Improvement of the stabilities and antioxidant activities of polyphenols from the leaves of Chinese star anise (Illicium verum Hook. f.) using ß-cyclodextrin-based metal-organic frameworks.

BACKGROUND: Polyphenols extracted from plants are usually highly unstable and rapidly transformed into various reaction products during food and drug processing, thus limiting their applications. To improve the stability and solubility of polyphenols from the leaves of Chinese star anise (Illicium verum Hook. f.), and hence to expand their application to food and medicine, the extracted anise leaf polyphenols (ALPs) were microencapsulated using ß-cyclodextrin (ß-CD) and cyclodextrin-based metal-organic frameworks (ß-CD-MOFs). RESULTS: The optimum inclusion rate of ALP/ß-CD-MOFs was 97.80% at a core-wall ratio of 1:10. Meanwhile, the stabilities, solubilities and antioxidant activities of the polyphenols before and after inclusion were compared. The results showed both the stabilities and solubilities of ALP/ß-CD-MOFs were significantly improved compared with those of ALPs and ALP/ß-CD, suggesting the potential of ß-CD-MOFs as newer and better carriers than ß-CD for polyphenols in food industry applications. The free radical (including superoxide, hydroxyl and DPPH radicals) scavenging activities were also improved by microencapsulation. Superoxide radical scavenging reaction also showed slow-release property of ALP/ß-CD-MOFs. The formation of the inclusion complex was further confirmed using Fourier transform infrared spectral characterization. CONCLUSIONS: Microencapsulation with ß-CD-MOFs could expand the application scope of ALPs, and it is more effective than encapsulation with ß-CD. This is important for a better understanding and application of this useful traditional Chinese plant. As a new material with high efficiency and edibility, ß-CD-MOFs are not limited to the chemical field, but also have potential in new areas of food, medicine and healthcare products. © 2020 Society of Chemical Industry.

Comparing acaricidal and ovicidal activity of five terpenes from essential oils against Psoroptes cuniculi.

Essential oils and their components represent an appealing alternative strategy against parasitic mites. The chemical complexity and variability of essential oils limit their use and additional work is required to analyze the efficacy and application rate of essential oils' individual components. In the present study, the activity of five terpenes (terpinen-4-ol, citral, linalool, eugenol, and geraniol) was evaluated against Psoroptes cuniculi motile stages and eggs collected from naturally infected rabbits. Eugenol presented the best acaricidal efficacy with a median lethal concentration (LC50) value of less than 0.1% at 24 h, followed by geraniol (0.33%), linalool (0.38%), citral (0.46%), and terpinen-4-ol (0.66%). Geraniol and eugenol were able to kill all mites within 5 min at 1% concentration. The effective concentration to inhibit 50% (EC50) of egg hatching was 0.65%, 0.66%, 0.85%, 1.47%, and 2.87% for eugenol, geraniol, citral, terpinen-4-ol, and linalool, respectively. In conclusion, eugenol, geraniol, citral, terpinen-4-ol, and linalool should be considered as promising agents for the development of botanical acaricides against Psoroptes cuniculi.

Antioxidant activity screening and chemical constituents of the essential oil from rosemary by ultra-fast GC electronic nose coupled with chemical methodology.

BACKGROUND: Traditional chemical methods were mainly used to evaluate the total antioxidant activity of essential oils. How to determine the bioactivity of each compound in mixtures is an interesting research topic. Nowadays, an ultra-fast gas chromatography electronic nose (E-nose) has been gradually used in the detection of volatile compounds, but the screening of the active components of essential oils has not been reported. E-nose coupled with chemical methodology was established using the essential oil from rosemary (EOR) as a specific application example. The proposed method can both identify the chemical constituents of EOR and quickly screen the antioxidant by comparing the change of chromatographic peak area of every component in EOR before and after reaction with free radicals. RESULTS: Among all chemical constituents in EOR, verbenone, eucalyptol and o-cymene showed the strongest scavenging abilities in 1,1'-diphenyl-2-picrylhydrazine (DPPH·), 2,2'-azino-bis(3-ethyl-benzothiazoline-6-sulphonate) (ABTS·+ ) and hydroxyl (·OH) radicals, respectively, with scavenging rates of 67.9%, 39.5%, and 69.9%. The reliability and feasibility of using E-nose to identify chemical constituents of EOR were verified by gas chromatography-tandem mass spectrometry (GC-MS/MS). The GC-MS/MS results showed that the main components of EOR were α-pinene (422.2 µg g-1 ), p-cymene (208.4 µg g-1 ), camphor (203.5 µg g-1 ), verbenone (160.2 µg g-1 ), and eucalyptol (129.1 µg g-1 ). CONCLUSIONS: The E-nose methods can be used as a complementary method to traditional spectrophotometric techniques. Furthermore, this study will be of great significance for the rapid screening of antioxidant active components in essential oils from natural products. © 2020 Society of Chemical Industry.

Prediction of Hemodialysis Timing Based on LVW Feature Selection and Ensemble Learning.

We propose an improved model based on LVW embedded model feature extractor and ensemble learning for improving prediction accuracy of hemodialysis timing in this paper. Due to this drawback caused by feature extraction models, we adopt an enhanced LVW embedded model to search the feature subset by stochastic strategy, which can find the best feature combination that are most beneficial to learner performance. In the model application, we present an improved integrated learners for model fusion to reduce errors caused by overfitting problem of the single classifier. We run several state-of-the-art Q&A methods as contrastive experiments. The experimental results show that the ensemble learning model based on LVW has better generalization ability (97.04%) and lower standard error (± 0.04). We adopt the model to make high-precision predictions of hemodialysis timing, and the experimental results have shown that our framework significantly outperforms several strong baselines. Our model provides strong clinical decision support for physician diagnosis and has important clinical implications.

Flavonoids in Juglans regia L. leaves and evaluation of in vitro antioxidant activity via intracellular and chemical methods.

Flavonoids are rich in Juglans regia L. leaves. They have potent antioxidant properties, which have been related to regulating immune function and enhancing anticancer activity. Herein, qualitative and quantitative determination of flavonoids from J. regia leaves was carried out using high performance liquid chromatography coupled with tandem mass spectrometry with electrospray ionization and negative ion detection (HPLC-ESI-MS/MS) by comparison of the retention times and mass spectral fragments with standard substances or related literatures. Seventeen compounds were identified and major components are quercetin-3-O-rhamnoside (453.11 µg/g, dry weight), quercetin-3-O-arabinoside (73.91 µg/g), quercetin-3-O-xyloside (70.04 µg/g), kaempferol-O-pentoside derivative (49.04 µg/g), quercetin-3-O-galactoside (48.61 µg/g), and kaempferol-O-pentoside (48.46 µg/g). The in vitro intracellular antioxidation indicated that flavonoids from J. regia leaves could reduce the reactive oxygen species (ROS) level in RAW264.7 cells and showed good radical scavenging activities. These results proved to be more related to the flavonoids that could be considered in the design of new formulations of dietary supplements or functional foods.

Rapid, simultaneous and non-destructive determination of multiple adulterants in Panax notoginseng powder by front-face total synchronous fluorescence spectroscopy.

The authentication of traditional herbal medicines in powder form is of great significance, as they are always of high values but vulnerable to adulteration. Based on the distinct fluorescence of protein tryptophan, phenolic acids and flavonoids, front-face synchronous fluorescence spectroscopy (FFSFS) was applied for the fast and non-invasive authentication of Panax notoginseng powder (PP) adulterated with the powder of rhizoma curcumae (CP), maize flour (MF) and whole wheat flour (WF). For either single or multiple adulterants in the range of 5-40% w/w, prediction models were built based on the combination of unfolded total synchronous fluorescence spectra and partial least square (PLS) regression, and were validated by both five-fold cross-validation and external validation. The constructed PLS2 models simultaneously predicted the contents of multiple adulterants in PP and gave suitable results, with most of the determination coefficients of prediction (Rp2) >0.9, the root mean square error of prediction (RMSEP) no >4% and residual predictive deviation (RPD) >2. The limits of detections (LODs) were 12.0, 9.1 and 7.6% for CP, MF and WF, respectively. All the relative prediction errors for simulated blind samples were between -22% and + 23%. FFSFS offers a novel alternative to the authentication of powdered herbal plants.

Enhanced preservation effects of clove (Syzygium aromaticum) essential oil on the processing of Chinese bacon (preserved meat products) by beta cyclodextrin metal organic frameworks (ß-CD-MOFs).

The applications of clove (Syzygium aromaticum) essential oil (CEO) are limited by instability, low solubility and high volatility. The present study aimed to improve the properties of CEO by microencapsulation with cyclodextrin metal organic frameworks (ß-CD-MOFs) to enhance the preservation effects on Chinese bacon (preserved meat products). The microencapsulated CEO by ß-CD-MOFs (CEO/ß-CD-MOFs) not only did not inhibit the antioxidant activities of CEO, but also showed significant improvements on their ROS scavenging abilities and thermo-/pH-stabilities. The increases of superoxide anion and hydroxyl radical scavenging activities were 20.74% and 12.84%, respectively. In addition, less lipid oxidation, including malondialdehyde (MDA) contents and peroxide values (POV), of Chinese bacon was found after the CEO/ß-CD-MOFs treatment than CEO and synthetic antioxidant (BHT) treatments. These results suggested the enhanced preservation effects of microencapsulated CEO on the processing of Chinese bacon and the great potential of ß-CD-MOFs as carriers for essential oils in food industry applications.

Comparative Analysis of Intracellular and in vitro Antioxidant Activities of Essential Oil From White and Black Pepper (Piper nigrum L.).

Ethnopharmacological Relevance: Pepper essential oils have potential immunomodulatory, anti-tumor, and anti-cancer activities. Pepper exhibits the potential to prevent or attenuate carcinogenesis as therapeutic tools. However, the related mechanism remains unelucidated. Aim of the Study: The present study aims to provide reasonable information for the explanation of the dissimilarity of the essential oils from white (WPEO) and black pepper (BPEO). Materials and Methods: WPEO, BPEO, and their single active component, as well as synthetic antioxidants, were compared by the cell model methods and chemical methods, including intracellular antioxidant activity (CAA), total antioxidant activities (TAA), superoxide radical (SR), hydroxyl radical (HR), DPPH radical (DR) scavenging activities and inhibition ability of lipoprotein lipid peroxidation (ILLP). Results: The median effective concentration (EC50) values (mg/mL) of the WPEO and BPEO of SR, HR, DR, and ILLP were 0.437 and 0.327, 0.486 and 0.204, 7.332 and 6.348, 0.688, and 0.624 mg/mL, respectively. The CAA units of WPEO and BPEO were 50.644 and 54.806, respectively. CAA, DR, and TAA of BPEO were significantly higher than those of WPEO (p < 0.05). The BPEO and WPEO can be differentiated as the former have higher correlations with 3-carene, α-pinene, ß-pinene, and limonene while the latter has a higher caryophyllene correlation. The WPEO and BPEO show a good intracellular scavenging ability of reactive oxygen species in HeLa cells. Conclusion: Generally, pepper oil has stronger activities than single components, indicating that pepper is a broad-spectrum natural antioxidant.

Front-face synchronous fluorescence spectroscopy for rapid and non-destructive determination of free capsanthin, the predominant carotenoid in chili (Capsicum annuum L.) powders based on aggregation-induced emission.

Capsanthin is the major natural carotenoid pigment in red chili pepper possessing important bioactivity. Its conventional determination method is high performance liquid chromatography (HPLC) with complex and tedious sample pretreatment. In this study, synchronous front-face fluorescence spectroscopy (FFFS) was applied for the fast and non-invasive detection of free capsanthin in chili powders. Although capsanthin was only weak fluorescent in solution state, it showed strong fluorescence in two separated regions in front-face geometry which could also be clearly observed in chili powders. The mechanisms of these emissions are revealed to be aggregation-induced emission (AIE) and J-aggregate formation (JAF). The free capsanthin in 85 chili powder samples were determined by HPLC as in the range of 0.6-3.0 mg/g. The total synchronous FFFS spectra of these samples were scanned. Simple first-order models were built by partial least square regression (PLSR), and were validated by 5-fold cross-validation and external validation. The coefficients of determination (R2) were higher than 0.9, and the root mean square errors (RMSE) were less than 0.2 mg/g. The relative error of prediction (REP) was 9.9%, and the residual predictive deviation (RPD) was 3.7. The method was applied for the estimation of free capsanthin in several real-world samples with satisfactory analytical results. The average relative error to HPLC reference values was -11.8%.

Polyethylene mesh knitted fabrics mulching the soil to mitigate China's haze: A potential source of PBDEs.

The fate of polybrominated diphenyl ethers (PBDEs) from polyethylene mesh knitted fabrics (PMKFs) to mulched soil and nearby plants was studied. PBDEs in the soil sample collected from Tianjin University of Commerce in April 2019 increased significantly after 6 months of PMKF mulching owing to PMKFs as the main input source. The compositional profiles/congener patterns of the PBDEs in the soil and PMKFs became similar after 6 months. High correlations were found between ΣPBDEs in the soil and PMKFs in October 2019, with no significant correlation in April. Plants could take up, accumulate and biotransform PBDEs in contaminated soil. The uptake of BDE-209 by plants was the highest compared with other lesser brominated PBDE congeners, due to its higher log Kow value and molecular weight or size. BDE-47 taken up in the plant was biotransformed via hydroxylation. These results prove that the government's PMKF solution to haze is causing environmental problems in bare soil, i.e., PBDE pollution in both soil and nearby plants. The present study provides important pieces of evidence for government and policymakers, and it is recommended that one environmental problem is not solved by creating another.

Effect of ethanol fumigation on pericarp browning associated with phenol metabolism, storage quality, and antioxidant systems of wampee fruit during cold storage.

Wampee fruit is a popular fruit cultivar in South-East Asia due to its high levels of nutrients and antioxidants; however, pericarp browning leads to a short storage life with great economic loss during years. The purpose of this work was to determine whether postharvest ethanol fumigation affected pericarp browning development of wampee fruit during 12 days of storage at 8 ± 0.5°C, and if so, how it is related to phenol metabolism and how it affects quality attributes and antioxidant systems during storage. After fruits were fumigated with 100, 300, 500, and 800 µl/L for 5 hr at 22 ± 0.5°C, ethanol significantly reduced the development of pericarp browning by increasing total phenolics (TP) content and decreasing the activity of polyphenol oxidase (PPO), especially in 500 µl/L ethanol treatment. Additionally, ethanol delayed the losses in fruit firmness (FF), soluble solid content (SSC), and titratable acidity (TA), retarded weight loss and accumulation of malondialdehyde (MDA) content and maintained relatively high contents of ascorbic acid (AsA), total flavonoids (TF), and total antioxidant capacity (TAC) and activities of superoxide dismutase (SOD), catalase (CAT), and peroxidase (POD). In conclusion, results demonstrated that postharvest ethanol fumigation in wampee fruit has ability to reduce pericarp browning development by regulating phenol metabolism and enhancing antioxidant systems.

Antioxidant compound screening and chemical composition of sweet ginger (Alpinia coriandriodora D. Fang) essential oil and the mechanism of scavenging radicals.

The chemical components of an edible spice, sweet ginger (Alpinia coriandriodora D. Fang) essential oil (AEO) were identified by an ultra-fast gas chromatography electronic nose (E-nose) and the main components were ß-pinene (27.9%), 1,8-cineole (17.3%), p-cymene (13.5%), camphene (7.3%), myrcene (5.4%), and pseudolimonene (4.3%). The antioxidant activity of each component was evaluated and the mechanisms of scavenging free radical were studied by E-nose combined with chemical methodology. Decanal and α-copaene in AEO showed strong scavenging activities against DPPH radical, and the scavenging rates were over 85%. Decanal had a strong scavenging activity for ABTS radical and the scavenging rate was more than 60%. Similarly, terpinen-4-ol and eugenol had strong scavenging abilities to OH radical and the scavenging rates were more than 50%. Gas chromatography-mass spectrography results showed that it was feasible to identify the chemical components of essential oil by E-nose, and the similarity reached 88.9%. PRACTICAL APPLICATIONS: Many essential oils have antioxidant activities and can be used in functional foods. In the present work, the antioxidant active components in AEO were identified and screened by ultra-fast GC E-nose. We aimed to target the components with strong antioxidant activity quickly and efficiently through the analysis of the reaction process of DPPH, ABTS and OH radicals with a high scavenging rate in a short time. These results indicate that ultra-fast GC E-nose can be used to screen the antioxidant active components in the essential oil.

Polyphenol oxidase plays a critical role in melanin formation in the fruit skin of persimmon (Diospyros kaki cv. 'Heishi').

In this study, the melanin in persimmon and its formation were investigated. Melanin was found to be deposited on the cell walls of the upper epidermis and subepidermal cells in persimmon skin and the isolated pigment appears to have lamellar structures. Diagnostic analysis of the isolated pigment showed results that were similar to those of melanin from other sources. Ultraviolet-visible spectroscopy revealed that the extracted skin pigment displayed a broadband, structureless absorption profile that increased progressively towards shorter wavelengths. The Fourier transform infrared spectroscopy assay revealed that melanin in persimmon skin exhibits many characteristic absorption peaks. The phenolic profile analysis suggested that the precursors of this pigment may include gallic acid, procyanidin B1, procyanidin B2, ferulic acid and epigallocatechin gallate. The PPO activity and DkPPO expression significantly increased during melanin formation, and transient overexpression of DkPPO promoted melanin synthesis. These results indicate that the isolated pigment was a type of melanin and that PPO plays a critical role in its formation.

One pot synthesis of water-soluble quercetin derived multifunctional nanoparticles with photothermal and antioxidation capabilities.

As a member of flavonoids, the application of quercetin has been mainly focused on antioxidation study. Fabrication of multifunctional nanoplatforms with quercetin is limited. In the present study, water-soluble quercetin derived nanoparticles (QFNPs) were fabricated through the one pot synthesis strategy with Fe3+, quercetin and poly (vinyl pyrrolidone) (PVP). The raw materials were dissolved in absolute ethanol and the mixed together. After stirring at room temperature for 6 h, the QFNPs could be simply harvested by centrifugation without the need of time-consuming dialysis procedure. Due to the protective effect of PVP, the synthesized nanoparticles could be well dispersed in water with the hydrodynamic size about 23 nm. DPPH free radical scavenging capacity assay showed QFNPs could act as efficient antioxidant. Besides antioxidation activity, the QFNPs also exhibited good photothermal capacity. Temperature stability result suggested the good stability of QFNPs between 35 and 95 °C. MTT and hemolysis assay showed the good biocompatibility of QFNPs. What's more, the QFNPs showed good cellular antioxidation activity and efficient photothermal killing effect to cancer cells (4T1 cells). The QFNPs could be promising nanoplatform for biomedical application.

Antioxidant activity evaluation of rosemary ethanol extract and their cellular antioxidant activity toward HeLa cells.

Rosemary ethanol extract (REE) from Rosmarinus officinalis was identified by LC-ESI-MS/MS and 12 compounds were found. Among them, rosmarinic acid (389.78 µg/mg in REE), luteolin-3'-O-glucuronide (325.58 µg/mg), luteolin-5-O-glucuronide (120.92 µg/mg), and geniposide (120.83 µg/mg) are the major components. The antioxidant activity evaluation of REE by off-line HPLC methods indicated that among the 12 compounds, rosmarinic acid had the strongest scavenging activities in both DPPH· and ·OH. The cytotoxicity experiment showed that REE with the concentration ranges from 1 to 100 µg/ml did not significantly affect the cell viability of HeLa, while inhibitory rate reduced to 62.3% when the concentration was increased to 1,000 µg/ml. The results of intracellular antioxidation assay showed that the ability of REE in reducing the reactive oxygen species (ROS) in HeLa cells was higher than rosmanol, and lower than rosmarinic acid without cell toxicity. PRACTICAL APPLICATIONS: Plant polyphenols are essential components of functional foods, due to their antioxidant and enzyme inhibition activities. This paper is the first study about the quantification of antioxidant compounds, antioxidant activity evaluation, and their cellular antioxidant activity of polyphenols extract from R. officinalis toward HeLa cells. We aimed to elucidate the chemical composition and recognition of antioxidant components with DPPH and OH free radicals scavenging activity. In addition, the polyphenols dose-response correlations with cellular antioxidant activity were also determined. These results indicated that off-line HPLC method with DPPH and OH free radicals as markers is available for screening antioxidant activity of polyphenols from the mixture.

Complexation study of brilliant cresyl blue with beta-cyclodextrin and its derivatives by UV-vis and fluorospectrometry.

The complexation reactions of brilliant cresyl blue (BCB) with beta-cyclodextrin (beta-CD), mono[2-O-(2-hydroxypropyl)]-beta-CD (2-HP-beta-CD), mono[2-O-(2-hydroxyethyl)]-beta-CD (2-HE-beta-CD), and heptakis(2,6-di-methyl) -beta-CD (DM-beta-CD) were investigated using UV-vis and fluorospectrometry. The complexation between BCB and CDs could inhibit the aggregation of BCB molecules and could cause its absorbance at 634nm gradually increasing. The fluorescence of BCB was also enhanced with the addition of CDs. The fluorescence enhancement was more notable in neutral and acidic media than in basic media. Hildebrand-Benesi equation was used to calculate the formation constants of beta-CDs with BCB based on the fluorescence differences in the CDs solution. The stoichiometry ratio was found to be 1:1. The complexing capacities of beta-CD and its three derivatives were compared and the results followed the order: 2-HP-beta-CD>2-HE-beta-CD>DM-beta-CD>beta-CD. The effect of temperature on the formation of BCB-beta-CD inclusion complexes has also been examined. The results revealed that the formation constants decreased with the increase of temperature from 1038.9 to 491.6l/mol. Enthalpy and entropy values were calculated and the values were -25.77kJ/mol and 35.04J/kmol, respectively. The thermodynamic measurements suggest that the inclusive process was enthalpic favor. The release of high-energy water molecules and Van der Waals force played an important role in the inclusive process.

The preservation effect of Metschnikowia pulcherrima yeast on anthracnose of postharvest mango fruits and the possible mechanism.

This study aimed to determine the effects of Metschnikowia pulcherrima yeast on storage quality of 'Tainong' mango, and elucidate it's possible anti-disease mechanism. The results showed that M. pulcherrima could inhibit the changes in peel colour, fruit firmness, the contents of total soluble solids, total acid and vitamin C, and maintain the storage quality of mango fruits. An investigation of the mechanism showed that M. pulcherrima competed not only for the primary carbon source, but also for living space with Colletotrichum gloeosporioides. In addition, M. pulcherrima promoted the activities of defence-related enzymes, including ß-1,3-glucanase(GLU) and chitinase (CHT), and secreted a small amount of antimicrobial substances composed of volatile and nonvolatile anti-fungal compounds. The results strongly demonstrated that antagonistic yeast M. pulcherrima could be applied as a biocontrol agent for deducing the spoilage and decay of mango fruit.

Screening and evaluation of active compounds in polyphenol mixtures by HPLC coupled with chemical methodology and its application.

An off-line high performance liquid chromatography (HPLC) coupled with chemical methods has been developed to evaluate antioxidant activity of 11 standard polyphenol compounds (SPCs) and vitamin C (Vc) in terms of radical scavenging abilities. The structure-activity relationships of each SPC were also discussed. SPCs showed different abilities in scavenging 2,2-diphenyl-1-picrylhydrazyl (DPPH), 2,2'-azinobis-3-ethyl-benzthiazoline-6-sulphonate (ABTS+) and hydroxyl (OH) free radicals. Among SPCs, quercetin and kaempferol, as typical flavonoids, displayed the greatest radical-scavenging activities and even exhibited higher activity in OH radical removal ability than that of Vc. Furthermore, the proposed method was also applied to screening polyphenolic antioxidant components from Cichorium endivia L. (C. endivia) seed extract. The results indicated that cynarin in the extract was a more active compound to scavenge DPPH and ABTS+ radicals than chlorogenic acid, while chlorogenic acid had stronger capacity in scavenging OH free radicals.

Synchronous front-face fluorescence spectroscopy for authentication of the adulteration of edible vegetable oil with refined used frying oil.

Synchronous front-face fluorescence spectroscopy has been developed for the discrimination of used frying oil (UFO) from edible vegetable oil (EVO), the estimation of the using time of UFO, and the determination of the adulteration of EVO with UFO. Both the heating time of laboratory prepared UFO and the adulteration of EVO with UFO could be determined by partial least squares regression (PLSR). To simulate the EVO adulteration with UFO, for each kind of oil, fifty adulterated samples at the adulterant amounts range of 1-50% were prepared. PLSR was then adopted to build the model and both full (leave-one-out) cross-validation and external validation were performed to evaluate the predictive ability. Under the optimum condition, the plots of observed versus predicted values exhibited high linearity (R(2)>0.96). The root mean square error of cross-validation (RMSECV) and root mean square error of prediction (RMSEP) were both lower than 3%.

Simultaneous determination of cobalt, copper and zinc by energy dispersive X-ray fluorescence spectrometry after preconcentration on PAR-loaded ion-exchange resin.

A sensitive method for the preconcentration and determination of trace amounts of Co, Cu and Zn by energy-dispersive X-ray fluorescence spectrometry (EDXRF) has been developed. The method is based on the fact that 4-(2-pyridylazo)-resorcinol (PAR) loaded Dowex anion-exchange resin (PAR-resin) can effectively adsorb Co, Cu and Zn at pH 9.0 to form PAR-metal complexes. The detection limits for Co, Cu and Zn were 1.53, 0.31 and 0.21 ppb, respectively. The precisions for five replicate measurements of the three metals were 3.4, 2.7 and 2.1% RSD, and the calibration curves were linear up to 75 microg with correlation coefficients of 0.9975, 0.9980 and 0.9985, respectively. The method was successfully applied for the simultaneous determination of Co, Cu and Zn in seawater samples at ppb levels.