Normal-phase high-performance liquid chromatographic separations using ethoxynonafluorobutane as hexane alternative. II. Liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry applications with methanol gradients

We have reported recently that high-speed normal-phase (NP) HPLC separations of a broad range of organic compounds can be performed on cyano columns using gradients of methanol in hexane-like solvent-ethoxynonafluorobutane (ENFB), available commercially. In this communication, we demonstrate that atmospheric pressure chemical ionization (APCI) in combination with mass spectrometry (MS) can be effectively used for detection in such separations. The efficiency of APCI under conditions studied has also been compared to the efficiency of traditional electrospray ionization (ESI) in combination with MS for reversed-phase (RP) HPLC of the same compounds. The compounds included in this study were steroids, benzodiazepines, and other central nervous system-active substances, nonsteroidal anti-inflammatory drugs, tricyclic antidepressants, and beta-adrenergic blocking agents. Non-polar compounds were found to respond stronger when APCI-MS technique was used, whereas APCI and ESI ionization efficiencies were comparable when polar substances were studied. The combination of normal-phase HPLC separation conditions with mass spectral detection may expand the range of LC-MS applications traditionally associated with reversed-phase HPLC and ESI-MS detection.     

Determination of trace rhodium by supramolecular catalytic kinetic spectrofluorimetry of β-CD-rhodium-KBrO3-vanillin salicylhydrazone

A sensitive catalytic kinetic spectrofluorimetric approach for determining ng mL⁻¹ levels of rhodium is presented, and the possible mechanism of the catalytic reaction was investigated. The determination is based on the catalytic property of rhodium to enhance the reaction of o-vanillin salicylhydrazone (OVSH) with potassium bromate in a water-ethanol medium at pH 4.80 and 45 °C. The presence of β-cyclodextrin (β-CD) obviously sensitized the assay due to its high inclusion ability towards OVSH. Under optimized experimental conditions, fluorescence measurements of the β-CD-rhodium-KBrO₃-OVSH catalytic kinetic reaction system were carried out in its fluorescent band centered at λ_ex = 333 nm and λ_em = 476 nm, respectively. The calibration graph was linear over the concentration range of 0.47–100 ng mL⁻¹ with a detection limit of 0.14 ng mL⁻¹. The effect of interferences was discussed, and the results show that the extraction method can be used to separate rhodium from interference species such as iridium. The proposed method, applied to several synthetic mixtures containing rhodium mixed with varying amounts of metal salts, produced satisfactory results.     

Silver (I)-promoted asymmetric halohydrin reaction of chiral N-enoyl-2-oxazolidinones: scope and limitations

The halohydrin reaction of chiral N-enoyl-2-oxazolidinones 1 by halogen (Br₂/I₂) and water were efficiently carried out in aqueous organic solvent promoted by silver(I) with high anti- and regioselectivity and moderate to good diastereoselectivities. The alkenoyl, cinnamoyl and electron-deficient cinnamoyl substrates smoothly underwent bromohydrin reaction in aqueous acetone but no iodohydrin reaction, where as electron-rich cinnamoyl substrates preferred to undergo iodohydrin reaction in aqueous acetone with moderate diastereoselectivity and enhanced diastereoselectivity was observed in aqueous THF.     

Hydrolytic and transglycosylation reactions of N-acyl modified substrates catalysed by β-N-acetylhexosaminidases

The hydrolytic and transglycosylation capabilities of 35 fungal β-N-acetylhexosaminidases with p-nitrophenyl 2-amino-2-deoxy-β-d-glucopyranoside and its four N-acyl derivatives (CHO, COCH₂OH, COCH₂CH₃, COCF₃) as substrates were tested. The preparation of four novel p-nitrophenyl disaccharides from these unnatural substrates catalysed by enzymes from Aspergillus oryzae, Penicillium oxalicum and Talaromyces flavus represents a considerable extension of the synthetic potential of glycosidases.     

Synthesis of cyclopentane building blocks via an intramolecular CH insertion reaction of a chiral pool derived α-diazo-γ-hydroxy-β-ketosulfone

A highly functionalized cyclopentanone building block 13 was prepared by a facile Rh-catalyzed intramolecular CH insertion reaction of an enantiopure α-diazo-γ-hydroxy-β-ketosulfone 12, in turn derived from an α-hydroxy acid 2. A cyclic γ-hydroxy vinyl sulfone 16 was also prepared from 13.     

A simple and efficient one-step, regioselective, enzymatic glucosylation of arbutin by α-glucosidase

4-Hydroxyphenyl-β-isomaltoside has been synthesized by α-glucosidase assisted transglycosylation between arbutin as acceptor and sucrose as donor molecules, respectively. Optimum conditions for the transglucosylation reaction were 40 °C for 20 h with 10 mM arbutin and 1.5 M sucrose in a 100 mM sodium citrate/phosphate buffer at pH 5.0. The new glucoside was obtained in a 50% molar yield with respect to arbutin.     

Probing in vitro digestion at oil–water interfaces

Interfacial layers have been widely applied to study the formation and stability of emulsion-based systems. However, the application of isolated interfaces to address digestibility of emulsions is often limited because of the complexity of experimental methods and results. This review summarizes the latest developments in analytical methods and literature data on effects of digestion on interfacial layers. Particular emphasis is given to understand the changes on interfacial magnitudes during oral, gastric, and duodenal digestion, either applied separately or sequentially. Limitations of interfacial aspects and key factors that influence emulsion microstructure in bulk and lipid digestion are identified. Understanding the behavior of interfacial layers upon gastrointestinal digestion promotes an accurate tracking of the physiological fate of emulsions.     

A DFT study of lithium battery materials: application to the β-VOXO4 systems (X=P, As, S)

VOXO₄ systems have been considered as potential lithium battery electrodes. They mainly present two distinct structural types: the tetragonal “α” type with a two-dimensional framework, and the three-dimensional orthorhombic “β”. DFT calculations were performed on this latter system for several β-Li_xVOXO₄ compounds (x=0, 1; X=P, As, S). They allowed to propose structural models for VOAsO₄ and LiVOSO₄, not fully crystallographically well described yet. Based on an experimental model of two-phase processes, these calculations led also to a good simulation of electrochemical potential values. A density of states analysis put in evidence the “inductive effect” and the role played by (XO₄)ⁿ⁻ groups inside the host frameworks on these potentials.     

Stereoselective synthesis of (Z)-γ-cyano-β-perfluoroalkyl-β,γ-unsaturated esters

(Z)-γ-Cyano-β-perfluoroalkyl-β,γ-unsaturated esters have been synthesized by the reaction of perfluoroacylated phosphonates with organozinc reagent in 50-71% (three steps) yields.     

Molecule-Responsive Fluorescent Sensors of α-Helix Peptides Bearing α-Cyclodextrin, Pyrene and Nitrobenzene Units in Their Side Chains

-Helix peptides bearing one unit of -cyclodextrin (-CD), one unit of pyrene and one unit of nitrobenzene (NB) in their side chains have been designed and synthesized as novel molecule-responsive devices.In both the CD-peptides, -PR17 and -PL17, the NB unit is separated from the CD unit by two turns of the helix. Two reference peptides (PL17, and -P17,) have also been synthesized. The circular dichroism studies in the peptide absorption region (200–250 nm)of -PR17 and -PL17 suggestthat the CD-peptides form stable-helixstructures (83–77%), which was destabilized by accommodating guest molecules (e.g., n-pentanol) into the CD cavity. It suggests that formation of intramolecular host–guest(CD–NB) complex stabilized thehelical structure and exogenous guest molecule excluded the appending NB moiety from inside to outside of the CD cavity, thereby causing destabilization of the helical structure and increasing the random coil content. The ICD spectra of the peptides in the pyrene and nitrobenzene absorption region (250–40 nm) suggest that NB forms inclusion complex with CD. The fluorescence studies revealed that the fluorescence of the pyrene unit is quenched by the NB unit in -PR17 and -PL17. The fluorescence intensity increases with increasing guest concentration for the CD-peptides.This guest-responsiveenhancement in the fluorescence intensity can be explained in terms of increased distance between the pyrene and NB moieties, which is caused by exclusion of the NB moiety from the CD cavity by guest accommodation. Using the guest-responsive fluorescence quenching properties of the CD-peptides, we have obtained binding constants for various short chain alkanols. -PL17 has higher binding affinity to the guest molecules than its isomer, -PR17, indicating that the location of functional groups on the peptide scaffold is important in molecule detection.