Archive for August, 2016

Crystal growth control via orientated aggregation.

A recent paper in CrystEngComm details a new synthetic method to create magnenite (iron oxide) nanoparticles (NPs), based on the orientated aggregation of particles using a calixarene macrocycle. The new method allows for control of the type of NPs produced and could potentially be applied to the growth of other nanomaterials.

Magnetite has promising biomedical applications due to its interesting magnetic and electrochemical properties and has been studied for drug delivery, biosensing and cancer treatment.  The NPs can reduce oxidative stress from electromagnetic radiation and raise temperature around the tumour cells in the presence of an applied magnetic field, killing cancer cells through localised heating. In contrast to traditional strategies of crystal growth, orientated aggregation is a mediated approach in which primary crystallites assemble into secondary crystals. The mediator can be other particles, specific molecules or an applied field. NPs grown this way often exhibit different morphologies and properties to the starting material.

Images of multicore (a,b) and octahedral (d,e) NPs

The authors postulated that the use of an organic molecule that complexes with iron could be used to induce aggregation and chose p-tert-butylcalix[8]arene,  calixarene molecules are used in host-guest chemistry to induce efficient and selective hosts.  A reaction mixture of the calixarene, iron(III) acetylacetonate and oleic acid was heated at 200°C for 2 hours, before being refluxed for one hour to promote crystal growth. The initial ratio of the reactants (0.5:1:2) produced multicore NPs with an average size of 40nm and primary crystallites of 7nm. Raising the iron:calixarene ratio to 1:1 resulted in a new morphology being produced, octahedral NPs were now produced exclusively with an average size of 50nm. An experiment without the calixarene produced different NPs again, this time much smaller (7nm) single core NPs. Further experiments varying the heating time and ratios resulted in defect octahedral NPs.

The colloidal and magnetic properties of the NPs were then measured with the multicore structures exhibiting excellent properties. The authors conclude that their synthesis method is easy to perform, reproducible and controllable.

For more information, read the full paper at:

Tuning morphology and magnetism of magnetite nanoparticles by calix[8]arene-induced oriented aggregation

Francesco Vita,  Helena Gavilán, Francesca Rossi, César de Julián Fernández, Andrea Secchi, Arturo Arduini, Franca Albertini and  M. Puerto Morales

CrystEngComm, 2016, Advance Article

DOI: 10.1039/C6CE01252C

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Use of nanolimes in conservation

Nanolimes, alcoholic dispersions of colloidal Ca(OH)2 nanoparticles, are commonly used for the conservation of porous materials such as stone and marble.  However, only the basics of the process they undergo – carbonation to produce CaCO3 – are understood and this limits their potential use.

A new paper by Rodriguez-Navarro looks at the carbonation process in detail, with the aims of increasing the effectiveness of and understanding any limitations in the use of nanolimes in conservation.

Conservation of materials using nanolimes is typically carried out in humid air at room temperature.  Under these conditions, amorphous calcium carbonate (ACC) initially forms.  This can then transform into the metastable vaterite (up to 35 wt%) and a small amount of aragonite (up to 5%), but only in the presence of alcohol.  These polymorphs partially dissolve and the stable polymorph, calcite, precipitates.  Alternatively, calcite can form directly after dissolution of ACC.

Nanolime carbonation

Results of the kinetic studies show that the rate-limiting step in the production of calcite is the amount of unreacted Ca(OH)2.  Although the formation of metastable states might be considered a limitation to the use of nanolimes in conservation, the fast kinetics of the vaterite to calcite conversion (72 % in 10 days) means that almost the full consolidation potential can be reached within weeks of application and it is only over very short time-scales that the performance might be sub-optimal.

These results may also have implications for the design of new CaCO3 materials for other applications, using syntheses analogous to the multi-step crystallisation shown in the carbonation of nanolimes in the presence of alcohol.

For more information, read the full paper at:

Amorphous and crystalline calcium carbonate phases during carbonation of nanolimes: implications in heritage conservation

Carlos Rodriguez-Navarro, Kerstin Elert and Radek Ševčík

CrystEngComm, 2016, Advance Article
DOI: 10.1039/C6CE01202G, Paper

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Gwenda Kyd

Gwenda Kyd has a PhD in metallocarborane chemistry from the University of Edinburgh. Other research work includes the spectroscopic study of the structure of glasses and organometallic electron-transfer reactions and the preparation of new inorganic phosphors. She published a book, ‘Molecules, Medicines and Mischief’, in 2014, on some of the chemicals found in plants and is currently working on a follow-up.

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