LC/ESI-MS n and 1H HR-MAS NMR analytical methods as useful taxonomical tools within the genus Cystoseira C. Agardh (Fucales; Phaeophyceae)

Species of the genus Cystoseira are particularly hard to discriminate, due to the complexity of their morphology, which can be influenced by their phenological state and ecological parameters. Our study emphasized on the relevance of two kinds of analytical tools, (1) LC/ESI-MSⁿ and (2) ¹H HR-MAS NMR, also called in vivo NMR, to identify Cystoseira specimens at the specific level and discuss their taxonomy. For these analyses, samples were collected at several locations in Brittany (France), where Cystoseira baccata, C. foeniculacea, C. humilis, C. nodicaulis and C. tamariscifolia were previously reported. To validate our chemical procedure, the sequence of the ITS2 has been obtained for each species to investigate their phylogenetic relationships at a molecular level. Our study highlighted the consistency of the two physico-chemical methods, compared to “classical” molecular approach, in studying taxonomy within the genus Cystoseira. Especially, LC/ESI-MSⁿ and phylogenetic analyses converged into the discrimination of two taxonomical groups among the 5 species. The occurrence of some specific signals in the ¹H HR-MAS NMR spectra and/or some characteristic chemical compounds during LC/ESI-MSⁿ analysis could be regarded as discriminating factors. LC/ESI-MSⁿ and ¹H HR-MAS NMR turned out to be two relevant and innovative techniques to discriminate taxonomically this complex genus.     

Ionic liquid salt bridge based on tributyl(2-methoxyethyl)phosphonium bis(pentafluoroethanesulfonyl)amide for stable liquid junction potentials in highly diluted aqueous electrolyte solutions

A moderately hydrophobic ionic liquid, tributyl(2-methoxyethyl)phosphonium bis(pentafluoroethanesulfonyl)amide ([TBMOEP⁺][C₂C₂N⁻]), shows a very stable liquid junction potential upon contact with an aqueous solution whose ionic strength is as low as 1 μmol dm⁻³. The stability with the maximum excursion of the potential within ±0.5 mV for 30 min is very promising for accurate determination of pH and other single ion activities potentiometrically.     

Elucidation of triacylglycerols in cod liver oil by liquid chromatography electrospray tandem ion-trap mass spectrometry

Though liquid chromatography electrospray tandem mass spectrometry (LC-ESI-MS²) has been widely used in the structural elucidation of triacylglycerols (TAG) in vegetable oils, its potentiality for the identification of TAG molecules in omega-3 rich oils remains unexplored till date. Hence, this article investigates the applicability of LC-ESI-MS² for the structural characterization of naturally occurring TAG in cod liver oil without the TAG fractionation during the sample preparation. A computational algorithm was developed to automatically interpret the mass spectra and elucidate the TAG structures respectively. The results were compared against the lipase benchmark method. A principal component analysis study revealed that it is possible to discriminate genuine from adulterated cod liver oil.     

Preparation of a new 1,3-alternate-calix[4]arene-bonded HPLC stationary phase for the separation of phenols, aromatic amines and drugs

We have synthesized the 1,3-alternate 25,27-dioctyloxy-26,28-bis-[3-aminopropyloxy]-calix[4]arene and then immobilized onto γ-chloropropylsilica gel (CPS). The high-performance liquid chromatographic behavior of some aromatic hydrocarbons, phenolic compounds, aromatic amines and drug compounds was studied on this 1,3-alternate-calix[4]arene-bonded silica gel stationary phase (CIMS). The effect of organic modifier content and pH of the mobile phase on retention and selectivity of these compounds were investigated. According to chromatographic data, it can be concluded that the selectivity of CIMS for analytes ascribes to various interactions between CIMS and the analytes, such as hydrophobic interaction, hydrogen bonding interaction, π-π interaction and inclusion interaction.     

Visual detection of melamine in milk products by label-free gold nanoparticles

A simple, rapid, field-portable colorimetric method for the detection of melamine based on melamine-induced color change of label-free gold nanoparticles (Au NPs) was developed in this study. Melamine can induced the aggregation of Au NPs and results in the color change from wine-red to purple, which provided a platform for rapid and field-portable colorimetric detection of melamine. The proposed method can be used to detect melamine in liquid milk and infant formula with a detection limit of 1.0 and 4.2 ppm, respectively, within 30 min by naked eyes observation without the aid of any advanced instrument and the need of any complex pretreatment, and detect as low as 0.15 ppm of melamine in liquid milk and 2.5 ppm of melamine in infant formula with UV-vis-spectroscopy. The proposed method is promising for on-site screening of melamine adulterant in milk products.     

Characterisation of commercially available linear alkylbenzenesulfonates by LC-SPE-NMR/MS (liquid chromatography-solid phase extraction-nuclear magnetic resonance spectroscopy-mass spectroscopy)

Commercially available linear alkylbenzenesulfonates (LASs) are a mixture of various homologues and isomers, leading to 20 major species. In this work we investigated the commercial product by liquid chromatography-solid phase extraction-nuclear magnetic resonance spectroscopy-mass spectrometry (LC-SPE-NMR/MS). The commercial product was separated into 17 fractions by liquid chromatography (LC). After chromatographic separation, 5% of the flow was split to a mass spectrometer (MS) while 95% was send to post-column solid phase extraction cartridges for enrichment of the analytes (LC-SPE). After elution from the SPE-cartridges a NMR-spectrometer equipped with a cryo-probe was used for the characterisation of the different LASs species. For the first time ¹H-1D and H-H-COSY spectra for 14 LASs species out of 20 major isomers are presented, whereas the 6 remaining species are detected as mixtures in 3 ¹H-1D and H-H-COSY spectra. These data were used to correlate the chromatographic retention of the LASs isomers to the substitution pattern of the alkyl chain.     

High Tg nematic thermosets: Synthesis, characterization and thermo-mechanical properties

In this paper the synthesis and characterization of a new family reactive nematic oligomers based on 4-hydroxybenzoic acid (4-HBA) will be presented. We modified the backbone using para- and meta-substituted aromatic monomers such as terephthalic acid (TA), isophthalic acid (IA), hydroquinone (HQ), resorcinol (RS), 4,4′-bisphenol (BP) and 3-hydroxybenzoic acid (3-HBA). All oligomers, with a target M_n of 5000 and 9000 g mol⁻¹, were end-capped with reactive phenylethynyl functionalities and synthesized using standard melt condensation techniques. Curing of the phenylethynyl reactive functionalities proceeds through chain extension and crosslinking, depending upon the temperature and time and can be carried out between 310 and 400 °C. Fully cured nematic thermosets could be obtained with glass-transition temperatures previously not accessible (T_g > 400 °C). The cured polymers exhibit excellent tensile properties, i.e. tensile strength (83 MPa) and elongation at break (9%). This approach allows us to prepare all-aromatic polymers with a combination of useful properties such as ease of processing, high T_g’s, and excellent mechanical properties.     

Non-covalent dendrimer-based liquid crystalline complexes: Synthesis and characterization

The synthesis and structural characterization of dendritic macromolecules based on 3,5-dihydroxybenzoic acid are described. The molecular structures and purity of all new compounds were confirmed by ¹H NMR, ¹³C NMR spectroscopy and elemental analysis. The dendritic non-covalent liquid crystalline complexes were prepared through the formation of hydrogen bonds between different generation of dendritic acids (proton donor) and stilbazole derivative containing bipyridyl units (proton acceptor). We found that, the hydrogen-bonded dendritic liquid crystals supramolecules (G1-2py, G2-2py and G3-2py) exhibits nematic and semectic phase. The polarizing optical microscopy (POM) and differential scanning calorimetry (DSC) were used for investigation of the liquid crystalline properties of the hydrogen-bonded dendritic supramolecular complexes.     

Development of a Xanthine Oxidase Modified Amperometric Electrode for the Determination of the Antioxidant Capacity

This paper describes the development of a xanthine oxidase/poly‐m‐phenylenediamine (XOD‐PPD)‐modified electrode. The biosensor was constructed by encapsulating XOD in a sol‐gel matrix deposited onto a platinum based screen‐printed electrode functionalized with a permselective PPD membrane. The hydrogen peroxide generated as a final product of the enzymatic reaction between the hypoxanthine and the XOD or by the spontaneous dismutation of superoxide radicals was selectively monitored at +700 mV. The use of a highly selective PPD layer blocked the nonspecific oxidation of other oxidizable molecules. Finally the biosensor was applied to the determination of the antioxidant capacity of acetylsalicylic acid.     

Sensitive Determination of Water Insoluble Dyes Used as Marking of Commercial Petroleum Products Using High‐Performance Liquid Chromatography with Electrochemical Detection

This paper describes an analytical method using high‐performance liquid chromatographic (HPLC) separation coupled with electrochemical detection to detect three dyes, Solvent Blue 14 (SB‐14), Solvent Blue 35 (SB‐35) and Solvent Red 24 (SR‐24). The dyes were eluted and separated using a reversed‐phase column (C‐8) under isocratic elution with the mobile phase containing a mixture of acetonitrile/ammonium acetate (5.0 mmol L^?1) at the ratio of 75 : 25 (v/v). Two sample pretreatment methods were tested and successfully applied to quantify SB14, SB‐35 and SR‐24 dyes in gasoline samples. The proposed method was simple, fast and suitable to detect and quantify marker dyes in gasoline sample at low concentration.