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COMMON PART


Project Number22-73-10039

Project titleNew approaches for environmentally safe and automated quality control of food products, agro and aquatic facilities using deep eutectic solvents

Project LeadShishov Andrei

AffiliationFederal State Budgetary Educational Institution of Higher Education "Saint-Petersburg State University",

Implementation period 07.2022 - 06.2025 

Research area 03 - CHEMISTRY AND MATERIAL SCIENCES, 03-205 - Analytical chemistry

KeywordsFood products, chemical analysis, sample preparation, separation and concentration methods, microextraction, deep eutectic solvents


 

PROJECT CONTENT


Annotation
At present, it is impossible to imagine any modern technological production of food products without the introduction and use of operational and express methods of chemical analysis of both the products used and raw materials for the production of food products, and the products themselves. Strict control of all stages will make it possible to obtain a high-quality product that will be useful to the end consumer and will comply with all established state quality standards. At the same time, both food products and agro- and aquatic objects used in their production technologies are complex complex objects of analysis, the quality control of which cannot be imagined without the use of both high-tech analytical instruments such as chromatographic, spectral and electrochemical devices, and without the use of modern methods of sample preparation, separation and concentration, to isolate analytes to be determined in order to obtain reliable information about the chemical composition of the objects under study. At the same time, the stage of sample preparation remains one of the longest, labor- intensive, and difficult to implement in terms of automation of chemical analysis. But it is the high-quality performance of all stages of the sample preparation stage that is necessary to obtain reliable and timely information about the composition of the final object. Currently, most of the chemical analysis procedures used do not meet the standards of environmental friendliness and automatability. This results in lengthy, labor-intensive sample preparation procedures using environmentally unsound and sometimes toxic organic solvents that are detrimental to laboratory chemists and the environment. And if we take into account that the chemical analysis of food products is one of the largest chemical analyzes, then we can get an idea of the huge amount of toxic waste generated that requires special disposal and can harm the environment. All this leads to the need to develop new automated and environmentally friendly procedures for the chemical analysis of food products without loss of selectivity and accuracy of analysis. To solve the above problems, within the framework of this project, it is planned to develop a set of highly efficient environmentally friendly and automated procedures for quality control of food products in aquatic and agricultural facilities. As a universal automated platform, it is planned to use the flow analysis methods already being introduced into modern analytical practice, which have proven themselves well in the analysis of various objects, including food. And to improve the environmental friendliness of chemical analysis, within the framework of the proposed project, it is planned to introduce the use of new, promising, environmentally friendly solvents of deep eutectic solvents into the analytical practice of chemical analysis of food products of agro- and aquatic objects. At the same time, it should be noted that in the scientific literature, all presented methods for automating chemical analysis based on the principles of in-line analysis methods using deep eutectic solvents were proposed by the authors of this project, and currently have no analogues abroad. Within the framework of this project, it is planned to develop a set of highly effective environmentally friendly procedures for the chemical analysis of food products and agro- and aquatic objects using environmentally friendly solvents. At the same time, a number of procedures are planned to be automated using flow methods of analysis, which will, on the one hand, make it possible to radically reduce the consumption of both the objects themselves, if necessary without loss of sample representativeness, and the solvents and reagents used, which will significantly increase the productivity of chemical analysis. As objects of chemical analysis, it is planned to use both solid- phase and liquid-phase food products, such as meat, plant foods, milk, and edible oils. In addition, it is planned to develop analytical procedures for the chemical analysis of soils used in food production and irrigation water, which will also minimize contamination of final food products. It is planned to use a wide range of both organic and inorganic substances as analytes. Heavy metals will be used as inorganic analytes, the content of which is unacceptable both in natural water and in soils, and in final food products. Various classes of compounds such as pesticides, carcinogens, dyes, phenolic compounds, and antibiotics will be considered as organic analytes. The versatility of the proposed approaches is planned to be demonstrated by combining the developed preparation procedures with various modern high-performance methods of chemical analysis, such as high-performance liquid chromatography, electrochemical, and spectral methods of analysis. The use of a wide range of objects of analysis, analytes, detection methods will allow, on the one hand, to develop a set of highly efficient procedures for the chemical analysis of both food products and to demonstrate the versatility of these approaches, which will allow further scaling up these technologies to solve more local specific analytical problems. specific analytes in other objects of analysis. At the same time, in addition to the direct development of analytical procedures for solving a wide range of chemical analysis problems, within the framework of this project, a more detailed study of the nature of deep eutectic solvents themselves is planned for a more detailed understanding of the processes of separation and concentration of analytes using them. In the future, this will allow, on the basis of the solvents used, to develop more efficient procedures for the chemical analysis of various food products and other objects of analysis for the introduction of these technologies into real analytical practice to solve an increasing range of problems. Thus, the project pursues both practical and more fundamental tasks.

Expected results
During the implementation of the project, it is planned, on the one hand, to develop a set of highly efficient analytical procedures using deep eutectic solvents for the chemical analysis of food products, agro- and aquatic objects, on the other hand, it is planned to study in more detail the properties, structure, stability and extraction properties of a new class of environmentally friendly solvents - deep eutectic solvents. For the analysis of solid phase food products, it is planned to develop a series of analytical procedures using deep eutectic solvents as effective extractants. For the determination of pesticides in plant materials, it is planned to develop a procedure during which deep eutectic solvents will be generated in- situ. Fatty acids obtained directly from the object of analysis will be used as its precursors. To do this, at the preliminary stage of sample preparation, alkaline hydrolysis of the food product will be carried out to convert fatty acid triglycerides into free acids. Then, when natural environmentally friendly terpenoids, such as thymol or menthol, are added to the resulting mixture, the formation of a eutectic compound between acids and terpenes will occur with simultaneous extraction of pesticides into the phase of the formed eutectic compound. After separating such a mixture, the extractant will be analyzed by gas chromatography to determine the concentration of pesticides. The use of this approach will minimize the costs for the preliminary synthesis of eutectic solvents, as well as increase the efficiency of the extraction of pesticides into the phase of the formed eutectic compound due to their high solubility in fatty acids. This will allow the development of a simple, environmentally friendly and efficient procedure for the determination of pesticides without the use of organic toxic solvents. To determine dyes in food products, it is planned to develop an extraction procedure for their extraction of analytes into hydrophobic eutectic solvents. These solvents will be pre-dispersed in an aqueous solution which will be used as an effective extractant to isolate water insoluble carcinogenic dyes such as Sudan dyes. These dyes, due to their cheapness and stability, are often added to give food products color, but they have carcinogenic properties, which leads to the need to control their content in food products. To solve this problem, hydrophobic waterproof eutectic solvents will be synthesized, after which they will be dispersed in an aqueous solution to create their emulsion, which will be used as an effective extractant for extracting dyes from food products. After mixing the sample and the extraction mixture, the extraction of analytes into the emulsion phase will occur. This emulsion will be separated by centrifugation and analytes will be determined in the eutectic solvent phase. This will make it possible to significantly concentrate analytes and use the developed procedure to determine even microconcentrations. To determine carcinogens such as acrylic acid amide in solid- phase food products, it is planned to develop a procedure for vapor-phase microextraction with the release of an analyte into the gas phase, followed by its absorption into a eutectic solvent. To implement this task, eutectic solvents based on environmentally friendly compounds such as choline chloride, citric, oxalic, tartaric, malonic, and malic acids will be used. The use of solvents based on water-soluble compounds will completely avoid the use of organic solvents at all stages of sample preparation, which will allow the procedure to be considered from the point of view of green analytical chemistry. For the determination of heavy metals in edible oils, it is planned for the first time to combine the preliminary stage of liquid extraction and separation of analytes into the eutectic solvent phase with the direct determination of metals by the potentiometric method in the eutectic solvent phase. It should be noted that at present the direct potentiometer method has not yet been implemented using eutectic solvents, and will be implemented for the first time during the implementation of this project. This procedure will be automated on the principles of flow analysis methods. For environmental monitoring and analysis of natural and technological waters used in agricultural and aquaculture, it is planned to develop a procedure for the simultaneous automated extraction and detection of such analytes as phenol and its derivatives, heavy metals, antibiotics of various classes such as tetracyclines, sulfonamides, fluoroquinolones, on one analytical device . This will allow integrating it into the control system of aquatic environments to solve various technological problems. The scheme of the device will consist in the use of a special rotating disk modified with a deep eutectic solvent to isolate various classes of analytes depending on the problem being solved. The water sample will be continuously fed through the extraction device while the analytes will be efficiently extracted on the rotating disc. Thereafter, depending on the analyte, they can be detected directly on the disk or after eluting in the extract by an appropriate instrumental method. For the analysis of agricultural objects, such as soils, it is planned to develop effective procedures for the recovery of both organic analytes, such as petroleum products or phenol derivatives, and inorganic analytes, such as heavy metals. It should be noted that at present, the literature does not present the possibility of implementing the chemical analysis of soils and agricultural objects using deep eutectic solvents. This will also be implemented for the first time within the framework of this project. Thus, within the framework of this project, new, environmentally friendly and effective procedures for the chemical analysis of food products, agricultural and aquatic objects will be proposed.


 

REPORTS


Annotation of the results obtained in 2022
During the implementation of the project, automated and miniaturized procedures for the chemical analysis of food products were developed using deep eutectic solvents as effective and environmentally friendly extractants. An automated microextraction method was developed to reconcile hydrophobic DES based on menthol and hexanoic acid for the determination of Sudan I, Sudan II and Sudan III in chili-based sauces for HPLC-UV analysis. To determine lead (as a toxic element) and copper (as an oxidation catalyst) in edible oils, schemes for automated liquid microextraction using hydrophilic DESs based on choline chloride and carboxylic acids were proposed. Atomic absorption spectroscopy with electrothermal atomization was used as an analysis method. The effect of water content in three-component DESs on their viscosity and mass transfer of metals has been studied. To extract melamine (a prohibited additive) from milk and dairy products, a deep eutectic solvent based on a natural terpenoid (thymol) and a medium chain fatty acid (nonanoic acid) was used. The results obtained showed that the proposed DES provides efficient liquid-phase microextraction of melamine from samples of dairy products, followed by its determination by HPLC-UV. Compared with the methods proposed in the literature, this method does not require the stage of analyte derivatization, provides low consumption of the extraction solvent, and is not inferior in such parameters as analysis time and detection limit. To determine acrylic acid amide (carcinogen) in food products by HPLC-UV, a procedure was proposed for microextraction extraction of the analyte into hydrophobic deep eutectic solvents based on natural terpenoids (thymol and menthol) and carboxylic acids. The developed procedure was used to determine acrylamide in foods with a high content of acrylamide, in particular, vegetable chips and coffee. To determine organochlorine pesticides (α-hexachlorocyclohexane, γ-hexachlorocyclohexane) in peanut butter by GC-ECD, a method was developed for liquid microextraction using DES formed in situ directly during sample preparation during alkaline hydrolysis of triglycerides that are part of peanut butter samples. To miniaturize liquid microextraction in DES, a method was developed using a membrane impregnated with natural terpene, on the surface of which DES was formed from fatty acids and the target analytes were extracted into it. The method allows performing liquid microextraction of alkaline hydrolysis-resistant analytes from complex matrices of food products containing fatty acid triglycerides without additional extraction removal of the latter. The achieved detection limits allow the determination of organochlorine pesticides in peanut butter below the MPC.

 

Publications

1. Andrey Shishov Egor Nizov, Andrey Bulatov, Microextraction of melamine from dairy products by thymol-nonanoic acid deep eutectic solvent for High-Performance Liquid Chromatography-Ultraviolet determination Journal of Food Composition and Analysis, Том 116 Номер статьи 105083 (year - 2023) https://doi.org/10.1016/j.jfca.2022.105083

2. Shishov, A. , Gurev, I. , Bulatov, A. Automated reversed-phase liquid-liquid microextraction based on deep eutectic solvent for the determination of copper as vegetable oil oxidation catalyst Journal of Food Composition and Analysis, Том 119 June 2023 Номер статьи 105247 (year - 2023) https://doi.org/10.1016/j.jfca.2023.105247

3. Shishov, A. , Pochivalov, A. , Dubrovsky, I. , Bulatov, A. Deep eutectic solvents with low viscosity for automation of liquid-phase microextraction based on lab-in-syringe system: Separation of Sudan dyes Talanta, Том 2551 April 2023 Номер статьи 124243 (year - 2023) https://doi.org/10.1016/j.talanta.2022.124243

4. Daria Meshcheva, Firuza Krekhova, Andrey Shishov, Andrey Bulatov Способ микроэкстракционного выделения хлорорганических пестицидов из пищевых продуктов ХХVI Всероссийская конференция молодых учёных-химиков (с международным участием): тезисы докладов (Нижний Новгород, 18–20 апреля 2023 г.), с. 301 (year - 2023)

5. Egor Nizov, Andrey Shishov Определение меламина в молочных продуктах с использованием глубоких эвтектических растворителей ХХVI Всероссийская конференция молодых учёных-химиков (с международным участием): тезисы докладов (Нижний Новгород, 18–20 апреля 2023 г.), с. 308 (year - 2023)

6. Egor Nizov, Andrey Shishov Хроматографическое определение меламина в молоке и молочных продуктах с использованием глубоких эвтектических растворителей Материалы XXIV Международной научно-практической конференции студентов и молодых ученых "Химия и химическая технология" (15-19 мая 2023 года, г. Томск), стр 45 (year - 2023)

7. Firuza Krekhova, Andrey Shishov, Andrey Bulatov In situ образование эвтектических растворителей для инструментального анализа пищевых продуктов и биологических жидкостей ХХVI Всероссийская конференция молодых учёных-химиков (с международным участием): тезисы докладов (Нижний Новгород, 18–20 апреля 2023 г.), с. 288 (year - 2023)

8. Ulyana Markova, Andrey Shishov, Andrey Bulatov ВЭЖХ-УФ определение акриламида в пищевых продуктах с предварительным выделением в глубокие эвтектические растворители Материалы XXIV Международной научно-практической конференции студентов и молодых ученых "Химия и химическая технология" (15-19 мая 2023 года, г. Томск), стр. 50 (year - 2023)

9. Ulyana Markova, Andrey Shishov, Andrey Bulatov Хроматографическое определение акриламида в пищевых продуктах с предварительным выделением в глубокие эвтектические растворители ХХVI Всероссийская конференция молодых учёных-химиков (с международным участием): тезисы докладов (Нижний Новгород, 18–20 апреля 2023 г.), с. 298 (year - 2023)


Annotation of the results obtained in 2023
To determine heavy metals in food products, a method was developed that included the extraction of analytes into natural deep eutectic solvents based on choline chloride and carboxylic acids. This study is the first to thoroughly compare the efficiency of ultrasonic extraction of heavy metals (Cu, Cd, Co, Cr, Fe, Pb and Zn) from solid food products using acidic deep eutectic solvents and saturated aqueous solutions of these acids (lactic, citric, tartaric, glycolic, malonic, apple). During the work, it was shown that eutectic solvents more efficiently extract all the studied metals compared to aqueous solutions of acids (extraction efficiency 85-95%), which is comparable to the results obtained with complete mineralization of the sample using the microwave mineralization method. Also in the work, the extraction mechanism was studied for the first time and the contribution of choline chloride to the extraction efficiency was demonstrated. To determine bisphenols in natural water, a fully automated flow analysis scheme was developed within the framework of this study, including chromatomembrane concentration of analytes. This work was the first to demonstrate the possibility of using deep eutectic solvents as an alternative to organic solvents to implement the process of chromatomembrane microextraction. Unlike traditional organic solvents, deep eutectic solvents provide environmentally friendly membrane chromatography microextraction and are compatible with liquid chromatography. The developed method was successfully used to determine analytes in real samples. To determine PAHs in natural water, an automated scheme for the extraction of analytes using a rotating disk modified with a eutectic solvent has been proposed. For this purpose, a flow cell was manufactured using 3D printing, inside which a PTFE disk modified with DES was placed. During the work, it was found that EDESR based on menthol and alcohol are the most effective extractants for the extraction of polycyclic aromatic hydrocarbons from aqueous media. Hydrodynamic extraction conditions, such as time and disk rotation speed, as well as elution conditions, were studied and optimized. The developed method was successfully used to determine analytes in real samples.

 

Publications

1. A. Yu. Shishov, A. V. Bulatov Automated Microextraction Separation of Lead from Vegetable Oils for Determination by Atomic Absorption Spectrometry Journal of Analytical Chemistry, Vol. 79, No. 1, pp. 35–41. (year - 2024) https://doi.org/10.1134/S1061934824010088

2. Andrey Shishov, David Israelyan, Andrey Bulatov Automated deep eutectic solvent-based chromatomembrane microextraction: Separation and preconcentration of bisphenols from aqueous samples Separation and Purification Technology, Volume 338, 19 June 2024, 126480 (year - 2024) https://doi.org/10.1016/j.seppur.2024.126480

3. Krekhova F., Meshcheva D., Shishov A., Bulatov A. In situ formation of natural deep eutectic solvent on membrane after fat hydrolysis for lindane isomers determination in peanut paste Talanta, Volume 271, 1 May 2024, 125737 (year - 2024) https://doi.org/10.1016/j.talanta.2024.125737

4. Ninayan R., Markova U., Nizov E., Melesova M., Novikov A., Shishov A. Deep eutectic solvents vs. Aqueous acids in metal extraction from animal tissues Microchemical Journal, Volume 200, May 2024, 110252 (year - 2024) https://doi.org/10.1016/j.microc.2024.110252

5. Shishov A., Markova U., Ekaterina D., Bulatov A. Automated liquid-liquid deep eutectic solvents based microextraction procedure for determination of acrylamide in foodstuffs by high-performance liquid chromatography with ultraviolet detection Journal of Food Science and Technology, - (year - 2024)

6. ardani N.I., Samkumpim T., Alahmad V., King E.U., Varanusupakul P., Shishov A., Yahaya N., Zein N.N.M. Recent cutting-edge approaches to the integration of solid-liquid extraction with deep eutectic solvents: Toward a greener procedure for biomass valorization Advances in Sample Preparation, Volume 10, May 2024, 100113 (year - 2024) https://doi.org/10.1016/j.sampre.2024.100113

7. Shishov A.Yu., Mokhodoeva O.B. Индексы экологичности в аналитической химии Journal of Analytical Chemistry, - (year - 2024)

8. Melesova M.A., Kirsanov D.O., Shishov A.Yu., Bulatov A.V. Хемометрические алгоритмы и глубокие эвтектические растворители для экологически безопасного многокомпонентного анализа неполярных матриц Тезисы конференции «Химия и химическая технология в XXI веке» (2024 г.), стр 45 (year - 2024)

9. Nizov E., Shishov A. Хроматографическое определение полициклических ароматических углеводородов в природных объектах с использованием гидрофобных глубоких эвтектических растворителей в качестве экстрагентов Тезисы конференции «Химия и химическая технология в XXI веке» (2024 г.), стр 14 (year - 2024)

10. Shishov A. Глубокие эвтектические растворители в анализе и переработке лекарственного растительного сырья: возможности и ограничения Тезисы конференции «Химия и химическая технология в XXI веке», стр 26 (year - 2024)

11. Shishov A. ПРИМЕНЕНИЕ ГЛУБОКИХ ЭВТЕКТИЧЕСКИХ РАСТВОРИТЕЛЕЙ В АНАЛИЗЕ ЛЕКАРСТВЕННОГО РАСТИТЕЛЬНОГО СЫРЬЯ. ВОЗМОЖНОСТИ И ОГРАНИЧЕНИЯ тезисы конференции ХIII Международная научная конференция и школа молодых ученых «Химия и технология растительных веществ», стр 54 (year - 2024)

12. Shishov A., Markova U., Bulatov A Новый серосодержащий глубокий эвтектический растворитель для селективного извлечения и определения тяжелых металлов в пищевых продуктах методом АЭС-ИСП Тезисы конференции «Химия и химическая технология в XXI веке» (2024 г.) (2024 г.), стр 81 (year - 2024)

13. Shishov A.Yu., Krekhova F.M., Markova U.O., Nizov E.R., Melesova M.A., Mescheva D.A. Глубокие эвтектические растворители как экстрагенты нового поколения в аграрной и пищевой химии ТРЕТИЙ МЕЖДУНАРОДНЫЙ СИМПОЗИУМ «ХИМИЯ ДЛЯ БИОЛОГИИ, МЕДИЦИНЫ, ЭКОЛОГИИ И СЕЛЬСКОГО ХОЗЯЙСТВА» ISCHEM 2024, стр 41 (year - 2024)

14. - Химики СПбГУ разработали процедуру быстрого и экологичного определения тяжелых металлов в мясе Сайт СПбГУ, - (year - )