Development of an integrated informatics toolbox: HT kinetic and virtual screening

We discuss thoroughly aspects and issues for the development of a bespoke, but generic, electronic infrastructure designed to cope with the dynamic in high-throughput experimentation and knowledge management, is applicable to large or contract research organizations. We present the first generation of an informatics platform developed for TOPCOMBI, a research project funded by the European Commission for Nanotechnology and Nanoscience. It is composed by an infrastructure and a collection of modules dealing with laboratory analytics, robotics, data handling and analytics, optimization, in-database processing and visualization, which are developed collegially by the partners of the Consortium. This best-of-breed informatics system enables the capture and the re-usage of processes and methodologies, i.e. process and data flows, using the workflow paradigm. Complex workflows designed by power users can be eventually used by either other domain experts or by novices through a web portal. Workflows can also be run interactively to allow visual analytics for instance, or automatically. We present two case studies dealing with the kinetic study of glycerol catalytic oxidation using parallel equipments, and a novel, fully integrated QSAR applied in heterogeneous catalysis, respectively.     

Characterisation of the supramolecular structure of malonamides by application of pulsed field gradients in NMR spectroscopy

Malonamides are known and extensively studied for their lanthanide and actinide extracting properties. Those studies have also highlighted aggregated phenomena and a splitting of the organic phase, in some particular experimental conditions. To explain this behaviour of extractants, (1)H NMR was used to study micellar phenomena by the determination of the self-diffusion coefficients of two malonamides only different by the length of their alkyl chain (DMDBTDMA and DMDBPMA), in presence of n-dodecane and for systems saturated with water or anhydrous. Several information on the aggregates and on the malonamide supramolecular structure were obtained by fitting the curves of self-diffusion coefficient vs. concentration and by conjugated NMR experimental data to potentiometric titrations and physical measurements.     

Design and Implementation of a Novel Quench Flow Reactor for the Study of Nascent Olefin Polymerisation

A novel stopped flow reactor system is described in the current work, along with the underlying design philosophy. While the concept of stopped flow technology is not recent, this system is the first to be designed with the objective of studying particle morphology, and to work at extremely short (40 ms) residence times. It is shown that traditional chemical engineering principles are required to properly design and operate this type of reactor, and that when correctly design, it is a very flexible tool for the study of nascent polymerisation of olefins.

     

The Electronic Structure of Some Cyanohydrins—A Spectroscopically Under‐Investigated Family of Compounds

Cyanohydrins are usually formed by addition of hydrogen cyanide to aldehydes or ketones while the elimination of HCN from cyanohydrins is easily observed upon heating. The low thermal stability of these highly boiling compounds leads to difficult studies in the gas phase where partial or complete decomposition is usually observed. Consequently, the reported physicochemical properties of such compounds in the gas phase are still scarce. Keeping with this, four simple cyanohydrins, the glycolonitrile and methyl, vinyl and ethynyl derivatives, have been selected. These are possible candidates for the Interstellar Medium, where the corresponding aldehydes and HCN have been detected, and could have played an important role in prebiotic chemistry, as already proposed for some of them. Three well‐suited spectroscopic techniques, namely, UV photoelectron, infrared, and Raman spectroscopies, in tandem with quantum calculations, have been chosen for the structure analysis. Photoelectron spectroscopy, successfully performed with gaseous compounds, provides the first comparative study on cyanohydrins in the gas phase.     

Detection of volatile organic compounds indicative of human presence in the air

Volatile organic compounds were collected and analyzed from a variety of indoor and outdoor air samples to test whether human‐derived compounds can be readily detected in the air and if they can be associated with human occupancy or presence. Compounds were captured with thermal desorption tubes and then analyzed by gas chromatography with mass spectrometry. Isoprene, a major volatile organic compound in exhaled breath, was shown to be the best indicator of human presence. Acetone, another major breath‐borne compound, was higher in unoccupied or minimally occupied areas than in human‐occupied areas, indicating that its majority may be derived from exogenous sources. The association of endogenous skin‐derived compounds with human occupancy was not significant. In contrast, numerous compounds that are found in foods and consumer products were detected at elevated levels in the occupied areas. Our results revealed that isoprene and many exogenous volatile organic compounds consumed by humans are emitted at levels sufficient for detection in the air, which may be indicative of human presence.     

Poly[diaquadi‐μ6‐oxalato‐μ5‐oxalato‐chromium(III)rubidium(I)]: a new supramolecular isomer

The title compound, [CrRb(C₂O₄)₂(H₂O)₂]_n, obtained under hydrothermal conditions and investigated structurally at 100 K, is a three‐dimensional supramolecular isomer of the layered structure compound studied at room temperature. This novel polymer is built up from crosslinked heterobimetallic units. The linkage of alternating edge‐ and vertex‐shared RbO₇(H₂O)₂ and CrO₄(H₂O)₂ polyhedra running along three different directions gives a dense packing. The two independent ligands display two η⁴‐chelation modes and two conventional carboxylate bridges. However, the pentadentate ligand connects the Cr^III and Rb^I ions through one O‐atom bridge, while the hexadentate ligand exhibits an additional η³‐chelation and two O‐atom bridges. Each coordinated water molecule forms an O‐atom bridge between the two metals. Moreover, in the absence of protonated ligands, these water molecules act as donors through their four H atoms in strong‐to‐weak hydrogen bonds. This results in zigzag chains of alternating oxalate and aqua ligands parallel to the twofold screw axis. The six double oxalates known to date containing an alkali and Cr^III all present layered two‐dimensional structures. In the series, this supramolecular isomer is the first three‐dimensional framework.     

A new look at the homogeneous risk model

The present paper aims to revisit the homogeneous risk model investigated by [De Vylder and Goovaerts, 1999] and [De Vylder and Goovaerts, 2000]. First, a claim arrival process is defined on a fixed time interval by assuming that the arrival times satisfy an order statistic property. Then, the variability and the covariance of an aggregate claim amount process is discussed. The distribution of the aggregate discounted claims is also examined. Finally, a closed-form expression for the non-ruin probability is derived in terms of a family of Appell polynomials. This formula holds for all claim distributions, even dependent. It generalizes several results obtained so far.     

CCZ-equivalence of bent vectorial functions and related constructions

We observe that the CCZ-equivalence of bent vectorial functions over ${{\bf F}_2^n}$ (n even) reduces to their EA-equivalence. Then we show that in spite of this fact, CCZ-equivalence can be used for constructing bent functions which are new up to EA-equivalence and therefore to CCZ-equivalence: applying CCZ-equivalence to a non-bent vectorial function F which has some bent components, we get a function F?? which also has some bent components and whose bent components are CCZ-inequivalent to the components of the original function F. Using this approach we construct classes of nonquadratic bent Boolean and bent vectorial functions.     

Relating three nonlinearity parameters of vectorial functions and building APN functions from bent functions

We survey the properties of two parameters introduced by C. Ding and the author for quantifying the balancedness of vectorial functions and of their derivatives. We give new results on the distribution of the values of the first parameter when applied to F + L, where F is a fixed function and L ranges over the set of linear functions: we show an upper bound on the nonlinearity of F by means of these values, we determine then the mean of these values and we show that their maximum is a nonlinearity parameter as well, we prove that the variance of these values is directly related to the second parameter. We briefly recall the known constructions of bent vectorial functions and introduce two new classes obtained with Gregor Leander. We show that bent functions can be used to build APN functions by concatenating the outputs of a bent (n, n/2)-function and of some other (n, n/2)-function. We obtain this way a general infinite class of quadratic APN functions. We show that this class contains the APN trinomials and hexanomials introduced in 2008 by L. Budaghyan and the author, and a class of APN functions introduced, in 2008 also, by Bracken et al.; this gives an explanation of the APNness of these functions and allows generalizing them. We also obtain this way the recently found Edel?CPott cubic function. We exhibit a large number of other sub-classes of APN functions. We eventually design with this same method classes of quadratic and non-quadratic differentially 4-uniform functions.