Renewable nanocomposite layer-by-layer assembled catalytic interfaces for biosensing applications

A novel, easily renewable nanocomposite interface based on layer-by-layer (LbL) assembled cationic/anionic layers of carbon nanotubes customized with biopolymers is reported. A simple approach is proposed to fabricate a nanoscale structure composed of alternating layers of oxidized multiwalled carbon nanotubes upon which is immobilized either the cationic enzyme organophosphorus hydrolase (OPH; MWNT−OPH) or the anionic DNA (MWNT−DNA). The presence of carbon nanotubes with large surface area, high aspect ratio and excellent conductivity provides reliable immobilization of enzyme at the interface and promotes better electron transfer rates. The oxidized MWNTs were characterized by thermogravimetric analysis and Raman spectroscopy. Fourier transform infrared spectroscopy showed the surface functionalization of the MWNTs and successful immobilization of OPH on the MWNTs. Scanning electron microscopy images revealed that MWNTs were shortened during sonication and that LbL of the MWNT/biopolymer conjugates resulted in a continuous surface with a layered structure. The catalytic activity of the biopolymer layers was characterized using absorption spectroscopy and electrochemical analysis. Experimental results show that this approach yields an easily fabricated catalytic multilayer with well-defined structures and properties for biosensing applications whose interface can be reactivated via a simple procedure. In addition, this approach results in a biosensor with excellent sensitivity, a reliable calibration profile, and stable electrochemical response.

Nanopartículas magnéticas como suporte para imobilização de lipases

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Abordagem alternativa para síntese de melanina

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Modificação da superfície de óxidos de ferro por dextrana derivatizada para aplicações em liberação de fármaco

Pós-graduação em Química - IQ

Modificação da superfície de óxidos de ferro por dextrana derivatizada para aplicações em liberação de fármaco

Pós-graduação em Química - IQ

DNA - novel nanomaterial for applications in photonics and in electronics

Functionalization with surfactants and with active molecules of deoxyribonucleic acid (DNA), thin film processing as well as their nonlinear optical and electrical properties are reviewed and discussed. On the basis of a quantum three level model, we show that the anomalous concentration variation of cubic susceptibility chi((3))(-3 omega; omega, omega, omega) in thin films of DNA-CTMA complexes doped with Disperse Red 1 chromophore can be explained by the concentration variation of two-photon resonance contribution. We show also that the DNA complexes, plasticized with glycerol and adequately doped can be processed into self standing conducting membranes with a high electrical conductivity. The measured ionic conductivity at room temperature, depending on dopant used and its concentration, is in the range of 3.5 x 10(-4)-10(-5) S/cm and increases linearly as a function of temperature, reaching 10(-3) S/cm at 358 K for the most conducting sample, obeying predominantly the Arrhenius law. Practical applications of DNA complexes are also described and discussed. (C) 2012 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.

Cyto and genotoxicity of gold nanoparticles in human hepatocellular carcinoma and peripheral blood mononuclear cells

Engineered nanomaterials have been extensively applied as active materials for technological applications. Since the impact of these nanomaterials on health and environment remains undefined, research on their possible toxic effects has attracted considerable attention. It is known that in humans, for example, the primary site of gold nanoparticles (AuNps) accumulation is the liver. The latter has motivated research regarding the use of AuNps for cancer therapy, since specific organs can be target upon appropriate functionalization of specific nanoparticles. In this study, we investigate the geno and cytotoxicity of two types of AuNps against human hepatocellular carcinoma cells (HepG2) and peripheral blood mononuclear cells (PBMC) from healthy human volunteers. The cells were incubated in the presence of different concentrations of AuNps capped with either sodium citrate or polyamidoamine dendrimers (PAMAM). Our results suggest that both types of AuNps interact with HepG2 cells and PBMC and may exhibit in vitro geno and cytotoxicity even at very low concentrations. In addition, the PBMC were less sensitive to DNA damage toxicity effects than cancer HepG2 cells upon exposure to AuNps. (C) 2012 Elsevier Ireland Ltd. All rights reserved.

Biocompatible Magnetic Microspheres for Use in PDT and Hyperthermia

Loaded microspheres with a silicon (IV) phthalocyanine derivative (NzPC) acting as a photosensitizer were prepared from polyhydroxybutyrate-co-valerate (PHBHV) and poly(ecaprolactone) (PCL) polymers using the emulsification solvent evaporation method (EE). The aim of our study was to prepare two systems of these biodegradable PHBHV/PCL microspheres. The first one containing only photosensitizer previously incorporated in the PHBHV and poly(ecaprolactone) (PCL) microspheres and the second one with the post magnetization of the DDS with magnetic nanoparticles. Magnetic fluid is successfully used for controlled incorporation of nanosized magnetic particles within the micron-sized template. This is the first time that we could get a successful pos incorporation of nanosized magnetic particles in a previously-prepared polymeric template. This procedure opens a great number of possibilities of post-functionalization of polymeric micro or nanoparticles with different bioactive materials. The NzPC release profile of the systems is ideal for PDT, the zeta potential and the size particle are stable upon aging in time. In vitro studies were evaluated using gingival fibroblastic cell line. The dark citotoxicity, the phototoxicity and the AC magnetic field assays of the as-prepared nanomagnetic composite were evaluated and the cellular viability analyzed by the classical test of MU.

Practical synthesis of a functionalized 1-oxo-1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid

The synthesis of a functionalized 1-oxo-1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid has been performed in 10 steps from the readily available dimedone. Only three purifications by flash chromatography are required through the whole sequence. The key step is the reaction between a dimedone derivative and a chlorotetrolic ester, that gives a tetrasubstituted benzene ring (through a Diels-Alder/retro- Diels-Alder process) bearing the substituents in the suitable positions for further functionalization. (C) 2012 Elsevier Ltd. All rights reserved.

Multi-Walled Carbon Nanotubes and Poly(lactic acid) Nanocomposite Fibrous Membranes Prepared by Solution Blow Spinning

Nanocomposite fibers based on multi-walled carbon nanotubes (MWCNT) and poly(lactic acid) (PLA) were prepared by solution blow spinning (SBS). Fiber morphology was characterized by scanning electron microscopy (SEM) and optical microscopy (OM). Electrical, thermal, surface and crystalline properties of the spun fibers were evaluated, respectively, by conductivity measurements (4-point probe), thermogravimetric analyses (TGA), differential scanning calorimetry (DSC), contact angle and X-ray diffraction (XRD). OM analysis of the spun mats showed a poor dispersion of MWCNT in the matrix, however dispersion in solution was increased during spinning where droplets of PLA in solution loaded with MWCNT were pulled by the pressure drop at the nozzle, producing PLA fibers filled with MWCNT. Good electrical conductivity and hydrophobicity can be achieved at low carbon nanotube contents. When only 1 wt% MWCNT was added to low-crystalline PLA, surface conductivity of the composites increased from 5 x 10(-8) to 0.46 S/cm. Addition of MWCNT can slightly influence the degree of crystallinity of PLA fibers as studied by XRD and DSC. Thermogravimetric analyses showed that MWCNT loading can decrease the onset degradation temperature of the composites which was attributed to the catalytic effect of metallic residues in MWCNT. Moreover, it was demonstrated that hydrophilicity slightly increased with an increase in MWCNT content. These results show that solution blow spinning can also be used to produce nanocomposite fibers with many potential applications such as in sensors and biosensors.

A Facile, Versatile, and Mild Morita-Baylis-Hillman-Type Reaction for the Modular One-Pot Synthesis of Highly Functionalized MBH Adducts

MoritaBaylisHillman derivatives have been extensively investigated as intermediates in the preparation of important classes of compounds. However, there are intrinsic limitations regarding the structure of the Michael electrophile acceptors, the aldehydes, and the catalysts. Therefore, this transformation has several drawbacks, including, for example, its long reaction times. Herein we present a simple, general, fast, and high-yielding protocol for the one-pot synthesis of MoritaBaylisHillman derivatives. Our approach is driven by a lithium selenolate Michael/aldol operation with concomitant O-functionalization/selenoxide elimination cascade sequences.

Metáteses árabes da metáfora: desvelar/velar

Um dos mais intrigantes fatos semânticos da língua árabe é a metátese, transposição de fonemas dentro de uma palavra, frequentemente com relação de sentido entre as formas metatéticas. Em m-th-l, a raiz triconsonantal para a palavra “metáfora”, as metáteses são imensamente sugestivas: Th-L-M and L- Th-M; a ambígua função da metáfora: mostrar e ocultar. A partir desse fato, o artigo discute esses aspectos da metáfora

New materials for electrochemiluminescence

The study of electrochemiluminescence (ECL) involves photophysical and electrochemical aspects. Excited states are populated by an electrical stimulus. The most important applications are in the diagnostic field where a number of different biologically-relevant molecules (e.g. proteins and nucleic acids) can be recognized and quantified with a sensitivity and specificity previously not reachable. As a matter of fact the electrochemistry, differently to the classic techniques as fluorescence and chemiluminescence, allows to control the excited state generation spatially and temporally. The two research visits into A. J. Bard electrochemistry laboratories were priceless. Dr. Bard has been one of ECL pioneers, the first to introduce the technique and the one who discovered in 1972 the surprising emission of Ru(bpy)3 2+. I consider necessary to thank by now my supervisors Massimo and Francesco for their help and for giving me the great opportunity to know this unique science man that made me feel enthusiastic. I will never be grateful enough… Considering that the experimental techniques of ECL did not changed significantly in these last years the most convenient research direction has been the developing of materials with new or improved properties. In Chapter I the basics concepts and mechanisms of ECL are introduced so that the successive experiments can be easily understood. In the final paragraph the scopes of the thesis are briefly described. In Chapter II by starting from ECL experimental apparatus of Dr. Bard’s laboratories the design, assembly and preliminary tests of the new Bologna instrument are carefully described. The instrument assembly required to work hard but resulted in the introduction of the new technique in our labs by allowing the continuation of the ECL studies began in Texas. In Chapter III are described the results of electrochemical and ECL studies performed on new synthesized Ru(II) complexes containing tetrazolate based ligands. ECL emission has been investigated in solution and in solid thin films. The effect of the chemical protonation of the tetrazolate ring on ECL emission has been also investigated evidencing the possibility of a catalytic effect (generation of molecular hydrogen) of one of the complexes in organic media. Finally, after a series of preliminary studies on ECL emission in acqueous buffers, the direct interaction with calf thymus DNA of some complexes has been tested by ECL and photoluminescence (PL) titration. In Chapter IV different Ir(III) complexes have been characterized electrochemically and photophysically (ECL and PL). Some complexes were already well-known in literature for their high quantum efficiency whereas the remaining were new synthesized compounds containing tetrazolate based ligands analogous to those investigated in Chapt. III. During the tests on a halogenated complex was unexpectedly evidenced the possibility to follow the kinetics of an electro-induced chemical reaction by using ECL signal. In the last chapter (V) the possibility to use mono-use silicon chips electrodes as ECL analitycal devices is under investigation. The chapter begins by describing the chip structure and materials then a signal reproducibility study and geometry optimization is carried on by using two different complexes. In the following paragraphs is reported in detail the synthesis of an ECL label based on Ru(bpy)3 2+ and the chip functionalization by using a lipoic acid SAM and the same label. After some preliminary characterizations (mass spectroscopy TOF) has been demonstrated that by mean of a simple and fast ECL measurement it’s possible to confirm the presence of the coupling product SAM-label into the chip with a very high sensitivity. No signal was detected from the same system by using photoluminescence.

Biomimetica per l'ingegneria tissutale dell'osso

Reconstruction of bone is needed for high bone loss due to congenital deformities, trauma or neoplastic diseases. Commonly, orthopaedic surgical treatments are autologus or allogenic bone implant or prosthetic implant. A choice to the traditional approaches could be represented by tissue engineering that use cells (and/or their products) and innovative biomaterials to perform bone substitutes biologically active as an alternative to artificial devices. In the last years, there was a wide improvement in biology on stem cells potential research and in biomedical engineering through development of new biomaterials designed to resemble the physiological tissues. Tissue engineering strategies and smart materials aim together to stimulate in vivo bone regeneration. This approaches drive at restore not only structure integrity and/or function of the original tissue, but also to induce new tissue deposition in situ. An intelligent bone substitute is now designed like not only a scaffold but also as carrier of regeneration biomolecular signals. Biomimetics has helped to project new tissue engineered devices to simulate the physiological substrates architecture, such extracellular matrix (ECM), and molecular signals that drive the integration at the interface between pre-existing tissue and scaffold. Biomimetic strategies want to increase the material surface biological activity with physical modifications (topography) o chemical ones (adhesive peptides), to improve cell adhesion to material surface and possibly scaffold colonization. This study evaluated the effects of biomimetic modifications of surgical materials surface, as poly-caprolattone (PCL) and titanium on bone stem cells behaviour in a marrow experimental model in vitro. Two biomimetic strategies were analyzed; ione beam irradiation, that changes the surface roughness at the nanoscale, and surface functionalization with specific adhesive peptides or Self Assembled Monolayers (SAMs). These new concept could be a mean to improve the early (cell adhesion, spreading..) and late phases (osteoblast differentiation) of cell/substrate interactions.

Realizzazione di riporti funzionalizzanti su superfici ceramiche per la produzione di energia elettrica mediante effetto fotovoltaico

This research, carried out during the PhD in Materials Engineering, deals with the creation of layers, with different functionality, deposited on a ceramic substrate, to obtain photovoltaic cells for electricity production. The research activities are included in the project PRRIITT, Measure 4 (Development of Networks), Action A (Research and Technology Transfer Laboratories), Thematic reference 3 (Advanced materials applications development), co-financed by the Emilia Romagna Region, for the creation of CECERBENCH laboratory, which aims to develop "Tiles with a functionalised surface”. The innovation lies in the study of materials and in the development of technologies to achieve a "photovoltaic surface", directly in the tiles production process. The goal is to preserve the technical characteristics, and to make available new surfaces, exploiting renewable energy sources. The realization of Building Integrated PhotoVoltaic (BIPV) is nowadays a more and more spread tendency. The aims of the research are essentially linked to the need to diversify the actual ceramic tile production (which is strongly present in the Emilia Romagna Region ), and to provide a higher added value to the tiles. Solar energy production is the primary objective of the functionalization, and has a relevant ecological impact, taking into account the overwhelming global energy demand. The specific activities of the PhD were carried out according to the achievement of scientific and technological objectives of CECERBENCH laboratory, and involved the collaboration in design solutions, to obtain the cells directly on the tiles surface. The author has managed personally a part of the research project. Layers with different features were made: - Electrically conductive layers, directly on the ceramic tiles surface; - Layers to obtain the photovoltaic functionality; - Electrically insulating, protective layers (double function). For each layer, the most suitable materials have been selected. Among the technical application, the screen printing was used. This technique, widely used in ceramics, has many application areas, including the electronics and photovoltaic industries. It is an inexpensive technique, easy to use in industrial production lines. The screen printing technique was therefore studied in depth by theoretical considerations, and through the use of rheological measurements.