Field-flow fractionation for nanoparticle characterization.

This review presents field-flow fractionation: The elements of theory enable the link between the retention and the characteristics of the nanometer-sized analytes to be highlighted. In particular, the nature of force and its way of being applied are discussed. Four types of forces which determine four types of techniques were considered: hydrodynamic, sedimentation, thermal, and electrical; this is to show the importance of the choice of technique in relation to the characterization objectives. Then the separation performance is presented and compared with other separation techniques: field-flow fractionation has the greatest intrinsic separation capability. The characterization strategies are presented and discussed; on the one hand with respect to the characteristics needed for the description of nanoparticles; on the other hand in connection with the choice of the nature of the force, and also of the detectors used, online or offline. The discussion is based on a selection of published study examples. Finally, current needs and challenges are addressed, and as response, trends and possible characterization solutions.

Characterization of Glioblastoma Cancer Stem Cells Sorted by Sedimentation Field-Flow Fractionation Using an Ultrahigh-Frequency Range Dielectrophoresis Biosensor.

Cancer stem cells (CSCs) appear to be an essential target for cancer therapies, in particular, in brain tumors such as Glioblastoma. Nevertheless, their isolation is made difficult by their low content in culture or tumors (<5% of the tumor mass) and is essentially based on the use of fluorescent or magnetic labeling techniques, increasing the risk of differentiation induction. The use of label-free separation methods such as sedimentation field-flow fractionation (SdFFF) is promising, but it becomes necessary to consider a coupling with a detection and characterization method for future identification and purification of CSCs from patient-derived tumors. In this study, we demonstrate for the first time the capability of using an ultrahigh-frequency range dielectrophoresis fluidic biosensor as a detector. This implies an important methodological adaptation of SdFFF cell sorting by the use of a new compatible carrier liquid DEP buffer (DEP-B). After SdFFF sorting, subpopulations derived from U87-MG and LN18 cell lines undergo biological characterization, demonstrating that using DEP-B as a carrier liquid, we sorted by SdFFF subpopulations with specific differentiation characteristics: F1 = differentiated cells/F2 = CSCs. These subpopulations presented high-frequency crossover (HFC) values similar to those measured for standard differentiated (around 110 MHz) and CSC (around 80 MHz) populations. This coupling appeared as a promising solution for the development of an online integration of these two complementary label-free separation/detection technologies.

Self-Assembly of Nucleoside-Derived Low-Molecular-Weight Gelators: A Thermodynamics and Kinetics Study on Different Length Scales.

Biocompatible materials are of paramount importance in numerous fields. Unlike chemically bridge polymer-based hydrogels, low-molecular-weight gelators can form a reversible hydrogel as their structures rely on noncovalent interaction. Although many applications with this type of hydrogel can be envisioned, we still lack their understanding due to the complexity of their self-assembly process and the difficulty in predicting their behaviors (transition temperature, gelation kinetics, the impact of solvent, etc.). In this study, we extend the investigations of a series of nucleoside-derived gelators, which only differ by subtle chemical modifications. Using a multitechnique approach, we determined their thermodynamic and kinetic features on various scale (molecular to macro) in different conditions. Monitored at the supramolecular level by circular dichroism as well as macroscopic scales by rheology and turbidimetry, we found out that the sol-gel and gel-sol transitions are greatly dependent on the concentration and on the mechanisms that are probed. Self-assembly kinetics depends on hydrogel molecules and is modulated by temperature and solvent. This fundamental study provides insight on the impact of some parameters on the gelation process, such as concentration, cooling rate, and the nature of the solvent.

Separation of nanoparticles from polydisperse environmental samples: comparative study of filtration, sedimentation, and coiled tube field-flow fractionation.

Nanoparticles (NPs) in the environment have a potential risk for human health and the ecosystem due to their ubiquity, specific characteristics, and properties (extreme mobility in the environment, abilities to accumulate of toxic elements and penetrate into living organisms). There is still a gap in studies on the chemical composition of natural NPs. The main reason is the difficulty to recover NPs, which may represent only one-thousandth or less of the bulk environmental sample, for further dimensional and quantitative characterization. In the present study, a methodology for the recovery of the nanoparticle fraction from polydisperse environmental samples was developed taking as example volcanic ashes from different regions of the world. For the first time, three separation methods, namely, filtration through a 0.45-µm membrane, sedimentation, and coiled tube field-flow fractionation (CTFFF), were comparatively studied. The separated fractions were characterized by laser diffraction and scanning electron microscopy and then analyzed by inductively coupled plasma atomic emission and mass spectrometry. It has been shown that all three methods provide the separation of NPs less than 400 nm from the bulk material. However, the fraction separated by sedimentation also contained a population (5% in mass) of submicron particles (~ 400-900 nm). The filtration resulted in low recovery of NPs. The determination of most trace elements was then impossible; the concentration of elements was under the limit of detection of the analytical instrument. The sedimentation and CTFFF made it possible to determine quantifiable concentrations for both major and trace elements in separated fractions. However, the sedimentation took 48 h while CTFFF enabled the fractionation time to be decreased down to 2 h. Hence, CTFFF looked to be the most promising method for the separation of NPs followed by their quantitative elemental analysis.

Design and Cellular Fate of Bioinspired Au-Ag Nanoshells@Hybrid Silica Nanoparticles.

Silica-coated gold-silver alloy nanoshells were obtained via a bioinspired approach using gelatin and poly-l-lysine (PLL) as biotemplates for the interfacial condensation of sodium silicate solutions. X-ray photoelectron spectroscopy was used as an efficient tool for the in-depth and complete characterization of the chemical features of nanoparticles during the whole synthetic process. Cytotoxicity assays using HaCaT cells evidenced the detrimental effect of the gelatin nanocoating and significant induction of late apoptosis after silicification. In contrast, PLL-modified nanoparticles had less biological impact that was further improved by the silica layer, and uptake rates of up to 50% of those of the initial particles could be achieved. These results are discussed considering the effect of nanosurface confinement of the biopolymers on their chemical and biological reactivity.

Adsorption and degradation processes of tributyltin and trimethyltin in landfill leachates treated with iron nanoparticles.

Biotic and abiotic degradation of toxic organotin compounds (OTCs) in landfill leachates is usually not complete. In this work adsorption and degradation processes of tributyltin (TBT) and trimethyltin (TMeT) in leachate sample treated with different iron nanoparticles (FeNPs): Fe(0) (nZVI), FeO and Fe3O4 were investigated to find conditions for their efficient removal. One sample aliquot was kept untreated (pH 8), while to the others (pH 8) FeNPs dispersed with tetramethyl ammonium hydroxide (TMAH) or by mixing were added and samples shaken under aerated conditions for 7 days. The same experiments were done in leachates in which the pH was adjusted to 3 with citric acid. Size distribution of TBT and TMeT between particles >5 µm, 0.45-5 µm, 2.5-0.45 µm, and <2.5 nm was determined by sequential filtration and their concentrations in a given fraction by gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS). Results revealed that most of the TBT or TMeT was present in fractions with particles >2.5 or <2.5 nm, respectively. At pH 8 adsorption of TBT to FeNPs prevailed, while at pH 3, the Fenton reaction provoked degradation of TBT by hydroxyl radicals. TBT was the most effectively removed (96%) when sequential treatment of leachate with nZVI (dispersed by mixing) was applied first at pH 8, followed by nZVI treatment of the aqueous phase, previously acidified to pH 3 with citric acid. Such treatment less effectively removed TMeT (about 40%). It was proven that TMAH provoked methylation of tin, so mixing was recommended for dispersion of nZVI.

Determination of total and electrolabile copper in agricultural soil by using disposable modified-carbon screen-printed electrodes.

The objective of the study is to evaluate modified-carbon screen-printed working electrodes (SPE) combined with square wave anodic stripping voltammetry (SWASV) to determine electrolabile and total copper in soils with the perspective to assess the environmental hazard resulting from copper anthropogenic contamination. The voltammetric method was investigated using a mineralized certified reference soil such that it can be assumed that the copper was totally under electrolabile form in the solution of mineralized soil. In optimal conditions, a copper recovery of 97% and a relative standard deviation (RSD) of 9% were found. The limits of detection and quantification for copper were 0.4 and 1.3 µg L(-1), respectively. Finally, the method was applied on soil leachates, which allowed evaluating the cupric transfer from the soil to the leachates and quantifying the electrolabile copper part in leachates.

Asymmetric flow-field flow fractionation-multidetection coupling for assessing colloidal copper in drain waters from a Bordeaux wine-growing area.

The objective of this study was to show that on-line asymmetric flow-field flow fractionation (AFFFF)-multidetection coupling is useful for studying environmental colloids in a qualitative and quantitative way. The utility of the technique was illustrated by assessing the colloidal fraction of the copper that was extracted from the soil, transferred to an aqueous phase and then transported by drain waters in a wine-growing area. To determine the size and composition of the colloids, AFFFF was coupled to UV, multi-angle light scattering and inductively coupled plasma mass spectrometry detectors. Colloidal copper represents between 20 and 60% of the total copper in the sub 450 nm of drain waters. Copper is mainly associated with organic-rich colloids with a size below 10 nm. It is also found in organo-mineral populations (as clay or (oxy)hydroxides), with sizes ranging between 10 and 450 nm.

Optimization of flow field-flow fractionation for the characterization of natural colloids.

The methodological approach used to robustly optimize the characterization of the polydisperse colloidal phase of drain water samples is presented. The approach is based on asymmetric flow field-flow fractionation coupled to online ultraviolet/visible spectrophotometry, multi-angle light scattering, and inductively coupled plasma mass spectrometry. Operating factors such as the amount of sample injected and the ratio between main-flow and cross-flow rates were considered. The evaluation of the injection and fractionation steps was performed considering the polydispersity index and the contribution to the polydispersity of the plate height, the recovery, the retention ratio and the size range of the fractionated colloids. This approach allows the polydispersity of natural colloid samples to be taken into consideration to achieve the most efficient and representative fractionation. In addition to the size characterization, elemental analysis was also evaluated using the recovery, precision, and limits of detection and quantification relative to a trace element of interest (copper) in drain water. To complete this investigation, the potential application of the methodology was assessed using several independent drain water samples from different soils. The contribution of the polydispersity to the plate height ranges from 4.8 to 8.9 cm with a mean precision of 6%. The mean colloidal recovery was 81 ± 3 %, and the mean retention ratio was 0.043-0.062. The limits of detection and quantification for copper were 0.6 and 1.8 µg L(-1), respectively.

A new analytical approach based on asymmetrical flow field-flow fractionation coupled to ultraviolet spectrometry and light scattering detection for SWCNT aqueous dispersion studies.

This work demonstrates the potential of asymmetrical flow field-flow fractionation (A4F) coupled to Ultraviolet spectrometry (UV) and multi-angle light scattering (MALS) for the study of single-walled carbon nanotube (SWCNT) dispersion in aqueous solutions containing a surfactant. The results indicate that this technique is a powerful analytical tool that is able to evaluate SWCNT dispersion states in aqueous media and, more importantly, determine the presence or absence of aggregates, the numbers and sizes of different SWCNT populations and the SWCNT size distribution. Dynamic light scattering was employed to complete and demonstrate the relevance of the data that were obtained via A4F-UV-MALS. Two different anionic surfactants that are used to disperse SWCNTs were then studied. The dispersing powers of the surfactants were experimentally evaluated based on their structural organizations. This study demonstrates that surfactant concentration and sonication energy are key parameters that control the SWCNT dispersion state and SWCNT structural integrity therein.

Nucleoside-Derived Low-Molecular-Weight Gelators as a Synthetic Microenvironment for 3D Cell Culture.

For the last few decades, many efforts have been made in developing cell culture methods in order to overcome the biological limitations of the conventional two-dimensional culture. This paradigm shift is driven by a large amount of new hydrogel-based systems for three-dimensional culture, among other systems, since they are known to mimic some living tissue properties. One class of hydrogel precursors has received interest in the field of biomaterials, low-molecular-weight gelators (LMWGs). In comparison to polymer gels, LMWG gels are formed by weak interactions upon an external trigger between the molecular subunits, giving them the ability to reverse the gelation, thus showing potential for many applications of practical interest. This study presents the use of the nucleoside derivative subclass of LMWGs, which are glyco-nucleo-bola-amphiphiles, as a proof of concept of a 3D cell culture scaffold. Physicochemical characterization was performed in order to reach the optimal features to fulfill the requirements of the cell culture microenvironment, in terms of the mechanical properties, architecture, molecular diffusion, porosity, and experimental practicality. The retained conditions were tested by culturing glioblastoma cells for over a month. The cell viability, proliferation, and spatial organization showed during the experiments demonstrate the proof of concept of nucleoside-derived LMWGs as a soft 3D cell culture scaffold. One of the hydrogels tested permits cell proliferation and spheroidal organization over the entire culture time. These systems offer many advantages as they consume very few matters within the optimal range of viscoelasticity for cell culture, and the thermoreversibility of these hydrogels permits their use with few instruments. The LMWG-based scaffold for the 3D cell culture presented in this study unlocked the ability to grow spheroids from patient cells to reach personalized therapies by dramatically reducing the variability of the lattice used.

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.

Multi-wall carbon nanotube aqueous dispersion monitoring by using A4F-UV-MALS.

In this work, the potentiality of asymmetrical flow field-flow fractionation (A4F) hyphenated to UV detector and multi-angle light scattering (MALS) was investigated for accurately determining multi-walled carbon nanotube (MWCNT) length and its corresponding dispersion state in aqueous medium. Fractionation key parameters were studied to obtain a method robust enough for heterogeneous sample characterization. The main A4F conditions were 10(-5) mL min(-1) NH(4)NO(3), elution flow of 1 mL min(-1), and cross flow of 2 mL min(-1). The recovery was found to be (94 ± 2)%. Online MALS analysis of eluted MWCNT suspension was performed to obtain length distribution. The length measurements were performed with a 4% relative standard deviation, and the length values were shown to be in accordance with expected ones. The capabilities of A4F-UV-MALS to size characterize various MWCNT samples and differentiate them according to their manufacturing process were evaluated by monitoring ball-milled MWCNT and MWCNT dispersions. The corresponding length distributions were found to be over 150-650 and 150-1,156 nm, respectively. A4F-UV-MALS was also used to evaluate MWCNT dispersion state in aqueous medium according to the surfactant concentration and sonication energy involved in the preparation of the dispersions. More especially, the presence or absence of aggregates, number and size of different populations, as well as size distributions were determined. A sodium dodecyl sulfate concentration of 15 to 30 mmol L(-1) and a sonication energy ranged over 20-30 kJ allow obtaining an optimal MWCNT dispersion. It is especially valuable for studying nanomaterials and checking their manufacturing processes, size characterization being always of high importance.

Platinum group elements contamination in soils: Review of the current state.

Platinum group elements (PGE: Ru, Rh, Pd, Os Ir, Pt) are rare metals with low abundance in the continental crust. The elements of the palladium subgroup of PGE (PPGE: Pt, Pd, Rh) have been exploited more and more over the last thirty years for their physicochemical properties such as high melting point, high resistance to corrosion, mechanical strength and ductility. This led to emerging environmental contamination in different media such as air, road dust, soil, sediment, vegetation, and snow. The aim of this review is to summarize the available data on soil contamination by PPGE and its potential environmental impact. In this paper, the environmental issue of PPGE is discussed with regard to their anthropogenic emission and fate, which includes speciation, possible transformations into bioavailable forms and toxicity. Soil contamination by PPGE is described taking into account urban and non-urban areas. The analytical determination process is also discussed.

Centrifugal ultrafiltration preconcentration for studying the colloidal phase of a uranium-containing soil suspension.

The objective of this work was to explore centrifugal ultrafiltration (UF) to separate and / or preconcentrate natural colloidal particles for their characterization. A soil suspension obtained by batch leaching was used as a laboratory reference sample. It was preconcentrated with concentration factors (CF) varying from 10 to 450. The dimensional analysis of the colloidal phase was carried out by Asymmetric Flow Field-Flow Fractionation (AF4)-multidetection. The colloidal masses were estimated by mass balance of the initial suspension, its concentrates and filtrates. The size-dependent distribution (expressed in gyration radius) and total colloidal mass (especially recovery), as well as chemical composition and concentration (including species partitioning between dissolved and colloidal phases) were determined to assess the effects of UF preconcentration on colloidal particles. The gyration radius of the colloidal particles recovered in these concentrated suspensions ranged from about 20 nm to over 150 nm. Neither de-agglomeration nor agglomeration was observed. However, only (64 ± 4) % (CF = 10) of the colloidal particles initially in the soil suspension were found in the recovered concentrated suspensions, and this percentage decreased as CF increased. The filter membrane trapped all other particles, mainly the larger ones. Whatever the CF, the centrifugal UF did not appear to change the dissolved-colloidal partitioning of certain species (Al, organic carbon); whereas it led to an enrichment of the colloidal phase for others (Fe, U). The enrichment rate was specific to each species (15% for Fe; 100% for U). By fitting the observed trends (i.e. conservation, depletion or enrichment of the colloidal phase in the concentrate) as a function of CF, the colloidal concentrations (total and species) were assessed without bias. This methodology offers a new perspective for determining physicochemical speciation in natural waters, with a methodology applicable for environmental survey or site remediation studies.

Characterization of volcanic ash nanoparticles and study of their fate in aqueous medium by asymmetric flow field-flow fractionation-multi-detection.

Dimensional and elemental characterization of environmental nanoparticles is a challenging task that requires the use of a set of complementary analytical methods. Asymmetric flow field-flow fractionation coupled with UV-Vis, multi-angle laser light scattering and ICP-MS detection was applied to study the nanoparticle fraction of a volcanic ash sample, in a Milli-Q water suspension at pH 6.8. It has been shown that the separated by sedimentation nanoparticle fraction of the Klyuchevskoy volcano ash suspension contains 3 polydisperse populations for which size ranges (expressed in gyration radius, rG), hydrodynamic behaviours (evaluated via shape index) and elemental compositions are different. These 3 populations did not dissolve over the 72-h study but aggregated and settled out differently. Thus, the population of particles with gyration radii <140 nm (P1), which contained 6% Al2O3 and represented approximately 20% by mass of the nanoparticle fraction, remained in suspension without observable aggregation. The populations P2 and P3, which represented 67% and 13% by mass in the initial suspension, covered the rG range 25-250 nm and contained 17% and 15% Al2O3, respectively. Over time, populations P2 and P3 aggregated and their concentration in suspension at 72 h decreased by approximately 40% compared with the initial suspension. The decrease of these nanoparticle populations occurred either from the beginning of the temporal monitoring (P2) or after 30 h (P3). Aggregation generated a new population (P4) in suspension with rG up to 300 nm and mostly consisting of P2. This population represented only up to 6 to 7% of the nanoparticle fraction and decreased beyond 50 h. As a result, the trace elements present in the nanoparticle fraction and monitored (Cu and La) were also no longer found in the suspension. The results obtained can offer additional insights into the fate of volcanic ash nanoparticles in the environment.

Biomaterials for Three-Dimensional Cell Culture: From Applications in Oncology to Nanotechnology.

Three-dimensional cell culture has revolutionized cellular biology research and opened the door to novel discoveries in terms of cellular behavior and response to microenvironment stimuli. Different types of 3D culture exist today, including hydrogel scaffold-based models, which possess a complex structure mimicking the extracellular matrix. These hydrogels can be made of polymers (natural or synthetic) or low-molecular weight gelators that, via the supramolecular assembly of molecules, allow the production of a reproducible hydrogel with tunable mechanical properties. When cancer cells are grown in this type of hydrogel, they develop into multicellular tumor spheroids (MCTS). Three-dimensional (3D) cancer culture combined with a complex microenvironment that consists of a platform to study tumor development and also to assess the toxicity of physico-chemical entities such as ions, molecules or particles. With the emergence of nanoparticles of different origins and natures, implementing a reproducible in vitro model that consists of a bio-indicator for nano-toxicity assays is inevitable. However, the maneuver process of such a bio-indicator requires the implementation of a repeatable system that undergoes an exhaustive follow-up. Hence, the biggest challenge in this matter is the reproducibility of the MCTS and the associated full-scale characterization of this system's components.

Comparison of preconcentration methods of the colloidal phase of a uranium-containing soil suspension.

Three methods of membrane separation by dead-end, tangential, and centrifugal ultrafiltration (UF) were considered in order to understand the physicochemical phenomena occurring during the preconcentration of the colloidal phase of soil water. The analytical approach used involved dynamic light scattering (DLS), transmission electron microscopy (TEM), determination of total organic carbon (TOC-metry) and mass spectrometry (ICP-MS). The mass amounts of the major components of the colloidal phase, i.e. Al, Fe and total organic carbon (TOC), as well as the mass amount of uranium considered as a trace element of environmental interest, were determined, both in soil water, and in the concentrates (i.e. retentates) and filtrates of this water obtained by the 3 methods tested. Dead-end ultrafiltration led to an enlargement of the size distribution towards larger sizes because of agglomeration/aggregation phenomena. This method also generated enrichment of concentrates, in particular in organic matter. The consequence was that large structures were observed coating or embedding the particles initially present individually dispersed in the test sample. The mass amounts of elements and TOC increased more importantly than expected, which confirmed the enrichment of the concentrates from the dissolved phase probably by sorption on colloidal objects. To a lesser extent similar effects were observed after tangential ultrafiltration. Such phenomena were not observed after centrifugal ultrafiltration. From a practical point of view, both tangential and centrifugal ultrafiltration proved to be both the most practical and the best suited for the preconcentration of soil water sample. Finally, centrifugal ultrafiltration has proved to be the best compromise given the preservation of colloidal particles and method practicality.

Nanoanalytics: history, concepts, and specificities.

This article deals with analytical chemistry devoted to nano-objects. A short review presents nano-objects, their singularity in relation to their dimensions, genesis, and possible transformations. The term nano-object is then explained. Nano-object characterization activities are considered and a definition of nanoanalytics is proposed. Parameters and properties for describing nano-objects on an individual scale and on the scale of a population are also presented. They enable the specificities of analytical activities to be highlighted in terms of multi-criteria description strategies and observation scale. Special attention is given to analytical methods, their dimensioning and validation.