High Performance Liquid Chromatography Coupled With Diode Array Detector Research Articles

Chemical fingerprinting and multicomponent quantitative analysis for quality control of Cinnamomum tamala collected from Western Himalaya by HPLC-DAD

Cinnamomum tamala, commonly known as “Indian bay leaf” or “Tejpat”, is an economically important plant widely used in medicine, food and cosmetic industries. Growing demand for its leaf and bark in the herbal trade and non-availability of quality materials lead to large-scale species admixture and adulteration in the global market. The present study aims at developing a validated HPLC-DAD (High-performance liquid chromatography coupled with diode array detection) method and multiple markers-based chemical fingerprints for quality evaluation of C. tamala leaf extracts. Five bioactive compounds, viz., coumarin, cinnamyl alcohol, cinnamic acid, cinnamaldehyde and cinnamyl acetate, were identified and quantified in 28 samples collected from the western Himalayan region of India. The chromatographic separation was achieved on Shimadzu Shimpak C18 column (dimension 250 × 4.6 mm, pore size 5 μm) with a gradient elution of mobile phase using acetonitrile and 0.1 percent phosphate buffer and the chromatograms were obtained at a wavelength of 265 nm. The method validation was done by analyzing the linearity, LOD, LOQ, precision, stability, repeatability and recovery rates of standard compounds for quantitative analysis. The values of coefficient of correlation (R2) were found to be close to 1 for linearity and similarity analysis; and standard deviation was less than 3 percent in case of precision, stability, repeatability and recovery rates. The content of target compounds such as coumarin, cinnamyl alcohol, cinnamic acid, cinnamaldehyde and cinnamyl acetate varied in the range of 0–1.09, 0–0.05, 0.07–0.51, 0.39–1.27 and 0–0.27 percent, respectively. In the chemical fingerprint of C. tamala leaves, a total of 13 peaks were assigned as common peaks. The results of the study indicated that the HPLC method now developed combining chemical fingerprint with quantification of analytes could serve as a useful tool for quality evaluation of herbal raw materials of C. tamala and a valuable reference for further study.

Chemical Profile and Bioactivity of Rubus idaeus L. Fruits Grown in Conventional and Aeroponic Systems.

Raspberry (Rubus idaeus L.) is a fruit of great interest due to its aroma, nutritional properties, and the presence of many bioactive compounds. However, differences among cultivation systems can affect its composition and, consequently, its potential bioactivity. Herein, for the first time, raspberries grown in an aeroponic system were investigated for their chemical profile and antioxidant and anti-inflammatory activity, as well as their enzyme (α-glucosidase and pancreatic lipase) inhibitory properties in comparison to wild and conventionally cultivated fruits. High-performance liquid chromatography coupled with diode array detection (HPLC-DAD) analyses revealed the presence of gallic acid, caffeic acid, chlorogenic acid, p-coumaric acid, ferulic acid, rutin, and catechin in all the samples. The extracts exhibited in vitro anti-inflammatory activity (inhibition of nitric oxide production) regardless of the cultivation method. Of particular interest is the ability of raspberries to inhibit pancreatic lipase. With the exception of the β-carotene bleaching test, the raspberries grown in conventional and aeroponic systems were more active in terms of antioxidants than wild fruits, as evidenced by the ABTS (IC50 in the range 1.6-3.4 μg/mL), DPPH (IC50 in the range 8.9-28.3 μg/mL), and FRAP tests (24.6-44.9 μM Fe(II)/g). The raspberries from aeroponic cultivation were generally able to exert the same bioactivity as those obtained from both conventionally cultivated and wild fruits, supporting the consideration that in the future, this technology could reshape agriculture by mitigating resource constraints, fostering sustainable practices and increasing yields.

Copaifera mildbraedii Desf.: Phytochemical Composition of Extracts, Essential Oil, and In Vitro Biological Activities of Bark

Copaifera mildbraedii Desf. is an evergreen tree with an umbrella-like crown. It is distributed from south-eastern Nigeria eastward to the Central African Republic (CAR). The aim of this study was to assess the chemical composition and biological activities of C. mildbraedii bark, as well as the chemical composition of the essential oil. Ethyl acetate (EtOAc) and methanol (MeOH) extracts showed a high total phenolic content (TPC) (149.9 and 148.8 mg GAE/g dry residue (dr), respectively), which was related to good antioxidant activity (DPPH) with an IC50 of 21.2 and 12.9 µg/mL, respectively. High-performance liquid chromatography coupled with diode array detector (HPLC-DAD) analysis revealed seven phenolic compounds with myricitrin (13.3 mg/g dr) and 2,4-dihydroxy-3,6-dimethyl benzoic acid (30.7 mg/g dr) as major compounds, while gas chromatography-mass spectrometry (GC-MS) analysis enabled detection of 13 volatile compounds (3 before and 10 after derivatization). Thirty compounds were identified in the essential oil, which corresponds to 65% of all identified compounds. Among the latter, E,E-farnesylacetone and γ-gurjunene were considered as major compounds (8.08 and 10.43%, respectively). The EtOAc extract showed a potent potential, simultaneously, against anti-acetylcholinesterase (AChE), anti-15-lipoxygenase (15-LOX), anti-xanthine oxidase (XOD), and cytotoxic (OVCAR) activities, whereas cyclohexane (CYHA) and dichloromethane (DCM) extracts showed a cytotoxic effect with high percentages of inhibition (95.2%).

Performance evaluation of Moringa oleifera seeds aqueous extract for removing Microcystis aeruginosa and microcystins from municipal treated-water.

Introduction: Toxic microcystins (MCs) produced by cyanoprokaryotes -particularly by the cosmopolitan cyanobacterium Microcystis aeruginosa- pose adverse effects on aquatic organisms and their ecosystem and may also cause serious impacts on human health. These harmful monocyclic heptapeptides are the most prevalent cyanotoxins reported in freshwaters and must be eliminated for avoiding MCs release in receiving water bodies. Hence, this work aimed to test the efficacy of Moringa oleifera seeds water-based extract (MO) as a natural coagulant for removing cyanobacteria (especially M. aeruginosa), microalgae, and its associated MCs from pre-treated municipal wastewaters. Methodology: Four different MO coagulant doses (25, 50, 75 and 100mgL-1) were investigated for cyanobacteria and microalgae removal by conventional coagulation assays and morphology-based taxonomy studies. Additionally, water turbidity and chlorophyll a (Chl a) content were also determined. Further, the presence and concentration of MCs soluble in water, remaining in the particulate fraction, and flocculated within the residual sludge were assessed using high-performance liquid chromatography coupled with diode array detection (HPLC-DAD). Results: The treatment with MO at 100mg L-1 substantially reduced the number of cyanobacterial and microalgal species in the treated samples (average removal rate of 93.8% and 86.9%, respectively). These results agreed with a ∼44% concomitant reduction in Chl a and ∼97% reduction in water turbidity (a surrogate marker for suspended solids content). Notably, MCs concentrations in the treated water were significantly lowered to 0.6 ± 0.1µg L-1 after addition of 100mg L-1 MO. This value is below the WHO recommended limits for MCs presence in drinking water (<1.0µg L-1). Discussion: The present study provides promising insights into the applicability of MO as a cost-effective, reliable, and sustainable natural coagulant, particularly for using in developing countries, to eliminate harmful cyanobacteria and cyanotoxins in municipal water treatment facilities.

Studies on the orange red color development on the surface of the dried Ume (Prunus mume Sieb. et Zucc.) in a drying system equipped with full spectrum artificial sunlight

An orange-red fraction was obtained from fully sun-dried Ume (Prunus mume Sieb. et Zucc.) using a layer extraction method with acetone, methanol, and chloride as organic solvents. Liquid chromatography tandem-mass spectrometry (LC-MS/MS) analysis revealed a series of (-)-epicatechin (EC) dimers and trimers. The polymers were compared with published m/z negative mode and their fragments were characterized as procyanidin B2–2 (A-type dimer), procyanidin C1–2 (A-type trimer), and procyanidin C1–4 (dehydrotriepicatechin B1). High-performance liquid chromatography coupled with diode array detection (HPLC-DAD) analysis showed that the dehydrotriepicatechin B1 peak had an absorption maximum of 425 nm in the visible light range (400–600 nm). Similar results were obtained when salted Ume were subjected to simulated sunlight drying conditions using a low-temperature artificial drying system. Testing of blue light in an (-)-epicatechin (EC) model system showed the strongest catalytic effect. This study suggests that during sun-drying of salted Ume, (-)-epicatechin (EC) concentrates on the epidermis and undergoes photooxidative polymerization after sufficient sun exposure, further producing double bonds that cause the surface of sun-dried Ume to appear orange-red. This research has led to an innovative drying system that can replace sun-drying and avoid external factors such as insects, bacteria, meteorology, and food nutrition improvement that affect the quality of dried products.

Cytotoxicity and Genotoxicity Evaluation of Zanthoxylum rhoifolium Lam and In Silico Studies of Its Alkaloids.

The alkaloids isolated from Zanthoxylum rhoifolium have demonstrated great pharmacological potential; however, the toxic profiles of these extracts and fractions are still not well elucidated. This study evaluated the toxicity of the ethanol extract (EEZR) and neutral (FNZR) and alkaloid (FAZR) fractions. Chemical characterization was performed by chromatographic methods: thin-layer chromatography (TLC) and high-performance liquid chromatography coupled with diode array detection (HPLC-DAD). The cytotoxicity of the samples was evaluated in human hepatocellular carcinoma (HepG2) cells using the cell viability method (MTT) and mutagenicity by the Allium cepa assay (ACA). Alkaloids isolated from the species were selected for toxicity prediction using preADMET and PROTOX. The molecular docking of the topoisomerase II protein (TOPOII) was used to investigate the mechanism of cell damage. In the EEZR, FNZR, and FAZR, the presence of alkaloids was detected in TCL and HPLC-DAD analyses. These samples showed a 50% inhibitory concentration (IC50) greater than 400 μg/mL in HepG2 cells. In ACA, time- and concentration-dependent changes were observed, with a significant reduction in the mitotic index and an increase in chromosomal aberrations for all samples. Nuclear sprouts and a micronucleus of the positive control (PC) were observed at 10 µg/mL and in the FAZR at 30 µg/mL; a chromosomal bridge in FNZR was observed at 105 µg/mL, CP at a concentration of 40 µg/mL, and nuclear bud and mitotic abnormalities in the EEZR were observed at 170 µg/mL. The alkaloids with a benzophenanthridine were selected for the in silico study, as structural alterations demonstrated certain toxic effects. Molecular docking with topo II demonstrated that all alkaloids bind to the protein. In summary, the fractionation of Z. rhoifolium did not interfere with toxicity; it seems that alkaloids with a benzophenanthridine nucleus may be involved in this toxicity.

Wine Lees as Source of Antioxidant Molecules: Green Extraction Procedure and Biological Activity

An ultrasound-assisted extraction method, employing ethanol and water as solvents at low temperature (30 °C) and reduced time (15 min), was proposed to extract bioactive molecules from different cultivars (Magliocco Canino, Magliocco Rosato, Gaglioppo, and Nocera Rosso) of wine lees. All the extract yields were evaluated and their contents of phenolic acids, flavonoids, and total polyphenols were determined by means of colorimetric assays and high-performance liquid chromatography coupled with diode-array detection (HPLC-DAD) and Fourier transform infrared (FTIR) techniques. Radical scavenging assays were performed and the Magliocco Canino extracted with a hydroalcoholic mixture returned the best results both against ABTS (0.451 mg mL-1) and DPPH (0.395 mg mL-1) radicals. The chemometric algorithms principal component analysis (PCA) and partial least square regression (PLS) were used to process the data obtained from all qualitative-quantitative sample determinations with the aim of highlighting data patterns and finding possible correlations between composition and antioxidant features of the different wine lees cultivars and the extraction procedures. Wine lees from Magliocco Canino and Magliocco Rosato were found to be the best vegetable matrices in terms of metabolite content and antioxidant properties. The components extracted with alcoholic or hydroalcoholic solvents, specifically (-)-epigallocatechin gallate, chlorogenic acid, and trans-caftaric acid, were found to be correlated with the antioxidant capacity of the extracts. Multivariate data processing was able to identify the compounds related to the antioxidant features. Two PLS models were optimized by using their concentration levels to predict the IC50 values of the extracts in terms of DPPH and ABTS with high values of correlation coefficient R2, 0.932 and 0.824, respectively, and a prediction error lower than 0.07. Finally, cellular (SH-SY5Y cells) antioxidant assays were performed on the best extract (the hydroalcoholic extract of Magliocco Canino cv) to confirm its biological performance against radical species. All these recorded data strongly outline the aptness of valorizing wine lees as a valuable source of antioxidants.

Optimization of ultrasound-assisted extraction based on response surface methodology using HPLC-DAD for the analysis of red clover (Trifolium pretense L.) isoflavones and its anti-inflammatory activities on LPS-induced 3D4/2 cell.

Trifolium pratense L. has anti-inflammatory, antioxidant, cardiovascular disease prevention, and estrogen-like effects. The existing method for the assay of effective components is commonly based on a spectrophotometer, which could not meet the requirement of quality control. Furthermore, although there have been many studies on the anti-inflammation effect of red clover, a few have been reported on the regulatory effect of red clover isoflavones (RCI) on lipopolysaccharide (LPS)-induced inflammatory response in porcine alveolar macrophages (3D4/2 cells), and its mechanism of action is still unclear. The main components of RCI including daidzein, genistein, and biochanin A were accurately quantified by high-performance liquid chromatography coupled with diode array detection (HPLC-DAD) after optimizing the extraction process through response surface methodology. The anti-inflammatory potential of RCI was carried out by detecting the level of inflammatory cytokines and mRNA expression of related genes. Furthermore, its anti-inflammatory mechanism was explored by investigating two signaling pathways (NF-κB and MAPK). The optimal extraction conditions of RCI were as follows: the concentration of ethanol is 86% and the solid-liquid ratio is 1:29, with the herb particle size of 40 mesh sieve. Under the optimal conditions, the total extraction of target components of RCI was 2,641.469 μg/g. The RCI could significantly suppress the production and expression of many pro-inflammatory cytokines. The results of the Western blot revealed that RCI dramatically reduced the expression of p65, p-p65, IκB-α, p38, and p-p38. These results are associated with the suppression of the signal pathway of p38 MAPK, and on the contrary, activating the NF-κB pathway. Collectively, our data demonstrated that RCI reversed the transcription of inflammatory factors and inhibited the expression of p65, p-p65, IκB-α, and p38, indicating that RCI had excellent anti-inflammatory properties through disturbing the activation of p38 MAPK and NF-κB pathways. The extraction conditions of RCI were optimized by HPLC-DAD combined with response surface methodology, which will contribute to the quality control of RCI. RCI had anti-inflammatory effects on the LPS-induced 3D4/2 cells. Its mechanism is to control the activation of NF-κB and p38 MAPK pathways, thereby reducing the expression of inflammatory-related genes and suppressing the release of cytokines.

A Validated HPLC Multichannel DAD Method for the Simultaneous Determination of Amoxicillin and Doxycycline in Pharmaceutical Formulations and Wastewater Samples

The quality of marketed pharmaceutical formulations must be guaranteed to attain better remedial effects and lower toxicity. The wide exploitation of antibiotics may lead to their presence as residues in body fluids and wastewaters, potentially toxic to human health. Consequently, determining antibiotics in pharmaceutical formulations and water samples is of significant importance. This paper aims to explore the possibilities of a high-performance liquid chromatography coupled with diode array detection (HPLC-DAD) method to obtain a simple, fast, and efficient analytical tool for the simultaneous determination of antibiotics in pharmaceutical formulations and environmental samples. The method was completely validated with regard to specificity, linearity, detection and quantification limits, precision, accuracy, and robustness according to the requirements of existing guidelines, and was proven to be reliable and suitable for the envisioned application. The linearity study was conducted for the calibration curves in the range of 10–100 μg/mL. The limits of detection and quantification were found to be 0.2 and 0.7 μg/mL for amoxicillin and 0.3 and 1.0 μg/mL for doxycycline, respectively. The high recovery of drugs from their commercial pharmaceutical formulations (93%) and from wastewater samples (98%) indicated good accuracy and precision. The method is robust for small or deliberate changes to the chromatographic parameters, and it was successfully applied for the quantitative determination of amoxicillin and doxycycline in wastewater and commercial tablets. The obtained results proved that the validated method is appropriate for its intended use in the routine quality control and assay of both antibiotics studied.

Removal of clinically significant antibiotics from aqueous solutions by applying unique high-throughput continuous-flow plasma pencil and plasma brush systems

High demands of medical and husbandry sectors led to a massive annual production of 100,000 tonnes of various antibiotics on a global scale. Considering that an access to sublethal doses of these pharmaceuticals causes subsequent increase in resistance of virulent human bacterial pathogens, there is a substantial need for development of novel methods and techniques for degradation of antibiotics from aqueous solutions. Here, high-throughput continuous flow plasma pencil and plasma brush methodologies were developed and verified for their applicability for removal of antibiotics from solutions, as estimated by high-performance liquid chromatography coupled with diode-array detection (HPLC-DAD) or ultraperformance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS). The removal efficiency of drugs treated by the plasma pencil was in the range from 3 to 24%, and was corresponded to with 1.39% to 10.76% losses in the antibacterial properties of the plasma-treated solutions. However, application of a unique plasma brush increased the antibiotics degradation rates significantly, now falling in the range from 29 to 67% that led to 12.06–81.59% decrease in the antimicrobial properties of the plasma-exposed antibiotics solutions. The deviations in the effectiveness of the plasma pencil and the plasma brush methods were assigned with the types and amounts of generated species. Various intermediate degradation products were also detected in the post-plasma solutions, which derived from the oxygen attack to nucleophilic sides of the antibiotic molecules. We assume that such novel high-throughput, continuous flow methodological setups may find application in hospitals as an end-of-pipe technology for routine elimination of pollutants before reaching municipal sewage treatment plants.

Isoquinoline Alkaloid Contents in Macleaya cordata Extracts and Their Acetylcholinesterase and Butyrylcholinesterase Inhibition.

An important strategy for treating neurodegenerative disorders is to maintain the levels of acetylcholine in the synaptic cleft by blocking the cholinesterases. Searching for new effective compounds with inhibited acetylcholinesterase and butyrylcholinesterase activity is one of the most significant challenges of the modern scientific research. The aim of this study was the optimization of the condition for cholinesterase activity determination by high-performance liquid chromatography coupled with diode array detector (HPLC-DAD) in terms of concentrations of enzymatic reaction mixture components, temperature of incubation, and incubation time. In vitro investigation of acetylcholinesterase and butyrylcholinesterase activity inhibition by some isoquinoline alkaloids and extracts obtained from the aerial part and roots of Macleaya cordata collected in May, July, and September. Acetylcholinesterase and butyrylcholinesterase activity inhibition of the extracts obtained from the plant had not been tested previously. The application of the HPLC method allowed eliminating absorption of interfering components, for example, alkaloids such as sanguinarine and berberine. The HPLC method was successfully applied for the evaluation of the acetylcholinesterase inhibitory activity in samples such as plant extracts, especially those containing colored components adsorbing at the same wavelength as the adsorption wavelength of 5-thio-2-nitro-benzoic acid, which is the product of the reaction between thiocholine (product of the hydrolysis of acetyl/butyrylthiocholine reaction) with Ellman’s reagent. Moreover, liquid chromatography coupled with a triple quadrupole mass spectrometer (LC–QqQ–ESI–MS/MS) analysis allowed evaluating the identification of relevant bioactive compounds in the obtained plant extracts. The investigated alkaloids, especially sanguinarine and chelerythrine, and all the Macleaya cordata extracts, especially the extract obtained from the aerial part collected in May, exhibited very high cholinesterase activity inhibition. HPLC-DAD was also applied for the kinetics study of the most active alkaloids sanguinarine and chelerythrine. Our investigations demonstrated that these plant extracts can be recommended for further in vivo experiments to confirm their cholinesterase inhibition activity.

A New Approach for Histamine Functionalized Nanoparticles as Sorbent Phase for Bar Adsorptive Microextraction (BAµE) and Determination of Parabens in Water by HPLC-DAD

In this study, for the first time, histamine-functionalized magnetic nanoparticles (HIS-MNP) were used as sorbent phase combined with bar adsorptive microextraction (BAµE) for the determination of methylparaben (MP), ethylparaben (EP), propylparaben (PP), and butylparaben (BP) in water samples by high performance liquid chromatography coupled with diode array detection (HPLC-DAD). Extraction and desorption conditions, including desorption time and solvent, ionic strength effect and extraction time, were investigated. The extractions were performed for 90 min, 30% of NaCl and sample pH 5. Desorption was carried out using 250 μL of acetonitrile:methanol (25:75 v/v) for 30 min. The limits of detection (LODs) were of 1.5 μg L−1 and limits of quantification (LOQs) were 5.0 μg L−1 for all analytes. The intra-day precision ranged from 1% for EP, PP and BP to 3% for MP, EP, PP and BP. The inter-day precision ranged from 3% for EP to 18% for BP. The relative recoveries varied from 81 to 125%, and relative standard deviations (RSD) ranged between 1 and 16%.

Analysis of HMF and furfural in hydrolyzed lignocellulosic biomass by HPLC-DAD-based method using FDCA as internal standard

HMF (hydroxymethylfurfural), a compound that occurs naturally in food, is derived from the dehydration of monosaccharides (glucose and fructose) in products subjected to high-temperature treatments or to aging processes. HMF can be obtained by acid-catalyzed dehydration of lignocellulosic biomasses such as sugarcane bagasse and other agricultural residues. In this work, analytical quantification of HMF and furfural (the main co-product) was performed using high-performance liquid chromatography coupled with diode array detection (HPLC-DAD). The official method employs isocratic elution with a mobile phase composed of water and acetonitrile at a ratio of 80:20 (v/v). The analytical method proposed here was developed using 2,5-furandicarboxylic acid (FDCA) as internal standard, for the first time, with 0.01 mol L−1 trisodium citrate and ultrapure water as the mobile phase, adjusted to pH 2.5. The acidity of the mobile phase was required to avoid FDCA deprotonation. Good peak resolution and selectivity were obtained, without differences in the retention times of the analytes present in the standard solutions used to obtain the analytical curve and in the aqueous and organic phases from the synthesis of HMF using lignocellulosic biomass hydrolysis. The method complies with the current recommendations of AOAC regarding validation parameters.•The proposed HPLC method improves peak selectivity and resolution.•The method is suitable for acid sample media, such as aqueous and organic hydrolysis phases.•2,5-Furandicarboxylic acid (FDCA) was used as internal standard.

Carotenoid extraction and analysis from blood plasma/serum.

Accurate and sensitive methods to quantify carotenoids in blood plasma/serum are the basis for assessing carotenoid intake and associating physiological effects. This chapter introduces carotenoid chemistry, an overview of carotenoid food sources, and current knowledge of carotenoid absorption and metabolism, along with factors that affect these processes. We also detail a commonly used method to extract plasma/serum carotenoids using liquid-liquid extraction and analysis by high performance liquid chromatography coupled with diode array detection (HPLC-DAD). A spreadsheet to aid in this quantitative analysis can be found at www.github.com/CooperstoneLab/carotenoid-analysis.

Additive effect of the probiotics Lactobacillus exopolysaccharides and the Satureja calamintha extracts on enteropathogenic Escherichia coli adhesion

This study assessed the inhibitory potential of the probiotics Lactobacillus (LB) exopolysaccharides (EPS) with or without extracts of Satureja calamintha on enteropathogenic Escherichia coli (EPEc) responsible for gastroenteritis. Methanolic and hydromethanolic extracts were prepared by cold maceration and subjected to phytochemical screening. The compounds of the extracts were determined with the colorimetric assays and identified using high-performance liquid chromatography coupled with diode array detector (HPLC-DAD). Antioxidant activities of the extracts were also evaluated by using 2,2-diphenyl-1-picrylhydrazil (DPPH) radical scavenging. Antibacterial effect on EPEc was evaluated by using both agar disc diffusion and microdilution methods. The in vitro test of auto-aggregation was investigated. Microbiological analysis showed that 63% of the isolated LB were producing EPS, with the amount ranging from 8.21 to 43.13 mg/L. Chemical analysis of the extracts revealed the presence of polyphenols and flavonoids, more abundant in the hydromethanolic extract, which presented the highest content with 2.11 mg EGA/g of polyphenol and 1.64 mg EC/g of flavonoids and 1.71 mg EGA/g of polyphenol and 1.15 mg EC/g of flavonoids in the methanolic extract. Hydromethanolic extracts and EPS exhibited a more important activity than did the methanolic extract against EPEc. The combined action of EPS and extracts reduced the aggregation ability of EPEc and decreased the rate of their adhesion.

Combination of zeolitic imidazolate framework-67 and magnetic porous porphyrin organic polymer for preconcentration of neonicotinoid insecticides in river water

A nanostructured material composed of zeolitic imidazolate framework-67 and magnetic porous porphyrin organic polymer (ZIF-67@MPPOP) was successfully synthesized and applied for the enrichment of neonicotinoid insecticides in river water. The analytes were detected and quantified using high performance liquid chromatography coupled with diode array detector (HPLC-DAD) and liquid chromatography mass spectrometry (LC-MS). Influential experimental parameters were optimized using response surface methodology based on Box Behnken design. The adsorption capacities were 69.46, 80.53, 85.39 and 90.0 mg g−1 for thiamethoxam, imidacloprid, acetamiprid and clothianidin, respectively. At optimal experimental conditions, low limit of detection (LOD), limit of quantification (LOQ) and linearity were 0.0091–0.04 µg L−1, 0.04–0.13 µg L−1 and (0.04-600 µg L−1), respectively. The relative standard deviation used to evaluate the reproducibility and repeatability of the method was less than 5%. Finally, the method was employed for determination of four neonicotinoid insecticides in river water.

Mulinum spinosum root extract, rich in antioxidant compounds, mitigates harmful effects in mice with diet-induced metabolic syndrome

Background: Metabolic syndrome (MetS) is a health issue with a high incidence in adult population. Using herbal medicines for the management of serious complications of MetS, such as dyslipidemia and hyperglycemia, is highly promising. An aqueous extract from Mulinum spinosum (M. spinosum), traditionally used as hyperglycemic and anti-inflammatory, could have beneficial effects on the treatment of MetS.Purpose: The present study was aimed to characterize the composition of M. spinosum roots decoction, and to evaluate antidiabetic, antilipemic and antioxidant effects in an animal model of MetS.Study design and methods: M. spinosum roots extract was characterized using high-performance liquid chromatography coupled with diode array detection (HPLC-DAD) method. Total Phenolic Content (TPC) was spectrophotometrically measured and the antioxidant capacity was determined by the oxygen radical absorbance capacity (ORAC) assay. To generate the MetS model, adult male C57BL/6 mice were fed with a 20% w/v fructose (Fru) in drinking water combined with 30% w/w high fat diet (HFD) over a period of 12 weeks. M. spinosum aqueous extracts (3 or 6 g/kg/day) were administered in drinking water together with Fru-HFD. At the end of the exposure period, mice were weighed and glucose tolerance test was determined. After sacrifice, adipose tissues were isolated and blood samples were collected to evaluate lipid profile, lipid peroxidation level (LPO) and ferric reducing antioxidant power (FRAP).Results: The characterization of M. spinosum revealed the presence of caffeic acid, trans-resveratrol, kaempferol-3-glucoside, (-)-epicatechin, (-)-gallocatechin gallate, (-)-epigallocatechin and (+)-catechin. A high antioxidant capacity of the extract was revealed by ORAC test. Mice fed a Fru-HF diet and treated with M. spinosum, reduced diet-induced weight gain and significantly decreased mesenteric fat compared with Fru-HFD group (p<0.01). Post prandial glycaemia significantly diminished when mice were treated with M. spinosum, and also total cholesterol, LDL-cholesterol and triglycerides (TG) were reduced. Regarding the antioxidant effect of the consumption of M. spinosum, we found a decrease in plasmatic LPO, and a significant increase in plasmatic FRAP.Conclusion: To our knowledge, the phenolic composition and the antioxidant capacity of M. spinosum roots decoction is reported for the first time. In addition, we provide evidence that M. spinosum root extract is a promising source of antioxidants able to alleviates Fru-HFD-induced metabolic alterations and slow the progression of MetS.

Application of Chemometrics-assisted HPLC-DAD Strategies for Simultaneous Determination of Paracetamol, Pseudoephedrine HCl, Dextromethorphan HBr, Doxylamine Succinate and Saccharin in Syrup Formulation

Introduction:This study introduces an effective strategy, which combines high performance liquid chromatography coupled with diode array detection (HPLC-DAD) with multivariate calibration methods for the simultaneous determination of paracetamol (PAR), pseudoephedrine HCl (PSE), dextromethorphan HBr (DEX) and doxylamine succinate (DOX) along with sweetener saccharin (SAC) in syrup formulation. Methods: PLS-2 and PCR calibration algorithms were selected for data processing. Based on the strategy, all target analytes were rapidly quantified within 5.3 min under the simple isocratic elution (water: methanol, 20/80, v/v) without a complete separation. The performances of the proposed methods were confirmed by analyzing a series of synthetic solutions including different concentrations of analytes. Results:The average recovery values were in the range of 100.33 to 103.70%, and the REP (relative error of prediction) values ranged from 1.96 to 4.36% showed that these methods could provide satisfactory predictions. Conclusion:Novel HPLC methods coupled with PLS and PCR algorithm enable a simple, fast and low-cost analysis of similar pharmaceutical products for simultaneous determination of the target compounds.

Optimization of an analytical HPLC-DAD method for detecting hydroxycinnamic acid derivatives from mixtures of Saussurea grandifolia and Taraxacum coreanum

An analytical method was established to identify and quantify hydroxycinnamic acids, such as 1,5-dicaffeoylquinic acid (DCQA) and chicoric acid (CA), in mixtures of Saussurea grandifolia and Taraxacum coreanum (MST) by using reverse-phase high-performance liquid chromatography coupled with diode array detector (HPLC-DAD). Analyses were carried out by using an INNO C18 column with a gradient elution system, and different parameters were used to validate our optimized method. Results demonstrated limits of detection and quantification of 5.46 × 10–3 and 16.54 × 10–3 mg/mL for DCQA and 0.37 × 10–3 and 1.14 × 10–3 mg/mL for CA, respectively. The calibration curves for DCQA and CA showed good linearity over the concentration ranges of 0.025–0.4 and 0.00625–0.1 mg/mL, respectively, and both exhibited r2 = 1.0000. In the accuracy test, high recovery rates were obtained ranging from 101.16–104.18% for DCQA and 97.55–108.49% for CA, while the precision values were ≤ 1.00% for DCQA and ≤ 1.21% for CA. The values obtained from our analyses support the use of this analytical method for the accurate identification and quantification of DCQA and CA from MST. Our methodology could be used further to determine the content of hydroxycinnamic acid derivatives in routine analyses and large-scale extraction processes.

The condensed tannin chemistry and astringency properties of fifteen Vitis davidii Foex grapes and wines

This study sought to determine the effects of variety on the astringency and chemistry of condensed tannins of spine grapes and wines. Fifteen varieties of red spine grape (Vitis davidii Foex) were used. Condensed tannin content, composition, and wine astringency were determined. The condensed tannin profiles were assessed by high-performance liquid chromatography coupled with diode array detector (HPLC-DAD). The condensed tannin content highly depended on the variety ranging from 0.30 mg/g to 7.80 mg/g (in skins), from 3.12 mg/g to 8.82 mg/g (in seeds), and from 62.60 mg/L to 225.90 mg/L (in wines). There were significant differences in proportions of certain constitutive subunits (as mole%) and mean degree of polymerization (mDp) among the varieties. Correlation analysis revealed that condensed tannin concentration and composition had a significant effect on the sensory evaluation and quantitative analysis of astringency. A positive correlation between mDp and astringency was also observed. The present results expand knowledge of the characterization of spine grape and wine condensed tannin chemistry and astringency.