Validated chromatographic methods for determination of teriflunomide and investigation of its intrinsic stability.

Two rapid, precise, and sensitive stability-indicating high performance chromatographic methods for the measurement of Teriflunomide in its degradation products' existence were developed. These were RP-HPLC and HPTLC using UV detector. HPLC separation was accomplished utilizing Thermo BDS hypercil C18 column (250 × 4.6 mm, 5 µm) and acetonitrile: 0.03 M potassium dihydrogen phosphate: triethylamine (50:50:0.1%, by volume) as mobile phase at flow rate of 1mL/min. The separated peaks were detected at 250.0 nm. The densitometric approach was conducted utilizing HPTLC 60 F254 silica gel plates, and a developing system of benzene: ethanol: acetic acid (7.5:1:0.25, by volume) and detection was done at 250.0 nm. The developed approaches were evaluated regarding the International Conference on Harmonization (ICH) instructions. The calibration curves of both techniques were constructed with linearity ranges of (5-100) µg/mL and (2-10) µg /band, for HPLC and densitometric determination, consecutively. Teriflunomide was exposed to base and acid hydrolysis, oxidation using H2O2 and finally, thermal degradation as stated in ICH guidelines. The degradation product structures' elucidation was achieved through LC-MS.

Electrochemically-selective electrode for quantification of dorzolamide in bulk drug substance and dosage form.

Three smart carbon paste electrodes were fabricated to quantify dorzolamide hydrochloride DRZ, including conventional carbon paste I, modified carbon paste embedding Silica II, and modified carbon paste embedding ß-cyclodextrin III. This study is based on the insertion of DRZ with phosphomolybdic acid to create an electroactive moiety dorzolamide-phosphomolybdate ion exchanger using a solvent mediator dibutyl phthalate. The three constructed carbon paste electrodes displayed Nernstian responses and linear concentration ranges with lower detection limits. The vital performance of the created electrodes was verified in relation to various parameters. The electrodes enhance the selective determination of DRZ in the presence of inorganic ions, a co-formulated drug in the dosage form timolol maleate, and the excipient benzalkonium chloride. The modified carbon paste electrode including Silica was utilized to detect DRZ in ophthalmic eye drop form utilizing the direct calibration curve and potentiometric titration methods. Satisfactory findings were achieved by comparing them to other reported methods.

Optimizing the performance of Auy/Nix/TiO2NTs photoanodes for photoelectrochemical water splitting.

Water splitting using photoelectrochemical (PEC) techniques is thought to be a potential method for creating green hydrogen as a sustainable energy source. How to create extremely effective electrode materials is a pressing concern in this area. In this work, a series of Nix/TiO2 anodized nanotubes (NTs) and Auy/Nix/TiO2NTs photoanodes were prepared by electrodeposition via cyclic voltammetry and UV-photoreduction, respectively. The photoanodes were characterized by several structural, morphological, and optical techniques and their performance in PEC water-splitting for oxygen evolution reaction (OER) under simulated solar light was investigated. The obtained results revealed the nanotubular structure of TiO2NTs was preserved after deposition of NiO and Au nanoparticles while the band gap energy was reduced allowing for effective utilization of solar light with lower charge recombination rate. The PEC performance was monitored and it was found that the photocurrent densities of Ni20/TiO2NTs and Au30/Ni20/TiO2NTs were 1.75-fold and 3.25-fold that of pristine TiO2NTs, respectively. It was confirmed that the performance of the photoanodes depends on the number of electrodeposition cycles and duration of photoreduction of gold salt solution. The observed enhanced OER activity of Au30/Ni20/TiO2NTs could be attributed to the synergism between the local surface plasmon resonance (LSPR) effect of nanometric gold which increased solar light harvesting and the p-n heterojunction formed at the NiO/TiO2 interface which led to better charge separation and transportation suggesting its potential application as an efficient and stable photoanode in PEC water splitting for H2 production.

A chemically modified solid-state sensor for magnesium(ii) ions and esomeprazole magnesium potentiometric assay.

The use of electrochemical sensors offers a simple, affordable solution with great reliability. Magnesium is a mineral that the body requires to function properly. It encourages preserving a stable pulse, strong bones, and healthy blood pressure. Herein, a novel ion-selective electrode using esomeprazole magnesium trihydrate as an ion-association complex was developed for magnesium(ii) ion determination in mineral water, drug substances, and pharmaceutical formulations. The electrode response was optimized in terms of plasticizer type, ion exchanger concentration, and membrane composition. To find the best sensor combination, the initial optimization research was performed using eight different sensors. A membrane containing 20% esomeprazole magnesium trihydrate, 36% carbon, and 44% o-Nitrophenyl Octyl Ether (NPOE) as a plasticizer yielded the best potentiometric response. The developed sensor demonstrated a Nernstian response with a slope of 29.93 ± 0.1 mV per decade in the concentration range of 1.41 × 10-5 mol L-1 to 1 × 10-2 mol L-1. Within a pH range of 5-8, it had a low detection limit of 4.13 × 10-6 mol L-1. When compared to the official method, there are no statistically significant differences.

Author Correction: Morphology Transition Engineering of ZnO Nanorods to Nanoplatelets Grafted Mo8O23-MoO2 by Polyoxometalates: Mechanism and Possible Applicability to other Oxides.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Development and Validation of HPLC Fluorescence and UPLC/DAD Stability-Indicating Methods for Determination of Hepatitis C Antiviral Agent Daclatasvir.

Background: Few stability-indicating chromatographic methods were published for determination of daclatasvir. All used UV detection. Objective: This work aimed to develop rapid, specific, and novel stability-indicating methods using HPLC with fluorescence detection and ultra performance liquid chromatography (UPLC) with UV detection for the determination of daclatasvir in bulk powder and in its dosage form. Methods: The drug was subjected to hydrolysis (acidic and alkaline) as per International Conference on Harmonization (ICH) guidelines. The fragmentation pattern of the drug was studied using LC-MS. Separation was carried out first by HPLC using Thermo BDS Hypersil Phenyl (300 mm × 4 mm, 5 µm) column and a mobile phase consisting of ammonium phosphate buffer (0.02 M) pH 3-methanol (40+60, v/v) at flow rate 1 mL/min. Quantitation was achieved by fluorescence detection at 305 and 457 nm for excitation and emission, respectively. The second method used UPLC equipped with diode-array detector. Acquity BEH C18 (50 mm × 2.1 mm, 1.7 µm) column was used with the same mobile phase at flow rate 0.4 mL/min and detection wavelength at 305 nm. ICH guidelines were used for validation. Results: The mean percentage recovery ± SD values for tablet assay were found to be 101.12 ± 0.655 and 99.78 ± 0.632 by HPLC and UPLC methods, respectively. The assay results showed a good agreement with the reported method. Conclusions: The developed HPLC and UPLC methods provide simple, accurate, and reproducible analysis of daclatasvir without interference from degradates. Highlights: This is the first research using fluorescence detection in a stability-indicating chromatographic method for determination of daclatasvir.

Study of Oxyclozanide's Innate Stability Coupled with the Assessment of its Aquatic Photo-Transformation Using a Validated Isocratic HPLC Method.

Background: Oxyclozanide (OXY) is a veterinary medicine used for control of fascioliasis in farm animals. Literature review shows absence of sufficient information regarding its stability. Such information is important as it affects many stages of a drug's life cycle, from pharmaceutical manufacturing to its environmental fate understanding of the degradation of the drug once it is placed in the environment. Objective: An HPLC method was developed to address the impact of different stress conditions on OXY's stability. Methods: OXY's stability was investigated by exposure to forced acid and alkaline hydrolysis, thermal, oxidative and photolytic degradation, which are different stress conditions applied to the forced degradation study. Separation was performed on Eurosphere C18 analytical column (125 × 4.6 mm, 5 µm particle size) using 50 mM sodium acetate trihydrate (pH 4.5) and acetonitrile (50:50, v/v) as mobile phase and UV detection at 254 nm. A photolytic kinetics study was conducted by monitoring OXY photolysis under monochromatic and polychromatic light sources (UV lamp at 366 nm and natural sunlight) in aqueous buffers of different pHs (5, 7, and 9). LC-MS was used to identify the major photolytic degradate. Results: OXY was quantified over a concentration range of 1-80 µg/mL with mean recovery of 99.32 ± 1.80%. The drug was susceptible to oxidative and photolytic degradation. The photolytic kinetics were pH dependent. The LC-MS result supported photo-dehalogenation degradation mechanism. Conclusions: The developed method could be used in OXY stability testing. The results of the photolytic kinetics study can address OXY aquatic photo-transformation, thereby predicting its environmental fate and risks imposed on the ecosystem. Highlights: An HPLC method was developed for monitoring OXY degradation behavior and studying its photolytic kinetics with identification of its photodegradate.

Ternary CNTs@TiO2/CoO Nanotube Composites: Improved Anode Materials for High Performance Lithium Ion Batteries.

TiO2 nanotubes (NTs) synthesized by electrochemical anodization are discussed as very promising anodes for lithium ion batteries, owing to their high structural stability, high surface area, safety, and low production cost. However, their poor electronic conductivity and low Li⁺ ion diffusivity are the main drawbacks that prevent them from achieving high electrochemical performance. Herein, we report the fabrication of a novel ternary carbon nanotubes (CNTs)@TiO2/CoO nanotubes composite by a two-step synthesis method. The preparation includes an initial anodic fabrication of well-ordered TiO2/CoO NTs from a Ti-Co alloy, followed by growing of CNTs horizontally on the top of the oxide films using a simple spray pyrolysis technique. The unique 1D structure of such a hybrid nanostructure with the inclusion of CNTs demonstrates significantly enhanced areal capacity and rate performances compared to pure TiO2 and TiO2/CoO NTs, without CNTs tested under identical conditions. The findings reveal that CNTs provide a highly conductive network that improves Li⁺ ion diffusivity, promoting a strongly favored lithium insertion into the TiO2/CoO NT framework, and hence resulting in high capacity and an extremely reproducible high rate capability.

Morphology Transition Engineering of ZnO Nanorods to Nanoplatelets Grafted Mo8O23-MoO2 by Polyoxometalates: Mechanism and Possible Applicability to other Oxides.

A new fundamental mechanism for reliable engineering of zinc oxide (ZnO) nanorods to nanoplatelets grafted Mo8O23-MoO2 mixed oxide with controlled morphology, composition and precise understanding of the nanoscale reaction mechanism was developed. These hybrid nanomaterials are gaining interest due to their potential use for energy, catalysis, biomedical and other applications. As an introductory section, we demonstrate a new expansion for the concept 'materials engineering' by discussing the fabrication of metal oxides nanostructures by bottom-up approach and carbon nanoparticles by top-down approach. Moreover, we propose a detailed mechanism for the novel phenomenon that was experienced by ZnO nanorods when treated with phosphomolybdic acid (PMA) under ultra-sonication stimulus. This approach is expected to be the basis of a competitive fabrication approach to 2D hybrid nanostructures. We will also discuss a proposed mechanism for the catalytic deposition of Mo8O23-MoO2 mixed oxide over ZnO nanoplatelets. A series of selection rules (SRs) which applied to ZnO to experience morphology transition and constitute Abdelmohsen theory for morphology transition engineering (ATMTE) will be demonstrated through the article, besides a brief discussion about possibility of other oxides to obey this theory.

Validated Stability-Indicating RP-HPLC Method for Simultaneous Determination of Clorsulon and Ivermectin Employing Plackett-Burman Experimental Design for Robustness Testing.

A sensitive and highly selective stability-indicating gradient HPLC method was developed and validated for simultaneous determination of clorsulon (CLO) and ivermectin (IVM) in the presence of their degradation products. The drugs were subjected to different stress conditions, including acid and alkaline hydrolysis, oxidative, thermal, and photolytic forced degradation. The robustness of the proposed method was assessed using the Plackett-Burman experimental design, the factors affecting system performance were defined, and nonsignificant intervals for the significant factors were determined. The separation was carried out on a ZORBAX SB phenyl analytical column (250 × 4.6 mm id, 5 µm particle size), with gradient elution utilizing 10 mM sodium dihydrogen phosphate and acetonitrile as mobile phase. UV detection was performed for CLO and IVM at 254 nm over a concentration range of 4-140 and 5-50 µg/mL, respectively, with mean percentage recoveries of 99.90 ± 1.30 and 98.59 ± 1.16%, respectively. The proposed method was successfully applied to a pharmaceutical dosage form containing the investigated drugs. The results were statistically compared with the official HPLC methods, and no significant differences were found.

Validated derivative and ratio derivative spectrophotometric methods for the simultaneous determination of levocetirizine dihydrochloride and ambroxol hydrochloride in pharmaceutical dosage form.

Three simple, precise, accurate and validated derivative spectrophotometric methods have been developed for the simultaneous determination of levocetirizine dihydrochloride (LCD) and ambroxol hydrochloride (ABH) in bulk powder and in pharmaceutical formulations. The first method is a first derivative spectrophotometric method ((1)D) using a zero-crossing technique of measurement at 210.4 nm for LCD and at 220.0 nm for ABH. The second method employs a second derivative spectrophotometry ((2)D) where the measurements were carried out at 242.0 and 224.4 nm for LCD and ABH, respectively. In the third method, the first derivative of the ratio spectra was calculated and the first derivative of the ratio amplitudes at 222.8 and 247.2 nm was selected for the determination of LCD and ABH, respectively. Calibration graphs were established in the ranges of 1.0-20.0 µg mL(-1) for LCD and 4.0-20.0 µg mL(-1) for ABH using derivative and ratio first derivative spectrophotometric methods with good correlation coefficients. The developed methods have been successfully applied to the simultaneous determination of both drugs in commercial tablet dosage form.