Carbon Corrosion in Proton-Exchange Membrane Fuel Cells: Spectrometric Evidence for Pt-Catalysed Decarboxylation at Anode-Relevant Potentials

The carbon oxidation reaction (COR) is a critical issue in proton-exchange membrane fuel cells (PEMFCs), as carbon in various forms is the most used electrocatalyst support material. The COR is thermodynamically possible above the C/CO₂ standard potential, but its rate becomes significantly important only at high overpotential (e. g. PEMFC cathode potential). Herein, using on-line differential electrochemical mass spectrometry, we show that oxygen-containing carbon surface groups present on high-surface aera carbon, Vulcan XC72 or reinforced graphite are oxidized at PEMFC anode-relevant potential (E=0.1 V vs. the reversible hydrogen electrode, RHE), but not at E=0.4 V vs. RHE. We rationalized our findings by considering a Pt-catalysed decarboxylation mechanism in which Pt nanoparticles provide adsorbed hydrogen species to the oxygen-containing carbon surface groups, eventually leading to evolution of carbon dioxide and carbon monoxide. These results shed fundamental light on an unexpected degradation mechanism and facilitate the understanding of the long-term stability of PEMFC anode nanocatalysts.     

The first immobilization of pyridine-bis(oxazoline) chiral ligands

[formula: see text] A chiral pyridine-bis(oxazoline) ligand, functionalized with a vinyl group in the pyridine ring, can be polymerized with styrene and divinylbenzene to obtain supported chiral ligands. As proof of the usefulness of this supported ligands, the corresponding ruthenium complexes are catalysts for the cyclopropanation reaction of styrene with ethyl diazoacetate with up to 85% ee.     

Electrochromic properties of WO<Subscript>3</Subscript> and WO<Subscript>3</Subscript>:P thin films

WO₃ and WO₃:P (5 mol% H₃PO₄) thin films were prepared using the sol-gel route and the electrochromic properties of the films were investigated using in situ spectroelectrochemical methods. The measurements were performed in propylene carbonate solution with 0.1 M LiClO₄ as electrolyte. During the cathodic polarization at –0.8 V a blue coloration is observed with a reversible variation between 14% and 84% of the transmittance at λ=633 nm. The kinetics for the bleaching process is faster for the WO₃:P film than for the undoped WO₃ film. Electronic Publication     

Quassinoids from Picrasma crenata

From woods of Picrasma crenata, a new stereoisomer dihydronorneoquassin was obtained together with others well knowns dihydronorneoquassin, parain, alpha-neoquassin, beta-neoquassin and quassin. The structures were determined by spectroscopic data and chemical evidence.     

Gelation of β-lactoglobulin in the presence of propylene glycol alginate: kinetics and gel properties

The role of the non-gelling polysaccharide, propyleneglycol alginate (PGA), on the dynamics of gelation and gel properties of β-lactoglobulin (β-lg) under conditions where the protein alone does not gel (6%) was analyzed. To this end, the kinetics of gelation, aggregation and denaturation of β-lg in the mixed systems (pH 7) were studied at different temperatures (64–88 °C). The presence of PGA increased thermal stability of β-lg. The rate of β-lg denaturation was decreased and the onset and peak denaturation temperatures increased by 2.2–2.4 °C. PGA promoted the formation of larger aggregates that continued to grow in time. An average aggregate diameter of approximately 300 nm is reached at the gel point in the mixed β-lg+PGA systems, irrespective of the heating temperature. Comparing the activation energies for the aggregation (193 kJ/mol), denaturation (422 kJ/mol) and formation of the primary gel structure (1/t_gel) (256 kJ/mol) processes in the mixed protein–polysaccharide system, it can be concluded that the rate determining step in the formation of the primary gel structure would be the aggregation of protein. E_a values for the processes after the gel point (solid phase gelation) suggest a diffusion limited process because of the high viscosity of the solid gelling matrix. The characteristics of the mixed β-lg+PGA gels in terms of rheological and textural parameters, water loss and microstructure were studied as a function of heating temperature and time. The extent of aggregation and the type of interactions involved, prior to denaturation seem to be very important in determining the gel structure and its properties.     

A density functional theory study of the gas-phase elimination reactions of 4-arylideneimino-1,2,4-triazol-3(2H )-ones and their 3(2H )-thione analogues

Theoretical studies on the thermolysis in the gas phase of 4-arylideneimino-1,2,4-triazol-3(2H)-ones and 4-arylideneimino-1,2,4-triazol-3(2H)-thiones were carried out using density functional theory methods, at the B3LYP/6-31G(d) and B3LYP/6-311+G(2d,p) levels of theory. The proposed reaction mechanism occurs in one step, leading to the formation of 3-hydroxy-(2H)-1,2,4-triazole or 3-mercapto-(2H)-1,2,4-triazole and a 4-substituted benzonitrile, via a six-membered cyclic transition state. The progress of the reactions was followed by means of the Wiberg bond indices. The results indicate that the transition states have character intermediate between reactants and products, and the calculated synchronicities show that the reactions are slightly asynchronous, in the case of triazolones, and show a higher asynchronicity in the case of triazolthiones. The bond-breaking processes are slightly more advanced than the bond-forming ones, indicating a small bond deficiency in the transition states. Kinetic and activation parameters for the reactions studied have been calculated and compared with available experimental data.From the Proceedings of the 28th Congreso deQuímicos Teóricos de Expresión Latina (QUITEL 2002)     

Multicolor luminescence patterning by photoactivation of semiconductor nanoparticle films

Indiscriminate adsorption of nanoparticles (NPs) significantly complicates the preparation of mesoscale NP patterns considered as enabling technology for many devices and processes. Instead of selected chemical functionalization of the substrate surface prior to the assembly of nanocolloids, the required optical properties - in our case, high quantum yield luminescence - are imparted to the layer-by-layer assembled films by spatially selected photoactivation. The films are made by sequential adsorption of a positively charged polyelectrolyte and a negatively charged CdSe/CdS aqueous dispersion with an initial quantum yield of 0.5-2%. The photoactivation process takes place in the presence of oxygen and may be accompanied by photoetching. A 50-500-fold increase in the luminescence intensity of CdSe/CdS citrate-stabilized particles (quantum yield 25-45%) after visible light illumination provides excellent pattern contrast. Micron scale luminescence patterns were produced from NPs of various CdSe core diameters with red, yellow, and green emission. It was also demonstrated that different emission colors such as orange and green can be combined in one image by taking advantage of spatially selective photoetching. The presented optical patterning technique significantly simplifies the preparation of luminescence patterns as compared to conventional methods. The high signal-to-noise ratio associated with it is essential for optical devices, information processing, and biophotonics. The most immediate use of this approach is expected in cryptography and cell monitoring.     

Scaffolds for Sustained Release of Ambroxol Hydrochloride,a Pharmacological Chaperone That Increases the Activity of Misfolded β‐Glucocerebrosidase

Ambroxol is a pharmacological chaperone (PC) for Gaucher disease that increases lysosomal activity of misfolded β‐glucocerebrosidase (GCase) while displaying a safe toxicological profile. In this work, different poly(ε‐caprolactone) (PCL)‐based systems are developed to regulate the sustained release of small polar drugs in physiological environments. For this purpose, ambroxol is selected as test case since the encapsulation and release of PCs using polymeric scaffolds have not been explored yet. More specifically, ambroxol is successfully loaded in electrospun PCL microfibers, which are subsequently coated with additional PCL layers using dip‐coating or spin‐coating. The time needed to achieve 80% release of loaded ambroxol increases from ≈15 min for uncoated fibrous scaffolds to 3 days and 1 week for dip‐coated and spin‐coated systems, respectively. Furthermore, it is proven that the released drug maintains its bioactivity, protecting GCase against induced thermal denaturation.     

Spontaneous trans‐Selective Transfer Hydrogenation of Apolar Boron–Boron Double Bonds

The transfer hydrogenation of N‐heterocyclic carbene (NHC)‐supported diborenes with dimethylamine borane proceeds with high selectivity for the trans‐1,2‐dihydrodiboranes. DFT calculations, supported by kinetic studies and deuteration experiments, suggest a stepwise proton‐first‐hydride‐second reaction mechanism via an intermediate μ‐hydrodiboronium dimethylaminoborate ion pair.     

Guest Exchange Mechanisms in Mono‐Metallic PdII/PtII‐Cages Based on a Tetra‐Pyridyl Calix[4]pyrrole Ligand

Planar pyridyl N‐oxides are encapsulated in mono‐metallic Pd^II/Pt^II‐cages based on a tetra‐pyridyl calix[4]pyrrole ligand. The exchange dynamics of the cage complexes are slow on both the NMR chemical shift and EXSY timescales, but encapsulation of the guests by the cages is fast on the human timescale. A “French doors” mechanism, involving the rotation of the meso‐phenyl walls of the cages, allows the passage of the planar guests. The encapsulation of quinuclidine N‐oxide, a sterically more demanding guest, is slower than pyridyl N‐oxides in the Pd^II‐cage, and does not take place in the Pt^II counterpart. A modification of the encapsulation mechanism for the quinuclidine N‐oxide is postulated that requires the partial dissociation of the Pd^II‐cage. The substrate binding selectivity featured by the cages is related to their different guest uptake/release mechanisms.