Identification Of Photodegradation Products Research Articles

Phototransformation of three selected pharmaceuticals, naproxen, 17α-Ethinylestradiol and tetracycline in water: Identification of photoproducts and transformation pathways

Transformation products (TPs) may be formed during various processes, however, it was proved that one of the main mechanisms responsible for degradation of pharmaceuticals in natural waters is photolysis. Three compounds were selected, tetracycline (TC), 17-α-ethinylestradiol (EE2) and naproxen (NAP), for degradation experiments which were performed using a xenon lamp emitting light with a spectrum closely approximating that of natural sunlight. Identification of photodegradation products was achieved via liquid chromatography coupled with high resolution quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) providing accurate mass measurements and MS/MS experiments for structural elucidation. Results indicate that degradation of compounds under the study follows pseudo-first-order kinetics. Photolysis rate constants (k) were determined and half-lifes (t1/2) calculated to be 11, 120, and 13 min for TC, EE2 and NAP, respectively. Xenon lamp irradiation led to the formation of several photoproducts. Many of them have been identified for the first time. LC-QTOF-MS analysis allowed for the identification of seven, four, and eight TPs of TC, EE2 and NAP, respectively. Finally, the presence of parent compounds and identified TPs was investigated in various real-world water samples. Only three degradation products of 17-α-ethinylestradiol and naproxen were detected in wastewater effluent and treated water samples. Quantitative structure-activity relationship (QSAR) approach was applied in order to estimate physical-chemical properties of selected pharmaceuticals and their TPs. This allowed predicting the fate of all analytes in the aqueous environment.

Retrospective analysis for the identification of 4-aminocarminic acid photo-degradation products in beverages

This article deals with the identification of the photo-degradation products of 4-aminocarminic acid potentially present in commercial beverages. Sixteen beverages of different composition but all containing the E120 dye were previously analysed by ultra-high-performance liquid chromatography (UHPLC) coupled with quadrupole-time of flight mass spectrometry to identify the common degradation products of the E120 dye. Since it is plausible to find unauthorised 4-aminocarminic acid in beverages which report generic E120 dye on the label, retrospective analysis was employed here not only to search for the possible presence of 4-aminocarminic acid but also to investigate the potential formation of photo-degradation products derived from this compound. For this purpose, a statistical approach based on Student’s t-test was used to compare the degraded beverages containing 4-aminocarminic acid with all the others. Five degradation products were identified and their structures were elucidated on the basis of the high-accuracy and high-resolution of mass and mass/mass spectra. The toxicity of the degradation products was evaluated through the Ames Salmonella/microsome mutagenicity assay. No evidence of mutagenicity was obtained for the beverages subjected or not to irradiation, whereas a toxic effect of the 4-aminocarminic acid standard solution already at 100.0 µg l−1 was found. This leads, once again, to the conclusion that the toxicity study must be carried out on the beverages in order to take into account of all the possible masking/protection interactions among the ingredients.

Photodegradation assessment of ciprofloxacin, moxifloxacin, norfloxacin and ofloxacin in the presence of excipients from tablets by UPLC-MS/MS and DSC

BackgroundCiprofloxacin (CIP), moxifloxacin (MOX), norfloxacin (NOR) and ofloxacin (OFL), are the antibacterial synthetic drugs, belonging to the fluoroquinolones group. Fluoroquinolones are compounds susceptible to photodegradation process, which may lead to reduction of their antibacterial activity and to induce phototoxicity as a side effect. This paper describes a simple, sensitive UPLC-MS/MS method for the determination of CIP, MOX, NOR and OFL in the presence of photodegradation products.ResultsChromatographic separations were carried out using the Acquity UPLC BEH C18 column; (2.1 × 100 mm, 1.7 μm particle size). The column was maintained at 40°C, and the following gradient was used: 0 min, 95% of eluent A and 5% of eluent B; 10 min, 0% of eluent A and 100% of eluent B, at a flow rate of 0.3 mL min-1. Eluent A: 0.1% (v/v) formic acid in water; eluent B: 0.1% (v/v) formic acid in acetonitrile. The method was validated and all the validation parameters were in the ranges acceptable by the guidelines for analytical method validation. The photodegradation of examined fluoroquinolones in solid phase in the presence of excipients followed kinetic of the first order reaction and depended upon the type of analyzed drugs and coexisting substances. Photodegradation process of analyzed drugs was confirmed by differential scanning calorimetry. In addition, the identification of degradation products was carried out by mass spectrometry.ConclusionThe developed UPLC-MS/MS method enables the determination of CIP, MOX, NOR and OFL in the presence of photodegradation products and identification of photodegradation products.

Photolytic degradation of norfloxacin, enrofloxacin and ciprofloxacin in various aqueous media

The photolytic degradation of norfloxacin, enrofloxacin and ciprofloxacin, fluoroquinolone antibacterials widely used in human and veterinary medicine, was investigated under simulated solar irradiation in different water matrices (river water and synthetic wastewater similar by composition to wastewater of pharmaceutical industry). The results showed that investigated fluoroquinolones degrade very quickly and photodegradation followed pseudo first order kinetics. The slowest photodegradation rate was observed in river water for all three fluoroquinolones. In the case of pharmaceutical mixture irradiation, no significant differences in rate constants were observed compared to single-component experiments. The structures of photodegradation products were determined and photodegradation pathways were suggested. Two main processes occurred primary from enrofloxacin depending on pH values: (I) cyclopropane ring cleavage at pH 4 and (II) oxidative photodegradation at pH 8. The structures of the photoproducts E-1 to E-6 are unknown and have not been reported for this fluoroquinolone. For ciprofloxacin two main processes were also identified depending on experimental conditions. Under acidic conditions (pH 4), reactions involved rather the quinolone ring (cleavage of the cyclopropane ring and fluorine solvolysis), while at pH 8 the side-chain reactions took place. The photodegradation pathway of norfloxacin somewhat differed from the previous two. There was no significant dependence on reaction conditions and there were no two different pathways. Determination and identification of photodegradation products were performed by liquid chromatography–mass spectrometry (LC–MS/MS). The obtained results are of importance for assessing the environmental fate of fluoroquinolones in aqueous media.

Inclusion Complexes of Manidipine with γ-Cyclodextrin and Identification of Photodegradation Products

The paper presents results of a study of photochemical decomposition of manidipine and its inclusion complexes with γ-cyclodextrin and identification of photodegradation products. The process was qualitatively assessed by the UV spectrophotometry and by HPLC-MS. The quantitative assessment of its efficiency was performed on the basis of kinetic parameters and quantum yields. The main product of photodegradation was nitrophenylpyridine derivative, while the concentration of nitrozophenylpyridine derivative being the other product of this process, was about 20 times lower. The inclusion complexes of manidipine with γ-cyclodextrin were obtained in the liquid phase. The stoichiometry of the complexes was determined from the Benesi–Hildebrand equation. The photochemical stability of manidipine in inclusion complexes was compared with that of manidipine in non-complexed form.