Flurbiprofen: A Study of the Behavior of the Scalemate by Chromatography, Sublimation, and NMR

2-(2-Fluoro-4-biphenyl) propionic acid (flurbiprofen), from the phenylalkanoic acid family of nonsteroidal anti-inflammatory drugs (NSAID’s), is currently on the pharmaceutical market as a racemate. This racemic compound was tested for its propensity to undergo the self-disproportionation of enantiomers (SDE) phenomenon by various forms of chromatography (SDEvC), such as routine gravity-driven column chromatography, medium-pressure liquid chromatography (MPLC), preparative thin-layer chromatography (PTLC), and size-exclusion chromatography (SEC), as well as by sublimation (SDEvS). Furthermore, examination by nuclear magnetic resonance (NMR) in various solvents found that flurbiprofen exhibited the phenomenon of self-induced diastereomeric anisochronism (SIDA). By measurement of the diffusion coefficient (D), the longitudinal relaxation time (T1), and the transverse relaxation time (T2) using NMR, as well as by electrospray ionization-mass spectrometry (ESI-MS) examinations, the preferred intermolecular association was found to be solvent dependent, e.g., heterochiral association was preferred in toluene, while homochiral association was preferred in more polar solvents. This study also attempted, unsuccessfully, to correlate the NMR measurements of flurbiprofen with chromatographic outcomes for the rationalization and prediction of chromatographic results based on NMR measurements. Because the intermolecular hydrogen bonding of the acid groups in flurbiprofen overwhelmingly predominates over other intermolecular interactions, flurbiprofen seemed to represent a good test case for this idea. The behavior of scalemic samples of flurbiprofen is important, as, although it is currently dispensed as a racemate, clinical applications of the R enantiomer have been investigated. SDEvC and SDEvS both have ramifications for the preparation, handling, and storage of enantioenriched flurbiprofen, and this concern applies to other chiral drugs as well.The authors gratefully acknowledge financial support from the Ministry of Science and Higher Education, Poland (grant no. 668, A.W.; grant no. 659, M.K.; and SMGR.RN.20.264, A.K.) and IKERBASQUE, the Basque Foundation for Science, Spain (V.A.S.)

Distributions of first passage times in a bistable thermochemical system with a low temperature stationary state

We consider the influence of internal fluctuations on the behavior of a bistable thermochemical system with a low temperature stable focus surrounded by a stable limit cycle arising from the subcritical Hopf bifurcation. We use a master equation approach to study the transitions between basins of these attractors. Distribution functions of first passage times from the limit cycle to the focus are obtained for systems with various numbers of molecules and reaction heats. We consider in detail the specific, multi-peak form of the distributions caused by eccentric location of the limit cycles with respect to the focus

Fluorescent Sensor Based on 1<i>H</i>-Pyrazolo[3,4-<i>b</i>]quinoline Derivative for Detecting Zn²⁺ Cations

The photophysical and sensory properties of the donor–acceptor pyrazoloquinoline derivative (PQPc) were investigated using absorption, steady-state, and time-resolved fluorescence measurements. The compound synthesized from commercial, readily available substrates exhibited absorptions in the UV–Vis range, with a maximum of the longwave band around 390 nm. The maximum fluorescence was around 460–480 nm, depending on the solvent. The quantum yield was between 12.87% (for n-hexane) and 0.75% (for acetonitrile) and decreased with increasing solvent polarity. The PET mechanism was implicated as the cause of fluorescence quenching. Divalent ions such as Zn2+, Pb2+, Cd2+, Ca2+, Mg2+, Co2+, Ni2+, and Cu2+ were introduced to study the fluorescent response of PQPc. A 13-times increase in fluorescence quantum yield was observed after the addition of Zn2+ ions. Detailed research was carried out for the PQPc-Zn2+ system in order to check the possibility of analytical applications of PQPc as a fluorescent sensor. A detection limit of Zn2+ was set at the value level 1.93 × 10−7 M. PQPc-Zn2+ complexes had a stoichiometry of 1:1 with a binding constant of 859 M−1. Biological studies showed that the sensor was localized in cells near the membrane and cytoplasm and may be used to detect zinc ions in eukaryotic cells

Ordered Mesoporous Carbons for Adsorption of Paracetamol and Non-Steroidal Anti-Inflammatory Drugs: Ibuprofen and Naproxen from Aqueous Solutions

The adsorption of paracetamol and non-steroidal anti-inflammatory drugs (ibuprofen and naproxen) on ordered mesoporous carbons (OMC) and, for comparison, on commercial activated carbon, were investigated in this work. OMC adsorbents were obtained by the soft-templating method and were characterized by low-temperature nitrogen adsorption and scanning electron microscopy (SEM). The effects of contact time and initial concentration of organic adsorbates on the adsorption were studied. The contact time to reach equilibrium for maximum adsorption was 360 min for all the studied adsorbates. The adsorption mechanism was found to fit pseudo-second-order and intra particle-diffusion models. Freundlich, Langmuir and Langmuir-Freundlich isotherm models were used to analyze equilibrium adsorption data. Based on the obtained experimental data, the adsorption isotherm in the applied concentration range for all the studied adsorbates was well represented by the Freundlich-Langmuir model. The adsorption ability of ordered mesoporous carbon materials was much higher for paracetamol and naproxen in comparison to commercial activated carbon. The removal efficiency for ibuprofen was significantly lower than for other studied pharmaceuticals and comparable for all adsorbents. Theoretical calculations made it possible to obtain optimized chemical structures of (S)-naproxen, ibuprofen, and paracetamol molecules. Knowledge of charge distributions of these adsorbate molecules can be helpful to explain why paracetamol and naproxen can react more strongly with the surface of adsorbents with a large numbers of acidic groups compared to ibuprofen facilitating more efficient adsorption of these pharmaceuticals on ordered mesoporous carbons