Homoleptic and Heteroleptic Metal Carbonyl Clusters and Nanoclusters

This Thesis aims at presenting the general results achieved during my PhD, that was focused on the study and characterisation of new homoleptic and heteroleptic metal carbonyl clusters. From a dimensional point of view, the nuclearity of such species ranges from 2 to 44 metal atoms. Lower nuclearity compounds may be viewed as polymetallic complexes, whereas higher nuclearity species can reach the nanocluster size, by resembling to ultrasmall nanoparticles (USNPs). Initially, my research was focused on the investigation of small MCCs stabilised by N-Heterocyclic carbene (NHCs) ligands. At this regard, a general strategy for the synthesis of mono-anionic [Fe(CO)4(MNHC)]− and neutral Fe(CO)4(MNHC)2, Co(CO)4(MNHC) (M = Cu, Ag, Au; NHC = IMes, IPr) species has been developed. Furthermore, during this investigation, neutral trimetallic Fe(CO)4(MNHC)(M’NHC) (M, M’ = Cu, Ag, Au; M ≠ M'; NHC = IPr) and neutral heteroleptic Fe(CO)4(MNHC)(MNHC’) (M = Au; NHC = IMes, IPr) compounds have been isolated. Thermal treatment turned out to be an efficient method for the growth of the dimension of MCCs. Indeed, species of the type [M3Fe3(CO)12]3– and [M4Fe4(CO)16]4– (M = Ag, Au) as well as larger clusters were formed during the thermal treatment of the new Fe-M (M = Ag, Cu, Au) carbonyl compounds. These species inspired the investigation of promising reaction paths for the synthesis of Fe-M (M = Ag, Cu, Au) carbonyl compounds devoid of ancillary ligands and alloy MCCs, such as the heterometallic [MxM’5-xFe4(CO)16]3− (M, M' = Cu, Ag, Au; M ≠ M'; x = 0-5) carbonyl clusters. The second part of this Thesis regards high nuclearity MCCs. In particular, new strategies for the growth of platinum carbonyl clusters involving, for instance, the employment of bidentate phosphines are described, as well as the syntheses and the thermal decomposition of new Ni-M (Pd, Pt) carbonyl clusters.

Hybrid Artificial Intelligence to Extract Patterns and Rules from Argumentative and Legal Texts

This Thesis is composed of a collection of works written in the period 2019-2022, whose aim is to find methodologies of Artificial Intelligence (AI) and Machine Learning to detect and classify patterns and rules in argumentative and legal texts. We define our approach “hybrid”, since we aimed at designing hybrid combinations of symbolic and sub-symbolic AI, involving both “top-down” structured knowledge and “bottom-up” data-driven knowledge. A first group of works is dedicated to the classification of argumentative patterns. Following the Waltonian model of argument and the related theory of Argumentation Schemes, these works focused on the detection of argumentative support and opposition, showing that argumentative evidences can be classified at fine-grained levels without resorting to highly engineered features. To show this, our methods involved not only traditional approaches such as TFIDF, but also some novel methods based on Tree Kernel algorithms. After the encouraging results of this first phase, we explored the use of a some emerging methodologies promoted by actors like Google, which have deeply changed NLP since 2018-19 — i.e., Transfer Learning and language models. These new methodologies markedly improved our previous results, providing us with best-performing NLP tools. Using Transfer Learning, we also performed a Sequence Labelling task to recognize the exact span of argumentative components (i.e., claims and premises), thus connecting portions of natural language to portions of arguments (i.e., to the logical-inferential dimension). The last part of our work was finally dedicated to the employment of Transfer Learning methods for the detection of rules and deontic modalities. In this case, we explored a hybrid approach which combines structured knowledge coming from two LegalXML formats (i.e., Akoma Ntoso and LegalRuleML) with sub-symbolic knowledge coming from pre-trained (and then fine-tuned) neural architectures.

Photoredox Catalysis and Nucleophilic Organometallic Reagents – Application in Organic Synthesis

The main purpose of my PhD was the combination of the principles of transition metal catalysis with photoredox catalysis. We focused our attention on the development of novel dual catalytic protocols for the functionalization of carbonyl compounds through the generation of transient nucleophilic organometallic species. Specifically, we focused on the development of new methodologies combining photoredox catalysis with titanium and nickel in low oxidation state. Firstly, a Barbier-type allylation of aromatic and aliphatic aldehydes –catalytic in titanium– in the presence of a blue photon-absorbing dye was developed. Parallelly, we were pleased to observe that the developed methodology could also be extended to the propargylation of aldehydes under analogous conditions. After an extensive re–optimization of all the reaction parameters, we developed an enantioselective and diastereoselective pinacol coupling of aromatic aldehydes promoted by non-toxic, cheap and easy to synthetize titanium complexes. The key feature, that allows the complete (dia)stereocontrol played by titanium, is the employment of a red-absorbing organic dye. The tailored (photo)redox properties of the red-absorbing organic dye [nPr–DMQA+][BF4–] promote the selective reduction of Ti(IV) to Ti(III). Moreover, even if the major contribution in dual photoredox and nickel catalysis is devoted to the realization of cross-coupling-type reactions, we wanted to evaluate different possible scenarios. Our focus was on the possibility of exploiting intermediates arising from the oxidative addition of nickel complexes as transient nucleophilic species. The first topic considered regarded the possibility to perform allylation of aldehydes by dual photoredox and nickel catalysis. In the first instance, a non–stereocontrolled version of the reaction was presented. Finally, after a long series of drastic modification of the reaction conditions, a highly enantioselective variant of the protocol was also reported. All the reported methodologies are supported by careful photophysical analysis and, in some cases, computational modelling.

Organic photosensitizers and nanostructured semiconductors for photoredox catalysis and artificial photosynthesis

Over the course of evolution, Nature has elegantly learned to use light to drive chemical reactions. On the other hand, humans have only recently started learning how to play with this powerful tool to carry out chemical transformations. In particular, a step forward was possible thanks to molecules and materials that can absorb light and trigger a series of processes that can drive chemical reactions. However, scarce elements are extensively employed in the design of most of these compounds and considerations on their scarcity and toxicity have sparked interest on alternatives based on earth-abundant elements. In this framework, the focus of this thesis has been the development and employment of heavy-metal free chromophores and of earth-abundant oxides. The first chapter regards the functionalization of boron-dipyrromethenes (BODIPYs) so as to allow access to their triplet excited state and tune their redox potentials, which was achieved thanks to the design of orthogonal donor-acceptor dyads. The BODIPY dyads were used to promote a photoredox reaction, and the mechanism of the reaction was clarified. In the second chapter, organic chromophores that display thermally-activated delayed fluorescence (TADF) were studied. These were used to perform enantioselective photoredox reactions, and a mechanistic investigation allowed to elucidate the fate of these photosensitizers in the reaction. Thanks to their stronger reducing power, it was possible to demonstrate the employability of TADF dyes in artificial photosynthesis, as well. Last, the oxidation of biomass-derived compounds was studied in a photoelectrochemical cell. For this purpose, hematite photoanodes were synthesized in collaboration with Prof. Caramori’s group at the University of Ferrara (Italy) and they were tested in the presence of a redox mediator. In addition to this, the possibility of repurposing a copper(II) water oxidation catalyst for the oxidation of biomass was investigated in collaboration with Prof. Llobet’s group at ICIQ (Tarragona, Spain).

Public housing : information on backlogged modernization funds : fact sheet for the Chairman, Employment, Housing, and Aviation Subcommittee, Committee on Government Operations, House of Representatives /

"B-257330"--P. 1.

From the boom to the crisis: changes in employment conditions of immigrants in Spain and their effects on mental health

Background: Migrant workers have been one of the groups most affected by the economic crisis. This study evaluates the influence of changes in employment conditions on the incidence of poor mental health of immigrant workers in Spain, after a period of 3 years, in context of economic crisis. Methods: Follow-up survey was conducted at two time points, 2008 and 2011, with a reference population of 318 workers from Colombia, Ecuador, Morocco and Romania residing in Spain. Individuals from this population who reported good mental health in the 2008 survey (n = 214) were interviewed again in 2011 to evaluate their mental health status and the effects of their different employment situations since 2008 by calculating crude and adjusted odds ratios (aORs) for sociodemographic and employment characteristics. Findings: There was an increased risk of poor mental health in workers who lost their jobs (aOR = 3.62, 95%CI: 1.64–7.96), whose number of working hours increased (aOR = 2.35, 95%CI: 1.02–5.44), whose monthly income decreased (aOR = 2.75, 95%CI: 1.08–7.00) or who remained within the low-income bracket. This was also the case for people whose legal status (permission for working and residing in Spain) was temporary or permanent compared with those with Spanish nationality (aOR = 3.32, 95%CI: 1.15–9.58) or illegal (aOR = 17.34, 95%CI: 1.96–153.23). In contrast, a decreased risk was observed among those who attained their registration under Spanish Social Security system (aOR = 0.10, 95%CI: 0.02–0.48). Conclusion: There was an increase in poor mental health among immigrant workers who experienced deterioration in their employment conditions, probably influenced by the economic crisis.

Out of credit: Evaluating the impact of the EU structural funds on Hungarian small business growth and access to finance

Totaling EUR 29 billion, Hungary is in the midst of implementing its largest economic development program in its young democratic history. At the center of the European Union led development program is an effort to revitalize and reequip Hungary’s languishing small and medium sized enterprises (SME), long the country's heart of employment. This paper examines the efficiency and impact of two Structural Fund's instruments to enhance SME development – ECOP 2.1.1 and JEREMIE. A survey of 1275 SME and interviews with dozens of top policy-makers paint a flawed development program in dire need of reform. Despite this, empirical analysis suggests JEREMIE funds may have dampened the effects of the financial crisis and are crucial for the continued liquidity of SME, who have been particularly hit hard by the world financial crisis.

Efficiency of Effectiveness? The Hungarian Practice of Using the EU Funds

Efficiency or effectiveness? It not just the matter of definition. Experts and researchers have to make a difference between the qualitative and quantitative approach. The efficiency of EU subsidies means the ratio of the committed and disposable amount of EU subsidies can be measured, which was used and paid out within the given timeframe and along the legal regulations. The effectiveness of EU subsidies needs a much more complicated and complex approach than efficiency. The effectiveness of usage on a project level can be measured by the ‘added value’ of the project; and on the programme level by the added GDP growth or employment rate. The following research essentially analyses the project level or micro-effectiveness, however, it discusses the results of some macro-analyses as well (qualitative approach).

Impact of PL 94-566 on agricultural employers and UI trust funds in selected states.

"Prepared by G. Joachim [i.e. Joachim G.] Elterich and Linda Graham"--Prelim. p.