Crystal Growth with Macromolecular Additives

Shtukenberg, Alexander G.; Ward, Michael D.; Kahr, Bart

doi:10.1021/acs.chemrev.7b00285

Cited by 121 publications

(110 citation statements)

References 510 publications

(1,123 reference statements)

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“…Based on a large body of previous work into additive-mediated crystallisation, [50][51][52] the crystallisation behaviour of the I-TPI gel was further investigated through incorporation of a chemically diverse range of additives. Previous studies have shown crystallisation additives to have a variety of different effects, notably including suppression of the kinetically stable forms favoured by Ostwald's rule to promote production of a desired thermodynamic polymorph.…”

Section: Incorporating Crystallisation Additivesmentioning

confidence: 99%

Supramolecular Gelation as the First Stage in Ostwald’s Rule

Andrews

Pearson

Yufit

et al. 2018

Crystal Growth & Design

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Ostwald's rule of stages describes the observation that a metastable polymorph of a particular compound will crystallise before the thermodynamically stable form under the same conditions. Whilst traditionally applied to crystalline systems, there have been recent examples in which non-crystalline supramolecular assemblies transform according to this rule. In this work we report the highly selective organogelation behaviour of a mono-iodinated 2,4,5triphenylimidazole (lophine) derivative (I-TPI). The gel emerges as a kinetically trapped intermediate, prior to the crystallisation of a series of increasingly stable methanol solvates. As such, we describe the supramolecular gel as a pre-crystalline phase, representing the first of Ostwald's stages for this system. Similar behaviour can be observed when the gel is used as a medium for pharmaceutical crystallisation of diatrizoic acid (DTA). In this case, two solid forms are produced, both containing molecules of DTA, I-TPI and methanol in different stoichiometries, and once again crystallising in sequence according to Ostwald's rule. These results demonstrate that supramolecular gelation may be considered the first stage in the stepwise crystallisation of a gelator, as governed by Ostwald's rule, and that this behaviour also applies to multi-component systems, facilitating the production of metastable pharmaceutical solid forms.

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Section: Incorporating Crystallisation Additivesmentioning

confidence: 99%

Supramolecular Gelation as the First Stage in Ostwald’s Rule

Andrews

Pearson

Yufit

et al. 2018

Crystal Growth & Design

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“…By using Ellman's reagent,t he average number of thiol groups on aP PL molecule was determined to be four. [17] Herein, the enzymei sa ssigned as PPL-(SH) 4 .P roteinn anogelsw eres ynthesized throught he thiol-disulfide exchange reactionb etween pyridyl disulfide groups on P(NIPAM 120 -co-PDSMA 4 )a nd thiol groups on PPL-(SH) 4 . [17,18] The thiol-disulfide exchange reaction was performed in an icewater bath and the molar ratio of pyridyl disulfides to thiols was controlled at 2.12:1.00.…”

Section: Resultsmentioning

confidence: 99%

“…[19] The UV/Vis spectroscopy resultsindicated that 93 %o ft hiol groups were involved in the exchanger eaction. Figure 1a shows aT EM image of PPL nanogelsf ormed from P(NIPAM 120 -co-PDSMA 4 )a nd PPL-(SH) 4 ,i nw hich spherical nanogels with sizes in the range from 12 to 50 nm are observed.…”

Section: Resultsmentioning

confidence: 99%

“…Biomineralization is defined as the production of hard tissues comprising minerals and organic frameworks, which are arranged in hierarchicala rchitectures. [1][2][3][4] In nature, living organisms produce av ariety of biominerals for different purposes. For example, the shells of marine mollusks are able to effectively protect the inner soft tissues.I nt he biomineralization process,t he organic frameworks facilitatet he nucleation and growth of minerals.…”

Section: Introductionmentioning

confidence: 99%

“…a) TEM image of PPL nanogels formed by P(NIPAM 120 -co-PDSMA 4 ) and PPL-(SH)4 .b )TEM image of PPL-BSA nanogels with BSA on the surface. Am agnified TEM image of as pecific PPL-BSAn anogeliss hownint he inset of b) and the scale bar in the image represents20nm.…”

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confidence: 99%

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Biomimetic Mineralization of Protein Nanogels for Enzyme Protection

Liu

et al. 2019

Chemistry A European J

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Protein nanogelsh ave found aw idev ariety of applications, ranging from biocatalysis to drug/protein delivery. However,i np ractical applications, proteinsi nn anogelsm ay suffer from enzymic hydrolysis and denaturation. Inspired by the structure and functionalities of the fowl eggshells, biomimetic mineralization of protein nanogels was studied in this research. Protein nanogelsw ith embedded porcine pancreas lipase (PPL) in the cross-linked nanostructures were synthesized throught he thiol-disulfide reactionb etween thiol-functionalized PPL and poly(N-isopropylacrylamide) with pendant pyridyl disulfide groups.T he nanogels were further reacted with reducedb ovine serum albumin( BSA) and BSAmolecules were coated on the nanogels. Mineraliza-tion of BSA leads to the synthesis of biomineralized shells on the nanogels. With the growth of CaCO 3 on the shells, the nanogels aggregate into suprastructures. Thermogravimetric analysis, XRD, dynamic light scattering, and TEM were employed to study the mechanismo ft he biomineralization process and analyze the structureso ft he mineralized nanogels. The biomineralized shells can effectively protect the PPL molecules from hydrolysis by trypsin;m eanwhile, the nanosized channels on the mineralized shells allow the transport of small-molecule substrates across the shells.B ioactivity measurements indicatet hat PPL in the nanogels maintains more than 80 %b ioactivity after biomineralization.[a] Q.

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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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Crystal Growth with Macromolecular Additives

Cited by 121 publications

References 510 publications

Supramolecular Gelation as the First Stage in Ostwald’s Rule

Supramolecular Gelation as the First Stage in Ostwald’s Rule

Biomimetic Mineralization of Protein Nanogels for Enzyme Protection

Crystallization in Confinement

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