Raman spectroscopy study of the transformation of the carbonaceous skeleton of a polymer-based nanoporous carbon along the thermal annealing pathway

We report a multi-wavelength Raman spectroscopy study of the structural changes along the thermal annealing pathway of a poly(furfuryl alcohol) (PFA) derived nanoporous carbon (NPC). The Raman spectra were deconvoluted utilizing G, D, D′, A and TPA bands. The appropriateness of these deconvolutions was confirmed via recovery of the correct dispersive behaviours of these bands. It is proposed that the ID/IG ratio is composed of two parts: one associated with the extent of graphitic crystallites (the Tuinstra–Koenig relationship), and a second related to the inter-defect distance. This model was used to successfully determine the variation of the in-plane size and intra-plane defect density along the annealing pathway. It is proposed that the NPC skeleton evolves along the annealing pathway in two stages: below 1600 °C it was dominated by a reduction of in-plane defects with a minor crystallite growth, and above this temperature growth of the crystallites accelerates as the in-plane defect density approaches zero. A significant amount of transpolyacetylene (TPA)-like structures was found to be remaining even at 2400 °C. These may be responsible for resistance to further graphitization of the PFA-based carbon at higher temperatures.

Characterization of a zeolite-templated carbon by electrochemical quartz crystal microbalance and in situ Raman spectroscopy

Electrochemical quartz crystal microbalance was used to monitor the mass changes during the electrochemical characterization of a zeolite-templated carbon (ZTC) in 1 M H2SO4 medium. Under electrochemical oxidation conditions, a high anodic current and a net mass increase were recorded, resulting in the increase of the specific capacitance owing to the contribution of the pseudocapacitance, mainly derived from the hydroquinone–quinone redox couple. Under more severe electrochemical conditions, a net mass loss was observed, revealing that electrochemical gasification took place. Surface chemistry, before and after the electrochemical treatments, was analyzed through temperature programmed desorption experiments. Furthermore, in situ Raman spectroscopy was used to further characterize the structural changes produced in ZTC under the electrochemical conditions applied, supporting that high potential values produce the electrochemical oxidation and degradation of the carbon material.

Designing intrinsically photostable low band gap polymers:a smart tool combining EPR spectroscopy and DFT calculations

A rapid and efficient method to identify the weak points of the complex chemical structure of low band gap (LBG) polymers, designed for efficient solar cells, when submitted to light exposure is reported. This tool combines Electron Paramagnetic Resonance (EPR) using the 'spin trapping method' coupled with density functional theory modelling (DFT). First, the nature of the short life-time radicals formed during the early-stages of photo-degradation processes are determined by a spin-trapping technique. Two kinds of short life-time radical (R and R′O) are formed after 'short-duration' illumination in an inert atmosphere and in ambient air, respectively. Second, simulation allows the identification of the chemical structures of these radicals revealing the most probable photochemical process, namely homolytical scission between the Si atom of the conjugated skeleton and its pendent side-chains. Finally, DFT calculations confirm the homolytical cleavage observed by EPR, as well as the presence of a group that is highly susceptible to photooxidative attack. Therefore, the synergetic coupling of a spin trapping method with DFT calculations is shown to be a rapid and efficient method for providing unprecedented information on photochemical mechanisms. This approach will allow the design of LBG polymers without the need to trial the material within actual solar cell devices, an often long and costly screening procedure.

Amplification d’impulsions brèves de haute énergie par effet Raman stimulé dans les fibres optiques

Le développement au cours des dernières décennies de lasers à fibre à verrouillage de modes permet aujourd’hui d’avoir accès à des sources fiables d’impulsions femtosecondes qui sont utilisées autant dans les laboratoires de recherche que pour des applications commerciales. Grâce à leur large bande passante ainsi qu’à leur excellente dissipation de chaleur, les fibres dopées avec des ions de terres rares ont permis l’amplification et la génération d’impulsions brèves de haute énergie avec une forte cadence. Cependant, les effets non linéaires causés par la faible taille du faisceau dans la fibre ainsi que la saturation de l’inversion de population du milieu compliquent l’utilisation d’amplificateurs fibrés pour l’obtention d’impulsions brèves dont l’énergie dépasse le millijoule. Diverses stratégies comme l’étirement des impulsions à des durées de l’ordre de la nanoseconde, l’utilisation de fibres à cristaux photoniques ayant un coeur plus large et l’amplification en parallèle ont permis de contourner ces limitations pour obtenir des impulsions de quelques millijoules ayant une durée inférieure à la picoseconde. Ce mémoire de maîtrise présente une nouvelle approche pour l’amplification d’impulsions brèves utilisant la diffusion Raman des verres de silice comme milieu de gain. Il est connu que cet effet non linéaire permet l’amplification avec une large bande passante et ce dernier est d’ailleurs couramment utilisé aujourd’hui dans les réseaux de télécommunications par fibre optique. Puisque l’adaptation des schémas d’amplification Raman existants aux impulsions brèves de haute énergie n’est pas directe, on propose plutôt un schéma consistant à transférer l’énergie d’une impulsion pompe quasi monochromatique à une impulsion signal brève étirée avec une dérive en fréquence. Afin d’évaluer le potentiel du gain Raman pour l’amplification d’impulsions brèves, ce mémoire présente un modèle analytique permettant de prédire les caractéristiques de l’impulsion amplifiée selon celles de la pompe et le milieu dans lequel elles se propagent. On trouve alors que la bande passante élevée du gain Raman des verres de silice ainsi que sa saturation inhomogène permettent l’amplification d’impulsions signal à une énergie comparable à celle de la pompe tout en conservant une largeur spectrale élevée supportant la compression à des durées très brèves. Quelques variantes du schéma d’amplification sont proposées, et leur potentiel est évalué par l’utilisation du modèle analytique ou de simulations numériques. On prédit analytiquement et numériquement l’amplification Raman d’impulsions à des énergies de quelques millijoules, dont la durée est inférieure à 150 fs et dont la puissance crête avoisine 20 GW.

Polimorfismo do alelo HLA-B27 no desenvolvimento das espondilartropatias

A associação da molécula HLA-B27 com a espondilite anquilosante (AS) e outras espondilartropatias (SpA), permanece como uma das mais fortes verificada entre moléculas HLA e doenças humanas. Desde que foi descrita, em 1973, tem sido alvo de intensa investigação na tentativa de compreender o mecanismo patogénico que lhe está subjacente. Este artigo tem como objectivo fazer uma revisão dos conhecimentos actuais relativos à estrutura e polimorfismo da molécula HLA-B27, bem como descrever os modelos propostos para explicar o seu papel no desenvolvimento das espondilartropatias.

Electronic structure and magnetism of Mn-doped GaSb for spintronic applications: A DFT study

We have carried out first-principles spin polarized calculations to obtain comprehensive information regarding the structural, magnetic, and electronic properties of the Mn-doped GaSb compound with dopant concentrations: x¼0.062, 0.083, 0.125, 0.25, and 0.50. The plane-wave pseudopotential method was used in order to calculate total energies and electronic structures. It was found that the MnGa substitution is the most stable configuration with a formation energy of 1.60 eV/Mn-atom. The calculated density of states shows that the half-metallic ferromagnetism is energetically stable for all dopant concentrations with a total magnetization of about 4.0 lB/Mn-atom. The results indicate that the magnetic ground state originates from the strong hybridization between Mn-d and Sb-p states, which agree with previous studies on Mn-doped wide gap semiconductors. This study gives new clues to the fabrication of diluted magnetic semiconductors

DFT STUDIES ON THE MECHANISM OF RING-OPENING POLYMERIZATION OF LACTIDE WITH ADENINE

The use of organic molecules as catalysts for the ring-opening polymerization (ROP) of cyclic esters has gained much interest last years.[1] The use of a molecule of biological interest, able to initiate ROP of cyclic esters without any cocatalyst is even more interesting, as the resulting material will not contain any catalytic residue. Nucleobase-polymer conjugates development is thus an emerging area envisaging biomedical applications.[2] However, they are usually synthesized by tedious multistep procedures. Recently, adenine was used as organoinitiator for the ROP of L-lactide.[3] Reaction conditions involving short reaction times and relatively low temperatures enable the access to adenine-polylactide(Adn-PLA)conjugates in a simple one-step procedure, without additional catalyst and in the absence of solvent. In this study, computational investigations with density functional theory (DFT) were performed in order to clarify the reaction mechanism leading to the desired Adn-PLA. The results show that a hydrogen bond catalytic mechanism, involving a nucleophilic attack of the activated amine group of adenine onto the carbonyl group of lactide, seem to be plausible.

Evaluation of portable Raman spectroscopy and handheld X-ray fluorescence analysis (hXRF) for the direct analysis of glyptics

In archaeometry, the advantages of a combined use of Raman spectroscopy and X-ray fluorescence spectroscopy are extensively discussed for applications such as the analysis of paintings, manuscripts, pottery, etc. Here, we demonstrate for the first time the advantage of using both techniques for analysing glyptics. These engraved gemstones or glass materials were originally used as stamps, to identify the owner, for instance on letters, but also on wine vessels. For this research, a set of 64 glyptics (42 Roman glass specimens and 22 modern ones), belonging to the collection of the museum ‘Quinta das Cruzes’ in Funchal (Madeira, Portugal), was analysed with portable Raman spectroscopy and handheld X-ray fluorescence (hXRF). These techniques were also used to confirm the gemological identification of these precious objects and can give extra information about the glass composition. Raman spectroscopy identifies the molecular composition as well as on the crystalline phases present. On the other hand, hXRF results show that the antique Roman glass samples are characterised with low Pb and Sn levels and that the modern specimens can be discriminated in two groups: lead-based and non-lead-based ones.

A multi-methodological approach for the study of polymorphism in organic pigments and pharmaceuticals

The study of polymorphism has an important role in several fields of materials science, because structural differences lead to different physico-chemical properties of the system. This PhD work was dedicated to the investigation of polymorphism in Indigo, Thioindigo and Quinacridone, as case studies among the organic pigments employed as semiconductors, and in Paracetamol, Phenytoin and Nabumetone, chosen among some commonly used API. The aim of the research was to improve the understanding on the structures of bulk crystals and thin films, adopting Raman spectroscopy as the method of choice, while resorting to other experimental techniques to complement the gathered information. Different crystalline polymorphs, in fact, may be conveniently distinguished by their Raman spectra in the region of the lattice phonons (10-150 cm-1), the frequencies of which, probing the inter-molecular interactions, are very sensitive to even slight modifications in the molecular packing. In particular, we have used Confocal Raman Microscopy, which is a powerful, yet simple, technique for the investigation of crystal polymorphism in organic and inorganic materials, being capable of monitoring physical modifications, chemical transformations and phase inhomogeneities in crystal domains at the micrometre scale. In this way, we have investigated bulk crystals and thin film samples obtained with a variety of crystal growth and deposition techniques. Pure polymorphs and samples with phase mixing were found and fully characterized. Raman spectroscopy was complemented mainly by XRD measurements for bulk crystals and by AFM, GIXD and TEM for thin films. Structures and phonons of the investigated polymorphs were computed by DFT methods, and the comparison between theoretical and experimental results was used to assess the relative stability of the polymorphs and to assist the spectroscopic investigation. The Raman measurements were thus found to be able to clarify ambiguities in the phase assignments which otherwise the other methods were unable to solve.

Studio di catalizzatori a base di Ni modificati con La per la metanazione della CO2

Le emissioni di CO2 in atmosfera da fonti antropogeniche sono attualmente la principale causa del surriscaldamento globale. Tecnologie sostenibili note come Power-to-gas, consentono di valorizzare la CO2, per la produzione di metano, mediante reazione con H2 proveniente dall’elettrolisi dell’acqua, utilizzando energia prodotta da fonti rinnovabili. Il metano, essendo un vettore energetico molto importante, se possiede requisiti di purezza adeguati, può essere introdotto direttamente nella rete del gas. In questo lavoro di tesi sono state investigate le prestazioni catalitiche, nella reazione di metanazione della CO2, di catalizzatori derivati da composti tipo idrotalcite a base di Ni, modificati con La, e con l’aggiunta di Mg e Zn. I catalizzatori sono stati sintetizzati per coprecipitazione a pH costante, calcinati e ridotti prima di condurre le prove catalitiche. Sono stati inoltre caratterizzati mediante tecniche XRD, H2-TPR, analisi porosimetrica e spettroscopia micro-Raman, sia da calcinati che da spenti. I risultati ottenuti dalle prove catalitiche hanno dimostrato che la presenza del La in un catalizzatore Ni/Al aumenta notevolmente l’attività in termini di conversione di CO2 e selettività in CH4, soprattutto a temperature tra 250 e 300°C. L’aggiunta dello Zn nella struttura ad ossidi misti invece ne inibisce l’attività catalitica, portando ad una diminuzione drastica della conversione e selettività. La presenza del Mg promuove una migliore attività catalitica, rispetto ai catalizzatori con solo La, ma necessita di una temperatura di riduzione più elevata.

A DFT study on chemodivergent preparation of piperidinic and morpholinic heterocycles

The topic of this thesis is the DFT computational study of the mechanisms for the synthesis of chiral 3,4,5-trisubstituted piperidines and 2,6-disubstituted morpholines. The goal of this synthesis is to use, the same substrate containing two electrophilic sites: an α,β-unsaturated ester and a ketone, which evolve according to the nucleophile used (cyanide, phenyl sulfide) through different addition and cyclization reactions. A quaternary ammonium salt is used as a catalyst for these reactions, which leads to a diastereoisomeric excess both for the reactions of morpholine and piperidine products. Studies in silico of the pathways of these reactions explain the chemoselection and diasteroselection deriving from the two nucleophiles used. In this case of piperidine products, it was also possible to validate the hypothesis of a concerted nucleophilic addition mechanism on the α,β-unsaturated site and cyclization due to an intramolecular Michael addition.

Determinazione delle barriere rotazionali di nuovi atropisomeri N-N: confronto tra metodi DFT e sperimentali.

Theoretical DFT calculations on rotational barriers of tetrasubstituted hydrazines were performed in order to synthesize new enantioenriched atropoisomers with chiral N-N axis. The molecules studied were chosen to be subsequently synthesized through asymmetric organocatalysis. New atropoisomers with chiral N-N axis were synthesized through organocatalysis methods via enamine or phase transfer. Cinchona alkaloid derivatives were used as catalysts. HPLC analyzes show that the three new synthesized molecules are atropoisomers at room temperature. Using an asymmetric procedure to synthesize the molecules studied, it was possible to generate enantiomeric excesses that remained unchanged for more than three weeks. The experimental rotational barrier of one of the three synthesized compounds was calculated. The experimental energy barrier at 25°C (ΔG^≠=25,7 kcal/mol) was lower than the DFT calculations and with a tendency to increase with temperature, due to a negative reaction entropy.

Studio computazionale DFT e TD-DFT dei dimeri della Rodamina-B

L’oggetto di questo elaborato è lo studio computazionale, a livello della teoria del funzionale della densità (DFT) e della sua formulazione dipendente dal tempo (TD-DFT), dei dimeri della molecola di rodamina-B, parallelo allo sviluppo di una procedura di tuning ottimale del funzionale CAM-B3LYP. Questa molecola, che assume notevole rilevanza nei sistemi light harvesting grazie alle sue proprietà fotochimiche di emissione nel visibile, è impiegata nella sintesi di nanoparticelle (NPs) fluorescenti in ambito di diagnostica medica e bio-imaging, che sfruttano il fenomeno di trasferimento di energia per risonanza (FRET). Per via della notevole importanza che questa molecola riveste nell’ambito della fotochimica, essa è stata oggetto di esperimenti del gruppo di ricerca del laboratorio di biofotonica e farmacologia “Nanochemistry and Bioimaging”, che collabora con il gruppo di chimica computazionale dell’area chimico/fisica del Dipartimento. La dimerizzazione della rodamina all’interno delle NPs può innescare canali di self-quenching che abbassano la resa quantica di fluorescenza, pregiudicando l’efficienza dei dispositivi: l’obiettivo dello studio è la caratterizzazione dei dimeri, in solventi e con controioni diversi, impiegando dei modelli molecolari, per identificarne le specie più stabili e descrivere la fotofisica degli stati elettronici eccitati. Il carattere generalmente charge-transfer (CT) di questi stati elettronici richiede un “tuning ottimale” della metodologia computazionale DFT/TD-DFT per una descrizione quantitativa accurata.

Spettroscopia di fotocorrente su perovskiti ibride in diverse condizioni ambientali

Le perovskiti ibride ad alogenuri costituiscono una classe di materiali con proprietà elettroniche e bassi costi di fabbricazione tali da renderle ottime candidate per applicazioni quali la produzione di celle solari, detector, LED e laser. L’impiego pratico delle perovskiti tuttavia è limitato: i dispositivi basati su questi materiali sono instabili a causa della spiccata reattività con l’ambiente esterno, come umidità e ossigeno. Nelle perovskiti inoltre la conduzione non è solo elettronica, ma anche ionica, caratteristica che contribuisce alla rapida degradazione dei materiali. In questa tesi si vuole studiare il contributo del trasporto ionico ed elettronico alla corrente nella perovskite MAPbBr3 (tribromuro di metilammonio piombo) e la reattività di tale materiale con l’ambiente. A tal proposito si usa la tecnica Intensity Modulated Photocurrent Spectroscopy (IMPS), che consiste nel misurare la fotocorrente prodotta da un dispositivo optoelettronico in funzione della frequenza di modulazione di una sorgente luminosa, quale LED o laser. Si ripetono le misure IMPS in aria, vuoto e argon, per studiare l’impatto dell’atmosfera sulla risposta del campione. Con un apposito software si esegue il fit dei dati sperimentali e si estrapolano i tempi caratteristici dei portatori di carica: si ottengono valori dell’ordine del μs per elettroni e lacune, del s per gli ioni mobili. Si confronta quindi il comportamento del campione nelle varie atmosfere. Si evince come in aria sia presente un maggior numero di specie ioniche che migrano nel materiale rispetto ad atmosfere controllate come il vuoto e l’argon. Tali specie sono associate a ioni mobili che si formano in seguito all’interazione del materiale con molecole di ossigeno e acqua presenti nell’ambiente.