High-performance Liquid Chromatography-diode Array Research Articles

Innovative fabrication of porous polyvinylpyrrolidone-graphene-chitosan adsorbent beads for the extraction of parabens from beverages

Microporous polyvinylpyrrolidone-graphene-chitosan (PVP-G-CS) adsorbent beads were fabricated using a novel technique. The acidic PVP-G-CS mixture was aerated with an air pump, causing bubbles to form in drops that solidified in an alkaline solution to form the adsorbent beads. The beads were applied to simultaneously extract four parabens in beverage samples for analysis by high performance liquid chromatography-diode array detection. The results exhibited linearity in the range of 5.0 – 1000 µg kg−1 under optimal conditions. The ranges of the limits of detection and limits of quantitation were 4.3 – 7.3 µg kg−1 and 14.3 – 24.3 µg kg−1, respectively. The developed beads demonstrated good repeatability (RSD < 5.7 %, n = 6) and were reusable for up to 15 times in juice samples (RSD ≤ 5.3, n = 3). Recoveries of the target parabens from beverage samples ranged from 72.2 % to 102.8 %. Two alcoholic beverages and four juice samples were found to contain paraben concentrations ranging from 7.2 to 14.2 µg kg−1.

Effervescent-assisted Liquid-phase Microextraction Employing Switchable Hydrophilicity Solvent for the Determination of Cortisol and Testosterone in Oral Fluid by High-Performance Liquid Chromatography-Diode Array Detection.

Cortisol and testosterone are important biomarkers for diagnosing complex disorders, including polycystic ovary syndrome and Cushing's syndrome, where symptomatology usually overlaps with other prevalent disorders. This work proposes, for the first time, an analytical method based on a switchable hydrophilicity solvent as an extraction phase for the determination of cortisol and testosterone in oral fluid (OF) by high-performance liquid chromatography with diode-array detection. The optimized extraction conditions consisted of 1000µL of OF, 100µL of decanoic acid solution (65mg/mL), 170µL of Na2CO3, 900µL of H2SO4 and 150µL of acetonitrile for dilution. The method was validated, and coefficients of determination higher than 0.9926, the limit of detection of 4.55ng/mL and the limit of quantification of 15.00ng/mL were obtained. Intra-day precision varied from 5.6% to 11.9%, inter-day precision ranged from 6.1% to 13.5%, and relative recoveries ranged from 98.9% to 104.6% for cortisol, and 89.1% to 103.9% for testosterone. This methodology was successfully applied to five OF samples from volunteers. Moreover, the greenness of this methodology was evaluated based on the sample preparation metric of sustainability achieving a global score of 7.37 which can be considered sustainable.

Application of Fabric Phase Sorptive Extraction as a Green Method for the Analysis of 10 Anti-Diabetic Drugs in Environmental Water Samples

Due to the increased prevalence of diabetes, the consumption of anti-diabetic drugs for its treatment has likewise increased. Metformin is an anti-diabetic drug that is commonly prescribed for patients with type 2 diabetes and has been frequently detected in surface water and wastewaters, thus representing an emerging contaminant. Metformin can be prescribed in combination with other classes of anti-diabetic drugs; however, these drugs are not sufficiently investigated in environmental samples. Fabric phase sorptive extraction (FPSE) has emerged as a simple and green method for the extraction of analytes in environmental samples. In this study, FPSE coupled with a high-performance liquid chromatography diode array detector (HPLC-DAD) was employed for the simultaneous analysis of different classes of anti-diabetic drugs (metformin, dapagliflozin, liraglutide, pioglitazone, gliclazide, glimepiride, glargine, repaglinide, sitagliptin, and vildagliptin) in environmental water samples. Four different fabric membranes were synthesized but the microfiber glass filter coated with sol-gel polyethylene glycol (PEG 300) was observed to be the best FPSE membrane. The parameters affecting the FPSE process were optimized using a combination of one-factor-at-a-time processes and the design of experiments. The FPSE was evaluated as a green extraction method, based on green sample preparation criteria. The FPSE-HPLC-DAD method achieved acceptable validation results and was applied for the simultaneous analysis of anti-diabetic drugs in surface and wastewater samples. Glimepiride was detected below the quantification limit in both lake and river water samples. Dapagliflozin, liraglutide, and glimepiride were detected at 69.0 ± 1.0 μg·L−1, 71.9 ± 0.4 μg·L−1, and 93.9 ± 1.3 μg·L−1, respectively, in the city wastewater influent. Dapagliflozin and glimepiride were still detected below the quantification limit in city wastewater effluent. For the hospital wastewater influent, metformin and glimepiride were detected at 1158 ± 21 μg·L−1 and 28 ± 0.8 μg·L−1, respectively, while only metformin (392.6 ± 7.7 μg·L−1) was detected in hospital wastewater effluent.

Geographical origin identification of cinnamon using HPLC-DAD fingerprints and chemometrics

The commercial value of cinnamon depends largely on its geographical origin. This study proposed high-performance liquid chromatography-diode array detection (HPLC-DAD) fingerprints combined with chemometrics to identify geographical origins of cinnamons. Alternating trilinear decomposition (ATLD) algorithm was applied to extract meaningful chemical information from the HPLC fingerprint data. Then, non-targeted HPLC fingerprints and chemical component information were used as chemical descriptors to distinguish geographical origins using principal component analysis (PCA) and partial least squares-discriminant analysis (PLS-DA)/N-way partial least squares-discriminant analysis (NPLS-DA). Satisfactory classification results were acquired for each discriminant model and the correct classification rates (CCRs) of training and test sets were 100%. Moreover, four characteristic variables were screened by variable importance in projection (VIP) method, three of which were reasonably identified as cinnamic acid, cinnamaldehyde and 2-methoxycinnamaldehyde, which can be regarded as potential markers to distinguish cinnamon from different geographical origins. The results indicated that HPLC-DAD fingerprints combined with chemometrics can be a promising means to identify the geographical origins and screen potential markers of cinnamon samples, especially in the absence of high-cost and sophisticated analytical instrumentals (e.g., high-resolution mass spectrometry and nuclear magnetic resonance spectroscopy). This work can help to prevent cinnamon fraud practices and maintain the normal order of the cinnamon market.

Assessment of Veterinary Antibiotic Use and Occurrence of Veterinary Antibiotics in Livestock Manure from Farms in Rongai Sub-County, Kenya

Veterinary antibiotics are commonly used in livestock rearing to prevent diseases and stimulate growth. The release of antibiotics into the environment has become a significant environmental and public health concern. This research evaluated antibiotic use, livestock treatment, manure utilization, livestock waste treatment methods and antibiotic residues in livestock manure. Questionnaires were administered to 170 farmers rearing both cattle and poultry. Subsequently, 28 livestock manure samples from 15 cattle and 13 poultry rearing farms were collected from various farms to assess concentrations of tetracyclines (Tetracycline, Oxytetracycline) and sulfonamides (Sulfadiazine, Sulfamethoxazole) residues. Residues analysis was done using High Performance Liquid Chromatography-Diode Array Detector (HPLC-DAD). Veterinarians were the most preferred in treating both cattle and poultry in farms. Tetracyclines and sulfonamides were the most consumed class of antibiotics among both poultry and cattle rearing farmers. Compost manure and Biogas were the most preferred use of animal waste within farms. Antibiotic presence in samples was detected in 80% and 93% of cattle and poultry manure respectively. Maximum antibiotic concentrations of 16.24 and 15.18 (mg/kg) were recorded in poultry and cattle manure, respectively. There was a statistically significant difference in antibiotic concentrations in poultry and cattle manure (P&lt;0.05). The results of this research are important in monitoring rising concerns about veterinary antibiotics on environmental and public health.

Cyanide profiling in stone fruit syrups: A comparative study of distillation techniques, a novel derivatization method, and cyanide composition in Maesil (Prunus Mume) syrup

Cyanide ion was derivatized with o-phthalaldehyde and 3-mercaptopropionic acid for high-performance liquid chromatography-diode array detector analysis. The structure was elucidated using nuclear magnetic resonance spectroscopy and ultra-high performance liquid chromatography coupled with triple quadrupole tandem mass spectrometry. Method validation was conducted for three distillation methods to analyze cyanogenic glycosides, cyanohydrins, and free cyanide in fruit syrup. Acid-aided distillation only detected free cyanide, while direct distillation detected both free cyanide and cyanohydrins, and enzyme-aided distillation reflected all three types. These approaches were applied to stone fruit syrups in South Korean markets and households. Among tested, maesil (Prunus mume) syrup contained the highest amount of total cyanide, reaching a maximum of 21.9 mg/kg (cyanide ion equivalent), compared to other syrups. Investigation of cyanide composition changes during maesil syrup production revealed that free cyanide occupies the lowest proportion. Cyanogenic glycosides degraded gradually during aging, while cyanohydrins remained the majority after 12 months aging.

Development of analytical method for determination of 1,3-dimethylamylamine in sports nutrition and bodybuilding supplements using pH-switchable deep eutectic solvents followed by high-performance liquid chromatography-diode array detector.

In this work, an easy, safe, simple, and efficient pH-switchable deep eutectic solvents (DESs)-based liquid phase microextraction followed by high-performance liquid chromatography-diode array detector analysis was developed for the determination of 1,3-dimethylamylamine (DMAA). The switchability of the obtained DESs was investigated by changing the pH. Then the best-selected DES was characterized and the application of the selected DES in the extraction of DMAA from sports nutrition and bodybuilding supplements was investigated. The DES synthesized from l-menthol: oleic acid in a molar ratio of 1:2 had the highest efficiency in the extraction of the target compound. Under the optimum conditions, (50µL of DES, 100µL of 4mol/L KOH, 100µL of 4mol/L HCl, extraction time of 40 s and without salt addition) the calibration graph was linear in the range of 0.05-100µg/kg and limit of detection was 0.02µg/kg. The relative standard deviations including intra-day and inter-day for 10.0µg/kg of DMAA in real samples were 2.7% (n=7) and 5.3% (n=7), respectively. The enrichment factor and percentage extraction recovery of the method were 283 and 85%, respectively. The relative recoveries for DMAA in different samples were in the range of 90%-109%.

Adsorptive removal of organophosphate pesticides from aqueous solution using electrospun carbon nanofibers.

Organophosphate pesticides (OPPs) are widely prevalent in the environment primarily due to their low cost and extensive use in agricultural lands. However, it is estimated that only about 5% of these applied pesticides reach their intended target organisms. The remaining 95% residue linger in the environment as contaminants, posing significant ecological and health risks. This underscores the need for materials capable of effectively removing, recovering, and recycling these contaminants through adsorption processes. In this research, adsorbent materials composed of electro-spun carbon nanofibers (ECNFs) derived from polyacrylonitrile was developed. The materials were characterized through several techniques, including scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Fourier Transform Infrared Spectroscopy (FTIR), Brunauer-Emmett-Teller (BET) analysis, and contact angle measurements. SEM analysis revealed details of the structural properties and inter-fiber spacing variations of the carbon nanofibers. The results revealed that ECNFs possess remarkable uniformity, active surface areas, and high efficiency for adsorption processes. The adsorption studies were conducted using batch experiments with ethion pesticide in aqueous solution. High-Performance Liquid Chromatography-Diode Array Detector (HPLC-DAD) was utilized to quantify the concentrations of the OPP. Various parameters, including adsorbent dosage, pH, contact time, and initial ethion concentration, were investigated to understand their impact on the adsorption process. The adsorption isotherm was best described by the Freundlich model, while the kinetics of adsorption followed a non-integer-order kinetics model. The adsorption capacity of the ECNFs for OPP removal highlights a significant advancement in materials designed for environmental remediation applications. This study demonstrates the potential of ECNFs to serve as effective adsorbents, contributing to the mitigation of pesticide contamination in agricultural environments.

Phenolic profiles of Australian monofloral Eucalyptus, Corymbia, Macadamia and Lophostemon honeys via HPLC-DAD analysis

Australian honey samples from four botanical genera (Lophostemon, Eucalyptus, Macadamia and Corymbia) were investigated for their phenolic content. An improved phenolic extraction and high-performance liquid chromatography-diode array detection (HPLC-DAD) analysis method allowed for the rapid and reliable identification of phenolic compounds. A concentrated liquid-liquid extraction method with an acidified aqueous solution and acetonitrile was optimised to isolate phenolic compounds from the honey matrix. The concentrated extraction method improved sensitivity and permitted the identification of phenolics present at low concentrations (LOD: 0.012–0.25 mg/kg and LOQ: 0.040–2.99 mg/kg). The optimised HPLC-DAD chromatographic conditions gave stable retention times, improved peak separation and allowed for the inexpensive detection of each of the 109 phenolic compounds at their maximum absorbance wavelength. Out of the 109 phenolic compounds included in this study, 49 were identified in the Australian honeys tested. Furthermore, 25 of the 49 compounds were determined to be markers specific to honey floral origin.

Dispersive solid phase extraction of some sulfonamide antibiotics from milk combined with dispersive liquid-liquid microextraction

A covalent organic framework based dispersive solid phase extraction was developed for extraction of several antibiotics from raw cow's milk samples. For this purpose, first, the milk proteins were precipitated by zinc sulfate and after centrifugation, the analytes were extracted by the sorbent. Then, the analytes were desorbed by a proper eluent and were more concentrated by a microextraction procedure. The extractant was used for the analysis of the analytes by high-performance liquid chromatography-diode array detector. Based on the results, acceptable extraction recoveries (62–71 %) and sensitive limits of detection and quantification in the ranges of 0.11–0.19 and 0.37–0.63 ng mL−1, respectively, were obtained. The method can analyze the analytes in broad concentration range. The introduced approach was used in the analysis of fifteen raw cow's milk samples. The obtained data showed that all samples were free of the analytes. According to these results, the method can be considered an efficient procedure for extracting the analytes from raw milk samples.

Novel polyvinyl alcohol/gum tragacanth molecularly imprinted-electrospun nanofibers as adsorbent for selective solid phase extraction of bisphenol A

A polyvinyl alcohol/gum tragacanth molecularly imprinted nanofiber fabricated by electrospinning (PVA/GT-MIN) was used as an efficient adsorbent for the solid phase extraction (SPE) of bisphenol A (BPA) in water samples. PVA and GT were functional polymers and BPA was the template for molecular imprinting. BPA was bound to the polymer matrix through hydrogen bonding. The SEM image of PVA/GT-MIN demonstrated a rough morphology with pores and a diameter of 501 nm. The data for the adsorption of BPA on PVA/GT-MIN fitted the Freundlich isotherm and pseudo-second-order kinetics models. The proposed SPE using PVA/GT-MIN coupled with high performance liquid chromatography-diode array detection presented good linearity from 50 μg/L–5 mg/L (R2 = 0.9999) and yielded a limit of detection of 21 μg/L. The PVA/GT-MIN was applied to extract bottled water for BPA analysis and recoveries were 93.1–97.7 % (RSDs ≤ 3.6 %). This study presents a novel, easily prepared PVA/GT-MIN adsorbent for the extraction of BPA in water.

Inhibitory Activity of Red and Yellow Araçá Genotypes Towards Carbohydrate-Hydrolyzing Enzymes: Putative Role of Ellagitannins

Psidium cattleianum Sabine (araçá) is a species native to Southeast Brazil that grows under abiotic stress conditions conferring high content of bioactive compounds to its fruits. The presence of these compounds is thought to be responsible for the many health-promoting effects including antioxidant, anti-inflammatory, anti-aging and antidiabetic activities. In this study, we evaluated the inhibitory potential of 10 (red and yellow) araçá genotypes towards carbohydrate-hydrolyzing enzymes (CHEs) using cell-free (α-glucosidase, α-amylase) and cell-based assays (sucrase). Araçá extracts displayed stronger inhibition towards α-glucosidase than α-amylase, and only 3 inhibited sucrase activity. The high variability towards the in vitro inhibitory CHEs activity was reflected in the total phenolics content with values ranging between 38.9 and 117 mg/100 g. Of the thirty compounds identified by High-Performance Liquid Chromatography-Diode Array Detection-Electrospray Ionization-Tandem Mass Spectrometry (HPLC-DAD-ESIMS/MS), including caffeic acids (9), organic acids (3) ellagitannins (15) and flavonoids (3), ellagitannins were the most abundant class. Statistical analysis showed ellagitannins were the main discriminators to the CHEs inhibitory activity. In summary, by expanding the panel of red and yellow araçá varieties studied, our results show that not all araçá genotypes inhibit CHE as only YA-23, RA-29, and RA-87 inhibited all 3 CHE which were related to the presence of ellagitannins. Information on the araçá genotypes with greater CHE inhibitory activity allied with the health-promoting effects of ellagitannin-rich foods, can be used to scale-up commercially exploitable genotypes with the aim to develop araçá-containing food formulations targeted to the pre-diabetic population.

Bioactive (Poly)phenol Concentrations in Plant-Based Milk Alternatives in the US Market.

Plant-based milk alternatives (PBMAs) are increasingly consumed as a dairy alternative [Olson, S. Milk and Non-Dairy Milk - US - 2021, 2021.]. Plant foods are rich sources of (poly)phenols, but concentrations of these bioactive phytochemicals in processed PBMAs are not well documented. We procured twenty-seven PBMA products of 6 types (almond, coconut, oat, pea, rice, and soy) for (poly)phenol analysis. Samples were analyzed via ultra high-performance liquid chromatography-diode array with mass spectrometry. The (poly)phenol content of PBMAs varies and is dependent on plant source, brand, and added flavorings. Soy milk had the highest concentration and rice milk had the lowest (91.9 ± 2.7 and 0.9 ± 0.2 mean mg ± SD/cup serving, respectively). Almond milk, the most widely consumed PBMA, averaged 12.1 ± 8.2 mg/cup serving, but the majority of (poly)phenols are derived from added flavorings. PBMAs contain a wide range of potentially bioactive (poly)phenols and may contribute significantly to overall dietary (poly)phenol intake with the potential to impact health outcomes.

Exploring Conventional and Green Extraction Methods for Enhancing the Polyphenol Yield and Antioxidant Activity of Hyssopus officinalis Extracts.

Hyssopus officinalis L. (HO) is, as one of the most prevalently utilized plants, used in traditional medicine to cure various diseases as well as the in food and cosmetic industries. Moreover, HO is a rich source of polyphenols with potent antioxidant properties. However, the studies on the extraction of such compounds from HO are scanty and sparse. This study aims to optimize the extraction of polyphenols and maximize the antioxidant activity in HO extracts. A comprehensive experimental design was employed, encompassing varied extraction parameters to determine the most effective ones. Alongside conventional stirring (ST), two green approaches, the ultrasonic treatment (US) and the pulsed electric field (PEF), were explored, either alone or in combination. The extracted polyphenolic compounds were identified with a high-performance liquid chromatography-diode array detector (HPLC-DAD). According to the results, the employment of ST along with an ethanolic solvent at 80 °C for 150 min seems beneficial in maximizing the extraction of polyphenols from HO, resulting in extracts with enhanced antioxidant activity. The total polyphenol was noted at 70.65 ± 2.76 mg gallic acid equivalents (GAE)/g dry weight (dw) using the aforementioned techniques, and the antioxidant activity was noted as 582.23 ± 16.88 μmol ascorbic acid equivalents (AAE)/g dw (with FRAP method) and 343.75 ± 15.61 μmol AAE/g dw (with the DPPH method). The as-prepared extracts can be utilized in the food and cosmetics industries to bestow or enhance the antioxidant properties of commercial products.

Effects of different postharvest drying processes on flavonoid content and enzymatic activity of Styphnolobium japonicum (L.) Schott flowers for industrial and medicinal use

Traditionally, fresh S. japonicum flowers (SJF) and S. japonicum flowers buds (SJFB) are dried prior to further processing and use. Here, we investigated the ways in which drying techniques, including sun drying (SD), steam drying (STD), microwave drying (MD), hot air drying (HAD, 40 °C, 60 °C, 80 °C, 100 °C), and freeze drying (FD), alter the flavonoid composition of freshly-harvested SJF and SJFB. The flavonoid content of dried samples was determined by Ultra High Performance Liquid Chromatography-Diode Array Detector (UPLC-DAD). Overall, different drying techniques had significantly different effects on the RU content, ranging from 10.63 % (HAD-80 °C) to 34.13 % (HAD-100 °C) in SJF and from 18.91 % (HAD-100 °C) to 29.16 % (HAD-40 °C) and 30.53 % (SD) in SJFB. To clarify the mechanism by which drying affects the RU content of S. japonicum flowers, we studied the activity of a rutin-hydrolyzing enzyme (RHE) isolated from SJF and SJFB using multiple separation and assay methods. According to the Sodium Dodecyl Sulfate-Polyacrylamide Gel Electrophoresis (SDS-PAGE) results, the apparent molecular weight of the purified RHE was approximately 38 kDa. According to UPLC-DAD, RHE catalyzes the production of quercetin (QU) from rutin (RU), but not from other flavonoid glycosides. Drying fresh SJF and SJFB at low and high temperatures can inhibit RHE activity and prevent RU hydrolysis. Therefore, subjecting freshly-harvest SJF to HAD-100 °C, and freshly-harvest SJFB to SD or HAD-40 °C, can greatly increase the RU content. In particular, HAD is viable for large-scale application due to its simplicity and industrial feasibility.

Development and Validation of a High-Performance Liquid Chromatography Diode Array Detector Method to Measure Seven Neonicotinoids in Wheat.

Neonicotinoids (NEOs), used as insecticides against aphids, whiteflies, lepidopterans, and beetles, have numerous detrimental impacts on human health, including chronic illnesses, cancer, infertility, and birth anomalies. Monitoring the residues in food products is necessary to guarantee public health and ecological balance. The present work validated a new method to measure seven neonicotinoid insecticides (acetamiprid ACT, clothianidin CLT, dinotefuran DNT, imidacloprid IMD, nitenpyram NTP, thiacloprid TCP, and thiamethoxan THT) in wheat. The analytical procedure was based on simple and fast wheat sample cleanup using solid-phase extraction (SPE) to remove interferents and enrich the NEOs, alongside the NEOs' separation and quantification by reverse-phase chromatography coupled with a diode array detector (DAD). The validation process was validated using the accuracy profile strategy, a straightforward decision tool based on the measure of the total error (bias plus standard deviation) of the method. Our results proved that, in the future, at least 95% of the results obtained with the proposed method would fall within the ±15% acceptance limits. The test's cost-effectiveness, rapidity, and simplicity suggest its use for determining the levels of acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam in routine analyses of wheat.

Phytocannabinoid profile and potency of cannabis resin (hashish) of northwest Himalayas of India.

Cannabis is one of the most consumed illicit drugs and the potency of cannabis products is of note due to health-related concerns. Hand-rubbed hashish is the ancient technique of extracting psychoactive resin from cannabis plants and is practiced in the Indian Himalayas. This study establishes the cannabinoid profile and potency of hand-rubbed hashish collected from 20 regions of the northwest Himalayas. Fifty-eight hashish samples were analyzed using a validated high-performance liquid chromatography-diode array detection (HPLC-DAD) method. Ten cannabinoids were quantified including acidic (THCA & CBDA), and neutral compounds (CBDV, THCV, CBD, CBG, CBN, Δ9-THC, Δ8-THC, and CBC). The mean concentration (w/w%) of Δ9-THC is 26%; THCA is 15% and THCTotal is 40% is observed in the studied hashish samples. The majority (70%) of the hashish samples were categorized in chemotype I with the THC:CBD:CBN ratio of 91:3:4, and the remaining 30% were categorized under chemotype II with the ratio of 76:15:8. Diverse qualities of hashish are produced in the studied regions as per the seed, plant selection, and skills of manual rubbing, which results in potency variations. The average difference between the least and highest potent hand-rubbed hashish of a region is 27 w/w% (THCTotal). The other studied non-psychoactive cannabinoids have a mean w/w% of <5%, followed by 6% of CBDA. It is concluded that the cultivated and wild cannabis fields in the northwest Himalayas belong to the drug-type cannabis subspecies. Hand-rubbed hashish holds traditional significance and impacts the current policies of legislation.

Chemical fingerprint analysis for quality assessment and control of Curcuma longa L. rhizomes from Vietnam using a high-performance liquid chromatography-diode array detector (HPLC-DAD)

Turmeric, extensively cultivated across Southeast Asia, especially in Vietnam, harbors active polyphenols, primarily curcumin (2–5%), renowned for its diverse health benefits. Pharmacopoeias recognize turmeric, yet it lacks standardized quality assessments and encounters challenges in extraction and identification due to natural variations and adulteration. This analytical method is vital for verifying the authenticity, purity, and quality of turmeric products in both the pharmaceutical and nutraceutical industries. This study successfully developed an efficient extraction process for curcumin (CUR), demethoxycurcumin (DMC), and bisdemethoxycurcumin (BDMC) from Curcuma longa L. rhizomes. The herbal powder was extracted with methanol (1:30, w/v) by the ultrasound-assisted method for 10 minutes, and this process was repeated three times. A high-performance liquid chromatography-diode array detector (HPLC-DAD) method was validated for the simultaneous quantification of three analytes, following the AOAC guideline and achieving a correlation coefficient (R2) value greater than 0.9950. Utilizing the HPLC-DAD method, the study developed a chemical fingerprint analysis for three analytes to identify the characteristic chemical components distinguishing turmeric from each region. Nineteen samples collected from various provinces across Vietnam were subjected to analysis. In all analyzed samples, the concentrations of CUR, DMC, and BDMC ranged from 0.77–10.30%, 0.33–6.92%, and 0.03–3.23%, respectively. CUR was determined to be the dominant compound in most samples, while BDMC consistently exhibited the lowest levels of content. Utilizing the findings derived from the analysis of RRT and RPA metrics, the research assessed variances across sample batches. It is suggested that this newly established approach can be applied to construct and develop raw material areas to serve the needs of each field.

Solvent bar microextraction based on using deep eutectic solvent and multivariate optimization for simultaneous determination of antidepressant and antiepileptic drugs in biological fluids

AbstractMonitoring medications in biological fluids is an essential aspect of patient care, particularly in cases of altered mental status where accurate diagnosis, effective treatment, and even forensic examinations are crucial. In this study, a new approach combining hydrophobic-deep-eutectic and solvent-bar-microextraction (HDE-SBME) followed by a high-performance liquid chromatography-diode array detector (HPLC-DAD) was developed for the simultaneous determination of desipramine, clomipramine, as antidepressant and carbamazepine as antiepileptic agents in untreated human urine and plasma samples. The HDE solvents, synthesized using various ratios of menthol and fatty acids, were utilized in the SBME setups. Computational methods were employed to predict the structure and modes of interaction between HDE and the chosen analytes. Central composite design methodology (CCD) was used for multivariate optimization of the effects of different parameters influencing the extraction efficiency of the proposed method. Under optimized experimental conditions, the calibration graph of the spiked selected drugs in urine and plasma samples demonstrated excellent linearity (R2 ≥ 0.994), with limits of detection/quantification below 0.60/2.02 μg L−1. The extraction recoveries achieved were 88–97%, and the repeatability/reproducibility (RSD%, n = 5) was less than 6.12/7.57. The proposed method was successfully applied to determine selected drugs in patients' urine and plasma samples. The proposed method detects three drugs in patients' urine and plasma samples without using toxic volatile organic solvents. The proposed microextraction technique exhibited a confident sensitivity, feasible operation, and simplicity compared with other published methods. Thus, it can be considered a promising method for monitoring the therapeutic levels of specific antidepressant and antiepileptic drugs in urine and plasma samples.

Discovery and determination of misuse and chemotypes of Pogostemon cablin by liquid chromatography-quadrupole time-of-flight mass spectrometry and liquid chromatography with diode-array detector.

Traditional Chinese medicine (TCM) has garnered significant scientific interest in healthcare but faces increased regulatory scrutiny due to concerns about uncontrolled usage. This study focuses on characterizing Pogostemon cablin (PC) to mitigate potential misuse and identify chemotype differences. Leveraging untargeted metabolomics, we identified 222 distinctive features effectively differentiating PC from Agastache rugosa (AR), reducing misidentification risks. Pogostone and tilianin emerged as potential markers, leading to a high-performance liquid chromatography-diode array detection (HPLC-DAD) method development for PC and AR discrimination. Evaluation of PC chromatograms revealed notable profile and pogostone level differences among samples, suggesting chemotype associations. Untargeted metabolic profiling identified 78 features with significant differences, highlighting 7,3',4'-tri-O-methyleriodictyol as a potential discriminatory marker between PC chemotypes. The developed HPLC-DAD method quantified pogostone and 7,3',4'-tri-O-methyleriodictyol, effectively discriminating PC chemotypes. This platform differentiates PC and AR and distinguishes chemical types within PC, like pogostone-type and patchoulol-type. Applied to local TCM stores, it ensures PC authenticity. This approach addresses TCM control concerns, enhancing understanding and application of herbal medicine by providing insights into PC chemical composition and discrimination.