大環状分子、大環状高分子

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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2015/03/24 00:13:47」(JST)

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A macrocycle is, as defined by IUPAC, "a cyclic macromolecule or a macromolecular cyclic portion of a molecule."^[1] In the chemical literature, organic chemists may consider any molecule containing a ring of twelve or more atoms to be a macrocycle.^[2] In general, coordination chemists define a macrocycle more narrowly as a cyclic molecule with three or more potential donor atoms that can coordinate to a metal center. A well-known example is the group of drugs known as macrolides.

IUPAC definition

A cyclic macromolecule or a macromolecular cyclic portion of a macromolecule.

Notes

1. A cyclic macromolecule has no end-groups but may nevertheless be regarded as a chain.

2. In the literature, the term macrocycle is sometimes used for molecules of low relative molecular
mass that would not be considered macromolecules. ^[1]

Macrocycle effect

Crystal structure of a Zn(II) ion coordinated to cyclen and ethanol reported in Inorg. Chem., 1997, 4579-4584.

The macrocyclic effect was discovered in 1969.^[3] Coordination chemists study macrocycles with three or more potential donor atoms in rings of greater than nine atoms, as these compounds often have strong and specific binding with metals.^[4] This property of coordinating macrocyclic molecules is the macrocycle effect. It is a special example of the chelate effect.

Synthesis

In general, macrocycles are synthesized from smaller, usually linear, molecules.

Historical uses

Macrocycles have been in use for several decades as synthetic dyes. Phthalocyanine is a porphyrin analogue, which is arguably the most useful, in uses as dyes and pigments since their discovery in 1928, due to their dark-blue colour. However, there are many other uses for them. Their name comes from their synthetic precursor, phthalodinitrile.^[5]

Biological macrocycles

Heme, the active site in the hemoglobin (the protein in blood that transports oxygen), is a porphyrin containing iron.
Chlorophyll, the green photosynthetic pigment found in plants, contains a chlorin ring.
Vitamin B12 contains a corrin ring.

Related molecular categories

Ligand: an atom, ion, or functional group that is bonded to one or more central atoms or ions.
Chelate: a multidentate ligand, containing more than one donor atom.
Cryptand: a macrocycle with multiple loops (e.g., bicyclic).
Rotaxane: macrocycle(s) stuck on a stick, generally freely
Catenane: interlocked molecular rings (like a chain).
Molecular knot: a molecule in the shape of a knot such as a trefoil knot.

References

^ "Glossary of basic terms in polymer science (IUPAC Recommendations 1996)". Pure and Applied Chemistry 68 (12): 2287–2311. 1996. doi:10.1351/pac199668122287.

^ Parker, S.P. (2002). McGraw-Hill Science & Technology Dictionary. McGraw-Hill. ISBN 978-0070423138.
^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "macrocycle".
^ Milgrom, L.R (1997). The Colours of Life: An Introduction to the Chemistry of Porphyrins and Related Compounds. New York: Oxford University Press. ISBN 0-19-855380-3. (hardbound) ISBN 0-19-855962-3 (pbk.)
^ D. K. Cabbines and D. W. Margerum (1969). "Macrocyclic effect on stability of copper(II) tetramine complexes". J. Am. Chem. Soc. 91: 6540-6541. http://dx.doi.org/10.1021/ja01051a091
^ Melson, G.A., Ed. (1979). Coordination Chemistry of Macrocyclic Compounds. New York: Plenum Press. ISBN 0-306-40140-1.
^ Jung, J.E.; Seung, S.Y., Bulletin of the Korean Chemical Society 2002, 23(10) 1483-1486.

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Development of Conductometric Sensor Based on 25,27-Di-(5-thio-octyloxy)calix[4]arene-crown-6 for Determination of Ammonium.

Saiapina OY1, Kharchenko SG2, Vishnevskii SG2, Pyeshkova VM3, Kalchenko VI2, Dzyadevych SV3.
Nanoscale research letters.Nanoscale Res Lett.2016 Dec;11(1):105. doi: 10.1186/s11671-016-1317-9. Epub 2016 Feb 25.
The conductometric sensor based on 25,27-di-(5-thio-octyloxy)calix[4]arene-crown-6 was developed for the quantitative analysis of ammonium. The calixarene was immobilized on the surface of the planar interdigitated electrodes by attachment of its dialkyl sulfide groups to the surface of the gold ele
PMID 26911569

N2S2 and N4S4 precursors to PS2 macrocycles and cyclic amidinium salts.

Cox K1, Kariuki BM, Smyth A, Newman PD.
Dalton transactions (Cambridge, England : 2003).Dalton Trans.2016 May 28;45(20):8485-93. doi: 10.1039/c6dt00806b. Epub 2016 Apr 26.
The cyclo-condensation of 1R,2R-diaminocyclohexane with 2,2'-(ethane-1,2-diyldisulfanediyl)dibenzaldehyde gave the 1 : 1 addition compound chxn-(im)N2S2 in high yield. When the same condensation reaction was performed with 1R,3S-diamino-1,7,7-trimethylcyclopentane as the diamine, the 2 : 2 a
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Macrocyclic Tetraimines: Synthesis and Reversible Uptake of Diethyl Phthalate by a Porous Macrocycle.

Sanna E, Escudero-Adán EC, López C, Ballester P, Rotger C, Costa A.
The Journal of organic chemistry.J Org Chem.2016 May 20. [Epub ahead of print]
The imine bond has attracted much attention for the synthesis of macrocycles used to construct porous materials. In the present article, we report on the synthesis of two series of isomeric macrocyclic tetraimines based on bis-alkynylbenzene diamines. Under heterogeneous solid-liquid conditions the
PMID 27200454