Properso Veesler
CRYSTALLIZATION FROM SOLUTION
Stéphane VEESLER (E-mail)
Directeur de recherche au CNRS (section 05)Recherche au sein du département Sources et Sondes Ponctuelles
A parameter to probe microdroplet dynamics and crystal nucleation
| We present a simple and efficient digital-image processing method to simultaneously monitor the contraction of a statistically relevant number of microdroplets of the same size and the nucleation of single salt crystals inside. Each individual microdroplet image is reduced to a scalar, standard deviation of the grey-level of pixels inside a region of interest containing the microdroplet image, and overall microdroplet dynamics is monitored using standard-deviation time-evolution plots. It is shown that this approach makes it possible to measure the nucleation time and also that microdroplets interact viawater diffusion dynamics. This effect actually decreases the nucleation rate, contrary to previous findings. This “ approach” can be compared to recording the order parameter in phase transition, which makes it ideal for studying |
Référence: Grossier, R.; Tishkova, V.; Morin, R.; Veesler, S., A parameter to probe microdroplet dynamics and crystal nucleation. AIP Advances 2018, 8, 075324.. Open access
Acknowledgements: The authors would like to thank Marion Pellen and Marin Jourdan. We thank Marjorie Sweetko for English revision.
- VIDEO Rasburicase crystallization in a microfluidic droplet
- VIDEO Rasburicase Oswald ripening in a microfluidic droplet
We present a simple and easy-to-use microfluidic set-up for the crystallization of mineral, organic and biological materials. After briefly presenting the hydrodynamic properties of the set-up, we test and validate it with viscous media by crystallizing a protein in an aqueous solution of PEG. We obtain nucleation data in nano-crystallizers using a droplet-based method and precisely controlling input flows to test different crystallization conditions.
Référence: Zhang, S., N. Ferté, N. Candoni, and S. Veesler, Versatile Microfluidic Approach to Crystallization. Organic Process Research & Development, 2015. http://dx.doi.org/10.1021/acs.oprd.5b00122
Acknowledgements: We thank Marjorie Sweetko for English revision. We thank Région PACA and C'Nano PACA for financial supports. We thank Dr. M. El-Hajji (Sanofi) for the rasburicase and Minh Phat La, B. Benhaim, T. Bactivelane (CINaM) and Mr. Audiffren (ANACRISMAT) for technical assistance.Do the differing properties of materials influence their nucleation mechanisms?
We present different experimental approaches to study and control nucleation, and shed light on some of the factors affecting the nucleation process. Faraday Discussions
Référence: Hammadi, Z., R. Grossier, A. Ikni, N. Candoni, R. Morin, and S. Veesler, Localizing and inducing primary nucleation. Faraday Discussions, 2015. 179: p. 489-501. http://dx.doi.org/10.1039/C4FD00274A
Acknowledgements: We thank N. Ferte for protein characterization and fruitful discussions. We thank M. Sweetko for English revision.Transient Calcium Carbonate Hexahydrate (Ikaite) Nucleated and Stabilized in Confined Nano- and Picovolumes
Calcium carbonate precipitation at different
values of the nominal ionic activity product (IAP) is studied in
nanoliter and picoliter droplets at (20 ± 2 °C). Experiments
are carried out through direct mixing of equimolar reactant
solutions using two different setups: first, droplet-based
microfluidics using Teflon capillaries (nanoliter experiments)
and second, the microinjection technique under oil (picoliter
droplets). Instantaneous precipitation of a metastable CaCO3
phase is initially observed. This phase is stabilized in time by
reducing the initial volume of the experiments from the nanoto
picoliters range and when the CaCl2/Na2CO3 ratio approaches 1. Further analysis by X-ray diffraction, transmission electron
microscopy, and selected area electron diffraction confirms the first nucleated phase is CaCO3·6H2O (ikaite) and in few droplets
ikaite plus CaCO3·H2O (monohydrocalcite). No evidence of amorphous calcium carbonate (ACC) is found even in conditions
where the IAP exceeds the solubility product of this phase. The in vitro finding of ikaite formation and stabilization due to
volume confinement is an unexpected result since it is the first time that this hydrous phase is stabilized at room temperature (it
is normally found at near 0 °C) in the absence of additives. This result can be of interest for those biomineralization processes
occurring in the confined volumes of intracellular vesicles and for biomimetic materials science in general.
Référence: I. Rodríguez-Ruiz, S. Veesler, J. Gómez-Morales, J.M. Delgado-López, O. Grauby, Z. Hammadi, N. Candoni, J.M. García-Ruiz, Transient Calcium Carbonate Hexahydrate (Ikaite) Nucleated and Stabilized in Confined Nano- and Picovolumes, Crystal Growth & Design, (2014),14,792-802. http://dx.doi.org/10.1021/cg401672v
Acknowledgements: The authors thank Damien Chaudansson and Serge Nietsche for HRTEM and SAED experiments and Luis David PatinÞo Loìpez for his valuable help with Mach.Zehnder interferometry experiments. We also thanks Dr. Frederic Harb for the fruitful discussions. We thank Dr. Marcus O’Mahony for English revision.Monitoring picoliter sessile microdroplet dynamics shows that size doesn't matter
- VIDEO "150 pL NaCl microdroplets contraction and nucleation in oil
We monitor the dissolution of arrayed picoliter-size sessile microdroplets of aqueous phase in oil, generated using a recently developed fluidic device. Initial pinning of the microdroplet perimeter leads to a nearly constant contact diameter; thus contraction proceeds via microdroplet (micrometer diameter) height and contact angle reductions. This confirms that picoliter microdroplets contraction or dissolution due to selective diffusion of water in oil has comparable dynamics with microliter droplets evaporation in air. We observe a constant microdroplet dissolution rate in different aqueous solutions. The application of this simple model to solvent-diffusion-driven crystallization experiments in confined volumes, for instance, would allow us to precisely determine the concentration in the microdroplet during an experiment and particularly at nucleation. .
Référence: Rodríguez-Ruiz, I.; Hammadi, Z.; Grossier, R.; Gómez-Morales, J.; Veesler, S. Langmuir 2013, 29, 12628-12632. http://dx.doi.org/10.1021/la402735k
Acknowledgements: We thank M. Sweetko for English revision.Small-volume nucleation
The nucleation mechanisms behind crystallized products remain mysterious. In this communication, we describe experiments performed using small volumes, microdroplets, to control nucleation and thus product properties. The effect of small-volume systems on nucleation is discussed.
Référence: Hammadi Z., Candoni N., Grossier R., Ildefonso M., Morin R., Veesler S., Small-volumes nucleation, C. R. Physique, 14 (2013 ) 192-198. http://dx.doi.org/10.1016/j.crhy.2012.12.004
Acknowledgements: We thank N. Ferté for protein characterization and fruitful discussions and for technical assistanceWe thank M. Audiffren (ANACRISMAT), T. Bactivelane(CINaM) and Minh Phat La for their technical help. We thank M. Sweetko for English revision.
Crystallization via tubing microfluidics permits both in situ and ex situ X-ray diffraction
| We used a microfluidic platform to address the problems of obtaining diffraction quality crystals and crystal handling during transfer to the X-ray diffractometer VIDEO crystal extraction from microdroplet. We optimize crystallization conditions of a protein of pharmaceutical interest and collect X-ray data both in situ and ex situ. |
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Acknowledgements: We thank the Institut de Recherche Servier for financial support. We thank T. Bactivelane (CINaM), M. Lagaize (CINaM) and M. Audiffren (ANACRISMAT) for technical assistance. We thank G. Sulzenbacher, S. Spinelli and P. Cantau (AFMB) for the transport of the crystals and their support about crystallography. Experiments at Synchrotron SOLEIL were performed under the in house proposal number 99150097. Results incorporated in this note received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 708130.
Microfluidic platform for optimization of crystallization conditions
This paper presents a universal, high-throughput droplet-based microfluidic platform for crystallization studies. The platform offers four modular functions: droplet formation, on-line characterization, incubation and observation. We validate the platform for fine-gradient screening and optimization of crystallization conditions.
Référence: Shuheng Zhang, Charline J.J. Gerard, Aziza Ikni, Gilles Ferry, Laurent M. Vuillard, Jean A. Boutin, Nathalie Ferte, Romain Grossier, Nadine Candoni, Stéphane Veesler, Microfluidic platform for optimization of crystallization conditions. Journal of Crystal growth, accepted. http://dx.doi.org/10.1016/j.jcrysgro.2017.01.026
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Acknowledgements: We thank the Institut de Recherche Servier and ANR BAcMolMot (ANR-14-CE09-0023-03) for financial support. We thank T. Bactivelane (CINaM), M. Lagaize (CINaM) and M. Audiffren (ANACRISMAT) for technical assistance. We thank Marjorie Sweetko for English revision.
A versatile microfluidic approach to crystallization
- VIDEO "crystal driving" copyright RG 2011
The birth of crystals via crystal nucleation lies at the heart both of many natural processes like the formation of bones, teeth and shells, and of technological
processes used for pharmaceuticals and nanomaterials. However, most experiments on crystal nucleation have to deal with random events: we do not know where and
when an indefinite number of nucleation events will occur. Here, we used a sharp tip to tap a supersaturated confined metastable solution, and found that a single
nucleation event was launched as soon as the tip touched the confined solution. This shows that spatial and temporal factors can be controlled through confinement.
The approach we describe should open the way to predictive nucleation experiments, yielding the much-needed direct method for studying nucleation.
Réference: Predictive nucleation of crystals in small volumes and its consequences Grossier R. ; Hammadi Z. ; Morin R. ; Veesler S. Phys. Rev. Lett. 2011, 107 (2), 025504
http://prl.aps.org/abstract/PRL/v107/i2/e025504
Ackowledgments: We thank ANR-06-Blan-0355 "MICROCRISTAL" and CEA Marcoule for financial supports. We thank A. Ranguis for AFM (CINaM), O. Grauby for SEM (CINaM), F. Bedu for spin coating (CINaM), T. Bactivelane (CINaM), B. Detailleur (CINaM), M. Audiffren (Anacrismat) for technical assistance and to M. Sweetko for English revision.
Predictive nucleation of crystals in small volumes and its consequences
- VIDEO Lysozyme crystallization in a chip
Here we measure lysozyme nucleation kinetics using an easy-to-use and simply-constructed microfluidics set-up previously described. We confirm that microfluidics is a direct, accurate and fast method to measure nucleation frequency using only a few milligrams of molecules. Moreover our microfluidics set-up, by diminishing crystallizer volumes, increases the experimental supersaturation range accessible, and can be applied to all water-soluble molecules.
Reference: Using microfluidics for fast, accurate measurement of lysozyme nucleation kinetics. Ildefonso M., Candoni N., and Veesler S., Cryst. Growth Des., 2011. 11(5): p. 1527-1530. http://dx.doi.org/10.1021/cg101431g
Ackowledgments: We thank M. Audiffren (ANACRISMAT) and T. Bactivelane for their technical help. We thank N. Ferte for protein characterization and fruitful discussions. We thank M. Sweetko for English revision.
USING MICROFLUIDICS FOR FAST, ACCURATE MEASUREMENT OF NUCLEATION KINETICS
- VIDEO Generation of microdroplets
In this letter, we present a simply-constructed and easy-to-use fluidic device that generates arrayed aqueous phase microdroplets in oil of controlled size with
volumes ranging from nanoliter to femtoliter without surfactant. This can be applicable with a range of materials, allowing production and storage of monodisperse
microdroplets. We illustrate the potential of our methodology in the field of nanoparticle generation
figure: Array of droplets generated through the layer of liquid oil. (sizes:5-50µm).
Reference: Generating nanoliter to femtoliter microdroplets with ease Grossier R.; Hammadi Z.; Morin R.; Magnaldo A.; Veesler S, Appl. Phys. Lett. 2011, 98, (9), 091916-3 http://apl.aip.org/resource/1/applab/v98/i9/p091916_s1
Ackowledgments: We thank ANR-06-Blan-0355 "MICROCRISTAL" and CEA Marcoule for financial supports. We thank A. Ranguis for AFM (CINaM), O. Grauby for SEM (CINaM), F. Bedu for spin coating (CINaM), T. Bactivelane (CINaM), B. Detailleur (CINaM), M. Audiffren (Anacrismat) for technical assistance and to M. Sweetko for English revision.
This article has been selected: for the March 21, 2011 issue of Virtual Journal of Nanoscale Science & Technology. The Virtual Journal, which is published by the American Institute of Physics and the American Physical Society in cooperation with numerous other societies and publishers, is an edited compilation of links to articles from participating publishers, covering a focused area of frontier research. You can access the Virtual Journal at http://www.vjnano.org
GENERATING NANOLITER TO FEMTOLITER MICRODROPLETS WITH EASE
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