102,101 research outputs found
Approccio clinico alle patologie prostatiche nel cane: Quali sono e come fare diagnosi (Clinical approach for prostatic disease in the dog: Which are and how to do diagnosis)
No full textNella pratica ambulatoriale le patologie prostatiche si osservano frequentemente,
soprattutto in cani anziani. Tra tutte le patologie prostatiche la più
frequente è rappresentata dall’iperplasia prostatica benigna, seguita dalle
prostatiti, dai tumori prostatici e dalla metaplasia squamosa. Tali patologie
non presentano una sintomatologia patognomonica rendendo pertanto difficile
ottenere una diagnosi specifica. È quindi importante effettuare una visita
clinica accurata, non solo al fine di stabilire il miglior protocollo diagnostico
con lo scopo di impostare la terapia più idonea, ma anche per eseguire una
buona prevenzione dove possibile. Lo scopo di questo lavoro è quello di
descrivere l’eziopatogenesi delle patologie prostatiche, i vari sintomi correlati
e le tecniche diagnostiche più appropriate al fine impostare il processo
diagnostico più adeguato al caso.In small animal practice, prostatic diseases are encountered frequently, especially in old dogs. The most common prostatic disease is the benign prostatic hyperplasia followed by prostatitis, prostatic neoplasia and prostate squamous metaplasia. These diseases do not have pathognomonic symptoms, and that makes difficult to do an exact diagnosis. It is therefore important to perform an accurate clinical examination, not just for the purpose of establish the best diagnostic protocol, in order to begin the most appropriate treatment, but also for doing a good prophylaxis where it is possible. The aim of these paper is to lay down the most appropriate diagnostic process describing the aetiologies of prostatic disease, their symptom and the right investigative tools
Late rejection of an entire polytetrafluoroethylene carotid patch with complete restitution of vascular continuity.
No full text
Computational development of models and tools for the kinetic study of astrochemical gas-phase reactions
No full textThis PhD thesis focuses on the application and development of computational tools and methodologies for the modeling of the kinetics of gas-phase reactions of astrophysical interest in the interstellar medium (ISM). The complexity related to the investigation of chemical reactivity in space is mostly due to the extreme physical conditions of temperature, pressure and exposure to high-energy radiation, which in turn also lead to the formation of exotic species, like radicals and ions. Nevertheless, there is still much to be understood about the formation of molecules, the major issue being the lack of sufficient laboratory (experimental and computational) studies. A more detailed and accurate study of all the chemical processes occurring in the ISM will allow us to obtain the data necessary to simulate the chemical evolution of an interstellar cloud over time using kinetic models including thousands of reactions that involve hundreds of species. The collection of the kinetic parameters required for the relevant reactions has led to the growth of different astrochemical databases, such as KIDA and UMIST. However, the data gathered in these catalogues are incomplete, and rely extensively on crude estimations and extrapolations. These rates are of paramount importance to get a better comprehension of the relative abundances of the chemical compounds extrapolated by the astronomers from the spectral data recorded through the radio telescopes and the in-orbit devices, like the satellites. Accurate state-of-the-art computational approaches play a fundamental role in analyzing feasible reaction mechanisms and in accurately predicting the associated kinetics. Such approaches usually rely on chemical intuition where a by-hand search of the most likely pathways is performed. Unfortunately, thisprocedure can lead to overlook significant mechanisms, especially when large molecular systems are investigated. Increasing the size of a molecule can also increase the number of its possible conformers which can show a different chemical reactivity with respect to the same chemical partner. This brings to get very complex chemical reaction networks in which hundreds of chemical species are involved and thousands of chemical reactions can occur.During the last decades, a lot of effort has been done to develop computational techniques able to perform extensive and thorough investigations of complex reaction mechanisms. Such approaches rely on automated computational protocols which drastically decrease the risk of making blunders during the search for significant reaction pathways.Furthermore, the accurate characterization of the potential energy surfaces (PESs) critical points, like reactants, intermediates, transition states and products involved in the reaction mechanism, is crucial in order to carry out a reliable kinetic investigation. The kinetic analysis of an erroneous potential energy surface, would lead to gross errors in the estimation of the rate constants of the chemical species involved in the reaction.In order to avoid such errors, the combination of high-level electronic structure calculations via composite scheme can be helpful to get a more precise estimation of the energy barriers involved in the reaction mechanism. It has been proven that "cheap"[1] composite schemes can achieve subchemical accuracy without any empirical parameters and with convenient computation times, making them perfect for the purpose of this thesis.In recent decades, many efforts have been made to develop theoretical and computational methodologies to perform accurate numerical simulations of the kinetics of such complex reaction mechanisms in a wide range of thermodynamic conditions that mimic extreme reaction environmentsas for combustion systems, the atmosphere and the ISM. Such methodologies are based on the ab initio-transition-state-theory-based master equation approach, which allows the determination of rate coefficients and branching ratios of chemical species involved in complex chemical reactions. This methodology allows to make accurate predictions of the relative abundances of the reaction products for complex reactions even under conditions of temperature and pressure not experimentally accessible, such as those that characterize the ISM. Based on these premises, this dissertation has been focused on the application of a computational protocol for the ab initio-based computational modeling and kinetic investigation of gas-phase reactions which can occur in the ISM.This protocol is based on the application of validated methodologies for the automated discovery of complex reaction mechanisms by means of the AutoMeKin[2] program, the accurate calculation of the energetic of the potential energy surfaces (PESs) through the junChS and junChS-F12a "cheap" composite schemes and the kinetic investigation using the StarRate computer program specifically designed to study gas-phase reactions of astrochemical interest in conjunction with the MESS program. Furthermore, this dissertation has been also focused on the development and implementation of StarRate, a computer program for the accurate calculation of kinetics through a chemical master equation approach of multi-step chemical reactions. StarRate is an object-based program written in the so-called F language. It is structured in three main modules, namely molecules, steps and reactions, which extract the properties needed to calculate the kinetics for the single-step reactions partecipating in the overall reaction. Another module, in_out, handles program’s input and output operations. The main program,starrate, controls the sequences of the calling of the procedures contained in each of the three main modules.Through these modular structure, StarRate[3] can compute canonical and microcanonical rate coefficients taking into account for the tunneling effect and the energy-dependent and time-dependent evolution of the species concentrations involved in the reaction mechanism. Such protocol has been applied to investigate the formation reaction mechanisms of some complex interstellar polyatomic molecules, named interstellar complex organic molecules (iCOMs). More specifically, the formation of prebiotic iCOMs in space has raised considerable interest in the scientific community, because they are considered as precursors of more complex biological systems involved in the origin of life in the Universe. Debate on the origins of these biomolecular building blocks has been further stimulated by the discovery of nucleobases and amino acids in meteorites and other extraterrestrial sources. However, few insights on the chemistry which brings to the formation of such compounds is known. References: [1] Jacopo Lupi,Silvia Alessandrini,Cristina Puzzarini,and Vincenzo Barone.junchs and junchs-F12 models:Parameter-free efficient yet accurate compositeschemes for energies and structures of noncovalent complexes. Journal of Chem-ical Theory and Computation, 17(11):6974–6992, 2021. PMID: 34677974.[2] Emilio Martínez-Núñez, George L. Barnes, David R. Glowacki, Sabine Kopec,Daniel Peláez, Aurelio Rodríguez, Roberto Rodríguez-Fernández, Robin J. Shan-non, James J. P. Stewart, Pablo G. Tahoces, and Saulo A. Vazquez.Au-tomekin2021: An open-source program for automated reaction discovery. Journalof Computational Chemistry, 42(28):2036–2048, 2021.[3] Surajit Nandi, Bernardo Ballotta, Sergio Rampino, and Vincenzo Barone.Ageneral user-friendly tool for kinetic calculations of multi-step reactions withinthe virtual multifrequency spectrometer project. Applied Sciences, 10(5), 2020
Local charge-displacement analysis : targeting local charge-flows in complex intermolecular interactions
No full textCharge-displacement (CD) analysis has recently proven to be a simple and powerful scheme for quantitatively analyzing the profile the charge redistribution occurring upon intermolecular interactions along a given interaction axis. However, when two molecular fragments bind through complex interactions involving multiple concurrent charge flows, ordinary CD analysis is capable of providing only an averaged picture of the related charge-flow profiles and no detailed information on each of them. In this article, we combine CD analysis with a Hirshfeld partitioning of the molecular charge redistribution for a local analysis on focused portions of the molecule, allowing for a detailed characterization of one charge flow at a time. The resulting scheme-the local charge-displacement (LCD) analysis-is tested on the intriguing case of the dimethyl sulfide-sulfur dioxide complex, characterized by concurrent charge flows relating to a sulfur-sulfur homochalcogen interaction and a pair of hydrogen bonds. The LCD scheme is then applied to the analysis of multiple hydrogen bonding in the acetic acid dimer, of base-pairing interactions in DNA, and of ambifunctional hydrogen bonding in the ammonia-pyridine complex
Carotid endarterectomy and contralateral internal carotid artery occlusion:perioperative risks and long-term stroke and survival rates.
No full textBackground. The aim of this article was to analyze the perioperative mortality and stroke risk rates and late benefits of carotid endarterectomy (CE) contralateral to an occluded internal carotid artery (ICA), on the basis of our surgical experience from July 1990 to June 1996.
Methods. In 57 (14.7%) of 336 patients undergoing 388 CEs, the contralateral ICA was occluded (group I). All operations were performed under general anesthesia with selective shunting based on electroencephalographic criteria. Shunting was used in 36 (63.1%) of 57 revascularizations in group I and 47 (14.2%) of 331 operations performed on the remaining 279 patients with patent contralateral ICAs (group II) (p < 0.001).
Results. Perioperative strokes occurred in two patients (3.5%) in group I and three patients (1%) in group II (difference not significant). The only perioperative death, which occurred in one patient (1.7%) in group I, was the result of a perioperative stroke; two patients (0.7%) in group II died within 30 days of operation (difference not significant). Life-table cumulative stroke-free rates at 1, 3, and 5 years were 95%, 95%, and 95% in group I and 98.8%, 98.2%, and 98.2% in group II, respectively
(p = 0.272). Life-table cumulative survival rates at 1, 3, and 5 years were 97.5%, 94.2%, and 78.1% in group I and 99.2%, 94.8%, and 71.7% in group II, respectively (p = 0.306).
Conclusions. The results of this analysis indicate that CE contralateral to an occluded ICA can be performed with acceptable perioperative mortality and stroke risk rates and late stroke-free and survival rates comparable to those seen in patients without contralateral ICA occlusion who have undergone operation. Nevertheless, we think it is misleading to imply that the risks of operating on the two groups are the same. Moreover, because no late stroke-related death occurred in patients with contralateral ICA
occlusion, it would appear that superior late stroke-free rates did not translate into a prolonged survival advantage
Integrated Structural Approach to Credit Value Adjustment
No full textThis paper proposes an integrated pricing framework for Credit Value Adjustment of equity and commodity products. The given framework, in fact, generates dependence endogenously, allows for calibration and pricing to be based on the same numerical schemes (up to Monte Carlo simulation), and also allows the inclusion of risk mitigation clauses such as netting, collateral and initial margin provisions. The model is based on a structural approach which uses correlated Levy processes with idiosyncratic and systematic components; the pricing numerical scheme, instead, efficiently combines Monte Carlo simulation and Fourier transform based methods. We illustrate the tractability of the proposed framework and the performance of the proposed numerical scheme by means of a case study on a portfolio of commodity swaps using real market data
Infrapopliteal arterial revascularization for limb-threatening ischemia in patients with chronic kidney disease.
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