Luminescent Citrate-Functionalized Terbium-Substituted Carbonated Apatite Nanomaterials: Structural Aspects, Sensitized Luminescence, Cytocompatibility, and Cell Uptake Imaging.

This work explores the preparation of luminescent and biomimetic Tb-doped citrate-functionalized carbonated apatite nanoparticles. These nanoparticles were synthesized employing a citrate-based thermal decomplexing precipitation method, testing a nominal Tb doping concentration between 0.001 M to 0.

Biomimetic Citrate-Coated Luminescent Apatite Nanoplatforms for Diclofenac Delivery in Inflammatory Environments.

Luminescent nanoparticles are innovative tools for medicine, allowing the imaging of cells and tissues, and, at the same time, carrying and releasing different types of molecules. We explored and compared the loading/release ability of diclofenac (COX-2 antagonist), in both undoped- and luminescent Terbium (Tb)-doped citrate-coated carbonated apatite nanoparticles at different temperatures (25, 37, 40 °C) and pHs (7.4, 5.

Crystallization, Luminescence and Cytocompatibility of Hexagonal Calcium Doped Terbium Phosphate Hydrate Nanoparticles.

Luminescent lanthanide-containing biocompatible nanosystems represent promising candidates as nanoplatforms for bioimaging applications. Herein, citrate-functionalized calcium-doped terbium phosphate hydrate nanophosphors of the rhabdophane type were prepared at different synthesis times and different Ca/Tb ratios by a bioinspired crystallization method consisting of thermal decomplexing of Ca/Tb/citrate/phosphate/carbonate solutions. Nanoparticles were characterized by XRD, TEM, SEM, HR-TEM, FTIR, Raman, Thermogravimetry, inductively coupled plasma spectroscopy, thermoanalysis, dynamic light scattering, electrophoretic mobility, and fluorescence spectroscopy.

Self-Assembled Type I Collagen-Apatite Fibers with Varying Mineralization Extent and Luminescent Terbium Promote Osteogenic Differentiation of Mesenchymal Stem Cells.

This work explores in depth the simultaneous self-assembly and mineralization of type I collagen by a base-acid neutralization technique to prepare biomimetic collagen-apatite fibrils with varying mineralization extent and doped with luminescent bactericidal Tb ions. Two variants of the method are tested: base-acid titration, a solution of Ca(OH) is added dropwise to a stirred solution containing type I collagen dispersed in H PO ; and direct mixing, the Ca(OH) solution is added by fast dripping onto the acidic solution. Only the direct mixing variant yielded an effective control of calcium phosphate polymorphism.

Polycyclic aromatic hydrocarbons in edible oils: An overview on sample preparation, determination strategies, and relative abundance of prevalent compounds.

Polycyclic aromatic hydrocarbons (PAHs) are food contaminants whose presence in foodstuffs is especially alarming due to their carcinogenic character. These substances are highly lipophilic and thus, unsafe levels of these compounds have been found in edible fats and oils. Efficient methodologies to determine such molecules in lipidic matrixes are therefore essential.

Self-Referenced Multifrequency Phase-Resolved Luminescence Spectroscopy.

Phase-resolved luminescence chemical sensors provide the analyte determination based on the estimation of the luminescence lifetime. The lifetime is estimated from an analysis of the amplitudes and/or phases of the excitation and emission signals at one or several modulation frequencies. This requires recording both the excitation signal (used to modulate the light source) and the emission signal (obtained from an optical transducer illuminated by the luminescent sensing phase).

A Polynomial-Exponent Model for Calibrating the Frequency Response of Photoluminescence-Based Sensors.

In this work, we propose a new model describing the relationship between the analyte concentration and the instrument response in photoluminescence sensors excited with modulated light sources. The concentration is modeled as a polynomial function of the analytical signal corrected with an exponent, and therefore the model is referred to as a polynomial-exponent (PE) model. The proposed approach is motivated by the limitations of the classical models for describing the frequency response of the luminescence sensors excited with a modulated light source, and can be considered as an extension of the Stern-Volmer model.

Eu-Doped Citrate-Coated Carbonated Apatite Luminescent Nanoprobes for Drug Delivery.

In the field of Nanomedicine, there is an increasing demand for new inorganic nanophosphors with low cytotoxicity and efficient loading-release ability of drugs for applications in bioimaging and drug delivery. This work assesses the potentiality of matured Eu-doped citrate-coated carbonated apatite nanoparticles to be used as theranostic platforms, for bioimaging, as luminescent nanoprobes, and for drug delivery applications, using Doxorubicin as a model drug. The drug adsorption isotherm fits the Langmuir-Freundlich (LF) model, showing that the Eu:cit-cAp nanoparticles can carry a maximum of 0.

Bioinspired crystallization, sensitized luminescence and cytocompatibility of citrate-functionalized Ca-substituted europium phosphate monohydrate nanophosphors.

Biocompatible nanosystems exhibiting long-lifetime (∼millisecond) luminescence features are particularly relevant in the field of bioimaging. In this study, citrate-functionalized calcium-doped europium phosphates nanophosphors of the rhabdophane type were prepared at different synthesis times by a bioinspired crystallization route, consisting in thermal decomplexing of Ca/Eu /citrate/phosphate/carbonate solutions. The general formula of this material is CaEu(PO)(HPO)·nHO, with α ranging from 0 to 0.

Development of a folic acid molecularly imprinted polymer and its evaluation as a sorbent for dispersive solid-phase extraction by liquid chromatography coupled to mass spectrometry.

This work shows the development of a molecularly imprinted polymer to determine folic acid (FA) in food extracts by using dispersive solid-phase extraction and liquid chromatography coupled to mass spectrometry (LC-MS). Herewith, combinations of monomers (methacrylic acid (MAA), 4-vinylpyridine (4VPy) and vinylbenzyl trimethylammonium chloride (VBTMAC)) and crosslinkers (ethylene glycol dimethacrylate (EGDMA) and divinyl benzene (DVB)) were tested in appropriate solvents. Isotherm tests revealed that the MIP with the highest affinity was obtained by combining VBTMAC and EGDMA.

Evaluation of two sterically directed attachments of biomolecules on a coaxial nanofibre membrane to improve the development of optical biosensors.

In this study, we have optimised the sterically directed attachment of biomolecules on the surface of coaxial membranes prepared by co-electrospinning which have been proved to be a material with very high performance for the development of biosensors with optical oxygen transduction. Uricase has been used as model enzyme. Two sterically directed strategies: a) covalent attachment via maleimide, and b) affinity bonding via biotin-streptavidin interaction, have been tested in order to preserve the enzymatic activity of uricase and to improve the analytical figures of merits on the determination of uric acid.

A multifunctional material based on co-electrospinning for developing biosensors with optical oxygen transduction.

A multifunctional material based on co-electrospinning has been developed as a basic material for the development of biosensors with optical oxygen transduction. It is based on coaxial nanofibres: inner fibres containing an oxygen sensitive dye and outer fibres containing aldehyde groups to allow the formation of Schiff bases with the amino groups of the enzyme. The resulting material preserves the oxygen sensing properties of the inner optical transducer as well as exhibits a high capacity for immobilizing molecules on its surface.

Luminescent biomimetic citrate-coated europium-doped carbonated apatite nanoparticles for use in bioimaging: physico-chemistry and cytocompatibility.

Nanomedicine covers the application of nanotechnologies in medicine. Of particular interest is the setup of highly-cytocompatible nanoparticles for use as drug carriers and/or for medical imaging. In this context, luminescent nanoparticles are appealing nanodevices with great potential for imaging of tumor or other targetable cells, and several strategies are under investigation.

High performance optical oxygen sensors based on iridium complexes exhibiting interchromophore energy shuttling.

A doubly pyrene-grafted bis-cyclometallated iridium complex with engineered electronically excited states demonstrates reversible electronic energy transfer between adjacent chromophores giving rise to extremely long-lived red luminescence in solution (τ = 480 μs). Time-resolved spectroscopic studies afforded determination of pertinent photophysical parameters including rates of energy transfer and energy distribution between constituent chromophores in the equilibrated excited molecule (ca. 98% on the organic chromophores).

A novel optical biosensor for direct and selective determination of serotonin in serum by Solid Surface-Room Temperature Phosphorescence.

This paper describes a novel biosensor which combines the use of nanotechnology (non-woven nanofibre mat) with Solid Surface-Room Temperature Phosphorescence (SS-RTP) measurement for the determination of serotonin in human serum. The developed biosensor is simple and can be directly applied in serum; only requires a simple clean-up protocol. Therefore it is the first time that serotonin is analysed directly in serum with a non-enzymatic technique.

Novel optical sensing film based on a functional nonwoven nanofibre mat for an easy, fast and highly selective and sensitive detection of tryptamine in beer.

In this paper, the combination of Solid Surface-Room Temperature Phosphorescence (SS-RTP) and nanotechnology has led to a new approach in the detection of biogenic amines in complex matrices. This novel approach allows, for the first time, the direct determination of the concentration of tryptamine in beers. The novelty of the proposed optical sensor resides in its simplicity, rapidity, absence of complex chromatographic separation, sample clean-up, preconcentration, and derivatization protocols.

Copper(I) complexes as alternatives to iridium(III) complexes for highly efficient oxygen sensing.

The complex [Cu(xantphos)(dmp)][PF6] (dmp = 2,9-dimethyl-1,10-phenanthroline) in a nanostructured metal oxyde matrix shows better sensitivity to oxygen (KSV = 9.74 ± 0.87 kPa(-1) between 0 and 1 kPa pO2 and 5.

Improved multifrequency phase-modulation method that uses rectangular-wave signals to increase accuracy in luminescence spectroscopy.

We propose a novel multifrequency phase-modulation method for luminescence spectroscopy that uses a rectangular-wave modulated excitation source with a short duty cycle. It is used for obtaining more detailed information about the luminescence system: the information provided by different harmonics allows estimating a model for describing the global frequency response of the luminescent system for a wide range of analyte concentration and frequencies. Additionally, the proposed method improves the accuracy in determination of the analyte concentration.

Direct observation of reversible electronic energy transfer involving an iridium center.

A cyclometalated iridium complex is reported where the core complex comprises naphthylpyridine as the main ligand and the ancillary 2,2'-bipyridine ligand is attached to a pyrene unit by a short alkyl bridge. To obtain the complex with satisfactory purity, it was necessary to modify the standard synthesis (direct reaction of the ancillary ligand with the chloro-bridged iridium dimer) to a method harnessing an intermediate tetramethylheptanolate-based complex, which was subjected to acid-promoted removal of the ancillary ligand and subsequent complexation. The photophysical behavior of the bichromophoric complex and a model complex without the pendant pyrene were studied using steady-state and time-resolved spectroscopies.

Electrophoretic deposition as a new approach to produce optical sensing films adaptable to microdevices.

We report the fabrication of optical oxygen sensor films using electrophoretic deposition (EPD) of poly(styrene-co-maleic anhydride) nanoparticles containing the oxygen-sensitive dye platinum(ii) meso-tetra(pentafluorophenyl)porphine. Compared to other deposition methods, the EPD is simple and allows easy control over deposition, which is crucial for the implementation of optical sensing films in microdevices. By optimizing the synthesis of the functional nanoparticles, anodic EPD can be performed.

High performance optical sensing nanocomposites for low and ultra-low oxygen concentrations using phase-shift measurements.

The accurate and real-time measurement of low and ultra-low concentrations of oxygen using non-invasive methods is a necessity for a multitude of applications, from brewing beer to developing encapsulating barriers for optoelectronic devices. Current optical methods and sensing materials often lack the necessary sensitivity, signal intensity, or stability for practical applications. In this report we present a new optical sensing nanocomposite resulting in an outstanding overall performance when combined with the phase-shift measurement method (determination of luminescence lifetime in the frequency domain).

New fluorescent pH sensors based on covalently linkable PET rhodamines.

A new class of rhodamines for the application as indicator dyes in fluorescent pH sensors is presented. Their pH-sensitivity derives from photoinduced electron transfer between non-protonated amino groups and the excited chromophore which results in effective fluorescence quenching at increasing pH. The new indicator class carries a pentafluorophenyl group at the 9-position of the xanthene core where other rhodamines bear 2-carboxyphenyl substituents instead.

In vitro oxygen sensing using intraocular microrobots.

We present a luminescence oxygen sensor integrated with a wireless intraocular microrobot for minimally-invasive diagnosis. This microrobot can be accurately controlled in the intraocular cavity by applying magnetic fields. The microrobot consists of a magnetic body susceptible to magnetic fields and a sensor coating.

Synthesis of caffeic acid molecularly imprinted polymer microspheres and high-performance liquid chromatography evaluation of their sorption properties.

In the current work, a molecularly imprinted polymer (MIP) has been synthesised and used to enable the extraction of a naturally-occurring antioxidant from complex media. More specifically, we describe the first example of a caffeic acid (CA) MIP which has been synthesised in the form of well-defined polymer microspheres, and its use for the extraction of CA from fruit juice sample. The CA MIP was synthesised by precipitation polymerisation using 4-vinylpyridine as functional monomer, divinylbenzene-80 as crosslinker and acetonitrile:toluene (75/25, v/v) as porogen.