Effect of mobile phase additives on solute retention at low aqueous pH in hydrophilic interaction liquid chromatography

© 2016 Elsevier B.V. Trifluoracetic acid (TFA) added to the aqueous acetonitrile mobile phase induces some unexpected changes in the ionic component of retention in hydrophilic interaction separations when using Type B silica and amide-bonded silica columns. TFA use results in anion exchange properties which contrast with the cation exchange typically found with ammonium salt buffers. The significant cation exchange properties of silica hydride columns are also moderated by TFA. Similar behaviour was shown in a metal- free amide column operated on a system washed with a metal complexing agent, suggesting that adsorbed metal cations were not responsible for this anion exchange behaviour. Both suppression of silanol ionisation at low pH and ion pairing of bases with TFA could contribute to this effect. It is also possible that the column surface acquires some positive charges at the low pH of TFA. A surprising reversal of the properties of the columns back to predominately cation exchange behaviour was shown using methanesulfonic acid (MSA), which appears to be a stronger acid than TFA in high concentrations of acetonitrile. MSA maintains sufficient ionic strength in the mobile phase even at low concentrations, giving good peak shape, which could be useful for mass spectrometry detection. Besides giving different selectivity to TFA, MSA also gives different selectivity to that of ammonium salt buffers, suggesting it may be useful in manipulating the selectivity of a separation. Similar changes to the selectivity with TFA could be achieved by adding neutral methylsulfonate salts to the TFA mobile phase. While it is possible that methylsulfonate ions are retained on the stationary phase surface, experiments using ion pair reagents of opposite charge yielded the same results as MSA salts. It therefore seems more likely that the higher ionic strength of these solutions negates the influence of charges that may be formed in TFA solutions. Ion pairing effects with MSA are expected to be limited

Методы лазерной спектроскопии в средствах непрерывного контроля содержания О2 и СО в дымовых газах котлов

Application efficiency of various absorption laser spectroscopy methods for determination of gas component concentration in boiler smoke gases has been studied in the paper, O2 and CO absorption spectra have been analyzed, optimum absorption lines in near IR spectral range (about 0.76 µm for O2 and 1.56 µm for CO) have been selected and graphical dependences of intensity and half-width of the selected lines on the investigated medium temperature and pressure have been shown. Processes of monitoring CO and O2 content in boiler smoke gases while using basic laser spectroscopy methods have been simulated and measuring errors have been analyzed. It has been found out that in order to decrease methodical errors of concentration measuring it is necessary to take into account the investigated medium temperature and pressure. The paper shows that the least errors of continuous CO and O2 concentration monitoring at the presence of variations in dissipative losses have been ensured by the modified correlation method though its threshold sensitivity is less than integral and correlation ones.Исследована эффективность применения различных методов абсорбционной лазерной спектроскопии для определения концентрации газовых компонент в дымовых газах котлов. Проанализированы спектры поглощения О2 и СО, выбраны оптимальные линии поглощения в ближней ИК области спектра (в районе 0,76 мкм для О2 и 1,56 мкм для СО) и приведены графические зависимости интенсивности выбранных линий и их полуширины от температуры контролируемой среды и давления в ней. Смоделированы процессы контроля содержания СО и О2 в дымовых газах котлов при использовании основных методов лазерной спектроскопии и проанализированы погрешности измерений. Выяснено, что для уменьшения методических погрешностей измерений концентрации необходимо учитывать температуру контролируемой среды и давление в ней. Показано, что наименьшие погрешности непрерывного контроля концентрации СО и О2 при наличии вариаций диссипативных потерь обеспечивает модифицированный корреляционный метод, хотя его пороговая чувствительность меньше, чем интегрального и корреляционного

Advances in structure elucidation of small molecules using mass spectrometry

The structural elucidation of small molecules using mass spectrometry plays an important role in modern life sciences and bioanalytical approaches. This review covers different soft and hard ionization techniques and figures of merit for modern mass spectrometers, such as mass resolving power, mass accuracy, isotopic abundance accuracy, accurate mass multiple-stage MS(n) capability, as well as hybrid mass spectrometric and orthogonal chromatographic approaches. The latter part discusses mass spectral data handling strategies, which includes background and noise subtraction, adduct formation and detection, charge state determination, accurate mass measurements, elemental composition determinations, and complex data-dependent setups with ion maps and ion trees. The importance of mass spectral library search algorithms for tandem mass spectra and multiple-stage MS(n) mass spectra as well as mass spectral tree libraries that combine multiple-stage mass spectra are outlined. The successive chapter discusses mass spectral fragmentation pathways, biotransformation reactions and drug metabolism studies, the mass spectral simulation and generation of in silico mass spectra, expert systems for mass spectral interpretation, and the use of computational chemistry to explain gas-phase phenomena. A single chapter discusses data handling for hyphenated approaches including mass spectral deconvolution for clean mass spectra, cheminformatics approaches and structure retention relationships, and retention index predictions for gas and liquid chromatography. The last section reviews the current state of electronic data sharing of mass spectra and discusses the importance of software development for the advancement of structure elucidation of small molecules

Methods of Laser Spectroscopy in Devices for Continuous Monitoring of O2 and CO Content in Boiler Smoke Gases

Application efficiency of various absorption laser spectroscopy methods for determination of gas component concentration in boiler smoke gases has been studied in the paper, O2 and CO absorption spectra have been analyzed, optimum absorption lines in near IR spectral range (about 0.76 µm for O2 and 1.56 µm for CO) have been selected and graphical dependences of intensity and half-width of the selected lines on the investigated medium temperature and pressure have been shown. Processes of monitoring CO and O2 content in boiler smoke gases while using basic laser spectroscopy methods have been simulated and measuring errors have been analyzed. It has been found out that in order to decrease methodical errors of concentration measuring it is necessary to take into account the investigated medium temperature and pressure. The paper shows that the least errors of continuous CO and O2 concentration monitoring at the presence of variations in dissipative losses have been ensured by the modified correlation method though its threshold sensitivity is less than integral and correlation ones