Twisted mannitol crystals establish homologous growth mechanisms for high-polymer and small-molecule ring-banded spherulites

Alexander G. Shtukenberg, Xiaoyan Cui, John Freudenthal, Erica Gunn, Eric Camp, Bart Kahr

Research output: Contribution to journalArticle

Abstract

d-Mannitol belongs to a large and growing family of crystals with helical morphologies (Yu, L. J. Am. Chem. Soc.2003, 125, 6380). Two polymorphs of d-mannitol, α and δ, when grown in the presence of additives such as poly(vinylpyrrolidone) (PVP) or d-sorbitol, form ring-banded spherulites composed of handed helical fibrils, where the helix axes correspond to the radial growth directions. The two polymorphs form helices with opposite senses in the presence of PVP but the same sense in the presence of d-sorbitol. The characteristic dimensions of the fibrils, including thickness, aspect ratio, and pitch, were determined by scanning probe and electron microscopies. These values must form the basis of any theory that presupposes what forces give rise to crystal twisting, a problem that has been broached but unsettled in the literature of polymer crystallization. The interdependence of the rhythmic variations of both linear and circular birefringence, as determined by Mueller matrix microscopy, informs the cooperative organization of mannitol fibers. The microstructure of mannitol ring-banded spherulites compares favorably to that of high polymers and is evaluated within the context of current theories of crystal twisting.

Original languageEnglish (US)
Pages (from-to)6354-6364
Number of pages11
JournalJournal of the American Chemical Society
Volume134
Issue number14
DOIs
StatePublished - Apr 11 2012

Fingerprint

Mannitol
Polymers
Polymorphism
Crystals
Molecules
Sorbitol
Growth
Scanning probe microscopy
Scanning Probe Microscopy
Birefringence
Aspect ratio
Microscopic examination
Crystallization
Microscopy
Electron Microscopy
Microstructure
Scanning electron microscopy
Fibers

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Twisted mannitol crystals establish homologous growth mechanisms for high-polymer and small-molecule ring-banded spherulites. / Shtukenberg, Alexander G.; Cui, Xiaoyan; Freudenthal, John; Gunn, Erica; Camp, Eric; Kahr, Bart.

In: Journal of the American Chemical Society, Vol. 134, No. 14, 11.04.2012, p. 6354-6364.

Research output: Contribution to journalArticle

Shtukenberg, Alexander G. ; Cui, Xiaoyan ; Freudenthal, John ; Gunn, Erica ; Camp, Eric ; Kahr, Bart. / Twisted mannitol crystals establish homologous growth mechanisms for high-polymer and small-molecule ring-banded spherulites. In: Journal of the American Chemical Society. 2012 ; Vol. 134, No. 14. pp. 6354-6364.
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