Editorial Catalysts: Supported Metal Catalysts and Their Applications in Fine Chemicals

Editorial to the Special" Issue Supported Metal Catalysts and Their Applications in Fine Chemicals

Long-lived polymer-supported dimeric Cinchona alkaloid organocatalyst in the asymmetric α-amination of 2-oxindoles

Nearly quantitative yields and high enantiomeric purity (89–95% ee) were attained in the course of 100 reaction cycles of a polystyrene resin-supported Cinchona alkaloid organocatalyst in the enantioselective α-amination of 2-oxindoles with diethyl azodicarboxylate. The catalytic material proved stable for >5300 h operation time over 8 months

Le strategie acquisitive delle imprese italiane dal 2011 al 2014

Negli ultimi decenni il fenomeno delle mergers and acquisition ha raggiunto dimensioni di rilievo, sia a livello globale che europeo, rappresentando una modalità di crescita dimensionale per le imprese. Questo fenomeno ha iniziato ad assumere dimensioni considerevoli, in Europa, dal secondo dopoguerra. Lo stesso non si può dire per l’Italia, in quanto, il mercato italiano fino agli anni ‘50 era dominato da pochi grandi gruppi, a conduzione familiare, con la diffusa presenza dello Stato nel capitale di molte imprese, inoltre, i mercati finanziari erano ancora arretrati. Le operazioni di M&A difatti richiedono la presenza di un mercato finanziario attivo. Solo negli ultimi anni si è assistito ad una crescita dei processi di concentrazione nel nostro Paese, grazie ad una maggiore apertura dei mercati, ad uno sviluppo dei processi di globalizzazione e alla crescente integrazione dell’economia europea. La severa crisi che ha colpito i mercati finanziari a livello mondiale e italiano, nel 2008, ha determinato un rallentamento dell’attività M&A. Di conseguenza, dopo un picco elevato registrato nel 2007, negli anni successivi si sono ridotti notevolmente i valori circa le operazioni merger and acquisition. In questi ultimi anni, 2011-2014, si assiste ad una leggera ripresa del mercato mergers and acquisition. Numerosi studi, infatti, evidenziano la ciclicità dei processi di acquisizione, le cosiddette merger waves, che caratterizzano la storia dell’attività M&A. Nonostante ciò, rimane alto l’interesse nelle operazioni di M&A. Grazie ad esse, infatti, è possibile sviluppare una crescita dimensionale dell’azienda, la quale avviene in tempi brevi perché si ottiene l’immediata disponibilità di un’impresa già operante sul mercato, inoltre si ha la possibilità di accedere velocemente a risorse, capacità e competenze utili a fronteggiare la competitività e a superare le barriere all’entrata in nuovi mercati. Il presente lavoro fornisce una panoramica circa le operazioni di mergers and acquisition definendo le caratteristiche principali, i motivi che spingono un’impresa a effettuare operazioni di M&A e le principali fasi che caratterizzano il processo di acquisizione. Dopo di che viene illustrato l’andamento del mercato M&A secondo un’ottica globale, europea e italiana. Infine, nell’ultima parte di questo lavoro viene presentata un’analisi empirica relativa ad un campione di 135 imprese italiane quotate sulla Borsa Italiana. Nel primo capitolo di questo elaborato, dopo aver definito le peculiari caratteristiche relative al concetto di acquisizione e di fusione, viene esposto il concetto di crescita dimensionale, in particolare la crescita esterna e la conseguente creazione di valore, evidenziando i vantaggi che porta una crescita esterna piuttosto di una crescita interna. La parte finale di questo capitolo viene dedicata al mercato M&A italiano, mettendo in risalto gli aspetti principali che lo hanno caratterizzato negli anni precedenti alla crisi che ha colpito i mercati finanziari a fine 2007 e negli anni successivi, dove si è assistito ad un rallentamento dell’economia reale e delle operazioni di M&A a livello globale, facendo particolare attenzione al fenomeno dell’internazionalizzazione, il quale sembra essere una risposta per la ripresa dell’economia italiana. Nel secondo capitolo viene illustrato il processo di acquisizione, mostrando le principali fasi che lo caratterizzano, partendo da una valutazione strategica preventiva fino all’integrazione ex-post. Sono state evidenziate le variabili da non sottovalutare in quanto possono determinare il buon esito o meno dell’operazione di acquisizione. Il terzo capitolo prende in considerazione l’andamento generale dell’attività M&A a livello mondiale, europeo e italiano, secondo il rapporto di KPMG, facendo particolare riferimento agli anni 2011, 2012 e 2013. In particolare viene evidenziato l’andamento del mercato M&A secondo le tre diverse ottiche, l’andamento dell’attività cross border e i settori di appartenenza delle imprese target. Nell’ultimo capitolo, dopo aver indagato a livello teorico nell’ambito dell’attività di M&A, viene fatta un’analisi di natura empirica circa un campione di 135 aziende italiane quotate. Di queste aziende appartenenti al campione, si provvederà, in un primo momento, a fare una distinzione tra le imprese che hanno concluso operazioni di M&A e quelle che, invece, non ne hanno realizzate. Lo studio farà sempre riferimento alle sole imprese del campione che hanno svolto operazioni di acquisizione. L’obiettivo di questo studio riguarda l’individuazione delle strategie acquisitive delle imprese del campione, esaminando i settori in cui sono andati ad acquisire; i mercati, se esteri o domestici, evidenziando in quali Paesi sono state concluse le operazioni di M&A. Infine, vengono evidenziate le prime 10 imprese più attive del campione, con le relative scelte strategiche attuate, in un arco di tempo che va dal 2011 al primo trimestre del 2014

Prognostic value of echo-derived peak cardiac power output-to-left ventricular mass compared to cardiopulmonary exercise testing in patients with heart failure with reduced ejection fraction

ABSTRACT Background. Peak cardiac power output (peak CPO) at exercise echocardiography showed to be closely related to peak VO2 at cardiopulmonary exercise testing (CPET). To gain further perspective in the evaluation of left ventricular (LV) remodeling in myocardial hypertrophy, the peak cardiac power output-to-LV mass (peak CPOM), a measure of the rate at which cardiac work is delivered with respect to the potential energy stored in LV mass, was recently introduced. Aim. To compare the value of peak CPOM with CPET variables in the prognostic stratification of patients with chronic stable heart failure (HF) due to LV dysfunction. Materials and methods. 115 patients with chronic stable HF (mean LV EF% 0.31±0.6) underwent CPET and exercise echocardiography. The two tests were performed within 7 days according to standard symptom-limited exercise protocols. Peak CPOM was calculated as the product of a constant (K=2.22 x 10-1) with cardiac output (CO) and the mean arterial pressure (MAP) divided by LV mass (M) to convert the units to watts/100 g: CPO = K x CO (l/min) x MAP (mmHg) x M-1(g). Patients were followed-up for the composite end point of all-cause mortality or hospitalization for HF. Results. There were 16 deaths and 21 hospitalizations for worsening HF during a mean follow-up of 24 months. At ROC analyses, the areas under the curve for the composite end point were greater for peak CPOM (AUC=0.82) and VE/VCO2 (AUC=0.76), followed by CPO (AUC=0.75), peakVO2 predicted (AUC 0.72), VO2 (AUC =0.69), LV EF (AUC=0.69) and NYHA class (AUC=0.68). At the multivariate logistic regression analysis, peak CPOM was the most powerful predictor of outcome (p 0.60 watts/100 g, while it was 29% in those with a peak CPOM ≤0.60 watts/100 g (p <0.0001, Logrank: 34.1). Conclusion. The assessment of LV ratio power-to-mass by the echo-derived peak CPOM can provide additional insights in the prognostic stratification of patients with HF

New Polymer-Supported Mono- and Bis-Cinchona Alkaloid Derivatives: Synthesis and Use in Asymmetric Organocatalyzed Reactions

The straightforward synthesis of polystyrene-supported Chinchona alkaloids and their application in the asymmetric dimerization of ketenes is reported. Six different immobilized derivatives, consisting of three dimeric and two monomeric 9-O ethers, were prepared by “click” anchoring of soluble alkaloid precursors on to azidomethyl resins. The resulting insoluble polymer-bound (IPB) organocatalysts were employed for promoting the dimerization of in-situ generated ketenes. After opening of the ketene dimer intermediates with N,O-dimethylhydroxylamine, valuable Weinreb amides were eventually obtained in good yield (up to 81 %) and excellent enantiomeric purity (up to 96 % ee). All of the IPB catalysts could be recycled effectively without significant loss of activity and enantioselectivity. The extension to other asymmetric transformations (meso-anhydride desymmetrization and α-amination of 2-oxindoles) is also briefly discussed

The sandbox strategy : the why and how of federal law enforcement integration

CHDS State/LocalThis thesis examines the interoperability of federal law enforcement's Big Six investigative agencies, to include the Federal Bureau of Investigation, Immigration and Customs Enforcement, Drug Enforcement Administration, Alcohol Tobacco Firearms and Explosives, Internal Revenue Service-CID, and the United States Secret Service-Investigations. The main issue is whether, in the post-9/11 environment of transnational and terrorist criminal threats, the current administrative and jurisdictional configuration of the Big Six within three executive epartments with overlapping duties marginalizes the nation's investigative work-product. This discussion includes the establishment of metrics used to gauge the functionality of the Big Six and, thus, to determine whether Negative Characteristics are present that materially affect the "total" mission. Ultimately, the conclusion is drawn that the integration of the Big Six into a single agency, namely the FBI, would better serve the nation's federal investigative law enforcement needs. This leads into the next area of discussion, which is how to integrate the Big Six. Associated with both these topics is an analysis of what the federal investigative mission means and whether it should include a domestic intelligence product.http://archive.org/details/thesandboxstrate109452576Special Agent, Department of Homeland Security, IC

Aminopropyl-silica-supported Cu nanoparticles: An efficient catalyst for continuous-flow Huisgen azide-alkyne cycloaddition (CuAAC)

Cu nanoparticles prepared by metal vapor synthesis (MVS) were immobilized on 3-aminopropyl-functionalized silica at room temperature. HRTEM analysis of the catalyst showed that the copper nanoparticles are present with mean diameters limited in the range 1.0-4.5 nm. TPR analysis was performed in order to study the oxidation state of the supported copper nanoparticles. The supported catalyst was used both in batch and in a packed-bed reactor for continuous-flow CuAAC reaction. The activation of the copper catalyst by reduction using phenyl hydrazine in continuous-flow conditions was demonstrated. Along with the high catalytic activity (productivity up to 1689 mol/mol), the catalyst can be used several times with negligible Cu leaching in the product (<9 ppm), less than allowed Cu contaminant in pharmaceuticals. The applicability of packed-bed flow reactor was showed by sequentially converting different substrates in their corresponding products using same column

Nanopatterned acellular valve conduits drive the commitment of blood-derived multipotent cells

Considerable progress has been made in recent years toward elucidating the correlation among nanoscale topography, mechanical properties, and biological behavior of cardiac valve substitutes. Porcine TriCol scaffolds are promising valve tissue engineering matrices with demonstrated self-repopulation potentiality. In order to define an in vitro model for investigating the influence of extracellular matrix signaling on the growth pattern of colonizing blood-derived cells, we cultured circulating multipotent cells (CMC) on acellular aortic (AVL) and pulmonary (PVL) valve conduits prepared with TriCol method and under no-flow condition. Isolated by our group from Vietnamese pigs before heart valve prosthetic implantation, porcine CMC revealed high proliferative abilities, three-lineage differentiative potential, and distinct hematopoietic/endothelial and mesenchymal properties. Their interaction with valve extracellular matrix nanostructures boosted differential messenger RNA expression pattern and morphologic features on AVL compared to PVL, while promoting on both matrices the commitment to valvular and endothelial cell-like phenotypes. Based on their origin from peripheral blood, porcine CMC are hypothesized in vivo to exert a pivotal role to homeostatically replenish valve cells and contribute to hetero- or allograft colonization. Furthermore, due to their high responsivity to extracellular matrix nanostructure signaling, porcine CMC could be useful for a preliminary evaluation of heart valve prosthetic functionality

A Catalytic Reactor for the Organocatalyzed Enantioselective Continuous Flow Alkylation of Aldehydes

The use of immobilized metal-free catalysts offers the unique possibility to develop sustainable processes in flow mode. The challenging intermolecular organocatalyzed enantioselective alkylation of aldehydes was performed for the first time under continuous flow conditions. By using a packed-bed reactor filled with readily available supported enantiopure imidazolidinone, different aldehydes were treated with three distinct cationic electrophiles. In the organocatalyzed α-alkylation of aldehydes with 1,3-benzodithiolylium tetrafluoroborate, excellent enantioselectivities, in some cases even better than those obtained in the flask process (up to 95 % ee at 25 °C), and high productivity (more than 3800 h−1) were obtained, which thus shows that a catalytic reactor may continuously produce enantiomerically enriched compounds. Treatment of the alkylated products with Raney-nickel furnished enantiomerically enriched α-methyl derivatives, key intermediates for active pharmaceutical ingredients and natural products

Ultrafine palladium nanoparticles immobilized into poly(4-vinylpyridine)-based porous monolith for continuous-flow Mizoroki-Heck reaction

Ultrafine Pd nanoparticles (dm = 2.3 nm), obtained by metal vapor synthesis technique, were immobilized into a poly(4-vinylpyridine)-based porous monolith by means of a new synthetic approach. The synthesis involves stabilization of Pd nanoparticles with 4-vinylpyridine ligand and their subsequent immobilization into the monolith by radical co-polymerization of the resulting metal-embedding monomer with ethylene glycol dimethacrylate in presence of porogenic agents (i.e. DMF and PEG-400) inside stainless-steel columns (HPLC type). The hybrid monolithic reactors containing highly dispersed Pd nanoparticles were effectively used as catalyst for Mizoroki-Heck cross-coupling reactions carried out under continuous-flow conditions. The devices showed long life-time (>65 h) and very low Pd leaching (<2 ppm)