Crystallisation in printed droplets: understanding crystallisation of <scp>d</scp>-mannitol polymorphs

Buanz, Asma; Gurung, Monica; Gaisford, Simon

doi:10.1039/c8ce01780h

Cited by 12 publications

(19 citation statements)

References 58 publications

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“…Inject printing provides an alternative method for depositing individual droplets of sizes 5-200 pL on substrates, and can be used to generate crystals with different structures. [180][181][182] Droplets generated in this way have been explored for studies of the effects of confinement on the crystallization of a number of polymers [180] and organic compounds [183,184] on different substrates. Glycine was precipitated on evaporation of droplets of sizes 100 pL to 0.1 µL on glass and aluminum substrates, where larger droplets were created by merging the small droplets.…”

Section: Droplets On Surfacesmentioning

confidence: 99%

“…The crystallization of D‐mannitol was also investigated and the stable β‐polymorph formed on evaporation of the smallest 100 pL droplets, while both metastable α‐ and δ‐polymorphs in larger droplets up to 200 nL size. [ 183 ] Larger droplets of 60 µL created using a micropipette also showed evidence of the β‐form in addition to the least stable δ‐polymorph.…”

Section: Crystallization In Dropletsmentioning

confidence: 99%

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Crystallization in Confinement

2020

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Many crystallization processes of great importance, including frost heave, biomineralization, the synthesis of nanomaterials, and scale formation, occur in small volumes rather than bulk solution. Here, the influence of confinement on crystallization processes is described, drawing together information from fields as diverse as bioinspired mineralization, templating, pharmaceuticals, colloidal crystallization, and geochemistry. Experiments are principally conducted within confining systems that offer well‐defined environments, varying from droplets in microfluidic devices, to cylindrical pores in filtration membranes, to nanoporous glasses and carbon nanotubes. Dramatic effects are observed, including a stabilization of metastable polymorphs, a depression of freezing points, and the formation of crystals with preferred orientations, modified morphologies, and even structures not seen in bulk. Confinement is also shown to influence crystallization processes over length scales ranging from the atomic to hundreds of micrometers, and to originate from a wide range of mechanisms. The development of an enhanced understanding of the influence of confinement on crystal nucleation and growth will not only provide superior insight into crystallization processes in many real‐world environments, but will also enable this phenomenon to be used to control crystallization in applications including nanomaterial synthesis, heavy metal remediation, and the prevention of weathering.

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Section: Droplets On Surfacesmentioning

confidence: 99%

Section: Crystallization In Dropletsmentioning

confidence: 99%

Crystallization in Confinement

2020

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“…d -Mannitol exhibits an enantiotropic relationship between δ and β- d -mannitol. 54 Thus, considering Ostwald’s rule of stages, 1 , 8 it is possible that the unstable δ form nucleates first and subsequently transforms to the stable β form. This would provide an explanation as to why abundant mixture (of β and δ) and pure β form were obtained in the absence of SDS.…”

Section: Resultsmentioning

confidence: 99%

“… 56 The α polymorph, in its turn, presents a monotropic relation with the other two, thus reversal stability until their melting point is not expected. 54 , 57 …”

Section: Resultsmentioning

confidence: 99%

“…56 The α polymorph, in its turn, presents a monotropic relation with the other two, thus reversal stability until their melting point is not expected. 54,57 Based on the observations summarized in Figure 3, we hypothesize that the presence of SDS as monomers (or a monolayer at the air−solution interface) would favor the formation of the β form. SDS as a micelle present at 25 and 15 °C at 1.22 wt % favored the crystallization of the α form and consequently reduced the β form at both temperatures.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Selective Crystallization of d-Mannitol Polymorphs Using Surfactant Self-Assembly

Penha

Gopalan

Meijlink

et al. 2021

Crystal Growth & Design

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Selective crystallization of polymorphs is highly sought after in industrial practice. Yet, state-of-the-art techniques either use laboriously engineered solid surfaces or strenuously prepared heteronucleants. We propose an approach where surfactants in solution self-assemble effortlessly into mesoscopic structures dictating the polymorphic outcome of the target solute. Sodium dodecyl sulfate (SDS) surfactant is used as a tailored additive to crystallize different polymorphic forms of a model active pharmaceutical ingredient, d -mannitol. Different mesoscopic phases of SDS template particular polymorphs: packed monolayers, micelles, and crystals favored the β, α, and δ forms of d -mannitol, respectively. A synergistic effect of topological templating and molecular interactions is proposed as the rationale behind the observed selective crystallization of polymorphs. This crystal engineering technique suggests that surfactant self-assemblies can be used as tailored templates for polymorphic control.

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Development of a Workflow to Engineer Tailored Microparticles Via Inkjet Printing

et al. 2022

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Crystallisation in printed droplets: understanding crystallisation of d-mannitol polymorphs

Abstract: Crystallising d-mannitol in printed droplets provides new insights into understanding the effect of foreign surfaces on the formation of its polymorphs.

Cited by 12 publications

References 58 publications

Crystallization in Confinement

Crystallization in Confinement

Selective Crystallization of d-Mannitol Polymorphs Using Surfactant Self-Assembly

Development of a Workflow to Engineer Tailored Microparticles Via Inkjet Printing

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