Microwave synthesis of polymer-embedded Pt-Ru catalyst for direct methanol fuel cell

Platinum-ruthenium nanoparticles stabilized within a conductive polymer matrix are prepared using microwave heating. Polypyrrole di(2-ethylhexyl) sulfosuccinate, or PPyDEHS, has been chosen for its known electrical conductivity, thermal stability, and solubility in polar organic solvents. A scalable and quick two-step process is proposed to fabricate alloyed nanoparticles dispersed in PPyDEHS. First a mixture of PPyDEHS and metallic precursors is heated in a microwave under reflux conditions. Then the nanoparticles are extracted by centrifugation. Physical characterization by TEM shows that crystalline and monodisperse alloyed nanoparticles with an average size of 2.8 nm are obtained. Diffraction data show that crystallite size is around 2.0 nm. Methanol electro-oxidation data allow us to propose these novel materials as potential candidates for direct methanol fuel cells (DMFC) application. The observed decrease in sulfur content in the polymer upon incorporation of PtRu nanoparticles may have adversely affected the measured catalytic activity by decreasing the conductivity of PPyDEHS. Higher concentration of polymer leads to lower catalyst activity. Design and synthesis of novel conductive polymers is needed at this point to enhance the catalytic properties of these hybrid materials.     

γγ-Disubstituted Itaconic Acids. Part 1. The Stobbe condensation of 1-arylnaphthyl ketones with diethyl succinate

Arylnaphthyl ketones condense with diethyl succinate yielding the stereoisomeric half-esters 2a–2d which were subjected to a series of reactions leading to 1-phenylphenanthrene and 1,1′-binaphthyl derivatives. (E)-3-Ethoxycarbonyl-4-(4-methoxynaphth-1-yl)-4-arylbut-3-enoic acids ( 2b–d ) were converted finally into the corresponding naphtho[1,2-c]fluorenones ( 9 ). The structure of the products was established by IR. and UV. spectroscopy. The effect of substituents on the relative proportions of (E)- and (Z)-half-esters 2 was determined by chromatography and UV. spectroscopy.     

SATURATION OF DNA REPAIR IN MAMMALIAN CELLS*

Abstract—Excision repair seems to reach a plateau in normal human cells at a 254 nm dose near 20J/m². We measured excision repair in normal human fibroblasts up to 80J/m². The four techniques used (unscheduled DNA synthesis, photolysis of BrdUrd incorporated during repair, loss of sites sensitive to a UV endonuclease from Micrococcus luteus , and loss of pyrimidine dimers from DNA) showed little difference between the two doses. Moreover, the loss of endonuclease sites in 24 h following two 20J/m² doses separated by 24 h was similar to the loss observed following one dose. Hence, we concluded that the observed plateau in excision repair is real and does not represent some inhibitory process at high doses but a true saturation of one of the, rate limiting steps in repair.     

Combined Application of Picosecond Transient Absorption and Emission Measurements in Studies of Radical-Ion Pair Dynamics

Abstract— Much of the emphasis in the development of methods for time-resolved measurements is on increasing experimental time resolution. Equally important, however, is the establishment of methods to apply existing techniques to problems of increasing complexity. Here we describe the application of a combination of picosecond absorption and emission measurements to solve a complex kinetic problem in organic photophysics, namely, the dynamics of interconverting radical-ion pairs. Although fairly routine, the emission measurements require higher time resolution and the absorption measurements require higher signal-to-noise ratios than are often achieved. In the first part of this paper we describe the ways in which these experimental requirements have been met. Next, the radical-ion pair kinetic problem and its solution are described. Finally, we discuss some future directions for the techniques as they relate to studies of radical-ion pair dynamics.     

Benzimidazole condensed ring systems. 5. Studies on the Synthesis of Pyrimido[1,6-α]benzimidazole-1,3(2H,5H)-diones

The reaction of ethyl 1H-benzimidazole-2-acetate (1) with methyl or ethyl isocyantes 2a,b resulted in excellent yields of the respective 2-methyl- or 2-ethylpyrimido[1,6-a]benzimidazole-1,3(2H,5H)-diones 3a,b , while the reaction of 1 with phenyl isocyanate (2c) gave, unexpectedly, ethyl 2-(1-phenylcarbamoyl-1H,3H-benzimidazol-2-ylidene)-2-phenylcarbamoylacetate (4). Alkylation of 3 with trimethyl or triethyl phosphates 5a,b led to the 5-methyl or 5-ethyl derivatives 6a-d . Chlorination of 6 with sulfuryl chloride afforded the 4-chloro derivatives 7a-d.     

Some topologies on a Šerstnev probabilistic normed space

In this paper we will introduce two other topologies, coarser than the so-called strong topology, on a class of Šerstnev probabilistic normed spaces, and obtain some important properties of these topologies. We will show that under the first topology, denoted by τ₀, our probabilistic normed space is decomposable into the topological direct sum of a normable subspace and the subspace of probably null elements. Under the second topology, which is in fact the inductive limit topology of a family of locally convex topologies, the dual space becomes a locally convex topological vector space.     

Polariton luminescence and additional boundary conditions: comparison between theory and experiment

Polariton luminescence spectra in semiconductors have been calculated as a function of temperature and impurity trapping rates using a two branch polariton model. Typically, the theoretical spectra show two structures: a peak near the transverse exciton energy and a shoulder near the longitudinal exciton energy. While the lower energy peak is relatively insensitive to the choice of additional boundary conditions (ABC), the higher energy shoulder strongly depends on ABC. The theoretical curves obtained with Pekar's ABC are in quantitative agreement with experimental spectra reported in CdS, CdSe and CuCl. However, significant discrepancies between theory and experiment are found in GaAs and ZnTe.     

Reaction of 1,2-trans-glycosyl acetates with phosphorus pentachloride: new efficient approach to 1,2-trans-glycosyl chlorides

Reaction of phosphorus pentachloride with 1,2-trans-glycosyl esters is described. The reaction mechanism presumably involves formation of a tetrachlorophosphonium ion as one of the key reactive intermediates, which can be induced either by Lewis acids or by using acetonitrile as the reaction solvent. Two novel, efficient methods for the synthesis of the thermodynamically unstable glycosyl chlorides were developed based on this reaction.     

A comparison of the fcc(111) and (100) crystal-melt interfaces by molecular dynamics simulation

The molecular dynamics simulation technique is employed to study the fcc (100) and (111) crystal—melt interfaces of a system of Lennard-Jones atoms near the triple-point. A comparison of the structure and thermodynamics of the two interfaces results in a simple picture concerning the role of crystal orientation on the structure of the liquid neighboring the crystal face.