Synthesis and photoluminescent properties of silica-coated LaCeF3 : Tb nanocrystals

La0.45Ce0.45F3:Tb (10 mol% Tb) nanoparticles was synthesized via sonochemical method and then coated with silica (SiO2) shells through a microemulsion process, resulting in the formation of core/shell structured LaCeF3:Tb/SiO2 nanoparticles. The obtained core/shell LaCeF3:Tb/SiO2 nanoparticles are spherical and uniform in size (average size about 60 nm), strongly fluorescent, and long fluorescence lifetime (1.87 ms). This kind of nanoparticles was water-soluble, which could be applied in biological labeling and other fields.

Controllable Red, Green, Blue (RGB) and Bright White Upconversion Luminescence of Lu2O3:Yb3+/Er3+/Tm3+ Nanocrystals through Single Laser Excitation at 980 nm

Lu2O3:Yb3+/Er3+/Tm3+ nanocrystals have been successfully synthesized by a solvothermal process followed by a subsequent heat treatment at 800 degrees C. Powder X-ray diffraction, transmission electron microscopy, upconversion photoluminescence spectra, and kinetic decay were used to characterize the samples. Under single-wavelength diode laser excitation of 980 nm, the bright blue emissions of Lu2O3:Yb3+, Tm3+ nanocrystals near 477 and 490 nm were observed due to the (1)G(4)-> H-3(6) transition of Tm3+. The bright green UC emissions of Lu2O3:Er3+ nanocrystals appeared near 540 and 565 nm were observed and assigned to the H-2(11/2)-> I-4(15/2) and S-4(3/2)-> I-4(15/2) transitions, respectively, of Er3+. The ratio of the intensity of green luminescence to that of red luminescence decreases with an increase of concentration of Yb3+ in Lu2O3:Er3+ nanocrystals.

Bifunctional nanostructure of magnetic core luminescent shell and its application as solid-state electrochemiluminescence sensor material

Bifunctional nanoarchitecture has been developed by combining the magnetic iron oxide and the luminescent Ru(bpy)(3)(2+) encapsulated in silica. First, the iron oxide nanoparticles were synthesized and coated with silica, which was used to isolate the magnetic nanoparticles from the outer-shell encapsulated Ru(bpy)(3)(2+) to prevent luminescence quenching. Then onto this core an outer shell of silica containing encapsulated Ru(bpy)(3)(2+) was grown through the Stober method. Highly luminescent Ru(bpy)(3)(2+) serves as a luminescent marker, while magnetic Fe3O4 nanoparticles allow external manipulation by a magnetic field. Since Ru(bpy)(3)(2+) is a typical electrochemiluminescence (ECL) reagent and it could still maintain such property when encapsulated in the bifunctional nanoparticle, we explored the feasibility of applying the as-prepared nanostructure to fabricating an ECL sensor; such method is simple and effective. We applied the prepared ECL sensor not only to the typical Ru(bpy)(3)(2+) co-reactant tripropylamine (TPA), but also to the practically important polyamines. Consequently, the ECL sensor shows a wide linear range, high sensitivity, and good stability.

Síntese hidrotérmica de nanopartículas de 'TI''O IND.2', de nanocompósitos metal/'TI''O IND.2' e degradação oxidativa de 4-clorofenol em reator membranar fotocatalítico

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Formação e crescimento do óxido de zinco e óxido de zinco dopado com cobre

Pós-graduação em Química - IQ

Propriedades ópticas de nanopartículas de halogenetos de cobre preparadas in situ em filmes híbridos de sílica

The sol-gel process is a technique based on the hydrolysis and polycondensation of metal alkoxides have been investigated as an alternative for the preparation of vitreous or glassceramic materials, for allowing the obtaining of high-purity materials at low temperatures, and to obtain hybrid materials with different compositions. When ORMOSILs are doped with nanoparticles, are called nanocomposites, and its functionality arises when electrons confined in scale three-dimensional structures near zero are excited. In principle, such materials exhibit discrete energy level, with peaks in the absorption spectrum. Therefore, the glasses doped semiconductor nanocrystals are important candidates for the preparation of optical filters with sharp cut-off, and are being exploited commercially for coloring glasses. This study evaluates the optical properties presented by hybrid films of silica doped with copper nanoparticles. The matrix was prepared using the alkoxides 3-glycidoxypropyltrimethoxysilane (GPTS) and tetraethylorthosilicate (TEOS) doped with Cu2O and hydrolyzed under reflux conditions in two different acidic conditions (HCl and HBr). After thermal treatment at temperatures between 100 °C and 170 °C and/or under the action of commercial black light radiation, CuCl and CuBr present in the hybrid film are transformed into nanoparticles of CuCl or CuBr. The UV-VIS absorption identified the absorption bands, and its variation

Luminescent Systems for Genomics and Proteomics

The present PhD project was focused on the development of new tools and methods for luminescence-based techniques. In particular, the ultimate goal was to present substantial improvements to the currently available technologies for both research and diagnostic in the fields of biology, proteomics and genomics. Different aspects and problems were investigated, requiring different strategies and approaches. The whole work was thus divided into separate chapters, each based on the study of one specific aspect of luminescence: Chemiluminescence, Fluorescence and Electrochemiluminescence. CHAPTER 1, Chemiluminescence The work on luminol-enhancer solution lead to a new luminol solution formulation with 1 order of magnitude lower detection limit for HRP. This technology was patented with Cyanagen brand and is now sold worldwide for Western Blot and ELISA applications. CHAPTER 2, Fluorescescence The work on dyed-doped silica nanoparticles is marking a new milestone in the development of nanotechnologies for biological applications. While the project is still in progress, preliminary studies on model structures are leading to very promising results. The improved brightness of these nano-sized objects, their simple synthesis and handling, their low toxicity will soon turn them, we strongly believe, into a new generation of fluorescent labels for many applications. CHAPTER 3, Electrochemiluminescence The work on electrochemiluminescence produced interesting results that can potentially turn into great improvements from an analytical point of view. Ru(bpy)3 derivatives were employed both for on-chip microarray (Chapter 3.1) and for microscopic imaging applications (Chapter 3.2). The development of these new techniques is still under investigation, but the obtained results confirm the possibility to achieve the final goal. Furthermore the development of new ECL-active species (Chapter 3.3, 3.4, 3.5) and their use in these applications can significantly improve overall performances, thus helping to spread ECL as powerful analytical tool for routinary techniques. To conclude, the results obtained are of strong value to largely increase the sensitivity of luminescence techniques, thus fulfilling the expectation we had at the beginning of this research work.

Design and Characterization of New Luminescent Sensors and Labels

The aim of this Ph.D. project has been the design and characterization of new and more efficient luminescent tools, in particular sensors and labels, for analytical chemistry, medical diagnostics and imaging. Actually both the increasing temporal and spatial resolutions that are demanded by those branches, coupled to a sensitivity that is required to reach the single molecule resolution, can be provided by the wide range of techniques based on luminescence spectroscopy. As far as the development of new chemical sensors is concerned, as chemists we were interested in the preparation of new, efficient, sensing materials. In this context, we kept developing new molecular chemosensors, by exploiting the supramolecular approach, for different classes of analytes. In particular we studied a family of luminescent tetrapodal-hosts based on aminopyridinium units with pyrenyl groups for the detection of anions. These systems exhibited noticeable changes in the photophysical properties, depending on the nature of the anion; in particular, addition of chloride resulted in a conformational change, giving an initial increase in excimeric emission. A good selectivity for dicarboxylic acid was also found. In the search for higher sensitivities, we moved our attention also to systems able to perform amplification effects. In this context we described the metal ion binding properties of three photoactive poly-(arylene ethynylene) co-polymers with different complexing units and we highlighted, for one of them, a ten-fold amplification of the response in case of addition of Zn2+, Cu2+ and Hg2+ ions. In addition, we were able to demonstrate the formation of complexes with Yb3+ an Er3+ and an efficient sensitization of their typical metal centered NIR emission upon excitation of the polymer structure, this feature being of particular interest for their possible applications in optical imaging and in optical amplification for telecommunication purposes. An amplification effect was also observed during this research in silica nanoparticles derivatized with a suitable zinc probe. In this case we were able to prove, for the first time, that nanoparticles can work as “off-on” chemosensors with signal amplification. Fluorescent silica nanoparticles can be thus seen as innovative multicomponent systems in which the organization of photophysically active units gives rise to fruitful collective effects. These precious effects can be exploited for biological imaging, medical diagnostic and therapeutics, as evidenced also by some results reported in this thesis. In particular, the observed amplification effect has been obtained thanks to a suitable organization of molecular probe units onto the surface of the nanoparticles. In the effort of reaching a deeper inside in the mechanisms which lead to the final amplification effects, we also attempted to find a correlation between the synthetic route and the final organization of the active molecules in the silica network, and thus with those mutual interactions between one another which result in the emerging, collective behavior, responsible for the desired signal amplification. In this context, we firstly investigated the process of formation of silica nanoparticles doped with pyrene derivative and we showed that the dyes are not uniformly dispersed inside the silica matrix; thus, core-shell structures can be formed spontaneously in a one step synthesis. Moreover, as far as the design of new labels is concerned, we reported a new synthetic approach to obtain a class of robust, biocompatible silica core-shell nanoparticles able to show a long-term stability. Taking advantage of this new approach we also showed the synthesis and photophysical properties of core-shell NIR absorbing and emitting materials that proved to be very valuable for in-vivo imaging. In general, the dye doped silica nanoparticles prepared in the framework of this project can conjugate unique properties, such as a very high brightness, due to the possibility to include many fluorophores per nanoparticle, high stability, because of the shielding effect of the silica matrix, and, to date, no toxicity, with a simple and low-cost preparation. All these features make these nanostructures suitable to reach the low detection limits that are nowadays required for effective clinical and environmental applications, fulfilling in this way the initial expectations of this research project.

Engineered atherosclerosis-specific zinc ferrite nanocomplex-based MRI contrast agents

BACKGROUND: Cardiovascular diseases are the most prevalent cause of morbidity and mortality affecting millions of people globally. The most effective way to counter cardiovascular complications is early diagnosis and the safest non-invasive diagnostic approach is magnetic resonance imaging (MRI). In this study, superparamagnetic ferrite nanoparticles doped with zinc, exhibiting highly enhanced saturation magnetization and T2 and computed tomography (CT) contrast were synthesized. These nanoparticles have been strategically engineered using bovine lactoferrin (Lf), polyethylene glycol (PEG), and heat shock protein (Hsp)-70 antibody specifically targeting atherosclerosis with potential therapeutic value. The nanocomplexes were further validated in vitro to assess their cytotoxicity, internalization efficiency, effects on cellular proliferation and were assessed for MRI as well as X-ray CT in ex vivo Psammomys obesus rat model.

RESULTS: Optimized zinc doped ferrite nanoparticles (Zn0.4Fe2.6O4) with enhanced value of maximum saturation magnetization value on 108.4 emu/g and an average diameter of 24 ± 2 nm were successfully synthesized. Successfully incorporation with bovine lactoferrin, PEG and Hsp-70 (70 kDa) antibody led to synthesis of spherical nanocomplexes (size 224.8 nm, PDI 0.398). A significantly higher enhancement in T2 (p < 0.05, 1.22-fold) and slightly higher T1 (1.09-fold) and CT (1.08-fold) contrast compared to commercial ferrite nanoparticles was observed. The nanocomplexes exhibited effective cellular internalization within 2 h in both THP-1 and Jurkat cells. MRI scans of contrast agent injected animal revealed significant arterial narrowing and a significantly higher T2 (p < 0.05, 1.71-fold) contrast in adult animals when compared to juvenile and control animals. The excised heart and aorta agar phantoms exhibited weak MRI contrast enhancement in juvenile animal but significant contrast enhancement in adult animal specifically at the aortic arch, descending thoracic aorta and iliac bifurcation region with X-ray CT scan. Histological investigation of the contrast agent injected aorta and heart confirmed site target-specific accumulation at the atherosclerotic aortic arch and descending thoracic aorta of the adult animal with severely damaged intima full of ruptured microatheromas.

CONCLUSION: Overall, the study demonstrates the strategic development of nanocomplex based bimodal MRI and CT contrast agents and its validation on Psammomys obesus for atherosclerosis diagnostics.

In situ surface modification of molybdenum-doped organic-inorganic hybrid TiO2 nanoparticles under hydrothermal conditions and treatment of pharmaceutical effluent

Molybdenum-doped TiO2 organic-inorganic hybrid nanoparticles were synthesized under mild hydrothermal conditions by in situ surface modification using n-butylamine. This was carried out at 150 degrees C at autogeneous pressure over 18 h. n-Butylamine was selected as a surfactant since it produced nanoparticles of the desired size and shape. The products were characterized using powder X-ray diffraction, Fourier transform infrared spectrometry, dynamic light-scattering spectroscopy, UV-Vis spectroscopy and transmission electron microscopy. Chemical oxygen demand was estimated in order to determine the photodegradation efficiency of the molybdenum-doped TiO2 hybrid nanoparticles in the treatment of pharmaceutical effluents. It was found that molybdenum-doped TiO2 hybrid nanoparticles showed higher photocatalytic efficiency than untreated TiO2 nanoparticles.

Investigations on structural and optical properties of co-doped (Ag, Co) ZnO nanoparticles

Undoped and co-doped (Ag, Co) ZnO powders were synthesized by chemical co-precipitation method without using any capping agent. The X-ray diffraction results indicate that the undoped and co-doped ZnO powders have pure hexagonal structure and are consisting of nanosized single-crystalline particles. The size of the nanoparticles increases with increasing Ag concentration from 1 to 5 mol% as compared to that of undoped ZnO. The presence of substitution dopants of Ag and Co in the ZnO host material was confirmed by the Energy dispersive analysis of X-rays (EDAX). Optical absorption measurements indicate blue shift and red-shift in the absorption band edge upon doping concentration of Ag and blue emission was observed by photoluminescence (PL) studies.

Laser receptive polyelectrolyte thin films doped with biosynthesized silver nanoparticles for antibacterial coatings and drug delivery applications

We report a simple method to fabricate multifunctional polyelectrolyte thin films to load and deliver the therapeutic drugs. The multilayer thin films were assembled by the electrostatic adsorption of poly (allylamine hydrochloride) (PAH) and dextran sulfate (DS). The silver nanoparticles (Ag NPs) biosynthesized from novel Hybanthus enneaspermus leaf extract as the reducing agent were successfully incorporated into the film. The biosynthesized Ag NPs showed excellent antimicrobial activity against the range of enteropathogens, which could be significantly enhanced when used with commercial antibiotics. The assembled silver nano composite multilayer films showed rupture and deformation when they are exposed to laser. The Ag NPs act as an energy absorption center, locally heat up the film and rupture it under laser treatment. The antibacterial drug, moxifloxacin hydrochloride (MH) was successfully loaded into the multilayer films. The total amount of MH release observed was about 63% which increased to 85% when subjected to laser light exposure. Thus, the polyelectrolyte thin film reported in our study has significant potential in the field of remote activated drug delivery, antibacterial coatings and wound dressings. (C) 2013 Elsevier B.V. All rights reserved.

Comparison of the photocatalytic degradation of trypan blue by undoped and silver-doped zinc oxide nanoparticles

Zinc oxide (ZnO) and silver doped zinc oxide (ZnO:Ag) nanoparticles were prepared using nitrates of zinc and silver as oxidizers and ethylene diaminetetraacetic acid (EDTA) as a fuel via low-temperature combustion synthesis (LCS) at 500 degrees C. X-ray diffraction (XRD) pattern indicates the presence of silver in the hexagonal wurtzite structure of ZnO. Fourier transform infrared (FTIR) spectrum indicates the presence of Ag-Zn-O stretching vibration at 510 cm(-1). Transmission electron microscopy (TEM) images shows that the average particle size of ZnO and ZnO:Ag nanoparticles were found to be 58 nm and 52 nm, respectively. X-ray photoelectron spectroscopy (XPS) data clearly indicates the presence of Ag in ZnO crystal lattice. The above characterization techniques indicate that the incorporation of silver affects the structural and optical properties of ZnO nanoparticles. ZnO:Ag nanoparticles exhibited 3% higher photocatalytic efficiency than pure ZnO nanoparticles. ZnO:Ag nanoparticles show better photocatalytic activity for the degradation of trypan blue (TrB) compared to undoped ZnO nanoparticles. (C) 2014 Elsevier Ltd. All rights reserved.

Facile green fabrication of iron-doped cubic ZrO2 nanoparticles by Phyllanthus acidus: Structural, photocatalytic and photoluminescent properties

Cubic ZrO2: Fe3+ (0.5-4 mol%) nanoparticles (NPs) were synthesized via bin-inspired, inexpensive and simple route using Phyllanthus acidus as fuel. PXRD, SEM, TEM, FTIR, UV absorption and PL studies were performed to ascertain the formation of NPs. Rietveld analysis confirmed the formation of cubic structure. The influence of Fe3+ on the structure, morphology, UV absorption, PL emission and photocatalytic activity of NPs were investigated. The CIE chromaticity coordinates (0.36, 0.41) show that NPs could be a promising candidate for white LEDs. The influence of Fe3+ on ZrO2 matrix for photocatalytic degradation of AO7 was evaluated under UVA and Sunlight irradiation. The enhanced photocatalytic activity of spherical shaped ZrO2: Fe3+ (2 mol%) under UVA light was attributed to dopant concentration, crystallite size, narrow band gap, textural properties and capability for reducing the electron-hole pair recombination. The trend of inhibitory effect in the presence of different radical scavengers were followed the order SO42- > Cl- > C2H5OH > HCO3- > CO32-. The recycling catalytic ability of the ZrO2: Fe3+ (2 mol%) was also evaluated with a negligible decrease in the degradation efficiency even after the sixth successive run. (C) 2014 Elsevier B.V. All rights reserved.

Space-selective co-precipitation of silver and gold nanoparticles in femtosecond laser pulses irradiated Ag+, Au3+ co-doped silicate glass

We report on space-selective co-precipitation of silver and gold nanoparticles in Ag+, Au3+ co-doped silicate glasses by irradiation of femtosecond laser pulses and subsequent annealing at high temperatures. The color of the irradiated area in the glass sample changed from yellow to red with the increase of the annealing temperature. The effects of average laser power and annealing temperature on precipitation of the nanoparticles were investigated. A reasonable mechanism was proposed to explain the observed phenomena. (c) 2006 Elsevier Ltd. All rights reserved.