Julien Gigault

Hyphenated analytical techniques for multidimensional characterisation of submicron particles: A review

The stakes concerning the characterisation of particles ranged in the size from 1 to 1000 nm, namely submicron particles, are today more and more important. Because of the variety of particles even inside a given sample in terms of dimension, mass, charge or chemical composition a characterisation as complete as possible is needed. The possibility of obtaining a multidimensional information by relevant analytical methods is then of the greatest interest. One very interesting strategy consists in using hyphenated techniques, which are intrinsically capable to provide rapidly and accurately such information. This paper summarises the different hyphenated techniques that can be used to characterise submicron particles and is focussed on their main applications to illustrate their current and potential uses. In order to have a relevant overview various on-line separation techniques are considered in a comparative way. In the same way various on-line detectors are then presented. Finally the concepts of multidetection and multidimensional analysis are discussed and their interest showed through different typical examples of hyphenated techniques illustrating submicron particle characterisation in fields of applications such as environmental and nanomaterial sciences.

Marine plastic litter: the unanalyzed nano-fraction

In this work, we present for the first time undeniable evidence of nano-plastic occurrence due to solar light degradation of marine micro-plastics under controlled and environmentally representative conditions. As observed during our recent expedition (Expedition 7th Continent), plastic pollution will be one of the most challenging ecological threats for the next generation. Up to now, all studies have focused on the environmental and the economic impact of millimeter scale plastics. These plastics can be visualized, collected and studied. We are not aware of any studies reporting the possibilities of nano-plastics in marine water. Here, we developed for the first time a new solar reactor equipped with a nanoparticle detector to investigate the possibility of the formation of nano-plastics from millimeter scale plastics. With this system, correlated with electronic microscopy observations, we identified for the first time the presence of plastics at the nanoscale in water due to UV degradation. Based on our observations, large fractal nano-plastic particles (i.e., >100 nm) are produced by UV light after the initial formation of the smallest nano-plastic particles (i.e., <100 nm). These new results show the potential hazards of plastic waste at the nanoscale, which had not been taken into account previously.

Single walled carbon nanotube length determination by asymmetrical-flow field-flow fractionation hyphenated to multi-angle laser-light scattering

Asymmetrical flow field-flow fractionation (AFlFFF) hyphenated to multi-angle laser-light scattering (MALS) was evaluated in order to determine single walled carbon nanotube (SWCNT) length distribution. Fractionation conditions were investigated by examining mobile phase ionic strength and pH, channel components and cross-flow rate. Ammonium nitrate-based mobile phase with 10(-5)molL(-1) ionic strength and pH 6 allows the highest sample recovery (89±3%) to be obtained and the lowest loss of the longest SWCNT. A cross-flow rate of 0.9mLmin(-1) leads to avoid any significant membrane-sample interaction. Length was evaluated from gyration radius measured by MALS by comparing SWCNT to prolate ellipsoid. In order to validate the fractionation and the length determination obtained by AFlFFF-MALS, different SWCNT aliquots were collected after fractionation and measured by dynamic light scattering (DLS). AFlFFF is confirmed to operate in normal mode over 100-2000nm length. MALS length determination after fractionation is found to be accurate with 5% RSD. Additionally, a shape analysis was performed by combining gyration and hydrodynamic radii.

Nanoparticle characterization by cyclical electrical field-flow fractionation.

In this work, the analytical potential of cyclical electrical field flow fractionation (CyElFFF) for nanomaterial and colloidal particle characterization has been experimentally demonstrated. Different operating parameters were investigated in order to evaluate their effect on the mechanisms of retention and fractionation power of CyElFFF. The voltage and frequency of the oscillating electrical field appeared to be the most influential parameters controlling the separation mode. Mobile phase flow rate was also found to be a key parameter controlling the fractionation efficiency. This work allowed the definition of operating conditions such that a reliable CyElFFF analysis could be performed on different nanoparticles on the basis of the direct comparison of their theoretical and experimental behavior. The results show that this technique in optimized conditions is a powerful tool for electrophoretic mobility based separation and characterization of various nanoparticles.

Size characterization of the associations between carbon nanotubes and humic acids in aqueous media by asymmetrical flow field-flow fractionation combined with multi-angle light scattering

This work focuses on the influence of humic acids (HAs) on the fate of carbon nanotubes (CNTs) in aqueous media. This influence was demonstrated by mixing CNT powder with HAs in aqueous solution in varying concentrations. The aqueous media containing HAs and CNTs were size-characterized by asymmetrical flow field-flow fractionation (AsFlFFF) coupled with multi-angle light scattering (MALS). This coupling yielded information concerning the size distribution of single- and multi-walled CNTs (SWCNTs and MWCNTs) and HAs under different physico-chemical conditions that can occur in environmental water. HAs can disperse individual CNTs in aqueous media. However, the difference in the physical structure between SWCNTs and MWCNTs leads to significant differences in the quantity of HA that can adsorb onto the nanotube surface and in the stability of the CNT/HA complex. Compared with MWCNTs, SWCNTs suspended in HAs are less affected by changing ionic strength with respect to stability and the amount suspended.

The removal of colloidal lead during estuarine mixing: seasonal variations and importance of iron oxides and humic substances

In the present study, seven colloidal fractions of lead (Pb) were analysed along the mixing zone of the Penze estuary over the Year 2009, with the aim to provide some insight into the mechanism that removes the metal from the 300 kDa) and was removed in the salinity range 0-10 from all of the size fractions where it was significantly found. Because the colloidal fractionation of Pb was strongly linked to that of iron (Fe) and humic substances (HS), the removal of Pb in the mixing area must occur under flocculation of organomineral complexes. A key period corresponding to the first strong autumnal precipitations was also revealed in the present work. At this time of the year, the mobilisation of Pb (and Fe) from catchment soils is enhanced by the mobilisation of HS and the metal is associated with smaller colloids (30-300 kDa).

An assessment of retention behavior for gold nanorods in asymmetrical flow field-flow fractionation

AbstractApplications of asymmetrical flow field-flow fractionation (AF4) continue to expand rapidly in the fields of nanotechnology and biotechnology. In particular, AF4 has proven valuable for the separation and analysis of particles, biomolecular species (e.g., proteins, bacteria) and polymers (natural and synthetic), ranging in size from a few nanometers to several micrometers. The separation of non-spheroidal structures (e.g., rods, tubes, etc.) with primary dimensions in the nanometer regime, is a particularly challenging application deserving of greater study and consideration. The goal of the present study was to advance current understanding of the mechanism of separation of rod-like nano-objects in the AF4 channel. To achieve this, we have systematically investigated a series of commercially available cetyltrimethylammonium bromide stabilized gold nanorods (AuNRs), with aspect ratios from 1.7 to 10. Results show clearly that the retention time is principally dependent on the translational diffusion coefficient of the AuNRs. Equations used to calculate translational and rotational diffusion coefficients (cylinder and prolate ellipsoid models) yield similarly good fits to experimental data. Well characterized gold nanorods (length and diameter by transmission electron microscopy) can be used as calibrants for AF4 measurements allowing one to determine the aspect ratio of nanorod samples based on their retention times. Graphical abstractᅟ