Isolation and Characterization of Precise Dye/Dendrimer Ratios

Fluorescent dyes are commonly conjugated to nanomaterials for imaging applications using stochastic synthesis conditions that result in a Poisson distribution of dye/particle ratios and therefore a broad range of photophysical and biodistribution properties. We report the isolation and characterization of generation 5 poly(amidoamine) (G5 PAMAM) dendrimer samples containing 1, 2, 3, and 4 fluorescein (FC) or 6‐carboxytetramethylrhodamine succinimidyl ester (TAMRA) dyes per polymer particle. For the fluorescein case, this was achieved by stochastically functionalizing dendrimer with a cyclooctyne “click” ligand, separation into sample containing precisely defined “click” ligand/particle ratios using reverse‐phase high performance liquid chromatography (RP‐HPLC), followed by reaction with excess azide‐functionalized fluorescein dye. For the TAMRA samples, stochastically functionalized dendrimer was directly separated into precise dye/particle ratios using RP‐HPLC. These materials were characterized using ¹H and ¹⁹F NMR spectroscopy, RP‐HPLC, UV/Vis and fluorescence spectroscopy, lifetime measurements, and MALDI.     

Investigation of a Pt–Fe/C catalyst for oxygen reduction reaction in direct ethanol fuel cells

Three cathode catalysts (60% Pt/C, 30% Pt/C and 60% Pt–Fe/C), with a particle size of about 2–3 nm, were prepared to investigate the effect of ethanol cross-over on cathode surfaces. All samples were studied in terms of structure and morphology by using X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses. Their electrocatalytic behavior in terms of oxygen reduction reaction (ORR) was investigated and compared using a rotating disk electrode (RDE). The tolerance of cathode catalysts in the presence of ethanol was evaluated. The Pt–Fe/C catalyst showed both higher ORR activity and tolerance to ethanol cross-over than Pt/C catalysts. Moreover, the more promising catalysts were tested in 5 cm² DEFC single cells at 60 and 80 °C. An improvement in single cell performance was observed in the presence of the Pt–Fe catalyst, due to an enhancement in the oxygen reduction kinetics. The maximum power density was 53 mW cm⁻² at 2 bar rel. cathode pressure and 80 °C.     

Spiky nanostructured metal particles as filler of polymeric composites showing tunable electrical conductivity

This work presents a comprehensive investigation of the piezoresistive response of a composite material based on conductive nickel filler in a silicone‐insulating matrix. In the absence of a deformation, the prepared composite shows no electric conductivity, even though the metal particle content is well above the expected percolation threshold. Upon samples deformation (compressive or tensile stress), the composite exploits a variation of electrical resistance up to nine orders of magnitude. This huge variation can be explained with the quantum tunnelling mechanism where the probability of an electron to tunnel from a particle to the next one is exponentially proportional to the thickness of the insulating layer between them and strongly enhanced by the morphology of the nickel particles, showing spiky nanostructured tips. Two different conduction theoretical models are proposed and compared with the experimental results. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Interactions of poly(amidoamine) dendrimers with Survanta lung surfactant: the importance of lipid domains

The interaction of generation 5 (G5) and 7 (G7) poly(amidoamine) (PAMAM) dendrimers with mica-supported Survanta bilayers is studied with atomic force microscopy (AFM). In these experiments, Survanta forms distinct gel and fluid domains with differing lipid composition. Nanoscale defects are induced by the PAMAM dendrimers. The positively charged dendrimers remove lipid from the fluid domains at a significantly greater rate than for the gel domains. Dendrimer accumulation on lipid edges and terraces preceding lipid removal has been directly imaged. Immediately following lipid removal, the mica surface is clean, indicating that lipid defects are not induced by dendrimers binding to the mica substrate and displacing the lipid.     

Drawing and extruding: Theoretical and approximate formulas

Summary The problem of drawing of wires and of strips has been treated in several studies; among these the studies of Sachs seem essential. However, the results deduced according to similar theories are not always in accordance with the experimental results: reduction of area or of thickness are in fact usually smaller than those resulting from the theory. This is in dependance of the fact that Sachs has adopted the Limiting Condition of Yielding by v. Mises, according to which the limit values of stress in traction and compression are equal. More recently other AA. (Alberti, Noto La Diega, Bugini), admitting the Limiting Condition of Yielding by A. (or of the Paraboloid of Revolution) of which we have treated in one of our previous works, attain results tallying with the experience. In the present study the above said subjects are treated as to evidence their unitarian signifiance and clarify their several aspects. The approximate formulas proposed by A. result of easy and quick application. In the same manner are treated other problems, among which the problem of the extrusion (Bagarello, Ammendola).

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Sommario Il problema della trafilatura dei fili metallici e delle strisce di lamiera è stato trattato in diverse Memorie, fra le quali fondamentali sono quelle del Sachs. I risultati dedotti in base a tali studi non sempre però concordano con le risultanze sperimentali: i rapporti di riduzione delle aree o degli spessori sono infatti di norma inferiori a quelli che risultano da tali teorie. Ciò dipende dal fatto che il Sachs ha posto a base dei suoi studi la Condizione di Plastificazione del v. Mises secondo la quale i limiti di resistenza del materiale che si considera alla trazione e alla compressione semplice sono uguali. Più recentemente altri AA. (Alberti, Noto La Diega, Bugini), adottando la Condizione di Plastificazione dell' A. (o del Paraboloide di Rivoluzione), del quale abbiamo trattato in un precedente lavoro, pervengono a risultati più attinenti alla practica. Col presente studio gli argomenti vengono trattati mettendone in evidenza il significato unitario e chiarendone i vari aspetti. Le formule approssimate proposte dall' A. risultano di facile e immediata applicazione. In maniera analoga vengono trattati altri problemi, fra i quali quello dell'estrusione (Bagarello, Ammendola).

     

On-line Calibration and Determination of the Heat of Reaction for Laboratory Scale Heat Transfer Calorimeters

A simple method for the on-line calibration, in which both the heat transfer coefficient and the heat capacity of the reactor contents are determined, is described for laboratory scale heat transfer calorimeters. The calorimeter is operated in the isoperibolic mode for the calibration and a constant power is supplied to a resistor placed inside the reactor. The reactor heat balance differential equation is used to produce a set of linear simultaneous equations with each data acquisition cycle giving one equation. The heat transfer coefficient and the heat capacity are obtained from this set of equations by linear least squares. The application of the calibration procedure is illustrated by experiments in which the heat of reaction is determined on-line fora simulated reaction with first order kinetics and for the hydrolysis of acetic anhydride. This revised version was published online in July 2006 with corrections to the Cover Date.     

Investigation of Pt–Ru nanoparticle catalysts for low temperature methanol electro-oxidation

Pt–Ru nanoparticle-based methanol electro-oxidation catalysts with high concentration of metallic phase on carbon black have been synthesised by a low-temperature colloidal preparation route. Amorphous Pt–Ru oxide nanoparticles were deposited on carbon and subsequently reduced in hydrogen stream at different temperatures to obtain crystalline phases with tailored particle size. The electro-catalytic activity for methanol oxidation was investigated in half-cell from 30 to 60 °C. The results were interpreted in terms of particle size, crystallographic structure, degree of alloying and carbon monoxide adsorption properties. The best performance was achieved for the catalyst with intermediate particle size in the investigated range. Furthermore, it is observed that the optimal properties for these catalysts depend on the operating temperature.