Small molecules induce mesocrystal formation: nanoparticle aggregation directed by self-assembling calixarenes

Baynton, Andrew; Radomirovic, Tomoko; Ogden, Mark I.; Raston, Colin L.; Richmond, William R.; Jones, Franca

doi:10.1039/c0ce00579g

Cited by 18 publications

(51 citation statements)

References 24 publications

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“…[33] Furthermore, it has been previously reported that even low con-centrationsofP Calix [4] preventt he precipitation of barium sulfate. [34] Hence, in the presents tudy at ac oncentration of 0.25 mm phosphonated calixarenes (PCalix[n]t oF e II /Fe III ratio of 1t o1 00)c omplex formation appearst op revail over particle production.…”

Section: Resultsmentioning

confidence: 99%

p‐Phosphonated Calix[n]arene Stabilizes Superparamagnetic Nanoparticles for Nitrate and Phosphate Uptake

et al. 2017

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Section: Resultsmentioning

confidence: 99%

p‐Phosphonated Calix[n]arene Stabilizes Superparamagnetic Nanoparticles for Nitrate and Phosphate Uptake

et al. 2017

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“…There has been a great deal of recent efforts in the formation and understanding of ordered nanoparticle superstructures with a vast range of architectures; in particular, crystallographically oriented nanoparticle superstructures, or mesocrystals, have been the central focus of such intrigue since described by Cölfen and Antonietti 13–16. Until recently, mesocrystals were only studied in biomineral materials, but current research efforts have shifted towards the development of mesocrystalline organic molecules,15, 17 metal oxides,18–21 and other functional materials 22, 23…”

Section: Introductionmentioning

confidence: 99%

Enhanced Intercalation Dynamics and Stability of Engineered Micro/Nano‐Structured Electrode Materials: Vanadium Oxide Mesocrystals

Uchaker

Zhou

et al. 2013

Small

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An additive and template free process is developed for the facile synthesis of VO2 (B) mesocrystals via the solvothermal reaction of oxalic acid and vanadium pentoxide. The six-armed star architectures are composed of stacked nanosheets homoepitaxially oriented along the [100] crystallographic register with respect to one another, as confirmed by means of selected area electron diffraction and electron microscopy. It is proposed that the mesocrystal formation mechanism proceeds through classical as well as non-classical crystallization processes, and is possibly facilitated or promoted by the presence of a reducing/chelating agent. The synthesized VO2 (B) mesocrystals are tested as a cathodic electrode material for lithium-ion batteries, and show good capacity at discharge rates ranging from 150-1500 mA g(-1) and a cyclic stability of 195 mA h g(-1) over fifty cycles. The superb electrochemical performance of the VO2 (B) mesocrystals is attributed to the porous and oriented superstructure that ensures large surface area for redox reaction and short diffusion distances. The mesocrystalline structure ensures that all the surfaces are in intimate contact with the electrolyte, and that lithium-ion intercalation occurs uniformly throughout the entire electrode. The exposed (100) facets also lead to fast lithium intercalation, and the homoepitaxial stacking of nanosheets offers a strong inner-sheet binding force that leads to better accommodation of the strain induced during cycling, thus circumventing the capacity fading issues typically associated with VO2 (B) electrodes.

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“…All calixarene molecules were synthesized in-house. They were: p-phosphonic acid calix [4]arene 16 (1), p-phosphonic acid calix [5]arene 29 (2), p-phosphonic acid calix [6]arene 29 (3) and p-phosphonic acid calix [8]arene 29 (4).…”

Section: Synthesismentioning

confidence: 99%

“…The resulting molecules exhibit a range of interesting behaviours in their own right, often tending to have selfassembling properties that lead to a wide range nanostructures 24,25 that can induce macroscale phenomena such as hydrogelation, 26 for example. We have previously shown that calixarenes functionalised at the lower phenolic rim, 27 and at the upper rim, 16,28 can be powerful inhibitors of barium sulphate crystallization. Some of these molecules have shown complex effects on crystallization whereby promotion is observed at low concentrations and inhibition at high concentrations.…”

Section: Introductionmentioning

confidence: 99%

Impact of Tunable Oligophosphonates on Barium Sulfate Crystallization

Ogden

Raston

Radomirovic

et al. 2014

Crystal Growth & Design

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Calixarenes can be used as well-defined scaffolds for investigating structure-activity relationships of additives and their impact on crystallization. In this work we present the crystal growth modification of barium sulfate by p-phosphonic acid calix[n]arene, which vary in size, n = 4, 5, 6 and 8, and thus vary in the size of the internal cavity for the same functionality in the upper rim. The tetrameric, hexameric and octameric macrocycles induce nanoparticle formation with clear superstructure. In the case of the hexameric calix[6]arene, the initial mesocrystalline superstructure fuses over time forming almost hollow spheres, while the mesocrystals formed in the presence of the tetramer and octamer are stable over an extended period. The pentameric calix[5]arene forms more disordered aggregates of single crystals. Thermogravimetric data show that a significant proportion of the weight of the barium sulfate containing solid is the macrocycle, regardless of the choice of macrocycle.

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Small molecules induce mesocrystal formation: nanoparticle aggregation directed by self-assembling calixarenes

Abstract: Calixarenes have been shown to induce mesocrystal formation of barium sulfate, despite being relatively low molecular weight additives. Scanning probe microscopy has shown that a possible 65 Research Council for financial support.

Cited by 18 publications

References 24 publications

p‐Phosphonated Calix[n]arene Stabilizes Superparamagnetic Nanoparticles for Nitrate and Phosphate Uptake

p‐Phosphonated Calix[n]arene Stabilizes Superparamagnetic Nanoparticles for Nitrate and Phosphate Uptake

Enhanced Intercalation Dynamics and Stability of Engineered Micro/Nano‐Structured Electrode Materials: Vanadium Oxide Mesocrystals

Impact of Tunable Oligophosphonates on Barium Sulfate Crystallization

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