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Industria ligeras y aglomeraciones territoriales en Latinoamérica: el caso del clúster textil de Medellín (Colombia).
No full textIn globalization, commercial capital has encouraged the relocation of productive activities of light industries. The textile-manufacturing chain of Latin American countries, like that of others that arrived at the global chain in 1980s, has been linked to the basic assembly of imported parts (maquila), through its comparative advantages (low wages, natural resources), being relegated to compete for costs, under the governance of large global buyers.
Although Medellín and the Aburrá Valley textile-manufacturing chain achieved higher productive integration than those of other Latin American regions, its linkage to global trade in the absence of a coherent industrial policy and local capacities for development produced a reduction in its contribution to the Gross Domestic Product (GDP) and life quality in the territory.
Development policies focused on local productive systems (SPL) have a multidimensional vision that helps to clarify the possible trajectories that clusters could follow in the processes of productive transformation and to improve the governance of competitive strategies; from those based on low costs, to others that may arise from the particularities of the local system and its valuation and can be developed through the action of the actors of the same local system.
Some of Latin American best practices inspired by local /regional development studies have been reviewed in order to identify principles that could help those who are committed to industrial development policies, to lead the way to innovation and creation of dynamic competitive advantages, which could allow small and medium-sized companies in clusters to overcome the vicious circle of cost competitiveness
Employing theoretical methods for chemical prediction: a ticket into copolymerization, metal-organic catalysis and antioxidants.
No full textThe thesis shows how ab initio and DFT quantum chemical methods can be useful toward the interpretation and the prediction of chemical properties and reactivities. Well know post-Hartree-Fock quantum chemical methods and stochastic simulation approaches are intermixed, the synergy between them providing all the tools needed to evaluate the impact and validity of reaction mechanisms, for instance helping to rationalize radical and homogeneously catalyzed copolymerizations. The potentially positive impact that theoretical chemistry can have in those contexts was exploited to put the basis of new theoretical protocols able to predict the chemical features, that is still an attractive goal in academic and industrial field.
The first study regards an example of how theoretical chemistry can provide information otherwise not achievable from experimental measurement. Specifically, by means of ab initio perturbation theory, we study novel anion receptors acting via hydrogen-bonding and halogen-bonding: UV-Vis and 1H-NMR titrations show that Iodine on the target receptor enhance the anion binding tendencies and X-ray structures evidenc the formation of halogen-bonding.
The geometries in solution computed via MP2, however, reveal few possible conformers of the proposed molecules: theoretical energies allow the calculation of the ion pair dissociation energy (IPDE) as a way to evaluate the affinity between the molecules and an anion. IPDE values gave the same trend of experimental affinity constants, confirming the experimental constant affinities; moreover, computed chemical shifts of conformers help the interpretation of 1H-NMR titrations, giving the right importance at the HB and XB conformers in solution.
The second topic is the prediction of the antioxidant activity through a theoretical approach, that led to the benchmark of DFT methods. The in depth study of two prototype molecules, edaravone and quercetin, carries out the bond dissociation enthalpy (BDE), the ionization potential (IP) and the proton dissociation enthalpy (PDE); the examination of the cumulative mean absolute error on the three parameters, compared to CBS-Q3 reference values, indicates the most suitable methods (LC-!PDE, M05-2X and M06-2X). Once the method was defined, we have studied 15 antioxidant belonging to the flavonols family, computating BDE, IP, PDE, proton affinity (PA) and electron transfer enthalpy (ETE) in vacuum and in water; these theoretical parameters are then correlated individually to several experimental data set. Among all attempts, the best correlation was found with ETE in vacuum (showing a R2=0.93 on 6 data set), that allows us to suppose that ETE is the theoretical parameter determining for prediction of antioxidant activity.
After the analysis about the properties of a single molecule, DFT is employed to rationalize the products of a chemical reaction. In particular, we study the alkoxyhalogenation of alkynyl ureas and carbamates catalyzed by CuCl2, with the final aim of defining the reactive step that influence the selectivity. First, we propos a mechanism coherent with experimental product, characterizing all the minima and the transition states via DFT vibrational analysis. Studying in depth the equilibria involved at the beginning of the reaction, we characterize the two tautomers and two coordination site of CuCl2, the C-C triple bond and the heteroatom; moreover, we describe the formation of dimers between two urea and the catalyst. Dimers’ stabilization plus the comparison of the energy paths lead to expect the production of the 5-exo-O product, in total accord with experiments. Successively, we attempt to apply the same mechanism on two carbamates, following the same approach than before. The results however rationalize only partially the experiments, in fact, for the phenyl-N-carbamate we observe a strong kinetic competition between two paths, at the same time the experiments carry out a mixture of products; instead, the reaction on tosyl-N-carbamate experimentally leads to a single product, while the theoretical investigation is not able to discriminate between two different products.
In the last Chapter we aim higher, trying to predict the copolymer features boosting the DFT method with stochastic simulations; the ability to predict the microstructure of a copolymer would be a great help during the design process and the set up of a catalyzed copolymerization. In this regards, we decided to study the copolymerization of methyl methacrylate (MMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) obtained via atomic-transfer radical-polymerization (ATRP), since the macroscopic properties used in biological fields are strictly related to the microscopic structure. Here we propose a synergistic DFT/kinetic Monte Carlo approach: by means of DFT, we compute the energies of monomers, dimers and transition states, thanks to which e calculate the reactivity ratios r1 and r2; employing the DFT data, we wrote a kMC code that, treating the copolymerization as a Markov chain, carries out the chains’ microstructure, the distributions of monomers, diads and triads along the chains. The results give indication about the presence of a preferential partitioning of one of the two monomers close to each one of the two radicals, known as bootstrap effect. Moreover, the triad distributions along the chain reveal the gradient nature of the copolymer, suggesting different features of the chains at the proximity of the core of PEG and at the end, influencing directly the behavior of the materials in solution. Then, our attention moves on the homogeneous-catalyzed copolymerization. The aim of the investigation pointed the attention on the characterization of copolymerization mechanism and on the effect of penultimate monomers and the counter ion on the reactivity. The synergistic DFT-kMC approach is applied on the ethene/propene copolymerization catalyzed by two C2-symmetric catalyst, carrying out several interesting results; among all simulated systems, we reproduce the experimental data only taking into account specific features. In order to obtain results close to the experiments, the model has to include: the presence of two coordination sites, both giving active paths for the insertion, the coordination preequilibrium as well-defined step, the influence of the counter ion on the coordination barriers. These claim underline the importance of several aspect generally overlooked during the copolymerization; moreover, the ability to reproduce the experimental results can open the way to a theoretical model able to predict the product of a homogeneous catalyzed copolymerization
Sequences of refinements of rough sets: logical and algebraic aspects
No full textIn this thesis, a generalization of the classical Rough set theory is developed considering the so-called sequences of orthopairs that we define as special sequences of rough sets.
Mainly, our aim is to introduce some operations between sequences of orthopairs, and to discover how to generate them starting from the operations concerning standard rough sets. Also, we prove several representation theorems representing the class of finite centered Kleene algebras with the interpolation property, and some classes of finite residuated lattices (more precisely, we consider Nelson algebras, Nelson lattices, IUML-algebras and Kleene lattice with implication) as sequences of orthopairs.
Moreover, as an application, we show that a sequence of orthopairs can be used to represent an examiner's opinion on a number of candidates applying for a job, and we show that opinions of two or more examiners can be combined using operations between sequences of orthopairs in order to get a final decision on each candidate.
Finally, we provide the original modal logic SOn with semantics based on sequences of orthopairs, and we employ it to describe the knowledge of an agent that increases over time, as new information is provided. Modal logic Son is characterized by the sequences (□1,…, □n) and (O1,…, On) of n modal operators corresponding to a sequence (t1,…, tn) of consecutive times. Furthermore, the operator □i of (□1,…, □n) represents the knowledge of an agent at time ti, and it coincides with the necessity modal operator of S5 logic. On the other hand, the main innovative aspect of modal logic SOn is the presence of the sequence (O1,…, On), since Oi establishes whether an agent is interested in knowing a given fact at time ti
Beta-blockers in oncology setting: paving the way for lung cancer
No full textWith the growing amount of studies revealing the involvement of β-adrenoceptors (β-AR) in the progression of multiple types of tumours, the hypothesis that β-blockers could be potential candidates for drug repurposing in oncology setting has gaining momentum. In lung cancer, it could be particularly meaningful considering the disappointing results of the current therapeutic approaches.
The compilation of studies disclosed in this thesis intended to investigate the presence β-AR in non-small cell lung cancer (NSCLC) as well as discuss the potential for repurposing β-blockers as a new therapeutic approach for lung cancer. The studies included in this thesis comprise a narrative review, a clinicopathologic study, an in vitro study, and a meta-analysis exploring the effect of β-blockers on overall survival of lung cancer patients and a letter to the editor.
The obtained results suggest that β01 and β2-AR are differently expressed in the histologic subtypes, adenocarcinoma (ADC) and squamous cell carcinoma (SCC). We found that β1-AR expression is present at low levels in both SCC and ADC whereas β2-AR is higher expressed on both histologic subtypes but clearly higher expressed in ADC. The meta-analysis performed, including 7448 patients, showed that lung cancer patients using β-blockers had no increased overall survival when compared to non-users.
Altogether, this work increased the knowledge on the expression pattern of β-AR on NSCLC. Despite the lack of a positive effect of β-blockers on lung cancer overall survival obtained in the meta-analysis, this study should prompt the attention of the scientific community to the fact that there is still a huge margin for improving the concept of β-blockers repurposing in cancer
Politiche rurali e disparità territoriali in Italia: una valutazione di impatto sulle aree interne.
No full textThis work focuses on the role that rural policies had in targeting territorial disparities between rural areas and non-rural areas. In particular, we emphasize the so-called inner areas, recently assumed as objectives of policy in Italy. This work presents a new integrated national policy implemented in Italy in the 2014-2020 programming period. This policy, applicable to every region and macro-area of Italy, is named National Strategy for Inner Areas (NSIA) and aims to contribute to the country’s economic and social recovery, creating jobs, fostering social inclusion and reversing the demographic decline of Inner Areas, both in terms of resident numbers and in terms of age and birth group. This Strategy is implemented by capitalising on countrywide experiences of local development of the past years and supported by the EU programme, along with the dedicated funding provided for under the Stability Law (national funds).
This work is presented in five main chapters:
- Chapter 1 describes the evolution of rural policies in Europe and the diverse phases of this evolution;
- Chapter 2 presents some relevant cases of innovative interplay between rural policies, local governance and market forces;
- Chapter 3 illustrates how NSIA has been facing main challenges of rural areas, what are the main novelties of this policy within the EU context and potentials and obstacles which emerged throughout the implementation process;
- Chapter 4 provide insights on the employment impacts of CAP measures in Italian agriculture over the period 2007-14, and explores the diversity of these impacts in four types of area, including Inner areas;
- Chapter 5 presents main conclusions of the work.
The national policy in favour of rural areas (national strategy for inner areas)
Italy’s Inner Areas are those rural areas characterised by significant distance from the main essential service centres (education, health and mobility)1. Inner Areas make up 53 % of the Italian municipalities (4.261) and are home to 23 % of the Italian population, 1 according to the latest census, equal to more than 13.540.000 inhabitants resident in over 60 % of the national territory. There are strong differences even within Inner Areas, especially when we focus on the peripheral and ultra-peripheral areas, which are considered as priority focus area for policy interventions.
The demographic and agricultural profile of Inner Areas is notably different form the average profile emerging at the national level. Demographic decline and ageing of population is more relevant in Inner Areas than in the rest of Italian territory, although is counterbalanced by a stronger contribution of new population by immigrants (which doubled in the last decade across all regions). Farming abandonment and waste land have been more frequent in Inner Areas than elsewhere, as effect of lower farm land productivity in these areas. Economic productivity and quality of services are strongly affected in these areas by high digital divide.
The national strategy is based on four main innovations, which make this policy a further step in promoting and developing more effective and participatory processes in rural areas.
The first policy innovation is in the mix of interventions to enhance the provision of essential services (primary and secondary school and vocational training, local mobility and transports, health care and medical services) and – at the same time- in promoting local development initiatives. These initiatives are based on local resources and in particular in five key potentials: a) land management and forests; b) local food products; c) renewable energy; d) natural and cultural heritage; d) traditional handicraft and SMEs.
Inner Areas are assumed as a national priority, but the strategy conceived and implemented within a multi-level framework, involving national, regional and local tiers. Local communities are essential in this process: they can interpret the variety and complexity of the local society and territorial capital and turn them into projects, by stimulating innovators that already exist in some Inner Areas. Removing the obstacles to access to essential services and to local development, however, can only arise from an effective integration between national and local action.
Third innovation is the multi-fund approach: the local development interventions in the selected project areas will be financed by all the available European Structural and Investment funds (ERDF, ESF, EAFRD, EMFF), through the regional programmes, and by the National Stability Fund. The participation of European Funds is mandatory for the approval of the local strategy.
The last innovation is local participation: the local strategy is elaborated by a group of mayors and is based on the pre-requisite of the cooperation between the municipalities involved in the project area. They have to work together in managing services for the community life, and also in designing and managing the strategy.
Agricultural and rural development initiatives are always relevant components of the local strategies, due to the predominant rural characteristics of project areas.
Rural Development Plans (RDPs) can contribute to Inner Areas Strategy in three ways: a) the Leader approach; b) the single measures; c) a mix of Leader approach and single measures. The choice of the method and financial resources allocated to Inner Areas are set in regional RDPs. Given the low adoption of the CLLD method (multi-fund), the Leader approach is generally funded only by EAFRD.
Pre-existing capacity building in Local Action Groups (LAGs) was a key element in designing good quality strategies in Inner areas. Many local experts involved in the process of strategy design come from the Leader experience in the field of local development. Moreover, more targeted and non-blind approach, typical of the Leader, is very helpful to build up pilot projects in Inner areas. Broader and more innovative impact on the territories can derive from the integration between Inner areas strategies and Leader local plans. There is also a more efficient division of work: Inner Areas partnerships are oriented to promote effective interventions on access to services, while LAGs are well-experienced in local development initiatives. The number of pilot areas selected until April 2017 is 71 (1.066 municipalities, 2,1 million inhabitants, 3,5% of the national population, 16,7% of the national territory). In these areas the population decline was -4,2% in the period 2001-2011, and -2,3% in 2011-2016, while national population increased in the same period (2,1%). Selected areas are on average quite small: about 29.000 inhabitants.
The territorial impact of the CAP on inner areas
The Lisbon Treaty states that all policies should contribute to territorial and social cohesion, and strengthens the need to include territorial diversity when looking at how the CAP has affected territorial cohesion. This work explores the diversity of agricultural employment impacts of CAP measures in different territorial settings in Italy for the period 2007-2014.
Patterns and trends in agricultural employment differ greatly according to the type of socio-economic system. To identify these differences, we use the territorial typology which includes four types of areas, with population shares in parentheses:
1. Urban Poles, identified by the metropolitan areas and principal cities in each region (40%);
2. Areas with Broad Economic Development (‘Belt Areas’), including the most industrialised and intensive agriculture and agri-food sectors (37%);
3. Intermediate Areas, characterised by more extensive and diversified agriculture, and medium-low access to public services (15%);
4. Peripheral (and Ultra-Peripheral) Areas, characterised by problematic access to services, due partly to low economic development and partly to shrinking public resources (8%).
In contrast to area shares in terms of Utilised Agricultural Area (UAA) and gross Agricultural product (GAP), about 60 per cent of total CAP First and Second Pillar payments in 2010 went to Belt and Intermediate areas, while 23 per cent went to Peripheral Areas, where the share of total CAP expenditures represents more than one third of the value of agricultural production.
The CAP’s impact on agricultural employment was evaluated through an econometric model which tries to explain farm labour use as dependent on variables for structure and context (UAA, land productivity, per capita income and immigration) and for CAP expenditures (SFPs, decoupled payments, LFA payments, etc.), with data at the Local Administrative Unit (LAU2) level (the municipality) for the period 2007-2013. The results suggest that structural developments contributed to changes in farm employment more than policy measures. Immigration appeared to provide opportunities for using less expensive labour and/or replacing family labour that could be allocated to more profitable non-farm employment in the local area or elsewhere. Better-paid off-farm jobs also reduced the labour force available for farming.
Focusing on policy measures, the most remarkable result was that First Pillar measures (SFPs and payments coupled to farm production) appeared to affect farm employment negatively, perhaps due to the introduction of activities requiring lower labour input, or to risk-averse behaviour by farmers who benefit from SFPs, thus tending to limit farm development. The Second Pillar measures of the Rural Development Plan (RDP) all showed positive effects. These RDP effects differ according to the type of measure: farm and agro-industrial investment support generates higher employment effects than AEM, LFA or rural diversification measures. The employment effects decrease from Belt Areas to Peripheral Areas, except for rural diversification investment support, where the highest employment effects are in Peripheral Areas. The diversity of the policy impact at territorial level can be explained by three main factors: a) in several RDP programmes, approval of funding is conditional on proof of achieving an employment target (e.g. farm/agroindustrial and diversification support); b) the intensity of public expenditure per hectare is usually higher in Belt areas than elsewhere; c) the productivity of public and private investment in the different areas, depending on the natural, infrastructural and human capital resources, can be crucial in increasing labour opportunities for younger family members. The second and third factors may explain the highest employment effects of farm and agro-industrial investment in the most developed areas, while the second factor explains why employment effects of rural diversification are higher in Peripheral Areas than elsewhere.
1 Essential service centres are those municipalities able to provide simultaneously: schools with a full range of secondary education, at least one grade 1 emergency care hospitals and at least one Silver category railway station (medium/small systems with an average degree of uptake for metropolitan/regional services and short-distance journeys)
MonoNuclear Peripheral Cells at high content of stem cells CD34+ after mobilization with G-CSF for the treatment of Critical Limb Ischemia (CLI).
No full textINTRODUCTION: Critical Limb Ischemia (CLI) patients have a poor prognosis despite they are submitted to conventional treatment. Still up to 30% of these patients is not eligible for either surgical nor endovascular procedures.
AIM OF THE STUDY: Evaluate feasibility and outcome of inoculation of mononuclear peripheral cells at high content of stem cells CD34+ as treatment of critical limb ischemia in order to reduce the risk of major amputation of the inferior limb.
MATHERIALS AND METHODS: CLI patients unresponsive to pharmacological therapy or with clinically unsatisfactory revascularization are submitted to Mobilized Peripheral Blood MonoNuclear Cell Implantation after G-CSF stimulation.
RESULTS: Sixty-two patients have been treated. Amputation Free Survival (AFS) was 81% at 6 months and 77% at 1 and 2 years. The transplanted patients showed a reduction of pain and severity of ulcers’ grade after the procedure.
DISCUSSION: The obtained 77% of Amputation Free Survival (AFS) permitted to achieve the primary end point of the study and could be considered an encouraging result in limb salvage. The dose of cells administered (about twice the amount reported in other studies) could be a reason of this good result. This procedure seems to be safe even in the elderly patients.
CONCLUSIONS: Stem cells transplantation therapy confirms to be promising for the effective treatment of “no-option” CLI patients with a favorable safety profile. CD34+ cells could have a central role in this treatment as injection of higher doses of these cells seem to be associated with good clinical results. On the other hand, the most advanced stages of arterial disease and limb ischemia are associated with worse clinical response
Population properties, dissipation and radiative processes in GRBs.
No full textGamma Ray Bursts (GRBs) are short and intense flashes of γ–rays with typical energies between keV and a few MeV. They reach luminosities (assuming isotropy) of 1054 erg/s. The γ–ray emission, called “prompt”, is highly variable (with timescales as short as few milliseconds) and can last a fraction of a second (short GRBs, T90 2 s). The prompt is followed by the “afterglow” emission, at lower frequencies (in the X–ray, Optical and Radio band) which has been detected also up to several months after the trigger and is typically smooth and decaying as a function of time. GRBs are cosmological sources having average redshift ∼ 2.5. The progenitors of long GRBs are thought to be very massive stars that collapse at the end of their life, while the progenitors of short GRBs are thought to be the merging of two neutron stars.
Two of the key properties characterizing the population of GRBs are their cosmic formation rate ψ(z) (GRBFR) and their luminosity function φ(L) (LF). Recovering ψ (z) and φ(L) of GRBs allows us to test the nature of their progenitor (e.g. through the comparison with the cosmic star formation rate), to study the possible presence of sub–classes of GRBs and to infer intrinsic properties such as the structure of their jetted outflows. The knowledge of the intrinsic population properties is becoming even more compelling with the recent association of short GRBs with gravitational wave signals produced by the merger of two neutron stars. I also concentrated my work on the prompt emission dissipation and radiation mechanism operating in GRBs
L’infermiere come agente morale della professione, la sensibilità etica e i valori professionali
No full textThe purpose of this thesis is aimed to answer to the question: nurse's ethical sensitivity today is consistent with the definition of nurse as moral agent of the profession? In order to answer, nurses will be defined as moral agent of the profession through the revision of most representive ethical currents in bioethics (Principialism, ethics of virtues, ethics of natural law and ethics of respect for people) motivating so his ethical/deontological involvement within the intellectual professions and the health system; we will proceed to identify which values underlie the profession and form the foundation for the professional moral agent, starting from those explained in the UN declaration in 1948 and researching them in the most representative codes of ethics, Italy, Canada, Australia, New Zealand, International Council of Nurses. The concepts that define the professionals, caring, advocacy, accountability and cooperation, will be a useful basis, together with the compassion defined as a qualifying component, to help to define the moral agent. Then the Nurses Professional Values Scale-R (NPVS) questionnaire, of the American colleagues Darlene Weis and Mary Jane Schank, will be administered to a representative sample of professionals in order to identify the ethical sensitivity of the same today; in the conclusions will be compared the data collected through the questionnaire with the definition of nurse as moral agent of the profession
Synthesis of novel conjugates based on a functionalized cyclo[DKP-isoDGR] integrin ligand and potent cytotoxic agents
No full textTargeted drug delivery is a growing-interest field in cancer therapy as a strategy for overcoming the systemic cytotoxicity associated to traditional chemotherapy. One important approach in this research area is represented by the small molecule-drug conjugates (SMDCs), where the drug-targeting is performed by a low molecular weight ligand (peptide, vitamin or peptidomimetic) connected to a potent warhead through a stable linker. This PhD thesis describes the synthesis and biological evaluation of novel SMDCs containing the functionalized cyclo[DKP-isoDGR] integrin ligand developed by our research group and potent cytotoxic drugs (α-amanitin, MMAE and MMAF) combined via different linkers and spacers. The conjugates were evaluated for their binding affinity to the isolated αvβ3 receptor and for their antiproliferative activity on cancer cell lines with different levels of αVβ3 expression in order to study the efficacy of the cyclo[DKP-isoDGR] integrin ligand as a vector for tumor drug-delivery
La moneta di ghiaccio. Il ruolo delle monete complementari: misura anticiclica o strumento di rifondazione del processo di circolazione – il caso delle BCC in Bergamasca
No full textThe research deepens the nature and functions of money in a monetary production economy by addressing monetary issues held to be of minor importance by the contemporary mainstream. After defining the functions institutionally attributed to money, the research analyzes the theoretical contributions of Proudhon, Gesell and Keynes in order to emphasize how, according to these authors, money plays an essential role for the explanation of the instability of the economic system in which we actually live. The projects for the re-foundation of money thus developed by Proudhon, Gesell and Keynes are all characterized by the necessity of reserving to money the sole function of means of payment and exchange. To this end, money should be transformed into ‘ice money’, that is, a kind of money that, like goods, is subject to a process of temporal deterioration affecting its nominal value through demurrage, so as to prevent its hoarding. The transformation of money into ‘ice money’ represents the necessary, although not sufficient, condition to trigger a virtuous dynamic process towards full employment, while favoring the downsizing of capital income up to its progressive elimination. Inspired by these projects for the re-foundation of money, the experiences of Banca WIR and SARDEX.net analyzed in this work are characterized by the realization of multilateral clearing houses for commercial credits allowing to apply to local realities the plans originally conceived by the authors mentioned above to re-build the national and international process of circulation of goods and capitals. The ultimate goal of the research was to verify the efficacy of such multilateral clearing houses with respect to the urgencies currently expressed by cooperative credit banks in terms of the recovery of their profitability, which was compromised by the deterioration of credits, and in terms of the reaffirmation of their mutualistic purpose with regard to the local economic reality as a fundamental distinctive character compared to commercial banks. The research also contains a specific study devoted to the economic reality of the province of Bergamo, in which the phenomenon of cooperative credit banking has its roots. Within this context, and with the third sector acting as a flywheel, the multilateral clearing house for commercial credits is able to express its full potential not only as an anti-cyclical tool benefitting the local economy, but also as a more ambitious structural re-foundation tool of the process of circulation of the real economic system