Boric acid: an efficient and environmentally benign catalyst for transesterification of ethyl acetoacetate

An efficient and environmentally benign boric acid catalyzed protocol for the transesterification of ethyl acetoacetate with a variety of primary and secondary alcohols in good to excellent yields is described. The versatility of this transformation is demonstrated with problematic substrates such as propargyl alcohol and allyl alcohol, which are known to undergo Carroll rearrangement during transesterification.     

On path correlation and PERT bias

Most studies of project time estimation assume that (a) activity times are mutually independent random variables; many also assume that (b) path completion times are mutually independent. In this paper, we subject the impact of both these assumptions to close scrutiny. Using tools from multivariate analysis, we make a theoretical study of the direction of the error in the classical PERT method of estimating mean project completion time when correlation is ignored. We also investigate the effect of activity dependence on the normality of path length via simulation.     

Synthesis and characterization of sulfonated‐fluorinated,hydrophilic‐hydrophobic multiblock copolymers for proton exchange membranes

Hydrophilic/hydrophobic block copolymers as proton exchange membranes (PEMs) has become an emerging area of research in recent years. These copolymers were obtained through moderate temperature (～ 100 °C) coupling reactions, which minimize the ether‐ether interchanges between hydrophobic and hydrophilic telechelic oligomers via a nucleophilic aromatic substitution mechanism. The hydrophilic blocks were based on the nucleophilic step polymerization of 3,3′‐disulfonated, 4,4′‐dichlorodiphenyl sulfone with an excess 4,4′‐biphenol to afford phenoxide endgroups. The hydrophobic (fluorinated) blocks were largely based on decafluoro biphenyl (excess) and various bisphenols. The copolymers were obtained in high molecular weights and were solvent cast into tough membranes, which had nanophase separated hydrophilic and hydrophobic regions. The performance and structure‐property relationships of these materials were studied and compared to random copolymer systems. NMR results supported that the multiblock sequence had been achieved. They displayed superior proton conductivity, due to the ionic proton conducting channels formed through the self‐assembly of the sulfonated blocks. The nano‐phase separated morphologies of the copolymer membranes were studied and confirmed by atomic force microscopy. Through control of a variety of parameters, including ion exchange capacity and sequence lengths, performances as high, or even higher than those of the state‐of‐the‐art PEM, Nafion, were achieved. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1038–1051, 2009     

Ligand exchange synthesis of organometallic Rh nanoparticles and application in explosive sensing

Alkyne {phenyl acetylene (PA) and 9-ethynylphenanthrene (EPT)}-ligated Rh nanoparticles (1 and 2, respectively) with mean diameter of 1.5 ± 0.2 nm were synthesized via a facile and high-yield biphasic ligand exchange protocol using similar sized ethylene glycol (EG)-stabilized Rh nanoparticles as precursors (EG:Rh). The synthesized organometallic Rh nanoparticles were convincingly characterized using several spectroscopic and microscopic techniques, e.g., Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (¹H NMR), optical absorption spectroscopy (UV-Vis), photoluminescence spectroscopy (PL), powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscope (TEM). We propose that the syntheses mechanism relies on catalytic acetylenic (≡C–H, carbon–hydrogen) bond breaking by EG:Rh followed by strong metal–carbon bond formation with a vinyldiene (>C═C═M) motif. The obtained 1 and 2 showed luminescence property, which arises from ligand structure through intraparticle conjugation. Electron-rich phenanthrene-ligated Rh nanoparticles (2) showed good sensing performance for detection of electron deficient nitro-aromatic explosive molecules (NA) in solution phase through luminescence quenching method.     

Torus actions,fixed-point formulas,elliptic genera and positive curvature

We study fixed points of smooth torus actions on closed manifolds using fixed point formulas and equivariant elliptic genera. We also give applications to positively curved Riemannian manifolds with symmetry.     

Comparison of frequency-domain and time-domain fluorescence lifetime tomography

We compare frequency-and time-domain formulations of deep-tissue fluorescence imaging of turbid media. Simulations are used to show that time-domain fluorescence tomography, implemented via the asymptotic lifetime-based approach, offers a significantly better separability of multiple lifetime targets than a frequency-domain approach. We also demonstrate experimentally, using complex-shaped phantoms, the advantages of the asymptotic time-domain approach over a Fourier-based approach for analyzing time-domain fluorescence data.     

Analysis of open dielectric waveguides using the finite-element penalty method

This paper analyzes open dielectric waveguides using the vector finite-element method and boundary integral equations derived from the second Green's theorem. This finite-element formulation, together with the boundary operator, is solved using a penalty function method. Comparison with previously published results shows good agreement for the analysis of the rectangular dielectric waveguide.     

Effect of macromolecular crowding on the rate of diffusion-limited enzymatic reaction

The cytoplasm of a living cell is crowded with several macromolecules of different shapes and sizes. Molecular diffusion in such a medium becomes anomalous due to the presence of macromolecules and diffusivity is expected to decrease with increase in macromolecular crowding. Moreover, many cellular processes are dependent on molecular diffusion in the cell cytosol. The enzymatic reaction rate has been shown to be affected by the presence of such macromolecules. A simple numerical model is proposed here based on percolation and diffusion in disordered systems to study the effect of macromolecular crowding on the enzymatic reaction rates. The model qualitatively explains some of the experimental observations.      

Improving the Power-Conversion Efficiency through Alloying in Common Anion CdZnX (X=S,Se) Nanocrystal Sensitized Solar Cells

In this paper, we have investigated the possibility of utilizing CdZnS and CdZnSe alloy nanocrystals (NCs) as sensitizers in quantum-dot solar cells (QDSCs). The alloy NCs were synthesized by a high-temperature hot injection method and subsequently characterized through high photoluminescence quantum yield, along with larger size compared to binary NCs. Femtosecond transient absorption measurements revealed long-lived charge carriers in the alloy structure due to more structural rigidity and less defect states. Finally, the solar-cell efficiencies of the CdZnS (CdZnSe) NCs were found to be 3.05 % (3.69 %) as compared to 1.23 % (3.12 %) efficiencies for CdS (CdSe) NCs. Thus, common anion ternary NCs have been successfully utilized for solar-cell assembly and can be helpful for constructing tandem solar cells to harvest the high-energy portion of solar radiation.