Chromatographic determination of sulfasalazine and its active metabolites: greenness assessment and application to spiked human plasma

Green TLC-densitometric and RP-HPLC methods were developed and validated for the determination of the active prodrug sulfasalazine (SZ), its active metabolite mesalazine (MZ) and the major active metabolite of mesalazine, N-acetyl-5-aminosalicylic acid (AS). In the developed TLC-densitometric method, chromatographic separation was carried out on TLC silica gel plates 60 F₂₅₄ using a developing system consisting of ethyl acetate–methanol–ammonia solution 33% (8:2.5:0.3, by volume) and then scanning the separated bands at 215 nm using hydrochlorothiazide as an internal standard with linearity ranges of 0.4–3, 0.4–2.4 and 0.3–2 for SZ, MZ and AS, respectively. The developed RP-HPLC method depended on chromatographic separation using a C₁₈ column with a solvent mixture of methanol–aqueous acetic acid solution (pH 5) as a mobile phase with gradient elution mode and UV scanning at 243 nm using pyrazinamide as internal standard with linearity ranges of 5–50, 5–40, and 3–20 for SZ, MZ and AS, respectively. US Food and Drug Administration guidelines were followed during validation of the methods. The greenness of the developed methods was estimated using the greenness profile and the Eco-Scale approach. Both methods passed the four quadrants of the greenness profile and had Eco-Scale score ˃75, thus they were considered to be green according to these approaches.     

Spectrophotometric determination of ethanol by an enzymatic method with 2, 2'-azino-di(3-ethylbenzthiazo- line-6-sulfonate)

The method is based on the oxidation of ethanol in the presence of alcohol oxidase, followed by oxidation of 2,2'-azino-di(3-ethylbenzthiazoline-6-sulfonate) in the presence of peroxidase.     

Study of the Retention Behavior of Newly Synthesized s-Triazine Derivatives in RP TLC Systems,and the Lipophilicity of the Compounds

JPC – Journal of Planar Chromatography – Modern TLC - The chromatographic behavior of nine newly synthesized s-tri-azines has been studied by thin-layer chromatography on C18/UV254...     

Signature of the conformational preferences of small peptides: a theoretical investigation

An extensive computational study of the conformational preferences of N-acetylphenylalaninylamide (NAPA) is reported, including conformational and anharmonic frequency analyses, as well as calculations of excitation energies of the four NAPA conformers lowest in energy. Particular attention is paid to the influence of hydrogen-bonding interactions on the relative stability of the conformers, which was found to be very sensitive to both the level of quantum chemical computations and the anharmonic treatment of molecular vibrations. The assignments of the UV spectral peaks are well supported by the multireference CASSCF/MS-CASPT2 calculations. Upon consideration of the second-order M?ller-Plesset (MP2) and density functional theory (DFT) structures, overall energetics, and harmonic and anharmonic corrections, we found no conclusive theoretical evidence for the assumed conformational propensity of small model peptides toward extended beta-strand structures.     

Photoinduced charge separation reactions of J-aggregates coated on silver nanoparticles

The photochemistry of cyanine J-aggregates on the surface of colloidal Ag nanoparticles is reported. The photochemistry is initiated through ultrafast photoexcitation of the plasmon band in Ag nanoparticles, producing an enhanced near-field that interacts with the J-aggregate monolayer. Through transient absorption spectroscopy, we show that photoexcitation of the plasmon in Ag nanoparticles leads to exciton dynamics that differ strongly from J-aggregates alone or for J-aggregate monolayers on bulk metal surfaces. Specifically, charge-separated states with a lifetime of approximately 300 ps between the J-aggregate and Ag colloid are formed. The reduction of the Ag nanoparticles is shown to be a multielectron process.     

Novel polycarbonate-based polyurethane elastomers: Composition–property relationship

Novel all-aliphatic polycarbonate-based polyurethane (PC-PU) elastomers, as well as PC-PU nanocomposites filled with organic-modified clays were synthesized, characterized and studied. It was found that they have very attractive mechanical properties (e.g., elongation at break between 600% and 800%). The prepared PC-PUs possess a distinctly segmented structure, which is the key prerequisite for their behavior as strong physical rubbery networks. All synthesized materials melt at elevated temperatures (between 110 and 200 °C) and hence can be processed like normal thermoplastics. The dispersion of the clay nanofiller was achieved by its one day swelling in the alcohol and a brief successive stirring. This procedure is very successful and leads to a partial exfoliation of the clay (documented by X-ray diffraction and TEM). The best nanocomposites with very good tensile properties, particularly with significantly increased moduli were obtained using the bentonite nanofiller. The study shows that the nanofiller interacts strongly with the hard domains and influences their melting temperature (DMTA and DSC), but it does not affect the glass transition temperature of soft domains. While Cloisite 15A was found to interact preferentially with the hard domains, the organic modified bentonite shows a strong interaction with both soft and hard segments, behaving as a blending agent. Hard domains in neat matrices, formed by hydrogen bonding of hard segments, were practically invisible by X-ray or TEM, but were successfully detected by AFM. Besides excellent mechanical properties, the prepared elastomers and their nanocomposites showed an interesting phase behavior (which was studied by combining DMTA and modulated DSC).     

Synthesis of azafluorenones and related compounds using deprotocupration–aroylation followed by intramolecular direct arylation

The efficiency of the deprotocupration–aroylation of 2-chloropyridine using lithiocuprates prepared from CuX (X=Cl, Br) and LiTMP (TMP=2,2,6,6-tetramethylpiperidido, 2 equiv) was investigated. CuCl was identified as a more suitable copper source than CuBr for this purpose. Different diaryl ketones bearing a halogen at the 2 position of one of the aryl groups were synthesized in this way from azines and thiophenes. These were then involved in palladium-catalyzed ring closure: substrates underwent expected CH-activation-type arylation to afford fluorenone-type compounds, and were also subjected to cyclization reactions leading to xanthones, notably in the presence of oxygen-containing substituents or reagents.     

Effect of surfactants on the voltammetric response and determination of an antihypertensive drug

The effect of adding surface-active agents to electrolytes containing terazosin, an antihypertensive drug, on the voltammetric response of glassy carbon electrode was studied. The current signal due to the oxidation process was a function of the amount of terazosin, pH of the medium, type of surfactant, and accumulation time at the electrode surface. Two surfactants were used, an anionic type, sodium dodecyl sulfate (SDS) and a cationic type, cetyl trimethyl ammonium bromide (CTAB). Addition of SDS to the terazosin-containing electrolyte was found to enhance the oxidation current signal while CTAB showed an opposite effect. Beside the interfacial interaction of the surfactant with the electrode surface in reference to the bias applied potential and the charge of surfactant, terazosin-surfactant interaction in the electrolytic solution was found to be critical to the magnitude of current signal. Addition of SDS to terazosin-containing buffer solution resulted in a decrease in the drug absorption spectrum both in the ultra-violet and visible (UV-vis) regions. Moreover, NMR measurements showed considerable chemical shifts for the aromatic protons of the quinazolinyl moiety of the terazosin in presence of SDS. The affected aromatic protons are positioned next to the interacting protonated amino-group of the terazosin with the charged sulfonate-group of SDS. On the other hand, addition of CTAB did not cause noticeable changes both to the UV-vis and NMR spectra of the drug. The use of SDS in the electrochemical determination of terazosin using linear sweep voltammetry and differential pulse voltammetry at solid glassy carbon electrode enhanced the detection limit from 6.00 × 10⁻⁷ mol L⁻¹ in absence of surfactant to 4.58 × 10⁻⁹ mol L⁻¹ when present. The validity of using this method in the determination of drug active ingredient in urine samples and tablet formulations was also demonstrated.     

Tandem Michael imino–aldol reactions catalyzed by samarium diiodide

Samarium diiodide catalyzes a one-pot procedure allowing to perform sequentially the Michael addition of a ketene silyl acetal on a cyclic ,β-unsaturated ketone, followed by the addition of a glyoxylic or aromatic imine. The presence of a coordinating group on the imine increases the rate of the reaction.     

Power-Modified Kies-Exponential Distribution: Properties,Classical and Bayesian Inference with an Application to Engineering Data

We introduce here a new distribution called the power-modified Kies-exponential (PMKE) distribution and derive some of its mathematical properties. Its hazard function can be bathtub-shaped, increasing, or decreasing. Its parameters are estimated by seven classical methods. Further, Bayesian estimation, under square error, general entropy, and Linex loss functions are adopted to estimate the parameters. Simulation results are provided to investigate the behavior of these estimators. The estimation methods are sorted, based on partial and overall ranks, to determine the best estimation approach for the model parameters. The proposed distribution can be used to model a real-life turbocharger dataset, as compared with 24 extensions of the exponential distribution.