Surface-enhanced Raman spectroscopic-encoded beads for multiplex immunoassay

A new type of encoded bead, which uses surface-enhanced Raman scattering (SERS), is described for multiplex immunoassays. Silver nanoparticles were embedded in sulfonated polystyrene (PS) beads via a polyol method, and they were used as SERS-active substrates. Raman-label organic compounds such as 4-methylbenzenethiol (4-MT), 2-naphthalenethiol (2-NT), and benzenethiol (BT) were then adsorbed onto the silver nanoparticles in the sulfonated PS bead. Although only three kinds of encoding have been demonstrated here, various combinations of these Raman-label organic compounds have the potential to give a large number of tags. The Raman-label-incorporated particles were then coated with a silica shell using tetraethoxyorthosilicate (TEOS) for chemical stability and biocompatibility. The resulting beads showed unique and intense Raman signals for the labeled organic compounds. We demonstrated that SERS-encoded beads could be used for multiplex detection with a model using streptavidin and p53. In our system, the binding event of target molecules and the type of ligand can be simultaneously recognized by Raman spectroscopy using a single laser-line excitation (514.5 nm).     

A Unique Tryptophan C‐Prenyltransferase from the Kawaguchipeptin Biosynthetic Pathway

Cyanobactins are a rapidly growing family of linear and cyclic peptides produced by cyanobacteria. Kawaguchipeptins A and B, two macrocyclic undecapeptides reported earlier from Microcystis aeruginosa NIES‐88, are shown to be products of the cyanobactin biosynthetic pathway. The 9 kb kawaguchipeptin (kgp) gene cluster was identified in a 5.26 Mb draft genome of Microcystis aeruginosa NIES‐88. We verified that this gene cluster is responsible for the production of the kawaguchipeptins through heterologous expression of the kgp gene cluster in Escherichia coli. The KgpF prenyltransferase was overexpressed and was shown to prenylate C‐3 of Trp residues in both linear and cyclic peptides in vitro. Our findings serve to further enhance the structural diversity of cyanobactins to include tryptophan‐prenylated cyclic peptides.     

Biomimetic hydrocarbon oxidation catalyzed by nonheme iron(III) complexes with peracids: evidence for an Fe(V)=O species

Mononuclear nonheme iron(III) complexes of tetradentate ligands containing two deprotonated amide moieties, [Fe(Me(2)bpb)Cl(H(2)O)] (3 a) and [Fe(bpc)Cl(H(2)O)] (4 a), were prepared by substitution reactions involving the previously synthesized iron(III) complexes [Et(3)NH][Fe(Me(2)bpb)Cl(2)] (3) and [Et(3)NH][Fe(bpc)Cl(2)] (4). Complexes 3 a and 4 a were characterized by IR and elemental analysis, and complex 3 a also by X-ray crystallography. Nonheme iron(III) complexes 3, 3 a, 4, and 4 a catalyze olefin epoxidation and alcohol oxidation on treatment with m-chloroperbenzoic acid. Pairwise comparisons of the reactivity of these complexes revealed that the nature of the axial ligand (Cl(-) versus H(2)O) influences the yield of oxidation products, whereas an electronic change in the supporting chelate ligand has little effect. Hydrocarbon oxidation by these catalysts was proposed to involve an iron(V) oxo species which is formed on heterolytic O-O bond cleavage of an iron acylperoxo intermediate (FeOOC(O)R). Evidence for this iron(V) oxo species was derived from KIE (k(H)/k(D)) values, H(2) (18)O exchange experiments, and the use of peroxyphenylacetic acid (PPAA) as the peracid. Our results suggest that an Fe(V)=O moiety can form in a system wherein the supporting chelate ligand comprises a mixture of neutral and anionic nitrogen donors. This work is relevant to the chemistry of mononuclear nonheme iron enzymes that are proposed to oxidize organic substrates via reaction pathways involving high-valent iron oxo species.     

Heat capacity measurements in carboxylic polyelectrolyte solutions

Apparent molal heat capacities as a function of the degree of neutralization have been determined for dilute aqueous solutions of poly(acrylic acid) (PAA), poly(methacrylic acid) (PMA), copoly(maleic acid-ethylene) (MAEt), and copoly(maleic acid-styrene) (MASt) using direct flow microcalorimetry. Apparent molal volumes were measured as well. Both molal heat capacity and molal volume decrease with increasing ionization of the polymer. The effect of the hydrophobic interactions of the methyl group or phenyl group was obtained from the difference in the molal quantities of PMA and PAA, or MASt and MAEt. No evidence of hydrophobic effects, as determined from the heat capacity, was found for the conformational transition of PMA, but the hydration of the phenyl groups in MASt was found to be changed significantly at a degree of neutralization of 0.4.     

Photogating effects of HgTe nanoparticles on a single ZnO nanowire

In this study, we demonstrate the photogating effects of p-type HgTe nanoparticles (NPs) on an n-type ZnO nanowire (NW). The photogating effects are due to the charge separation of the charge carriers photogenerated in the NPs under illumination and the subsequent accumulation of the photogenerated electrons in the pn junction of the NPs and the NW. The presence of the electrons in the junction reduces the current in the ZnO NW. The photogating effects are proved by the different photocurrent behavior of the ZnO NW to which the HgTe NPs are attached from that of a bare ZnO NW. In addition, the dependence of the photogating effects on the power of the incident light is discussed.     

Dependence structure of the Korean stock market in high frequency data

This paper analyzes the evolution of the dependence structure for various time window intervals, known as Epps effect, using the Trade and Quote data of 663 actively traded stocks in Korean stock market. It is found that the random matrix theory analysis could not represent the dependence structure of the stock market in the microstructure regime. The Cook-Johnson copula is introduced as a parsimonious alternative method to handle this problem, and the existence of the Epps effect is confirmed for the 663 stocks using high frequency data. It was also found that large capitalization companies tend to have a stronger dependence structure, except for the largest capitalization group, since the phenomenon of price level resistance leads to the weak dependence structure in the largest capitalization group. In addition, grouping the industry as a sub-portfolio is an appropriate approach for hour interval traders, whereas this approach is not a strategy recommended for high frequency traders.     

A formal construction of a divergence-free basis in the nonconforming virtual element method for the Stokes problem

Numerical Algorithms - We develop a formal construction of a pointwise divergence-free basis in the nonconforming virtual element method of arbitrary order for the Stokes problem introduced in Zhao...     

On translation lengths of Anosov maps on the curve graph of the torus

Geometriae Dedicata - We show that an Anosov map has a geodesic axis on the curve graph of the torus. The direct corollary of our result is the stable translation length of an Anosov map on the...     

Mixed finite volume methods on nonstaggered quadrilateral grids for elliptic problems

We construct and analyze a mixed finite volume method on quadrilateral grids for elliptic problems written as a system of two first order PDEs in the state variable (e.g., pressure) and its flux (e.g., Darcy velocity). An important point is that no staggered grids or covolumes are used to stabilize the system. Only a single primary grid system is adopted, and the degrees of freedom are imposed on the interfaces. The approximate flux is sought in the lowest-order Raviart-Thomas space and the pressure field in the rotated- nonconforming space. Furthermore, we demonstrate that the present finite volume method can be interpreted as a rotated- nonconforming finite element method for the pressure with a simple local recovery of flux. Numerical results are presented for a variety of problems which confirm the usefulness and effectiveness of the method.