Chemistry and Chemical Engineering

Abstract

A simple, rapid, and green high-performance liquid chromatography-mass spectrometry (HPLC-MS) method was developed for determination of tauroursodeoxycholic acid (TUDCA), taurocholic acid (TCA), and taurochenodeoxycholic acid (TCDCA) in bio-transformed Jindanfen (BTJDF), which is obtained from chicken bile through a bioconversion process. The sample was prepared using water. The HPLC separation was operated on a poroshell 120 EC-C18 column with a 2.0 min gradient elution procedure. Detection was performed on a single quadrupole mass spectrometer in negative mode with selected ion monitoring mode (SIM). This developed HPLC-MS method presented good linearity (r > 0.997) and sensitivity (limit of quantification, 30.0–80.0 pg) for three analytes. The relative standard deviations (RSDs) for precision, repeatability, and stability were all below 3.00%. The matrix effects and average recoveries of three analytes were 91.2–97.9% (RSDs < 1.50%) and 95.4–103% (RSDs < 3.00%), respectively. The average contents of TUDCA, TCA, and TCDCA in ten batches of samples were 33.8, 13.2, and 20.5%, respectively. Finally, the greenness of the developed method was validated by Analytical Eco-Scale and Complex-GAPI. The developed method was proved to be an eco-friendly, effective, and reliable approach for assaying the three cholic acids in BTJDF, which is help to improve the quality evaluation level of the BTJDF industry.

Abstract

The current technologies for substandard and counterfeit drug detection are either too expensive for low-resource settings or only provide qualitative or semi-quantitative results. GPHF minilab™ is one of them based on thin layer chromatography(TLC) principles with a semi-quantitative capability by visual observation of the spot area and intensity for medicine quality analysis. Thus, its use as a quality control tool for pharmaceutical products has limitations as spot area and intensity visual observation by the naked eye highly varies from analyst to analyst. As such, in this study, the semi-quantitative technique has been transferred to a quantitative approach by capturing the developed TLC plate image using an Android-based mobile phone inside a simple carton box. Then, the spot area was quantified using justTLC software. The quantitative results were compared with the-high performance liquid chromatography (HPLC) method as the golden standard. Accordingly, linearity was observed in the assayed range (80–120% label claim), and the correlation coefficients found were (R ² = 0.958, 0.997, 0.941, and 0.956 for Albendazole, Mebendazole, Artemether, and Lumefantrine, respectively.). The values are satisfactory. The %RSDs found were less than 2% for all drugs [intraday (n = 6) (RSD = 1.17, 1.61, 1.87, and 1.64), and interday (n = 18) (RSD = 1.16, 0.72, 1.12, and 1.18) for Artemether, Lumefantrine, Mebendazole, and Albendazole, respectively]. Moreover, comparisons of results obtained from the sophisticated CAMAG UV cabinet (R ² =0.991, 0.971, 0.946, and 0.967) and the developed simple carton box (R ² = 0.958, 0.997, 0.941, and 0.956) for Albendazole, Mebendazole, Artemether, and Lumefantrine, respectively. The values are comparable and reveal the accuracy of the method. Robustness testings' that were performed under different altered conditions revealed the robustness of the method (RSD less than 2% for all factors). Additionally the deviations from the golden HPLC results were on average −8.62% for albendazole, −3.79% for artemether, and −4.52% for lumefantrine samples. The developed method shows a satisfactory performance capability to utilize the GPHF minilab™ as a quantitative technique for medicine quality control purposes. It will be a very useful tool in a resource-limited setting. The target method profile, which encompasses a simple, low-cost, linear, precise, robust, accurate, and quantitative GPHF minilab™ system, was obtained for Albendazole, Mebendazole, and Arthemeter lumefantine combinations (Co-artem). The proposed method was successfully applied to analyze the content of the marketed medicines in the above mentioned tablets and offered acceptable deviations from the golden HPLC method. Automation of quantitative GPHF minilab™ was highly recommended to enhance the appropriateness and use of this system.

Abstract

Due to the frequent use of paracetamol formulations, it is useful to develop an analytical technique for the determination of intact paracetamol in presence of other drugs and excipients or the degradation products. In this study, a simple, isocratic, fast, specific, accurate and precise stability-indicating high performance liquid chromatography (HPLC) method has been developed and validated for simultaneous quantitative determination of paracetamol (PCM) and potassium sorbate (PS) in oral liquid formulations. The chromatographic separation was achieved on Zorbax SB C18 column (150 × 4.6 mm, 5 µm) with Zorbax SB C18 precolumn (12.5 × 4.6 mm, 5 µm) using distilled water pH 2 with ortho-phosphoric acid and acetonitrile (70:30, v/v) as a mobile phase, and UV detection at 235 nm. The temperature of the column was kept constant at 25 °C. The method was validated according to International Conference on harmonization (ICH) guidelines. The method demonstrated excellent linearity, with a correlation coefficient of 0.9996 and 0.9998 for PCM and PS, respectively, over the concentration ranges of 10–600 μg mL⁻¹ (PCM) and 6–500 μg mL⁻¹ (PS). The retention time was found to be 1.98 and 4.86 min for PCM and PS, respectively. Oral liquid formulation samples were subjected to various stress conditions (acidic and alkaline hydrolysis, as well as oxidative, heat and photolytic degradation) for the purpose of forced degradation study. The major degradation of paracetamol was achieved in acidic and basic stress conditions, while thermal and photolytic degradation generally had the least influence. On the other hand, potassium sorbate was highly susceptible to photolytic degradation. It was also shown that the formulation has strong influence on stability of tested compounds. Forced degradation studies demonstrated the stability-indicating power of the method and can be used to assess the stability of paracetamol and potassium sorbate in oral liquid formulations.

Abstract

Baricitinib (BRT) is a drug substance with potent anti-inflammatory activity indicated in rheumatoid arthritis, atopic dermatitis, severe alopecia areata and recently for the treatment of Covid-19. Process impurities of the drug during its formulation are quite known, however studies regarding its degradation products (DPs) under stress conditions are limited. In this study, the drug was subjected to forced degradation under various degradation conditions, including acidic hydrolysis, alkaline hydrolysis, oxidative and thermal, to determine its inherent stability. To this purpose, a novel HPLC method was developed for the determination of degradation impurities of BRT. Alkaline hydrolysis test showed a selectivity towards breaking C–C bonds. This resulted to five DPs formed by chain scission reactions occurred at the pyrrolo-pyrimidine group between C6–C10 and C8–C9. Also, the ethylsulfonyl-azetidin-ylidene group was subjected to C–C bond cleavage at C12–C15 and C16–C18. Degradation products were further characterized with the use of liquid chromatography quadrupole time of flight tandem mass spectrometry (LC-Q-TOF-MS/MS).

Abstract

A gradient high-performance liquid chromatography (HPLC) method has been developed to determine the concentrations of latanoprost (LP) and latanoprost free acid (LPA) in aqueous solutions. It is novel due to a combination of its simplicity, speed, and detection capability in aqueous solutions for both active drug (LPA) and prodrug (LP). This method is applicable for the research and development of novel drug delivery devices and quality control assays for experimental and commercial laboratory settings, as it allows for a high sample throughput. Samples were chromatographed across a C₁₈ + 2.7 µm 4.6 × 7.5 mm reversed-phase column with gradient elution using a mobile phase of aqueous acetic acid (pH 3.1) and acetonitrile with 0.1% acetic acid. UV spectrophotometry was used to monitor the eluents at 210 nm. Drug concentrations from 1.0 to 150 μg mL⁻¹ were tested, with good linearity observed across the range. LPA had a signature peak at approximately 4.82 min (SD < 0.08) and LP at 9.27 min (SD < 0.07). For both drug and pro-drug, LOD and LOQ were 1.0 and 2.5 μg mL⁻¹, respectively. This assay which accurately measures both prodrug and drug in a single injection, has significant applicability in determining the release kinetics of novel LP drug delivery systems.

Abstract

The advection-convection models (ACM) have practical applications in the investigation of separation processes, where mass (heat) is transferred by convection and diffusion (dispersion) along mass/heat exchanger, eq. adsorption, chromatography column, tubular reactor, etc. The ACM consists of nonlinear partial differential equations which can be solved only with numerical methods. In the article, a comparison of the volume method (VM) and orthogonal collocation on finite elements (OCFE) is presented in terms of their reliability, accuracy of calculations, and speed of calculation. The OCFE proved to be more robust than VM.

The linear ACM model for the chromatography column has an analytical solution in the form of the equation for the number of theoretical plates (N). This equation is often applied in the interpretation and evaluation of model parameters. However, the versions of N equation published in the literature are not correct. The error can lead to significant imprecision for specific cases. Here, in the paper, the revised equations are presented and discussed for the most frequently used chromatography column models.

Abstract

Plant protection products (PPP), crucial for agricultural production, are experiencing increased global demand, particularly with the growing need for food production. To meet this demand, robust analytical methods are essential for confirming the presence and determining active substance concentrations in PPP. This study introduces an analytical method utilizing high-performance liquid chromatography with a diode array detector (HPLC-DAD) for determination of acetamiprid in water-soluble powder formulations. The method, validated according to SANCO/3030/99 rev.5, demonstrated exhibited adequate accuracy and precision, with repeatability expressed as the ratio of the standard deviation (% RSD) to the relative standard deviation (% RSDr) being lower than 1. Recoveries for the active substance at concentrations above 10% ranged from 97% to 103%. The developed method is also characterized by suitable linearity, confirmed by a correlation coefficient >0.99. Specific chromatographic profiles were generated, and acetamiprid content in 180 formulations was analyzed, including reference products. The developed method aligns with “green chemistry” principles, minimizing solvent use and emphasizing energy efficiency. Overall, it offers a comprehensive approach for qualitative and quantitative analysis, ensuring the reliability of PPP quality control.

A vizes élőhelyek a vízi és a szárazföldi ökoszisztémák között elhelyezkedő, igen változatos, és általában nehezen lehatárolható területek. Kiemelt jelentőségük annak köszönhető, hogy bár csak a globális szárazföldi területek mintegy 6–7%-át borítják, kulcsfontosságú szerepet játszanak az éghajlat szabályozásában, a vizes ökoszisztémák biodiverzitásának és hidrológiai viszonyainak fenntartásában, valamint számos további ökológiai és társadalmi funkciót is szolgáltatnak, beleértve az árvízvédelmi, víztisztítási, szén-dioxid-tárolási, élőhelytámogatási és kulturális, rekreációs előnyöket. A vizes élőhelyek azonban mind természetes, mind antropogén hatások következtében térben és időben is dinamikusan változnak, ezért védelmük és megfigyelésük napjainkra igen fontos kutatási területté nőtte ki magát. A műholdas távérzékelés nagyobb területek egyidejű megfigyelését teszi lehetővé, azonban érzékeny a felhőzetre és a légköri hatásokra, bizonytalanságot okozva ezzel az eredményekben. A hagyományos monitoring technológiák mellett a pilóta nélküli légi járművek térnyerése egyre kifejezettebb, köszönhetően rugalmasságának, hatékonyságának és alacsony költségének, miközben nagy térbeli és időbeli felbontású, szisztematikus adatszolgáltatásra képes. Tanulmányunk a pilóta nélküli légi járművek alkalmazási lehetőségeibe nyújt betekintést a vizes élőhelyek felmérésében, valamint áttekinti és összehasonlítja az egyéb távérzékelés technológiák alkalmazhatóságát ezen területek megfigyelésében. Célja, hogy elősegítse a dróntechnológia további terjedését és széles körű alkalmazását a vizes élőhelyek monitorozásában.

Abstract

In this work, an assessment of effective solvents and extraction methods was carried out to recover the bioactive compounds from hawthorn fruit (Crataegus monogyna Jacq.). Extractions assisted by heat, microwave, and ultrasound were carried out using various organic solvents (methanol, ethanol, and isopropanol). pH differential, Folin–Ciocalteu's, and aluminum chloride methods were used to determine total monomeric anthocyanin (TMA), total phenolic compound (TPC), and total flavonoid content (TFC), consecutively. Ferric Reducing Antioxidant Power (FRAP), 2,2-Diphenyl-1-picrylhydrazyl Hydrate (DPPH), and 2,2′- azino- bis (3-ethylbenzothiazoline-6- sulfonic acid) (ABTS) assays were used to measure the antioxidant activity (AA) of the extracts. The outputs revealed that extraction methods and solvents significantly affect anthocyanin concentration, TPC, TFC, AA, and color values of hawthorn fruit extracts. Due to the highest recovered TMA (0.152 ± 0.002 mg ECy3Gl/g of dry weight), TPC (49.14 ± 0.38 mg gallic acid equivalents/g of dry weight), and TFC (18.38 ± 0.19 mg quercetin equivalents/g of dry weight) contents, the ultrasonic-assisted extraction is superior to heat and microwave-assisted extractions. Accordingly, it was also observed that the methanol solvent is more profound than ethanol and isopropanol. Further, the bioactive compounds' content and the extracts' antioxidant activity are shown to be highly correlated. Thus, hawthorn extracts are considered to have antioxidant properties because of their concentrated bioactive compounds.

Abstract

Venetoclax is the first oral Bcl-2 inhibitor with high affinity targeting tumor cell apoptosis mechanism. In this study we developed a simple, sensitive and reliable LC–MS/MS method to determine venetoclax in children's hemolytic or lipemic samples. The method utilized an electrospray ion source and operated in multiple reaction monitoring mode. Venetoclax-d8 was used as an internal standard. Plasma samples were precipitated by acetonitrile containing 10% dimethyl sulfoxide and were separated by a Hypersil GOLD column (2.1 mm × 150 mm, 5 μm). The mobile phase consisted of acetonitrile-2 mM ammonium acetate (30:70, v/v) containing 0.4% formic acid. The quantification for venetoclax and venetoclax-d8 were m/z 868.1 → 636.1, m/z 876.1 → 644.1, respectively. The linear range was 10–2,000 ng mL⁻¹ for venetoclax. The matrix in normal plasma, hemolytic or lipemic plasma had no significant effect on the detection results. The specificity, recovery and stability also met the acceptance criteria of guiding principles for the validation of biological sample quantitative analysis presented in the Chinese Pharmacopoeia (2015). As a result, this method is particularly suitable for determining venetoclax in hemolytic or lipemic samples from children with acute myeloid leukemia. The method, with the application of monitoring drug concentrations in pediatric patients, was successful.