Polymorphic effects at the eutectic melting in the H2O–glycine system

Drebushchak, V. A.; Ogienko, A. G.; Boldyreva, Elena V.

doi:10.1007/s10973-012-2761-0

Cited by 14 publications

(4 citation statements)

References 31 publications

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“…The eutectic temperatures for α-, β-, and γ-glycine in water have been reported by various authors and recently reviewed . From the available data (see Supporting Information (Eutectic Temperature and Composition)), we note that β-glycine has the most reported measurements, followed by γ and finally α with a single measurement.…”

Section: Resultsmentioning

confidence: 99%

Temperature Dependence of Solubility Predicted from Thermodynamic Data Measured at a Single Temperature: Application to α, β, and γ-Glycine

Manson

Šefčı́k

Lue

2022

Crystal Growth & Design

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Understanding of solid–liquid equilibria for polymorphic systems is crucial for rational design and efficient operation of crystallization processes. In this work, we present a framework to determine the temperature dependent solubility based on experimentally accessible thermodynamic data measured at a single temperature. Using this approach, we investigate aqueous solubility of α, β, and γ-glycine, which, despite numerous studies, have considerable quantitative uncertainty, in particular for the most stable (γ) and the least stable (β) solid forms. We benchmark our framework on α-glycine giving predictions in excellent agreement with direct solubility measurements between 273–340 K, using only thermodynamic data measured at the reference temperature (298.15 K). We analyze the sensitivity of solubility predictions with respect to underlying measurement uncertainty, as well as the excess Gibbs free energy models used to derive required thermodynamic quantities before providing solubility predictions for β and γ-glycine between 273–310 and 273–330 K, respectively. Crucially, this approach to predict solubility as a function of temperature does not rely on measurement of solute melting properties which will be particularly useful for compounds that undergo thermal decomposition or polymorph transition prior to melting.

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Section: Resultsmentioning

confidence: 99%

Temperature Dependence of Solubility Predicted from Thermodynamic Data Measured at a Single Temperature: Application to α, β, and γ-Glycine

Manson

Šefčı́k

Lue

2022

Crystal Growth & Design

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“…As demonstrated in Section 3.2, GSM appears to be the result of shear-induced melting and re-crystallisation in the absence of a tablet. Initial stages of re-crystallisation may be characterised by a metastable product, as suggested for the nucleation of reactant glycine crystals, [80][81][82] which can be inhibited from full relaxationfor example by hindering self-assembly processesto the GSM product nuclei whilst treatment is continued. If sufficient treatment is provided, an energy barrier can be overcome, causing conversion of this hypothetical metastable phase (which may simply be characterised by nanometer metastable nuclei 82 ) to an alternative phase, either the novel or an amorphous GSM state.…”

Section: Faraday Discussionmentioning

confidence: 99%

Advances in elucidating mechanochemical complexities via implementation of a simple organic system

et al. 2014

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Mechanochemistry is becoming increasingly popular amongst both the academic and industrial communities as an alternative method for inducing physical and chemical reactions. Despite its rapidly expanding application, little is understood of its mechanisms, greatly limiting its capacity. In the present work the application of specialty devices allowed submission of the simple organic system, α-glycine + β-malonic acid, to isolated shearing and impact treatment. In doing so, unique products were observed to result from each of these major mechanical actions; shear inducing formation of the known salt, glycinium semi-malonate (GSM), and impact yielding formation of a novel phase. Correlation of these isolated treatments with a more common ball mill indicated two unique regions within the milling jar, each characterised by varying ratios of shear and impact, leading to different products being observed. It is widely accepted that, particularly when considering organic systems, mechanical treatment often acts by inducing increases in local temperature, leading to volatilisation or melting. A combination of DSC and TGA were used to investigate the role of temperature on the system in question. Invariably, heating induced formation of GSM, with evidence supporting a eutectic melt, rather than a gas-phase reaction. Shear heating alone is unable to describe formation of the novel phase obtained through impact treatment. By considering the formation and character of mechanically produced tablets, a model is described that may account for formation of this novel phase. This system and methodology for mechanochemical study offers intriguing opportunities for continued study of this widely used and exciting field.

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“…[316] At the same time, the thermal effects of the eutectic melting in the H 2 O-glycine system were shown to depend on the glycine polymorph. [317] It is likely that the differences are so subtle that their detection by physical methods requires highly sensitive tools. As an option one could try to compare the clusters detected in solutions prepared from different polymorphs by SAXS.…”

Section: Glycine As An Active Pharmaceutical Ingredientmentioning

confidence: 99%

Glycine: The Gift that Keeps on Giving

Boldyreva

2021

Israel Journal of Chemistry

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Glycine is a small molecule. It cannot change its conformation and is achiral. Despite the apparent simplicity, glycine shows endless diversity in its behavior over many phenomena. It was the first amino acid for which polymorphism was reported, first on crystallization and then on hydrostatic compression. The polymorphs differ in their physical properties and their biological activity. Glycine clusters persist in solution, leading to "solution memory". Phenomena at interfaces are critically important for crystal growth, dissolution, and for physical properties, which can be at times unexpected, like polarity in centrosymmetric αpolymorph. It is a great pleasure to remind of these remarkable phenomena in a special issue honoring professors Meir Lahav and Leslie Leiserowitz, who pioneered the study of the behavior of this unique molecule in many respects, and showed how complex and non-trivial phenomena can be at interfaces: between phases and between research fields.

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Polymorphic effects at the eutectic melting in the H2O–glycine system

Cited by 14 publications

References 31 publications

Temperature Dependence of Solubility Predicted from Thermodynamic Data Measured at a Single Temperature: Application to α, β, and γ-Glycine

Temperature Dependence of Solubility Predicted from Thermodynamic Data Measured at a Single Temperature: Application to α, β, and γ-Glycine

Advances in elucidating mechanochemical complexities via implementation of a simple organic system

Glycine: The Gift that Keeps on Giving

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