Confidence intervals and ellipsoids for estimable functions and estimable vectors in models with orthogonal block structure

Sub-models of mixed linear models are considered. The independence of these sub-models leads to sufficient statistics for the parameters relevant for their densities. Using pivot variables, confidence regions are obtained as well hypothesis testing for variance components, estimable functions, and estimable vectors. In addition, to compare the estimators and the models, we present the histograms with the empirical joint densities for positive and negative parts of the estimators. The figures, for the two-dimensional charts, contain the corresponding UMVUE and are all unimodal with the UMVUE near the mode. The nearness of the estimators and the modes validates the presented methodology and allows the safe use of induced densities. A numerical example applied to real data is presented.     

A Field Monte Carlo Formulation for Calculating the Probability Density Function of a Single Scalar in a Turbulent Flow

The probability density function (PDF) formulation of one scalar field undergoing diffusion, turbulent convection and chemical reaction is restated in terms of stochastic fields. These fields are smooth in space as they have a length scale similar to that of the PDF. Their evolution is described by a set of stochastic partial differential equations, which are solved using a finite volume scheme with a stochastic source term. The application of this methodology to a particular flow is shown first for a linear source term, with exact analytical solution for the mean and standard deviation, and then for a nonlinear reaction.     

The effects of displacement induced by thermal perturbations on the structure and stability of boundary-layer flows

The free-interaction influence of a thermal expansion process in boundary-layer gas flow is analyzed using the formalism of triple-deck theory. The physical model considered is the forced convection of a gas flowing over a flat plate subject to a heated slab. Both linearized and full nonlinear solutions are obtained using Fourier transform methods and spectral numerical techniques. The influence of monochromatic thermal perturbation on boundary-layer stability (lower branch) is studied and first-order correction of the lower branch neutral stability curve for the boundary-layer flow has been obtained. The shift of neutral stability is then computed for different values of the thermal perturbation wave number, making unstable some otherwise stable modes.This work has been supported by the Cray Research Inc. through a grant on supercomputing.     

A Highly Stabilizing Silver(I)‐Mediated Base Pair in Parallel‐Stranded DNA

The first parallel‐stranded DNA duplex with Hoogsteen base pairing that readily incorporates an Ag⁺ ion into an internal mispair to form a metal‐mediated base pair has been created. Towards this end, the highly stabilizing 6 FP ‐Ag⁺‐ 6 FP base pair comprising the artificial nucleobase 6‐furylpurine ( 6 FP ) was devised. A combination of temperature‐dependent UV spectroscopy, CD spectroscopy, and DFT calculations was used to confirm the formation of this base pair. The nucleobase 6 FP is capable of forming metal‐mediated base pairs both by the Watson–Crick edge (i.e. in regular antiparallel‐stranded DNA) and by the Hoogsteen edge (i.e. in parallel‐stranded DNA), depending on the oligonucleotide sequence and the experimental conditions. The 6 FP ‐Ag⁺‐ 6 FP base pair within parallel‐stranded DNA is the most strongly stabilizing Ag⁺‐mediated base pair reported to date for any type of nucleic acid, with an increase in melting temperature of almost 15 °C upon the binding of one Ag⁺ ion.     

Highly Stereoselective Synthesis of Natural‐Product‐Like Hybrids by an Organocatalytic/Multicomponent Reaction Sequence

In an endeavor to provide an efficient route to natural product hybrids, described herein is an efficient, highly stereoselective, one‐pot process comprising an organocatalytic conjugate addition of 1,3‐dicarbonyls to α,β‐unsaturated aldehydes followed by an intramolecular isocyanide‐based multicomponent reaction. This approach enables the rapid assembly of complex natural product hybrids including up to four different molecular fragments, such as hydroquinolinone, chromene, piperidine, peptide, lipid, and glycoside moieties. The strategy combines the stereocontrol of organocatalysis with the diversity‐generating character of multicomponent reactions, thus leading to structurally unique peptidomimetics integrating heterocyclic, lipidic, and sugar moieties.     

Phenanthriporphyrin: An Antiaromatic Aceneporphyrinoid as a Ligand for a Hypervalent Organophosphorus(V) Moiety

The incorporation of a phenanthrene moiety into a porphyrin framework results in the formation of a hybrid macrocycle—phenanthriporphyrin—merging the structural features of polycyclic aromatic hydrocarbons and porphyrins. An antiaromatic aceneporphyrinoid, adopting the trianionic {CCNN} core, is suitable for the incorporation of a phosphorus(V) center to form a hypervalent organophosphorus(V) derivative.     

Six‐Coordinate Group 13 Complexes: The Role of d Orbitals and Electron‐Rich Multi‐Center Bonding

Bonding in six‐coordinate complexes based on Group 13 elements (B, Al, Ga, In, Tl) is usually considered to be identical to that in transition‐metal analogues. We herein demonstrate through sophisticated electronic‐structure analyses that the bonding in these Group 13 element complexes is fundamentally different and better characterized as electron‐rich hypervalent bonding with essentially no role for the d orbitals. This characteristic is carried through to the molecular properties of the complex.     

Immobilization of Distinctly Capped CdTe Quantum Dots onto Porous Aminated Solid Supports

Immobilization of quantum dots (QDs) onto solid supports could improve their applicability in the development of sensing platforms and solid‐phase reactors by allowing the implementation of reusable surfaces and the execution of repetitive procedures. As the reactivity of QDs relies mostly on their surface chemistry, immobilization could also limit the disruption of solution stability that could prevent stable measurements. Herein, distinct strategies to immobilize QDs onto porous aminated supports, such as physical adsorption and the establishment of chemical linking, were evaluated. This work explores the influence of QD capping and size, concentration, pH, and contact time between the support and the QDs. Maximum QD retention was obtained for physical adsorption assays. Freundlich and Langmuir isotherms were used to analyze the equilibrium data. Gibbs free energy, enthalpy, and entropy were calculated and the stability of immobilized QDs was confirmed.     

High Sensitive Microsensor Based on Organic‐Inorganic Composite for Two‐Dimensional Mapping of H2O2 by SECM

The present work describes the development of a selective, sensitive and stable sensing microsensor for scanning electrochemical microscopy (SECM) to measure H₂O₂ during electrochemical reduction of oxygen. The microsensor is based on graphene and Poly(3,4‐ethylenedioxythiophene) composite as support to iron (III) hexacyanoferrate (II) (PEDOT/graphene/Fe^III₄[Fe^II(CN)₆]₃ microsensor). The electrochemical properties of the PEDOT/graphene/Fe^III₄[Fe^II(CN)₆]₃ microsensor were investigated by cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM). The PEDOT/graphene/Fe^III₄[Fe^II(CN)₆]₃ microsensor showed an excellent electrocatalytic activity toward hydrogen peroxide (H₂O₂) reduction with a diminution of the overpotential of about 500 mV in comparison to the process at a bare gold microelectrode. The microsensor presented excellent performance for two dimensional mapping of H₂O₂ by SECM in 0.1 mol L^?1 phosphate buffer solution (pH 7.0). Under optimized conditions, a linear response range from 1 up to 1000 µmol L^?1 was obtained with a sensitivity of 0.08 nA L µmol^?1 and limit of detection of 0.5 µmol L^?1.     

Electrochemical Immunosensor for the Determination of Total Ghrelin Hormone in Saliva

An electrochemical immunosensor for ghrelin (GHRL) determination in saliva is reported. Anti‐GHRL was immobilized onto Protein G‐magnetic beads and a competitive immunoassay involving biotinylated GHRL and alkaline phosphatase‐streptavidin was implemented. Once conjugate was magnetically captured on a screen‐printed carbon electrode, GHRL quantization was accomplished by DPV of 1‐naphtol formed upon addition of 1‐naphtyl phosphate. A linear range between 10^?3 and 10³ ng/mL GHRL, and a LOD of 7 pg/mL, much smaller than those from commercial ELISA kits, were found. The usefulness of the immunosensor was demonstrated by analyzing human saliva spiked with GHRL at 0.01, 0.1, 1 and 10 ng/mL.