Rosario Pereiro

Photoactivated luminescent CdSe quantum dots as sensitive cyanide probes in aqueous solutions

Water-soluble luminescent CdSe quantum dots surface-modified with 2-mercaptoethane sulfonate were synthesized for the selective determination of free cyanide in aqueous solution with high sensitivity (detection limit of 1.1 x 10(-6) M), via analyte-induced changes in their photoluminescence after photoactivation.

Bioanalytics and biolabeling with semiconductor nanoparticles (quantum dots)

In this mini-review recent applications of quantum dots in bioanalytics and biolabeling are discussed. The state-of-the-art of the field is summarized, some selected applications are highlighted, and future directions are suggested.

Nanoparticles as fluorescent labels for optical imaging and sensing in genomics and proteomics

AbstractOptical labelling reagents (dyes and fluorophores) are an essential component of probe-based biomolecule detection, an approach widely employed in a variety of areas including environmental analysis, disease diagnostics, pharmaceutical screening, and proteomic and genomic studies. Recently, functional nanomaterials, as a new generation of high-value optical labels, have been applied to molecular detection. The great potential of such recent optical labels has paved the way for the development of new biomolecule assays with unprecedented analytical performance characteristics, related to sensitivity, multiplexing capability, sample throughput, cost-effectiveness and ease of use. This review aims to provide an overview of recent advances using different nanoparticles (such as quantum dots, rare earth doped nanoparticles or gold nanoparticles) for analytical genomics and proteomics, with particular emphasis on the outlook for different strategies of using nanoparticles for bioimaging and quantitative bioanalytical applications, as well as possibilities and limitations of nanoparticles in such a growing field. FigureNanoparticles for analytical genomics and proteomics, with particular emphasis on bioimaging and quantitative bioanalytical applications of nanoparticles

Laser ablation ICP-MS for quantitative biomedical applications

AbstractLA-ICP-MS allows precise, relatively fast, and spatially resolved measurements of elements and isotope ratios at trace and ultratrace concentration levels with minimal sample preparation. Over the past few years this technique has undergone rapid development, and it has been increasingly applied in many different fields, including biological and medical research. The analysis of essential, toxic, and therapeutic metals, metalloids, and nonmetals in biomedical tissues is a key task in the life sciences today, and LA-ICP-MS has proven to be an excellent complement to the organic MS techniques that are much more commonly employed in the biomedical field. In order to provide an appraisal of the fast progress that is occurring in this field, this review critically describes new developments for LA-ICP-MS as well as the most important applications of LA-ICP-MS, with particular emphasis placed on the quantitative imaging of elements in biological tissues, the analysis of heteroatom-tagged proteins after their separation and purification by gel electrophoresis, and the analysis of proteins that do not naturally have ICP-MS-detectable elements in their structures, thus necessitating the use of labelling strategies. FigureNew developments and most relevant applications of LA-ICP-MS are critically described in this review, with particular emphasis on quantitative strategies currently employ for analysis of proteins in biological tissues

Determination of lead and mercury in sea water by preconcentration in a flow injection system followed by atomic absorption spectrometry detection

The capabilities of three solid chelating reagents were compared for the preconcentration of lead and mercury in high salinity aqueous samples (sea waters). The tested materials were 7-(4-ethyl-1-methyloctyl)-8-hydroxiquinoline (Kelex 100) adsorbed on Bondapack C18 (Kelex-100/C18), 8-hydroxiquinoline immobilized on vinyl co-polymer Toyopearl gel (TSK) and the commercial polystyrene/DVB ion exchange resin with paired iminodiacetate groups (Chelex-100). The two metals preconcentration and final determination were carried out in a flow injection system, coupled on-line to an atomic absorption spectrometric detector. Analytes were preconcentrated in the minicolumn, packed with the materials under investigation, while elution was achieved by injection of 500 mul of an adequate mineral acid solution. The different packing materials and minicolumn designs have been evaluated in terms of sensitivity for simultaneous preconcentration of both metals in sea water. Regarding the solid support, the best results were obtained for the TSK solid phase. Concerning the minicolumn design, the behavior was different for lead and mercury. Lead was quantitatively eluted with 0.5 M HCl and best performance was achieved when packing the solid material in a minicolumn with relatively small volume (1 cm length and 2.5 mm i.d.). In the case of mercury, bigger minicolumn volumes (5.5 cm length and 5.0 mm i.d.) and mixtures, 2 M HCl+1 M HNO(3), were required for its quantitative recovery and elution. The system has been evaluated for quantitative determination of the two metals under study in different Asturian coastal aqueous samples.

Room temperature phosphorescence optosensing of benzo[a]pyrene in water using halogenated molecularly imprinted polymers

A selective optosensor for benzo[a]pyrene (BaP) determination in water samples, using a molecularly imprinted polymer (MIP) for the recognition of the analyte, has been developed. Detection was based on measurements of the native strong room temperature phosphorescence (RTP) emission from the BaP recognized by the MIP. The non-covalent MIP was synthesized using BaP as a molecular template. Different halogenated-bisphenol A compounds were compared as precursors in the polymerization (thus ensuring the presence of a heavy atom, required to induce RTP emission from the analyte). In the developed optosensor, samples are injected in a flow system and the analyte is on-line retained onto the polymeric material. In the absence of oxygen (using sodium sulfite as the oxygen scavenger) the heavy atom present in the MIP structure induced analytically useful RTP emission from the recognized BaP. After measurement of the luminescent emission, the sensing material can be easily regenerated by passing 2 mL of methanol over the MIP. The optosensor demonstrated a very high selectivity for BaP determination in water even in the presence of other luminophores that could be non-specifically adsorbed onto the MIP surface. Under optimal experimental conditions, a benzo[a]pyrene detection limit of 10 ng L(-1) (20 mL sample injection volume) was achieved with good reproducibility (a RSD of 3% was obtained for 1 microg L(-1) BaP). Finally, the proposed optosensor was successfully applied to the analysis of spiked natural water with BaP.

Inorganic mass spectrometry as a tool for characterisation at the nanoscale

AbstractInorganic mass spectrometry techniques may offer great potential for the characterisation at the nanoscale, because they provide unique elemental information of great value for a better understanding of processes occurring at nanometre-length dimensions. Two main groups of techniques are reviewed: those allowing direct solid analysis with spatial resolution capabilities, i.e. lateral (imaging) and/or in-depth profile, and those for the analysis of liquids containing colloids. In this context, the present capabilities of widespread elemental mass spectrometry techniques such as laser ablation coupled with inductively coupled plasma mass spectrometry (ICP-MS), glow discharge mass spectrometry and secondary ion/neutral mass spectrometry are described and compared through selected examples from various scientific fields. On the other hand, approaches for the characterisation (i.e. size, composition, presence of impurities, etc.) of colloidal solutions containing nanoparticles by the well-established ICP-MS technique are described. In this latter case, the capabilities derived from the on-line coupling of separation techniques such as field-flow fractionation and liquid chromatography with ICP-MS are also assessed. Finally, appealing trends using ICP-MS for bioassays with biomolecules labelled with nanoparticles are delineated. FigureInorganic mass spectrometry: an emerging tool for nanotechnology

Pulsed radiofrequency glow discharge time of flight mass spectrometer for the direct analysis of bulk and thin coated glasses

Direct solid analysis of bulk and thin coated glasses by pulsed radiofrequency (rf) glow discharge time-of-flight mass spectrometry (GD-TOFMS) is investigated. Modulated low pressure plasma created by pulsed-rf-GD has been coupled to a fast TOFMS in order to obtain complete mass spectra information from the different GD pulse domains (pre-peak, plateau and afterglow). In particular, it was observed that the analytes show the highest atomic ion signals in the afterglow region some hundred microseconds after the maximum of the Ar ion signal. However, it should be highlighted that the analyte ions exhibited their peak maxima at different delay times, depending on the element, after the end of the GD pulse. Such ion signal delays have been measured for different selected isotopes, covering a mass spectrum from light to heavy isotopes at different conditions of pressure and applied power. The results showed that ion signal delays are influenced by both the isotope mass and the pressure of the GD. Furthermore, GD operating conditions (pressure and applied power) were optimised in terms of sensitivity, using a bulk glass certified reference material (NIST 1411). The best analytical performance was observed at low pressure (150–200 Pa) and high applied power (135 W). Moreover, different pulse GD duty cycles (relationship between pulse duration and pulse period) were investigated. An optimum value of 50–65% duty-cycle was selected considering the signal stability and the signal intensity. The previously optimized pulsed-rf-GD-TOFMS system was then evaluated for qualitative in-depth profile analysis of thin coatings deposited onto thick glass substrates. High depth resolution (nm range), comparable to that obtained using rf-GD-OES was achieved. However, the observed depth resolution using the ToF-SIMS system is still superior. In this sense, analytical figures of merit observed in our pulsed-rf-GD-TOFMS demonstrate its great analytical potential for high depth resolution analysis of coated glasses.

A comparison of non-pulsed radiofrequency and pulsed radiofrequency glow discharge orthogonal time-of-flight mass spectrometry for analytical purposes

The analytical potential of a radiofrequency glow discharge orthogonal time-of-flight mass spectrometer (RFGD-TOFMS) has been evaluated in both pulsed and non-pulsed modes. A certified reference steel was selected for this study. The operating conditions of the GD plasma (pressure and applied power) were optimized in terms of sensitivity. Additionally, duty cycle and pulse width parameters were investigated in the pulsed RF mode. In this case, high analyte ion signals and improved signal to background ratios were measured after the end of the pulse, in the so-called afterglow domain. The analyte ion signals were normalized to sputtering rates to compare different operating conditions. It was found that the sensitivity in the pulsed mode was improved in comparison to the non-pulsed mode; however, the factor of enhancement is element dependent. Moreover, improved analytical performance was obtained in terms of ion separation capabilities as well as in terms of accuracy and precision in the evaluation of the isotopic ratios, using the pulsed RFGD-TOFMS. Additionally, depth profile analyses of a Zn/Ni coating on steel were performed and the non-pulsed and pulsed RFGD-TOFMS analytical performances were compared.

Investigations of the effect of hydrogen, nitrogen or oxygen on the in-depth profile analysis by radiofrequency argon glow discharge-optical emission spectrometry

The effect of adding either hydrogen, nitrogen or oxygen (from 0.5 to 10% v/v) to an argon radiofrequency glow discharge (rf-GD) for optical emission spectrometric measurements has been investigated. Changes to the dc-bias voltage developed for conductive samples, to the crater shapes produced (both in homogeneous conductive materials, as austenitic stainless steels, and in a glass sample), and to the depth resolution for thin films on a glass substrate have been measured, operating the rf-GD at constant pressure and constant delivered power. Concerning the dc-bias voltages, the observed general effect was an increase of the voltage with increasing added hydrogen. For nitrogen and oxygen additions, an enhancement of the dc-bias was also observed, as compared to pure argon, but just in the interval 2–10% v/v of added gas. Experiments related to the crater shapes showed that working at 40 W and 600 Pa the craters produced in stainless steels increased their convexity with increasing percentages of any of the three molecular gases assayed. However, such convexity was reduced by working at lower delivered powers. The studies on adding hydrogen, nitrogen or oxygen to the argon rf-GD on the crater shapes produced in a homogeneous glass sample showed very good crater shapes in the glass at 20 W and 450 Pa, for most of the assayed plasma gas compositions in the interval 0.5–5% molecular gas/argon. Finally, qualitative profiles of two glass samples covered with multilayers, in the order of nanometres (6–27 nm), were measured for different plasma gas compositions and their relative depth resolution calculated. Results show that the plasma gas mixtures under investigation should be considered, at least for qualitative in-depth profile analysis, as they seem to offer a great potential to improve depth-resolution in rf-GD work.