María Teresa Fernández-Argüelles

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

Elemental ratios for characterization of quantum-dots populations in complex mixtures by asymmetrical flow field-flow fractionation on-line coupled to fluorescence and inductively coupled plasma mass spectrometry

Separation and identification of nanoparticles of different composition, with similar particle diameter, coexisting in heterogeneous suspensions of polymer-coated CdSe/ZnS quantum dots (QDs) have been thoroughly assessed by asymmetric flow field-flow fractionation (AF4) coupled on-line to fluorescence and inductively coupled plasma mass spectrometry (ICPMS) detectors. Chemical characterization of any previously on-line separated nanosized species was achieved by the measurement of the elemental molar ratios of every element involved in the synthesis of the QDs, using inorganic standards and external calibration by flow injection analysis (FIA). Such elemental molar ratios, strongly limited so far to pure single nanoparticles suspensions, have been achieved with adequate accuracy by coupling for the first time an ICP-QQQ instrument to an AF4 system. This hyphenation turned out to be instrumental to assess the chemical composition of the different populations of nanoparticles coexisting in the relatively complex mixtures, due to its capabilities to detect the hardly detectable elements involved in the synthesis. Interestingly such information, complementary to that obtained by fluorescence, was very valuable to detect and identify unexpected nanosized species, present at significant level, produced during QDs synthesis and hardly detectable by standard approaches.

Flow-through optosensing of 1-naphthaleneacetic acid in water and apples by heavy atom induced-room temperature phosphorescence measurements

A sensitive and selective phosphorimetric method for the determination of 1-naphthaleneacetic acid (1-NAA) based on a flow-injection system connected to a flow cell packed with a solid support and placed in the sample compartment of a conventional luminescence spectrometer is described. A non-ionic solid polymeric resin Amberlite XAD-7 is used for the packing. After injection of the sample, 1-NAA is on-line retained in the packed resin and measurements of the heavy atom induced (HAI)-room temperature phosphorescence (RTP) emission (lambda(ex)/lambda(em)=292/490nm) from this native luminescent compound are taken. The optimum experimental conditions were investigated by injecting 2ml samples of an aqueous solution of 1-NAA in the flow system. A concentration 0.15moll(-1) of thallium(I) ions, as heavy atom, both in the samples and the carrier flow, was finally selected. Also, a concentration of 6mmoll(-1) of sulphite was optimal for ensuring the necessary deoxygenation of the system at the selected flow rate of 0.8mlmin(-1). After measurement, the solid support was efficiently regenerated by injecting 1ml of a mixture water:acetone in a ratio 1:1 (v/v) into the flow. The detection limit (3sigma criterion) was 1.2ngml(-1) of 1-NAA. The repeatability (R.S.D.) for five replicates of a sample containing 50ngml(-1) of analyte turned out to be +/-3% and the calibration graphs proved to be linear up to 500ngml(-1) of 1-NAA (maximum concentration assayed). The effect of potential interferences from other organic species which can be also used as plant growth regulators, as well as from various inorganic cations and anions, has been investigated as well. The method was successfully applied to the determination of low levels of this plant growth regulator in natural waters (river and fountain waters) and apples.

The influence of surface coating on the properties of water-soluble CdSe and CdSe/ZnS quantum dots

It is well-known that ligands coating the surface of luminescent semiconductor nanocrystals (quantum dots [QDs]) play an important role in the preparation, stability and physical properties of the colloidal QDs in both organic and aqueous media. Here we report on the synthesis and characterization of core (CdSe QDs) and core–shell structured QDs (CdSe/ZnS QDs), both of them stabilized in aqueous medium through different mechanisms of modification of their surface chemistry. The approaches evaluated for QDs transfer to aqueous media were ligand exchange and polymer coating. Experiments were performed using two typical thioalkyl acids as ligands, namely mercaptoacetic acid (QDs-MAA) and 2-mercaptoethanesulphonic acid (QDs-MES), and an amphiphilic polymer (PQDs) based on poly(maleic anhydride) functional groups. The effects of pH (buffer solution), illumination and the presence of ions in the QD environment on the spectroscopic properties of the different synthesized QDs are reported. The stability of the prepared QDs has been comparatively evaluated aimed to elucidate which surface chemistry provides the suitable properties to be employed as fluorescence labels in distinct types of applications. The experimental results and conclusions will be useful for the development of sensitive sensors or assays adopting QDs as fluorescence labels.

Room temperature phosphorimetric determination of bromate in flour based on energy transfer.

Determination of bromate ions in contaminated flour samples by using a room temperature phosphorescence (RTP) optosensor is described. The optosensor is based on the non-radiative energy transfer from α-bromonaphthalene (a phosphorescent molecule insensitive to the presence of the analyte) acting as donor, to an energy acceptor bromate-sensitive molecule (trifluoperazine hydrochloride). The RTP emission of the selected donor greatly overlaps with the absorption spectrum of the acceptor, resulting in a decrease of the measured signal as the concentration of bromate ions increases. A simple and general procedure is proposed to carry out the incorporation of both the donor and acceptor molecules in an appropriate solid material (sensing phase) through the co-immobilization of the species in a sol-gel inorganic matrix. The optimum amounts of the sol-gel precursors, including silica precursors, type of catalysis, and concentrations of donor and acceptor molecules, have been evaluated in order to obtain the best analytical features of the proposed optosensor for bromate determination. The highly stable developed sensing phase shows a selective and reversible response towards bromate even in presence of dissolved oxygen (a well-known quencher of the RTP). The calibration graphs were linear up to 200 mg L(-1), with a detection limit for bromate dissolved in aqueous medium of 0.2 mg L(-1). Sample throughput of the proposed optosensor was about 18 measurements h(-1). Application of the developed sensing phase was successfully proved for the detection of bromate ions in commercial flours, obtaining good recoveries.

Green synthesis of multimodal ‘OFF–ON’ activatable MRI/optical probes

Diagnosis by MRI is frequently non-trivial due to the low sensitivity of the technique. Signal enhancing contrast agents (CAs) are used to aid in the analysis of MR images. We present here a simple protocol for the preparation of responsive CAs based on Mn nanosheets. Mn nanostructures presented here undergo a chemical and structural change in the presence of altered physiological conditions that activate their signal. This strategy allows for a reduction of background, increasing the sensitivity of the technique. The simple synthetic protocol followed allows for the combination of the nanosheets with reporter molecules for other imaging techniques, like carbon quantum dots for optical imaging.

In Vivo Applications of Inorganic Nanoparticles

Chapter 9 is primarily concerned with in vivo applications of nanoparticles. This very broad review includes aspects such as bioconjugation, which is a pre-requisite for any in vivo application, and nanotoxicity. We introduce the two main fields of in vivo applications of nanoparticles: bioimaging and therapy. In the field of imaging, magnetic resonance imaging and optical imaging are distinguished, and the latter is further subdivided into groups of luminophores. These groups include gold nanoparticles, semiconductor quantum dots and rare-earth-doped nanoparticles. In Section 9.4, we discuss the methods of hyperthermia, photodynamic therapy and magnetic targeting. The aim of this chapter is not to provide in-depth insights into the different applications but to give an overview of possibilities and limitations when nanoparticles are used within living organisms.

Capping of Mn-Doped ZnS Quantum Dots with DHLA for Their Stabilization in Aqueous Media: Determination of the Nanoparticle Number Concentration and Surface Ligand Density

Colloidal Mn2+-doped ZnS quantum dots (QDs) were synthesized, surface modified, and thoroughly characterized using a pool of complementary techniques. Cap exchange of the native l-cysteine coating of the QDs with dihydrolipoic acid (DHLA) ligands is proposed as a strategy to produce nanocrystals with a strong phosphorescent-type emission and improved aqueous stability. Moreover, such a stable DHLA coating can facilitate further bioconjugation of these QDs to biomolecules using established reagents such as cross-linker molecules. First, a structural and morphological characterization of the l-cysteine QD core was performed by resorting to complementary techniques, including X-ray powder diffraction (XRD) and microscopy tools. XRD patterns provided information about the local structure of ions within the nanocrystal structure and the number of metal atoms constituting the core of a QD. The judicious combination of the data obtained from these complementary characterization tools with the analysis of the QDs using inductively coupled plasma-mass spectrometry (ICP-MS) allowed us to assess the number concentration of nanoparticles in an aqueous sample, a key parameter when such materials are going to be used in bioanalytical or toxicological studies. Asymmetric flow field-flow fractionation (AF4) coupled online to ICP-MS detection proved to be an invaluable tool to compute the number of DHLA molecules attached to the surface of a single QD, a key feature that is difficult to estimate in nanoparticles and that critically affects the behavior of nanoparticles when entering the biological media (e.g., cellular uptake, biodistribution, or protein corona formation). This hybrid technique also allowed us to demonstrate that the elemental composition of the nanoparticle core remains unaffected after the ligand exchange process. Finally, the photostability and robustness of the DHLA-capped QDs, critical parameters for bioanalytical applications, were assessed by molecular luminescence spectroscopy.