Capillary Electrophoresis as a Complementary Analytical Tool for the Separation and Detection of Nanoplastic Particles.

Capillary electrophoresis (CE) is presented as a technique for the separation of polystyrene nanoparticles (NPs, particle diameters ranging from 30 to 300 nm) through a bare fused silica capillary and ultraviolet detection. The proposed strategy was also assessed for other types of nanoplastics, finding that stronger alkaline conditions, with an ammonium hydroxide buffer (7.5%, pH = 11.9), enabled the separation of poly(methyl methacrylate), polypropylene, and polyethylene NP for the first time by means of CE for particle diameters below 200 nm. Particle behavior has been investigated in terms of its effective electrophoretic mobility, showing an increasing absolute value of effective electrophoretic mobility from the smaller to the larger sizes. On the other hand, the absolute value of surface charge density decreased with increasing size of NPs. It was demonstrated and quantified that the separation mechanism was a combination of linear and nonlinear electrophoretic effects. This work is the first report on the quantification of nonlinear electrophoretic effects on nanoplastic particles in a CE system.

An ICP-MS-Based Analytical Strategy for Assessing Compliance with the Ban of E 171 as a Food Additive on the EU Market.

A method was developed for the determination of total titanium in food and food supplements by inductively coupled plasma mass spectrometry (ICP-MS) after microwave-assisted acid digestion of samples. Five food supplements, including one certified reference material, and 15 food products were used for method development. Key factors affecting the analytical results, such as the composition of the acid mixture for sample digestion and the bias from spectral interferences on the different titanium isotopes, were investigated. Resolution of interferences was achieved by ICP-MS/MS with ammonia adduct formation and viable conditions for control laboratories equipped with standard quadrupole instruments were identified. The method was successfully validated and enables rapid screening of samples subject to confirmatory analysis for the presence of TiO2 particles. For the latter, single-particle ICP-MS (spICP-MS) analysis after chemical extraction of the particles was used. The two methods establish a viable analytical strategy for assessing the absence of titania particles in food products on the EU market following the E 171 ban as a food additive.

Contributions of Capillary Electrophoresis in Analytical Nanometrology: A Critical View.

An overview on the increasing role of capillary electrophoresis in characterization and direct analysis of nanomaterials is herein presented. The niche of electrophoretic approaches in nanometrology is so relevant that nonmetallic, metal, metal oxide nanoparticles, and quantum dots have been analyzed to be targeted via capillary electrophoresis with conventional detection systems or coupling arrangements aimed at increasing selectivity and sensitivity toward either pristine or conjugated nanoparticles. Moreover, parameters altering intrinsic properties of nanoparticles may be optimized to gather the desired results and identify nanomaterials according to their size, shape, or associations with binding agents. The usefulness and quickness of capillary electrophoresis for quantifying or screening ultrasmall-sized particles enables this technique to set an example for analysis of standards or previously synthesized nanostructures in research or routine laboratories. Abundant evidence of the suitability of electrophoretic approaches for characterization and direct determination of nanomaterials in actual samples has been provided in this review, together with a discussion about hyphenation with state-of-the art detectors and comparison between capillary electrophoresis with other separation approaches. This permits scientific community to be optimistic in the short term.

A new nanometrological strategy for titanium dioxide nanoparticles screening and confirmation in personal care products by CE-spICP-MS.

A new nanometrological approach was developed for screening of titania nanoparticles by capillary electrophoresis after adsorption of a target analyte namely l-cysteine onto the nanoparticles in a sodium phosphate buffer, followed by titanium elemental analysis by means of inductively-coupled plasma-mass spectrometry and size distribution measurements by single-particle mode. This analytical strategy involved a first screening of nanotitania in actual samples by electrophoresis, sensitivity being enhanced by cysteine which acts as a nanoparticles stabiliser. Detection and quantitation limits were 0.31 ng µL-1 and 1.03 ng µL-1 respectively for anatase nanoparticles in capillary electrophoresis, and a high amount of titanium was found in the samples subject to study (lip balm and two types of toothpaste) by total elemental analysis. Besides, the potential of single-particle modality for inductively-coupled plasma-mass spectrometry was exploited for a verification of particle size distribution, then confirming the presence of titanium dioxide nanoparticles as an ingredient in the composition of the real samples and validating the overall strategy herein presented.

Magnetic nanocellulose hybrid nanoparticles and ionic liquid for extraction of neonicotinoid insecticides from milk samples prior to determination by liquid chromatography-mass spectrometry.

A simple and rapid microextraction procedure is reported on the use of ionic liquid in combination with magnetic nanocellulose hybrid nanoparticles. The procedure is ultrasound-assisted and applicable to selective preconcentration of neonicotinoid insecticides from milk samples, prior to being analysed by liquid chromatography-mass spectrometry. The extraction procedure uses small volume of organic solvents (<1 mL), and there is no need for centrifugation. In the experimental approach the ionic liquid was quickly disrupted by an ultrasonic probe and dispersed in milk samples in a cloudy form. At this stage, neonicotinoid insecticides were extracted into the fine droplets of ionic liquid. Then small amounts of magnetic nanocellulose hybrid nanoparticles were dispersed into the sample solutions to adsorb the ionic liquid containing the analytes and phase separation was completed. The ionic liquid allowed the microextraction of the analytes and a small volume of acetonitrile was used for elution. Magnetic nanocellulose favoured the adsorption of the ionic liquid with the analytes and improved the final recovery with respect to the use of simple magnetic nanoparticles as a sorbent material. Under the optimum conditions, decision capabilities were achieved in the 0.02-0.06 mg kg-1 range, with recoveries between 91.0% and 109.5%.

Magnetic multi-walled carbon nanotube poly(styrene-co-divinylbenzene) for propranolol extraction and separation by capillary electrophoresis.

AIM: The preparation of magnetic multi-walled carbon nanotube poly(styrene-co-divinylbenzene) for propranolol magnetic solid-phase extraction is described. MATERIALS & METHODS: A study comparing propranolol adsorption and desorption was performed with only magnetic multi-walled carbon nanotubes, and different poly(styrene-co-divinylbenzene) with and without magnetic multi-walled carbon nanotubes. Enantiomeric separation of propranolol took place by cyclodextrin-modified capillary electrophoresis and the method was validated in spiked human urine samples. RESULTS: Recovery values raised when styrene/divinylbenzene millimoles ratio was 19.57:15.80. Enrichment factors increased up to approximately 100, detection limits were 13.8 and 10.5 ng ml-1 for R- and S-propranolol respectively, quantitation limits were 46.0 and 34.8 ng ml-1 for R- and S-propranolol respectively, recoveries from spiked samples ranged from 90.9 to 109.0%, and relative standard deviations were <6.3%. CONCLUSION: This methodology was proven to be more effective than classical solid-phase extraction strategies and may be applied to other kind of biological samples.

Use of capillary electrophoresis for characterisation of vinyl-terminated Au nanoprisms and nanooctahedra.

It is described a simple, rapid and efficient methodology to characterise and separate gold nanoprisms and nanooctahedra by capillary electrophoresis. This technique is suitable to distinguish between morphologies and it can be used as a powerful separation tool after a customised synthesis of both structures. This synthesis was carried out by amending two parameters, temperature and pH, and a sharp decrease was found in nanotriangles when temperature was increased from 70 up to 95°C. However, when the synthesis was performed at a given temperature, an increase in pH did not promote an important change in isolation of any structure until pH = 9.5, critical in the final morphology of the nanoparticle. Gold nanoprisms and nanooctahedra were successfully separated by capillary electrophoresis according to differences in charge-to-mass ratio of the morphologies. Final particle morphology was confirmed by transmission electron microscopy analysis. Under optimal working conditions, a mixture containing both shapes of gold nanoparticles was initially injected and two major peaks were obtained for each structure. Capillary electrophoresis allowed to study pH and temperature influence on both morphologies. It was inferred that the ratio between triangles and octahedra decreased to a great extent when increasing both temperature and pH.

Analysis of silica nanoparticles by capillary electrophoresis coupled to an evaporative light scattering detector.

A simple and rapid methodology has been developed to identify and separate silica nanoparticles (SiO2NPs) of different sizes in aqueous solution by capillary zone electrophoresis coupled to an evaporative light scattering detector (CE-ELSD). SiO2NPs were separated using 3 mM ammonium acetate buffer, containing 1% methanol at pH 6.9. SiO2NPs of 20, 50 and 100 nm were successfully separated under the optimum experimental conditions. CE coupled to ELSD has been proven to be an effective separation technique to determine particles with such small sizes, although the peaks are very close to each other, and it is a promising technique that may allow the separation of other types of nanoparticles. Confirmation by TEM and quantification of the SiO2 content was also carried out by inductively coupled plasma-mass spectrometry (ICP-MS). The new method was applied to the analysis of real samples, in order to assess its ability to avoid matrix effects in the determination of SiO2NPs in these kinds of samples.