Analysis and control of transient spectra using time-dependent density functional theory.

215 p.

Near-infrared Instrumentation For Rapid-response Astronomy

Ɣ-ray bursts (GRBs) are the Universe's most luminous transient events. Since the discovery of GRBs was announced in 1973, efforts have been ongoing to obtain data over a broader range of the electromagnetic spectrum at the earliest possible times following the initial detection. The discovery of the theorized ``afterglow'' emission in radio through X-ray bands in the late 1990s confirmed the cosmological nature of these events. At present, GRB afterglows are among the best probes of the early Universe (z ≳ 9). In addition to informing theories about GRBs themselves, observations of afterglows probe the circum-burst medium (CBM), properties of the host galaxies and the progress of cosmic reionization. To explore the early-time variability of afterglows, I have developed a generalized analysis framework which models near-infrared (NIR), optical, ultra-violet (UV) and X-ray light curves without assuming an underlying model. These fits are then used to construct the spectral energy distribution (SED) of afterglows at arbitrary times within the observed window. Physical models are then used to explore the evolution of the SED parameter space with time. I demonstrate that this framework produces evidence of the photodestruction of dust in the CBM of GRB 120119A, similar to the findings from a previous study of this afterglow. The framework is additionally applied to the afterglows of GRB 140419A and GRB 080607. In these cases the evolution of the SEDs appears consistent with the standard fireball model. Having introduced the scientific motivations for early-time observations, I introduce the Rapid Infrared Imager-Spectrometer (RIMAS). Once commissioned on the 4.3 meter Discovery Channel Telescope (DCT), RIMAS will be used to study the afterglows of GRBs through photometric and spectroscopic observations beginning within minutes of the initial burst. The instrument will operate in the NIR, from 0.97 μm to 2.37 μm, permitting the detection of very high redshift (z ≳ 7) afterglows which are attenuated at shorter wavelengths by Lyman-ɑ absorption in the intergalactic medium (IGM). A majority of my graduate work has been spent designing and aligning RIMAS's cryogenic (~80 K) optical systems. Design efforts have included an original camera used to image the field surrounding spectroscopic slits, tolerancing and optimizing all of the instrument's optics, thermal modeling of optomechanical systems, and modeling the diffraction efficiencies for some of the dispersive elements. To align the cryogenic optics, I developed a procedure that was successfully used for a majority of the instrument's sub-assemblies. My work on this cryogenic instrument has necessitated experimental and computational projects to design and validate designs of several subsystems. Two of these projects describe simple and effective measurements of optomechanical components in vacuum and at cryogenic temperatures using an 8-bit CCD camera. Models of heat transfer via electrical harnesses used to provide current to motors located within the cryostat are also presented.

Towards near-infrared photoactivation of anticancer metal complexes.

171 p.

Fotodegradação de pesticidas: caso do fenarimol

Tese dout. em Química, Unidade de Ciências Exactas e Humanas, Univ. do Algarve, 1997

Comparative Study of Four Portuguese 16th Century Illuminated Manueline Charters based on Spectroscopy and Chemometrics Analysis

The comparative study based on spectroscopic analysis of the materials used to produce four sixteenth-century Manueline Charters (the Charters of Alcochete, Terena, Alandroal and Evora) was performed following a systematic analytical approach. SEM–EDS, l-Raman and l-FTIR analysis highlighted interesting features between them, namely the use of different pigments and colourants (such as different green and yellow pigments), the presence of pigments alterations and the use of a non-expected extemporaneous material (with the presence of titanium white in the Charter of Alcochete). Principal component analysis restricted to the C–H absorption region (3000–2840 cm-1) was applied to 36 infrared spectra of blue historical samples from the Charters of Alcochete,Terena, Alandroal and Évora, suggesting the use of a mixture of a triglyceride and polysaccharide as binder.

QUANTIFICATION OF CALCIUM IN SPARKLING WINES BY INFRARED SPECTROSCOPY

Markets are increasingly competitive and the companies feel the urge to improve their manufacturing processes. Blending that with a larger control of quality and safety it was created a need to develop new methods of analysis each time more accurate, faster and with lower costs. Alentejo is a region with a wide variety of soils, most of them are rich in calcium and potassium. In the production of sparkling wine many wineries use encapsulated yeast in alginate beads, instead of the traditional method, champenoise. The first method is faster, allowing a more versatile production, reducing the risk of contamination and features organoleptic characteristics similar to the traditional method (yeast free). However, encapsulated yeast spheres should be only used if the base wine matches a number of features, among them calcium content. In this study the calcium content in the wine was determined by atomic absorption spectroscopy (AAS) and by near-infrared spectroscopy. The AAS is a high sensitivity method clearly produces a reliable result, however it is very time consuming and produces great quantities of environmental waste, therefore the possibility of using near-infrared spectroscopy as a method was studied to be a fast, simple and clean alternative to the AAS. It was obtained a calibration model with a variation coefficient higher than 0.80 which indicates that the near-infrared spectroscopy as an adequately alternative the ASS.

Analysis of the high-resolution ro-vibrational spectrum of DC3N in the far and mid infrared regions

Cyanoacetylene HC3N is a molecule of great astronomical importance and it has been observed in many interstellar environments. Its deuterated form DC3N has been detected in number of sources from external galaxies to Galactic interstellar clouds, star-forming regions and planetary atmospheres. All these detections relied on previous laboratory investigations, which however still lack some essential information concerning its infrared spectrum. In this project, high-resolution ro-vibrational spectra of DC3N have been recorded in two energy regions: 150 – 450 cm-1 and 1800 – 2800 cm-1. In the first window the ν7← GS, 2ν7 ← ν7, ν5 ← ν7, ν5+ν7 ← 2ν7, ν6+ν7 → 2v7, 4ν7 ← 2ν7 bands have been assigned, while in the second region the three stretching fundamental bands ν1, ν2, ν3 have been observed and analysed. The 150 – 450 cm-1 region spectra have been recorded at the AILES beamline at the SOLEIL synchrotron (France), the 1800 – 2800 cm-1 spectra at the Department of Industrial Chemistry “Toso Montanari” in Bologna. In total, 2299 transitions have been assigned. Such experimental transition, together with data previously recorded for DC3N, were included in a least-squares fitting procedure from which several spectroscopic parameters have been determined with high precision and accuracy. They include rotational, vibrational and resonance constants. The spectroscopic data of DC3N have been included in a line catalog for this molecule in order to assist future astronomical observations and data interpretation. A paper which includes this research work has been published (M. Melosso, L. Bizzocchi, A. Adamczyk, E. Cane, P. Caselli, L. Colzid, L. Dorea, B. M. Giulianob, J.-C. Guillemine, M-A. Martin-Drumel, O. Piralif, A. Pietropolli Charmet , D. Prudenzano, V. M. Rivillad, F. Tamassia, Extensive ro-vibrational analysis of deuterated-cyanoacetylene (DC3N) from millimeter wavelengths to the infrared domain, Jour. of Quant. Spectr. and Rad. Tran. 254, 107221, 2020).

Retrieval of atmospheric trace gases from DOAS/MAX-DOAS ground-based spectra

The study of the atmospheric chemical composition is crucial to understand the climate changes that we are experiencing in the last decades and to monitor the air quality over industrialized areas. The Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) ground-based instruments are particularly suitable to derive the concentration of some trace gases that absorb the Visible (VIS) and Ultra-Violet (UV) solar radiation. The zenith-sky spectra acquired by the Gas Analyzer Spectrometer Correlating Optical Differences / New Generation 4 (GASCOD/NG4) instrument are exploited to retrieve the NO2 and O3 total Vertical Column Densities (VCDs) over Lecce. The results show that the NO2 total VCDs are significantly affected by the tropospheric content, consequence of the anthropogenic activity. Indeed, they present systematically lower values during Sunday, when less traffic is generally present around the measurement site, and during windy days, especially when the wind direction measured at 2 m height is not from the city of Lecce. Another MAX-DOAS instrument (SkySpec-2D) is exploited to create the first Italian MAX-DOAS site compliant to the Fiducial Reference Measurements for DOAS (FRM4DOAS) standards, in San Pietro Capofiume (SPC), located in the middle of the Po Valley. After the assessment of the SkySpec-2D’s performances through two measurement campaigns taken place in Bologna and in Rome, SkySpec-2D is installed in SPC on the 1st October 2021. Its MAX-DOAS spectra are used to retrieve the NO2 and O3 total VCDs, and aerosol extinction and NO2 tropospheric vertical profiles over the Po Valley exploiting the Bremen Optimal estimation REtrieval for Aerosol and trace gaseS (BOREAS) algorithm. Promising results are found, with high correlations against both in-situ and satellite data. In the future, these data will play an important role for air quality studies over the Po Valley and for satellite validation purposes.

Analysis Of The Dna Fourier Transform-infrared Microspectroscopic Signature Using An All-reflecting Objective.

The Fourier transform-infrared (FT-IR) signature of dry samples of DNA and DNA-polypeptide complexes, as studied by IR microspectroscopy using a diamond attenuated total reflection (ATR) objective, has revealed important discriminatory characteristics relative to the PO2(-) vibrational stretchings. However, DNA IR marks that provide information on the sample's richness in hydrogen bonds have not been resolved in the spectral profiles obtained with this objective. Here we investigated the performance of an all reflecting objective (ARO) for analysis of the FT-IR signal of hydrogen bonds in DNA samples differing in base richness types (salmon testis vs calf thymus). The results obtained using the ARO indicate prominent band peaks at the spectral region representative of the vibration of nitrogenous base hydrogen bonds and of NH and NH2 groups. The band areas at this spectral region differ in agreement with the DNA base richness type when using the ARO. A peak assigned to adenine was more evident in the AT-rich salmon DNA using either the ARO or the ATR objective. It is concluded that, for the discrimination of DNA IR hydrogen bond vibrations associated with varying base type proportions, the use of an ARO is recommended.

Ihwg-μnir: A Miniaturised Near-infrared Gas Sensor Based On Substrate-integrated Hollow Waveguides Coupled To A Micro-nir-spectrophotometer.

A miniaturised gas analyser is described and evaluated based on the use of a substrate-integrated hollow waveguide (iHWG) coupled to a microsized near-infrared spectrophotometer comprising a linear variable filter and an array of InGaAs detectors. This gas sensing system was applied to analyse surrogate samples of natural fuel gas containing methane, ethane, propane and butane, quantified by using multivariate regression models based on partial least square (PLS) algorithms and Savitzky-Golay 1(st) derivative data preprocessing. The external validation of the obtained models reveals root mean square errors of prediction of 0.37, 0.36, 0.67 and 0.37% (v/v), for methane, ethane, propane and butane, respectively. The developed sensing system provides particularly rapid response times upon composition changes of the gaseous sample (approximately 2 s) due the minute volume of the iHWG-based measurement cell. The sensing system developed in this study is fully portable with a hand-held sized analyser footprint, and thus ideally suited for field analysis. Last but not least, the obtained results corroborate the potential of NIR-iHWG analysers for monitoring the quality of natural gas and petrochemical gaseous products.

Study Of The Homogeneity Of Drug Loaded In Polymeric Films Using Near-infrared Chemical Imaging And Split-plot Design.

Split-plot design (SPD) and near-infrared chemical imaging were used to study the homogeneity of the drug paracetamol loaded in films and prepared from mixtures of the biocompatible polymers hydroxypropyl methylcellulose, polyvinylpyrrolidone, and polyethyleneglycol. The study was split into two parts: a partial least-squares (PLS) model was developed for a pixel-to-pixel quantification of the drug loaded into films. Afterwards, a SPD was developed to study the influence of the polymeric composition of films and the two process conditions related to their preparation (percentage of the drug in the formulations and curing temperature) on the homogeneity of the drug dispersed in the polymeric matrix. Chemical images of each formulation of the SPD were obtained by pixel-to-pixel predictions of the drug using the PLS model of the first part, and macropixel analyses were performed for each image to obtain the y-responses (homogeneity parameter). The design was modeled using PLS regression, allowing only the most relevant factors to remain in the final model. The interpretation of the SPD was enhanced by utilizing the orthogonal PLS algorithm, where the y-orthogonal variations in the design were separated from the y-correlated variation.

Dielectron Mass Spectra From Au+au Collisions At √[s(nn)]=200 gev.

We report the STAR measurements of dielectron (e(+)e(-)) production at midrapidity (|y(ee)|<1) in Au+Au collisions at √[s(NN)]=200  GeV. The measurements are evaluated in different invariant mass regions with a focus on 0.30-0.76 (ρ-like), 0.76-0.80 (ω-like), and 0.98-1.05 (ϕ-like)   GeV/c(2). The spectrum in the ω-like and ϕ-like regions can be well described by the hadronic cocktail simulation. In the ρ-like region, however, the vacuum ρ spectral function cannot describe the shape of the dielectron excess. In this range, an enhancement of 1.77±0.11(stat)±0.24(syst)±0.33(cocktail) is determined with respect to the hadronic cocktail simulation that excludes the ρ meson. The excess yield in the ρ-like region increases with the number of collision participants faster than the ω and ϕ yields. Theoretical models with broadened ρ contributions through interactions with constituents in the hot QCD medium provide a consistent description of the dilepton mass spectra for the measurement presented here and the earlier data at the Super Proton Synchrotron energies.

Atomic Charge Transfer-counter Polarization Effects Determine Infrared Ch Intensities Of Hydrocarbons: A Quantum Theory Of Atoms In Molecules Model.

Atomic charge transfer-counter polarization effects determine most of the infrared fundamental CH intensities of simple hydrocarbons, methane, ethylene, ethane, propyne, cyclopropane and allene. The quantum theory of atoms in molecules/charge-charge flux-dipole flux model predicted the values of 30 CH intensities ranging from 0 to 123 km mol(-1) with a root mean square (rms) error of only 4.2 km mol(-1) without including a specific equilibrium atomic charge term. Sums of the contributions from terms involving charge flux and/or dipole flux averaged 20.3 km mol(-1), about ten times larger than the average charge contribution of 2.0 km mol(-1). The only notable exceptions are the CH stretching and bending intensities of acetylene and two of the propyne vibrations for hydrogens bound to sp hybridized carbon atoms. Calculations were carried out at four quantum levels, MP2/6-311++G(3d,3p), MP2/cc-pVTZ, QCISD/6-311++G(3d,3p) and QCISD/cc-pVTZ. The results calculated at the QCISD level are the most accurate among the four with root mean square errors of 4.7 and 5.0 km mol(-1) for the 6-311++G(3d,3p) and cc-pVTZ basis sets. These values are close to the estimated aggregate experimental error of the hydrocarbon intensities, 4.0 km mol(-1). The atomic charge transfer-counter polarization effect is much larger than the charge effect for the results of all four quantum levels. Charge transfer-counter polarization effects are expected to also be important in vibrations of more polar molecules for which equilibrium charge contributions can be large.