High-performance liquid chromatography of biphenols and bis (hydroxyphenyl) propanes (dianes) with voltammetric and UV photometric detection

Summary The retention behaviour of mono- and dihydroxy derivatives of biphenol and bis(hydroxyphenyl)propanes was studied on chemically bonded C-18, CN-, phenyl, phenoxypropyl- and NH₂ stationary phases and on silica gel. The effects of the mobile phase, i.e., of the methanol content, the ionic strength, pH and the contents of cationic and anionic ion-pairing agents on the retention data were investigated. In the reversed-phase systems, all the substances are satisfactorily separated except for 3- and 4-hydroxybiphenyl; these isomers can be separated on silica gel, using a mixture of heptane and propanol as the mobile phase. Sodium dodecylsulphate, present at concentrations higher than the critical micelle concentration (about 10⁻² M, depending on the methanol content), causes a decrease in the retention times and an improvement in the separation. UV absorption spectra, calibration curves and the detection limit values were obtained at two wavelengths and at various salt concentrations in the mobile phase. Hydrodynamic voltammograms of the solutes were measured in a carbon fibre detector and the calibration curves and detection limit values were measured at the optimal voltage (+1.2 V/Ag/AgCl) as a function of the mobile phase composition. For most test substances voltammetric detection is two to three times more sensitive than UV detection. The combination of a UV and a voltammetric detector in series has been utilized to identify the products of microbial degradation of biphenyl.     

The empirical comparison of cyclofructans and cyclodextrins as chiral selectors in capillary electrophoretic separation of atropisomers of R,S‐1,1’‐binaphthalene‐2,2’‐diyl hydrogen phosphate

Native cyclofructans and their isopropyl derivatives were studied as chiral selectors in capillary electrophoresis and compared with α‐ and β‐cyclodextrin. R,S‐1,1’‐Binaphthalene‐2,2’‐diyl hydrogen phosphate was used as a model chiral compound. The empirical observation of the enantioselectivity of native cyclofructans and isopropyl derivatives of cyclofructans was described and compared with the cyclodextrins. The influence of methanol and acetonitrile, as the most commonly used organic solvents, and sodium dodecyl sulfate as a micelle forming additive on the separation of R,S‐1,1’‐binaphthalene‐2,2’‐diyl hydrogen phosphate atropisomers was achieved. The different enantiorecognition abilities resulting from unlike interaction mechanism with R,S‐1,1’‐binaphthalene‐2,2’‐diyl hydrogen phosphate were observed for the studied cyclodextrins and cyclofructans, especially when methanol or sodium dodecyl sulfate were used as modifiers of the separation conditions.     

Characterization of vestibular schwannoma tissues using liquid chromatography-tandem mass spectrometry analysis of specific peptide fragments separated by in-sample tryptic protein digestion followed by mathematical analysis

Vestibular schwannoma is the most common benign neoplasm of the cerebellopontine angle. Its first symptoms include hearing loss, tinnitus, and vestibular symptoms, followed by cerebellar and brainstem symptoms, along with palsy of the adjacent cranial nerves. However, the clinical picture has unpredictable dynamics and currently, there are no reliable predictors of tumor behavior. Hence, it is desirable to have a fast routine method for analysis of vestibular schwannoma tissues at the molecular level. The major objective of this study was to verify whether a technique using in-sample specific protein digestion with trypsin would have the potential to provide a proteomic characterization of these pathological tissues. The achieved results showed that the use of this approach with subsequent liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis of released peptides allowed a fast identification of a considerable number of proteins in two differential parts of vestibular schwannoma tissue as well as in tissues of control healthy samples. Furthermore, mathematical analysis of MS data was able to discriminate between pathological vestibular schwannoma tissues and healthy tissues. Thus, in-sample protein digestion combined with LC-MS/MS separation and identification of released specific peptides followed by mathematical analysis appears to have the potential for routine characterization of vestibular schwannomas at the molecular level. Data are available via ProteomeXchange with identifier PXD045261.     

Enantioselective separation of biologically active basic compounds in ultra-performance supercritical fluid chromatography

The enantioseparation of basic compounds represent a challenging task in modern SFC. Therefore this work is focused on development and optimization of fast SFC methods suitable for enantioseparation of 27 biologically active basic compounds of various structures. The influences of the co-solvent type as well as different mobile phase additives on retention, enantioselectivity and enantioresolution were investigated. Obtained results confirmed that the mobile phase additives, especially bases (or the mixture of base and acid), improve peak shape and enhance enantioresolution. The best results were achieved with isopropylamine or the mixture of isopropylamine and trifluoroacetic acid as additives. In addition, the effect of temperature and back pressure were evaluated to optimize the enantioseparation process. The immobilized amylose-based chiral stationary phase, i.e. tris(3,5-dimethylphenylcarbamate) derivative of amylose proved to be useful tool for the enantioseparation of a broad spectrum of chiral bases. The chromatographic conditions that yielded baseline enantioseparations of all tested compounds were discovered. The presented work can serve as a guide for simplifying the method development for enantioseparation of basic racemates in SFC.     

Microfluidic valves for flow control at low Reynolds numbers

Fluidics is a technology of generating and controlling fluid flows — preferably without the action of mechanical moving components. Microfluidics perform these tasks in small, typically micronsized structures. Essential part of almost all microfluidic systems are flow control valves. The basic problem is the low Reynolds numberRe: inertial effects used in large-scale fluidics are too small relative to viscous dissipation. New approaches, such as pressure or electrokinetic driving are required. In the subdynamic, viscosity dominated flow regime, Re ceases to be of importance and for pressure-driven valves a new characterisation number was to be introduced. An example of a diverter valve, developed by the author, is described and the meaning of the new dimensionless parameter is demonstrated.     

An insight into the use of dimethylphenyl carbamate cyclofructan 7 chiral stationary phase in supercritical fluid chromatography: The basic comparison with HPLC

Cyclofructan‐based chiral stationary phases were previously shown as a promising possibility for separation of chiral compounds in high performance liquid chromatography. In this work retention and enantiodiscrimination properties of the 3,5‐dimethylphenyl carbamate cyclofructan 7 chiral stationary phase are described in supercritical fluid chromatography. The results obtained in both of the separation methods were compared. A set of compounds with axial or central chirality was used as analytes. The effect of mobile phase composition, that is, addition of different alcohol modifiers and/or trifluoroacetic acid to carbon dioxide, was examined in the supercritical system. Similarly, mobile phases composed of hexane modified with propan‐2‐ol and/or trifluoracetic acid were used in liquid chromatography. A linear free energy relationship model was utilized for characterization of interactions that are decisive for retention and separation in both techniques. Dispersion interactions showed similar negative values using both methods. The main contribution of hydrogen bond acidity was also comparable for both methods. The propensity to interact with n‐ and/or π‐electron pairs of solutes was significant only in the supercritical system.     

Performance of synthetic jet actuators based on hybrid and double-acting principles

The design of the discussed fluid jet actuator followed two ideas: a double-acting operation of reciprocating pumps, and a hybrid synthetic jet (HSJ) actuation. The entire actuator consists of two basic parts, namely the front (central) and rear chambers, from which fluid is displaced by the opposite sides of the same diaphragm. The actuator operates in a double-acting (antiphase) regime with air as the working fluid. The central chamber generates the standard (zero-net-mass-flux) axisymmetric synthetic jet (SJ), while the rear chamber generates system of several non-zero-net-mass-flux HSJs arranged around the central SJ. A number of variants of HSJs with different geometry were designed, manufactured and tested. Their behavior was investigated experimentally using the smoke visualization, reaction force measurement, hot-wire anemometry, and naphthalene sublimation technique. The tests confirm the efficiency of the present design.     

Terahertz transmission of NbN superconductor thin film

Transmission of terahertz waves through a thin layer of the NbN superconductor deposited on a sapphire substrate was studied as a function of temperature in zero field as well as in magnetic field perpendicular to the sample. For photon energies lower than optical gap, detailed temperature measurements in zero field provide BCS-like curves with a pronounced peak below the critical temperature. In accordance with the BCS model, the temperature peak disappears as the energy of incident radiation is increased above the gap. In non-zero field, the temperature behavior of transmission is modified because the gap is suppressed and vanishes at upper critical field. In addition, the presence of quantized vortices in the superconducting film substantially changes shape of the temperature curves.     

Pulsating and synthetic impinging jets

This is the second part of a survey summarizing authors’ research over a period of two decades on enhancing impinging jet heat and/or mass transfer by periodic unsteadiness of nozzle flow rate. The first part, Tesař and Trávníček (2004 b), identified the reasons why pulsation does not always improve the transfer rate: the pulses do not reach up to the wall. The authors nevertheless demonstrate a transfer rate improvement, but in flows with inherent instability found in annular impinging jet. The excitation there causes a topological metamorphosis (reversal of flow character). Also in the extreme case of the synthetic (zero time-mean flow) jets the authors demonstrated a substantial improvement with the annular nozzle. The new approaches presented in the paper offer increased performance of drying and heating/cooling systems, in particular in microdevices with otherwise low or absent levels of natural jet turbulence.