On the gas storage properties of 3D porous carbons derived from hyper-crosslinked polymers

The preparation of porous carbons by post-synthesis treatment of hypercrosslinked polymers is described, with a careful physico-chemical characterization, to obtain new materials for gas storage and separation. Different procedures, based on chemical and thermal activations, are considered; they include thermal treatment at 380 degrees C, and chemical activation with KOH followed by thermal treatment at 750 or 800 degrees C; the resulting materials are carefully characterized in their structural and textural properties. The thermal treatment at temperature below decomposition (380 degrees C) maintains the polymer structure, removing the side-products of the polymerization entrapped in the pores and improving the textural properties. On the other hand, the carbonization leads to a different material, enhancing both surface area and total pore volumethe textural properties of the final porous carbons are affected by the activation procedure and by the starting polymer. Different chemical activation methods and temperatures lead to different carbons with BET surface area ranging between 2318 and 2975 m(2)/g and pore volume up to 1.30 cc/g. The wise choice of the carbonization treatment allows the final textural properties to be finely tuned by increasing either the narrow pore fraction or the micro- and mesoporous volume. High pressure gas adsorption measurements of methane, hydrogen, and carbon dioxide of the most promising material are investigated, and the storage capacity for methane is measured and discussed

Water diffusion modulates the cest effect on Tb(III)-mesoporous silica probes

The anchoring of lanthanide(III) chelates on the surface of mesoporous silica nanoparticles (MSNs) allowed their investigation as magnetic resonance imaging (MRI) and chemical exchange saturation transfer (CEST) contrast agents. Since their efficiency is strongly related to the interaction occurring between Ln-chelates and \u201cbulk\u201d water, an estimation of the water diffusion inside MSNs channels is very relevant. Herein, a method based on the exploitation of the CEST properties of TbDO3A-MSNs was applied to evaluate the effect of water diffusion inside MSN channels. Two MSNs, namely MCM-41 and SBA-15, with different pores size distributions were functionalized with TbDO3A-like chelates and polyethylene glycol (PEG) molecules and characterized by HR-TEM microscopy, IR spectroscopy, N2 physisorption, and thermogravimetric analysis (TGA). The different distribution of Tb-complexes in the two systems, mainly on the external surface in case of MCM-41 or inside the internal pores for SBA-15, resulted in variable CEST efficiency. Since water molecules diffuse slowly inside silica channels, the CEST effect of the LnDO3A-SBA-15 system was found to be one order of magnitude lower than in the case of TbDO3A-MCM-41. The latter system reaches an excellent sensitivity of ca. 55 \ub1 5 \ub5M, which is useful for future theranostic or imaging applications

Surprising Complexity of the [Gd(AAZTA)(H2O)2]- Chelate Revealed by NMR in the Frequency and Time Domains

Typically, Ln(III) complexes are isostructural along the series, which enables studying one particular metal chelate to derive the structural features of the others. This is not the case for [Ln(AAZTA)(H2O)x]- (x = 1, 2) systems, where structural variations along the series cause changes in the hydration number of the different metal complexes, and in particular the loss of one of the two metal-coordinated water molecules between Ho and Er. Herein, we present a 1H field-cycling relaxometry and 17O NMR study that enables accessing the different exchange dynamics processes involving the two water molecules bound to the metal center in the [Gd(AAZTA)(H2O)2]- complex. The resulting picture shows one Gd-bound water molecule with an exchange rate ∼6 times faster than that of the other, due to a longer metal-water distance, in accordance with density functional theory (DFT) calculations. The substitution of the more labile water molecule with a fluoride anion in a diamagnetic-isostructural analogue of the Gd-complex, [Y(AAZTA)(H2O)2]-, allows us to follow the chemical exchange process by high-resolution NMR and to describe its thermodynamic behavior. Taken together, the variety of tools offered by NMR (including high-resolution 1H, 19F NMR as a function of temperature, 1H longitudinal relaxation rates vs B0, and 17O transverse relaxation rates vs T) provides a complete description of the structure and exchange dynamics of these Ln-complexes along the series

Thermodynamic and Kinetic Stabilities of Al(III) Complexes with N2O3 Pentadentate Ligands

: Al(III) complexes have been recently investigated for their potential use in imaging with positron emission tomography (PET) by formation of ternary complexes with the radioisotope fluorine-18 (18F). Although the derivatives of 1,4,7-triazacyclononane-1,4,7-triacetic acid (NOTA) are the most applied chelators for [Al18F]2+ labelling and (pre)clinical PET imaging, non-macrocyclic, semi-rigid pentadentate chelators having two N- and three O-donor atoms such as RESCA1 and AMPDA-HB have been proposed with the aim to allow room temperature labelling of temperature-sensitive biomolecules. The paucity of stability data on Al(III) complexes used for PET imaging instigated a complete thermodynamic and kinetic solution study on Al(III) complexes with aminomethylpiperidine (AMP) derivatives AMPTA and AMPDA-HB and the comparison with a RESCA1-like chelator CD3A-Bn (trans-1,2-diaminocyclohexane-N-benzyl-N,N',N'-triacetic acid). The stability constant of [Al(AMPDA-HB)] is about four orders of magnitude higher than that of [Al(AMPTA)] and [Al(CD3A-Bn)], highlighting the greater affinity of phenolates with respect to acetate O-donors. On the other hand, the kinetic inertness of the complexes, determined by following the Cu2+-mediated transmetallation reactions in the 7.5-10.5 pH range, resulted in a spontaneous and hydroxide-assisted dissociation slightly faster for [Al(AMPTA)] than for the other two complexes (t1/2 = 4.5 h for [Al(AMPTA)], 12.4 h for [Al(AMPDA-HB)], and 24.1 h for [Al(CD3A-Bn)] at pH 7.4 and 25 °C). Finally, the [AlF]2+ ternary complexes were prepared and their stability in reconstituted human serum was determined by 19F NMR experiments

Dynamic update of discrete event controllers

Discrete event controllers are at the heart of many software systems that require continuous operation. Changing these controllers at runtime to cope with changes in its execution environment or system requirements change is a challenging open problem. In this paper we address the problem of dynamic update of controllers in reactive systems. We present a general approach to specifying correctness criteria for dynamic update and a technique for automatically computing a controller that handles the transition from the old to the new specification, assuring that the system will reach a state in which such a transition can correctly occur and in which the underlying system architecture can reconfigure. Our solution uses discrete event controller synthesis to automatically build a controller that guarantees both progress towards update and safe update

Assured and Correct Dynamic Update of Controllers

We present a general approach to specifying correctness criteria for dynamic update and a technique for automatically computing a controller that handles the transition from the old to the new specification, assuring that the system will reach a state in which such a transition can correctly occur. Indeed, using controller synthesis we show how to automatically build a controller that guarantees both progress towards update and safe update.Sociedad Argentina de Informática e Investigación Operativa (SADIO

Visualization through magnetic resonance imaging of DNA internalized following "in vivo" electroporation.

The ability to visualize plasmid DNA entrapment in muscle cells undergoing an "in vivo" electroporation treatment was investigated on BALB/c mice using a 7-T magnetic resonance imaging (MRI) scanner using the paramagnetic Gd–DOTA–spd complex as imaging reporter. Gd–DOTA–spd bears a tripositively charged spermidine residue that yields a strong binding affinity toward the negatively charged DNA chain (6.4 kb, K a = 2.2 × 10 3 M −1 for approximately 2500 ± 500 binding sites). Cellular colocalization of Gd-DOTA-spd and plasmid DNA has been validated by histological analysis of excised treated muscle. In vivo MRI visualization of Gd-DOTA-spd distribution provides an excellent route to access the cellular entrapment of plasmid DNA upon applying an electroporation pulse

752-6 Visualization of Coronary Arteries and Measurement of Coronary Blood Flow with Transthoracic Echocardiography After Intravenous Administration of a New Echocardlographic Contrast Agent

Imagent®US (AF0145, Alliance Pharmaceutical Corp.), a new hemodynamically inert perfluorochemical echocardiographic contrast agent, produces excellent left ventricular and blood pool contrast effect after intravenous administration when imaged with conventional (2-D) ultrasound. We evaluated the potential of Contrast Specific Imaging (Acuson) employing second harmonic principles to further enhance the visualization of structures containing contrast agents. Transthoracic images were obtained during injections of 10–40mg of the agent into the left femoral vein of seven closed chest dogs. Coronary Dopplerflow was simultaneously measured using an intracoronary Doppler wire. No alterations in flow velocities were observed with contrast administration. There was heterogenous opacification of the myocardium following contrast injection: a striking finding was of contrast-enhanced linear, branching structures in the myocardium consistent with coronary vessels. Further exploration of the largest structures (2–3mm diameter) in the region of the basal ventricular septum was technically possible with pulsed wave Doppler in two dogs. A characteristic coronary Doppler flow pattern was observed (Fig 1a). Transthoracic Doppler flow velocities transiently increased after intracoronary adenosine (Fig 1b). The calculated coronary flow reserve ratio was similar to simultaneous intracoronary Doppler measurements.ConclusionsIntramyocardial coronaryvasculature was observed and coronary flow velocites were measured during transthoracic Contrast Specific Imaging with an intravenously administered contrast agent. These findings suggest that noninvasive assessment of coronary blood flow is possible with echocardiographic contrast enhancement