Kinetics of chiral symmetry breaking in crystallization

Kondepudi, Dilip K.; Bullock, Kim L.; Digits, Jennifer A.; Hall, John K.; Miller, Jason

doi:10.1021/ja00075a041

Cited by 152 publications

(109 citation statements)

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“…Under these conditions, and from expression (1), we can expect an initial low nucleation rate at the low super saturation level. In fact this occurs and the rate of nucleation obtained by video observations in one of this usual symmetry breaking experiments was found to be in the range of 1 2 nuclei per minute for an entire solution of 100 ml [7]. In the same paper the authors calculated a nucleation rate of 0.2 nuclei/min when (Cl C,) � 1.001 and 2 nuclei/ min when (CIC,) � 1.04.…”

Section: Resultsmentioning

confidence: 86%

“…From this expression, and others similarly used to express the nucleation-supersaturation relation, it is clear that the nucleation rate is a direct function of supersaturation ratio C / Cs which is the most important feature in symmetry breaking processes [7]. The equation also indicates the catastrophic nature of the primary nucleation process: there IS a critical supersaturation below which the nucleation rate is very low and above which it becomes extremely high [8].…”

Section: Resultsmentioning

confidence: 99%

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Experimental evidence of chiral symmetry breaking in crystallization from primary nucleation

Viedma

2004

Journal of Crystal Growth

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Chiral symmetry breaking in stirred crystallization of sodium chlorate (NaCI03) is believed to occur via nucleation of a single chiral "mother crystal" that produces a new generation of crystals which inherit its chirality. We here report results of stirred crystallizations resulting in massive "instantaneous" primary nucleation and total symmetry breaking.The results of these experiments suggest that the current explanation for chiral symmetry breaking via nucleation of a single "mother crystal" is not adequate and that the mechanism to explain the chiral symmetry breaking in crystallization remains as an open question.

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Section: Resultsmentioning

confidence: 86%

Section: Resultsmentioning

confidence: 99%

Experimental evidence of chiral symmetry breaking in crystallization from primary nucleation

Viedma

2004

Journal of Crystal Growth

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“…Amyloid formation by the 13 (21), the lag time is extremely difficult to measure more accurately (4). Consequently, the error in our measurement of nucleation time, whether by the turbidity assay or by a radioassay, was approximately equal to the difference between apoE3 and apoE4.…”

mentioning

confidence: 97%

Apolipoprotein E is a kinetic but not a thermodynamic inhibitor of amyloid formation: implications for the pathogenesis and treatment of Alzheimer disease.

Evans

Berger

Cho

et al. 1995

Proc. Natl. Acad. Sci. U.S.A.

333

242

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The apolipoprotein E4 (APOE4) allele is associated with an early age of onset of the nonfamilial form of Alzheimer disease (AD) and with increased 8 protein amyloid deposition in the brain. These two observations may both arise from an effect of the apoE family of proteins on the rate of in vivo amyloidogenesis. We report here that apoE3, the common apoE isoform, is an in vitro amyloid nucleation inhibitor at physiological concentrations. A significant delay in the onset of amyloid fibril formation by the ,3-amyloid protein of AD (181-40) was observed at a low apoE3 concentration (40 nM), corresponding to an apoE3/13 protein molar ratio of 1:1000. The inhibitory activity of a proteolytic fragment of apoE3, containing the N-terminal 191 amino acids, is comparable to the native protein, whereas the C-terminal fragment has no activity. ApoE4 is equipotent or slightly less potent than apoE3, which may be due to its inability to form a disulfide dimer, since the apoE3 dimer is a significantly more potent nucleation inhibitor than apoE4. Neither apoE3 nor apoE4 inhibits the seeded growth of amyloid or affects the solubility or structure of the amyloid fibrils, indicating that apoE is not a thermodynamic amyloid inhibitor. We propose that the linkage between the APOE4 allele and AD reflects the reduced ability of APOE4 homozygotes to suppress in vivo amyloid formation.Amyloid plaque is an ordered, fibrous protein aggregate that is characteristic of the Alzheimer disease (AD) brain. The acceleration of amyloid deposition may be a primary event in AD (1, 2). Thus, endogenous factors that affect the rate of amyloid formation could play a significant role in the pathogenesis of AD (3, 4). The apolipoprotein E genotype (APOE) has recently been recognized as a susceptibility factor for AD (5-8). Three isoforms of apoE occur in the human population. They differ by single amino acid changes. APOE3 is the most common allele (0.78), followed by APOE4 (0.14) and APOE2 (0.07) (9). ApoE4 and apoE3 differ with respect to lipoprotein binding (10), but the two proteins are indistinguishable with respect to low density lipoprotein receptor binding (11). ApoE3 and apoE4 are distinguished by a single point mutation in a sequence of 299 amino acids (apoE3, C112; apoE4, R112) (12).TheAPOE4 allele correlates with an earlier age of AD onset (5) and an increased amount of cerebral amyloid plaque (13) at the time of death relative to the common APOE3 allele. (/3,,). Once the nucleus has formed, association becomes favorable (Kg >> 1) and is not inhibited by apoE. Exogenous seed fibrils will bypass the lag time and result in rapid growth that is not inhibited by apoE (see Fig. 2).

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“…Thus bimodal distributions of enantiomers in stirred crystallization are commonly formed. The preferred formation of bimodal distributions of enantiomers in stirred solutions instead of the monomodal racemate distribution can be also caused by much deeper drop in supersaturation in stirred solution after first acts of nucleation in comparison to unstirred crystallization as it was established by Kondepudi and co-workers (Kondepudi et al, 1993) The supersaturation drop occurring in stirred and unstirred solutions leads to the transition from regions IV or from III to region II in which only one type of enantiomer is formed and to region I where no nucleation takes place. In unstirred solution supersaturation drop also contributes to interruption of primary nucleation.…”

Section: Effect Of Supersaturation On Probability Of Nucleation Of Enmentioning

confidence: 85%

“…Breakage of chiral symmetry has been discovered by Kondepudi and co-workers in their studies of sodium chlorate crystallization from stirred solution (Kondepudi et al, 1990). The phenomenon has been investigated both experimentally and theoretically (McBride & Carter 1991;Kondepudi et al, 1995 a,b;Kondepudi et al, 1993;Kondepudi et al, a,1995Kondepudi & Sabanayagam, 1994;Qian & Botsaris, 1998, 2004. At present, efforts are made to establish the experimental conditions under which the phenomenon occurs, to determine all important parameters controlling its kinetics and mechanisms, and to develop a reliable theory (Veintemillas-Verdaguer et al, 2007;Viedma 2004;Cartwright et al, 2004;Martin et al , 1996;Metcalfe & Ottino, 1994;Bushe et al, 2000).…”

Section: Introductionmentioning

confidence: 99%

Parity Violation in Unstirred Crystallization from Achiral Solutions

Szurgot

2012

Crystallization and Materials Science of Modern Artificial and Natural Crystals

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Kinetics of chiral symmetry breaking in crystallization

Cited by 152 publications

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Experimental evidence of chiral symmetry breaking in crystallization from primary nucleation

Experimental evidence of chiral symmetry breaking in crystallization from primary nucleation

Apolipoprotein E is a kinetic but not a thermodynamic inhibitor of amyloid formation: implications for the pathogenesis and treatment of Alzheimer disease.

Parity Violation in Unstirred Crystallization from Achiral Solutions

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