La lunga diacronia di un sito archeologico toscano: il complesso di Pava (Siena) dal II al XIII sec. d.C.

The paper is centred on southern Tuscany on the archaeological complex of Pieve di Pava where archaeological research have been conducted since the 2000 by the University of Siena. The parish church is first mentioned as the baptisterium Sancti Petri in Pava in a document of AD 715 part of a long dispute between the bishop of Siena and the bishop of Arezzo. But the archaeological excavation revealed a longer history of the site that start from the Roman period with a villa dated between the second to the fourth century BC. The villa continued to grow in Late Antiquity since it was transformed by a church. The paper is centred on these fluctuations of the site and on the implications of the transformations on the landscape. One of the stronger element of the Pava site, in addition to the very particular plan of the early church (built with two opposing apses) was the huge cemetery around the church that was used from the seventh century BC until the Middle Ages. The 900 excavated graves make this one of the largest and most long-lasting late-Roman to medieval cemeteries excavated in Europe.

Delle Benemerenze di S. Tommaso d'Aquino verso le Arti Belle.

Mode of access: Internet.

Gli antichi cimiteri cristiani di Roma e d'Italia.

Mode of access: Internet.

Discorso dellʹeminentissimo e reverendissimo signor Cardinale Carlos di Reisach alle Pontificie accademie romane di S. Luca e di archeologia insieme adunate il dì XVII di Marzo MDCCCLIX.

Mode of access: Internet.

Studio di fattibilità della ricostruzione del decadimento $D^0\to K^-\mu^+\nu_{\mu}$ ad LHCb

Il Modello Standard delle particelle elementari prevede l’universalità del sapore leptonico, cioè l’uguaglianza della probabilità di accoppiamento dei bosoni di gauge carichi dell’interazione debole con tutti i leptoni. Recentemente, le Collaborazioni LHCb, BaBar e Belle, misurando il rapporto tra i branching ratio dei decadimenti $B^0\to D^{∗− }\tau^+\nu_{\tau} e $B^0 →D^{∗−}\mu^+\nu_{\mu}, hanno osservato una deviazione dai valori previsti dal Modello Standard di 3.9 deviazioni standard. Questo interessante risultato, se confermato, indicherebbe l’esistenza di nuove particelle, come per esempio il bosone di Higgs carico. Analogamente ai decadimenti del mesone $B^0$ , è possibile cercare effetti analoghi anche nel rapporto di branching ratio dei decadimenti $D^0\to K^ −\mu^+\nu_{\mu}$ e $D^0\to K^−e^+\nu_e$ . In questo lavoro di tesi è stato realizzato uno studio preliminare di questa misura. In particolare, è stato studiata, tramite simulazioni Monte Carlo, la ricostruzione del processo $D^{*\pm}\to D^0 (\to K^− \mu+\nu_{\mu})\pi_s^{\pm}$ nell’esperimento LHCb. Questo canale ha la particolarità di avere una particella invisibile, il neutrino, al rivelatore LHCb. Tuttavia, mediante vincoli cinematici e topologici, è possibile ricavare le componenti dell’impulso del neutrino, con risoluzioni non paragonabili a quelle di una particella visibile, ma comunque accettabili. In questa tesi sono riportati i calcoli che permettono di ottenere queste informazioni ed è stata studiata la risoluzione sulla massa invariante del $D^{∗\pm}$ . La tesi è organizzata nel seguente modo: il primo capitolo riporta le motivazioni della misura dei rapporti dei branching ratio e l’attuale stato sperimentale; il secondo capitolo contiene una breve descrizione del rivelatore LHCb; il terzo capitolo, infine, descrive lo studio di fattibilità della ricostruzione del decadimento $D^0\to K^-\mu^+\nu_{\mu}.

Estudo e análise técnica e interpretativa do papel principal de tenor nas óperas Lucia di Lammermoor (Edgardo) e L' Elisir d' Amore (Nemorino) de Gaetano Donizetti

Nesta dissertação pretendemos analisar a interpretação do papel do tenor nas óperas Lucia di Lammermoor e L´Elisir d´Amore de Gaetano Donizetti, estudando os principais fatores que influenciaram a interpretação do papel do tenor e como esta mudou ao longo dos anos, por comparação de gravações destas óperas com 50 anos de intervalo entre si. O período do bel canto está associado à linha de canto ornamentada para exprimir emoções, o que, em conjunto com outros aspetos, fez com que a voz de tenor passasse a ter uma emissão distinta, especialmente no registo agudo. O contexto histórico e musical desta época, bem como os desenvolvimentos técnicos que se verificaram, influenciaram a forma de cantar e introduziram o tenor como papel principal nas óperas, com todos os desafios de cantar na zona de passagem, de domínio da respiração e de respeito pelas diversas formas de expressão musical que os compositores do período do bel canto usavam como veículos de interpretação e expressão dos sentimentos. A escolha destas duas óperas de Donizetti assenta num gosto pessoal e no meu interesse em estudar os contrastes dos personagens Edgardo e Nemorino, que são apresentados nesta dissertação sob o ponto de vista interpretativo, analisando a problemática de cada papel e a forma como o percurso tonal destas obras influencia as performances dos intérpretes; Abstract: STUDY AND ANALYSIS TECHNICAL-INTERPRETATION OF THE LEADING ROLE OF THE TENOR IN THE OPERAS LUCIA DI LAMMERMOOR (EDGARDO) AND L´ELISIR D´AMORE (NEMORINO) OF GAETANO DONIZETTI In this dissertation we analyze the interpretation of the tenor role in the operas Lucia di Lammermoor and L´Elisir d´Amore by Gaetano Donizetti, studying the major factors that influenced the tenor role interpretation and how it developed along the years, by comparing two recordings of these operas recorded 50 years apart from each other. The period of the bel canto is associated with the vocal ornamentation to express emotions which, as a consequence and together with other aspects, required technical changes to the tenor voice, in particular the high register. The historic and musical context of this time, as well as the technical developments that happened then, influenced the way of singing and introduced the tenor as the main role in operas, with all the challenges to sing in the passagio, to master the breathing process and to use all the forms of musical expression that the bel canto composers used as vehicles to interpret and express feelings. The choice of these two operas by Donizetti is based on personal taste and also on the interpretative contrasts between the roles of Edgardo and Nemorino, studied in this dissertation in terms of their interpretation, their problematic and how the harmony of these operas influences the interpretation of the singers.

Poly[di-mu-aqua-bis(mu-2-amino-4-nitrobenzoato)dicaesium]

In the structure of title compound [Cs2(C7H5N2O4)2(H2O)2]n the asymmetric unit comprises two independent and different Cs centres, one nine-coordinate, the other seven coordinate, with both having irregular stereochemistry. The CsO9 coordination comprises oxygen donors from three bridging water molecules, one of which is doubly bridging, three from carboxylate groups, and three from nitro groups, of which two are bidentate chelate bridging. The CsO6N coordination comprises the two bridging water molecules, one amine N donor, one carboxyl O donor and four O donors from nitro groups (two from the chelate bridges). The extension of the dimeric unit gives a two-dimensional polymeric structure which is stabilized by both intra- and intermolecular amine N-H...O and water O-H...O hydrogen bonds to carboxyl O acceptors, as well as inter-ring pi-pi interactions [minimum ring centroid separation, 3.4172(15)A].

5,7-di-N-acetyl-acinetaminic acid: A novel non-2-ulosonic acid found in the capsule of an Acinetobacter baumannii isolate

An Acinetobacter baumannii global clone 1 (GC1) isolate was found to carry a novel capsule biosynthesis gene cluster, designated KL12. KL12 contains genes predicted to be involved in the synthesis of simple sugars, as well as ones for N-acetyl-l-fucosamine (l-FucpNAc) and N-acetyl-d-fucosamine (d-FucpNAc). It also contains a module of 10 genes, 6 of which are required for 5,7-di-N-acetyl-legionaminic acid synthesis. Analysis of the composition of the capsule revealed the presence of N-acetyl-d-galactosamine, l-FucpNAc and d-FucpNAc, confirming the role of fnlABC and fnr/gdr genes in the synthesis of l-FucpNAc and d-FucpNAc, respectively. A non-2-ulosonic acid, shown to be 5,7-diacetamido-3,5,7,9-tetradeoxy-l-glycero-l-altro-non-2-ulosonic acid, was also detected. This sugar has not previously been recovered from biological source, and was designated 5,7-di-N-acetyl-acinetaminic acid (Aci5Ac7Ac). Proteins encoded by novel genes, named aciABCD, were predicted to be involved in the conversion of 5,7-di-N-acetyl-legionaminic acid to Aci5Ac7Ac. A pathway for 5,7-di-N-acetyl-8-epilegionaminic acid biosynthesis was also proposed. In available A. baumannii genomes, genes for the synthesis of 5,7-di-N-acetyl-acinetaminic acid were only detected in two closely related capsule gene clusters, KL12 and KL13, which differ only in the wzy gene. KL12 and KL13 are carried by isolates belonging to clinically important clonal groups, GC1, GC2 and ST25. Genes for the synthesis of N-acyl derivatives of legionaminic acid were also found in 10 further A. baumannii capsule gene clusters, and three carried additional genes for production of 5,7-di-N-acetyl-8-epilegionaminic acid.

Synthesis and Reactions of Binuclear Diolefin Rhodium(I) Compounds bridged by Nitrogen Heterocycles, Crystal Structure of Dichloro-Di-1,5-Cyclooctadiene(Mu-Pyrazine)-Dirhodium(I) [[Rh(1,5-C8h12)Cl]2(Mu-C4h4n2)]

Binuclear complexes of rhodium(I) of the type [(dien)(X)Rh(μ-N-N)Rh(X)(dien)] (dien = 1,5-cyclooctadiene or norbornadiene; N-N = pyrazine, 4,4′-bipyridine or Phenazine and X = Cl or Br) with bridging heterocycles have been isolated and their reactions with carbon monoxide, 2,2′-bipyridine and 1,10-phenanthroline investigated. The crystal structure of [(COD)(Cl)Rh(μ-pyrazine)Rh(Cl)(COD)] has been determined.

Structure of the K12 capsule containing 5,7-di-N-acetylacinetaminic acid from Acinetobacter baumannii isolate D36

The repeat unit of the K12 capsular polysaccharide isolated from the Acinetobacter baumannii global clone 1 clinical isolate, D36, was elucidated by means of chemical and spectroscopical methods. The structure was shown to contain N-acetyl-D-galactosamine (D-GalpNAc), N-acetyl-D-fucosamine and N-acetyl-L-fucosamine linked together in the main chain, with the novel sugar, 5,7-diacetamido-3,5,7,9-tetradeoxy-L-glycero-L-altro-non-2-ulosonic acid (5,7-di-N-acetylacinetaminic acid or Aci5Ac7Ac), attached to D-GalpNAc as a side branch. This matched the sugar composition of the K12 capsule and the genetic content of the KL12 capsule gene cluster reported previously. D-FucpNAc was predicted to be the substrate for the initiating transferase, ItrB3, with the Wzy polymerase making a α-D-FucpNAc-(1 → 3)-D-GalpNAc linkage between the repeat units. The three glycosyltransferases encoded by KL12 are all retaining glycosyltransferases and were predicted to form specific linkages between the sugars in the K12 repeat unit.

Hydrogen bonding with mono- and di-carbonyls

The electronic absorption and i.r. spectroscopic studies are reported for the hydrogen bonding systems involving alcohol and various ketones. It is shown that the hydrogen bonding abilities of ketones are determined by the extent of delocalization of the lone pair electrons in their non-bonding molecular orbitals. Evidence for the formation of very weak intermolecular hydrogen bonds between alcohol and the π-electron part of the dicarbonyls has also been presented from the i.r. studies in the 3400–3700 cm−1 region.

Complexes of rare earth perchlorates with di-2-pyridyl ketone

Abstract is not availabe.

Synthesis, Reactivity and Biological Activity of 17β-HSD1 Inhibitors Based on a Thieno[2,3-d]pryrimidin-4(3H)-one Core

Breast cancer is the most common cancer in women in Western countries. In the early stages of development most breast cancers are hormone-dependent, and estrogens, especially estradiol, have a pivotal role in their development and progression. One approach to the treatment of hormone-dependent breast cancers is to block the formation of the active estrogens by inhibiting the action of the steroid metabolising enzymes. 17beta-Hydroxysteroid dehydrogenase type 1 (17beta-HSD1) is a key enzyme in the biosynthesis of estradiol, the most potent female sex hormone. The 17beta-HSD1 enzyme catalyses the final step and converts estrone into the biologically active estradiol. Blocking 17beta-HSD1 activity with a specific enzyme inhibitor could provide a means to reduce circulating and tumour estradiol levels and thus promote tumour regression. In recent years 17beta-HSD1 has been recognised as an important drug target. Some inhibitors of 17beta-HSD1 have been reported, however, there are no inhibitors on the market nor have clinical trials been announced. The majority of known 17beta-HSD1 inhibitors are based on steroidal structures, while relatively little has been reported on non-steroidal inhibitors. As compared with 17beta-HSD1 inhibitors based on steroidal structures, non-steroidal compounds could have advantages of synthetic accessibility, drug-likeness, selectivity and non-estrogenicity. This study describes the synthesis of large group of novel 17beta-HSD1 inhibitors based on a non-steroidal thieno[2,3-d]pyrimidin-4(3H)-one core. An efficient synthesis route was developed for the lead compound and subsequently employed in the synthesis of thieno[2,3-d]pyrimidin-4(3H)-one based molecule library. The biological activities and binding of these inhibitors to 17beta-HSD1 and, finally, the quantitative structure activity relationship (QSAR) model are also reported. In this study, several potent and selective 17beta-HSD1 inhibitors without estrogenic activity were identified. This establishment of a novel class of inhibitors is a progressive achievement in 17beta-HSD1 inhibitor development. Furthermore, the 3D-QSAR model, constructed on the basis of this study, offers a powerful tool for future 17beta-HSD1 inhibitor development. As part of the fundamental science underpinning this research, the chemical reactivity of fused (di)cycloalkeno thieno[2,3-d]pyrimidin-4(3H)-ones with electrophilic reagents, i.e. Vilsmeier reagent and dimethylformamide dimethylacetal, was investigated. These findings resulted in a revision of the reaction mechanism of Vilsmeier haloformylation and further contributed to understanding the chemical reactivity of this compound class. This study revealed that the reactivity is dependent upon a stereoelectronic effect arising from different ring conformations.

Synthesis of Specifically Deuteriated Derivatives of D-Galactose and D-Galactosamine

Simple and convenient methods for introducing deuterium label at C-3 and C-6 position of N-acetyl-D-galactosamine and D-galactose, respectively, are described. For the synthesis of 2-acetamido-2-deoxy-D-3-[2H] galactopyranose, benzyl 2-acetamido-2-deoxy-4,6-O-benzylidene-agr-D-galactopyranoside was oxidized with dimethyl sulfoxide- acetic anhydride and the product was reduced with sodium borodeuteride to introduce the deuterium at C-3. After benzylidene reduction, the mixture was subjected to hydrogenolysis and purified by column chromatography. 1,2:3,4-di-O-isopropylidene-agr-D-galactopyranoside was oxidized followed by reduction with sodium borodeuteride and deprotection to yield D-6-[2H] galactose.

Complexes of lanthanide perchlorates with N,N,N′,N′-tetramethyl-α-carboxamido-O-anisamide and N,N′-di-t-butyl-α-carboxamido-O-anisamide

A survey of the literature on lanthanide coordination compounds reveals that ligands involving ether oxygens as donor atoms have received very little attention [ 11. Only recently have the complexes of lanthanides with cyclic polyethers been characterized [l-3]. We report in this communication that interaction of rareearth perchlorates with two new ligands namely N,N,N’,N’-tetramethyl-u-carboxamido-Oanisamide (TMCA) and N,N’-di-t-butyl-crcarboxamido- 0-anisamide (DTBCA). The two ligands are potentially tridentate possessing two amide moieties and an ether linkage in between. The isolated complexes have been characterized by analysis, electrolytic conductance, infrared and electronic spectra. The ‘H and “C NMR spectra for the diamagnetic La3+ and Y3+ complexes are also discussed.