Generation and characterization of air micro-bubbles in highly hydrophobic capillaries

The generation of air microbubbles in microfluidic systems or in capillaries could be of great interest for transportation (single cell analysis, organite transportation) or for liquid compartmentation. The physicochemical characterization of air bubbles and a better understanding of the process leading to bubble generation during electrophoresis is also interesting in a theoretical point of view. In this work, the generation of microbubbles on hydrophobic Glaco™ coated capillaries has been studied in water-based electrolyte. Air bubbles were generated at the detection window and the required experimental parameters for microbubbles generation have been identified. Generated bubbles migrated against the electroosmotic flow, as would do strongly negatively charged solutes, under constant electric field. They have been characterized in terms of dimensions, electrophoretic mobility, and apparent charge.     

Gas-Phase Lithium Cation Basicity: Revisiting the High Basicity Range by Experiment and Theory

According to high level calculations, the upper part of the previously published FT-ICR lithium cation basicity (LiCB at 373 K) scale appeared to be biased by a systematic downward shift. The purpose of this work was to determine the source of this systematic difference. New experimental LiCB values at 373 K have been measured for 31 ligands by proton-transfer equilibrium techniques, ranging from tetrahydrofuran (137.2 kJ mol^?1) to 1,2-dimethoxyethane (202.7 kJ mol^?1). The relative basicities (ΔLiCB) were included in a single self-consistent ladder anchored to the absolute LiCB value of pyridine (146.7 kJ mol^?1). This new LiCB scale exhibits a good agreement with theoretical values obtained at G2(MP2) level. By means of kinetic modeling, it was also shown that equilibrium measurements can be performed in spite of the formation of Li⁺ bound dimers. The key feature for achieving accurate equilibrium measurements is the ion trapping time. The potential causes of discrepancies between the new data and previous experimental measurements were analyzed. It was concluded that the disagreement essentially finds its origin in the estimation of temperature and the calibration of Cook’s kinetic method. Graphical Abstract

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The abelianization of almost free groups

We will construct an almost free non-free group of cardinality such that is a free abelian group.

     

Towards the Discrimination of Carboxylates by Hydrogen‐Bond Donor Anion Receptors

The binding constants (log K_ass) of small synthetic receptor molecules based on indolocarbazole, carbazole, indole, urea and some others, as well as their combinations were measured for small carboxylate anions of different basicity, hydrophilicity and steric demands, that is, trimethylacetate, acetate, benzoate and lactate, in 0.5 % H₂O/[D₆]DMSO by using the relative NMR‐based measurement method. As a result, four separate binding affinity scales (ladders) including thirty‐eight receptors were obtained with the scales anchored to indolocarbazole. The results indicate that the binding strength is largely, but not fully, determined by the strength of the primary hydrogen‐bonding interaction. The latter in turn is largely determined by the basicity of the anion. The higher is the basicity of the anion the stronger in general is the binding, leading to the approximate order of increasing binding strength, lactate<benzoate<acetate≤trimethylacetate, which holds with all investigated receptors. Nevertheless, there are a number of occasions when the binding order changes with changing of the carboxylate anion, sometimes quite substantially. Principal component analysis (PCA) reveals that this is primarily connected to preferential binding of trimethylacetate, supposedly caused by an additional hydrophobic/solvophobic interaction. These findings enable making better predictions, which receptor framework or cavity is best suited for carboxylate anions in receptor design.     

Photophysical properties of binuclear ruthenium(ii) bis(2,2':6',2'-terpyridine) complexes built around a central 2,2'-bipyrimidine receptor

A binuclear complex has been synthesized having ruthenium(ii) bis(2,2':6',2'-terpyridine) terminals attached to a central 2,2'-bipyrimidine unit via ethynylene groups. Cyclic voltammetry indicates that the substituted terpyridine is the most easily reduced subunit and the main chromophore involves charge transfer from the metal centre to this ligand. The resultant metal-to-ligand, charge-transfer (MLCT) triplet state is weakly emissive and has a lifetime of 60 ns in deoxygenated solution at room temperature. The luminescence yield and lifetime increase with decreasing temperature in a manner that indicates the lowest-energy MLCT triplet couples to at least two higher-energy triplets. Cations can bind to the central bipyrimidine unit, forming both 1:1 and 1:2 (ligand:metal) complexes as confirmed by electrospray MS analysis. The photophysical properties depend on the number of bound cations and on the nature of the cation. In the specific case of binding zinc(ii) cations, the 1:1 complex has a triplet lifetime of 8.0 ns while that of the 1:2 complex is 1.8 ns. The 1:1 complexes formed with Ba(2+) and Mg(2+) are more luminescent than is the parent compound while the 1:2 complexes are much less luminescent. It is shown that the coordinated cations raise the reduction potential of the central bipyrimidine unit and thereby increase the activation energy for coupling with the metal-centred state. Complexation also introduces a non-emissive intramolecular charge-transfer (ICT) state that couples to the lowest-energy MLCT triplet and provides an additional non-radiative decay route. The triplet state of the 1:2 complex formed with added Zn(2+) cations decays preferentially via this ICT state.     

Characterization of cetuximab Fc/2 dimers by off-line CZE-MS

Monoclonal antibody (mAb) therapeutics attract the largest concern due to their strong therapeutic potency and specificity. The Fc region of mAbs is common to many new biotherapeutics as biosimilar, antibody drug conjugate or fusion protein. Fc region has consequences for Fc-mediated effector functions that might be desirable for therapeutic applications. As a consequence, there is a continuous need for improvement of analytical methods to enable fast and accurate characterization of biotherapeutics. Capillary zone electrophoresis-Mass spectrometry couplings (CZE-MS) appear really attractive methods for the characterization of biological samples. In this report, we used CZE-MS systems developed in house and native MS infusion to allow precise middle-up characterization of F_c/2 variant of cetuximab. Molecular weights were measured for three F_c/2 charge variants detected in the CZE separation of cetuximab subunits. Two F_c/2 C-terminal lysine variants were identified and separated. As the aim is to understand the presence of three peaks in the CZE separation for two F_c/2 subunits, we developed a strategy using CZE-UV/MALDI-MS and CZE-UV/ESI-MS to evaluate the role of N-glycosylation and C-terminal lysine truncation on the CZE separation. The chemical structure of N-glycosylation expressed on the Fc region of cetuximab does not influence CZE separation while C-terminal lysine is significantly influencing separation. In addition, native MS infusion demonstrated the characterization of F_c/2 dimers at pH 5.7 and 6.8 and the first separation of these dimers using CZE-MS.     

Catalytic Effect of Cesium Cation Adduct Formation on the Decarboxylation of Carboxylate Ions in the Gas Phase

The effect of Cs⁺ ligation on the decarboxylation of malonic acids (unsubstituted and methyl‐, dimethyl‐, ethyl‐, and phenyl‐substituted) in their carboxylate form was studied in the gas phase using tandem mass spectrometry. The study is based on the comparison of the decarboxylation of the bare monoanion (hydrogen malonates) and of the cesium adduct of the cesium salt (Cs⁺[cesium hydrogen malonates]) under collisional activation. Energy‐resolved dissociation curves of the negative and positive ions exhibit major differences. Decarboxylation of the cationic adducts of substituted malonic acid salts occurs at significantly lower collisional activation than for the corresponding bare hydrogen malonate anions. The conclusions from these experiments are supported by DFT calculations. The calculated activation parameters (enthalpy and Gibbs energy) confirm that the cesium cation coordination assists the decarboxylation of the carboxylate form.     

An efficient convergent synthesis of novel anisotropic adsorbates based on nanometer-sized and tripod-shaped oligophenylenes end-capped with triallylsilyl groups

This article describes an efficient and convergent synthesis of a novel tripod-shaped oligophenylene compound. The compound consists of three oligophenylene heptamers as the tripod legs and one bromophenyl group as the functional arm, joining at a tetrahedron silicon atom. Each tripod leg is end-capped with a triallylsilyl group for covalently anchoring the molecules on hydrogen-terminated silicon surfaces via hydrosilylation. The compound may represent a new type of anisotropic adsorbates for controlling the orientation of and spacing between functional groups in organic thin films and nanostructures grown on silicon surfaces. An oligophenylene hexamer end-capped with a triallylsilyl group and a pinacol arylboronate group was readily derived from diiodoterphenyl with a bromophenyl boronic acid by selective Suzuki coupling. Reaction conditions for highly selective Suzuki coupling of sterically hindered pinacol boronate with aryl iodide in the presence of multiple ethenyl groups for the competing Heck reaction were developed. Under the optimal conditions (Pd(PPh3)4/KOH/Bu4NBr/toluene/H2O, 85 degrees C, overnight), p-bromophenyl-tris(p-iodo-phenyl)silane reacted with 3 equiv of the hexaphenylene boronate to provide the tripod-shaped oligophenylene, composed of 22 phenylene and 9 allyl groups, in 78% yield.     

Gas counter for low temperature Conversion Electron M?ssbauer Spectroscopy experiments

The operation of a gas counter, designed for Conversion Electron M?ssbauer Spectroscopy measurement at low temperature, has been investigated. The experimental setup is described and tested with two pure gases, He and Ne, and two mixtures, He-5%CH₄ and He-5%N₂. The impacts on the counter performances of the applied voltage, the gas composition and pressure as well as the gas renewing are investigated between 41?K and 300?K. This investigation is made using ¹¹⁹Sn M?ssbauer source and metallic tin absorber. The appropriate operating conditions of the present counter have been established for temperatures down to 41?K for both pure gases, and 61 and 85?K for He-5%N₂ and He-5%CH₄ respectively.