Electronic structure and optical absorption spectra of CdSe covered with ZnSe and ZnS epilayers

Using the first-principles methods we compute the electronic structure and the absorption spectra for a wurtzite CdSe (0001) slab covered with zincblende ZnSe and ZnS epilayers. For each structure we compute the DOS and the imaginary part of the dielectric function. We find that the semiconductor passivation shifts the ‘near Fermi-level’ states of the bare CdSe slab down to lower energy levels. The migration suggests the decrease of surface effects and energy loss. We observe the substantial reduction of the abnormal peaks in the absorption spectra of the bare CdSe slab, which seems to be a consequence of the DOS migration. This is consistent with the experimental results that a proper passivation enhance the luminescence efficiency. We also study the case that the epilayer surface is terminated with PH₃ and find the PH₃ passivation also reduces the surface state to some extent.     

Swirl effects on variable-density jet mixing in confined flows

An experimental investigation on swirl effects on inhomogeneous confined jet mixing in a combustor configuration is reported. The confined swirling flow was simulated by a swirler with a central jet mounted in a cyclindrical tube. Helium and air jets set at different velocities were injected into the confined swirling air flow. The resulting flow fields due to two vane swirlers with constant vane angles of 35° and 66° were compared. Results show that the 35° vane swirler produces a solid-body rotation core with a slope about twice that created by the 66° vane swirler. It is the behavior of this solid-body rotation core that determines jet mixing rather than the swirler vane angle. Consequently, the coaxial jet decays much faster, the mixing is more intense, and the turbulence intensities are higher for the 35° vane swirler. In view of these results, combustor designers should be more concerned with behavior of the solid-body rotation core produced by the swirler, instead of the swirler vane angle.     

Catalytic Stereoinversion of L‐Alanine to Deuterated D‐Alanine

A combination of an achiral pyridoxal analogue and a chiral base has been developed for catalytic deuteration of L ‐alanine with inversion of stereochemistry to give deuterated D ‐alanine under mild conditions (neutral pD and 25 °C) without the use of any protecting groups. This system can also be used for catalytic deuteration of D ‐alanine with retention of stereochemistry to give deuterated D ‐alanine. Thus a racemic mixture of alanine can be catalytically deuterated to give an enantiomeric excess of deuterated D ‐alanine. While catalytic deracemization of alanine is forbidden by the second law of thermodynamics, this system can be used for catalytic deracemization of alanine with deuteration. Such green and biomimetic approach to catalytic stereocontrol provides insights into efficient amino acid transformations.     

Serum exosomal microRNAs as novel biomarkers for hepatocellular carcinoma

Recent studies have shown that circulating microRNAs are a potential biomarker in various types of malignancies. The aim of this study was to investigate the feasibility of using serum exosomal microRNAs as novel serological biomarkers for hepatocellular carcinoma (HCC) in patients with chronic hepatitis B (CHB). We measured the serum exosomal microRNAs and serum circulating microRNAs in patients with CHB (n=20), liver cirrhosis (LC) (n=20) and HCC (n=20). Serum exosomal microRNA was extracted from 500 μl of serum using an Exosome RNA Isolation kit. The expression levels of microRNAs were quantified by real-time PCR. The expression levels of selected microRNAs were normalized to Caenorhabditis elegans microRNA (Cel-miR-39). The serum levels of exosomal miR-18a, miR-221, miR-222 and miR-224 were significantly higher in patients with HCC than those with CHB or LC (P<0.05). Further, the serum levels of exosomal miR-101, miR-106b, miR-122 and miR-195 were lower in patients with HCC than in patients with CHB (P=0.014, P<0.001, P<0.001 and P<0.001, respectively). There was no significant difference in the levels of miR-21 and miR-93 among the three groups. Additionally, the serum levels of circulating microRNAs showed a smaller difference between HCC and either CHB or LC. This study suggests that serum exosomal microRNAs may be used as novel serological biomarkers for HCC.     

Synthesis and antibacterial activity of versatile substrate‐coated biocidal material via catechol chemistry

We report a potential coating material showing durable and significant antimicrobial activity for preserving the surfaces of a broad range of materials. The structure of the prepared antimicrobial adhesive material features a catechol moiety of dopamine hydrochloride conjugated to 4‐bromobutanoyl chloride as an adhesive material. Antimicrobial properties against a wide range of microorganism species are achieved by quaternizing a long hydrophobic chain (N,N'‐dimethyldecylamine) onto 3,4‐dihydroxyphenylalanine (Dopa) to afford the prepared material (Dopa‐decyl). The successful formation of Dopa‐decyl is confirmed by hydrogen nuclear magnetic resonance (¹H‐NMR) and attenuated total reflectance‐infrared (ATR‐IR) measurements. The chemical composition of the quaternized adhesive material (Dopa‐decyl) is characterized by X‐ray photoelectron spectroscopy (XPS). Investigation of the antimicrobial activity of the Dopa‐decyl‐coated film against both gram‐positive Staphylococcus aureus (S. aureus) and gram‐negative Escherichia coli (E. coli) stains reveals a highly efficient antimicrobial effect under both normal and extreme stress conditions due to the biocidal effect of the quaternized amine when the materials are applied on the surface of various substrates. Copyright © 2014 John Wiley & Sons, Ltd.     

Trapping a Silicon(I) Radical with Carbenes: A Cationic cAAC–Silicon(I) Radical and an NHC–Parent-Silyliumylidene Cation

The trapping of a silicon(I) radical with N-heterocyclic carbenes is described. The reaction of the cyclic (alkyl)(amino) carbene [cAAC_Me] (cAAC_Me=:C(CMe₂)₂(CH₂)NAr, Ar=2,6-iPr₂C₆H₃) with H₂SiI₂ in a 3:1 molar ratio in DME afforded a mixture of the separated ion pair [(cAAC_Me)₂Si:^.]⁺I⁻ ( 1 ), which features a cationic cAAC–silicon(I) radical, and [cAAC_Me−H]⁺I⁻. In addition, the reaction of the NHC–iodosilicon(I) dimer [I_Ar(I)Si:]₂ (I_Ar=:C{N(Ar)CH}₂) with 4 equiv of I_Me (:C{N(Me)CMe}₂), which proceeded through the formation of a silicon(I) radical intermediate, afforded [(I_Me)₂SiH]⁺I⁻ ( 2 ) comprising the first NHC–parent-silyliumylidene cation. Its further reaction with fluorobenzene afforded the C_Ar−H bond activation product [1-F-2-I_Me-C₆H₄]⁺I⁻ ( 3 ). The isolation of 2 and 3 confirmed the reaction mechanism for the formation of 1 . Compounds 1 – 3 were analyzed by EPR and NMR spectroscopy, DFT calculations, and X-ray crystallography.     

Discriminantal arrangement, 3 × 3 minors of Plücker matrix and hypersurfaces in Grassmannian Gr(3,n)

We show that points in specific degree-2 hypersurfaces in the Grassmannian $Gr(3,n)$ correspond to generic arrangements of n hyperplanes in ${\mathbb{C}}^3$ with associated discriminantal arrangement having intersections of multiplicity three in codimension two.     

An explicit algebraic Reynolds stress and heat flux model for incompressible turbulence: Part I Non-isothermal flow

Tensor representation theory is used to derive an explicit algebraic model that consists of an explicit algebraic stress model (EASM) and an explicit algebraic heat flux model (EAHFM) for two-dimensional (2-D) incompressible non-isothermal turbulent flows. The representation methodology used for the heat flux vector is adapted from that used for the polynomial representation of the Reynolds stress anisotropy tensor. Since the methodology is based on the formation of invariants from either vector or tensor basis sets, it is possible to derive explicit polynomial vector expansions for the heat flux vector. The resulting EAHFM is necessarily coupled with the turbulent velocity field through an EASM for the Reynolds stress anisotropy. An EASM has previously been derived by Jongen and Gatski [10]. Therefore, it is used in conjunction with the derived EAHFM to form the explicit algebraic model for incompressible 2-D flows. This explicit algebraic model is analyzed and compared with previous formulations including its ability to approximate the commonly accepted value for the turbulent Prandtl number. The effect of pressure-scrambling vector model calibration on predictive performance is also assessed. Finally, the explicit algebraic model is validated against a 2-D homogeneous shear flow with a variety of thermal gradients. Dedicated to the memory of the late Professor Charles G. Speziale of Boston University     

Diffuser stall and rotating zones of separated boundary layer

Unsteady flows and rotating stall in vaneless diffusers were investigated by measuring both the wall fluctuating pressures and the unsteady velocity field using hot-wires and laser Doppler anemometers. Experiments were carried out with a fixed impeller and fixed diffuser inlet and outlet radii. However, the diffuser width was varied so that its effect on rotating stall could be examined. Results show that the variation of _r with b/r _i is in qualitative agreement with the prediction of Senoo et al. (1977). Therefore, the onset of stall is delayed as diffuser width is decreased. For diffusers with small width, stall emerges first with one stall cell and then develops into 2 and 4 stall cells as the mass flow rate is decreased. On the other hand, for the diffuser with the largest width tested, stall emerges with one stall cell and quickly develops into 3 stall cells. The ratio of the speed of rotation of the stall cell to impeller speed is independent of diffuser width, but decreases slightly as the number of stall cells increases. Finally, rotating stall is associated with reversed flow originating from the hub side rather than from the shroud side.     

Secondary cells and separation in developing laminar curved-pipe flows

Laminar flows through 180° curved bends of circular cross section are investigated numerically. For small curvature ratio, , defined as pipe radius over mean bend radius, the governing equations could be parabolized. The equations are solved for an range of from 0.04 to 0.143, a Dean number (De) range of from 277.5 to 1360, and for a uniform flow, a potential vortex, and a parabolic flow inlet condition. In all these studies a zero cross-stream flow at the inlet is assumed. A detailed study of the effects of , De, and inlet condition on the secondary flow pattern is carried out. Within the range of parameters investigated, up to three secondary cells are found in the cross-stream half-plane of a curved pipe. They are the Dean-type secondary cell, a secondary separation cell near the inner bend (closest to the center of curvature of the bend), and a third cell near the pipe center. The number of secondary cells in the cross-stream half-plane is greatly influenced by the inlet flow, and to a much lesser extent by and De. For example, only the Dean cell is found in a curved-pipe flow where and De are small and the inlet flow is either uniform or a potential vortex. When the inlet condition of the same case is changed to a parabolic flow, a three-cell structure results. Furthermore, as De increases to 1180, incipient axial flow separation begins at around 23° downstream of the curved-pipe entrance. The formation and extent of the separation and third cells are investigated together with their dependence on the parameters studied. This investigation further shows that, within the range of parameters examined, there is no secondary cell occurring near the outer bend, contrary to some earlier findings on fully developed curved-pipe flows.This work was supported by the Office of Naval Research under Grant No. N0014-81-K-0428 and by DTRC, Annapolis, Maryland, under Contract No. N00167-86-K-0075. Also, support in the form of an IPA awarded to RMCS during his sabbatical leave at DTRC, Annapolis, Maryland, in the spring of 1990 is gratefully acknowledged.