Reversed-phase liquid chromatography and argentation chromatography of the minor capsaicinoids

An investigation of the liquid chromatography of the minor capsaicinoids in a commercial capsaicinoid mixture is reported. Twelve stationary phases including C₈, C₁₈, C₃₀, phenyl, and cation-exchange chemistries were examined in combination with isocratic aqueous methanol and aqueous acetonitrile mobile phases. A phenyl stationary phase and aqueous acetonitrile mobile phase baseline-resolved 7 of 11 capsaicinoids, and selected ion chromatograms (LC–ESI-MS) demonstrated this was the most effective reversed-phase separation. Argentation chromatography with an alkyl or phenyl column and aqueous silver nitrate–methanol mobile phase revealed the presence of the 6-ene-8-methyl and 6-ene-9-methyl homocapsaicin isomers and the absence of 7-ene-9-methyl homocapsaicin. A mixed phenyl–cation-exchange stationary phase (charged with silver ion) enabled unique and useful separations of the capsaicinoids.     

Cholesteric liquid crystal displays as optical sensors of barbiturate binding

The influence on the optical properties of cholesteric liquid crystal displays (LCDs) was examined for neutral molecule binding by mesogen/receptors in the mesomorphic phase. The motivation was to prepare neutral molecule sensors that use a colour change to signal analyte binding. A receptor that binds barbiturate analytes was modified with two or one cholesteryl groups to yield compounds 2 and 3, respectively. LCDs were prepared by incorporating one of the receptor/mesogen compounds into a cholesteric LC blend along with a potential H‐bonding guest. The optical properties of the LCDs were then determined by measuring the absorbance of the displays. For various LCDs, the colour of the display depended upon several factors: the amount of guest molecule used, the number of cholesteryl side chains on the receptor and the mole concentration of receptor/mesogen in the blend. In particular, complementary host/guest binding of H‐bonding analytes by the bis(cholesteryl) receptor 2 in a cholesteric LCD caused a change of up to +70 nm, which was observed by the naked eye as a blue‐to‐orange colour change. Control experiments confirm that the colour of an LCD is a consequence of molecular recognition in the mesomorphic phase.     

Chip-based nLC-TOF-MS is a highly stable technology for large-scale high-throughput analyses

Many studies focused on the discovery of novel biomarkers for the diagnosis and treatment of disease states are facilitated by mass spectrometry-based technology. HPLC coupled to mass spectrometry is widely used; miniaturization of this technique using nano-liquid chromatography (LC)-mass spectrometry (MS) usually results in better sensitivity, but is associated with limited repeatability. The recent introduction of chip-based technology has significantly improved the stability of nano-LC-MS, but no substantial studies to verify this have been performed. To evaluate the temporal repeatability of chip-based nano-LC-MS analyses, N-glycans released from a serum sample were repeatedly analyzed using nLC-PGC-chip-TOF-MS on three non-consecutive days. With an average inter-day coefficient of variation of 4 %, determined on log₁₀-transformed integrals, the repeatability of the system is very high. Overall, chip-based nano-LC-MS appears to be a highly stable technology, which is suitable for the profiling of large numbers of clinical samples for biomarker discovery.     

Bipolar Electrochemistry

A bipolar electrode (BPE) is an electrically conductive material that promotes electrochemical reactions at its extremities (poles) even in the absence of a direct ohmic contact. More specifically, when sufficient voltage is applied to an electrolyte solution in which a BPE is immersed, the potential difference between the BPE and the solution drives oxidation and reduction reactions. Because no direct electrical connection is required to activate redox reactions, large arrays of electrodes can be controlled with just a single DC power supply or even a battery. The wireless aspect of BPEs also makes it possible to electrosynthesize and screen novel materials for a wide variety of applications. Finally, bipolar electrochemistry enables mobile electrodes, dubbed microswimmers, that are able to move freely in solution.     

Efficient alkyne homocoupling catalysed by copper immobilized on functionalized silica

Copper immobilized on a functionalized silica support is a good catalyst for the homocoupling of terminal alkynes. The so‐called Glaser–Hay coupling reaction can be run in air with catalytic amounts of base. The copper catalyst is active for multiple substituted alkynes, in both polar and non‐polar solvents, with good to excellent yields (75–95%). Depending on the alkyne, full conversion can be achieved within 3–24 h. The catalyst was characterized by TGA, inductively coupled plasma and X‐ray photoelectron spectroscopy. Leaching tests confirm that the catalyst is and remains heterogeneous. Importantly, the overall reaction requires only alkyne and oxygen (in this case, air) as reagents, making this a clean catalytic oxidative coupling reaction. Copyright © 2012 John Wiley & Sons, Ltd.     

Recognizing and overcoming analytical error in the use of ICP-MS for the determination of cadmium in breakfast cereal and dietary supplements

The potential effect of spectral interference on the accurate measurement of the cadmium (Cd) mass fraction in fortified breakfast cereal and a variety of dietary supplement materials using inductively coupled plasma quadrupole mass spectrometry was studied. The materials were two new standard reference materials (SRMs)—SRM 3233 Fortified Breakfast Cereal and SRM 3532 Calcium Dietary Supplement—as well as several existing materials—SRM 3258 Bitter Orange Fruit, SRM 3259 Bitter Orange Extract, SRM 3260 Bitter Orange-containing Solid Oral Dosage Form, and SRM 3280 Multivitamin/Multielement Tablets. Samples were prepared for analysis using the method of isotope dilution and measured using various operating and sample introduction configurations including standard mode, collision cell with kinetic energy discrimination mode, and standard mode with sample introduction via a desolvating nebulizer system. Three isotope pairs, ¹¹²Cd/¹¹¹Cd, ¹¹³Cd/¹¹¹Cd, and ¹¹⁴Cd/¹¹¹Cd, were measured. Cadmium mass fraction results for the unseparated samples of each material, measured using the three instrument configurations and isotope pairs, were compared to the results obtained after the matrix was removed via chemical separation using anion exchange chromatography. In four of the six materials studied, measurements using the standard mode with sample introduction via the desolvating nebulizer gave results for the unseparated samples quantified with the ¹¹²Cd/¹¹¹Cd isotope pair that showed a positive bias relative to the matrix-separated samples, which indicated a persistent inference at m/z?112 with this configuration. Use of the standard mode, without the desolvating nebulizer, also gave results that showed a positive bias for the unseparated samples quantified with the ¹¹²Cd/¹¹¹Cd isotope pair in three of the materials studied. Collision cell/kinetic energy discrimination mode, however, was very effective for reducing spectral interference for Cd in all of the materials and isotope pairs studied, except in the multivitamin/multielement matrix (SRM 3280) where the large corrections for known isobaric interferences or unidentified interferences compromised the accuracy. For SRM 3280, matrix separation provided the best method to achieve accurate measurement of Cd.     

Amidrazones 9. Convenient Syntheses of 1-Alkyl-1-Phenylhydrazines and α,β-Unsaturated Amidrazones Via Base-Promoted Reactions of 1,1-Disubstituted-3-Amino-4,5-Dihydro-1H-Pyrazolium Salts

A simple, efficient procedure for the conversion of phenylhydrazine to 1-alkyl-1-phenylhydrazines via base-promoted hydrolysis of 1-alkyl-3-amino-4,5-dihydro-1-phenyl-1H-pyrazolium iodides (2) is described. N¹, N¹-disubstituted hydrazones of trans-cinnamamide and acrylamide are obtained by Hofmann-type ring openings of 1,1 -disubstituted-3-amino-4,5-dihydro-5-phenyl (or 5-unsubstituted) -1H-pyrazolium halides (5, 7).     

Identification of Intermediates in Zeolite‐Catalyzed Reactions by In Situ UV/Vis Microspectroscopy and a Complementary Set of Molecular Simulations

The optical absorption properties of (poly)aromatic hydrocarbons occluded in a nanoporous environment were investigated by theoretical and experimental methods. The carbonaceous species are an essential part of a working catalyst for the methanol‐to‐olefins (MTO) process. In situ UV/Vis microscopy measurements on methanol conversion over the acidic solid catalysts H‐SAPO‐34 and H‐SSZ‐13 revealed the growth of various broad absorption bands around 400, 480, and 580 nm. The cationic nature of the involved species was determined by interaction of ammonia with the methanol‐treated samples. To determine which organic species contribute to the various bands, a systematic series of aromatics was analyzed by means of time‐dependent density functional theory (TDDFT) calculations. Static gas‐phase simulations revealed the influence of structurally different hydrocarbons on the absorption spectra, whereas the influence of the zeolitic framework was examined by using supramolecular models within a quantum mechanics/molecular mechanics framework. To fully understand the origin of the main absorption peaks, a molecular dynamics (MD) study on the organic species trapped in the inorganic host was essential. During such simulation the flexibility is fully taken into account and the effect on the UV/Vis spectra is determined by performing TDDFT calculations on various snapshots of the MD run. This procedure allows an energy absorption scale to be provided and the various absorption bands determined from in situ UV/Vis spectra to be assigned to structurally different species.     

Interactions between apolar,basic and acidic model oils and a calcite surface

Abstract

In this study, the atomic force microscopy colloidal probe technique was employed to investigate the interaction between apolar, basic and acidic model oil probes and a calcite surface in solutions containing different concentrations of NaCl, CaCl₂ and Na₂SO₄. In the presence of SO₄^2?, hydration and structural forces were observed between apolar model oil probes and a calcite surface on approach. Relatively low adhesion forces were observed between the basic model oil probes and the calcite surface, while higher adhesion forces were observed between the acidic model oil probes and the calcite surface. Furthermore, the adhesion forces between the basic model oil probes and the calcite surface significantly increased in the presence of SO₄^2?, while the adhesion force between the acidic model oil probes and the calcite surface decreased in the presence of Ca²⁺ or SO₄^2?. The differences in the adhesion forces are related to electrostatic attraction and ion bridging forces between the model oil probes and the calcite surface.