Clathrates of tetracyanonickelates containing 1,4-dioxane

We have studied the diffusive mobility of hydrogen molecules confined in different size cages in clathrate hydrates. In clathrate hydrate H2 molecules are effectively stored by confinement in two different size cages of the nanoporous host structure with accessible volumes of about 0.50 and 0.67 nm diameters, respectively. For the processes of sorption and desorption of the stored hydrogen the diffusive mobility of the molecules plays a fundamental role. In the present study we have focused on the dynamics of the H2 molecules inside the cages as one aspect of global guest molecule mobility across the crystalline host structure. We have found that for the two cage sizes different in diameter by only 34 % and in volume by about a factor of 2.4, the dimension can modify the diffusive mobility of confined hydrogen in both directions, i.e. reducing and surprisingly enhancing mobility compared to the bulk at the same temperature. In the smaller cages of clathrate hydrates hydrogen molecules are localized in the center of the cages even at temperatures >100 K. Confinement in the large cages leads to the onset already at T=10 K of jump diffusion between sorption sites separated from each other by about 2.9 Å at the 4 corners of a tetrahedron. At this temperature bulk hydrogen is frozen at ambient pressure and shows no molecular mobility on the same time scale. A particular feature of this diffusive mobility is the pronounced dynamic heterogeneity: only a temperature dependent fraction of the H2 molecules was found mobile on the time scale covered by the neutron spectrometer used. The differences in microscopic dynamics inside the cages of two different sizes can help to explain the differences in the parameters of macroscopic mobility: trapping of hydrogen molecules in smaller pores matching the molecule size can to play a role in the higher desorption temperature for the small cages.

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Transition metal tetracyano complexes, their thermal and sorption properties

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19860526 ◽

1986 ◽

Vol 51 (3) ◽

pp. 526-538 ◽

Cited By ~ 2

Author(s):

Anna Sopková ◽

Michal Šingliar

Keyword(s):

Organic Compound ◽

Transition Metal ◽

Guest Molecule ◽

Sorption Properties ◽

Organic Substances ◽

Hydrated Form ◽

Complex Lattice ◽

Lattice Space ◽

Tetracyano Complexes

The possibility of resorption of a guest molecule (G) or its substitution by other compounds is not known for M(NH3)2N(CN)4.2G (G = C6H6) or M(en)mM'(CN)4.nG clathrates, or even for the parent M(NH3)mM'(CN)4.nH2O, MM'(CN4).nH2O tetracyano complexes. These, however, are capable of sorption, and their lattice space can be reversibly or irreversibly filled with a suitable organic compound if the clathrates or tetracyano complexes in the hydrated form are allowed to be in contact with organic substances whose size and polarity fit the tetracyano complex lattice. The space within the lattice, however, develops as early as their formation from solution or suspension in the presence of the compound G (presence of water is actually sufficient).

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Bis(2-aminoethanol)cadmium(II) Tetracyanonickelate(II)-Pyrrole (1/1) and 2-Aminoethanolcadmium(II) Tetracyanonickelate(II)-Benzene (1/2). Variation of Metal Complex Host Structure with the Size of Aromatic Guest Molecule

Bulletin of the Chemical Society of Japan ◽

10.1246/bcsj.56.3246 ◽

1983 ◽

Vol 56 (11) ◽

pp. 3246-3252 ◽

Cited By ~ 10

Author(s):

Shin-ichi Nishikiori ◽

Toschitake Iwamoto

Keyword(s):

Metal Complex ◽

Guest Molecule ◽

Aromatic Guest ◽

Host Structure

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Interpretation of irradiation-induced changes in electron diffractograms and images of extinction contours at low temperatures

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100111458 ◽

1984 ◽

Vol 42 ◽

pp. 268-269

Author(s):

E. Knapek ◽

H. Formanek ◽

G. Lefranc ◽

I. Dietrich

Keyword(s):

Low Temperatures ◽

Carbon Films ◽

Organic Crystals ◽

Wide Spread ◽

Lens System ◽

Preparation Conditions ◽

Thin Carbon ◽

Electron Diffractograms ◽

Diffraction Patterns ◽

Induced Changes

A few years ago results on cryoprotection of L-valine were reported, where the values of the critical fluence De i.e, the electron exposure which decreases the intensity of the diffraction reflections by a factor e, amounted to the order of 2000 + 1000 e/nm2. In the meantime a discrepancy arose, since several groups published De values between 100 e/nm2 and 1200 e/nm2 /1 - 4/. This disagreement and particularly the wide spread of the results induced us to investigate more thoroughly the behaviour of organic crystals at very low temperatures during electron irradiation.For this purpose large L-valine crystals with homogenuous thickness were deposited on holey carbon films, thin carbon films or Au-coated holey carbon films. These specimens were cooled down to nearly liquid helium temperature in an electron microscope with a superconducting lens system and irradiated with 200 keU-electrons. The progress of radiation damage under different preparation conditions has been observed with series of electron diffraction patterns and direct images of extinction contours.

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The 3-Dimensional Molecular Structure of the Actin Filament Revisited

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100119223 ◽

1985 ◽

Vol 43 ◽

pp. 480-481

Author(s):

U. Aebi ◽

R. Millonig ◽

H. Salvo

Keyword(s):

Actin Filament ◽

Supramolecular Assembly ◽

Specimen Preparation ◽

X Ray Diffraction ◽

Single Filament ◽

X Ray ◽

3 Dimensional ◽

Filament Diameter ◽

Preparation Conditions ◽

Apparent Diameter

To date, most 3-D reconstructions of undecorated actin filaments have been obtained from actin filament paracrystal data (for refs, see 1,2). However, due to the fact that (a) the paracrystals may be several filament layers thick, and (b) adjacent filaments may sustantially interdigitate, these reconstructions may be subject to significant artifacts. None of these reconstructions has permitted unambiguous tracing or orientation of the actin subunits within the filament. Furthermore, measured values for the maximal filament diameter both determined by EM and by X-ray diffraction analysis, vary between 6 and 10 nm. Obviously, the apparent diameter of the actin filament revealed in the EM will critically depend on specimen preparation, since it is a rather flexible supramolecular assembly which can easily be bent or distorted. To resolve some of these ambiguities, we have explored specimen preparation conditions which may preserve single filaments sufficiently straight and helically ordered to be suitable for single filament 3-D reconstructions, possibly revealing molecular detail.

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Improving soil remediation through characterization

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100138300 ◽

1995 ◽

Vol 53 ◽

pp. 386-387

Author(s):

E. C. Buck ◽

N. L. Dietz ◽

J. K. Bates

Keyword(s):

Dust Particles ◽

Radiochemical Analysis ◽

Solid Product ◽

Uranium Contamination ◽

Physical Separation ◽

X Ray ◽

Rocky Flats ◽

Remediation Strategies ◽

Bearing Materials ◽

X Ray Absorption

Operations at former weapons processing facilities in the U. S. have resulted in a large volume of radionuclidecontaminated soils and residues. In an effort to improve remediation strategies and meet environmental regulations, radionuclide-bearing particles in contaminant soils from Fernald in Ohio and the Rocky Flats Plant (RFP) in Colorado have been characterized by electron microscopy. The object of these studies was to determine the form of the contaminant radionuclide, so that it properties could be established [1]. Physical separation and radiochemical analysis determined that uranium contamination at Fernald was not present exclusively in any one size/density fraction [2]. The uranium-contamination resulted from aqueous and solid product spills, air-borne dust particles, and from the operation of an incinerator on site. At RFP the contamination was from the incineration of Pu-bearing materials. Further analysis by x-ray absorption spectroscopy indicated that the majority of the uranium was in the 6+ oxidation state [3].

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