Theoretical spectroscopy of realistic condensed matter systems

This thesis is devoted to the ab initio calculation of ground state and excited state properties of different systems within the density functional theory and the time dependent density functional theory.From the numerical point of view we implemented an original method in a plane waves code devoted to calculate the independent particle response function.Moreover, we generalized the same code to the spin degree of freedom in order to study the magnetic properties of realistic condensed matter systems.We studied the reflectance anisotropy spectra and the energy loss spectraof the clean and oxidized surface, and we performed the analysis of the originof the main spectral features.Thanks to the comparison between experimental and theoretical REEL spectra,we could roule out the p(2x1) reconstruction for this surfcace.Moreover, we evidenced the problem of the correct description of the excitation spectra for open shell systems within the TDDFT framework, in thecase of the simple BeH molecule.In the second part of the thesis, we presented the study of the opticalproperties of magnetic systems such as FeS2, CoS2 or NiS2, interesting materialsfor possible technological applications in the growing field of spintronics.Within this context we calculated the ground state properties and the opticalcondictivity of BCC bulk iron, for which we found a nice agreement withavailable experimental data

The skulls of Borgo Cerreto (Perugia): medical, surgical, and anatomical activity of Baronio Vincenzi (XVII century)

In the Sixties of the last century the vault of a 17th century private chapel was opened, revealing three isolated skulls with evidence of surgical and anatomical activity. The chapel was built by Baronio Vincenzi, who lived and practiced medicine in Borgo Cerreto, a village in the province of Perugia, between the 16th and the 17th century. The skull bc 01 belongs to an adult male, aged 25-35 years. It shows a hole on the left front-parietal region (30 x 31 mm), that can be identified as the result of a skull trepanation. The margins of the lesion are regularly smoothed and inclined internally and the diplopic tissues result almost completely obliterated by a cicatricial bone. A bone splinter (10 x 8 mm), completely reabsorbed, can be observed on the right side of the hole. These findings are the proof of a long survival of the subject. X-ray examination confirms a regular process of ossification, without infection. Trepanation was performed with a Hippocratic trypanon, largely used in cranial surgery of Modern Age. The specimen bc 02 is without skullcap and the right upper part of the face; it belongs to an adult male, 25-30 years aged. The cuts were produced by a bone saw with a thin blade. The choice of these regions suggests the willingness to study the basal skull, the right eye cavity and the paranasal sinuses. The skull bc 03 consists only in a skullcap of an adult individual, which shows the signs of a bone saw. In conclusion, the recovery of a trepanned skull, at present the first specimen of this type recovered so far in Umbria, together with two others skulls with the signs of postmortem examination, inside the Vincenzi family vault can be probably related to the professional activity of Baronio. He was an experienced surgeon and a skilled anatomist, who certainly experienced the empirical surgery of the nearby surgical School of Preci, famous throughout Europe for the treatment of urinary bladder stones, cataract as well as the ability in skull trepanation

A new physeteroid cetacean from the Lower Miocene of southern Italy: CT imaging, retrodeformation, systematics and palaeobiology of a sperm whale from the Pietra leccese

Herein we describe a new finding of a medium-sized sperm whale from the Burdigalian (Lower Miocene) of the Pietra leccese formation (southern Italy) on the basis of a partly prepared specimen that includes a partial cranium, seven detached teeth, the fragmentary right mandible and two partial vertebral bodies. Because of the overall compression of the specimen, we carried out a retro deformation of a 3D model of the cranium obtained via CT-scanning. The combined analysis of the original specimen and the retrodeformed model has allowed us to recognise that the studied specimen constitutes a new physeteroid taxon: Angelocetus cursiensis n. gen. n. sp., a longirostrine sperm whale characterised by a sideward projected supracranial basin, as evidenced by the overall displacement of its posteriormost margin. Based on a phylogenetic analysis, A. cursiensis n. gen. n. sp. is determined to be a crown physeteroid that does not belong to either the Physeteridae or the Kogiidae. The wide temporal fossa, elongated rostrum and slender teeth, as well as the skull dimensions (estimated bizygomatic width c. 550 mm) suggest a diet based on medium to large-sized bony fish that were likely captured by a raptorial pierce feeding strategy (as for most of the coeval Burdigalian physeteroids). Despite a seemingly low ecomorphological disparity, the high degree of taxonomic diversity of the Burdigalian physeteroids suggests that this time span represents a crucial phase for the evolutionary history of sperm whales

Computational mechanistic study of thionation of carbonyl compounds with Lawesson's reagent

The thionation reaction of carbonyl compounds with Lawesson's reagent (LR) has been studied using density functional theory methods and topological analyses. After dissociation of LR, the reaction takes place through a two-step mechanism involving (i) a concerted cycloaddition between one monomer and the carbonyl compound to form a four-membered intermediate and (ii) a cycloreversion leading to the thiocarbonyl derivative and phenyl(thioxo)phosphine oxide. Topological analyses confirmed the concertedness and asynchronicity of the process. The second step is the rate-limiting one, and the whole process resembles the currently accepted mechanism for the lithium salt-free Wittig reaction. No zwitterionic intermediates are formed during the reaction, although stabilizing electrostatic interactions are present in initial stages. Phenyl(thioxo)phosphine oxide formed in the thionation reaction is capable of performing a second thionation, although with energy barriers higher than the first one. The driving force of the thionation reactions is the formation of trimers from the resulting monomers. In agreement with experimental observations, the amides are the most reactive when compared with esters, aldehydes, and ketones and the reaction is slightly influenced by the polarity of the solvent. Whereas for amides and esters substituents have little effect, aldehydes and ketones are influenced by both steric and electronic effects.This work was supported by the Spanish Ministerio de Economia y Competitividad (MINECO) (Project CTQ2013-44367-C2-1-P), by the Fondos Europeos para el Desarrollo Regional (FEDER), and by the Gobierno de Aragon (Zaragoza, Spain, Bioorganic Chemistry Group, E-10). M.A.C. thanks the University of Catania for partial financial support.Peer Reviewe

Multislice computed tomography SYNTAX score for coronary artery disease evaluation prior to transcatheter aortic valve implantation

Background: Coronary computed tomography angiography (CCTA) is a useful tool for the evaluation of coronary anatomy prior to both surgical and transcatheter aortic valve implantation (TAVI). Multislice Computed Tomography (MSCT) SYNTAX score (SXscore) strongly correlates with the traditional angiographic SXscore, and the latter has proven to predict cardiovascular events in patients with coronary artery disease (CAD) referred to TAVI. Purpose: The aim of the study is to evaluate the feasibility and accuracy of the calculation of MSCT SXscore in TAVI patients, compared to the gold standard angiographic SXscore. Materials and methods: We evaluated 65 patients eligible for TAVI who underwent both CCTA and invasive coronary angiography (ICA) prior to valve replacement. CCTA was compared to ICA in terms of sensitivity, specificity, and positive and negative predictive values. CCTA performance was evaluated at 3 levels: patient level, vessellevel and segmentlevel. MSCT SXscore was calculated, when possible (i.e. only in fullyevaluable scans), and compared to the angiographic SXscore. Results: Overall CCTA diagnostic performance was good, with high sensitivity and negative predictive values (97.2% and 96.0%, respectively) and good agreement with ICA (k=0.81). As expected, specificity and positive predictive values were lower (82.8% and 87.5%, respectively). At vessellevel, the circumflex artery (CA) was more often misdiagnosed than the other arteries. We were able to calculate MSCT SXscore in 50/65 scans (76.9%). The correlation between MSCT and angiographic SXscore was excellent (Pearson's R=0.965, P<0.001). Conclusions: MSCT SXscore emerges as an interesting tool with strong agreement with angiographic SXscore, providing a noninvasive ambulatory alternative to assess CAD severity in TAVI patients

Role of perfusion CT in the evaluation of metastatic nodal tumor response after radiochemotherapy in head and neck cancer: preliminary findings

OBJECTIVE: To assess changes of CT perfusion parameters (ΔPCTp) of cervical lymph node metastases from head and neck cancer (HNC) before and after radiochemotherapy (RT-CT) and their association with nodal tumor persistence. PATIENTS AND METHODS: Eligibility criteria included HNC (Stage III-IV) candidates for RT-CT. Patients underwent perfusion CT (PCT) at baseline 3 weeks and 3 months after RT-CT. Blood volume (BV), blood flow (BF), mean transit time (MTT) and permeability surface (PS) were calculated. PET/CT examination was also performed at baseline and 3 months after treatment for metabolic assessment. RESULTS: Between July 2012 and May 2016, 27 patients were evaluated. Overall, only 3 patients (11%) experienced tumor persistence in the largest metastatic lymph node. A significant reduction of all PCTp values (p<0.0001), except MTT (from 6.3 to 5.7 s; p=0.089), was observed at 3 weeks post-RT-CT compared to baseline. All PCTp values including MTT were significantly lower at 3-month follow-up compared to baseline (p<0.05). Moreover, a statistical significant association was observed between nodal tumor persistence and high BF values (p=0.045) at 3 months after treatment that did not occur for the other parameters. CONCLUSIONS: Our preliminary findings show that all PCTp except MTT are significantly reduced after RT-CT. High BF values at 3 months post-RTCT are predictive of nodal tumor persistence

Electronic structure and phase stability of oxide semiconductors: performance of dielectric-dependent hybrid functional DFT, benchmarked against GW band structure calculations and experiments

We investigate band gaps, equilibrium structures, and phase stabilities of several bulk polymorphs of wide-gap oxide semiconductors ZnO, TiO2,ZrO2, and WO3. We are particularly concerned with assessing the performance of hybrid functionals built with the fraction of Hartree-Fock exact exchange obtained from the computed electronic dielectric constant of the material. We provide comparison with more standard density-functional theory and GW methods. We finally analyze the chemical reduction of TiO2 into Ti2O3, involving a change in oxide stoichiometry. We show that the dielectric-dependent hybrid functional is generally good at reproducing both ground-state (lattice constants, phase stability sequences, and reaction energies) and excited-state (photoemission gaps) properties within a single, fully ab initio framework

Defect calculations in semiconductors through a dielectric-dependent hybrid DFT functional : the case of oxygen vacancies in metal oxides

We investigate the behavior of oxygen vacancies in three different metal-oxide semiconductors (rutile and anatase TiO2, monoclinic WO3, and tetragonal ZrO2) using a recently proposed hybrid density-functional method in which the fraction of exact exchange is material-dependent but obtained ab initio in a self-consistent scheme. In particular, we calculate charge-transition levels relative to the oxygen-vacancy defect and compare computed optical and thermal excitation/emission energies with the available experimental results, shedding light on the underlying excitation mechanisms and related materials properties. We find that this novel approach is able to reproduce not only ground-state properties and band structures of perfect bulk oxide materials but also provides results consistent with the optical and electrical behavior observed in the corresponding substoichiometric defective systems

Factors predicting survival in patients with locally advanced pancreatic cancer undergoing pancreatectomy with arterial resection

Pancreatectomy with arterial resection is a treatment option in selected patients with locally advanced pancreatic cancer. This study aimed to identify factors predicting cancer-specific survival in this patient population. A single-Institution prospective database was used. Pre-operative prognostic factors were identified and used to develop a prognostic score. Matching with pathologic parameters was used for internal validation. In a patient population with a median Ca 19.9 level of 19.8&nbsp;U/mL(IQR: 7.1–77), cancer-specific survival was predicted by: metabolic deterioration of diabetes (OR = 0.22, p = 0.0012), platelet count (OR = 1.00; p = 0.0013), serum level of Ca 15.3 (OR = 1.01, p = 0.0018) and Ca 125 (OR = 1.02, p = 0.00000137), neutrophils-to-lymphocytes ratio (OR = 1.16; p = 0.00015), lymphocytes-to-monocytes ratio (OR = 0.88; p = 0.00233), platelets-to-lymphocytes ratio (OR = 0.99; p = 0.00118), and FOLFIRINOX neoadjuvant chemotherapy (OR = 0.57; p = 0.00144). A prognostic score was developed and three risk groups were identified. Harrell’s C-Index was 0.74. Median cancer-specific survival was 16.0&nbsp;months (IQR: 12.3–28.2) for the high-risk group, 24.7&nbsp;months (IQR: 17.6–33.4) for the intermediate-risk group, and 39.0&nbsp;months (IQR: 22.7–NA) for the low-risk group (p = 0.0003). Matching the three risk groups against pathology parameters, N2 rate was 61.9, 42.1, and 23.8% (p = 0.04), median value of lymph-node ratio was 0.07 (IQR: 0.05–0.14), 0.04 (IQR:0.02–0.07), and 0.03 (IQR: 0.01–0.04) (p = 0.008), and mean value of logarithm odds of positive nodes was −&nbsp;1.07 ± 0.5, −&nbsp;1.3 ± 0.4, and −&nbsp;1.4 ± 0.4 (p = 0.03), in the high-risk, intermediate-risk, and low-risk groups, respectively. An online calculator is available at www.survivalcalculator-lapdac-arterialresection.org. The prognostic factors identified in this study predict cancer-specific survival in patients with locally advanced pancreatic cancer and low Ca 19.9 levels undergoing pancreatectomy with arterial resection