Indium-Mediated Cleavage of the Trityl Group from Protected 1H-Tetrazoles

On treatment with indium metal in MeOH–THF, trityl groups undergo reductive removal from 1H-protected tetrazoles (including aliphatic, aromatic, and heteroaromatic substituents), affording the corresponding free tetrazoles in excellent yields, without any decomposition of the tetrazole ring or reduction of any other group.

Effect of Urucu oil (Brazilian Amazon) on the biomass of the aquatic macrophyte Eichhornia crassipes (Mart.) Solms (Pontederiaceae)

Os rios e lagos de várzea da província petrolífera de Urucu, na Amazônia Central, são amplamente colonizados por macrófitas aquáticas, que podem ser afetadas por acidentes durante a exploração e o transporte de petróleo. Entre as macrófitas, a espécie flutuante Eichhornia crassipes (aguapé) ocorre abundantemente na região; OBJETIVO: O objetivo desse estudo foi verificar o efeito de diferentes dosagens do petróleo de Urucu (0; 0,5; 1,5 e 3,0 L.m-2) na biomassa viva e morta de E. crassipes e em algumas características físicas e químicas da água; MÉTODOS: O experimento teve oitenta e quatro dias de duração. A cada sete dias foi determinada a biomassa (viva e morta) de E. crassipes e os valores de temperatura, pH, condutividade elétrica e oxigênio dissolvido da água; RESULTADOS: A dosagem de 0,5 L.m-2 foi suficiente para causar mortalidade parcial (48%) em E. crassipes após trinta e cinco dias de exposição ao petróleo. A dosagem de 3,0 L.m-2 causou mortalidade total (100%) em E. crassipes em oitenta e quatro dias de exposição. A decomposição do petróleo e da biomassa morta de E. crassipes provocam a redução do oxigênio dissolvido e do pH, e aumento da condutividade elétrica e de fósforo total na água; CONCLUSÕES: Nós concluímos que um derramamento de petróleo pode provocar mortalidade total em uma população de uma espécie de macrófita, mas não em uma outra. Isto pode alterar a diversidade de espécies de macrófitas na região impactada. No caso de Eichhornia crassipes e Pistia stratiotes, um derramamento de petróleo de Urucu pode favorecer E. crassipes, a espécie menos sensível ao petróleo.

Nuclear Magnetic Resonance Spectroscopic and Computational Investigations of Chloroperoxidase Catalyzed Regio- and Enantio-Selective Transformations

Chloroperoxidase (CPO) is the most versatile heme-containing enzyme that catalyzes a broad spectrum of reactions. The remarkable feature of this enzyme is the high regio- and enantio-selectivity exhibited in CPO-catalyzed oxidation reactions. The aim of this dissertation is to elucidate the structural basis for regio- and enantio-selective transformations and investigate the application of CPO in biodegradation of synthetic dyes. To unravel the mechanism of CPO-catalyzed regioselective oxidation of indole, the dissertation explored the structure of CPO-indole complex using paramagnetic relaxation and molecular modeling. The distances between the protons of indole and the heme iron revealed that the pyrrole ring of indole is oriented toward the heme with its 2-H pointing directly at the heme iron. This provides the first experimental and theoretical explanation for the "unexpected" regioselectivity of CPO-catalyzed indole oxidation. Furthermore, the residues including Leu 70, Phe 103, Ile 179, Val 182, Glu 183, and Phe 186 were found essential to the substrate binding to CPO. These results will serve as a lighthouse in guiding the design of CPO mutants with tailor-made activities for biotechnological applications. To understand the origin of the enantioselectivity of CPO-catalyzed oxidation reactions, the interactions of CPO with substrates such as 2-(methylthio)thiophene were investigated by nuclear magnetic resonance spectroscopy (NMR) and computational techniques. In particular, the enantioselectivity is partly explained by the binding orientation of substrates. In third facet of this dissertation, a green and efficient system for degradation of synthetic dyes was developed. Several commercial dyes such as orange G were tested in the CPO-H2O2-Cl- system, where degradation of these dyes was found very efficient. The presence of halide ions and acidic pH were found necessary to the decomposition of dyes. Significantly, the results revealed that this degradation of azo dyes involves a ferric hypochlorite intermediate of CPO (Fe-OCl), compound X.

Study of ammonia borane and its derivatives: Influence of nanoconfinements and pressures

Recently, ammonia borane has increasingly attracted researchers’ attention because of its merging applications, such as organic synthesis, boron nitride compounds synthesis, and hydrogen storage. This dissertation presents the results from several studies related to ammonia borane. ^ The pressure-induced tetragonal to orthorhombic phase transition in ammonia borane was studied in a diamond anvil cell using in situ Raman spectroscopy. We found a positive Clapeyron-slope for this phase transformation in the experiment, which implies that the phase transition from tetragonal to orthorhombic is exothermic. The result of this study indicates that the rehydrogenation of the high pressure orthorhombic phase is expected to be easier than that of the ambient pressure tetragonal phase due to its lower enthalpy. ^ The high pressure behavior of ammonia borane after thermal decomposition was studied by in situ Raman spectroscopy at high pressures up to 10 GPa. The sample of ammonia borane was first decomposed at ∼140 degree Celcius and ∼0.7 GPa and then compessed step wise in an isolated sample chamber of a diamond anvil cell for Raman spectroscopy measurement. We did not observe the characteristic shift of Raman mode under high pressure due to dihydrogen bonding, indicating that the dihydrogen bonding disappears in the decomposed ammonia borane. Although no chemical rehydrogenation was detected in this study, the decomposed ammonia borane could store extra hydrogen by physical absorption. ^ The effect of nanoconfinement on ammonia borane at high pressures and different temperatures was studied. Ammonia borane was mixed with a type of mesoporous silica, SBA-15, and restricted within a small space of nanometer scale. The nano-scale ammonia borane was decomposed at ∼125 degree Celcius in a diamond anvil cell and rehydrogenated after applying high pressures up to ∼13 GPa at room temperature. The successful rehydrogenation of decomposed nano-scale ammonia borane gives guidance to further investigations on hydrogen storage. ^ In addition, the high pressure behavior of lithium amidoborane, one derivative of ammonia borane, was studied at different temperatures. Lithium amidoborane (LAB) was decomposed and recompressed in a diamond anvil cell. After applying high pressures on the decomposed lithium amidoborane, its recovery peaks were discovered by Raman spectroscopy. This result suggests that the decomposition of LAB is reversible at high pressures.^

Impact of potassium and phosphorus in biomass on the properties of fast Pyrolysis bio-oil

This study investigates fast pyrolysis bio-oils produced from alkali-metal-impregnated biomass (beech wood). The impregnation aim is to study the catalytic cracking of the pyrolysis vapors as a result of potassium or phosphorus. It is recognized that potassium and phosphorus in biomass can have a major impact on the thermal conversion processes. When biomass is pyrolyzed in the presence of alkali metal cations, catalytic cracking of the pyrolysis liquids occurs in the vapor phase, reducing the organic liquids produced and increasing yields of water, char, and gas, resulting in a bio-oil that has a lower calorific value and an increased chance of phase separation. Beech wood was impregnated with potassium or phosphorus (K impregnation and P impregnation, respectively) in the range of 0.10-2.00 wt %. Analytical pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) was used to examine the pyrolysis products during thermal degradation, and thermogravimetric analysis (TGA) was used to examine the distribution of char and volatiles. Both potassium and phosphorus are seen to catalyze the pyrolytic decomposition of biomass and modify the yields of products. 3-Furaldehyde and levoglucosenone become more dominant products upon P impregnation, pointing to rearrangement and dehydration routes during the pyrolysis process. Potassium has a significant influence on cellulose and hemicellulose decomposition, not just on the formation of levoglucosan but also other species, such as 2(5H)-furanone or hydroxymethyl-cyclopentene derivatives. Fast pyrolysis processing has also been undertaken using a laboratory-scale continuously fed bubbling fluidized-bed reactor with a nominal capacity of 1 kg h-1 at the reaction temperature of 525 °C. An increase in the viscosity of the bio-oil during the stability assessment tests was observed with an increasing percentage of impregnation for both additives. This is because bio-oil undergoes polymerization while placed in storage as a result of the inorganic content. The majority of inorganics are concentrated in the char, but small amounts are entrained in the pyrolysis vapors and, therefore, end up in the bio-oil.

Efficient removal of paracetamol using LaCu1-xMxO3 (M=Mn, Ti) perovskites as heterogeneous Fenton-like catalysts

A series of perovskite-like oxides LaCu1-xMxO3 (M=Mn, Ti; 0.0 ⩽ x ⩽ 0.8) was prepared by amorphous citrate decomposition and characterized by XRD, ICP-OES and XPS techniques. The catalysts were tested in the Fenton-like degradation of paracetamol with H2O2, under mild reaction conditions, 25 °C and nearly neutral pH. Values of decomposition of paracetamol between 80 and 97% at 300 min were achieved for most of samples. The presence of the Cu2+/Cu+ pair at the surface of the catalysts is necessary to carry out the reaction and the catalysts containing higher amount of copper at the surface, resulted to be more active. The leaching of metals was less than 1%, which discards the contribution of the homogenous Fenton-like reaction and remarks the high stability of the metals into the mixed oxide network. The catalytic activity of LaCu0.8Mn0.2O3 was maintained after three cycles of reaction, which proves the stability and reusability of the catalyst.

Altered oscillatory dynamics of CA1 parvalbumin-basket cells during theta-gamma rhythmopathies of temporal lobe epilepsy

Recent reports in human demonstrate a role of theta– gamma coupling in memory for spatial episodes and a lack of coupling in people experiencing temporal lobe epilepsy, but the mechanisms are unknown. Using multisite silicon probe recordings of epileptic rats engaged in episodic-like object recognition tasks, we sought to evaluate the role of theta– gamma coupling in the absence of epileptiform activities. Our data reveal a specific association between theta– gamma (30 – 60 Hz) coupling at the proximal stratum radiatum of CA1 and spatial memory deficits. We targeted the microcircuit mechanisms with a novel approach to identify putative interneuronal types in tetrode recordings (parvalbumin basket cells in particular) and validated classification criteria in the epileptic context with neurochemical identification of intracellularly recorded cells. In epileptic rats, putative parvalbumin basket cells fired poorly modulated at the falling theta phase, consistent with weaker inputs from Schaffer collaterals and attenuated gamma oscillations, as evaluated by theta-phase decomposition of current–source density signals. We propose that theta– gamma interneuronal rhythmopathies of the temporal lobe are intimately related to episodic memory dysfunction in this condition.

Synthesis of Anisotropic Magnetic Nanoobjects Designed for Locomotion in External Magnetic Fields

The subject of the present work is the synthesis of novel nanoscale objects, designed for self-propulsion under external actuation. The synthesized objects present asymmetric hybrid particles, consisting of a magnetic core and polymer flagella and their hydrodynamic properties under the actuation by external magnetic fields are investigated. The single-domain ferromagnetic cobalt ferrite nanoparticles are prepared by thermal decomposition of a mixture of metalorganic complexes based on iron (III) cobalt (II) in non-polar solvents. Further modification of the particles includes the growth of the silver particle on the surface of the cobalt ferrite particle to form a dumbbell-shaped heterodimer. Different possible mechanisms of dumbbell formation are discussed. A polyelectrolyte tail with ability to adjust the persistence length of the polymer, and thus the stiffness of the tail, by variation of pH is attached to the particles. A polymer tail consisting of a polyacrylic acid chain is synthesized by hydrolysis of poly(tert-butyl acrylate) obtained by atom transfer radical polymerization (ATRP). A functional thiol end-group enables selective attachment of the tail to the silver part of the dumbbell, resulting in an asymmetric functionalization of the dumbbells. The calculations on the propulsion force and the sperm number for the resulting particles reveal a theoretical possibility for the propelled motion. Under the actuation of the particles with flagella by alternating magnetic field an increase in the diffusion coefficient compared to non-actuated or non-functionalized particles is observed. Further development of such systems for application as nanomotors or in drug delivery is promising.

Fate of discards from deep water crustacean trawl fishery off the south coast of Portugal

Trawling for crustaceans takes place on the south coast of Portugal at depths between 200 and 800 m. Large amounts of discards are released back to sea, reaching the bottom in the general area where trawling occurs. The objective of this work was to study the time taken for decomposition of the discards, to identify the most important scavenging species involved, and to evaluate the impact on the species targeted by the fishery. We conducted a series of 22 trials, using traps baited with samples of the discards. The time of immersion varied between 1 and 40 h. The amount of tissue removed from the discards was evaluated on a qualitative scale of 1–3, and quantitatively. The species caught in the traps were identified. Considerable consumption of the bait had occurred after 5 h of immersion. After 24 h of immersion only fish bones were left; past 40 h, consumption was complete. The conger eel (Conger conger) was the most common fish species present in the traps. Two species, the amphipod Scopelocheirus hopei and the isopod Natatolana (Cirolana) borealis, were identified as most important for the recycling of organic matter in the system. The stomach contents of a sample of species caught in trawls were analysed for the presence of small scavengers. Preliminary results show that S. hopei and N. (C.) borealis are part of the diet of some of the target species of this fishery, such as the Norway lobster, Nephrops norvegicus and the rose shrimp Parapenaeus longirostris.

Tensor-Train decomposition for image classification problems

In these last years a great effort has been put in the development of new techniques for automatic object classification, also due to the consequences in many applications such as medical imaging or driverless cars. To this end, several mathematical models have been developed from logistic regression to neural networks. A crucial aspect of these so called classification algorithms is the use of algebraic tools to represent and approximate the input data. In this thesis, we examine two different models for image classification based on a particular tensor decomposition named Tensor-Train (TT) decomposition. The use of tensor approaches preserves the multidimensional structure of the data and the neighboring relations among pixels. Furthermore the Tensor-Train, differently from other tensor decompositions, does not suffer from the curse of dimensionality making it an extremely powerful strategy when dealing with high-dimensional data. It also allows data compression when combined with truncation strategies that reduce memory requirements without spoiling classification performance. The first model we propose is based on a direct decomposition of the database by means of the TT decomposition to find basis vectors used to classify a new object. The second model is a tensor dictionary learning model, based on the TT decomposition where the terms of the decomposition are estimated using a proximal alternating linearized minimization algorithm with a spectral stepsize.

Characterization of ENSO changes under idealised radiative forcing in an intermediate complexity general circulation model

Intermediate-complexity general circulation models are a fundamental tool to investigate the role of internal and external variability within the general circulation of the atmosphere and ocean. The model used in this thesis is an intermediate complexity atmospheric general circulation model (SPEEDY) coupled to a state-of-the-art modelling framework for the ocean (NEMO). We assess to which extent the model allows a realistic simulation of the most prominent natural mode of variability at interannual time scales: El-Niño Southern Oscillation (ENSO). To a good approximation, the model represents the ENSO-induced Sea Surface Temperature (SST) pattern in the equatorial Pacific, despite a cold tongue-like bias. The model underestimates (overestimates) the typical ENSO spatial variability during the winter (summer) seasons. The mid-latitude response to ENSO reveals that the typical poleward stationary Rossby wave train is reasonably well represented. The spectral decomposition of ENSO features a spectrum that lacks periodicity at high frequencies and is overly periodic at interannual timescales. We then implemented an idealised transient mean state change in the SPEEDY model. A warmer climate is simulated by an alteration of the parametrized radiative fluxes that corresponds to doubled carbon dioxide absorptivity. Results indicate that the globally averaged surface air temperature increases of 0.76 K. Regionally, the induced signal on the SST field features a significant warming over the central-western Pacific and an El-Niño-like warming in the subtropics. In general, the model features a weakening of the tropical Walker circulation and a poleward expansion of the local Hadley cell. This response is also detected in a poleward rearrangement of the tropical convective rainfall pattern. The model setting that has been here implemented provides a valid theoretical support for future studies on climate sensitivity and forced modes of variability under mean state changes.

Optimization of aqueous Zn-ion batteries

MnHCF was synthesized by simple co-precipitation method. In this work we investigate the electrochemical behavior of manganese hexacyanoferrate in zinc sulfate (ZnSO4), ZnSO4+MnSO4 and zinc triflate (Zn(OTF)2) aqueous electrolytes. Electrochemical tests were performed by both El-cell which is designed for reflection investigation and coin cell. In cyclic voltammetry curves, we observed redox peaks of both Fe3+/2+ and Mn3+/2+ pairs. The results based on current shows that the capacity of battery is controlled by diffusion process in aqueous electrolyte system. MnHCF undergoes severe dissolution and zinc displacement during cycling. Compared to ZnSO4, anions of Zn (OTF)2 electrolyte are strongly adsorbed on the electrolyte surface, in turn hindering the water oxidation reaction and reducing the decomposition of MnHCF. The MnHCF/Zn battery using 3M Zn (OTF)2 delivers a specific capacity of 41 mAhg-1 at 50 mAg-1 while by using 3M ZnSO4+1M MnSO4 the specific capacity reaches to 400 mAhg-1 for the pure sample and around 250 mAhg-1 for the MnHCF+A. Our results suggest that the anions in the aqueous electrolyte are of great importance to optimize the electrochemical performance of metal hexacyanoferrates. The pre-addition of MnSO4 into ZnSO4 solution is capable of easing the Mn2+ dissolution from the cathode.

PARAFAC: uma ferramenta quimiométrica para tratamento de dados multidimensionais. Aplicações na determinação direta de fármacos em plasma humano por espectrofluorimetria

Since the last decade, the combined use of chemometrics and molecular spectroscopic techniques has become a new alternative for direct drug determination, without the need of physical separation. Among the new methodologies developed, the application of PARAFAC in the decomposition of spectrofluorimetric data should be highlighted. The first objective of this article is to describe the theoretical basis of PARAFAC. For this purpose, a discussion about the order of chemometric methods used in multivariate calibration and the development of multi-dimensional methods is presented first. The other objective of this article is to divulge for the Brazilian chemical community the potential of the combination PARAFAC/spectrofluorimetry for the determination of drugs in complex biological matrices. For this purpose, two applications aiming at determining, respectively, doxorrubicine and salicylate in human plasma are presented.

Termogravimetria: um novo enfoque para a clássica determinação de cálcio em cascas de ovos

The use of thermoanalytical data in sample preparation is described as a tool to catch the students' attention to some details that can simplify both the analysis and the analytical procedure. In this case, the thermal decomposition of eggshells was first investigated by thermogravimetry (TGA). Although the classical procedures suggest long exposure to high temperatures, the TGA data showed that the decomposition of organic matter takes place immediately when the sample is heated up to 800 °C under air atmosphere. After decomposition, the calcium content was determined by flame atomic emission photometry and compared with the results obtained using classical volumetric titration with EDTA.

Estudo da decomposição térmica de propelente sólido compósito de baixa emissão de fumaça

The thermal decomposition of hydroxyl-terminated polybutadiene (HTPB)/ammonium nitrate (AN) based propellants, so called smokeless formulations, and raw materials were investigated by differential scanning calorimetry (DSC) and thermogravimetry (TG). The thermoanalytical profile of different components and of propellant were evaluated and the Arrhenius parameters for the thermal decomposition of the propellant sample were determined by the Ozawa method. The kinetic parameters of the thermal decomposition of propellant samples were determined by DSC measurements. The values obtained for activation energy (Ea) and pre-exponential factor were 163 kJ mol-1 and 1.94x10(6) min-1.