A portable extensional rheometer for measuring the viscoelasticity of pitcher plant and other sticky liquids in the field.

BACKGROUND: Biological fluids often have interesting and unusual physical properties to adapt them for their specific purpose. Laboratory-based rheometers can be used to characterise the viscoelastic properties of such fluids. This, however, can be challenging as samples often do not retain their natural properties in storage while conventional rheometers are fragile and expensive devices ill-suited for field measurements. We present a portable, low-cost extensional rheometer designed specifically to enable in situ studies of biological fluids in the field. The design of the device (named Seymour) is based on a conventional capillary break-up extensional rheometer (the Cambridge Trimaster). It works by rapidly stretching a small fluid sample between two metal pistons. A battery-operated solenoid switch triggers the pistons to move apart rapidly and a compact, robust and inexpensive, USB 3 high speed camera is used to record the thinning and break-up of the fluid filament that forms between the pistons. The complete setup runs independently of mains electricity supply and weighs approximately 1 kg. Post-processing and analysis of the recorded images to extract rheological parameters is performed using open source software. RESULTS: The device was tested both in the laboratory and in the field, in Brunei Darussalam, using calibration fluids (silicone oil and carboxymethyl cellulose solutions) as well as Nepenthes pitcher plant trapping fluids as an example of a viscoelastic biological fluid. The fluid relaxation times ranged from 1 ms to over 1 s. The device gave comparable performance to the Cambridge Trimaster. Differences in fluid viscoelasticity between three species were quantified, as well as the change in viscoelasticity with storage time. This, together with marked differences between N. rafflesiana fluids taken from greenhouse and wild plants, confirms the need for a portable device. CONCLUSIONS: Proof of concept of the portable rheometer was demonstrated. Quantitative measurements of pitcher plant fluid viscoelasticity were made in the natural habitat for the first time. The device opens up opportunities for studying a wide range of plant fluids and secretions, under varying experimental conditions, or with changing temperatures and weather conditions.The following financial support is gratefully acknowledged: a Henslow Research Fellowship from the Cambridge Philosophical Society and a Leverhulme Early Career Fellowship for UB; a visiting research fellowship (POS-A/2012/116) for MDT from Xunta de Galicia’s Consellería de Cultura, Educación e Ordenación Universitaria of Spain and the European Union’s European Social Fund; and a summer project grant for CC from Sidney Sussex College, Cambridge.This is the final version of the article. It first appeared at http://www.plantmethods.com/content/11/1/16

Monitoring the orientation of rare-earth-doped nanorods for flow shear tomography

Rare-earth phosphors exhibit unique luminescence polarization features originating from the anisotropic symmetry of the emitter ion's chemical environment. However, to take advantage of this peculiar property, it is necessary to control and measure the ensemble orientation of the host particles with a high degree of precision. Here, we show a methodology to obtain the photoluminescence polarization of Eu-doped LaPO4 nano rods assembled in an electrically modulated liquid-crystalline phase. We measure Eu3+ emission spectra for the three main optimal configurations ({\sigma}, {\pi} and {\alpha}, depending on the direction of observation and the polarization axes) and use them as a reference for the nano rod orientation analysis. Based on the fact that flowing nano rods tend to orient along the shear strain profile, we use this orientation analysis to measure the local shear rate in a flowing liquid. The potential of this approach is then demonstrated through tomographic imaging of the shear rate distribution in a microfluidic system.Comment: 8 pages, 3 figures + supplementary files for experimental and numerical method

Development of polarized nanoemitters as probes for orientation measurements

Les nanoparticules luminescentes sont particulièrement étudiées pour leur application dans les systèmes d’éclairages ou comme sondes en bio-imagerie. Parmi elles, les nanoparticules anisotropes de matrices cristallines dopées par des ions lanthanides présentent une émission polarisée, qui dépend de la symétrie des sites des ions émetteurs. Le lien entre direction de polarisation et axes cristallins des nanocristaux permet de déterminer leur orientation, et peut donc être exploité pour suivre l'orientation d’objets ou pour caractériser la déformation de milieux hôtes.Les objectifs de ce doctorat ont été de s’intéresser aux origines fondamentales de l’émission polarisée de nanobâtonnets de phosphate de lanthane dopés par des ions europium trivalents (LaPO4:Eu) et d’utiliser la luminescence polarisée à des mesures d’orientation.Dans une première partie, les nanobâtonnets de LaPO4:Eu ont été synthétisés puis alignés sous forme des films orientés. La luminescence de ces films a permis de suivre avec précision la transition de phase de la matrice hôte, de sa structure hexagonale à une structure monoclinique ; et de mettre en évidence la présence de défauts structuraux. La polarisation des spectres de luminescence a ensuite été étudiée. Les taux de polarisation mesurés sont plus élevés pour la phase monoclinique que pour la phase hexagonale. La sensibilité du spectre de polarisation au milieu diélectrique qui les entoure a été mise en évidence.La seconde partie de cette étude porte sur l’utilisation de la polarisation des nanobâtonnets de LaPO4:Eu pour déterminer leur orientation. La connaissance des spectres polarisés des films parfaitement alignés a permis de déterminer le paramètre d’ordre d’une suspension de nanobâtonnets désordonnés en écoulement dans un canal microfluidique puis d’estimer le taux de cisaillement de cet écoulement. Notre étude a permis de préciser quantitativement les conditions dans lesquelles l’utilisation de la luminescence polarisée comme sonde locale du taux de cisaillement d’un écoulement est valide.Luminescent nanoparticles have been studied for their applications in lighting devices or as probes in biology. Among these nanoparticles, the anisotropic crystals doped with lanthanides ions emit linearly polarized light. The relation between the polarized directions and the crystallographic axis of the nanocrystals allow determining their 3D orientation, which could be an asset to track objects or to characterize flows.The purposes of this thesis were to investigate the origin of the polarized light of nanorods of lanthanum phosphate doped with europium ions (LaPO4:Eu) and to apply this polarized light to determine their orientation.First, nanorods of LaPO4:Eu are synthesized and aligned to prepare oriented films. The phase transition of the LaPO4 matrix is investigated, from the hexagonal to the monoclinic structure. The luminescence is used to track precisely the transition and show the presence of structural defects. Then the polarized spectra are observed. The polarization degrees of the monoclinic phase are higher than those of the hexagonal one. The sensitivity of the polarization with the dielectric medium is also shown.Then, the polarized light is used to determine the orientation of the nanorods. The knowledge of the polarized spectra along he nanorods axis and perpendicularly to it is used to calculate the order parameter of disoriented nanorods in a microfluidic channel and then to estimate the shear rate of the flow. Our study allows quantifying the conditions in which the nanorods can be used as probes to measure the local shear rate

Développement de nanoémetteurs polarisés pour leur application comme sondes d'orientation

Luminescent nanoparticles have been studied for their applications in lighting devices or as probes in biology. Among these nanoparticles, the anisotropic crystals doped with lanthanides ions emit linearly polarized light. The relation between the polarized directions and the crystallographic axis of the nanocrystals allow determining their 3D orientation, which could be an asset to track objects or to characterize flows.The purposes of this thesis were to investigate the origin of the polarized light of nanorods of lanthanum phosphate doped with europium ions (LaPO4:Eu) and to apply this polarized light to determine their orientation.First, nanorods of LaPO4:Eu are synthesized and aligned to prepare oriented films. The phase transition of the LaPO4 matrix is investigated, from the hexagonal to the monoclinic structure. The luminescence is used to track precisely the transition and show the presence of structural defects. Then the polarized spectra are observed. The polarization degrees of the monoclinic phase are higher than those of the hexagonal one. The sensitivity of the polarization with the dielectric medium is also shown.Then, the polarized light is used to determine the orientation of the nanorods. The knowledge of the polarized spectra along he nanorods axis and perpendicularly to it is used to calculate the order parameter of disoriented nanorods in a microfluidic channel and then to estimate the shear rate of the flow. Our study allows quantifying the conditions in which the nanorods can be used as probes to measure the local shear rate.Les nanoparticules luminescentes sont particulièrement étudiées pour leur application dans les systèmes d’éclairages ou comme sondes en bio-imagerie. Parmi elles, les nanoparticules anisotropes de matrices cristallines dopées par des ions lanthanides présentent une émission polarisée, qui dépend de la symétrie des sites des ions émetteurs. Le lien entre direction de polarisation et axes cristallins des nanocristaux permet de déterminer leur orientation, et peut donc être exploité pour suivre l'orientation d’objets ou pour caractériser la déformation de milieux hôtes.Les objectifs de ce doctorat ont été de s’intéresser aux origines fondamentales de l’émission polarisée de nanobâtonnets de phosphate de lanthane dopés par des ions europium trivalents (LaPO4:Eu) et d’utiliser la luminescence polarisée à des mesures d’orientation.Dans une première partie, les nanobâtonnets de LaPO4:Eu ont été synthétisés puis alignés sous forme des films orientés. La luminescence de ces films a permis de suivre avec précision la transition de phase de la matrice hôte, de sa structure hexagonale à une structure monoclinique ; et de mettre en évidence la présence de défauts structuraux. La polarisation des spectres de luminescence a ensuite été étudiée. Les taux de polarisation mesurés sont plus élevés pour la phase monoclinique que pour la phase hexagonale. La sensibilité du spectre de polarisation au milieu diélectrique qui les entoure a été mise en évidence.La seconde partie de cette étude porte sur l’utilisation de la polarisation des nanobâtonnets de LaPO4:Eu pour déterminer leur orientation. La connaissance des spectres polarisés des films parfaitement alignés a permis de déterminer le paramètre d’ordre d’une suspension de nanobâtonnets désordonnés en écoulement dans un canal microfluidique puis d’estimer le taux de cisaillement de cet écoulement. Notre étude a permis de préciser quantitativement les conditions dans lesquelles l’utilisation de la luminescence polarisée comme sonde locale du taux de cisaillement d’un écoulement est valide

Polarized Luminescence of Anisotropic LaPO₄:Eu Nanocrystal Polymorphs

Lanthanide elements exhibit highly appealing spectroscopic properties that are extensively used for phosphor applications. Their luminescence contains precise information on the internal structure of the host materials. Especially, the polarization behavior of the transition sublevel peaks is a fingerprint of the crystal phase, symmetry, and defects. However, this unique feature is poorly explored in current research on lanthanide nanophosphors. We here report on a detailed investigation of the evolution of Eu³⁺ luminescence during the thermally induced phase transition of LaPO₄ nanocrystal hosts. By means of <i>c</i>-axis-aligned nanocrystal assemblies, we demonstrate a dramatic change of the emission polarization feature corresponding to the distinct Eu³⁺ site symmetries in different LaPO₄ polymorphs. We also show that changes of the nanocrystal structure can be identified by this spectroscopic method, with a much higher sensitivity than the X-ray diffraction analysis. This new insight into the nanostructure-luminescence relationship, associated with the unprecedented polarization characterizations, provides a new methodology to investigate phase transitions in nanomaterials. It also suggests a novel function of lanthanide emitters as orientation-sensing nanoprobes for innovative applications such as in bioimaging or microfluidics