From alkyl halides to alkyltrifluoromethyls using bromine trifluoride

Under the right conditions, bromine trifluoride can be a useful tool for generating new types of reactions and compounds. Thus, tris(methylthio)alkyl derivatives, easily prepared from the corresponding alkyl bromides, were converted to the corresponding RCHBrCF2SMe or RCHBrCF3 compounds. The bromine atom, however, could be easily reduced forming eventually R'CF2SMe or R'CF3. If desired, the bromine atom can serve as an entry for constructing terminal difluoroolefins.     

Numerical experiments with MALDI Imaging data

This article does not present new mathematical results, it solely aims at discussing some numerical experiments with MALDI Imaging data. However, these experiments are based on and could not be done without the mathematical results obtained in the UNLocX project. They tackle two obstacles which presently prevent clinical routine applications of MALDI Imaging technology. In the last decade, matrix-assisted laser desorption/ionization imaging mass spectrometry (MALDI-IMS) has developed into a powerful bioanalytical imaging modality. MALDI imaging data consists of a set of mass spectra, which are measured at different locations of a flat tissue sample. Hence, this technology is capable of revealing the full metabolic structure of the sample under investigation. Sampling resolution as well as spectral resolution is constantly increasing, presently a conventional 2D MALDI Imaging data requires up to 100 GB per dataset. A major challenge towards routine applications of MALDI Imaging in pharmaceutical or medical workflows is the high computational cost for evaluating and visualizing the information content of MALDI imaging data. This becomes even more critical in the near future when considering cohorts or 3D applications. Due to its size and complexity MALDI Imaging constitutes a challenging test case for high performance signal processing. In this article we will apply concepts and algorithms, which were developed within the UNLocX project, to MALDI Imaging data. In particular we will discuss a suitable phase space model for such data and report on implementations of the resulting transform coders using GPU technology. Within the MALDI Imaging workflow this leads to an efficient baseline removal and peak picking. The final goal of data processing in MALDI Imaging is the discrimination of regions having different metabolic structures. We introduce and discuss so-called soft-segmentation maps which are obtained by non-negative matrix factorization incorporating sparsity constraints.     

Photochemistry of homoconjugated ketones: 2-(carbomethoxy)spiro[5.5]undeca-1, 3-dien-7-one.

The direct and sensitized irradiation of the title compound ($\text{2}$c) was studied with particular attention to its oxa-di-π-methane rearrangement, the product of which is of notable structural and synthetic interest. X-ray diffraction data of the final product (8) are given to support structural assignments.     

Two-settlement electricity markets with price caps and Cournot generation firms

We compare two alternative mechanisms for capping prices in two-settlement electricity markets. With sufficient lead time, forward market prices are implicitly capped by competitive pressure of potential entry that will occur when forward prices rise above some backstop price. Another more direct approach is to cap spot prices through a regulatory intervention. In this paper we explore the implications of these two alternative mechanisms in a two-settlement Cournot equilibrium framework. We formulate the market equilibrium as a stochastic equilibrium problem with equilibrium constraints (EPEC) capturing congestion effects, probabilistic contingencies and horizontal market power. As an illustrative test case, we use the 53-bus Belgian electricity network with representative generator costs but hypothetical demand and ownership structure. Compared to a price-uncapped two-settlement system, a forward cap increases firms’ incentives for forward contracting, whereas a spot cap reduces such incentives. Moreover, in both cases, more forward contracts are committed as the generation resource ownership structure becomes more diversified.     

Templating nanostructures by mesoporous materials with an emphasis on room temperature and cryogenic TEM studies

Rapid strides realized in the field of ordered mesoporous silica (OMS) with a well-defined pore shape and nanometric sizes, provide new gateways for the preparation of nanostructured materials having controlled shape and size with a very narrow distribution. The focus of the current review is on the synthesis of nanostructures templated by OMS either in bulk or in thin film form. The importance of electron microscopy as an indispensable technique in the structural characterization of OMS templated nanostructures, including cryo-TEM, electron tomography and HR-SEM, is highlighted in this review.     

A conjugate directions method for subjective assessment of normal distributions

A procedure is developed that enables the encoding of a subjectiven-dimensional joint normal probability density function through the assessment of its marginal means and variances andn(n–1)/2 conditional means. The new method is based on the theory of conjugate directions for quadratic forms, and it exploits the fact that normal distributions have quadratic equal-likelihood surfaces. Unlike previous approaches, this new method enables easy detection and resolution of inconsistencies in the assessments that could lead to an indefinite estimate of the covariance matrix.     

High Affinity Recognition of a Selected Amino Acid Epitope within a Protein by Cucurbit[8]uril Complexation

Supramolecular interactions between the host cucurbit[8]uril (CB[8]) and amino acids have been widely interrogated, but recognition of specific motifs within a protein domain have never been reported. A phage display approach was herein used to select motifs with the highest binding affinity for the heteroternary complex with methyl viologen and CB[8] (MV?CB[8]) within a vast pool of cyclic peptide sequences. From the selected motifs, an epitope consisting of three amino acid was extrapolated and incorporated into a solvent‐exposed loop of a protein domain; the protein exhibited micromolar binding affinity for the MV?CB[8] complex, matching that of the cyclic peptide. By achieving selective CB[8]‐mediated conjugation of a small molecule to a recombinant protein scaffold we pave the way to biomedical applications of this simple ternary system.     

Effect of molecular conformations on the adsorption behavior of gold-binding peptides

Despite extensive recent reports on combinatorially selected inorganic-binding peptides and their bionanotechnological utility as synthesizers and molecular linkers, there is still only limited knowledge about the molecular mechanisms of peptide binding to solid surfaces. There is, therefore, much work that needs to be carried out in terms of both the fundamentals of solid-binding kinetics of peptides and the effects of peptide primary and secondary structures on their recognition and binding to solid materials. Here we discuss the effects of constraints imposed on FliTrx-selected gold-binding peptide molecular structures upon their quantitative gold-binding affinity. We first selected two novel gold-binding peptide (AuBP) sequences using a FliTrx random peptide display library. These were, then, synthesized in two different forms: cyclic (c), reproducing the original FliTrx gold-binding sequence as displayed on bacterial cells, and linear (l) dodecapeptide gold-binding sequences. All four gold-binding peptides were then analyzed for their adsorption behavior using surface plasmon resonance spectroscopy. The peptides exhibit a range of binding affinities to and adsorption kinetics on gold surfaces, with the equilibrium constant, Keq, varying from 2.5x10(6) to 13.5x10(6) M(-1). Both circular dichroism and molecular mechanics/energy minimization studies reveal that each of the four peptides has various degrees of random coil and polyproline type II molecular conformations in solution. We found that AuBP1 retained its molecular conformation in both the c- and l-forms, and this is reflected in having similar adsorption behavior. On the other hand, the c- and l-forms of AuBP2 have different molecular structures, leading to differences in their gold-binding affinities.     

Gas chromatography-mass spectrometry with supersonic molecular beams

Gas chromatography-mass spectrometry (GC-MS) with supersonic molecular beams (SMBs) (also named Supersonic GC-MS) is based on GC and MS interface with SMBs and on the electron ionization (EI) of vibrationally cold analytes in the SMBs (cold EI) in a fly-through ion source. This ion source is inherently inert and further characterized by fast response and vacuum background filtration capability. The same ion source offers three modes of ionization including cold EI, classical EI and cluster chemical ionization (CI). Cold EI, as a main mode, provides enhanced molecular ions combined with an effective library sample identification, which is supplemented and complemented by a powerful isotope abundance analysis method and software. The range of low-volatility and thermally labile compounds amenable for analysis is significantly increased owing to the use of the contact-free, fly-through ion source and the ability to lower sample elution temperatures through the use of high column carrier gas flow rates. Effective, fast GC-MS is enabled particularly owing to the possible use of high column flow rates and improved system selectivity in view of the enhancement of the molecular ion. This fast GC-MS with SMB can be further improved via the added selectivity of MS-MS, which by itself benefits from the enhancement of the molecular ion, the most suitable parent ion for MS-MS. Supersonic GC-MS is characterized by low limits of detection (LOD), and its sensitivity is superior to that of standard GC-MS, particularly for samples that are hard for analysis. The GC separation of the Supersonic GC-MS can be improved with pulsed flow modulation (PFM) GC x GC-MS. Electron ionization LC-MS with SMB can also be combined with the Supersonic GC-MS, with fast and easy switching between these two modes of operation.