Showing papers in "Journal of AOAC International in 2020"

Ultrahigh-Performance Hydrophilic Interaction Liquid Chromatography with Tandem Mass Spectrometry Method for the Determination of Paralytic Shellfish Toxins and Tetrodotoxin in Mussels, Oysters, Clams, Cockles, and Scallops: Collaborative Study.

Abstract: Background An ultrahigh-performance LC (UHPLC)-tandem MS (MS/MS) method for determination of paralytic shellfish poisoning toxins and tetrodotoxin (TTX) in bivalve molluscs was developed. To be used for regulatory testing, it needed to be validated through collaborative study. Objective The aim was to conduct a collaborative study with 21 laboratories, using results to assess method performance. Methods Study materials incorporated shellfish species mussels, oysters, cockles, scallops, and clams and were assessed to demonstrate stability and homogeneity. Mean concentrations determined by participants for blind duplicate samples were used to assess reproducibility, repeatability, and trueness. Results Method performance characteristics were excellent following statistical assessment of participant data, with method trueness showing excellent method accuracy against expected values. No significant difference was found in the trueness results determined by different chromatographic column types. Acceptability of the between-laboratory reproducibility for individual analytes was evidenced by >99% of valid Horwitz ratio values being less than the 2.0 limit of acceptability. With excellent linearity and sensitivity fit-for-purpose over a range of mass spectrometer instruments, the UHPLC-MS/MS method compared well against other detection methods. It includes additional paralytic shellfish toxin (PST) analogues as well as TTX, which, to date, have not been incorporated into any other hydrophilic marine toxin official method of analysis. Conclusions The results from this study demonstrate that the method is suitable for the analysis of PST analogues and TTX in shellfish tissues and is recommended as an official alternative method of analysis for regulatory control. Highlights A new mass spectrometric method for PST and TTX has been validated successfully through collaborative study.

A Green HPLC Method for Determination of Nine Sulfonamides in Milk and Beef, and Its Greenness Assessment with Analytical Eco-Scale and Greenness Profile.

Abstract: BACKGROUND Sulfonamides have been widely used in the prevention and clinical treatment of bacterial diseases in livestock and poultry. The use of sulfonamides increases the risk of veterinary drug residues in animal derived foods. The traditional reversed phase liquid chromatography methods for sulfonamides residues detection in animal derived foods have the problem of high consumption of organic solvents. OBJECTIVE The aim of this study was to establish a green high-performance liquid chromatography method for the detection of sulfonamides residues in different animal-origin foods. METHOD The sample extraction solutions were purified by the Agela Cleanert PEP-2 cartridge and analyzed by the high-performance liquid chromatography method using ethanol as the green alternative solvent. RESULTS The proposed method was validated in terms of linear range (20-1000 μg/kg), limit of detection (3.0-12.3 μg/kg), limit of quantitation (10-43 μg/kg), accuracy (80.7-101.3%), and repeatability and reproducibility (RSD <5.9% and RSD <8.5% respectively). CONCLUSIONS The proposed method is an environmentally friendly, sensitive and reliable high-performance liquid chromatography method for simultaneous determination of sulfonamide residues in animal-origin foods. HIGHLIGHTS In this work, we firstly developed a green high-performance liquid chromatography method for simultaneous determination of the residues of nine sulfonamides in milk and beef with ethanol as the green alternative solvent.

Anthocyanin Profiling Using UV-Vis Spectroscopy and Liquid Chromatography Mass Spectrometry.

Abstract: Background As a powerful antioxidant and natural colorant, anthocyanins are being used increasingly as a component of food supplements and nutraceutical products. Hence, its characterization is a prerequisite for further exploration of its nutraceutical potential. UV-Vis and MS are the two important techniques, which have been largely employed for the qualitative and quantitative determination of anthocyanins. However, a comprehensive review of the applications of these techniques in literature is scarce. Objective This paper aims to review the utilization of UV-Vis spectral data as well as mass spectral data for characterization and putative identification of anthocyanins with approaches of quantification. Methods The techniques described in literature have been thoroughly reviewed and comparatively evaluated. The complementary approaches of UV-Vis and MS spectra have been discussed for identification and quantification of these compounds. Results Valuable information about the chemical composition and structure of anthocyanins can be predicted from the UV-Vis spectral data, such as number and type of glycosylation as well as absence or presence of acylation, to name a few. It is also pointed out that for their structural confirmation, selectivity of mass detectors with unit and high-resolution analysis could be effective. Conclusions The combination of LC-MS with UV-Vis spectroscopy provides complementary information on structural details of anthocyanins. In case the analytical reference standards are available, a triple quadrupole mass spectrometer provides selectivity and quantitative sensitivity in analysis. On the other hand, high-resolution MS analysis provides valuable information for tentative identification during nontarget screening of compounds when the reference standard is not available. Highlights This paper reviews the applications of UV-Vis spectroscopy and LC-MS for qualitative and quantitative analysis of anthocyanins.

Phenols, Flavors, and the Mediterranean Diet.

Abstract: Phenols or phenolics are a class of compounds that have one or more hydroxyl groups attached to a 6-carbon aromatic ring, they occur as plant secondary metabolites, having in common the antioxidant activity. Their average daily intake varies widely around the world. Many researchers consider coffee, tea, wine, cocoa products, fruits and vegetables as the main sources of polyphenols in different diets. However, spices and culinary herbs have been referred to as the foods richest in polyphenols. Despite spices and culinary herbs are used in small amounts as seasonings, their contribution to the dietary supply of phytonutrients should not be disregarded. A diet rich in a variety of polyphenols (and other phytonutrients) has potential health benefits, namely in the prevention of chronic diseases and cancer. In addition, flavor and color are the most important factors for the selection of food by consumers. A multitude of endogenous food compounds, including phenolics, are involved in food flavor. The presence of phenolic compounds in the food matrix has been mainly associated with the perception of bitter taste and tactile sensation of astringency. However, these compounds can also impact the color and aroma notes of fruits and vegetables. Thus, understanding the sensory impact of these substances and relationships with consumers' approaches towards phenolic-rich fruits and vegetables may help find strategies to increase the consumption of such foods. A well-known example of a tasty, healthy and sustainable dietary model is the Mediterranean Diet. In this study, we summarize the dietary intake of some polyphenols from different dietary patterns around the world and the contribution of natural phenolic compounds to the flavor of food and beverages, in particularly those associated to the Mediterranean Diet.

Herbs and Medicinal Plants in Jordan.

Abstract: Background The presence of phenolic acids in edible products for human consumption is considered in relation to the production of odorant substances, with a variety of different aromas. Objective Phenolic substances anthocyanidins, anthocyanins, flavanols, flavones and isoflavones, flavones, flavonols, etc. - are extremely interesting as flavor additives, anti-aging or maturing agents, and color and aroma enhancers. Method The connection between flavoring properties on one hand and the presence of phenolic compounds on the other can be discussed in terms of food acceptance by consumers, especially with relation to the "Mediterranean Diet" lifestyle. Results The health perspectives of these and other food products related to Mediterranean Diet should be evaluated in the geographical ambit of the Mediterranean Basin, including several particular food and vegetable preparations - herbs and medicinal plants - of the Middle East. Conclusions The aim of this paper is to give a presentation on these specialties in relation to Jordan. Highlights Medicinal herbs have interesting health properties against digestive problems, parasitic worms, liver diseases, diabetes, skin problems, nervous, cardiocirculatory, and respiratory diseases.

Phenolics in Mediterranean and Middle East Important Fruits.

Abstract: Background Phenolic compounds (polyphenols) are common plant secondary metabolites playing different roles in plants, and some of these vegetables and correlated fruits-figs, grapes, pomegranates, olives, date palms, etc.-contain remarkable and diversified amounts of these substances. In addition, polyphenols are reported to show positive effects for human health, because of their antioxidant behavior. Figs are an excellent source of polyphenols with highest concentrations of proanthocyanidins. Actually, figs contain higher amounts of polyphenols than red wine and tea. Objective Antioxidant activity of several flavonoids (a group of polyphenols) in figs is higher than that of, vitamin C, glutathione, or vitamin E. Pomegranates contain very high levels of polyphenols as compared to other fruits and vegetables. It is used in folklore medicine for the treatment of various diseases, such as hepatic damage, snakebite, ulcer, etc. Method The health-positive potential of pomegranate fruit has been mainly attributed to ellagitannins, the predominant class of phenolics in pomegoxidation. Results The chief phenolic compound found in fresh olive is the bitter secoiridoid oleuropein.. Conclusions Processing of table olive decreases levels of oleuropein with correlated increases in the hydrolysis of hydroxytyrosol and tyrosol. Many of the health benefits reported for olives are thought to be associated with the levels of hydroxytyrosol. Date palm represents a staple food in most of the Arabian countries and is commonly consumed in several parts of the world. Highlights Numerous researches revealed the antibacterial, anti-hyperlipidemic, hepatoprotective, antimutagenic, and nephroprotective activity of date fruits, with reported anticancer and anti-fungal features.

Authentication of Coffea arabica Varieties through DNA Fingerprinting and its Significance for the Coffee Sector.

Abstract: Background: Locating the optimal varieties for coffee cultivation is increasingly considered a key condition for sustainable production and marketing. Variety performance varies when it comes to susceptibility to coffee leaf rust and other diseases, adaptation to climate change and high cup quality for specialty markets. But because of poor organization and the lack of a professional coffee seed sector, most existing coffee farms (and even seed lots and nurseries) do not know which varieties they are using. DNA fingerprinting of coffee planting material will contribute to professionalize the coffee seed sector. Objective: The objective of this paper is i) to check in a large scale the robustness of the existing coffee DNA fingerprinting method based on eight Single Sequence Repeats markers (SRR) and ii) to describe how it can help in moving the needle towards a more professional seed sector. Method : 2533 samples representing all possible genetic background of Arabica varieties were DNA fingerprinted with 8 SRR markers. The genetic diversity was analyzed and the genetic conformity to varietal references was assessed. Results: The DNA fingerprinting method proved to be robust in authenticating varieties and trace back the history of C. arabica breeding and of the movement of C. arabica varieties. The genetic conformity of two important coffee varieties, Marseillesa and Gesha, proved to be 91% and 39% respectively. Conclusions: DNA fingerprinting provides different actors in the coffee sector with a powerful new tool—farmers can verify the identity of their cultivated varieties, coffee roasters can be assured that marketing claims related to varieties are correct, and most of all, those looking to establish the a more professional and reliable coffee seed sector have a reliable new monitoring tool to establish and check genetic purity of seed stock and nursery plants. Highlights: While C. arabica is primarily self-pollinating, even fixed line varieties appear to be drifting away from their original genetic reference due to uncontrolled cross pollination. A set of 8 SSR markers applied to the largest possible genetically diverse set of samples prove to discriminate between a wide range of varieties Figures confirm that genetic non conformity of coffee varieties can represent up to 61% of checked samples.

Authenticity and the Potability of Coconut Water - a Critical Review.

Abstract: Background The content of the endosperm of the coconut (Cocos nucifera L.) contains "coconut water". This practically sterile liquid which is prized for its delicate, albeit labile, flavor when fresh, has had a recent dramatic increase in global demand. The organoleptic superiority of water from young coconuts means that degree of maturity at harvesting is the most influential factor in yield and composition. Objective To provide a guide to establishing the authenticity and the potability of samples of coconut water. Method Review and evaluate the literature on the factors that determine the composition and stability of coconut water. Results Data is presented on the variances in natural composition, maturity, processing-induced compositional changes, adulterations, product recalls, classical and instrumental methods of analysis and on the available composition standards of coconut water. Conclusions Advice is provided for official food analysts, and others, on prudent approaches as how to ascertain the authenticity and potability, or otherwise, of coconut water samples.

Analysis of Aflatoxins and Ochratoxin A in Cannabis and Cannabis Products by LC-Fluorescence Detection Using Cleanup with Either Multiantibody Immunoaffinity Columns or an Automated System with In-Line Reusable Immunoaffinity Cartridges

Abstract: Background Evidence of fungal contamination of cannabis plants during drying has raised concerns of potential mycotoxin contamination of leaves and flowers and subsequent contamination of derived edible cannabis products. Methods are, therefore, needed for routine monitoring of cannabis to ensure consumer safety consistent with long-standing controls for mycotoxins such as aflatoxins and ochratoxin A (OTA) in foodstuffs. Objective To generate preliminary validation data to demonstrate fitness-for-purpose of methods for aflatoxins and OTA in cannabis and cannabis products. Methods Extraction of solid matrices with acetonitrile-water (75 + 25) and direct analysis of energy drinks after dilution. Extracts were either passed manually though an immunoaffinity column (IAC) containing antibodies to both aflatoxins and OTA or were analyzed sequentially using an automated system with in-line reusable immunoaffinity cartridges for aflatoxins or OTA. In both cases, analysis was by LC with fluorescence detection. Results Recoveries were in the range of 76-120% with relative SDs from 0.8 to 6.6% for aflatoxins and OTA spiked into cannabis dried leaves and flowers, hemp tea, oils, capsules, cookies, chocolate brownies, and an energy drink. Conclusions The methods described in this paper are suitable for the cleanup of sample extracts of cannabis and cannabis products. Highlights Manual and automated methods with IAC cleanup have been shown to be suitable for routine control of aflatoxins and OTA in cannabis and cannabis products.

Fully automated identification of coffee species and simultaneous quantification of furfuryl alcohol using NMR spectroscopy

Abstract: Background Coffee is a popular beverage with two species, Coffea canephora and C. arabica, being commercially exploited. The quality and commercial value of coffee is dependent on species and processing. C. arabica typically obtains a higher price on the market compared to C. canephora. Coffee beans undergo roasting during processing, resulting in the formation of flavor compounds including furfuryl alcohol which has been classified by the International Agency for Research on Cancer as possibly carcinogenic to humans (Group 2B). Objective The aim of this study was to identify coffee species and other properties using nuclear magnetic resonance (NMR) spectroscopy, specifically to conduct quantification of the roasting process contaminant furfuryl alcohol. Method The quantification of furfuryl alcohol was performed from the NMR spectra using the pulse length-based concentration (PULCON) methodology. Prior to NMR analysis, samples were extracted using deuterated chloroform. Results Roasting experiments identified the maximum roasting temperature to be the most significant factor in the formation of furfuryl alcohol. Among the coffee species, C. canephora was found to contain a relatively lower amount of furfuryl alcohol compared to C. arabica. The roasting of wet processed coffee resulted in higher contents of furfuryl alcohol. Geographical origin and variety within species had no influence on the furfuryl alcohol content. Conclusion Validation results show that NMR spectroscopy is fit-for-purpose to obtain targeted information of coffee samples. Highlights The PULCON NMR methodology allows a simple, rapid and accurate determination of constituents of coffee.

Review of Analytical Methods to Detect Adulteration in Coffee.

Abstract: As one of the most consumed beverages in the world, coffee plays many major socioeconomical roles in various regions. Because of the wide coffee varieties available in the marketplaces, and the substantial price gaps between them (e.g., Arabica versus Robusta; speciality versus commodity coffees), coffees are susceptible to intentional or accidental adulteration. Therefore, there is a sustaining interest from the producers and regulatory agents to develop protocols to detect fraudulent practices. In general, strategies to authenticate coffee are based on targeted chemical profile analyses to determine specific markers of adulterants, or nontargeted analyses based on the "fingerprinting" concept. This paper reviews the literature related to chemometric approaches to discriminate coffees based on nuclear magnetic resonance spectroscopy, chromatography, infrared/Raman spectroscopy, and array sensors/indicators. In terms of chemical profiling, the paper focuses on the detection of diterpenes, homostachydrine, phenolic acids, carbohydrates, fatty acids, triacylglycerols, and deoxyribonucleic acid. Finally, the prospects of coffee authentication are discussed.

Reuse of Food Waste and Wastewater as a Source of Polyphenolic Compounds to Use as Food Additives

Abstract: The problem of waste and byproducts generated from agro-industrial activities worldwide is an increasing concern in terms of environmental sustainability. In this ambit, the quantity of food wastes-produced in all steps of the whole food chain-is enormous, and it may be forecasted that food waste could amount to more than 120 billion tonnes by 2020. The reuse of food waste and wastewater as source of polyphenolic compounds could be an interesting discussion in this ambit. In fact, polyphenols obtained in this way might be used for food and non-food purposes by means of new, improved, and safe extraction methods. In light of the opportunity represented by the treatment of agro-industrial waste, different systems concerning the winemaking and olive oil production industries have also been discussed as describing approaches applicable to other sectors. More research is needed before considering recovery of phenolic compounds from wastewater as an economically convenient choice for the food sector.

TLC-Bioautographic Evaluation for High-Throughput Screening and Identification of Free Radical Scavenging and Antidiabetic Compounds from Traditional Unani Medicinal Plant: Citrullus colocynthis Schrad.

Abstract: Background Interest in the antioxidant and antidiabetic activity of natural products are growing vastly in the modern world. Thin layer chromatography-bioautography-mass spectroscopy (TLC-bioautography-MS) plays an important role in chemico-biological screening of natural sources. TLC combined with 2, 2-Diphenyl-1-picrylhydrazyl (DPPH) free radical, α-amylase and α-glucosidase bioassay were used to evaluate antioxidant and antidiabetic activities, respectively, in different extracts of Citrullus colocynthis (Hanzal), a well-known traditional Indian Unani medicinal plant. Objective To develop a TLC-bioautographic-MS method for DPPH, α-amylase, and glucosidase inhibitors in different extract of C. colocynthis fruits. Method Fruits of C. colocynthis were successively extracted with toluene, dichloromethane, ethyl acetate, methanol, and water. TLC solvents were developed, and bioautographic-MS analysis was carried out to identify the antioxidant and antidiabetic compounds. Results HPTLC fingerprinting analysis showed maximum numbers of band separated in dichloromethane and ethyl acetate extracts of C. colocynthis, fourteen and thirteen at 254 and 366 nm, respectively. Whereas six and five separated bands were observed in toluene extract at 254 and 366 nm, respectively showed minimum numbers of metabolites. Based on TLC-bioautography-MS, maximum number of antioxidant compounds were identified in dichloromethane extract. Except aqueous extract of C. colocynthis, all the extracts have shown antidiabetic activity. On the other hand, there were no antioxidant compounds in methanolic extract of C. colocynthis. Conclusions The results of this study reveal that TLC-bioautography-MS-guided strategy used to identify antioxidant and antidiabetic compounds of C. colocynthis is very useful technique for high-throughput screening of bioactive compounds. Highlights TLC-MS bioautography is a simple and fast to enables bioactive compounds present in extracts.

Comparison of DAD and FLD Detection for Identification of Selected Bisphenols in Human Breast Milk Samples and Their Quantitative Analysis by LC-MS/MS

Abstract: Background Determination of bisphenols released from packaging material is undoubtedly a difficult and tricky task, requiring the chemical analyst to develop an individual approach to obtain reliable analytical information. Objective QuECHERS (Quick, Easy, Cheap, Effective, Rugged, and Safe)/dispersive solid-phase extraction (d-SPE) technique and high performance liquid chromatography (HPLC) coupled with modern detection techniques such as diode-array detector (DAD), fluorescence detector (FLD) or tandem mass spectrometry (MS/MS) for the determination of bisphenols such as bisphenol A (BPA), bisphenol S (BPS), bisphenol F (BPF), bisphenol B (BPB), 2-[[4-[2-[4-(Oxiran-2-ylmethoxy)phenyl]propan-2yl]phenoxy] methyl]oxirane (BADGE), 3-[4-[2-[4-(Oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenoxy]propane-1,2-diol (BADGE*H2O), 3-[4-[2-[4-(2,3-Dihydroxypropoxy)phenyl]propan-2-yl]phenoxy]propane-1,2-diol (BADGE*2H2O), 1-Chloro-3-[4-[2-[4-(3-chloro-2-hydroxypropoxy)phenyl] propan-2-yl]phenoxy]propan-2-ol (BADGE*2HCl) in human breast milk samples have been performed. Methods For the analysis of total analytes, prior to the extraction with acetonitrile, a deconjugation step was implemented in a tube by adding 1 mL of the enzymatic solution with the β-Glucuronidase to 5 mL of sample. The mix was homogenized and incubated for 17 h at 37°C. Ten milliliters of acetonitrile, and a QuEChERS salt packet with 4 g anhydrous MgSO4 and 1 g NaCl were added. During the d-SPE step the extract was transferred into tube with 30 mg Z-Sep and 50 mg PSA (and also 150 mg MgSO4 for LC-MS/MS analysis). MeOH-water (20:80, v/v) were added to the dry residue and the extract was reconstituted in 150 µL (25-fold analytes pre-concentration is achieved). Next bisphenols were identified by HPLC-DAD-FLD and quantified by LC-MS/MS equipment. Conclusions During the bisphenols HPLC-DAD-FLD analysis, from 6 min a reinforcement of 15 was used, which allowed analytes to be identified at 750 pg/mL. Application of LC-MS/MS allowed quantification of bisphenols in the range from 2.12 to 116.22 ng/mL in a total 27 human breast milk samples. Highlights First QuEChERS/d-SPE coupled with HPLC-DAD-FLD or LC-MS/MS method for the quantification of bisphenols and its analogues in breast milk Faster and cheaper alternative to traditional extraction methods The method was applied for the first biomonitoring of bisphenols and its analogues in breast milk.

Development of a New and Fast Extraction Method Based on Solvent-Assisted Dispersive Solid-Phase Extraction for Preconcentration and Trace Detection of Atrazine in Real Matrices.

Abstract: BACKGROUND Because of trace amounts of atrazine in water samples and the complexity of the matrix, direct trace monitoring of atrazine is not feasible by the abovementioned techniques. Hence, an efficient sample pretreatment procedure is necessary for cleanup and preconcentration of atrazine from sample matrices. OBJECTIVE In the current paper, a new and efficient sample preparation method named solvent-assisted dispersive solid-phase extraction (SA-DSPE), followed by HPLC-UV, was introduced for the monitoring of atrazine at trace levels in environmental water samples. METHODS In the present method, benzophenone was used as a sorbent for extraction of target molecules. For dispersing solid sorbents in sample solution, very low milligram amounts of benzophenone and dispersive solvent were mixed and fast-injected into the extraction media. A cloudy solution formed, and after interaction of atrazine and the dispersed solid sorbent, the cloudy solution was centrifuged. The extracted atrazine in the solid phase was dissolved in ethanol and analyzed by HPLC-UV. RESULTS The introduced method showed a low method detection limit (0.1 μg/L), good precision (relative SD: 3.9-6.9%), and appropriate relative recoveries (95-105%). CONCLUSIONS Within this study, a sensitive and reliable method for the quantification of atrazine in wastewater samples was successfully developed. HIGHLIGHTS The obtained figures of merit for the presented sample preparation method were appropriate. The applicability of the method for analysis of atrazine in real matrices was excellent.

Extract-and-Inject Analysis of Veterinary Drug Residues in Catfish and Ready-to-Eat Meats by Ultrahigh-Performance Liquid Chromatography – Tandem Mass Spectrometry

Abstract: BACKGROUND Validated analytical methods are needed to conduct regulatory monitoring of ready-to-eat meats and fish for food safety, risk assessment, and other purposes. The methods should be cost-effective, high-throughput, and meet acceptable performance standards for a wide scope of drugs and matrixes. OBJECTIVE The goal of this study was to demonstrate the validity for possible implementation in the US National Residue Program of an efficient method for qualitative and quantitative analysis of 176 targeted drugs at levels as low as 10 ng/g in hot dogs, catfish and swai (Siluriformes), chicken tenders, fried bacon, and sausage using ultrahigh-performance liquid chromatography - tandem mass spectrometry (UHPLC-MS/MS). METHODS Sample preparation simply involved a 5 min extraction by shaking 2 g comminuted samples with 10 mL of 4/1 (v/v) acetonitrile/water followed by centrifugation and UHPLC-MS/MS analysis of 2 μL injections. For cleanup comparison purposes only, sausage extracts were also prepared using a cartridge-based EMR-Lipid method prior to analysis. RESULTS Acceptable validation of 70-120% recoveries with <25% RSDs was met for 156-176 out of 186 drugs and quality control analytes without cleanup depending on the matrix. The EMR-Lipid method for sausage improved results for some analytes, such as mectin anthelmintics, due to reduction of indirectly interfering fats in the final extracts, but it also led to significantly worse results for several other drugs, resulting in 32 fewer analytes meeting the given validation criteria than without cleanup. CONCLUSIONS The simple, high-throughput method was demonstrated to be valid to meet routine regulatory and other monitoring needs for many diverse targeted drugs in fish and ready-to-eat meat matrixes.

Concepts and Quality Considerations in Unani System of Medicine.

Abstract: Unani medicine, based largely on herbs, is practiced as a traditional system of medicine in the Indian subcontinent. It owes its origination to the Greek philosopher Hippocrates (460-377 BC) and his associates. However, it progressed and got established under the patronage of Persian and Arab empires and later came to the Indian sub-continent around the middle of the 14th century. Unani scholars have been of the view that every person has their own distinct temperament constituted from four basic humoral combinations. Temperament of an individual is supposed to be influenced by various intrinsic and extrinsic factors such as age and mental status of individual, local climate, and environmental conditions, etc. Treatment is applied through dietotherapy and/or pharmacotherapy consonant with the patient's temperament. Unani medicine believes in health promotion and manages the disease through various modes of treatment such as regimental therapy, dietotherapy, and pharmacotherapy. A variety of clinical studies have shown that Unani medicines are effective with minimal side effects. Standardization, quality control, and toxicity profiling of many herbal drugs and the validation of formulations mentioned in the Unani Pharmacopeia of India have been accomplished in the recent past. Despite the mounting benefits of this system in the management of human health, it remains under-utilized. This article elucidates the basic concepts and a brief history of Unani medicine and summarizes information about its quality control, as well as its contribution to the health sector in India.

Critical Review of Analytical and Bioanalytical Verification of the Authenticity of Coffee

Abstract: Background The driving factors for the commercial adulteration of coffee are reviewed. Objective Methods have been assessed for the identification of the most common materials used to adulterate coffee by dilution, to establish the geographic origins, the genotypes of beans, and to assess the authenticity of Kopi Luwak coffee. Method The literature was surveyed manually and electronically from 1820 to 2018. Results A flow diagram has been developed to summarize the best approaches to deal with the authentication of coffee. Conclusions Encouragement is given to the interlaboratory validation of spectroscopic approaches, the exploration of civet cat deoxyribonucleic acid for the identification of Kopi Luwak, and the development of appropriately large and well-curated datasets of authenticity information across multiple techniques. Highlights The current analytical difficulties in the authentication of coffee are highlighted and suggestions made to improve the situation.

Advancing the FDA/Office of Regulatory Affairs Mycotoxin Program: New Analytical Method Approaches to Addressing Needs and Challenges.

Abstract: The U.S. Food and Drug Administration (FDA), Office of Regulatory Affairs (ORA) oversees FDA field laboratories, monitoring the occurrence and levels of toxic mycotoxins in domestic and imported human and animal food products that have the potential to impact human and animal health when consumed. The mycotoxins being routinely monitored in human and animal foods and feeds by the Agency include aflatoxins (B1, B2, G1, G2, and M1), fumonisins (FB1, FB2, and FB3), deoxynivalenol, ochratoxin A, patulin, and zearalenone. There has been an ongoing expansion of the Sample Collection Operation Planning Effort (SCOPE) for the mycotoxin program to monitor more mycotoxins in a wider variety of food and feed matrices. To meet this pressing need, we are in the process of modernizing and harmonizing the FDA/ORA mycotoxin program in the field laboratories using approaches such as adopting new analytical technologies/methods to further advance the service. This short perspective gives an overview of the FDA mycotoxin program in the field laboratories and the current program status, discusses the need to advance the program, strategies for modernization and harmonization by implementing liquid chromatography-mass spectrometry technologies for multi-mycotoxin analysis, benefits of doing this, and challenges in taking this new approach. Perspectives on finding solutions to tackle challenges and addressing emerging issues are also discussed.

Comparative Fingerprint Profiling of Unani Polyherbomineral (Safoof-e-Pathar Phori) Formulation by HPTLC, HPLC, and GC-MS.

Abstract: Background Standardization of Unani formulations is essential to assess the quality and safety of drugs to establish their acceptance internationally as well as in nationally. Safoof-e-Pathar phori is a polyherbomineral formulation that contains six different plant and mineral constituents: Didymocarpus pedicellata, Dolichos biflorus, Rheum emodi, Raphanus sativus, potassium carbonate, and potassium nitrate. Objective The objective of the study is to develop and establish the quality of Safoof-e-Pathar phori, used for antilithiatic activity using chromatographic analysis. Methods This study involves comparative fingerprint profiling of an Unani polyherbomineral formulation with its plant constituents by high-performance TLC (HPTLC), HPLC, and GC-MS. The authenticity of the Unani polyherbomineral formulation using comparative HPLC and GC-MS fingerprint profiling was achieved by comparing the retention time of peaks matching with plant drugs. Results In HPTLC, comparative fingerprinting was done on the basis of retardation factor values of compounds separated on HPTLC plates of the formulation and the single drugs. The relative retention times of the characteristic peaks in the HPLC fingerprinting were established for identification of the Unani poly-herbo-mineral formulation, whereas GC-MS was used for comparative fingerprint profiling of different compounds present in single drugs and in formulation through the National Institute of Standards and Technology and Wiley libraries using mass by charge ration (m/z) of detected compounds. Conclusions The fingerprint analysis approach is the most potent tool for quality control of polyherbal medicines because of its accuracy and reliability, and it also helps in identification and authentication and prevents adulteration. Highlights The developed chromatographic methods enable the quality and safety profile of the products.

Preparation of Validation Materials for Estimating Gluten Recovery by ELISA According to SMPR 2017.021.

Abstract: BACKGROUND In September 2017, the AOAC INTERNATIONAL Stakeholder Panel for Alternative Methods adopted Standard Method Performance Requirement (SMPR®) 2017.021, "Quantitation of Wheat, Rye, and Barley Gluten in Oats," as guidance for the validation of methods for measuring gluten in oat products. The SMPR requires prospective methods to demonstrate adequate recovery (50-200%) based on the analysis of a set of reference samples. OBJECTIVE This document provides specific methods and data on the preparation of such validation materials and their analysis by an R5 ELISA kit to demonstrate the SMPR recovery estimation procedure. METHODS Seven reference samples were made by spiking wheat, rye, and barley into gluten-free oat flour at two levels, 10 and 20 mg/kg. The levels of gluten were determined by a wet chemical method based on the Codex Alimentarius definition of gluten. RESULTS The recoveries for wheat, rye, and barley were 122, 425, and 349%, respectively, for the R5 ELISA kit. The wet chemical method for estimating gluten in a sample of pure grain demonstrated repeatability relative SDs ranging from 1.40 to 2.75%. CONCLUSIONS The reference materials are suitable to estimate ELISA kit responses to wheat, rye, and barley and calculate recoveries. HIGHLIGHTS A series of oat flours spiked with wheat, rye, and barley flours were developed to be used as reference materials. A wet chemical method was established to estimate gluten contents based on the Codex definition. The reference materials are available for purchase to support further method development and validation.

Sugar Profile Method by High-Performance Anion-Exchange Chromatography with Pulsed Amperometric Detection in Food, Dietary Supplements, Pet Food, and Animal Feeds: First Action 2018.16.

Abstract: Background: Numerous methods are routinely applied for sugar profile analysis. There is a need for a method that can analyze for the common mono- and disaccharides in human food, pet food, and animal feed. There was no compendia method that had such a large scope of coverage. This requires a method that can overcome the common issues seen with the methods available today, which can have interferences or issues with precision and accuracy when applying them to other matrices. Objective: To develop and validate a method that can meet the Standard Method Performance Requirements (SMPR®) outlined by the AOAC INTERNATIONAL Stakeholder Panel on Strategic Food Analytical Methods (SMPR 2018.001). Methods: The current work describes an optimized high-performance anion exchange with pulsed amperometric detection method that builds on the previously published work from this laboratory for the analysis of nutritionally relevant sugar compounds including galactose, glucose, fructose, sucrose, isomaltulose, lactose, and maltose. This method was optimized to provide coverage across a variety of different matrices, including human food, dietary supplements, pet food, and animal feed. A global multilaboratory validation was conducted to validate the method and compare against the SMPR requirements. Results: A summary of the validation data is presented. The requirements set forth by AOAC SMPR 2018.001 were all met with this method. Conclusions: The method and data from the global multilaboratory validation were reviewed by the AOAC Expert Review Panel, and determined the method met the SMPR requirements. Highlights: The method was granted AOAC First Action Official MethodsSM status.

Simultaneous Determination of Four Nonsteroidal Anti-Inflammatory Drugs and Three Estrogen Steroid Hormones in Wastewater Samples by Dispersive Liquid-Liquid Microextraction Based on Solidification of Floating Organic Droplet and HPLC.

Abstract: Background Nonsteroidal anti-inflammatory drugs (NSAIDs) and estrogen steroid hormones (estrogens) are pharmaceuticals intensively studied in environmental analysis due to their toxic effect on animal and human beings. Objective Development of a simple, fast, and sensitive extraction method for the simultaneously analysis of four NSAIDs (ketoprofen, naproxen, ibuprofen, and diclofenac) and three estrogens (17s-estradiol, 17α-ethynylestradiol, and estriol) from wastewater samples. Method Dispersive liquid-liquid microextraction based on solidification of floating organic droplet followed by HPLC analysis with UV detection was developed. The influence of the main extraction parameters, e.g., the volume of extraction solvent and of disperser, the pH, and the ionic strength of sample were evaluated. Results Good resolutions between the selected drugs were obtained using a reverse-phase column and a mobile phase of acetonitrile and water. This method provides good linearity (r > 0.999) in a concentration range of 1-100 µg/mL, good intra- and inter-day precision (RSD 80% for all analysed drugs, except estriol (59%) both in synthetic and real wastewater samples. Conclusions The developed method has been successfully applied for the analysis of the selected drugs in wastewater samples collected from the influent of a wastewater treatment plant. Highlights Four NSAIDs and three estrogens from wastewater samples were simultaneously extracted and analysed using only 10 mL of sample and 50 μL of extraction solvent.

Green Liquid Chromatographic Methods with Ultraviolet and Tandem Mass Spectrometry Detection: An Application to Ternary Mixture of Paracetamol, Pseudoephedrine, and Cetirizine in Capsules.

Abstract: Background Effective chromatographic methods were developed for the determination of a multicomponent capsule prescribed for treating the common cold. Greening approaches were adopted as opposed to conventional methods. Objectives Two novel, green chromatographic methods were established to quantitatively analyze the combination. Methods First, an HPLC/UV method utilizing green solvents (water and ethanol) and acetic acid to adjust pH at 5 was accomplished. The stationary phase was a ZorbaxSB-C18 column (150 × 4.6 mm, 5 μm), and peaks were detected at 215 nm. The second method is a highly sensitive ultra-performance LC (UPLC)-MS/MS method in which the greening approach was established through the reduction of the analysis time (2 min), decreased solvent consumption (flow rate 300 μL/min), and the utilization of a small volume of samples (injection volume 2 μL). The mixture was separated using a UPLC-BEH C18 column (50 × 2.1 mm, 1.7 μm) with an isocratic elution using methanol-0.1% formic acid aqueous solution (60+40, v/v) as mobile phase and utilizing diphenhydramine as an internal standard. Positive-ion electrospray ionization and multiple reaction monitoring were applied for detection. Results Recovery percentages for paracetamol, pseudoephedrine, and cetirizine were 101.70 ± 0.969, 100.18 ± 1.563, and 99.67 ± 1.429 for the HPLC method and 99.18 ± 1.172, 100.03 ± 0.883, and 99.82 ± 0.912 for the UPLC-MS/MS method, respectively. Conclusions The proposed methods efficiently analyzed paracetamol, pseudoephedrine, and cetirizine in Allercet Cold® capsules. Validation of the proposed methods was in accordance with the International Conference on Harmonization recommendations, and statistical comparison with the reported method displayed no significant difference regarding accuracy and precision. Highlights Paracetamol, pseudoephedrine, and cetirizine were successfully quantified using two chromatographic methods. The HPLC method developed is considered green, using water and ethanol as a mobile phase. The UPLC-MS/MS method was rapid and determined the three drugs with accuracy at nanogram levels.

Evaluation of Orchid-Like Aroma Between Different Grades of Taiping Houkui Tea by Solid-Phase Microextraction and Comprehensive Two-Dimensional Gas Chromatography Coupled with Time-of-Fight Mass Spectrometry.

Abstract: BACKGROUND Taiping houkui tea won the title of "the King of Green Tea" at the International Tea Exposition in 2004, which had an orchid fragrance but the material basis of the orchid fragrance had not been revealed yet. OBJECTIVE To investigate the material basis of the orchid fragrance and identify the quality grade of Taiping houkui tea. METHODS A method was developed for evaluating orchid-like aroma between different grades Taiping houkui tea by solid-phase micro extraction (SPME) and comprehensive two-dimensional gas chromatography coupled with time-of-fight mass spectrometry (GC×GC-TOFMS). The crushed tea sample in a 25 mL headspace bottle was incubated at 90°C for 10 min. Then the gaseous sample was extracted by SPME divinylbenzene/polydimethylsiloxane fiber for 50 min and thermally desorpted at 250°C for 2 min. RESULTS In total, 735 volatile compounds were determined by SPME- GC×GC-TOFMS and 15 compounds were related to orchid-like aroma. CONCLUSIONS The high-quality Taiping houkui tea has the orchid fragrance and the low-grade one does not; thus orchid-like aroma can be used as a reference of grades of Taiping houkui tea. HIGHLIGHTS Thirty different grades of Taiping houkui tea samples were compared and analyzed experimentally, and the results showed that the special aroma substances, which played a key role in grade discrimination of Taiping houkui tea, were found by the statistical method.

Detection and Quantitation of Selected Food Allergens by Liquid Chromatography with Tandem Mass Spectrometry: First Action 2017.17

Abstract: BACKGROUND In response to a need for accurate and reliable methods for food allergen regulatory compliance, a method for the detection and quantitation of whole egg, whole milk, peanut, and hazelnut in eight food matrices was developed and evaluated in a single-laboratory validation. The matrices include cookies, cookie dough, bread, breakfast cereal, salad dressing, ice cream, and red wine. OBJECTIVE The method was compared with Standard Method Performance Requirements (SMPR) 2016.002 established by the AOAC Stakeholder Panel on Strategic Food Analytical Methods. METHODS The method involves tryptic digestion of allergen proteins in food matrices incurred or spiked with allergen standards [reference materials (RMs), Standard RMs (SRMs), or in-house prepared standard] and uses labeled peptide internal standards. LC-tandem MS analysis of the signature tryptic peptides of the four allergens is performed using multiple reaction monitoring. RESULTS For 10 allergen/matrix combinations, the method demonstrated adequate sensitivity with a minimum quantitation limit of 3 mg/kg for whole egg and 10 mg/kg for milk, peanut, and hazelnut allergens. Repeatability precision across 3 days of analyses was <17% with analytical range of 10-1000 mg/kg. Recovery from incurred and spiked matrix-matched standards varied from 60 to 118%. CONCLUSIONS The method met the minimum performance requirements of SMPR 2016.002 for whole egg in cookies, bread, cookie dough, and salad dressing; whole milk in cookies and red wine; peanut in breakfast cereal; and hazelnut in cookies. HIGHLIGHTS The ERP determined that the data presented met the SMPR and accordingly recommended the method to be granted First Action status. In September 2017, the Official Methods Board approved the method as First Action.

Application of Automated Mini–Solid-Phase Extraction Cleanup for the Analysis of Pesticides in Complex Spice Matrixes by GC-MS/MS

Abstract: Background Pesticide residues are routinely tested in spices for trade compliance. This results in a huge sample load for food testing laboratories and demands automation in sample preparation. Although there exists a method for the analysis of pesticides in fruits using an automated sample cleanup by mini-solid-phase extraction (mini-SPE) technique, no study is available to date on spices. Objective This study aims to develop an automated sample cleanup method using mini-SPE technique in a range of spices, including chili powder, turmeric, black pepper, cumin, coriander, and cardamom. Methods This automated sample preparation workflow involved an X-Y-Z instrument autosampler, and a set of mini-SPE cartridges comprising cleanup sorbents. Spice samples were extracted by acetonitrile, and the extract was put into an autosampler vial for automated mini-SPE cleanup before analysis by GC tandem MS. For an efficient cleanup, three different sorbent compositions were compared along with various automated workflows. Results For the relatively simple matrixes (e.g., coriander, cumin, and cardamom), the LOQ for the target pesticides was 10 ng/g with acceptable recovery, and precision. The method provided an LOQ of 10 ng/g for around 77% of the compounds in the relatively complex matrixes (e.g., turmeric, chili powder, and black pepper). The remainder of the compounds had satisfactory recoveries at 20 ng/g and higher levels. Conclusions Given its time effectiveness and efficient analytical performance, this method can be adopted in commercial food testing laboratories for time-bound analysis of a large volume of samples. Highlights The study describes effectiveness of the automated mini-SPE cleanup in multiresidue analysis of pesticides in a range of spice matrixes. The method facilitates high-throughput residue analysis in compliance with the regulatory requirements of sensitivity and method performance.

Silver Nanoparticles Synthesis for Sensitive Spectrophotometric Determination of Sofosbuvir, Lamivudine, and Ritonavir in Pure Forms and Pharmaceutical Dosage Forms.

Abstract: Background Silver nanoparticles synthesis is now widely applicable as a method for sensitive spectrophotometric determination of many pharmaceuticals. Objective A highly sensitive, cheap, green, nonextractive, and accurate spectrophotometric method was developed for the determination of three important antiviral drugs. Methods The method depends on the formation of silver nanoparticles as a result of the redox reaction between antiviral drugs as a reducing agent and AgNO3 as an oxidizing agent in presence of polyvinyl pyrrolidone as a stabilizing agent. The UV absorbance of the resulted golden yellow silver nanoparticles can be easily measured at 421 nm for Sofosbuvir (SFS) and Ritonavir (RIT) and at 425 nm for Lamivudine (LAM). Results The LODs were 23.5, 30, and 21.5 nm/mL for SFS, LAM, and RIT, respectively. The LOQs were 70.5, 90, and 64.6 nm/mL for SFS, LAM, and RIT, respectively. The method was validated according to International Conference on Harmonization guidelines, and it was successively applied for the determination of the studied drugs in their different pharmaceutical dosage forms and gave excellent percent of recovery. The results showed excellent agreement with the reported method with respect to precision and accuracy. Conclusions Being simple, fast, robust, and economic, this method is eligible for use in the routine work in pharmaceutical quality control laboratories. Highlights A sensitive and economic spectrophotometric method was developed and validated for quantitative determination of SFS, LAM, and RIT. The method was validated and applied for determination of the studied drugs in their different formulations. The method used water as the main solvent, so our proposed method is considered environmentally friendly.

Development and Validation of a Method for Direct Analysis of Aflatoxins in Animal Feeds by Ultra-High-Performance Liquid Chromatography with Fluorescence Detection.

Abstract: Background and objective Aflatoxin (AF) contamination is one of the major regulatory concerns for animal feed. As feed is a complex analytical matrix, validated methods on AFs in feed are scanty. The available methods involve a derivatization step before AF analysis by high-performance liquid chromatography (HPLC) with fluorescence detection (FLD). The aim of this study was thus to develop and validate a simple and rapid method for direct analysis of AFs (AFB1, AFB2, AFG1, AFG2) in a range of animal feed matrices. Methods Feed samples were extracted with 80% methanol, followed by dilution with water and immmunoaffinity column cleanup. AFs were estimated using an ultra-high performance liquid chromatography (UHPLC) instrument. Use of a large volume flow cell in FLD allowed direct analysis of all AFs with high sensitivity. The method was thoroughly validated in a range of feed matrices. Results This sample preparation workflow minimized co-extractives, along with matrix interferences. In pigeon pea husk feed, the method provided a limit of quantification (LOQ) of 0.5 ng/g for each AF with recoveries of AF- B1, B2, G1, and G2 as 71.5, 75.6, 82.4, and 78.2%, respectively. The precision (relative standard deviation, RSD) was below 5%. A similar method performance was also recorded in other matrices, including wheat bran feed and poultry feed. Conclusions The optimized method is suitable for regulatory testing because it is simple, robust, cost-effective, and high throughput in nature, with high sensitivity and selectivity. Highlights Our workflow has provided a straightforward method for the analysis of AFs in a wide range of animal feed matrices with high sensitivity, selectivity, throughput, and cost-effectiveness. The method allowed a direct analysis of AFs by UHPLC-FLD without a step of derivatization.