Carbon???Carbon Bond Coupling of Vinyl Molecules with an Allenyl Ligand at a Diruthenium Complex

The room-temperature reactions of the diruthenium μ-allenyl complex [Ru2Cp2(CO)2(NCMe){μ-η1:η2-CH═C═CMe2}]BF4, 3-NCMe, with a series of alkenes, RCH═CH2, afforded the complexes [Ru2Cp2(CO)2{μ-η3:η2-CH(R)CHC(Me)C(Me)CH2}]BF4(R═Ph, 4; 4-C6H4Me, 5; Me, 6; nBu, 7; CO2Me, 8; and H, 9), containing an uncommon pentacarbon alkenyl-allyl ligand. Cross experiments with deuterated reagents, i.e., [Ru2Cp2(CO)2(NCMe){μ-η1:η2-CD═C═CMe2}]BF4(3b-NCMe) and CD2═CD(C6H5) (styrene-d3), revealed that the formation of 4-9 is initiated by an attack of the alkene to the central carbon of the allenyl moiety, triggering two distinct C-H activation processes. Compounds 4-9 were characterized by analytical and spectroscopic methods and by single-crystal X-ray diffraction in the cases of 4, 7, and 8. Reported here is the clean coupling on a metallic scaffold between two C2and C3functions invoked in Fischer-Tropsch mechanistic models

A new advanced railgun system for debris impact study

The growing quantity of debris in Earth orbit poses a danger to users of the orbital environment, such as spacecraft. It also increases the risk that humans or manmade structures could be impacted when objects reenter Earth's atmosphere. During the design of a spacecraft, a requirement may be specified for the surviv-ability of the spacecraft against Meteoroid / Orbital Debris (M/OD) impacts throughout the mission; further-more, the structure of a spacecraft is designed to insure its integrity during the launch and, if it is reusable, during descent, re-entry and landing. In addition, the structure has to provide required stiffness in order to allow for exact positioning of experiments and antennas, and it has to protect the payload against the space environment. In order to decrease the probability of spacecraft failure caused by M/OD, space maneuver is needed to avoid M/OD if the M/OD has dimensions larger than 10cm, but for M/OD with dimensions less than 1cm M/OD shields are needed for spacecrafts. It is therefore necessary to determine the impact-related failure mechanisms and associated ballistic limit equations (BLEs) for typical spacecraft components and subsys-tems. The methods that are used to obtain the ballistic limit equations are numerical simulations and la-borato-ry experiments. In order to perform an high energy ballistic characterization of layered structures, a new ad-vanced electromagnetic accelerator, called railgun, has been assembled and tuned. A railgun is an electrically powered electromagnetic projectile launcher. Such device is made up of a pair of parallel conducting rails, which a sliding metallic armature is accelerated along by the electromagnetic effect (Lorentz force) of a cur-rent that flows down one rail, into the armature and then back along the other rail, thanks to a high power pulse given by a bank of capacitors. A tunable power supplier is used to set the capacitors charging voltage at the desired level: in this way the Rail Gun energy can be tuned as a function of the desired bullet velocity. This facility is able to analyze both low and high velocity impacts. A numerical simulation is also performed by using the Ansys Autodyn code in order to analyze the damage. The experimental results and numerical simulations show that the railgun-device is a good candidate to perform impact testing of materials in the space debris energy range

Synthesis and study of the stability of amidinium/guanidinium carbamates of amines and α-amino acids

Thermally stable amidinium/guanidinium N,N-dialkylcarbamates, including vacuum stable compounds, have been prepared, and then isolated in the solid state, by reaction of tetramethylguanidine (TMG) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) with secondary amines under atmospheric pressure of CO2. The same method has been successfully applied to a-amino acids, thus the corresponding carbamates of sarcosine, L-proline and L-phenylalanine have been obtained. All the products are highly moisture sensitive, and have been characterized by analytical and spectroscopic (IR, multinuclear NMR) techniques

Insulin secretory granules labelled with phogrin-fluorescent proteins show alterations in size, mobility and responsiveness to glucose stimulation in living β-cells

The intracellular life of insulin secretory granules (ISGs) from biogenesis to secretion depends on their structural (e.g. size) and dynamic (e.g. diffusivity, mode of motion) properties. Thus, it would be useful to have rapid and robust measurements of such parameters in living β-cells. To provide such measurements, we have developed a fast spatiotemporal fluctuation spectroscopy. We calculate an imaging-derived Mean Squared Displacement (iMSD), which simultaneously provides the size, average diffusivity, and anomalous coefficient of ISGs, without the need to extract individual trajectories. Clustering of structural and dynamic quantities in a multidimensional parametric space defines the ISGs’ properties for different conditions. First, we create a reference using INS-1E cells expressing proinsulin fused to a fluorescent protein (FP) under basal culture conditions and validate our analysis by testing well-established stimuli, such as glucose intake, cytoskeleton disruption, or cholesterol overload. After, we investigate the effect of FP-tagged ISG protein markers on the structural and dynamic properties of the granule. While iMSD analysis produces similar results for most of the lumenal markers, the transmembrane marker phogrin-FP shows a clearly altered result. Phogrin overexpression induces a substantial granule enlargement and higher mobility, together with a partial de-polymerization of the actin cytoskeleton, and reduced cell responsiveness to glucose stimulation. Our data suggest a more careful interpretation of many previous ISG-based reports in living β-cells. The presented data pave the way to high-throughput cell-based screening of ISG structure and dynamics under various physiological and pathological conditions

Metal N,N-dialkylcarbamates as easily available catalytic precursors for the carbon dioxide/propylene oxide coupling under ambient conditions

A series of previously reported homoleptic and non-homoleptic N,N-dialkylcarbamates of a range of non precious metals and N,N-dialkylcarbamate of Al(III) were investigated as easily available and inexpensive catalysts in the solventless synthesis of propylene carbonate (PC) from propylene oxide (PO) and CO2. By operating at atmospheric CO2 pressure at ambient temperature, excellent results were achieved using Ti(O2CNEt2)4, Al(O2CNR2)3 (R = Et, iPr), Cu(O2CNEt2)2 and Sn(O2CNEt2)4, in combination with NBu4X (X = Br or Cl) as a co-catalyst. The reactions of MCl2(O2CNEt2)2 (M = Ti, Zr) with amorphous silica were straightforward through partial release of both chlorido and carbamato ligands, and readily afforded solid materials which were characterized by ICP-OES and EDS analyses, coupled to SEM. These heterogeneous catalytic systems revealed less efficient than the homogeneous counterparts

Approximate estimates of orbit transfer cost for efficient mission analysis and design

Symbolic Regression is investigated as a tool for identifying analytical expressions which provide an estimate of orbit transfer cost, evaluated in terms of required veloc- ity increment, as a function of initial and target orbit geometry. Different approaches are considered to identify the best approach to sample the problem parameter space and the algorithm which performs better, in the framework of Genetic Programming. Each resulting method is tested for five different orbit transfer geometries between coplanar circular and elliptical orbits. Results demonstrate the viability of the ap- proach, although when the number of problem parameter increases, computational cost becomes sizeable. Also, local minima may be filtered by the regression

The seismic microzonation of level 3 of Sant’Agata Fossili (northern Italy) based on a multidisciplinary approach.

In this paper the results of a detailed seismic microzonation, performed at Sant’Agata Fossili (Piemonte region, northern Italy) are presented. We study the local seismic response of this small village using a level 3, that is the most accurate level following the Italian code of seismic microzonation. The activity steps consist in a gradual widening of knowledge of the different aspects of the amplification phenomena. A multidisciplinary approach has been performed to obtain the local seismic response: including a study of local geology, geophysical and geotechnical characterization of the lithologies, and numerical and experimental analyses. We finally compare the obtained elastic response spectra to the prescribed spectra of the Italian Building Code (in Italian: Norme Tecniche per le Costruzioni). Our results show the geologic and geophysical differences of the subsoil, that produce different local seismic response in terms of amplification factors and acceleration response spectra.PublishedS01893T. Pericolosità sismica e contributo alla definizione del rischio5T. Sorveglianza sismica e operatività post-terremotoJCR Journalope

Qualitative Immune Modulation by Interleukin-2 (IL-2) Adjuvant Therapy in Immunological Non Responder HIV-Infected Patients

BACKGROUND: Treatment of HIV-infected patients with interleukin-2 (IL-2) produces significant increases in CD4 T cell counts; however an associated qualitative improvement in cells function has yet to be conclusively demonstrated. By measuring mycobacterial killing activity, we evaluated IL-2-mediated functional immune enhancement ex vivo in immunological non-responders (INRs). METHODS AND FINDINGS: PBMC from 12 immunological non-responders (INRs) (CD4+<200/µl, HIV-RNA<50 cp/ml) on combination antiretroviral treatment (cART) were collected at baseline, and after 3 IL-2 cycles. Eight INRs receiving only cART were studied as controls. After 21 days of PBMC incubation with a virulent M. avium suspension, counts of residual colony forming units (CFUs) and concentrations of TNF-α, IL-10 and IFN-γ were determined. In IL-2 treated patients, a significant reduction in mean residual CFUs of PBMC cultures was observed (p<0.01). Moreover, following IL-2 treatment, significant increases in PBMC's IFNγ production (p = 0.02) and substantial reductions in IL-10 levels were observed. CONCLUSIONS: IL-2 therapy restores the ability of the lympho-monocyte system in eliciting an effective response against mycobacterial infections. Our data indicate the possibility of a clinical role held by IL-2 in enhancing the immune function of subjects unable to achieve immune competence through cART alone

Total- and semi-bare noble metal nanoparticles@silica core@shell catalysts for hydrogen generation by formic acid decomposition

AbstractCatalysts are involved in a number of established and emerging chemical processes as well as in environmental remediation and energy conversion. Nanoparticles (NPs) can offer several advantages over some conventional catalysts, such as higher efficiency and selectivity. Nowadays, versatile and scalable nanocatalysts that combine activity and stability are still lacking. Here, we report a comprehensive investigation on the production and characterization of hybrid nano-architectures bringing a partial or total bare surface together with their catalytic efficiency evaluation on, as a proof-of-concept, the formic acid decomposition reaction. In this regard, formic acid (FA) is a convenient and safe hydrogen carrier with appealing features for mobile applications, fuel cells technologies, petrochemical processes and energetic applications. Thus, the design of robust catalysts for FA dehydrogenation is strongly demanded. Due to this, we produced and evaluated nano-architectures with various equilibrium between the size-increase of the active part and the barer catalytic surface. Overall, this work paves the way for the development of new approaches for green energy storage and safe delivery

The seismic microzonation of level 3 of Sant’Agata Fossili (northern Italy) based on a multidisciplinary approach

In this paper the results of a detailed seismic microzonation, performed at Sant’Agata Fossili (Piemonte region, northern Italy) are presented. We study the local seismic response of this small village using a level 3, that is the most accurate level following the Italian code of seismic microzonation. The activity steps consist in a gradual widening of knowledge of the different aspects of the amplification phenomena. A multidisciplinary approach has been performed to obtain the local seismic response: including a study of local geology, geophysical and geotechnical characterization of the lithologies, and numerical and experimental analyses. We finally compare the obtained elastic response spectra to the prescribed spectra of the Italian Building Code (in Italian: Norme Tecniche per le Costruzioni). Our results show the geologic and geophysical differences of the subsoil, that produce different local seismic response in terms of amplification factors and acceleration response spectra