<?xml version="1.0" encoding="UTF-8"?>
<!DOCTYPE article PUBLIC "-//NLM//DTD JATS (Z39.96) Journal Publishing DTD v1.3 20210610//EN" "JATS-journalpublishing1-3.dtd">
<article article-type="research-article" dtd-version="1.3" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xml:lang="ru"><front><journal-meta><journal-id journal-id-type="publisher-id">zldm</journal-id><journal-title-group><journal-title xml:lang="ru">Заводская лаборатория. Диагностика материалов</journal-title><trans-title-group xml:lang="en"><trans-title>Industrial laboratory. Diagnostics of materials</trans-title></trans-title-group></journal-title-group><issn pub-type="ppub">1028-6861</issn><issn pub-type="epub">2588-0187</issn><publisher><publisher-name>ООО «Издательство «ТЕСТ-ЗЛ»</publisher-name></publisher></journal-meta><article-meta><article-id pub-id-type="doi">10.26896/1028-6861-2022-88-5-5-12</article-id><article-id custom-type="elpub" pub-id-type="custom">zldm-1666</article-id><article-categories><subj-group subj-group-type="heading"><subject>Research Article</subject></subj-group><subj-group subj-group-type="section-heading" xml:lang="ru"><subject>АНАЛИЗ ВЕЩЕСТВА</subject></subj-group><subj-group subj-group-type="section-heading" xml:lang="en"><subject>SUBSTANCES ANALYSIS</subject></subj-group></article-categories><title-group><article-title>Использование смартфона и хемометрического анализа для определения тетрациклинов в природной воде по сенсибилизированной твердофазной флуоресценции европия на его гидроксиде</article-title><trans-title-group xml:lang="en"><trans-title>The use of smartphone and chemometric analysis for determination of tetracyclines in natural water by sensitized solid phase fluorescence of Eu on europium hydroxide</trans-title></trans-title-group></title-group><contrib-group><contrib contrib-type="author" corresp="yes"><name-alternatives><name name-style="eastern" xml:lang="ru"><surname>Амелин</surname><given-names>В. Г.</given-names></name><name name-style="western" xml:lang="en"><surname>Amelin</surname><given-names>V. G.</given-names></name></name-alternatives><bio xml:lang="ru"><p>Василий Григорьевич Амелин</p><p>600000, г. Владимир, ул. Горького, д. 87</p><p>123022, Москва, Звенигородское шоссе, д. 2 5</p></bio><bio xml:lang="en"><p>Vasily G. Amelin</p><p>87, Gor’kogo ul., Vladimir, 600000</p><p>5, Zvenigorodskoye shosse, Moscow, 123022</p></bio><email xlink:type="simple">amelinvg@mail.ru</email><xref ref-type="aff" rid="aff-1"/></contrib><contrib contrib-type="author" corresp="yes"><name-alternatives><name name-style="eastern" xml:lang="ru"><surname>Шаока</surname><given-names>З. А. Ч.</given-names></name><name name-style="western" xml:lang="en"><surname>Shogah</surname><given-names>Zen Alabden Ch.</given-names></name></name-alternatives><bio xml:lang="ru"><p>Зин Алабдин Чалави Шаока</p><p>600000, г. Владимир, ул. Горького, д. 87</p></bio><bio xml:lang="en"><p>Zen Alabden Ch. Shogah</p><p>87, Gor’kogo ul., Vladimir, 600000</p></bio><xref ref-type="aff" rid="aff-2"/></contrib><contrib contrib-type="author" corresp="yes"><name-alternatives><name name-style="eastern" xml:lang="ru"><surname>Большаков</surname><given-names>Д. С.</given-names></name><name name-style="western" xml:lang="en"><surname>Bolshakov</surname><given-names>D. S.</given-names></name></name-alternatives><bio xml:lang="ru"><p>Дмитрий Сергеевич Большаков</p><p>600005, г. Владимир, ул. Токарева, д. 2 5</p></bio><bio xml:lang="en"><p>Dmitry S. Bolshakov</p><p>5, Tokareva ul., Vladimir, 600005</p></bio><xref ref-type="aff" rid="aff-3"/></contrib><contrib contrib-type="author" corresp="yes"><name-alternatives><name name-style="eastern" xml:lang="ru"><surname>Третьяков</surname><given-names>А. В.</given-names></name><name name-style="western" xml:lang="en"><surname>Tretyakov</surname><given-names>A. V.</given-names></name></name-alternatives><bio xml:lang="ru"><p>Алексей Викторович Третьяков</p><p>123022, Москва, Звенигородское шоссе, д. 2 5</p></bio><bio xml:lang="en"><p>Alexey V. Tretyakov</p><p>5, Zvenigorodskoye shosse, Moscow, 123022</p></bio><xref ref-type="aff" rid="aff-4"/></contrib></contrib-group><aff-alternatives id="aff-1"><aff xml:lang="ru"><institution>Владимирский государственный университет имени Александра Григорьевича и Николая Григорьевича Столетовых; Всероссийский государственный центр качества и стандартизации лекарственных средств для животных и  кормов</institution><country>Россия</country></aff><aff xml:lang="en"><institution>Alexander and Nikolay Stoletov Vladimir State University; The Russian State Center for Animal Feed and Drug Standardization and Quality</institution><country>Russian Federation</country></aff></aff-alternatives><aff-alternatives id="aff-2"><aff xml:lang="ru"><institution>Владимирский государственный университет имени Александра Григорьевича и Николая Григорьевича Столетовых</institution><country>Россия</country></aff><aff xml:lang="en"><institution>Alexander and Nikolay Stoletov Vladimir State University</institution><country>Russian Federation</country></aff></aff-alternatives><aff-alternatives id="aff-3"><aff xml:lang="ru"><institution>Центр гигиены и эпидемиологии во Владимирской области</institution><country>Россия</country></aff><aff xml:lang="en"><institution>Center for Hygiene and Epidemiology in the Vladimir Region</institution><country>Russian Federation</country></aff></aff-alternatives><aff-alternatives id="aff-4"><aff xml:lang="ru"><institution>Всероссийский государственный центр качества и стандартизации лекарственных средств для животных и  кормов</institution><country>Россия</country></aff><aff xml:lang="en"><institution>The Russian State Center for Animal Feed and Drug Standardization and Quality</institution><country>Russian Federation</country></aff></aff-alternatives><pub-date pub-type="collection"><year>2022</year></pub-date><pub-date pub-type="epub"><day>23</day><month>05</month><year>2022</year></pub-date><volume>88</volume><issue>5</issue><fpage>5</fpage><lpage>12</lpage><permissions><copyright-statement>Copyright &amp;#x00A9; Амелин В.Г., Шаока З.Ч., Большаков Д.С., Третьяков А.В., 2022</copyright-statement><copyright-year>2022</copyright-year><copyright-holder xml:lang="ru">Амелин В.Г., Шаока З.Ч., Большаков Д.С., Третьяков А.В.</copyright-holder><copyright-holder xml:lang="en">Amelin V.G., Shogah Z.C., Bolshakov D.S., Tretyakov A.V.</copyright-holder><license xml:lang="ru" license-type="creative-commons-attribution" xlink:href="https://creativecommons.org/licenses/by/4.0/" xlink:type="simple"><license-p>Данная работа распространяется под лицензией Creative Commons Attribution 4.0.</license-p></license><license xml:lang="en" license-type="creative-commons-attribution" xlink:href="https://creativecommons.org/licenses/by/4.0/" xlink:type="simple"><license-p>This work is licensed under a Creative Commons Attribution 4.0 License.</license-p></license></permissions><self-uri xlink:href="https://www.zldm.ru/jour/article/view/1666">https://www.zldm.ru/jour/article/view/1666</self-uri><abstract><p>Изучена возможность идентификации и определения антибиотиков тетрациклинового ряда (тетрациклина, доксициклина, окситетрациклина, демеклоциклина, метациклина и хлортетрациклина) в природных водах с использованием цифровой цветометрии по сенсибилизированной флуоресценции европия (III) на его гидроксиде. Установлено, что комплексы европия (III) с тетрациклинами в щелочной среде адсорбируются на гидроксиде европия с сохранением их флуоресцентных свойств. При облучении осадка монохроматическим ультрафиолетовым излучением наблюдается розовая флуоресценция. Измерение цветометрических параметров осадка в аддитивной системе RGB после его центрифугирования проводили с помощью смартфона. Использование хемометрического анализа позволяет сократить время определения и визуализировать данные исследования. Обработку массива данных проводили методами главных компонент, иерархического кластерного анализа и метода k-средних c применением программного обеспечения XLSTAT. Дополнительное привлечение хемометрических методов для обработки аналитического сигнала способствует увеличению достоверности идентификации аналитов. Используемые в работе подходы позволяют количественно оценить содержание антибиотиков в водных объектах. Градуировочные зависимости для определения тетрациклина с использованием методов главных компонент и k-средних имеют логарифмический вид и линейны в диапазонах определяемых содержаний — 0,005 – 0,1 мкг/мл (R2≥ 0,99). Предложена методика определения содержания антибиотиков тетрациклинового ряда в природных водах, которая отличается простотой и доступностью аппаратурного состава. Экологичность предполагает обязательность малым набором неорганических солей, пищевых добавок для концентрирования хелатных комплексов тетрациклинов с ионами европия (III) на его гидроксиде. Применение мобильных цифровых технологий (смартфонов) и современных программных продуктов для обработки данных высокой частоты экспресс-методологии. Апробация методики проведена с использованием пробы речной воды, ее правильность определения метода применения. Относительная погрешность результатов анализа не превышает 15 %.</p></abstract><trans-abstract xml:lang="en"><p>The possibility of identification and determination of tetracycline antibiotics (tetracycline, doxycycline, oxytetracycline, demeclocycline, metacycline and chlortetracycline) in natural water using digital colorimetry based on sensitized fluorescence of Eu (III) on europium hydroxide is studied. It is shown that complexes of Eu (III) with tetracyclines in an alkaline medium are adsorbed on europium hydroxide with preservation of their fluorescent properties. When the precipitate is irradiated with monochromatic ultraviolet light, pink fluorescence is observed. The colorimetric parameters of the precipitate in the RGB additive system after centrifugation were measured using a smartphone. The use of chemometric analysis provides shortening of the analysis procedure and visualizing of data obtained. The data set was processed using principal component analysis (PCA), hierarchical cluster analysis (HCA), and k-means method with XLSTAT software. The additional use of chemometric methods for processing of the analytical signal contributes to an increase in the reliability of the analyte identification. The methods used in the study make it possible to quantify the content of antibiotics in water bodies. The calibration dependences in the methods of principal components and k-means have a logarithmic form and are linear in the ranges of the determined contents — 0.005 – 0.1 μg/ml (R2 ≥ 0.99). The developed method for determining the total content of tetracycline antibiotics in natural waters is easy to use and is characterized by the availability of instrumentation. The environmental friendliness of this approach is attributed to a small set of inorganic salts required for concentration of the chelate complexes of tetracyclines with Eu (III) ions on europium hydroxide. The use of mobile digital technology (smartphones) and modern software products for data processing contributes to the development of rapid analysis. The approbation of the method was carried out using a sample of river water, the correctness of the analysis was proved by the spike test. The relative error of the analysis results does not exceed 15%.</p></trans-abstract><kwd-group xml:lang="ru"><kwd>тетрациклины</kwd><kwd>цифровая цветометрия</kwd><kwd>сенсибилизированная флуоресценция</kwd><kwd>смартфон</kwd><kwd>вода</kwd><kwd>хемометрический анализ</kwd></kwd-group><kwd-group xml:lang="en"><kwd>tetracyclines</kwd><kwd>digital colorimetry</kwd><kwd>sensitized fluorescence</kwd><kwd>smartphone</kwd><kwd>water</kwd><kwd>chemometric analysis</kwd></kwd-group></article-meta></front><back><ref-list><title>References</title><ref id="cit1"><label>1</label><citation-alternatives><mixed-citation xml:lang="ru">Wang Y., Xu X. H., Han J., Yan Y. S. Separation/enrichment of trace tetracycline antibiotics in water by [Bmim]BF4– (NH4)2SO4 aqueous two-phase solvent sublation / Desalination. 2011. Vol. 266. P. 114 – 118. DOI:10.1016/j.desal.2010.08.010</mixed-citation><mixed-citation xml:lang="en">Wang Y., Xu X. H., Han J., Yan Y. S. Separation/enrichment of trace tetracycline antibiotics in water by [Bmim]BF4– (NH4)2SO4 aqueous two-phase solvent sublation / Desalination. 2011. Vol. 266. P. 114 – 118. DOI:10.1016/j.desal.2010.08.010</mixed-citation></citation-alternatives></ref><ref id="cit2"><label>2</label><citation-alternatives><mixed-citation xml:lang="ru">Supharoek S., Ponhong K., Weerasuk B., et al. A new spectrophotometric method based on peroxidase enzymatic reaction to determine tetracycline in pharmaceutical and water samples / J. Iran. Chem. Soc. 2020. Vol. 17. P. 2385 – 2395. DOI:10.1007/s13738-020-01934-x</mixed-citation><mixed-citation xml:lang="en">Supharoek S., Ponhong K., Weerasuk B., et al. A new spectrophotometric method based on peroxidase enzymatic reaction to determine tetracycline in pharmaceutical and water samples / J. Iran. Chem. Soc. 2020. Vol. 17. P. 2385 – 2395. DOI:10.1007/s13738-020-01934-x</mixed-citation></citation-alternatives></ref><ref id="cit3"><label>3</label><citation-alternatives><mixed-citation xml:lang="ru">Гончарова Л. А., Кобылинская Н. Г., Диас-Гарсия М. Е., Зайцев В. Н. Твердофазно-люминесцентное определение тетрациклина в бутилированной воде с использованием химически модифицированных кремнеземов / Журн. аналит. химии. 2017. Т. 72. ¹ 7. С. 618 – 627. DOI:10.7868/S0044450217070064</mixed-citation><mixed-citation xml:lang="en">Goncharova L. A., Kobylinska N. G., Díaz-Garcia M. E., Zaitsev V. N. Solid-phase luminescence determination of tetracycline in bottled water using chemically modified silica / J. Anal. Chem. 2017. Vol. 72. N 7. P. 724 – 733. DOI:10.1134/S106193481707005X</mixed-citation></citation-alternatives></ref><ref id="cit4"><label>4</label><citation-alternatives><mixed-citation xml:lang="ru">Si X., Wang H., Wu T., Wang P. Novel methods for the rapid detection of trace tetracyclines based on the fluorescence behaviours of Maillard reaction fluorescent nanoparticles / RSC Adv. 2020. Vol. 10. P. 43256 – 43261. DOI:10.1039/d0ra05298a</mixed-citation><mixed-citation xml:lang="en">Si X., Wang H., Wu T., Wang P. Novel methods for the rapid detection of trace tetracyclines based on the fluorescence behaviours of Maillard reaction fluorescent nanoparticles / RSC Adv. 2020. Vol. 10. P. 43256 – 43261. DOI:10.1039/d0ra05298a</mixed-citation></citation-alternatives></ref><ref id="cit5"><label>5</label><citation-alternatives><mixed-citation xml:lang="ru">Valverde R. S., Garcia M. D. G., Galera M. M., Goicoechea H. C. Determination of tetracyclines in surface water by partial least squares using multivariate calibration transfer to correct the effect of solid phase preconcentration in photochemically induced fluorescence signals / Anal. Chim. Acta. 2006. Vol. 562. P. 85 – 93. DOI:10.1016/j.aca.2006.01.035</mixed-citation><mixed-citation xml:lang="en">Valverde R. S., Garcia M. D. G., Galera M. M., Goicoechea H. C. Determination of tetracyclines in surface water by partial least squares using multivariate calibration transfer to correct the effect of solid phase preconcentration in photochemically induced fluorescence signals / Anal. Chim. Acta. 2006. Vol. 562. P. 85 – 93. DOI:10.1016/j.aca.2006.01.035</mixed-citation></citation-alternatives></ref><ref id="cit6"><label>6</label><citation-alternatives><mixed-citation xml:lang="ru">Tu C., Dai Y., Xu K., et al. Determination of tetracycline in water and honey by iron(II, III)/aptamer-based magnetic solid-phase extraction with high-performance liquid chromatography analysis / Anal. Lett. 2019. Vol. 52. N 10. P. 1653 – 1669. DOI:10.1080/00032719.2018.1560458</mixed-citation><mixed-citation xml:lang="en">Tu C., Dai Y., Xu K., et al. Determination of tetracycline in water and honey by iron(II, III)/aptamer-based magnetic solid-phase extraction with high-performance liquid chromatography analysis / Anal. Lett. 2019. Vol. 52. N 10. P. 1653 – 1669. DOI:10.1080/00032719.2018.1560458</mixed-citation></citation-alternatives></ref><ref id="cit7"><label>7</label><citation-alternatives><mixed-citation xml:lang="ru">Patyra E., Kowalczyk E., Kwiatek K. Screening method for the determination of selected tetracyclines in water by liquid chromatography with diode array detector / Bull. Vet. Inst. Pulawy. 2014. Vol. 58. P. 65 – 70. DOI:10.2478/bvip-2014-0010</mixed-citation><mixed-citation xml:lang="en">Patyra E., Kowalczyk E., Kwiatek K. Screening method for the determination of selected tetracyclines in water by liquid chromatography with diode array detector / Bull. Vet. Inst. Pulawy. 2014. Vol. 58. P. 65 – 70. DOI:10.2478/bvip-2014-0010</mixed-citation></citation-alternatives></ref><ref id="cit8"><label>8</label><citation-alternatives><mixed-citation xml:lang="ru">Guo D. G., Ni L., Wang L., Shao L. Separation and determination of tetracycline hydrochloride in real water samples using binary small molecule alcohol-salt aqueous two-phase system coupled with high-performance liquid chromatography / Chirality. 2019. Vol. 31. N. 9. P. 658 – 668. DOI:10.1002/chir.23080</mixed-citation><mixed-citation xml:lang="en">Guo D. G., Ni L., Wang L., Shao L. Separation and determination of tetracycline hydrochloride in real water samples using binary small molecule alcohol-salt aqueous two-phase system coupled with high-performance liquid chromatography / Chirality. 2019. Vol. 31. N. 9. P. 658 – 668. DOI:10.1002/chir.23080</mixed-citation></citation-alternatives></ref><ref id="cit9"><label>9</label><citation-alternatives><mixed-citation xml:lang="ru">Tsai W. H., Huang T. C., Chen H. H., et al. Determination of tetracyclines in surface water and milk by the magnesium hydroxide coprecipitation method / J. Chromatogr. A. 2010. Vol. 1217. P. 415 – 418. DOI:10.1016/j.chroma.2009.12.006</mixed-citation><mixed-citation xml:lang="en">Tsai W. H., Huang T. C., Chen H. H., et al. Determination of tetracyclines in surface water and milk by the magnesium hydroxide coprecipitation method / J. Chromatogr. A. 2010. Vol. 1217. P. 415 – 418. DOI:10.1016/j.chroma.2009.12.006</mixed-citation></citation-alternatives></ref><ref id="cit10"><label>10</label><citation-alternatives><mixed-citation xml:lang="ru">Liu M., Li Y., Lin S., Dong X. Determination of tetracycline residues in lake water by on-line coupling of molecularly imprinted solidphase extraction with high performance liquid chromatography / Anal. Methods. 2014. Vol. 6. N 23. P. 9446 – 9452. DOI:10.1039/c4ay02009j</mixed-citation><mixed-citation xml:lang="en">Liu M., Li Y., Lin S., Dong X. Determination of tetracycline residues in lake water by on-line coupling of molecularly imprinted solidphase extraction with high performance liquid chromatography / Anal. Methods. 2014. Vol. 6. N 23. P. 9446 – 9452. DOI:10.1039/c4ay02009j</mixed-citation></citation-alternatives></ref><ref id="cit11"><label>11</label><citation-alternatives><mixed-citation xml:lang="ru">Patyra E., Kowalczyk E., Grelik A., et al. Screening method for the determination of tetracyclines and fluoroquinolones in animal drinking water by liquid chromatography with diode array detector / Pol. J. Vet. Sci. 2015. Vol. 18. N 2. P. 283 – 289. DOI:10.1515/pjvs-2015-0037</mixed-citation><mixed-citation xml:lang="en">Patyra E., Kowalczyk E., Grelik A., et al. Screening method for the determination of tetracyclines and fluoroquinolones in animal drinking water by liquid chromatography with diode array detector / Pol. J. Vet. Sci. 2015. Vol. 18. N 2. P. 283 – 289. DOI:10.1515/pjvs-2015-0037</mixed-citation></citation-alternatives></ref><ref id="cit12"><label>12</label><citation-alternatives><mixed-citation xml:lang="ru">Da Silva D. C., Oliveira C. C. Development of micellar HPLC-UV method for determination of pharmaceuticals in water samples / J. Anal. Methods. Chem. 2018. Vol. 2018. ID 9143730. DOI:10.1155/2018/9143730</mixed-citation><mixed-citation xml:lang="en">Da Silva D. C., Oliveira C. C. Development of micellar HPLC-UV method for determination of pharmaceuticals in water samples / J. Anal. Methods. Chem. 2018. Vol. 2018. ID 9143730. DOI:10.1155/2018/9143730</mixed-citation></citation-alternatives></ref><ref id="cit13"><label>13</label><citation-alternatives><mixed-citation xml:lang="ru">Granados M., Encabo M., Compano R., Prat M. D. Determination of tetracyclines in water samples using liquid chromatography with fluorimetric detection / Chromatographia. 2005. Vol. 61. N 9/10. P. 471 – 477. DOI:10.1365/s10337-005-0546-3</mixed-citation><mixed-citation xml:lang="en">Granados M., Encabo M., Compano R., Prat M. D. Determination of tetracyclines in water samples using liquid chromatography with fluorimetric detection / Chromatographia. 2005. Vol. 61. N 9/10. P. 471 – 477. DOI:10.1365/s10337-005-0546-3</mixed-citation></citation-alternatives></ref><ref id="cit14"><label>14</label><citation-alternatives><mixed-citation xml:lang="ru">Skraskova K., Santos L. H. M. L. M., Satinsky D., et al. Fast and sensitive UHPLC methods with fluorescence and tandem mass spectrometry detection for the determination of tetracycline antibiotics in surface waters / J. Chromatogr. B. 2013. Vol. 927. P. 201 – 208. DOI:10.1016/j.jchromb.2012.12.032</mixed-citation><mixed-citation xml:lang="en">Skraskova K., Santos L. H. M. L. M., Satinsky D., et al. Fast and sensitive UHPLC methods with fluorescence and tandem mass spectrometry detection for the determination of tetracycline antibiotics in surface waters / J. Chromatogr. B. 2013. Vol. 927. P. 201 – 208. DOI:10.1016/j.jchromb.2012.12.032</mixed-citation></citation-alternatives></ref><ref id="cit15"><label>15</label><citation-alternatives><mixed-citation xml:lang="ru">Удалова А. Ю., Дмитриенко С. Г., Апяри В. В. Методы выделения, концентрирования и определения антибиотиков тетрациклиновой группы / Журн. аналит. химии. 2015. Т. 70. № 6. С. 577 – 593. DOI:10.7868/S0044450215060195</mixed-citation><mixed-citation xml:lang="en">Udalova A. Yu., Dmitrienko S. G., Apyari V. V. Methods for the separation, preconcentration, and determination of tetracycline antibiotics / J. Anal. Chem. 2015. Vol. 70. N 6. P. 661 – 676. DOI:10.1134/S1061934815060180</mixed-citation></citation-alternatives></ref><ref id="cit16"><label>16</label><citation-alternatives><mixed-citation xml:lang="ru">Амелин В. Г., Шаока З. А. Ч., Большаков Д. С. Использование смартфона для определения тетрациклинов в воде и молоке по сенсибилизированной твердофазной флуоресценции европия на его гидроксиде / Журн. аналит. химии. 2021. Т. 76. ¹ 10. С. 952 – 598. DOI:10.31857/S0044450221080028</mixed-citation><mixed-citation xml:lang="en">Amelin V. G., Shogah Z. A. C., Bol’shakov D. S. Using a smartphone for determining tetracyclines in water and milk by the sensitized solid state fluorescence of europium on its hydroxide / J. Anal. Chem. 2021. Vol. 76. N 10. P. 1211 – 1216. DOI:10.1134/S1061934821080025</mixed-citation></citation-alternatives></ref></ref-list><fn-group><fn fn-type="conflict"><p>The authors declare that there are no conflicts of interest present.</p></fn></fn-group></back></article>
