関: intercalating ligand、intercalator

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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2015/08/12 17:22:30」(JST)

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In chemistry, intercalation is the reversible inclusion or insertion of a molecule (or ion) into compounds with layered structures. Examples are found in graphite intercalation compounds.

Model of intercalation of potassium into graphite

Many layered solids intercalate guest molecules. A famous example is the intercalation of potassium into graphite.^[1] Intercalation expands the van der Waals gap between sheets, which requires energy. Usually this energy is supplied by charge transfer between the guest and the host solid, i.e., redox. Two potassium graphite compounds are KC₈ and KC₂₄. Carbon fluorides (e.g., (CF)_x and (C₄F)) are prepared by reaction of fluorine with graphitic carbon. The color is greyish, white, or yellow. The bond between the carbon and fluorine atoms is covalent, thus fluorine is not intercalated. Such materials have been considered as a cathodes in various lithium batteries.

Cartoon for intercalation of Li into a titanium disulfide cathode. The process involves swelling of one crystal axis and charge transfer from Li to Ti.

Treating graphite with strong acids in the presence of oxidizing agents, causes the graphite to oxidise. Graphite bisulfate, [C₂₄]⁺[HSO₄]⁻, is prepared by this approach using sulfuric acid and a little nitric acid or chromic acid. The analogous graphite perchlorate can be made similarly by reaction with perchloric acid.

Aside from graphite, well-known intercalation hosts are the layered metal dichalcogenides such as tantalum disulfide and iron oxychloride.^[2] In characteristic manner, intercalation is analyzed by X-ray diffraction, since the spacing between sheets increases, and by electrical conductivity, since charge transfer alters the number of charge carriers.

Exfoliation

An extreme case of intercalation is the complete separation of the layers of the material. This process is called exfoliation. Typically aggressive conditions are required involving highly polar solvents and aggressive reagents.^[3]

Related materials

In biochemistry, intercalation is the insertion of molecules between the bases of DNA. This process is used as an method for analyzing DNA and it is also the basis of certain kinds of poisoning.

Clathrates are chemical substances consisting of a lattice that traps or contains molecules. Usually, clathrate compounds are polymeric and completely envelop the guest molecule. Inclusion compounds are often molecules, whereas clathrates are typically polymeric. Intercalation compounds, which are not 3-dimensional, unlike clathrate compounds.^[4] According to IUPAC, clathrates are "Inclusion compounds in which the guest molecule is in a cage formed by the host molecule or by a lattice of host molecules."^[5]

Notes

^ Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. p. 794 ISBN 0-12-352651-5.
^ S. Kikkawa, F. Kanamaru, M. Koizumi "Layered Intercalation Compounds" Inorganic Syntheses, 1983, Volume 22, 86. doi:10.1002/9780470132531.ch17
^ V. Nicolosi, M. Chhowalla, M. G. Kanatzidis, M. S. Strano , J. N. Coleman, "Liquid Exfoliation of Layered Materials" Science 2013, Vol. 340 no. 6139. http://www.sciencemag.org/content/340/6139/1226419.abstract
^ J. L. Atwood "Inclusion Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, 2012, Wiley-VCH, Weinheim. doi: 10.1002/14356007.a14_119
^ http://goldbook.iupac.org/C01097.html

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Hyposmotic stress causes ATP release and stimulates Na,K-ATPase activity in porcine lens.

Shahidullah M, Mandal A, Beimgraben C, Delamere NA.SourceDepartment of Physiology, University of Arizona, Tucson, Arizona 85724, USA. shahidua@email.arizona.edu
Journal of cellular physiology.J Cell Physiol.2012 Apr;227(4):1428-37. doi: 10.1002/jcp.22858.
Purinergic receptors in lens epithelium suggest lens function can be altered by chemical signals from aqueous humor or the lens itself. Here we show release of ATP by intact porcine lenses exposed to hyposmotic solution (200 mOsm). 18α-glycyrrhetinic acid (AGA) added together with probenecid elimin
PMID 21618533

Interference of intrinsic curvature of DNA by DNA-intercalating agents.

Tan HK, Li D, Gray RK, Yang Z, Ng MT, Zhang H, Tan JM, Hiew SH, Lee JY, Li T.SourceDivision of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371. thli@ntu.edu.sg.
Organic & biomolecular chemistry.Org Biomol Chem.2012 Mar 21;10(11):2227-30. Epub 2012 Feb 14.
It has been demonstrated in our studies that the intrinsic curvature of DNA can be easily interrupted by low concentrations of chloroquine and ethidium bromide. In addition, the changes of DNA curvature caused by varying the concentration of these two DNA intercalators can be readily verified throug
PMID 22331171

Japanese Journal

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