, computers, and transducers. Water molecules are dipolar and thus ferroelectric alignment of water molecules is conceivable when water freezes into special forms of ice. Although the ferroelectric ice XI has been proposed to exist on Uranus, Neptune, or Pluto, evidence of a fully protonordered ferroelectric ice is still elusive. To date, existence of ferroelectric ice with partial ferroelectric alignment has been demonstrated only in thin films of ice grown on platinum surfaces or within microdomains of alkali-hydroxide doped ice I. Here we report a unique structure of quasi-one-dimensional ðH 2 OÞ 12n wire confined to a 3D supramolecular architecture of ½Cu I 2 Cu II ðCDTAÞð4,4 0 -bpyÞ 2 n H 4 CDTA, trans-1,2-diaminocyclohexane-N,N,N′,N′-tetraacetic acid; 4,4′-bpy, 4,4′-bipyridine). In stark contrast to the bulk, this 1D water wire not only exhibits enormous dielectric anomalies at approximately 175 and 277 K, respectively, but also undergoes a spontaneous transition between "1D liquid" and "1D ferroelectric ice" at approximately 277 K. Hitherto unrevealed properties of the 1D water wire will be valuable to the understanding of anomalous properties of water and synthesis of novel ferroelectric materials.ab initio molecular dynamics | phase transition | supramolecular nanochannel A n understanding of the properties of water wire and quasi-1D ice confined to a nanoscale channel has important implications for the biological sciences, geoscience, and nanoscience (1-5). The nanoscale channel can endow the water wire and 1D ice with unusual properties that differ from 3D water and ice. Hence, insights into these properties on the molecular level not only can offer explanation of intriguing phenomena such as proton and water transport in cell membranes (2) and the formation of a 1D ice tube with a water chain at the center (5), but can also assist synthesis of new nanochannels to influence the properties of water wire and 1D ice by changing the environment. In this article, our attention will be placed on the spontaneous formation of a 1D ferroelectric ice in a newly synthesized nanochannel.Does standalone single-phase ferroelectric ice exist in nature? This question has fascinated scientists for decades (6)(7)(8)(9)(10)(11)(12)(13)(14). If the single-phase ferroelectric ice does exist, it would have a net polarization toward one direction (15) because of the ordered alignment of the water molecules. However, achieving a standalone and pure 3D ferroelectric ice seems to be a formidable task in the laboratory because the full phase-transformation time required for a bulk 3D ferroelectric ice is estimated to be on the order of 10 5 y (8, 9) without any assistance of dopants as catalysts. To date, all ferroelectric ices produced in the laboratory are low dimensional and in mix...

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Distinct Dynamic Behaviors of Water Molecules in Hydrated Pores

Cited by 39 publications

References 26 publications

IR Studies of H/D Exchange of Water, Hydroxyl, and Carboxylic Groups Reveal Slowly Diffusing Lattice Defects in Sub-Nanometer Pores

IR Studies of H/D Exchange of Water, Hydroxyl, and Carboxylic Groups Reveal Slowly Diffusing Lattice Defects in Sub-Nanometer Pores

Intermolecular Interactions in Functional Crystalline Materials: From Data to Knowledge

Transition from one-dimensional water to ferroelectric ice within a supramolecular architecture

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