Computing multiple-output regression quantile regions from projection quantiles

In the multiple-output regression context, Hallin et al. (Ann Statist 38:635–669, 2010) introduced a powerful data-analytical tool based on regression quantile regions. However, the computation of these regions, that are obtained by considering in all directions an original concept of directional regression quantiles, is a very challenging problem. Paindaveine and Šiman (Comput Stat Data Anal 2011b) described a first elegant solution relying on linear programming techniques. The present paper provides another solution based on the fact that the quantile regions can also be computed from a competing concept of projection regression quantiles, elaborated in Kong and Mizera (Quantile tomography: using quantiles with multivariate data 2008) and Paindaveine and Šiman (J Multivar Anal 2011a). As a by-product, this alternative solution further provides various characteristics useful for statistical inference. We describe in detail the algorithm solving the parametric programming problem involved, and illustrate the resulting procedure on simulated data. We show through simulations that the Matlab implementation of the algorithm proposed in this paper is faster than that from Paindaveine and Šiman (Comput Stat Data Anal 2011b) in various cases.     

An Efficient Thiol‐Ene Chemistry for the Preparation of Amphiphilic PHA‐Based Graft Copolymers

We present a straightforward method to prepare amphiphilic graft copolymers consisting of hydrophobic poly(3‐hydroxyalkanoates) (PHAs) backbone and hydrophilic α‐amino‐ω‐methoxy poly(oxyethylene‐co‐oxypropylene) (Jeffamine®) units. Poly(3‐hydroxyoctanoate)‐co‐(3‐hydroxyundecenoate) (PHOU) was first methanolyzed to obtain the desired molar mass. The amino end groups of Jeffamine were converted into thiol by a reaction with N‐acetylhomocysteine thiolactone and subsequently photografted. This “one‐pot” functionalization prevents from arduous and time‐consuming functionalization of the hydrophilic precursor or tedious modifications of PHAs, thus simplifying the process. The amphiphilic nature of modified PHAs leads to water‐soluble copolymers exhibiting thermoresponsive behavior.     

An empirical model for the equivalent translational compliance of steel studs

The effect of the resilience of the steel studs on the sound insulation of steel stud cavity walls can be modeled as an equivalent translational compliance in simple models for predicting the sound insulation of walls. Recent numerical calculations have shown that this equivalent translational compliance varies with frequency. This paper determines the values of the equivalent translational compliance of steel studs which make a simple sound insulation theory agree best with experimental sound insulation data for 126 steel stud cavity walls with gypsum plaster board on each side of the steel studs and sound absorbing material in the wall cavity. These values are approximately constant as a function of frequency up to 400 Hz. Above 400 Hz they decrease approximately as a non-integer power of the frequency. The equivalent translational compliance also depends on the mass per unit surface area of the cladding on each side of the steel studs and on the width of the steel studs. Above 400 Hz, this compliance also depends on the stud spacing. The best fit approximation is used with a simple sound insulation prediction model to predict the sound insulation of steel stud cavity walls whose sound insulation has been determined experimentally.     

Design and development of a new program for data processing of mass spectra acquired by means of a high-resolution double-focusing glow-discharge mass spectrometer

An new program has been developed and implemented for data analysis of mass spectra obtained by use of the VG9000 glow-discharge mass spectrometer. The program, designed to run in a Windows 9X environment includes several tools for import and export of data, cluster generators, etc. An automated technique for the interpretation of mass spectra is also built into the program; this enables faster and operator-independent interpretation. When major interferences or not-well defined signals are involved, the automated technique might fail to find the correct result. Therefore, a manual, VG9000 software-like, bypass is at hand. A comparison of the different techniques and programs shows, in general, comparable results. An installable version of the software is available on the university FTP-server (ftp://PLASMA-FTP.uia.ac.be/ private/imsas/).     

Chlorkalkprüfung

Analytical and Bioanalytical Chemistry -     

Acetylene decomposition on Rh(100): theory and experiment.

The decomposition of acetylene on a Rh(100) single crystal was studied by a combination of experimental techniques [static secondary ion mass spectrometry (SSIMS), temperature-programmed desorption (TPD), and low-energy electron diffraction (LEED)] to gain insight into the reaction pathway and the nature of the reaction intermediates. The experimental techniques were combined with a computational approach using density functional theory (DFT). Acetylene adsorbs irreversibly on the Rh(100) surface and eventually decomposes to atomic carbon and gas-phase hydrogen. The combination of experimental and computational results enabled us to determine the most likely reaction pathway for the decomposition process.     

Atom-molecule interactions on transition metal surfaces: a DFT Study of CO and several atoms on Rh(100), Pd(100) and Ir(100).

Density functional theory (DFT) calculations have been performed to determine the interaction energy between a CO probe molecule and all atoms from the first three rows of the periodic table coadsorbed on Rh(100), Pd(100) and Ir(100) metal surfaces. Varying the coverage of CO or the coadsorbed atom proved to have a profound effect on the strength of the interaction energy. The general trend, however, is the same in all cases: the interaction energy becomes more repulsive when moving towards the right along a row of elements, and reaches a maximum somewhere in the middle of a row of elements. The absolute value of the interaction energy between an atom-CO pair ranges from about -0.40 eV (39 kJ mol(-1)) attraction to +0.70 eV (68 kJ mol(-1)) repulsion, depending on the coadsorbate, the metal and the coverage. The general trend in interaction energies seems to be a common characteristic for several transition metals.     

N-Heterocyclic Olefin-Ligated Palladium(II) Complexes as Pre-Catalysts for Buchwald–Hartwig Aminations

New N-heterocyclic olefins (NHOs) are described with functionalization on the ligand heterocyclic backbone and terminal alkylidene positions. Various Pd^II–NHO complexes have been formed and their use as pre-catalysts in Buchwald–Hartwig aminations was explored. The most active system for catalytic C−N bond formation between hindered arylamine and arylhalide substrates was accessed by combining a backbone methylated NHO with [Pd(cinnamyl)Cl]₂ in the presence of NaOtBu as a base. In these active systems evidence suggests that catalysis is mediated by colloidal palladium metal, highlighting a different coordination ability of NHOs in comparison with commonly used N-heterocyclic carbene co-ligands.