Emergence of a Single Solid Chiral State from a Nearly Racemic Amino Acid Derivative

Noorduin, Wim L.; Izumi, Toshiko; Millemaggi, Alessia; Leeman, Michel; Meekes, Hugo; Enckevort, W.J.P. van; Kellogg, Richard M.; Kaptein, Bernard; Vlieg, E.; Blackmond, Donna G.

doi:10.1021/ja7106349

Cited by 422 publications

(495 citation statements)

References 24 publications

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“…The result is consistent with that of experiments with grinding where homochiral state is achieved within an observable time. [10][11][12] The enhancement of chirality conversion of monomers at the cluster surface shortens the saturation time, but the essential feature of chirality selection does not require enhancement, contrary to the conclusion in our previous paper. 18 In a recent paper by Tsogoeva and coworkers, 14 conglomerate crystallization of chiral organic molecule is studied.…”

Section: Resultscontrasting

confidence: 91%

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Selection of Crystal Chirality: Equilibrium or Nonequilibrium?

Saitō

Hyuga

2009

J. Phys. Soc. Jpn.

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To study the solution growth of crystals composed of chiral organic molecules, a spin-one Ising lattice gas model is proposed. The model turns out to be equivalent to the BlumeEmery-Griffiths model, which shows an equilibrium chiral symmetry breaking at low temperatures. The kinetic Monte Carlo simulation of crystal growth, however, demonstrates that Ostwald ripening is a very slow process with a characteristic time proportional to the system size: The dynamics is nonergodic. It is then argued that by incorporating grinding dynamics, homochirality is achieved in a short time, independent of the system size. Grinding limits cluster sizes to a certain range independent of system size and at the same time keeps the supersaturation so high that population numbers of average-sized clusters grow. If numbers of clusters for two types of enantiomers differ by chance, the difference is amplified exponentially and the system rapidly approaches the homochiral state. Relaxation time to the final homochiral state is determined by the average cluster size. We conclude that the system should be driven and kept in a nonequilibrium state to achieve homochirality.

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Section: Resultscontrasting

confidence: 91%

“…11 This spontaneous conversion of molecular chirality is an essential process for chirality selection, and we denote the conversion rate as ν 0 ;…”

Section: Chirality Conversionmentioning

confidence: 99%

Selection of Crystal Chirality: Equilibrium or Nonequilibrium?

Saitō

Hyuga

2009

J. Phys. Soc. Jpn.

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“…Viedma ripening was first demonstrated for sodium chlorate, an intrinsically achiral compound that crystallizes as conglomerate crystals, but has since then been modified to work also for intrinsically chiral compounds e.g. amino acids [4][5][6][7] and pharmaceuticals [8][9][10] that crystallize as conglomerate crystals by incorporating a fast racemization reaction. The outcome of the deracemization process depends on the initial conditions 11,12 : mass or crystal size distribution (CSD) imbalance between the enantiomers 1,[13][14][15] , presence of chiral impurities 16 or additives [17][18][19] or circularly polarized light 20 .…”

Section: Introductionmentioning

confidence: 99%

Coupling Viedma Ripening with Racemic Crystal Transformations: Mechanism of Deracemization

Xiouras

Horst

Gerven

et al. 2017

Crystal Growth & Design

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It has been recently observed that coupling Viedma ripening with a seeded in-situ metastable racemic crystal to conglomerate transformation leads to accelerated and complete deracemization: crystal transformation-enhanced deracemization. By means of a simple kinetic model, we show that the mechanistic pathway of this new process depends profoundly on the interplay between the crystal transformation and racemization processes, which in turn influence the nucleation process of the counter enantiomer. If the nucleation of the counter enantiomer is suppressed (e.g. by sufficiently fast racemization, low amount of racemic compound or gradual feed, low relative solubility between racemic compound and conglomerate), deracemization proceeds via a second order asymmetric transformation (SOAT) and is limited primarily by the dissolution rate of the racemic crystals and the growth rate of the preferred enantiomer crystals. Breakage and agglomeration accelerate the process, but contrary to conventional Viedma ripening, they are not essential ingredients to explain the observed enantiomeric enrichment. If the nucleation process of the counter enantiomer is not sufficiently suppressed, deracemization is initially controlled by the dissolution rate of the racemic crystals, but Viedma ripening is subsequently required to convert the conglomerate crystals of the counter enantiomer formed by nucleation, resulting in slower deracemization kinetics. In both cases, the combined process leads to faster deracemization kinetics compared to conventional Viedma ripening, while it autocorrects for the main disadvantage of SOAT, i.e. the accidental nucleation of the counter enantiomer. In addition, crystal transformation-enhanced deracemization extends the range of applicability of solid-state deracemization processes to compounds that form metastable racemic crystals. interplay between the crystal transformation and racemization processes, which in turn influence the nucleation process of the counter enantiomer. If the nucleation of the counter enantiomer is 3 suppressed (e.g. by sufficiently fast racemization, low amount of racemic compound or gradual feed, low relative solubility between racemic compound and conglomerate), deracemization proceeds via a second order asymmetric transformation (SOAT) and is limited primarily by the dissolution rate of the racemic crystals and the growth rate of the preferred enantiomer crystals.Breakage and agglomeration accelerate the process, but contrary to conventional Viedma ripening, they are not essential ingredients to explain the observed enantiomeric enrichment. If the nucleation process of the counter enantiomer is not sufficiently suppressed, deracemization is initially controlled by the dissolution rate of the racemic crystals, but Viedma ripening is subsequently required to convert the conglomerate crystals of the counter enantiomer formed by nucleation, resulting in slower deracemization kinetics. In both cases, the combined process leads to faster deracemization kinetics compared ...

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“…Focusing on hydrodynamic effects [18][19][20] , the relationship between stirring and material-based chirality traces back to the observation of the single mirror-image crystallization of sodium chlorate from a solution of no handedness solute 21 . More striking is the report that the combination of soft aggregation and stirring may lead not only to chiral induction 22,23 but, more importantly, also to sign selection, in both three 24,25 and two dimensions 26,27 .…”

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confidence: 99%