In vivo antimicrobial activity of 2% chlorhexidine used as a root canal irrigating solution

The aim of the present study was to evaluate the in vivo antimicrobial activity of 2% chlorhexidine gluconate (FCFRP-USP) used as a root canal irrigating solution in teeth with pulp necrosis and radiographically visible chronic periapical reactions. Culture techniques and measurement of the inhibition zone were used. Twenty-two root canals of incisors and molars of 12 patients were used. After accessing the canal, the first root canal sample was collected with two sterile paper points that were transferred to a tube containing reduced transport fluid. The root canal was instrumented using chlorhexidine solution. A small sterile cotton pellet was placed at the root canal entrance, and the cavity was sealed with zinc oxide-eugenol cement. The canals were maintained empty for 48 h. Three sterile paper points were then introduced to absorb the root canal fluid (second sample). One paper point was placed on an agar plate inoculated with Micrococcus luteus ATCC 9341 and incubated for 24 h at 37°C, and the other two were submitted to microbiological evaluation. Present in 10 cases at baseline, mutans streptococci was reduced by 100% at the second assessment. Treatment showed an efficiency of 77.78% for anaerobic microorganisms at the second assessment. These data suggest that chlorhexidine prevents microbial activity in vivo with residual effects in the root canal system up to 48 h. Copyright © 1999 by The American Association of Endodontists.

Heparin and penicillamine-hypotaurine-epinephrine (PHE) solution during bovine in vitro fertilization procedures impair the quality of spermatozoa but improve normal oocyte fecundation and early embryonic development

The presence of heparin and a mixture of penicillamine, hypotaurine, and epinephrine (PHE) solution in the in vitro fertilization (IVF) media seem to be a prerequisite when bovine spermatozoa are capacitated in vitro, in order to stimulate sperm motility and acrosome reaction. The present study was designed to determine the effect of the addition of heparin and PHE during IVF on the quality and penetrability of spermatozoa into bovine oocytes and on subsequent embryo development. Sperm quality, evaluated by the integrity of plasma and acrosomal membranes and mitochondrial function, was diminished (P < 0.05) in the presence of heparin and PHE. Oocyte penetration and normal pronuclear formation rates, as well as the percentage of zygotes presenting more than two pronuclei, was higher (P < 0.05) in the presence of heparin and PHE. No differences were observed in cleavage rates between treatment and control (P > 0.05). However, the developmental rate to the blastocyst stage was increased in the presence of heparin and PHE (P > 0.05). The quality of embryos that reached the blastocyst stage was evaluated by counting the inner cell mass (ICM) and trophectoderm (TE) cell numbers and total number of cells; the percentage of ICM and TE cells was unaffected (P > 0.05) in the presence of heparin and PHE (P < 0.05). In conclusion, this study demonstrated that while the supplementation of IVF media with heparin and PHE solution impairs spermatozoa quality, it plays an important role in sperm capacitation, improving pronuclear formation, and early embryonic development. © 2013 The Society for In Vitro Biology.

Controlling the formation of ionic-liquid-based aqueous biphasic systems by changing the hydrogen-bonding ability of polyethylene glycol end groups

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Application of Mossbauer spectroscopy to the study of corrosion resistance in NaCl solution of plasma nitrided AISI 316L stainless steel

Corrosion research in steels is one of the areas in which Mossbauer spectroscopy has become a required analytical technique, since it is a powerful tool for both identifying and quantifying distinctive phases (which contain Fe) with accuracy. In this manuscript, this technique was used to the study of corrosion resistance of plasma nitrided AISI 316L samples in the presence of chloride anions. Plasma nitriding has been carried out using dc glow-discharge, nitriding treatments, in medium of 80 vol.% H-2 and 20 vol.% N-2, at 673 K, and at different time intervals: 2, 4, and 7 h. Treated samples were characterized by means of phase composition and morphological analysis, and electrochemical tests in NaCl aerated solution in order to investigate the influence of treatment time on the microstructure and the corrosion resistance, proved by conversion electron Mossbauer spectroscopy (CEMS), glancing angle X-ray diffraction (GAXRD), scanning electron microscopy (SEM) and potentiodynamic polarization. A modified layer of about 8 gin was observed for all the nitrided samples, independently of the nitriding time. A metastable phase, S phase or gamma(N), was produced. It seems to be correlated with gamma`-Fe-4 N phase. If the gamma(N) fraction decreases, the gamma` fraction increases. The gamma(N) magnetic nature was analyzed. When the nitriding time increases, the results indicate that there is a significant reduction in the relative fraction of the magnetic gamma(N) (in) phase. In contrast, the paramagnetic gamma(N) (p) phase increases. The GAXRD analysis confirms the Mossbauer results, and it also indicates CrN traces for the sample nitrided for 7 h. Corrosion results demonstrate that time in the plasma nitriding treatment plays an important role for the corrosion resistance. The sample treated for 4 h showed the best result of corrosion resistance. It seems that the epsilon/gamma` fraction ratio plays an important role in thin corrosion resistance since this sample shows the maximum value for this ratio. (c) 2008 Published by Elsevier B.V.

Interaction of cationic water-soluble meso-tetrakis(4-N-methylpyridiniumyl)porphyrin (TMPyP) with ionic and nonionic micelles: aggregation and binding

The equilibrium of meso-tetrakis(4-N-methylpyridiniumyl)porphyrin (TMPyP) in aqueous solution in the presence of surfactants was studied by optical spectroscopic techniques and SAXS (small angle X-ray scattering). Anionic SDS (sodium dodecyl sulfate), zwitterionic HPS (N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate) and nonionic TRITON X-100 (t-octyl-phenoxypolyethoxyethanol), surfactants were used. TMPyP is characterized by a protonation equilibrium with a pK(a) around 1.0, associated with the diacid-free base transition, and a second pK(a) around 12.0 related with the transition between the free base and the monoanion form. Three independent species were observed for TMPyP at pH 6.0 as a function of SDS concentration: free TMPyP, TMPyP-SDS aggregates and porphyrin monomer bound to micelles. For HPS and TRITON X-100, the equilibrium of TMPyP as a function of pH is quite similar to that obtained in pure aqueous solution: no aggregation was observed, suggesting that electrostatic contribution is the major factor in the interaction between TMPyP and surfactants. SAXS data analysis demonstrated a prolate ellipsoidal shape for SDS micelles; no significant changes in shape and size were observed for SDS-TMPyP co-micelles. Moreover, the ionization coefficient, alpha, decreases with the increase of the porphyrin concentration, suggesting the ""screening"" of the anionic charge of SDS by the cationic porphyrin. These results are consistent with optical absorption, fluorescence and RLS (resonance light scattering) spectroscopies data, allowing to conclude that neutral surfactants present a smaller interaction with the cationic porphyrin as compared with an ionic surfactant. Therefore, the interaction of TMPyP with the ionic and nonionic surfactants is predominantly due to the electrostatic contribution. Copyright (c) 2008 Society of Porphyrins & Phthalocyanines.

Influence of the use of Aliquat 336 in the immobilization procedure in sol-gel of lipase from Bacillus sp ITP-001

Aliquat 336, a liquid hydrophobic material, was used at different concentrations (0.5-3.0%, w/v) as an additive in the preparation of encapsulated lipase from Bacillus sp. ITP-001 on sol-gel silica matrices using tetraethoxysilane (TEOS) as the precursor. The resulting hydrophobic matrices and immobilized lipases were characterized with regard to specific surface area (BET method), adsorption-desorption isotherms, pore volume (Vp) and size (dp) by nitrogen adsorption (BJH method) and scanning electron microscopy (SEM). The catalytic activities and the corresponding coupling yields were assayed in the hydrolysis of olive oil. In comparison with pure silica matrices, the immobilization process in the presence of Aliquat 336 decreased the values for specific surface area and increased the values for pore specific volume (Vp) and mean pore diameter (dp). This behavior may be related to the partial adsorption of the enzyme on the external surface of the hydrophobic matrix as indicated by scanning electron microscopy. Aliquat 336 concentrations in the range from 0.5 to 1.5% (w/v) provided immobilized derivatives with higher coupling yields and better substrate affinity. The highest coupling yield (Y-A = 71%) was obtained for the immobilized enzyme prepared in the presence of 1.5% Aliquat which gave the following morphological properties: specific surface area = 183 m(2)/g, pore specific volume (Vp) = 0.36 cc/g and mean pore diameter (dp)= 91 angstrom. (c) 2012 Elsevier B.V. All rights reserved.

Extensive structural change of the envelope protein of dengue virus induced by a tuned ionic strength: conformational and energetic analyses

The Dengue has become a global public health threat, with over 100 million infections annually; to date there is no specific vaccine or any antiviral drug. The structures of the envelope (E) proteins of the four known serotype of the dengue virus (DENV) are already known, but there are insufficient molecular details of their structural behavior in solution in the distinct environmental conditions in which the DENVs are submitted, from the digestive tract of the mosquito up to its replication inside the host cell. Such detailed knowledge becomes important because of the multifunctional character of the E protein: it mediates the early events in cell entry, via receptor endocytosis and, as a class II protein, participates determinately in the process of membrane fusion. The proposed infection mechanism asserts that once in the endosome, at low pH, the E homodimers dissociate and insert into the endosomal lipid membrane, after an extensive conformational change, mainly on the relative arrangement of its three domains. In this work we employ all-atom explicit solvent Molecular Dynamics simulations to specify the thermodynamic conditions in that the E proteins are induced to experience extensive structural changes, such as during the process of reducing pH. We study the structural behavior of the E protein monomer at acid pH solution of distinct ionic strength. Extensive simulations are carried out with all the histidine residues in its full protonated form at four distinct ionic strengths. The results are analyzed in detail from structural and energetic perspectives, and the virtual protein movements are described by means of the principal component analyses. As the main result, we found that at acid pH and physiological ionic strength, the E protein suffers a major structural change; for lower or higher ionic strengths, the crystal structure is essentially maintained along of all extensive simulations. On the other hand, at basic pH, when all histidine residues are in the unprotonated form, the protein structure is very stable for ionic strengths ranging from 0 to 225 mM. Therefore, our findings support the hypothesis that the histidines constitute the hot points that induce configurational changes of E protein in acid pH, and give extra motivation to the development of new ideas for antivirus compound design.

Recent Advances in the Development of Magnetically Recoverable Metal Nanoparticle Catalysts

The aim of this Account is to provide an overview of our current research activities on the design and modification of superparamagnetic nanomaterials for application in the field of magnetic separation and catalysis. First, an introduction of magnetism and magnetic separation is done. Then, the synthetic strategies that have been developed for generating superparamagnetic nanoparticles spherically coated by silica and other oxides, with a focus on well characterized systems prepared by methods that generate samples of high quality and easy to scale- up, are discussed. A set of magnetically recoverable catalysts prepared in our research group by the unique combination of superparamagnetic supports and metal nanoparticles is highlighted. This Account is concluded with personal remarks and perspectives on this research field.

Enzyme Microheterogeneous Hydration and Stabilization in Supercritical Carbon Dioxide

Supercritical carbon dioxide is a promising green-chemistry solvent for many enzyme-catalyzed chemical reactions, yet the striking stability of some enzymes in such unconventional environments is not well understood. Here, we investigate the stabilization of the Candida antarctica Lipase B (CALB) in supercritical carbon dioxide-water biphasic systems using molecular dynamics simulations. The preservation of the enzyme structure and optimal activity depend on the presence of small amounts of water in the supercritical dispersing medium. When the protein is at least partially hydrated, water molecules bind to specific sites on the enzyme surface and prevent carbon dioxide from penetrating its catalytic core. Strikingly, water and supercritical carbon dioxide cover the protein surface quite heterogeneously. In the first solvation layer, the hydrophilic residues at the surface of the protein are able to pin down patches of water, whereas carbon dioxide solvates preferentially hydrophobic surface residues. In the outer solvation shells, water molecules tend to cluster predominantly on top of the larger water patches of the first solvation layer instead of spreading evenly around the remainder of the protein surface. For CALB, this exposes the substrate-binding region of the enzyme to carbon dioxide, possibly facilitating diffusion of nonpolar substrates into the catalytic funnel. Therefore, by means of microheterogeneous solvation, enhanced accessibility of hydrophobic substrates to the active site can be achieved, while preserving the functional structure of the enzyme. Our results provide a molecular picture on the nature of the stability of proteins in nonaqueous media.

Synthesis of supported metal nanoparticle catalysts using ligand assisted methods

The synthesis and characterization methods of metal nanoparticles (NPs) have advanced greatly in the last few decades, allowing an increasing understanding of structure-property-performance relationships. However, the role played by the ligands used as stabilizers for metal NPs synthesis or for NPs immobilization on solid supports has been underestimated. Here, we highlight some recent progress in the preparation of supported metal NPs with the assistance of ligands in solution or grafted on solid supports, a modified deposition-reduction method, with special attention to the effects on NPs size, metal-support interactions and, more importantly, catalytic activities. After presenting the general strategies in metal NP synthesis assisted by ligands grafted on solid supports, we highlight some recent progress in the deposition of pre-formed colloidal NPs on functionalized solids. Another important aspect that will be reviewed is related to the separation and recovery of NPs. Finally, we will outline our personal understanding and perspectives on the use of supported metal NPs prepared through ligand-assisted methods.

Heparin and penicillamine–hypotaurine–epinephrine (PHE) solution during bovine in vitro fertilization procedures impair the quality of spermatozoa but improve normal oocyte fecundation and early embryonic development

The presence of heparin and a mixture of penicillamine, hypotaurine, and epinephrine (PHE) solution in the in vitro fertilization (IVF) media seem to be a prerequisite when bovine spermatozoa are capacitated in vitro, in order to stimulate sperm motility and acrosome reaction. The present study was designed to determine the effect of the addition of heparin and PHE during IVF on the quality and penetrability of spermatozoa into bovine oocytes and on subsequent embryo development. Sperm quality, evaluated by the integrity of plasma and acrosomal membranes and mitochondrial function, was diminished (P<0.05) in the presence of heparin and PHE. Oocyte penetration and normal pronuclear formation rates, as well as the percentage of zygotes presenting more than two pronuclei, was higher (P<0.05) in the presence of heparin and PHE. No differences were observed in cleavage rates between treatment and control (P>0.05). However, the developmental rate to the blastocyst stage was increased in the presence of heparin and PHE (P>0.05). The quality of embryos that reached the blastocyst stage was evaluated by counting the inner cell mass (ICM) and trophectoderm (TE) cell numbers and total number of cells; the percentage of ICM and TE cells was unaffected (P>0.05) in the presence of heparin and PHE (P<0.05). In conclusion, this study demonstrated that while the supplementation of IVF media with heparin and PHE solution impairs spermatozoa quality, it plays an important role in sperm capacitation, improving pronuclear formation, and early embryonic development

Experimental investigation into the effect of stress on dissolution and growth of very soluble brittle salts in aqueous solution

Das Studium der Auflösungs- und Wachstumsprozesse an Feststoff-Flüssigkeits-Grenzflächen unter nicht-hydrostatischen Beanspruchungen ist wesentlich für das Verständnis von Defor-mationsprozessen, die in der Erde ablaufen. Unter diesen genannten Prozessen gehört die Drucklösung zu den wichtigsten duktilen Deformationsprozessen, von der Diagenese bishin zur niedrig- bis mittelgradigen metamorphen Bedingungen. Bisher ist allerdings wenig darüber bekannt, welche mechanischen, physikalischen oder chemischen Potentialenergie-Gradienten die Drucklösung steuern. I.a. wird angenommen, daß die Drucklösung durch Un-terschiede kristallplastischer Verformungsenergien oder aber durch Unterschiede der Normal-beanspruchung an Korngrenzen gesteuert wird. Unterschiede der elastischen Verformungs-energien werden dabei allerdings als zu gering erachtet, um einen signifikanten Beitrag zu leisten. Aus diesem Grund werden sie als mögliche treibende Kräfte für die Drucklösung vernachlässigt. Andererseits haben neue experimentelle und theoretische Untersuchungen gezeigt, daß die elastische Verformung in der Tat einen starken Einfluß auf Lösungs- und Wachstumsmechanismen von Kristallen in einer Lösung haben kann. Da die in der Erdkruste vorherrschenden Deformationsmechanismen überwiegend im elastischen Verformungsbereich der Gesteine ablaufen, ist es sehr wichtig, das Verständnis für die Effekte, die die elastische Verformung verursacht, zu erweitern, und ihre Rolle während der Deformation durch Drucklösung zu definieren. Die vorliegende Arbeit beschäftigt sich mit Experimenten, bei denen der Effekt der mechanisch kompressiven Beanspruchung auf Lösungs- und Wachstumsprozesse von Einzelkristallen unterschiedlicher, sehr gut löslicher, elastisch/spröder Salze untersucht wurde. Diese Salze wurden als Analoga gesteinsbildender Minerale wie Quarz und Calcit ausgewählt. Der Einfluß von Stress auf die Ausbildung der Oberflächenmikrostrukturen in einer untersättigten Lösung wurde an Kaliumalaun untersucht.Lösungsrillen (20 – 40 µm breit, 10 – 40 µm tief und 20 – 80 µm Abstand) entwickelten sich in den Bereichen, in denen die Beanspruchung im Kristall am größten war. Sie verschwanden wieder, sobald der Kristall entlastet wurde. Diese Rillen entwickelten sich parallel zu niedrig indizierten kristallographischen Richtungen und sub-perpendikular zu den Trajektorien, die der maximalen, lokalen kompressiven Beanspruchung entsprachen. Die Größe der Lösungsrillen hing von der lokalen Oberflächenbeanspruchung, der Oberflächenenergie und dem Untersättigungsgrad der wässrigen Lösung ab. Die mikrostrukturelle Entwicklung der Kristalloberflächen stimmte gut mit den theoretischen Vorhersagen überein, die auf den Modellen von Heidug & Leroy (1994) und Leroy & Heidug (1994) basieren. Der Einfluß der Beanspruchung auf die Auflösungsrate wurde an Natriumchlorat-Einzelkristallen untersucht. Dabei wurde herausgefunden, daß sich gestresste Kristalle schneller lösen als Kristalle, auf die keine Beanspruchung einwirkt. Der experimentell beobachtete Anstieg der Auflösungsrate der gestressten Kristalle war ein bis zwei Größenordnungen höher als theoretisch erwartet. Die Auflösungsrate stieg linear mit dem Stress an, und der Anstieg war um so größer, je stärker die Lösung untersättigt war. Außerdem wurde der Effekt der Bean-spruchung auf das Kristallwachstum an Kaliumalaun- und Kaliumdihydrogenphosphat-Ein-zelkristallen untersucht. Die Wachstumsrate der Flächen {100} und {110} von Kalium-alaun war bei Beanspruchung stark reduziert. Für all diese Ergebnisse spielte die Oberflächenrauhigkeit der Kristalle eine Schlüsselrolle, indem sie eine nicht-homogene Stressverteilung auf der Kristalloberfläche verursachte. Die Resultate zeigen, daß die elastische Verformung eine signifikante Rolle während der Drucklösung spielen kann, und eine signifikante Deformation in der oberen Kruste verursachen kann, bei Beanspruchungen, die geringer sind, als gemeinhin angenommen wird. Somit folgt, daß die elastische Bean-spruchung berücksichtigt werden muß, wenn mikrophysikalische Deformationsmodelle entwickelt werden sollen.

Electrode Materials for Ionic Liquid Based-Supercapacitors

The development of safe, high energy and power electrochemical energy-conversion systems can be a response to the worldwide demand for a clean and low-fuel-consuming transport. This thesis work, starting from a basic studies on the ionic liquid (IL) electrolytes and carbon electrodes and concluding with tests on large-size IL-based supercapacitor prototypes demonstrated that the IL-based asymmetric configuration (AEDLCs) is a powerful strategy to develop safe, high-energy supercapacitors that might compete with lithium-ion batteries in power assist-hybrid electric vehicles (HEVs). The increase of specific energy in EDLCs was achieved following three routes: i) the use of hydrophobic ionic liquids (ILs) as electrolytes; ii) the design and preparation of carbon electrode materials of tailored morphology and surface chemistry to feature high capacitance response in IL and iii) the asymmetric double-layer carbon supercapacitor configuration (AEDLC) which consists of assembling the supercapacitor with different carbon loadings at the two electrodes in order to exploit the wide electrochemical stability window (ESW) of IL and to reach high maximum cell voltage (Vmax). Among the various ILs investigated the N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR1(2O1)TFSI) was selected because of its hydrophobicity and high thermal stability up to 350 °C together with good conductivity and wide ESW, exploitable in a wide temperature range, below 0°C. For such exceptional properties PYR1(2O1)TFSI was used for the whole study to develop large size IL-based carbon supercapacitor prototype. This work also highlights that the use of ILs determines different chemical-physical properties at the interface electrode/electrolyte with respect to that formed by conventional electrolytes. Indeed, the absence of solvent in ILs makes the properties of the interface not mediated by the solvent and, thus, the dielectric constant and double-layer thickness strictly depend on the chemistry of the IL ions. The study of carbon electrode materials evidences several factors that have to be taken into account for designing performing carbon electrodes in IL. The heat-treatment in inert atmosphere of the activated carbon AC which gave ACT carbon featuring ca. 100 F/g in IL demonstrated the importance of surface chemistry in the capacitive response of the carbons in hydrophobic ILs. The tailored mesoporosity of the xerogel carbons is a key parameter to achieve high capacitance response. The CO2-treated xerogel carbon X3a featured a high specific capacitance of 120 F/g in PYR14TFSI, however, exhibiting high pore volume, an excess of IL is required to fill the pores with respect to that necessary for the charge-discharge process. Further advances were achieved with electrodes based on the disordered template carbon DTC7 with pore size distribution centred at 2.7 nm which featured a notably high specific capacitance of 140 F/g in PYR14TFSI and a moderate pore volume, V>1.5 nm of 0.70 cm3/g. This thesis work demonstrated that by means of the asymmetric configuration (AEDLC) it was possible to reach high cell voltage up to 3.9 V. Indeed, IL-based AEDLCs with the X3a or ACT carbon electrodes exhibited specific energy and power of ca. 30 Wh/kg and 10 kW/kg, respectively. The DTC7 carbon electrodes, featuring a capacitance response higher of 20%-40% than those of X3a and ACT, respectively, enabled the development of a PYR14TFSI-based AEDLC with specific energy and power of 47 Wh/kg and 13 kW/kg at 60°C with Vmax of 3.9 V. Given the availability of the ACT carbon (obtained from a commercial material), the PYR1(2O1)TFSI-based AEDLCs assembled with ACT carbon electrodes were selected within the EU ILHYPOS project for the development of large-size prototypes. This study demonstrated that PYR1(2O1)TFSI-based AEDLC can operate between -30°C and +60°C and its cycling stability was proved at 60°C up to 27,000 cycles with high Vmax up to 3.8 V. Such AEDLC was further investigated following USABC and DOE FreedomCAR reference protocols for HEV to evaluate its dynamic pulse-power and energy features. It was demonstrated that with Vmax of 3.7 V at T> 30 °C the challenging energy and power targets stated by DOE for power-assist HEVs, and at T> 0 °C the standards for the 12V-TSS and 42V-FSS and TPA 2s-pulse applications are satisfied, if the ratio wmodule/wSC = 2 is accomplished, which, however, is a very demanding condition. Finally, suggestions for further advances in IL-based AEDLC performance were found. Particularly, given that the main contribution to the ESR is the electrode charging resistance, which in turn is affected by the ionic resistance in the pores that is also modulated by pore length, the pore geometry is a key parameter in carbon design not only because it defines the carbon surface but also because it can differentially “amplify” the effect of IL conductivity on the electrode charging-discharging process and, thus, supercapacitor time constant.

Sviluppo dei materiali innovativi e studio della loro interazione con sistemi biologici e biomimetici

Nell’ambito della Chimica Sostenibile e dell’applicazione dei suoi principi per la salvaguardia dell’ambiente, il progetto di dottorato ha riguardato lo sviluppo di materiali innovativi e lo studio della loro interazione con sistemi biologici e biomimetici. In particolare l’attività si è focalizzata sulla sintesi di liquidi ionici ed indagini delle interazioni con membrane cellulari e sull’utilizzo ed isolamento di molecole da fonti rinnovabili. I liquidi ionici sono sali organici liquidi a temperature inferiori ai 100 °C; sono considerati promettenti solventi a ridotta tossicità, ma vanno chiarite a pieno le modalità di interazione con i sistemi biologici ed i meccanismi di tossicità. A questo scopo è stata impiegata una batteria di test bio-chimici, con saggi di fluorescenza e colorimetrici, che hanno permesso di discriminare le diverse tipologie di interazioni con varie strutture di membrana. Le informazioni raccolte sono servite per progettare sostanze meno dannose per le strutture cellulari, al fine di scegliere le funzionalità molecolari che consentano ai liquidi ionici di mantenere la loro attività ma di essere meno dannosi per l’ambiente. Per quanto riguarda l’utilizzo ed isolamento di molecole da fonte rinnovabili, si è utilizzata la tecnica della pirolisi per l’ottenimento di starting materials ed il loro impiego nella sintesi di chemicals in alternativa a composti derivanti da fonti fossili. La pirolisi tradizionale della cellulosa fornisce una molecola interessante, per semplicità denominata LAC, in quantità insufficienti ad un uso applicativo. Nell’ambito delle ricerche svolte è stato scoperto che la pirolisi condotta in presenza di catalizzatori meso-strutturati (MCM-41) drogati con metalli di transizione, fornisce buone quantità di LAC. LAC si è dimostrato promettente sia per la produzione di nuove molecole con possibili applicazioni nella chimica fine e farmaceutica, che come monomero per nuovi polimeri (copolimero ed omopolimero).

Luminescent Ionic Transition-Metal Complexes for Light-Emitting Electrochemical Cells

The European Union set the ambitious target of reducing energy consumption by 20% within 2020. This goal demands a tremendous change in how we generate and consume energy and urgently calls for an aggressive policy on energy efficiency. Since 19% of the European electrical energy is used for lighting, considerable savings can be achieved with the development of novel and more efficient lighting systems. In this thesis, accomplished in the frame of the EU project CELLO, I report some selected goals we achieved attempting to develop highly efficient, flat, low cost and flexible light sources using Light-Emitting Electrochemical Cells (LECs), based on ionic cyclometalated iridium(III) complexes. After an extensive introduction about LECs and solid-state lighting in general, I focus on the research we carried out on cyclometalated iridium(III) complexes displaying deep-blue emission, which has turned out to be a rather challenging task. In order to demonstrate the wide versatility of this class of compounds, I also report a case in which some tailored iridium(III) complexes act as near-infrared (NIR) sources. In fact, standard NIR emitting devices are typically expensive and, also in this case, LECs could serve as low-cost alternatives in fields were NIR luminescence is crucial, such as telecommunications and bioimaging. Since LECs are based on only one active material, in the last chapter I stress the importance of an integrated approach toward the right selection of suitable emitters not only from the photophysical, but also from the point of view of material science. An iridium(III) complex, once in the device, is interacting with ionic liquids, metal cathodes, electric fields, etc. All these interactions should be taken in to account if Europe really wants to implement more efficient lighting paradigms, generating light beyond research labs.