Dichroism in Helicoidal Crystals

Xiaoyan Cui, Shane M. Nichols, Oriol Arteaga, John Freudenthal, Froilanny Paula, Alexander G. Shtukenberg, Bart Kahr

Research output: Contribution to journalArticle

Abstract

Accounting for the interactions of light with heterogeneous, anisotropic, absorbing, optically active media is part of the characterization of complex, transparent materials. Stained biological structures in thin tissue sections share many of these features, but systematic optical analyses beyond the employ of the simple petrographic microscopes have not be established. Here, this accounting is made for polycrystalline, spherulitic bundles of twisted d-mannitol lamellae grown from melts containing light-absorbing molecules. It has long been known that a significant percentage of molecular crystals readily grow as helicoidal ribbons with mesoscale pitches, but a general appreciation of the commonality of these non-classical crystal forms has been lost. Helicoidal crystal twisting was typically assayed by analyzing refractivity modulation in the petrographic microscope. However, by growing twisted crystals from melts in the presence of dissolved, light-absorbing molecules, crystal twisting can be assayed by analyzing the dichroism, both linear and circular. The term "helicoidal dichroism" is used here to describe the optical consequences of anisotropic absorbers precessing around radii of twisted crystalline fibrils or lamellae. d-Mannitol twists in two polymorphic forms, α and δ. The two polymorphs, when grown from supercooled melts in the presence of a variety of histochemical stains and textile dyes, are strongly dichroic in linearly polarized white light. The bis-azo dye Chicago sky blue is modeled because it is most absorbing when parallel and perpendicular to the radial axes in the respective spherulitic polymorphs. Optical properties were measured using Mueller matrix imaging polarimetry and simulated by taking into account the microstructure of the lamellae. The optical analysis of the dyed, patterned polycrystals clarifies aspects of the mesostructure that can be difficult to extract from bundles of tightly packed fibrils.

Original languageEnglish (US)
Pages (from-to)12211-12218
Number of pages8
JournalJournal of the American Chemical Society
Volume138
Issue number37
DOIs
StatePublished - Sep 21 2016

ASJC Scopus subject areas

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

Fingerprint Dive into the research topics of 'Dichroism in Helicoidal Crystals'. Together they form a unique fingerprint.

  • Cite this

    Cui, X., Nichols, S. M., Arteaga, O., Freudenthal, J., Paula, F., Shtukenberg, A. G., & Kahr, B. (2016). Dichroism in Helicoidal Crystals. Journal of the American Chemical Society, 138(37), 12211-12218. https://doi.org/10.1021/jacs.6b06278