Quantum chemical mass spectrometry: ab initio prediction of electron ionization mass spectra and identification of new fragmentation pathways

The electron ionization mass spectra of four organic compounds are predicted based on the results of quantum chemical calculations at the DFT/B3LYP/6‐311 + G* level of theory. This prediction is performed ‘ab initio’, i.e. without any prior knowledge of the thermodynamics or kinetics of the reactions under consideration. Using a set of rules determining which routes will be followed, the fragmentation of the molecules' bonds and the complete resulting fragmentation pathways are studied. The most likely fragmentation pathways are identified based on calculated reaction energies ΔE when bond cleavage is considered and on activation energies ΔE^? when rearrangements are taken into account; the final intensities of the peaks in the spectrum are estimated from these values. The main features observed in the experimental mass spectra are correctly predicted, as well as a number of minor peaks. In addition, the results of the calculations allow us to propose fragmentation pathways new to empirical mass spectrometry, which have been experimentally verified using tandem mass spectrometry measurements. Copyright © 2016 John Wiley & Sons, Ltd.     

A General Method for Extracting Individual Coupling Constants from Crowded 1H NMR Spectra

Couplings between protons, whether scalar or dipolar, provide a wealth of structural information. Unfortunately, the high number of ¹H‐¹H couplings gives rise to complex multiplets and severe overlap in crowded spectra, greatly complicating their measurement. Many different methods exist for disentangling couplings, but none approaches optimum resolution. Here, we present a general new 2D J‐resolved method, PSYCHEDELIC, in which all homonuclear couplings are suppressed in F₂, and only the couplings to chosen spins appear, as simple doublets, in F₁. This approaches the theoretical limit for resolving ¹H‐¹H couplings, with close to natural linewidths and with only chemical shifts in F₂. With the same high sensitivity and spectral purity as the parent PSYCHE pure shift experiment, PSYCHEDELIC offers a robust method for chemists seeking to exploit couplings for structural, conformational, or stereochemical analyses.     

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/).     

Reagens auf Carbols?ure

Ohne Zusammenfassung     

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.