Deprotection Techniques for Phosphine-Borane Complexes: Methods and Extraction Coefficients

Triarylphosphine-, diarylalkylphosphine-, and trialkylphosphine-borane complexes were deprotected using various amines and acids. After deprotection, the resulting borane species were extracted from the free phosphines using various solvent systems. The aqueous layers were analyzed for borane making use of inductively coupled plasma optical emission spectroscopy; and extraction coefficients were then calculated from the analytical data.     

Conformation and dynamics of biopharmaceuticals: Transition of mass spectrometry-based tools from academe to industry

Mass spectrometry plays a very visible role in biopharmaceutical industry, although its use in development, characterization, and quality control of protein drugs is mostly limited to the analysis of covalent structure (amino acid sequence and post-translational modifications). Despite the centrality of protein conformation to biological activity, stability, and safety of biopharmaceutical products, the expanding arsenal of mass spectrometry-based methods that are currently available to probe higher order structure and conformational dynamics of biopolymers did not, until recently, enjoy much attention in the industry. This is beginning to change as a result of recent work demonstrating the utility of these experimental tools for various aspects of biopharmaceutical product development and manufacturing. In this work, we use a paradigmatic protein drug interferon β-1a as an example to illustrate the utility of mass spectrometry as a powerful tool not only to assess the integrity of higher order structure of a protein drug, but also to predict consequences of its degradation at a variety of levels.     

Liquid–liquid immiscibility under non-equilibrium conditions in a model membrane: An X-ray synchrotron study

Several non-random lipid mixtures have been proposed as models of lipid plasma membrane, as they mimic the ability of biomembranes to form lateral domains. Biological membranes are characterised by a succession of localised transient steady-state lipid organisations rather than stable equilibria. This suggests that several quasi at-equilibrium lipid organisations may exist at different times in the same local patch of membranes. Identification of the conditions which can mimic heterogeneous dynamic membrane states in a lipid membrane model is a challenge. This is of particular importance as the lateral organisation of lipids mixtures in fully equilibrated samples may differ from the arrangement found in quasi at-equilibrium conditions. To address this issue, we have performed a real-time synchrotron X-ray diffraction study in ternary mixtures of egg-phosphatidylcholine/egg-sphingomyelin and cholesterol using a 0.5 °C/15 s step within a 20–50–20 °C thermal cycle. In the present study, all ternary mixtures displayed lamellar phase separation. A d-spacing value was observed reversibly during the heating and cooling scan for each of the two coexisting phases. In mixtures with a cholesterol concentration from 20 to 50 mol%, a liquid-ordered (Lo) and liquid-disordered (Ld) phase separation was observed in the 20–50 °C thermal range. These results are discussed in terms of a specific interaction between lipid molecular aggregates.     

Continuous Synthesis of Peralkylated Imidazoles and their Transformation into Ionic Liquids with Improved (Electro)Chemical Stabilities

A versatile and efficient method to synthesize tetrasubstituted imidazoles via a one‐pot modified Debus–Radziszewski reaction and their subsequent transformation into the corresponding imidazolium ionic liquids is reported. The tetrasubstituted imidazoles were also synthesized by means of a continuous flow process. This straightforward synthetic procedure allows for a fast and selective synthesis of tetrasubstituted imidazoles on a large scale. The completely substituted imidazolium dicyanamide and bis(trifluoromethylsulfonyl)imide salts were obtained via a metathesis reaction of the imidazolium iodide salts. The melting points and viscosities are of the same order of magnitude as for their non‐substituted analogues. In addition to the superior chemical stability of these novel ionic liquids, which allows them to be applied in strong alkaline media, the improved thermal and electrochemical stabilities of these compounds compared with conventional imidazolium ionic liquids is also demonstrated by thermogravimetrical analysis (TGA) and cyclic voltammetry (CV). Although increased substitution of the ionic liquids does not further increase thermal stability, a definite increase in cathodic stability is observable.     

A proteomic approach to investigate potential biomarkers directed against membrane-associated breast cancer proteins

The identification of specific protein markers for breast cancer would provide the basis for early diagnosis. Particularly, membrane and membrane-associated proteins are rich in targets for antibodies that may constitute suitable biomarkers of carcinogenesis. However, membrane proteins separation using 2-DE remains difficult. In this work, the breast cancer cell line MCF7 was used as source of proteins for the screening of potential cell membrane-associated antigens recognized by autoantibodies in patients with breast cancer and healthy volunteers. The protein extract obtained using trifluoroethanol (TFE) as cosolvent was compared to a total cell lysate protein extract prepared by a current technique. After 2-DE separation of the two extracts, their protein patterns clearly differed. About 63% of the proteins identified in the TFE-extract were predicted to possess at least one transmembrane domain. 2-D blots probed with sera from cancer patients or from healthy volunteers showed that, as expected, additional antigens were provided in the TFE-extract. Thus, the method described here appeared well suited for proteomic investigation of potential biomarkers undetected by current techniques.     

Bis(germyl)ketones: Toward a New Class of Type I Photoinitiating Systems Sensitive Above 500 nm?

The ability of a bis(germyl)ketone Ph₃GeCOGePh₃ to act as a photoinitiator of free radical polymerization under visible light is investigated. The results suggest that this compound could be the starting point of a new high performance class of photoinitiators. The excited state processes, as well as the generation and the reactivity of the germyl radicals, are studied by laser flash photolysis, ESR spin trapping experiments, and molecular orbital calculations; they are compared to the results obtained on a mono‐ (germyl)ketone CH₃COGePh₃. Time dependent density functional theory calculations allow discussion of the strongly red‐shifted ground state absorption of Ph₃GeCOGePh₃.

     

Interpolation-based solution of a nonlinear eigenvalue problem in fluid-structure interaction

A nonlinear eigenvalue problem arising from a coupled finite element/boundary element approach for fluid-structure interaction is considered. We propose an approach based on polynomial interpolation and linearization for its numerical solution. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Patroids

A matroid M over a set E of elements is semiseparated by a partition {S¹, S²} of E iff rank E = rank S¹ + rank S² + 1. Such a semiseparation defines in each Sⁱ a pair of matroids or patroid Pⁱ = (Mⁱ, mⁱ); the two patroids P¹, P² weld to form M. The operations of removing and contracting a non-degenerate element of a matroid produce a patroid. The properties of patroids, their bases, and circuits are discussed.     

Effect of Different Electron Elastic-Scattering Cross Sections on Inelastic Mean Free Paths Obtained from Elastic-Backscattering Experiments

Inelastic mean free paths (IMFPs) of electrons with energies between 100eV and 5,000eV have been frequently obtained from measurements of elastic-backscattering probabilities for different specimen materials. A calculation of these probabilities is also required to determine IMFPs. We report calculations of elastic-backscattering probabilities for gold at energies of 100eV and 500eV with differential elastic-scattering cross sections obtained from the Thomas-Fermi-Dirac potential and the more reliable Dirac-Hartree-Fock potential. For two representative experimental configurations, the average deviation between IMFPs obtained with cross sections from the two potentials was 11.4%.     

Scanning electrochemical microscopy #54. Application to the study of heterogeneous catalytic reactions-hydrogen peroxide decomposition

A scanning electrochemical microscopy (SECM) approach for the analysis of heterogeneous catalytic reactions at solid-liquid interfaces is described and applied. In this scheme, reactant, generated at a tip, undergoes a reaction (e.g., disproportionation) at the substrate. The theoretical background for this study, performed by digital simulations using a finite difference method, considers a chemical reaction at the substrate with general stoichiometry. In this case, the fraction of regenerated mediator (nu(S)) may differ with respect to a substrate reaction that is the reverse of the tip reaction, resulting in an asymmetric mediator loop. Simulated tip current transients and approach curves at different values of the kinetic rate constant for reactions where nu(S) < 1 were used to analyze this new SECM situation. This approach was used to study the catalytic decomposition of hydrogen peroxide (HO2- --> 1/2O2 + OH-), where nu(S) = 0.5, on supported catalysts. A gold-mercury amalgam tip was used to quantitatively reduce dissolved O2 (mediator) to HO2-, which was decomposed back to oxygen at the catalyst substrate. Rate constants for the decomposition reaction on immobilized catalase and Pt particles were measured at different pH values by the correlation of experimental approach curves with the theoretical dependencies.