Micellar and microemulsion electrokinetic chromatography of hop bitter acids

The elution order of the hop α- and β-acids has been studied under different modes of electrokinetic separation. A model is advanced to explain the shorter migration times of the more hydrophobic β-acids compared to the α-acids in micellar electrokinetic chromatography (MEKC). For quality control of the bitter principles in hops, the ruggedness of electrokinetic separation could be improved by replacing MEKC by microemulsion electrokinetic chromatography (MEEKC).     

IR multiphoton dissociation of CF3I. Pressure effect with inert and reactive gases

The IR multiphoton dissociation of CF₃I has been studied in the presence of isobutane and with isobutane and Ar and CO₂ as inert gases. The dependence of the reaction probability P(Φ) with fluence (ϕ) is confirmed. Modeling of the experimental results shows that for the energy transfer processes the average energy transferred per collision 〈†E〉_d varies with (ϕ).     

High performance liquid chromatography analysis of wine anthocyanins revisited: Effect of particle size and temperature

The complex anthocyanin fraction of red wines poses a demanding analytical challenge. We have found that anthocyanins are characterised by extremely low optimal chromatographic velocities, and as a consequence generic HPLC methods suffer from limited resolving power. Slow on-column inter-conversion reactions, particularly between carbinol and flavylium species, are shown to occur on the same time scale as chromatographic separation, leading to increased plate heights at normal chromatographic velocities. In order to improve current routine HPLC separations, the use of small (1.7 μm) particles and high temperature liquid chromatography (HTLC) were investigated. 1.7 μm particles provide better efficiency and higher optimal linear velocities, although column lengths of ∼20 cm should be used to avoid the detrimental effects of conversion reactions. More importantly, operation at temperatures up to 50 °C increases the kinetics of inter-conversion reactions, and implies significantly improved efficiency under relatively mild analysis conditions. It is further demonstrated using relevant kinetic data that no on-column thermal degradation of these thermally labile compounds is observed at 50 °C and analysis times of <2 h.     

Regioisomeric analysis of triacylglycerols using silver-ion liquid chromatography-atmospheric pressure chemical ionization mass spectrometry: comparison of five different mass analyzers

Silver-ion high-performance liquid chromatography (HPLC) coupled to atmospheric pressure chemical ionization mass spectrometry (APCI-MS) is used for the regioisomeric analysis of triacylglycerols (TGs). Standard mixtures of TG regioisomers are prepared by the randomization reaction from 8 mono-acid TG standards (tripalmitin, tristearin, triarachidin, triolein, trielaidin, trilinolein, trilinolenin and tri-gamma-linolenin). In total, 32 different regioisomeric doublets and 11 triplets are synthesized, separated by silver-ion HPLC using three serial coupled chromatographic columns giving a total length of 75cm. The retention of TGs increases strongly with the double bond (DB) number and slightly for regioisomers having more DBs in sn-1/3 positions. DB positional isomers (linolenic vs. γ-linolenic acids) are also separated and their reverse retention order in two different mobile phases is demonstrated. APCI mass spectra of all separated regioisomers are measured on five different mass spectrometers: single quadrupole LC/MSD (Agilent Technologies), triple quadrupole API 3000 (AB SCIEX), ion trap Esquire 3000 (Bruker Daltonics), quadrupole time-of-flight micrOTOF-Q (Bruker Daltonics) and LTQ Orbitrap XL (Thermo Fisher Scientific). The effect of different types of mass analyzer on the ratio of [M+H-R(i)COOH](+) fragment ions in APCI mass spectra is lower compared to the effect of the number of DBs, their position on the acyl chain and the regiospecific distribution of acyl chains on the glycerol skeleton. Presented data on [M+H-R(i)COOH](+) ratios measured on five different mass analyzers can be used for the direct regioisomeric determination in natural and biological samples.     

High-efficiency hydrophilic interaction chromatography by coupling 25 cm × 4.6 mm ID × 5 μm silica columns and operation at 80 °C

Recently, hydrophilic interaction chromatography (HILIC) has emerged as a valuable orthogonal tool to reversed-phase liquid chromatography (RP-LC) as it allows for resolution of highly polar ionisable compounds. The relationships between separation efficiency, column length and speed of analysis for 4.6 mm ID × 5 μm silica particle columns in HILIC are demonstrated using kinetic plots. The kinetic plots constructed for conventional pressure systems operating at 350 bar and at 30 °C and 80 °C are confirmed using experimental data for different column lengths. Efficiencies of more than 130,000 theoretical plates could be achieved by connecting up to six columns of 25 cm. As expected, a significant gain in analysis speed without loss of efficiency could be obtained by operating at 80 °C compared to 30 °C. The advantages of using long columns in HILIC in combination with elevated column temperature for the pharmaceutical industry are illustrated using test mixtures comprised of commercially available ionisable compounds (including some containing functional groups with potential genotoxic typical structural alerts) as well as real polar ionisable pharmaceuticals.     

Enhanced detonation sensitivities of silicon analogs of PETN: reaction force analysis and the role of σ–hole interactions

Si-pentaerythritol tetranitrate (PETN), Si[CH₂ONO₂]₄, is a silicon analog of the widely used explosive PETN, C[CH₂ONO₂]₄. Si-PETN is extremely sensitive to impact, much more so than PETN. This was attributed by Liu et al. to Si-PETN having a much lower activation barrier to decomposition, via a facile rearrangement that is not as readily available to PETN, and which releases considerable energy that can promote further steps. We have investigated computationally why the barrier to the rearrangement is so much lower for Si-PETN than for PETN, using 5, (H₃C)₃C–CH₂ONO₂, and 6, (H₃C)₃Si–CH₂ONO₂, as models for PETN and Si-PETN. Reaction force analysis shows that most of the difference between the rearrangement barriers for 5 and 6 comes about in the initial (reactant) stages of the processes, in which 6 benefits from a 1,3 electrostatic interaction involving a positive σ–hole on the silicon and the negative linking oxygen. The analogous interaction is weaker in 5, since the central carbon does not have positive σ–holes; furthermore, this carbon is less able than silicon to temporarily expand its coordination sphere. A similar explanation involving a positive silicon σ–hole and a linking oxygen is proposed for Si-PETN. The greater exothermicity of the rearrangement of 6 (and also Si-PETN) can be rationalized, following Liu et al., in terms of the formation of the strong Si–O bond.