José Maurício Almeida Caiut

APTES-Modified RE2O3:Eu3+ Luminescent Beads: Structure and Properties

Europium-doped lanthanide oxide RE(2)O(3):Eu(3+) (RE = Y or Gd) luminescent beads, with a spherical shape and a diameter of 150 ± 15 nm, have been modified by reaction with 3-aminopropyltriethoxysilane (APTES), in order to introduce reactive amine groups at their surfaces. The direct silanation has resulted in the formation of a nanometric layer at the surface of the beads, with an optimum grafting rate of 0.055 ± 0.005 mol APTES/mol RE(2)O(3). Fourier transform infrared (FTIR) and X-ray photoelectron (XPS) spectroscopies confirmed the condensation of an organosilane layer, made of cross-linked -O-Si-O-Si- and of groups -O-Si-R (with R = (CH(2))(3)NH(2) or O-Et). Titration of the accessible amine groups has been performed by simultaneously measuring the luminescence of grafted fluorescein isothiocyanate and that of core particles: there are about 2.3 × 10(4) (2.8 × 10(4)) -NH(2) per Y(2)O(3):Eu(3+) (Gd(2)O(3):Eu(3+)) bead. The isoelectronic point was shifted by one pH unit after APTES modification. The surface modification by APTES at least preserved (for Gd(2)O(3):Eu(3+)) or improved (for Y(2)O(3):Eu(3+)) the red emission of the beads.

Synthesis and luminescence properties of water dispersible Eu3+-doped boehmite nanoparticles

Nanocrystallized boehmite γ-AlOOHnH2O had been synthesized by spray-drying (SD) of a solution of aluminium tri-sec-butoxide peptized by nitric acid. The sub-micronic spherical particles obtained had an average diameter of 500 nm and were built of 100 nm or less platelet-like sub-particles. The average crystallite size calculated from XRD was 1.6 nm following the axis (i.e. one unit cell) and 3–4 nm perpendicular to . As a result of the nanometric sizes of crystallites, there was a large surface free for water adsorption and it was found to be n = 1.18 ± 0.24H2O per AlOOH. The SD spheres spontaneously dispersed in water at room temperature and formed stable—over months—suspensions with nanometre-size particles (25–85 nm). Luminescent europium-doped nanocrystallized boehmites AlOOH:Eu (Al0.98Eu0.02OOHnH2O) were synthesized the same way by SD and demonstrated the same crystallization properties and morphologies as the undoped powders. It is inferred from the Eu3+ luminescence spectroscopy that partly hydrated europium species are immobilized on the boehmite nanocrystals where they are directly bonded to α(OH) groups of the AlOOH surface. The europium coordination is schematically written [Eu3+(OH)α(H2O)7−α/2 ]. The europium-doped boehmite from SD spontaneously dispersed in water: the luminescence spectroscopy proves that most of the Eu3+ ions were detached from the NPs during water dispersion. The AlOOH:Eu nanoparticles were modified by the amine acid asparagine (ASN). The modification aimed to render the NPs compatible for further bio-functionalization. After surface modification, the NPs easily dispersed in water; the luminescence spectra after dispersion prove that the Eu3+ ions were held at the boehmite surface.

Organosilylated Complex [Eu(TTA)3(Bpy-Si)]: A Bifunctional Moiety for the Engeneering of Luminescent Silica-Based Nanoparticles for Bioimaging

A new highly luminescent europium complex with the formula [Eu(TTA)3(Bpy-Si)], where TTA stands for the thenoyltrifluoroacetone, (C4H3S)COCH2COCF3, chelating ligand and Bpy-Si, Bpy-CH2NH(CH2)3Si(OEt)3, is an organosilyldipyridine ligand displaying a triethoxysilyl group as a grafting function has been synthesized and fully characterized. This bifunctional complex has been grafted onto the surface of dense silica nanoparticles (NPs) and on mesoporous silica microparticles as well. The covalent bonding of [Eu(TTA)3(Bpy-Si)] inside uniform Stöber silica nanoparticles was also achieved. The general methodology proposed could be applied to any silica matrix, allowed high grafting ratios that overcome chelate release and the tendency to agglomerate. Luminescent silica-based nanoparticles SiO2-[Eu(TTA)3(Bpy-Si)], with a diameter of 28 ± 2 nm, were successfully tested as a luminescent labels for the imaging of Pseudomonas aeruginosa biofilms. They were also functionalized by a specific monoclonal antibody and subsequently employed for the selective imaging of Escherichia coli bacteria.

Self-supported bacterial cellulose/boehmite organic-inorganic hybrid films

Self-supported organic-inorganic hybrid transparent films have been prepared from bacterial cellulose and boehmite. SEM results indicate that the BC membranes are covered by Boehmite and XRD patterns suggest structural changes on cellulose due to Boehmite addition. Thermal stability is accessed through TG curves and is dependent on Boehmite content. Transparency, as evaluated by UV–Vis absorption, increases with increasing content of boehmite suggesting application of these materials as transparent substrates for opto-electronic devices.

Non-leachable highly luminescent ordered mesoporous SiO2 spherical particles

Ordered mesoporous highly luminescent SiO2 particles have been synthesized by spray pyrolysis from solutions containing tetraethylorthosilicate (TEOS) and either cetyltrimethylammonium bromide (CTAB) or the block copolymer Pluronic F-68 as structure-directing agents. Rhodamine B (RhB)-containing samples were prepared by using a simple wet impregnation method followed by the growing of a second silica shell in order to prevent leaching of the dye. The obtained materials were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder x-ray diffraction (XRD), ultraviolet-visible spectroscopy (UV-vis) and photoluminescence (PL). Powders with polydisperse spherical grains were obtained displaying an ordered hexagonal array of mesochannels. Luminescence results reveal that RhB molecules have been successfully encapsulated into the channels of mesoporous particles as monomeric species and that a well-defined silica coating hindered dye leaching.

Bifunctional silica nanoparticles for the exploration of biofilms of Pseudomonas aeruginosa

Luminescent silica nanoparticles are frequently employed for biotechnology applications mainly because of their easy functionalization, photo-stability, and biocompatibility. Bifunctional silica nanoparticles (BSNPs) are described here as new efficient tools for investigating complex biological systems such as biofilms. Photoluminescence is brought about by the incorporation of a silylated ruthenium(II) complex. The surface properties of the silica particles were designed by reaction with amino-organosilanes, quaternary ammonium-organosilanes, carboxylate-organosilanes and hexamethyldisilazane. BSNPs were characterized extensively by DRIFT, 13C and 29Si solid state NMR, XPS, and photoluminescence. Zeta potential and contact angle measurements exhibited various surface properties (hydrophilic/hydrophobic balance and electric charge) according to the functional groups. Confocal laser scanning microscopy (CLSM) measurements showed that the spatial distribution of these nanoparticles inside a biofilm of Pseudomonas aeruginosa PAO1 depends more on their hydrophilic/hydrophobic characteristics than on their size. CLSM observations using two nanosized particles (25 and 68 nm) suggest that narrow diffusion paths exist through the extracellular polymeric substances matrix.

Luminescent multifunctional biocellulose membranes

Luminescent biocellulose membranes were obtained by incorporation of ethanolic solutions of the europium compounds [Eu(BTFAC)3(H2O)2], [Eu(BTFA)3(DBSO)2], [Eu(BTFA)3(PTSO)2] and [Eu(BTFA)3(FSO)2] (BTFAC- 4,4,4-Trifluoro-1- phenyl-1,3-butanedione DBSO- dibenzyl sulfoxide, PTSO- p-Tolyl sulfoxide and FSO- phenyl sulfoxide). Selfsustainable semi-transparent composite membranes were obtained showing strong emission under UV exctiation. The antenna hole played by the ligands was observed to be more efficient in the composite membranes than in the precursor complexes which by themselves are also strong red emitter compounds. These new multifuctional membranes could find application in different areas as phosphors and UV→Visible energy converting devices.

Decontamination Efficiency of a DBD Lamp Containing an UV-C Emitting Phosphor.

Among different physical and chemical agents, the UV radiation appears to be an important route for inactivation of resistant microorganisms. The present study introduces a new mercury‐free Dielectric Barrier Discharge (DBD) flat lamp, where the biocide action comes from the UV emission produced by rare‐earth phosphor obtained by spray pyrolysis, following plasma excitation. In this study, the emission intensity of the prototype lamp is tuned by controlling gas pressure and electrical power, 500 mbar and 15 W, corresponding to optimal conditions. In order to characterize the prototype lamp, the energetic output, temperature increase following lamp ignition and ozone production of the source were measured. The bactericidal experiments carried out showed excellent results for several gram‐positive and gram‐negative bacterial strains, thus demonstrating the high decontamination efficiency of the DBD flat lamp. Finally, the study of the external morphology of the microorganisms after the exposure to the UV emission suggested that other mechanisms than the bacterial DNA damage could be involved in the inactivation process.

Eletrodo de pasta de carbono em minicavidade de contato sólido

This work describes the preparation of carbon paste electrode (EPC) in a solid-contact minicavity and its evaluation when containing carbon paste without and with SiO2(Eu3+ 2%) and SiO2(Eu3+ 2%)-lysine sub-micrometrics particles. For this study cyclic voltammetry and electrochemical impedance measurements were performed at pH 7.4 in 0.1 mol L-1 PBS containing Fe(CN)6-3/-4 redox species. The impedance results were interpretated based on a charge-transfer reaction involving Fe(CN)6-3/-4 species and/or oxygen at higher frequencies and, diffusion of the electroactive species and carbon paste characteristics at lower frequencies. EPC-minicavity is suitable for electroanalysis using modified carbon paste.

Decontamination of metallic surfaces inocculated with bacillus atrophaeus spores using an UV-C neon-xenon dielectric barrier discharge lamp

The endospores produced by Bacillus spp. are known to be highly resistant to most disinfection methods. Due to their extreme resilience, spores of several Bacillus strains are widely used as biological indicators for sterility testing. In this work, the sporicidal efficacy of a lamp prototype on B. atrophaeus spores is investigated.