Phosphineoxide-Chelated Europium(III) Nanoparticles for Ceftriaxone Detection.

The present work demonstrates the optimization of the ligand structure in the series of bis(phosphine oxide) and ß-ketophosphine oxide representatives for efficient coordination of Tb3+ and Eu3+ ions with the formation of the complexes exhibiting high Tb3+- and Eu3+-centered luminescence. The analysis of the stoichiometry and structure of the lanthanide complexes obtained using the XRD method reveals the great impact of the bridging group nature between two phosphine oxide moieties on the coordination mode of the ligands with Tb3+ and Eu3+ ions. The bridging imido-group facilitates the deprotonation of the imido- bis(phosphine oxide) ligand followed by the formation of tris-complexes. The spectral and PXRD analysis of the separated colloids indicates that the high stability of the tris-complexes provides their safe conversion into polystyrenesulfonate-stabilized colloids using the solvent exchange method. The red Eu3+-centered luminescence of the tris-complex exhibits the same specificity in the solutions and the colloids. The pronounced luminescent response on the antibiotic ceftriaxone allows for sensing the latter in aqueous solutions with an LOD value equal to 0.974 µM.

Effect of the alkali vs iron ratio on glass transition temperature and vibrational properties of synthetic basalt-like glasses.

Volcanic eruptions generate huge amounts of material with a wide range of compositions and therefore different physicochemical properties. We present a combined Raman and calorimetric study carried out on four synthetic basaltic glasses with different alkali vs iron ratio which spans the typical compositions of basalts on Earth. Differential scanning calorimetry shows that changes of this ratio modify the glass transition interval whereas Raman spectra allow to gain insight about the structure of the glass in the microscopic and macroscopic range. Indeed, our Raman analysis is extended from the high frequency region, characterized by the molecular peaks, to the very low frequency region where glasses exhibit the boson peak. Spectra show a variation of the non-bridging oxygens number that affects the medium range order of the glass and the network interconnections. In the considered substitution interval, the boson peak shape is conserved while its position shift upwards. This means that increasing the alkali vs iron content, the elastic medium hardens but it does not change nature. This study emphasizes the importance of considering the full-range spectra when analysing multicomponent or natural systems with small chemical variations.

Role of PSS-based assemblies in stabilization of Eu and Sm luminescent complexes and their thermoresponsive luminescence.

The present work introduces self-assembled polystyrenesulfonate (PSS) molecules as soft nanocapsules for incorporation of Eu3+-Sm3+ complexes by the solvent exchange procedure. The high levels of Eu3+- and Sm3+-luminescence of the complexes derives from the ligand-to-metal energy transfer, in turn, resulted from the complex formation of Eu3+and Sm3+ ions with the three recently synthesized cyclophanic 1,3-diketones. The structural features of the ligands are optimized for the high thermal sensitivity of Eu3+- luminescence in DMF solutions. The PSS-nanocapsules (∼100 nm) provide both colloid and chemical stabilization of the ultrasmall (3-5 nm) nanoprecipitates of the complexes, although their luminescence spectra patterns and excited state lifetimes differ from the values measured for the complexes in DMF solutions. The specific concentration ratio of the Eu3+-Sm3+ complexes in the DMF solutions allows to tune the intensity ratio of the luminescence bands at 612 and 650 nm in the heterometallic Eu3+-Sm3+ colloids. The thermal sensitivity of the Eu3+- and Sm3+-luminescence of the complexes derives from the static quenching both in PSS-colloids and in DMF solutions, while the thermo-induced dynamic quenching of the luminescence is significant only in DMF solutions. The reversibility of thermo-induced luminescence changes of the Eu3+-Sm3+ colloids is demonstrated by six heating-cooling cycles. The DLS measurements before and after the six cycles reveal the invariance of the PSS-based capsule as the prerequisite for the recyclability of the temperature monitoring through the ratio of Eu3+-to- Sm3+ luminescence.

Investigation on the Luminescence Properties of InMO4 (M = V5+, Nb5+, Ta5+) Crystals Doped with Tb3+ or Yb3+ Rare Earth Ions.

We explore the potential of Tb- and Yb-doped InVO4, InTaO4, and InNbO4 for applications as phosphors for light-emitting sources. Doping below 0.2% barely change the crystal structure and Raman spectrum but provide optical excitation and emission properties in the visible and near-infrared (NIR) spectral regions. From optical measurements, the energy of the first/second direct band gaps was determined to be 3.7/4.1 eV in InVO4, 4.7/5.3 in InNbO4, and 5.6/6.1 eV in InTaO4. In the last two cases, these band gaps are larger than the fundamental band gap (being indirect gap materials), while for InVO4, a direct band gap semiconductor, the fundamental band gap is at 3.7 eV. As a consequence, this material shows a strong self-activated photoluminescence centered at 2.2 eV. The other two materials have a weak self-activated signal at 2.2 and 2.9 eV. We provide an explanation for the origin of these signals taking into account the analysis of the polyhedral coordination around the pentavalent cations (V, Nb, and Ta). Finally, the characteristic green (5D4 → 7F J ) and NIR (2F5/2 → 2F7/2) emissions of Tb3+ and Yb3+ have been analyzed and explained.

Impact of Oxalate Ligand in Co-Precipitation Route on Morphological Properties and Phase Constitution of Undoped and Rh-Doped BaTiO3 Nanoparticles.

In order to design and tailor materials for a specific application like gas sensors, the synthesis route is of great importance. Undoped and rhodium-doped barium titanate powders were successfully synthesized by two routes; oxalate route and classic route (a modified conventional route where solid-state reactions and thermal evaporation induced precipitation takes place). Both powders were calcined at different temperatures. X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDX) and Brunauer-Emmet-Teller (BET) analyses are employed to identify the phases and polymorphs, to determine the morphology, the chemical composition and the specific surface area of the synthesized materials, respectively. The so-called oxalate route yields pure BaTiO3 phase for undoped samples at 700 °C and 900 °C (containing both cubic and tetragonal structures), while the classic route-synthesized powder contains additional phases such as BaCO3, TiO2 and BaTi2O5. Samples of both synthesis routes prepared by the addition of Rh contain no metallic or oxide phase of rhodium. Instead, it was observed that Ti was substituted by Rh at temperatures 700 °C and 900 °C and there was some change in the composition of BaTiO3 polymorph (increase of tetragonal structure). Heat-treatments above these temperatures show that rhodium saturates out of the perovskite lattice at 1000 °C, yielding other secondary phases such as Ba3RhTi2O9 behind. Well-defined and less agglomerated spherical nanoparticles are obtained by the oxalic route, while the classic route yields particles with an undefined morphology forming very large block-like agglomerates. The surface area of the synthesized materials is higher with the oxalate route than with the classic route (4 times at 900 °C). The presence of the oxalate ligand with its steric hindrance that promotes the uniform distribution and the homogeneity of reactants could be responsible for the great difference observed between the powders prepared by two preparation routes.

Dual red-NIR luminescent EuYb heterolanthanide nanoparticles as promising basis for cellular imaging and sensing.

The present work introduces ternary Ln(III) (Ln = Eu, Yb, Lu) complexes with thenoyltriflouro1,3-diketonate (TTA-) and phosphine oxide derivative (PhO) as building blocks for core-shell nanoparticles with both Eu(III)- or Yb(III)-centered luminescence and the dual Eu(III)-Yb(III)-centered luminescence. Solvent-mediated self-assembly of the complexes is presented herein as the procedure for formation of EuLu, EuYb and YbLu heterometallic or homometallic cores coated by hydrophilic polystyrenesulfonate-based shells. Steady state and time resolved Eu-centered luminescence in homolanthanide and heterolanthanide EuLu and EuYb cores is affected by Eu → Eu and Eu → Yb energy transfer due to a close proximity of the lanthanide blocks within the core of nanoparticles. The Eu → Yb energy transfer is highlighted to be the reason for the enhancement of the NIR Yb-centered luminescence. Efficient cellular uptake, low cytotoxicity towards normal and cancer cells, and sensing ability of EuYb nanoparticles on lomefloxacin additives via both red and NIR channels make them promising as cellular imaging agents and sensors.

Ag-Sensitized Yb3+ Emission in Glass-Ceramics.

Rare earth doped materials play a very important role in the development of many photonic devices, such as optical amplifiers and lasers, frequency converters, solar concentrators, up to quantum information storage devices. Among the rare earth ions, ytterbium is certainly one of the most frequently investigated and employed. The absorption and emission properties of Yb3+ ions are related to transitions between the two energy levels ²F7/2 (ground state) and ²F5/2 (excited state), involving photon energies around 1.26 eV (980 nm). Therefore, Yb3+ cannot directly absorb UV or visible light, and it is often used in combination with other rare earth ions like Pr3+, Tm3+, and Tb3+, which act as energy transfer centres. Nevertheless, even in those co-doped materials, the absorption bandwidth can be limited, and the cross section is small. In this paper, we report a broadband and efficient energy transfer process between Ag dimers/multimers and Yb3+ ions, which results in a strong PL emission around 980 nm under UV light excitation. Silica-zirconia (70% SiO2-30% ZrO2) glass-ceramic films doped by 4 mol.% Yb3+ ions and an additional 5 mol.% of Na2O were prepared by sol-gel synthesis followed by a thermal annealing at 1000 °C. Ag introduction was then obtained by ion-exchange in a molten salt bath and the samples were subsequently annealed in air at 430 °C to induce the migration and aggregation of the metal. The structural, compositional, and optical properties were investigated, providing evidence for efficient broadband sensitization of the rare earth ions by energy transfer from Ag dimers/multimers, which could have important applications in different fields, such as PV solar cells and light-emitting near-infrared (NIR) devices.

Design of Carbon Dots for Metal-free Photoredox Catalysis.

The photoreduction potential of a set of four different carbon dots (CDs) was investigated. The CDs were synthesized by using two different preparation methods-hydrothermal and pyrolytic-and two sets of reagents-neat citric acid and citric acid doped with diethylenetriamine. The hydrothermal syntheses yielded amorphous CDs, which were either nondoped (a-CDs) or nitrogen-doped (a-N-CDs), whereas the pyrolytic treatment afforded graphitic CDs, either non-doped (g-CDs) or nitrogen-doped (g-N-CDs). The morphology, structure, and optical properties of four different types of CDs revealed significant differences depending on the synthetic pathway. The photocatalytic activities of the CDs were investigated as such, that is, in the absence of any other redox mediators, on the model photoreduction reaction of methyl viologen. The observed photocatalytic reaction rates: a-N-CDs ≥ g-CDs > a-CDs ≥ g-N-CDs were correlated with the presence/absence of fluorophores, to the graphitic core, and to quenching interactions between the two. The results indicate that nitrogen doping reverses the photoredox reactivity between amorphous and graphitic CDs and that amorphous N-doped CDs are the most photoredox active, a yet unknown fact that demonstrates the tunable potential of CDs for ad hoc applications.

Yttrium and lanthanide complexes of ß-dialdehydes: synthesis, characterization and luminescence of coordination compounds with the conjugate base of nitromalonaldehyde.

Coordination compounds having formulae [AsPh4][Ln(NMA)4] (1(Ln)), Ln(NMA)3(tppo)2 (2(Ln)), Ln(NMA)3(bipyO2) (3(Ln)), Ln(NMA)3(phen) (4(Ln)) and Ln(NMA)3(terpy) (5(Ln)) (Ln = Y and some lanthanides; NMA = conjugate base of nitromalonaldehyde; tppo = triphenylphosphine oxide; bipyO2 = 2,2'-bipyridine-N,N'-dioxide; phen = 1,10-phenanthroline; terpy = 2,2':6',2''-terpyridine) were synthesized and characterized and X-ray diffraction data were collected for [AsPh4][Y(NMA)4] (1(Y)). The neutral europium derivatives showed appreciable luminescence in the solid state upon excitation with UV light and photoluminescence measurements were carried out. These compounds were used as dopants for the preparation of luminescent poly(methyl methacrylate). Luminescent polyvinylpyrrolidone samples were obtained by reacting the pure polymer with water solutions containing NMA and trivalent europium ions.

Structural and photophysical properties of rare-earth complexes encapsulated into surface modified mesoporous silica nanoparticles.

The encapsulation of [Eu(dbm)3phen] into functionalized mesoporous silica nanoparticles (MSN) has been carried out to study the effect of chemical environments on the photoluminescence properties of the rare-earth complex. Surface functionalization was achieved by the reaction of the silanol groups on the surface of mesoporous silica with different organosilylating agents such as (3-aminopropyl)-triethoxysilane (APTES), (3-mercaptopropyl)-trimethoxysilane (MPTMS), and ethoxytrimethylsilane (ETMS). A change in the luminescence properties of the Eu(dbm)3phen complex has been observed on its encapsulation into surface modified mesoporous silica nanoparticles. The modification of photophysical properties is attributed to the interaction of Eu(dbm)3phen with the different chemical environments in the functionalized mesoporous silica nanoparticles (MSN). The luminescence properties of the rare-earth complex in surface-modified MSN increase in the order MSN < MSN-ETMS < MSN-MPTMS < MSN-APTES. The Eu(dbm)3phen complex encapsulated in the functionalized mesoporous silica nanoparticles shows an enhanced luminescence and an increased lifetime compared to the pure rare-earth complex in the solid state and that in unmodified MSN. This implies that some interactions of the lanthanide complexes take place during their incorporation process into the organically modified mesoporous silica nanoparticles. The organically modified mesoporous silica nanoparticles were characterized by Fourier transform infrared spectroscopy (FTIR) and N2 adsorption desorption measurements. The luminescence properties of the encapsulated Eu(dbm)3phen were studied in detail. Moreover, the effect of functionalized MSNs on the structural behaviour of the Eu(dbm)3phen was investigated by solid state nuclear magnetic resonance (SSNMR) techniques using an analogous diamagnetic model complex, Y(dbm)3phen, encapsulated into functionalized MSNs. These studies indicate that the encapsulated rare-earth complex shows some interactions with the functional groups anchored on the surface of MSNs.

Yttrium and lanthanide complexes of ß-dialdehydes: synthesis, characterization, luminescence and electrochemistry of coordination compounds with the conjugate base of bromomalonaldehyde.

Novel yttrium, europium and terbium coordination compounds having formulae [AsPh4][Ln(BrMA)4] (6LN), Ln(BrMA)3(bipyO2) (7Ln), Ln(NMA)3(phen) (8Ln) and Ln(NMA)3(terpy) (9Ln) (Ln = Y, Eu, Tb; BrMA = conjugate base of bromomalonaldehyde; bipyO2 = 2,2'-bipyridine-N,N'-dioxide; phen = 1,10-phenantroline; terpy = 2,2':6',2''-terpyridine) were synthesized and characterized by using spectroscopic and electrochemical techniques. Uncharged europium and, to a lesser extent, terbium complexes showed appreciable luminescence in the solid state upon excitation with UV light. Polymeric materials and ionic liquids containing BrMA and lanthanides were prepared and photoluminescence measurements were carried out. From an electrochemical point of view, europium(III) BrMA-complexes showed a quasi-reversible one-electron reduction process. The one electron transfer reaction Eu(III) to Eu(II) allowed the photoluminescence tuning of 8Eu deposited on the surface of a glassy carbon electrode.

Unexpected optical activity of cerium in Y2O3:Ce3+, Yb3+, Er3+ up and down-conversion system.

In this work we synthesized rare earth-doped yttria nanocrystals via the Pechini method. We used Ce(3+), Yb(3+) and Er(3+) as dopant ions and studied their behavior when they are simultaneously embedded in the yttrium oxide lattice. The tri-doped system exhibits both downshifting and up-converting properties, due to the presence of, respectively, cerium-erbium and ytterbium-erbium couples. Efforts were put into determination of the effects of the presence of increasing content of cerium. We synthesized a series of samples having the general formula (Y0.88-xCexYb0.1Er0.02)2O3, where x = 0.01, 0.02, 0.10, 0.20, and 0.40. The structural properties of the samples were analyzed by the X-ray powder diffraction (XRPD) technique and the morphological features were disclosed using transmission electron microscope (TEM) observations. Photoluminescence properties were tested by carrying out photoluminescence (PL) emission, photoluminescence excitation (PLE) and lifetime (LT) measurements.

Stepwise dansyl grafting on the kaolinite interlayer surface.

Here we describe the step-wise grafting of the fluorophore dansyl chloride on the interlayer aluminol groups of kaolinite. The modified clay was characterized by powder RD, TGA, FT-IR and (27)Al, (19)Si, (13)C MAS-NMR, which confirmed the achievement of the clay functionalization. The photophysical properties of the resulting nanohybrid material were evaluated by photoluminescence excitation and emission measurements.

Signal enhancement in DNA microarray using dye doped silica nanoparticles: application to human papilloma virus (HPV) detection.

DNA microarray is a powerful tool for the parallel of nucleic acids and other biologically significant molecules. In this communication we report an easy and cheap synthesis route for incorporating organic dyes into monodisperse inorganic silica nanoparticles and their application on the detection of carcinogenic risky Human Papilloma Virus using DNA microarray technology. We correlate our system with conventional direct dyes and commercial quantum dots, with a promising increase in optical signal, and a related decrease of the limit of detection, thus giving a remarkable improvement in this technique towards early diagnosis of diseases and trace level detection of dangerous biological contaminants.

Luminescent amino-functionalized or erbium-doped silica spheres for biological applications.

This work presents the morphological and optical properties of luminescent silica spheres, discussing applications in bioimaging and biosensing. The spheres are obtained by the hydrolysis and condensation of tetraethylorthosilicate (TEOS) and can be synthesized by following either a basic or an acidic route. Luminescence emission is induced after incorporation of aminopropyltriethoxysilane (APTES) during synthesis or by introducing an optically active element, such as erbium, or other rare-earth elements. The luminescence properties of APTES-functionalized silica spheres have been investigated and optimized by varying the annealing temperature. On the other hand, erbium incorporation in silica spheres was also studied and the corresponding Er(3+) luminescence emission at 1.54 microm was evaluated for intensity and lifetime. The basic pH environment in the synthesis allows good control of the size of the spheres (approximately 200 nm in diameter), whereas the acidic route produces a wide dispersion in particle size (200-5000 nm). Both these approaches, however, can be followed to obtain an efficient photoluminescence (PL) emission for the APTES-functionalized silica spheres after 400-600 degrees C thermal treatment. If Er(NO(3))(3) is introduced in the basic solution, a rapid precipitation of Er(OH)(3) occurs, but erbium can be easily and efficiently incorporated in the acid-synthesized spheres, showing high PL intensity at 1.54 microm with lifetime of 3.9 ms. Finally, I discuss perspectives for the applications of these luminescent silica spheres, in particular as biological markers for bioimaging and biosensing.

Acid synthesis of luminescent amine-functionalized or erbium-doped silica spheres for biological applications.

In this work we discuss and investigate the morphological and optical properties of luminescent silica spheres which can have interesting applications in bioimaging and biosensing. The spheres are synthesized following an acid route by the hydrolysis and condensation of tetraethylortosilicate (TEOS) and can be functionalized by incorporation of aminopropyl-triethoxysilane (APTES) during the synthesis, inducing a significant luminescence that can be attributed to a recombination mechanism from localized organic defects related to -NH(2) groups. It is shown that the acid synthesis route produces very regular spherical particles, but their diameter vary in the range of 200-4,000 nm. The luminescence properties have been investigated and optimized by variation of the annealing temperature for the functionalized spheres, obtaining the most efficient PL emission after a thermal treatment of 1 h at 600 degrees C in air. Moreover, the possibility to introduce rare earths like erbium in the spheres was also studied and the corresponding Er(3) luminescence emission at 1.53 microm is reported in terms of intensity and lifetime, pointing out that erbium can be easily and efficiently incorporated during the acid synthesis giving high PL intensity with a good lifetime of 3.9 ms.