Enantioselective Synthesis of Quaternary Carbon Stereocenters: Addition of 3‐Substituted Oxindoles to Vinyl Sulfone Catalyzed by Pentanidiums

A pentanidium‐catalyzed highly enantioselective conjugate addition of 3‐alkyloxindoles to phenyl vinyl sulfone has been demonstrated. This approach allows the construction of 3,3‐dialkyl‐substituted oxindole frameworks with high yield and excellent enantioselectivity (up to 99 %) under simple phase‐transfer conditions. A variety of oxindoles bearing all‐carbon quaternary stereogenic centers were obtained in the presence of 0.25 mol % pentanidium. Meanwhile, practicality was illustrated by a gram‐scale asymmetric synthesis of two 3,3‐dialkyl‐substituted oxindoles. The resulting adduct can be smoothly transformed to the natural product analogue in a short synthetic route.     

Highly luminescent CdTe/CdSe colloidal heteronanocrystals with temperature-dependent emission color

In this work we present the preparation of highly luminescent anisotropic CdTe/CdSe colloidal heteronanocrystals. The reaction conditions used (low temperature, slow precursor addition, and surfactant composition) resulted in a tunable shape from prolate to branched CdTe/CdSe nanocrystals. Upon CdSe shell growth the heteronanocrystals show a gradual evolution from type-I to type-II optical behavior. These heteronanocrystals show a remarkably high photoluminescence quantum yield (up to 82%) and negligible thermally induced quenching up to temperatures as high as 373 K.     

Multicanonical parallel simulations of proteins with continuous potentials

The determination of the three‐dimensional (3D) structure of a protein or peptide is a very important research problem in biological and medical sciences. Anfinsen's experiments (Science 1973, 181, 223) on renaturation of denatured proteins have shown that the native 3D structure of a (small) protein at low (room) temperatures is uniquely determined by its amino acid sequence, which suggests that it might be possible to determine the 3D structure of a protein from its amino acid sequence by pure computations. As a step toward that goal, in this article we present a simple approach for parallelization of multicanonical Monte Carlo simulations of proteins with continuous potentials. Our method is based on the parallel calculation of the protein energy function. The algorithm is tested by simulated annealing and multicanonical simulations of two small peptides, and known results are reproduced accurately. An acceptable degree of parallelization can be achieved in the simulation of Protein L using up to 30 PCs. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1287–1296, 2001     

Structures,vibrational spectra,and relative energies of HXSiS (X = H,F, and Cl) isomers

The potential energy surface for the decomposition of HXSiS (X = H, F, and Cl) on the singlet state has been explored by B3LYP and CCSD(T) calculations. Five different types of reaction are proposed: (A) 1,1‐HX elimination, (B) 1,2‐H shift, (C) 1,2‐X shift, (D) H · and XSiS · radical formation, and (E) X · and HSiS · radical formation. These results show interesting trends for the HXSiS isomers. Our theoretical investigations suggest that the doubly bonded species HXSiS should be the lowest energy structure among the isomers from both kinetic and thermodynamic viewpoints. We also report theoretical predictions of molecular parameters and vibrational infrared (IR) spectra of the monohalogen‐substituted silanethione, which should be useful for future experimental observations. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 82: 14–25, 2001     

Flame‐retardant epoxy resins: An approach from organic–inorganic hybrid nanocomposites

Phosphorus‐containing epoxy‐based epoxy–silica hybrid materials with a nanostructure were obtained from bis(3‐glycidyloxy)phenylphosphine oxide, diaminodiphenylmethane, and tetraethoxysilane in the presence of the catalyst p‐toluenesulfonic acid via an in situ sol–gel process. The silica formed on a nanometer scale in the epoxy resin was characterized with Fourier transform infrared, NMR, and scanning electron microscopy. The glass‐transition temperatures of the hybrid epoxy resins increased with the silica content. The nanometer‐scale silica showed an enhancement effect of improving the flame‐retardant properties of the epoxy resins. The phosphorus–silica synergistic effect on the limited oxygen index (LOI) enhancement was also observed with a high LOI value of 44.5. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 986–996, 2001     

Redox equilibria of iron oxides in aqueous-based magnetite dispersions: effect of pH and redox potential

The effect of pH and redox potential on the redox equilibria of iron oxides in aqueous-based magnetite dispersions was investigated. The ionic activities of each dissolved iron species in equilibrium with magnetite nanoparticles were determined and contoured within the Eh-pH framework of a composite stability diagram. Both standard redox potentials and equilibrium constants for all major iron oxide redox equilibria in magnetite dispersions were found to differ from values reported for noncolloidal systems. The "triple point" position of redox equilibrium among Fe(II) ions, magnetite, and hematite shifted to a higher standard redox potential and an equilibrium constant which was several orders of magnitude higher. The predominant area of magnetite stability was enlarged to cover a wider range of both pH and redox potentials as compared to that of a noncolloidal magnetite system.     

Compatibility and fungal degradation of poly[(R)-3-hydroxybutyrate]/aliphatic copolyester blend

Poly[(R)-3-hydroxybutyrate] (PHB) was blended with an aliphatic copolyester, which was synthesized by the esterification of adipic acid, ethylene glycol, and lactic acid. The blend showed a single T_g, which varied systematically but convexly upwards with the composition. The growth rate of PHB spherulites, the crystallization temperature, and the equilibrium melting temperature of the blend were decreased as the amount of the copolyester was increased. Therefore, the blend system was determined to be compatible. However, the degree of crystallinity, and the enthalpies of crystallization and fusion of PHB in the blend remained almost constant, regardless of the compositional change, although the crystallization rate was decreased upon blending. No chemical change such as transesterification was observed as a result of the blending, yet there was a slight change in the crystalline morphology of PHB. The rate of fungal degradation was lowered with an increase in the copolyester content of the blend. © 1996 John Wiley & Sons, Inc.     

Investigation of viscoelastic focusing of particles and cells in a zigzag microchannel

Microfluidic particle focusing has been a vital prerequisite step in sample preparation for downstream particle separation, counting, detection, or analysis, and has attracted broad applications in biomedical and chemical areas. Besides all the active and passive focusing methods in Newtonian fluids, particle focusing in viscoelastic fluids has been attracting increasing interest because of its advantages induced by intrinsic fluid property. However, to achieve a well-defined focusing position, there is a need to extend channel lengths when focusing micrometer-sized or sub-microsized particles, which would result in the size increase of the microfluidic devices. This work investigated the sheathless viscoelastic focusing of particles and cells in a zigzag microfluidic channel. Benefit from the zigzag structure of the channel, the channel length and the footprint of the device can be reduced without sacrificing the focusing performance. In this work, the viscoelastic focusing, including the focusing of 10 μm polystyrene particles, 5 μm polystyrene particles, 5 μm magnetic particles, white blood cells (WBCs), red blood cells (RBCs), and cancer cells, were all demonstrated. Moreover, magnetophoretic separation of magnetic and nonmagnetic particles after viscoelastic pre-focusing was shown. This focusing technique has the potential to be used in a range of biomedical applications.     

Multiple-filled skutterudites: high thermoelectric figure of merit through separately optimizing electrical and thermal transports

Skutterudites CoSb(3) with multiple cofillers Ba, La, and Yb were synthesized and very high thermoelectric figure of merit ZT = 1.7 at 850 K was realized. X-ray diffraction of the densified multiple-filled bulk samples reveals all samples are phase pure. High-resolution scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDS) analysis confirm that multiple guest fillers occupy the nanoscale-cages in the skutterudites. The fillers are further shown to be uniformly distributed and the Co-Sb skutterudite framework is virtually unperturbed from atomic scale to a few micrometers. Our results firmly show that high power factors can be realized by adjusting the total filling fraction of fillers with different charge states to reach the optimum carrier density, at the same time, lattice thermal conductivity can also be significantly reduced, to values near the glass limit of these materials, through combining filler species of different rattling frequencies to achieve broad-frequency phonon scattering. Therefore, partially filled skutterudites with multiple fillers of different chemical nature render unique structural characteristics for optimizing electrical and thermal transports in a relatively independent way, leading to continually enhanced ZT values from single- to double-, and finally to multiple-filled skutterudites. The idea of combining multiple fillers with different charge states and rattling frequencies for performance optimization is also expected to be valid for other caged TE compounds.     

Detection of acetaminophen using cyclic voltammetry on MnFe2O4/polyaniline

A novel sensing material, MnFe₂O₄/polyaniline (PANI), was fabricated by doping PANI to MnFe₂O₄ on a modified glassy carbon electrode (GCE). This sensing material was characterized using X‐ray diffraction (XRD), scanning electron microscopy (SEM), and high‐resolution transmission electron microscopy (HR‐TEM). Using a cyclic voltammetry electrochemical‐sensing method, we tested MnFe₂O₄/PANI, and an acetaminophen concentration of 0.0625–5 mM was recorded. Furthermore, the sensor responses were 2.05–22.44. The detection limit was 2.23 × 10^?7 M. Strong selectivity was observed for MnFe₂O₄/PANI, which is a possible sensing mechanism.