Major Adulterants Research Articles

MATLAB language assisted data acquisition and processing in liquid chromatography Orbitrap mass spectrometry: Application to the identification and differentiation of Radix Bupleuri from its adulterants

Comprehensive and rapid analysis of secondary metabolites like saponins remains challenging. This study aimed to establish a semi-automated workflow for filtration, identification, and characterization of saikosaponins in six Bupleurum species. Radix Bupleuri, a high-sales herbal medicine, is often adulterated, restricting its quality control and applications. Two authentic Radix Bupleuri species and four major adulterants were analyzed through UHPLC-LTQ-Orbitrap-MS for targeted saikosaponin analysis. To reveal trace saikosaponins and obtain quality fragment data, a MATLAB-based process automatically enumerating “sugar chain + aglycone + side chain” combinations and deduplicating generated a predicted saikosaponin database covering all possible saikosaponins as a precursor ion list for comprehensive targeted acquisition. To focus on informative ions and reduce MS analysis workload, we utilized MATLAB to automatically filtrate the false positive ions by MS1 and MS2 spectrometry. The newly established MATLAB-assisted data acquisition approach exhibited 50 % improvement in characterization of targeted saikosaponins. Furthermore, positive and negative ionization workflows were designed for accurate saikosaponins characterization based on fragmentation rules. In total, 707 saikosaponins were characterized, including over 500 potential new compounds and previously unreported C29 aglycones. We identified 25 saikosaponins present in both authentic species but absent in adulterants as potential markers. This unprecedented comprehensive multi-origin species differentiation demonstrates the promise of MATLAB-assisted acquisition and processing to advance saponin identification and standardize the Radix Bupleuri market.

Real Time Fuel Adulteration Detection System for preventing Health Hazards

Adulteration of automobile fuel is a prevailing problem because of the financial incentives it entails. It results in sub-optimal performance of engines and increased tailpipe emissions. Better detection techniques are required to weaken the fuel adulteration market. This paper is based on an electronic system to detect adulteration in hydrocarbon-based fuels. High-Speed-Diesel Oil (HSDO) was selected as the testing fuel of which Kerosene is a major adulterant. The proposed system incorporates a 3D-printed polylactide channel, Microchip Technologies’ ATmega328p microcontroller and Espressif Systems’ ESP8266 Wi-Fi module. The testing mechanism is based on fluid capacitance. The capacitance varies directly as the percentage of Adulteration while voltage varies inversely with it. The detection technique proposed in this paper offers portability, rapid testing with quantized results

Analytical methods to detect the Adulterants in Milk - An Overview

Milk contains whole nutrients and is consumed by the majority of population in the form of drinking as well as dietary products. Milk adulteration is one of the most common phenomena, this milk adulteration can be over looked in many countries. it shows serious health hazards leading to fatal diseases. Milk adulterants have been reported globally by adding various instances such as adding water, whey proteins, melamine, urea, detergents, starch hydrogen peroxide, boric acid. This paper presents a detailed review of common milk adulterants as well as different methods such as the chromatographic methods such as HPLC and GC coupled with mass spectrometry to detect the adulterants in milk, and immunological techniques such as ELISA and various DNA based procedures like PCR have also been used to detect the adulterants both qualitatively and quantitatively. This study is organized to be an adulterants-based study instead of a techniques-based one, where qualitative detection for most of the common adulterants are enlisted and quantitative detection methods are limited to a few major adulterants of milk. Apart from regular techniques, recent development in these detection techniques has also been reported. Nowadays milk is being adulterated in more sophisticated ways that demand for cutting- edge research for the detection of adulterants. This review intends to contribute towards the common knowledge base regarding possible milk adulterants and their detection techniques.

Milk Adulterants in Quetta: A Threat to Public Health

Milk a natural rich lacteal secretion that provides all essential nutrients required by body. This study was designed to detect milk adulterants alongwth various physiochemical factors in milk sold in Quetta market. A total of 120 raw milk samples were collected hygienically and subjected to milk adulteration Kit (UVAS Lahore). Results revealed that overall, 11.66 % samples revealed adulteration with any single chemical adulterant. Water and powdered milk were the major adulterants found almost in all samples. On towns basis Zarghoon town samples were more adulterated (18%) than Chiltan Town samples (5%). Other parameters such as, Electrical Conductivity, pH, Fat percentage, Total Solids and Solid Not Fat were observed below than normal values in most of the samples. Adulterants like Urea, Hydrogen Peroxide, Sorbitol, Boric acid, Quaternary Ammonium Compound, Carbonate, Soap and Alcohol were not detected in any sample. However, Sodium chloride (1.66 %), Formalin (3.33 %), Hypochlorite (2.5 %), Starch (2.5 %) and sugar (4.16 %) were detected.
 This study explores the potential health hazard due to adulterated milk sold in retail outlets in Quetta market. There is dire need of regular monitoring of milk and its products by concerned food authority. These findings will help to build a concrete strategy to curtail this problem and improve the life standards of people.

Development of a detector tube for rapid detection of tadalafil in adulterated dietary supplements

ABSTRACT Introduction Products marketed as dietary supplements for improving sexual performance at times include phosphodiesterase type 5 (PDE5) inhibitors, such as sildenafil and analogues. The ingestion of these dietary supplements is extremely dangerous as these are not evaluated for their efficacy and safety as pharmaceuticals, and their manufacture is not controlled. For this reason, regulatory authorities conduct inspections on these products to prevent the occurrence and spread of health hazards. Tadalafil is one of the PDE5 inhibitors, and its analogues are found as the most major adulterants in sexual products after analogues of sildenafil. Tadalafil has two chiral carbons that are both R configuration, which is important for PDE5 inhibitory activity. To confirm the molecular configuration of the tested compound, it is subject to instrumental analysis such as circular dichroism detection or X-ray crystal structure analysis. Therefore, it takes longer for testing tadalafil than for other compounds that do not require these processes. Meanwhile, in 2020, the product containing 120 times more tadalafil than the normal dosage was detected in Tokyo, making it an urgent issue to remove these dangerous products from the market. This study proposes a simple and rapid method to detect tadalafil with a newly devised detector tube. Objective Development of a detector tube for the rapid screening of tadalafil with simple functioning. Methods Approximately 80 mg of silica gel powder impregnated with sulfuric acid was filled in a glass tube, having a 3-mm inner diameter, to prepare a detector tube. The measuring method of this detector tube is quite simple; first, both tips of the detector tube are cut, then the sample solution is aspirated, and a decision is made by the colour of the detector tube after 5 minutes. It was defined as a positive result when the detector tube turned violet and negative when it showed other colours. First, the reaction of tadalafil and analogues were confirmed using the prepared detector tube. Then, specificity was tested for active pharmaceutical ingredients and common additives. The tube was also tested for the applicability to some commercially available dietary supplements. Results All tested tadalafil and analogues showed positive results in the test. The limit of detection was 5 μg/mL for tadalafil. Except for levomepromazine, results for additives and any pharmaceutical ingredients tested were negative. This tube was able to detect all real samples containing tadalafil and analogues. None of the real samples that did not contain tadalafil and analogues gave false positives. Conclusions The developed detector tube could rapidly detect tadalafil and analogues with high sensitivity in a simple procedure. It was suggested that false-positive results could occur only if levomepromazine was included in the sample. Other than that, no significant interference that leads to false results was observed in tested common adulterants and additives of supplements. Furthermore, the tube was able to detect tadalafil and analogues in all tested real samples. Accordingly, the proposed test method has the potential for the use of preliminary screening of tadalafil.

Adulteration detection of Sudan Red and metanil yellow in turmeric powder by NIR spectroscopy and chemometrics: The role of preprocessing methods in analysis

Turmeric powder is valued both for its medicinal properties and for its popular culinary use, such as being a component of curry powder. Due to its high demand in international trade, turmeric powder has been subject to economically driven and hazardous chemical adulteration. The objective of this study was to classify and quantify two major adulterants (Sudan Red and Metanil yellow) in turmeric powder using near-infrared (NIR) spectroscopy associated with chemometric models. The absorbance spectra of samples were obtained in frequency regions of 10,000–4200 cm−1. A Soft Independent Modeling of Class Analogy (SIMCA) model was established to determine the authenticity of the turmeric powder. A partial least squares (PLS) regression was used to predict the adulteration level. The different combinations of preprocessing methods such as standard normal variate transformation (SNV), median filter, Savitzky-Golay, wavelet, multiplicative scatter correction (MSC), first derivative (D1) and second derivative (D2) were applied to preprocess the spectral data, in which SNV combined with median filter and D1 performed best. The sample correct classification rate in SIMCA model were found 96.7 and 93.4 in both calibration and validation set respectively. The PLS regression models were evaluated by the coefficient of determination (r2) and root mean square error (RMSE). All PLS regression models established with the combination of different spectral pretreatment except of MSC, Savitzky-Golay, D1 and MSC, Wavelet, D1 showed low values of RMSE and ideal coefficient of determination for both calibration and prediction sets while using relatively few factors. Also, the PLS regression results showed that first derivative led to better calibration models when compared with the second derivative. The obtained statistical parameters for Sudan Red were r2 = 0.90, RMSE = 0.059 in test set and r2 = 0.91 and RMSE = 0.058 for metanil yellow in test set.

A Systematic Review of the European Rapid Alert System for Food and Feed: Tendencies in Illegal Food Supplements for Weight Loss.

Background: Slimming products represent a dynamically growing group of food supplements worldwide. The efficacy of safely usable natural ingredients is usually below consumers’ expectations. Certain manufacturers add unauthorized or prohibited ingredients to weight loss supplements in order to increase their efficacy. Hence, many of these products are adulterated and may pose a risk to the consumers’ health. Aims: The aim of our work was to give an overview on natural ingredients used in slimming products, to summarize the frequently used synthetic adulterants and also to assess the trends of adulterated and illegal food supplements in the European Union based on the warnings of the Rapid Alert System for Food and Feed (RASFF) in the time period of 1988–2019. Methods: Reports between 1988–2019 were extracted from the RASFF portal on January 1, 2020. Each entry was individually reviewed. Results: 2,559 records of food supplements with quality problems were identified in the RASFF, several of which [319 (12,5%)] were marketed to facilitate weight loss. 202 (63,3%) contained unapproved, synthetic drug ingredients. The major adulterant (113 of 319, 35.4%) was DNP (2,4-dinitrophenol), whereas sibutramine was the second most frequent adulterant agent (69 products, 21,6%) between 1988 and 2019. Conclusion: The number of approved medicines for the indication of weight loss is relatively low and their efficacy (and also that of the natural ingredients) is limited. Therefore, a significant number of weight loss supplements is adulterated to satisfy patients’ expectations. Hence, these products may cause serious adverse effects in sensitive patients.

Evaluation of cytotoxicity of areca nut and its commercial products on normal human gingival fibroblast and oral squamous cell carcinoma cell lines

Consumption of areca nut products is the most common cause of oral cancers, particularly in South Asian countries. This study evaluates the cytotoxic and necrotizing effects of areca nut and its formulations on normal human gingival fibroblasts (HGF-1) and oral squamous cell carcinoma (OSCC, CAL-27) cell lines. Identification of various carcinogens and adulterants using LC-HR-ESI-MS/MS analysis was performed in the extracts of areca nut and its products. Apart from alkaloids and flavonoids, a major adulterant, saccharin was found in all the samples of chalia (one of the most common chewing products of areca nut) in the ranges between 1.697–7.170 mg/g of the sample. Cytotoxic studies showed that most of the areca nut products were found cytotoxic to HGF-1 cells while being relatively non-cytotoxic against CAL-27 cells, rather they promote the growth of cancer cells. Our findings revealed that the components of areca nut and its products were injurious to HGF-1 cells and caused necrosis, which may attenuate HGF-1 protection toward oral epithelial cells. Moreover, the non-cytotoxic effect of these products on cancer cell lines suggests further predisposal of the habitual chewers for developing oral carcinomas. This study will give a better understanding of the hazardous effects of areca nut products.

Isolation and identification of ten new sildenafil derivatives in an alleged herbal supplement for sexual enhancement

A sexual enhancer dietary supplement in pre-commercialization phase was analyzed. It contained the two phosphodiesterase-5 inhibitors (PDE-5i) sildenafil and methisosildenafil as major adulterants. Fourteen more sildenafil derivatives were detected and after isolation, their structures were elucidated thanks to NMR, high resolution and tandem mass spectrometry, and UV spectroscopy. Ten of them were never described. All these compounds are probably by-products of different reaction steps during the synthesis of the two PDE-5i that were not properly eliminated during the purification procedure. The total amount of sildenafil-related compounds was estimated at 68 mg per capsule, sildenafil and methisosildenafil accounting for 20 mg and 38 mg respectively.

Effects of Coca-paste (CP) on the sleep-wake cycle of the rat. Relevance of caffeine as a major adulterant

Effects of Coca-paste (CP) on the sleep-wake cycle of the rat. Relevance of caffeine as a major adulterant

Chromatography methods and chemometrics for determination of milk fat adulterants

Milk and milk-based products are among the leading food categories according to reported cases of food adulteration. Although many authentication problems exist in all areas of the food industry, adequate control methods are required to evaluate the authenticity of milk and milk products in the dairy industry. Moreover, gas chromatography (GC) analysis of triacylglycerols (TAGs) or fatty acid (FA) profiles of milk fat (MF) in combination with multivariate statistical data processing have been used to detect adulterations of milk and dairy products with foreign fats. The adulteration of milk and butter is a major issue for the dairy industry. The major adulterants of MF are vegetable oils (soybean, sunflower, groundnut, coconut, palm and peanut oil) and animal fat (cow tallow and pork lard). Multivariate analysis enables adulterated MF to be distinguished from authentic MF, while taking into account many analytical factors. Various multivariate analysis methods have been proposed to quantitatively detect levels of adulterant non-MFs, with multiple linear regression (MLR) seemingly the most suitable. There is a need for increased use of chemometric data analyses to detect adulterated MF in foods and for their expanded use in routine quality assurance testing.

Heroin in Malaysia and Singapore.

Clandestine heroin laboratories have been a feature of the Malaysian illicit drug scene since soon after the abuse of heroin emerged in 1972. The first few clandestine heroin laboratories which synthesised heroin via the acetylation of imported morphine were uncovered in 1973 and 1977. By the mid-1980s, this type of laboratory was replaced by heroin-cutting laboratories whereby imported high-grade heroin was cut to street heroin. This was to meet the rising demand for the drug owing to the rapid escalation of the number of drug users. Over the years, the most significant change in the composition of the street heroin is the decrease in its purity from 30%-50% to 3%-5%. Caffeine has remained the major adulterant and chloroquine is detected in virtually all recent seizures.

Levamisole in Illicit Trafficking Cocaine Seized: A One-Year Study

ABSTRACTCocaine use is increasing around the world and its purity is frequently altered through dilution, substitution, contamination, and adulteration. Sugars, talc, starch, and carbonates represent the principal diluents of cocaine, while phenacetin, levamisole, caffeine, and lidocaine are its major adulterants in Europe. Levamisole is used because it is an odorless powder, with physical properties similar to cocaine, and it has reasonable cost and availability, being widely used in veterinary medicine. For this study, we analyzed 88 cocaine samples. The seized cocaine analyzed showed an average purity of 55% and the most frequent adulterants identified were: levamisole (31.8%), caffeine (6.8%), lidocaine (2.3%), acetaminophen (2.3%), and phenacetin (1.1%). Our aim is the study of the presence of levamisole, over other adulterants in seized cocaine samples, due to its recognized human toxicity. The chronic use of levamisole-adulterated cocaine represents a serious public health issue because it may be responsible for side-effects such as dermal vasculopathy, leukoencephalopathy, leukopenia, agranulocytosis, pulmonary hemorrhage, multiple emboli, and several other effects. Moreover, aminorex can cause idiopathic pulmonary hypertension, presenting another harmful and mostly lethal side-effect from cocaine cut with levamisole. In conclusion, levamisole determination should be performed in routine toxicological analysis in deaths due to cocaine use.

Common milk adulteration and their detection techniques

Food adulteration is a global concern and developing countries are at higher risk associated with it due to lack of monitoring and policies. However, this is one of the most common phenomena that has been overlooked in many countries. Unfortunately, in contrast to common belief, milk adulterants can pose serious health hazards leading to fatal diseases. This paper presents a detailed review of common milk adulterants as well as different methods to detect the adulterants both qualitatively and quantitatively. This study is organized to be an 'adulterant based' study instead of 'techniques based' one, where qualitative detection for most of the common adulterants are enlisted and quantitative detection methods are limited to few major adulterants of milk. Apart from regular techniques, recent development in these detection techniques have also been reported. Nowadays milk is being adulterated in more sophisticated ways that demands for cutting edge research for the detection of the adulterants. This review intends to contribute towards the common knowledge base regarding possible milk adulterants and their detection techniques.

Dispersive liquid-liquid microextraction based on solidification of floating organic drop and high-performance liquid chromatography to the analysis of cocaine's major adulterants in human urine.

A simple method has been proposed for the determination of cocaine's major adulterants (caffeine, levamisole, lidocaine, phenacetin, diltiazem, and hydroxyzine) in human urine by dispersive liquid-liquid microextraction based on solidification of floating organic drop (DLLME-SFO) in combination with high-performance liquid chromatography - photodiode array detector (HPLC-PDA). The reversed-phase chromatographic separation was obtained with a column C18 extended (250×4.6mm; 5μm; 80Å) in gradient elution mode using acetonitrile-trifluoroacetic acid 0.026% (v,v) (pH=2.5) at 1mLmin-1 as mobile phase, at 25°C, and detection at 235nm. The analysis time was 25min. This condition had the best resolution factors (>1.15), retention factors (>0.68), number of plates (>2094.9), and separation factors (>1.05) for all targets, indicating a good separation. The kind of extraction and dispersive solvent were investigated for unifactorial design. The buffer pH, the volume of extraction and disperser solvent, and the amount of salt were optimized for full factorial design. Under optimum conditions, human urine samples were alkalized with 0.5M sodium phosphate buffer (pH 10) and added to sodium chloride (20%m/v). Acetonitrile (150μL) and 1-dodecanol (30μL) were used as dispersive and extraction solvent, respectively. The method presented linear range of 312.5-3125ngmL-1 to caffeine and levamisole and 187.5-1875ngmL-1 to lidocaine, phenacetin, diltiazem, and hydroxyzine. The limit of quantification was 187.5ngmL-1 to lidocaine, phenacetin, diltiazem, and hydroxyzine and 312.5ngmL-1 for caffeine and levamisole. The recovery mean values were between 6.0 and 42.6%. The method showed good precision and accuracy, with within- and between-run relative standard deviation and relative error less than 15%. The samples were stable after freeze-thaw cycle and short-term room temperature stability tests. Besides, this method was satisfactorily applied in urine of cocaine users. It is expected that this method, which was the first to combine the use of DLLME-SFO and HPLC-PDA for the determination of cocaine's major adulterants in human urine, will contribute to the accuracy in the diagnosis of acute intoxication, the proper planning of therapeutic measures, as well as to the favorable prognostic of cocaine intoxicated patients.

Discrimination and quantification of cocaine and adulterants in seized drug samples by infrared spectroscopy and PLSR

Middle infrared spectroscopy and multivariate analysis have been applied for the development of methods to perform both quantitative and qualitative analysis of real drug samples seized by the Brazilian Police Federal (BPF). Currently, quantification of cocaine and determination of adulterants in seizures is performed using gas chromatography with flame ionization detection. However, this technique requires a relatively complex sample preparation, higher time of analysis, the destruction of sample and a high cost. In this context, this paper presents a simpler method to quantify cocaine and its major adulterants in seized materials. Out of 375 seizures, taken within a time frame of 2009–2013. A total of 1085 samples were analyzed of which 500 were selected for the calibration set and 585 for the validation set. Cocaine concentration in seized samples was determined by using middle infrared spectroscopy and partial least squares regression (PLSR), obtaining an average prediction error of 3.0% (w/w), precision of 2.0 and 11.8% (w/w) of minimum detectable cocaine concentration in a range varying from 24.2 to 99.9% (w/w). Results indicate that the developed method is able to discriminate between cocaine hydrochloride and free base samples, to quantify cocaine content as well as to estimate the concentration of main adulterants phenacetin, benzocaine, caffeine, lidocaine and aminopyrine.

Brazilian Federal District Cocaine Chemical Profiling - Mass Balance Approach and New Adulterant Routinely Quantified (Aminopyrine)

From a set of 159 samples seized by Brazilian Federal Police between 2010 to 2013 in the Federal District, the major component chemical profiling routine analyses revealed the presence of cocaine with purity range of 5.5 to 99.9% (mean 69.8%). Most cocaine base samples show moderately and not oxidized levels, whereas cocaine hydrochloride samples exhibit moderate to high oxidation degrees. More than 40% of the analyzed samples did not have any adulterant. Phenacetin was the most abundant adulterant (24% average purity). Aminopyrine, a new adulterant, was identified and quantified only in cocaine base samples, mainly as a trace adulterant but also as a major compound. In most samples adulterated with aminopyrine, phenacetin was also identified as a major adulterant, suggesting a possible association of the two pharmaceuticals in the cutting process. Aminopyrine was not detected in 2010 seizures, but became a common adulterant throughout the years of 2011 to 2013. A mass balance approach analysis also established that adulterants are responsible for only 12% of the mass of all seizures (i.e., 84 kg), whereas 77% (i.e., 553 kg) is due to alkaloids (cocaine and cis/trans-cinnamoylcocaine), contributing to provide forensic intelligence information to police investigators.

Chemical Profiling of Cocaine Seized by Brazilian Federal Police in 2009-2012: Major Components

Cocaine chemical profiling can provide relevant information for law enforcement authorities. Since 2006, Brazilian Federal Police has been working on its own cocaine impurity profiling program (PeQui project). In the effort to establish chemical profiling routines, this work describes major component results (cocaine purity, degree of oxidation and pharmaceutical products used as cutting agents), identified by gas chromatography with flame ionization detection (GC-FID) analysis of 210 samples seized in several Brazilian states between 2009 and 2012. The mean purity of cocaine was 71% (expressed as base) and the degree of oxidation, determined by the relative content between cis/trans-cinnamoylcocaine and cocaine, depends on the location where the seizures were performed. Most of the not oxidized samples were seized on traditional cocaine producer country border states. Cocaine is mainly present in free base form (59%) and more than 50% of the analyzed samples did not have any major adulterant. Among the identified cutting agents, phenacetin was the most abundant (30% of the total samples). Levamisole, caffeine and lidocaine were also identified. The PeQui project has been used on regular basis to provide technical and scientifically based information to law enforcement intelligence analysis and statistical data that might contribute to the better understanding of the cocaine trafficking.

Coca-paste seized samples characterization: Chemical analysis, stimulating effect in rats and relevance of caffeine as a major adulterant

Coca-paste (CP) is a drug of abuse that so far has not been extensively characterized. CP is an intermediate product of the cocaine alkaloid extraction process from coca leaves, hence it has a high content of cocaine base mixed with other chemical substances (impurities) and it is probably adulterated when it reaches the consumers. Despite its high prevalence and distribution through South America, little is known about its effects on the central nervous system. In the present study, a chemical analysis of CP samples from different police seizures was performed to determine the cocaine base content and the presence and content of impurities and adulterants. Some CP representative samples were selected to study the effects on the locomotor activity induced after acute systemic administration in rats as a measure of its stimulant action. The behavioral response was compared to equivalent doses of cocaine. As expected, cocaine was the main component in most of the CP samples assayed. Caffeine was the only active adulterant detected. Interestingly, several CP samples elicited a higher stimulant effect compared to that observed after cocaine when administered at equivalent doses of cocaine base. Combined treatment of cocaine and caffeine, as surrogate of different CP samples mimicked their stimulant effect. We demonstrated that cocaine and caffeine are the main components responsible for the CP-induced stimulant action while the contribution of the impurities was imperceptible.

Toward the Authentication of Wines of Nemea Denomination of Origin through Cleaved Amplified Polymorphic Sequence (CAPS)-Based Assay

In the present study, we developed a cleaved amplified polymorphic sequence (CAPS)-based assay as a first attempt to detect fraud in grapevine musts with a long-term objective to establish an analytical methodology to authenticate wines of Nemea denomination of origin (Agiorgitiko). The analytical assay makes use of a single nucleotide polymorphism that discriminates Agiorgitiko and Cabernet Sauvignon varieties. The latter grape variety is one of the major adulterants for Nemea wines. Agiorgitiko grapevine must was spiked with Cabernet Sauvignon in several ratios (v/v) from 50 down to 10%, and the subsequent mixes were subjected to alcoholic microfermentation. DNA was extracted from all mixture samples up to the end of the fermentation process and was subjected to the CAPS assay. Both standard agarose gel and lab-on-a-chip capillary electrophoresis illustrated the ability of the method to detect the presence of Cabernet Sauvignon down to 10% throughout the whole fermentation process.