Probability distributions of enantiomeric excess in unstirred and stirred crystallization of 1,1′-binaphthyl melt

Kouichi Asakura, Tomomi Soga, Tadashi Uchida, Shuichi Osanai, Dilip K. Kondepudi

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

Crystallization of 1, 1′-binaphthyl from its melt can generate optical activity spontaneously. Since crystallization is a stochastic process, the enantiomeric excess (ee) generated in each crystallization varies randomly. We investigated the qualitative features of probability distribution of the ee for crystallization at two temperatures, 150°C and 152°C, at which conglomerate crystallization occurs. No clear transparent crystals were produced at either temperature, indicating that the solid states formed in the melt were polycrystalline. The ee randomly fluctuated from run to run, with an average of 26.9% and 2.7% when the crystallization was carried out at 152°C, and 150°C, respectively. The spread of the probability distribution is also substantially different. We also studied the probability distribution of ee in stirred crystallization at different stirring RPM. The results show probability contribution's broadening and evolution to a bimodality with increasing stirring RPM - a typical behavior in symmetry-breaking transitions. These results shed light on the nature of enantioselectivity in secondary nucleation and crystal growth.

Original languageEnglish
Pages (from-to)85-89
Number of pages5
JournalChirality
Volume14
Issue number1
DOIs
Publication statusPublished - 2002

Fingerprint

Crystallization
Probability distributions
Stochastic Processes
Optical Rotation
Enantioselectivity
Temperature
Random processes
Crystal growth
Nucleation
Crystals

Keywords

  • 1,1′-binaphthyl
  • Chiral asymmetry generation
  • Chiral autocatalysis
  • Conglomerate
  • Crystallization
  • Supercooling
  • Total spontaneous resolution

ASJC Scopus subject areas

  • Analytical Chemistry
  • Drug Discovery
  • Organic Chemistry
  • Pharmacology

Cite this

Probability distributions of enantiomeric excess in unstirred and stirred crystallization of 1,1′-binaphthyl melt. / Asakura, Kouichi; Soga, Tomomi; Uchida, Tadashi; Osanai, Shuichi; Kondepudi, Dilip K.

In: Chirality, Vol. 14, No. 1, 2002, p. 85-89.

Research output: Contribution to journalArticle

Asakura, Kouichi ; Soga, Tomomi ; Uchida, Tadashi ; Osanai, Shuichi ; Kondepudi, Dilip K. / Probability distributions of enantiomeric excess in unstirred and stirred crystallization of 1,1′-binaphthyl melt. In: Chirality. 2002 ; Vol. 14, No. 1. pp. 85-89.
@article{66e2fb0df20243da80f78c39278a7640,
title = "Probability distributions of enantiomeric excess in unstirred and stirred crystallization of 1,1′-binaphthyl melt",
abstract = "Crystallization of 1, 1′-binaphthyl from its melt can generate optical activity spontaneously. Since crystallization is a stochastic process, the enantiomeric excess (ee) generated in each crystallization varies randomly. We investigated the qualitative features of probability distribution of the ee for crystallization at two temperatures, 150°C and 152°C, at which conglomerate crystallization occurs. No clear transparent crystals were produced at either temperature, indicating that the solid states formed in the melt were polycrystalline. The ee randomly fluctuated from run to run, with an average of 26.9{\%} and 2.7{\%} when the crystallization was carried out at 152°C, and 150°C, respectively. The spread of the probability distribution is also substantially different. We also studied the probability distribution of ee in stirred crystallization at different stirring RPM. The results show probability contribution's broadening and evolution to a bimodality with increasing stirring RPM - a typical behavior in symmetry-breaking transitions. These results shed light on the nature of enantioselectivity in secondary nucleation and crystal growth.",
keywords = "1,1′-binaphthyl, Chiral asymmetry generation, Chiral autocatalysis, Conglomerate, Crystallization, Supercooling, Total spontaneous resolution",
author = "Kouichi Asakura and Tomomi Soga and Tadashi Uchida and Shuichi Osanai and Kondepudi, {Dilip K.}",
year = "2002",
doi = "10.1002/chir.10046",
language = "English",
volume = "14",
pages = "85--89",
journal = "Chirality",
issn = "0899-0042",
publisher = "Wiley-Liss Inc.",
number = "1",

}

TY - JOUR

T1 - Probability distributions of enantiomeric excess in unstirred and stirred crystallization of 1,1′-binaphthyl melt

AU - Asakura, Kouichi

AU - Soga, Tomomi

AU - Uchida, Tadashi

AU - Osanai, Shuichi

AU - Kondepudi, Dilip K.

PY - 2002

Y1 - 2002

N2 - Crystallization of 1, 1′-binaphthyl from its melt can generate optical activity spontaneously. Since crystallization is a stochastic process, the enantiomeric excess (ee) generated in each crystallization varies randomly. We investigated the qualitative features of probability distribution of the ee for crystallization at two temperatures, 150°C and 152°C, at which conglomerate crystallization occurs. No clear transparent crystals were produced at either temperature, indicating that the solid states formed in the melt were polycrystalline. The ee randomly fluctuated from run to run, with an average of 26.9% and 2.7% when the crystallization was carried out at 152°C, and 150°C, respectively. The spread of the probability distribution is also substantially different. We also studied the probability distribution of ee in stirred crystallization at different stirring RPM. The results show probability contribution's broadening and evolution to a bimodality with increasing stirring RPM - a typical behavior in symmetry-breaking transitions. These results shed light on the nature of enantioselectivity in secondary nucleation and crystal growth.

AB - Crystallization of 1, 1′-binaphthyl from its melt can generate optical activity spontaneously. Since crystallization is a stochastic process, the enantiomeric excess (ee) generated in each crystallization varies randomly. We investigated the qualitative features of probability distribution of the ee for crystallization at two temperatures, 150°C and 152°C, at which conglomerate crystallization occurs. No clear transparent crystals were produced at either temperature, indicating that the solid states formed in the melt were polycrystalline. The ee randomly fluctuated from run to run, with an average of 26.9% and 2.7% when the crystallization was carried out at 152°C, and 150°C, respectively. The spread of the probability distribution is also substantially different. We also studied the probability distribution of ee in stirred crystallization at different stirring RPM. The results show probability contribution's broadening and evolution to a bimodality with increasing stirring RPM - a typical behavior in symmetry-breaking transitions. These results shed light on the nature of enantioselectivity in secondary nucleation and crystal growth.

KW - 1,1′-binaphthyl

KW - Chiral asymmetry generation

KW - Chiral autocatalysis

KW - Conglomerate

KW - Crystallization

KW - Supercooling

KW - Total spontaneous resolution

UR - http://www.scopus.com/inward/record.url?scp=0036135286&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0036135286&partnerID=8YFLogxK

U2 - 10.1002/chir.10046

DO - 10.1002/chir.10046

M3 - Article

VL - 14

SP - 85

EP - 89

JO - Chirality

JF - Chirality

SN - 0899-0042

IS - 1

ER -