Ruthenium(II) Arene Complexes Bearing Tris(pyrazolyl)methanesulfonate Capping Ligands.Electrochemistry, Spectroscopic, and X-ray Structural Characterization

Novel [Ru(L)(Tpms)]Cl and [Ru(L)(Tpms(Ph))]Cl complexes (L = p-cymene, benzene, or hexamethylbenzene, Tpms = tris(pyrazolyl)-methanesulfonate, Tpms(Ph) = tris(3-phenylpyrazoly)methanesulfonate) have been prepared by reaction of [Ru(L)(mu-Cl)(2)](2) with Li[Tpms] and Li[Tpms(Ph)], respectively. [Ru(p-cymene)(Tpms)]BF4 has been synthesized through a metathetic reaction of [Ru(p-cymene)(Tpms)]Cl with AgBF4. [RuCl(cod)(Tpms)] (cod = 1,5-cyclooctadiene) and [RuCl(cod)(Tpms(Ph))] are also reported, being obtained by reaction of [RuCl2(cod)(MeCN)(2)] with Li[Tpms] and Li[Tpms(Ph)], respectively. The structures of the complexes and the coordination modes of the ligands have been established by IR, NMR, and single-crystal X-ray diffraction (for [RuL(Tpms)]X (L = p-cymene or HMB, X = Cl; L = p-cymene, X = BF4)) studies. Electrochemical studies showed that each complex undergoes a single-electron R-II -> R-III oxidation at a potential measured by cyclic voltammetry, allowing to compare the electron-donor characters of the tris(pyrazolyl)methanesulfonate and arene ligands, and to estimate, for the first time, the values of the Lever E-L ligand parameter for Tmps(Ph), HMB, and cod.

Image quality and dose analysis for a PA chest X-ray: comparison between AEC mode acquisition and manual mode using the 10 kVp ‘rule’

Purpose - To compare the image quality and effective dose applying the 10 kVp rule with manual mode acquisition and AEC mode in PA chest X-ray. Method - 68 images (with and without lesions) were acquired using an anthropomorphic chest phantom using a Wolverson Arcoma X-ray unit. These images were compared against a reference image using the 2 alternative forced choice (2AFC) method. The effective dose (E) was calculated using PCXMC software using the exposure parameters and the DAP. The exposure index (lgM provided by Agfa systems) was recorded. Results - Exposure time decreases more when applying the 10 kVp rule with manual mode (50%–28%) when compared with automatic mode (36%–23%). Statistical differences for E between several ionization chambers' combinations for AEC mode were found (p = 0.002). E is lower when using only the right AEC ionization chamber. Considering the image quality there are no statistical differences (p = 0.348) between the different ionization chambers' combinations for AEC mode for images with no lesions. Considering lgM values, it was demonstrated that they were higher when the AEC mode was used compared to the manual mode. It was also observed that lgM values obtained with AEC mode increased as kVp value went up. The image quality scores did not demonstrate statistical significant differences (p = 0.343) for the images with lesions comparing manual with AEC mode. Conclusion - In general the E is lower when manual mode is used. By using the right AEC ionising chamber under the lung the E will be the lowest in comparison to other ionising chambers. The use of the 10 kVp rule did not affect the visibility of the lesions or image quality.

A survey in Portuguese X-ray fluoroscopy equipment: dose rates and image quality

X-ray fluoroscopy is essential in both diagnosis and medical intervention, although it may contribute to significant radiation doses to patients that have to be optimised and justified. Therefore, it is crucial to the patient to be exposed to the lowest achievable dose without compromising the image quality. The purpose of this study was to perform an analysis of the quality control measurements, particularly dose rates, contrast and spatial resolution of Portuguese fluoroscopy equipment and also to provide a contribution to the establishment of reference levels for the equipment performance parameters. Measurements carried out between 2007 and 2013 on 143 fluoroscopy equipment distributed by 34 nationwide health units were analysed. The measurements suggest that image quality and dose rates of Portuguese equipment are congruent with other studies, and in general, they are as per the Portuguese law. However, there is still a possibility of improvements intending optimisation at a national level.

Mining protein structure data

The principal topic of this work is the application of data mining techniques, in particular of machine learning, to the discovery of knowledge in a protein database. In the first chapter a general background is presented. Namely, in section 1.1 we overview the methodology of a Data Mining project and its main algorithms. In section 1.2 an introduction to the proteins and its supporting file formats is outlined. This chapter is concluded with section 1.3 which defines that main problem we pretend to address with this work: determine if an amino acid is exposed or buried in a protein, in a discrete way (i.e.: not continuous), for five exposition levels: 2%, 10%, 20%, 25% and 30%. In the second chapter, following closely the CRISP-DM methodology, whole the process of construction the database that supported this work is presented. Namely, it is described the process of loading data from the Protein Data Bank, DSSP and SCOP. Then an initial data exploration is performed and a simple prediction model (baseline) of the relative solvent accessibility of an amino acid is introduced. It is also introduced the Data Mining Table Creator, a program developed to produce the data mining tables required for this problem. In the third chapter the results obtained are analyzed with statistical significance tests. Initially the several used classifiers (Neural Networks, C5.0, CART and Chaid) are compared and it is concluded that C5.0 is the most suitable for the problem at stake. It is also compared the influence of parameters like the amino acid information level, the amino acid window size and the SCOP class type in the accuracy of the predictive models. The fourth chapter starts with a brief revision of the literature about amino acid relative solvent accessibility. Then, we overview the main results achieved and finally discuss about possible future work. The fifth and last chapter consists of appendices. Appendix A has the schema of the database that supported this thesis. Appendix B has a set of tables with additional information. Appendix C describes the software provided in the DVD accompanying this thesis that allows the reconstruction of the present work.

In-situ X-ray diffraction studies during growth of Ni-Ti shape memory alloy films and their complementary ex-situ characterization

Shape Memory Alloy (SMA) Ni-Ti films have attracted much interest as functional and smart materials due to their unique properties. However, there are still important issues unresolved like formation of film texture and its control as well as substrate effects. Thus, the main challenge is not only the control of the microstructure, including stoichiometry and precipitates, but also the identification and control of the preferential orientation since it is a crucial factor in determining the shape memory behaviour. The aim of this PhD thesis is to study the optimisation of the deposition conditions of films of Ni-Ti in order to obtain the material fully crystallized at the end of the deposition, and to establish a clear relationship between the substrates and texture development. In order to achieve this objective, a two-magnetron sputter deposition chamber has been used allowing to heat and to apply a bias voltage to the substrate. It can be mounted into the six-circle diffractometer of the Rossendorf Beamline (ROBL) at the European Synchrotron Radiation Facility (ESRF), Grenoble, France, enabling an in-situ characterization by X-ray diffraction(XRD) of the films during their growth and annealing. The in-situ studies enable us to identify the different steps of the structural evolution during deposition with a set of parameters as well as to evaluate the effect of changing parameters on the structural characteristics of the deposited film. Besides the in-situ studies, other complementary ex-situ characterization techniques such as XRD at a laboratory source, Rutherford backscattering spectroscopy(RBS), Auger electron spectroscopy (AES), cross-sectional transmission electron microscopy (X-TEM), scanning electron microscopy (SEM), and electrical resistivity (ER) measurements during temperature cycling have been used for a fine structural characterization. In this study, mainly naturally and thermally oxidized Si(100) substrates, TiN buffer layers with different thicknesses (i.e. the TiN topmost layer crystallographic orientation is thickness dependent) and MgO(100) single crystals were used as substrates. The chosen experimental procedure led to a controlled composition and preferential orientation of the films. The type of substrate plays an important role for the texture of the sputtered Ni-Ti films and according to the ER results, the distinct crystallographic orientations of the Ni-Ti films influence their phase transformation characteristics.

Image quality and dose analysis in PA chest x-ray: comparison between AEC and manual mode acquisition using the 10 kVp rule

Purpose: To compare image quality and effective dose when the 10 kVp rule is applied with manual and AEC mode in PA chest X-ray. Methods and Materials: A total of 68 images (with and without lesions) were acquired of an anthropomorphic chest phantom in a Wolverson Arcoma X-ray unit. The images were evaluated against a reference image using image quality criteria and the 2 alternative forced choice (2 AFC) method by five radiographers. The effective dose was calculated using PCXMC software using the exposure parameters and DAP. The exposure index (lgM) was recorded. Results: Exposure time decreases considerably when applying the 10 kVp rule in manual mode (50%-28%) compared to AEC mode (36%-23%). Statistical differences for effective dose between several AEC modes were found (p=0.002). The effective dose is lower when using only the right AEC ionization chamber. Considering image quality, there are no statistical differences (p=0.348) between the different AEC modes for images with no lesions. Using a higher kVp value the lgM values will also increase. The lgM values showed significant statistical differences (p=0.000). The image quality scores did not present statistically significant differences (p=0.043) for the images with lesions when comparing manual with AEC modes. Conclusion: In general, the dose is lower in the manual mode. By using the right AEC ionising chamber the effective dose will be the lowest in comparison to other ionising chambers. The use of the 10 kVp rule did not affect the detectability of the lesions.

A balance between image quality and effective dose in orbital X-ray screening for ferromagnetic IOFBs: a pilot study

Purpose: To investigate whether standard X-ray acquisition factors for orbital radiographs are suitable for the detection of ferromagnetic intra-ocular foreign bodies in patients undergoing MRI. Method: 35 observers, at varied levels of education in radiography, attending a European Dose Optimisation EURASMUS Summer School were asked to score 24 images of varying acquisition factors against a clinical standard (reference image) using two alternative forced choice. The observers were provided with 12 questions and a 5 point Likert scale. Statistical tests were used to validate the scale, and scale reliability was also measured. The images which scored equal to, or better than, the reference image (36) were ranked alongside their corresponding effective dose (E), the image with the lowest dose equal to or better than the reference is considered the new optimum acquisition factors. Results: Four images emerged as equal to, or better than, the reference in terms of image quality. The images were then ranked in order of E. Only one image that scored the same as the reference had a lower dose. The reference image had a mean E of 3.31μSv, the image that scored the same had an E of 1.8μSv. Conclusion: Against the current clinical standard exposure factors of 70kVp, 20mAs and the use of an anti- scatter grid, one image proved to have a lower E whilst maintaining the same level of image quality and lesion visibility. It is suggested that the new exposure factors should be 60kVp, 20mAs and still include the use of an anti-scatter grid.

Energy-dispersive x-ray fluorescence analysis of modern coloured glasses from Marinha Grande (Portugal)

X-Ray Spectrom. 2003; 32: 396–401

Crystallographic studies on molybdopterin-dependent enzymes

Dissertação para obtenção do Grau de Doutor em Bioquímica, Especialidade Bioquímica Estrutural

Cobalt-, zinc- and iron-bound forms of adenylate kinase (AK) from the sulfate-reducing bacterium Desulfovibrio gigas: purification, crystallization and preliminary X-ray diffraction analysis

Acta Crystallogr Sect F Struct Biol Cryst Commun. 2009 Sep 1;65(Pt 9):926-9

Heterodimeric nitrate reductase (NapAB) from Cupriavidus necator H16: purification, crystallization and preliminary X-ray analysis

Acta Cryst. (2007). F63, 516–519

On the analysis of data emerging in non-linear and complex systemscomparison of two X-Ray prony spectra

New arguments proving that successive (repeated) measurements have a memory and actually remember each other are presented. The recognition of this peculiarity can change essentially the existing paradigm associated with conventional observation in behavior of different complex systems and lead towards the application of an intermediate model (IM). This IM can provide a very accurate fit of the measured data in terms of the Prony's decomposition. This decomposition, in turn, contains a small set of the fitting parameters relatively to the number of initial data points and allows comparing the measured data in cases where the “best fit” model based on some specific physical principles is absent. As an example, we consider two X-ray diffractometers (defined in paper as A- (“cheap”) and B- (“expensive”) that are used after their proper calibration for the measuring of the same substance (corundum a-Al2O3). The amplitude-frequency response (AFR) obtained in the frame of the Prony's decomposition can be used for comparison of the spectra recorded from (A) and (B) - X-ray diffractometers (XRDs) for calibration and other practical purposes. We prove also that the Fourier decomposition can be adapted to “ideal” experiment without memory while the Prony's decomposition corresponds to real measurement and can be fitted in the frame of the IM in this case. New statistical parameters describing the properties of experimental equipment (irrespective to their internal “filling”) are found. The suggested approach is rather general and can be used for calibration and comparison of different complex dynamical systems in practical purposes.

Giant Pericardial Cyst Mimicking Dextrocardia on Chest X-Ray

Pericardial cysts are rare benign congenital malformations, usually small, asymptomatic and detected incidentally on chest X-ray as a mass located in the right costophrenic angle. Giant pericardial cysts are very uncommon and produce symptoms by compressing adjacent structures. In this report, the authors present a case of a symptomatic giant pericardial cyst incorrectly diagnosed as dextrocardia on chest X-ray.

An NMR structural study of nickel-substituted rubredoxin

J Biol Inorg Chem (2010) 15:409–420 DOI 10.1007/s00775-009-0613-6

Correlating EPR and X-ray structural analysis of arsenite-inhibited forms of aldehyde oxidoreductase

J Biol Inorg Chem (2007) 12:353–366 DOI 10.1007/s00775-006-0191-9