Gold nanoparticles electrochemically deposited on carbon nanomaterials and thiacalixarenes in immunosensors for determining tricyclic antidepressants
- Authors: Brusnitsyn D.V.1, Ramazanova A.N.1, Medyantseva E.P.1, Ramazanova E.R.2, Prytkova A.V.1, Karimova E.R.3, Ziganshin M.A.1, Burilov V.A.1, Makarov E.G.1, Khamidullin T.L.1
-
Affiliations:
- Kazan (Volga region) Federal University, Alexander Butlerov Institute of Chemistry
- Kazan National Research Technological University, Institute of Petroleum, Chemistry and Nanotechnology
- Interregional clinical diagnostic center
- Issue: Vol 80, No 3 (2025)
- Pages: 323-336
- Section: ORIGINAL ARTICLES
- Submitted: 09.06.2025
- URL: https://edgccjournal.org/0044-4502/article/view/683424
- DOI: https://doi.org/10.31857/S0044450225030077
- EDN: https://elibrary.ru/agcqfk
- ID: 683424
Cite item
Abstract
Composite materials based on electrochemically deposited gold nanoparticles obtained by cyclic voltammetry and chronoamperometry on a carbon substrate of functionalized graphene oxide, reduced graphene oxide and carbon nanotube paper have been proposed. Composite materials were screened by atomic force microscopy, electrochemical impedance spectroscopy and voltammetry, which allowed us to select the best ones as modifiers of planar electrodes, on the basis of which highly sensitive immunosensors were developed. For the best amperometric immunosensors based on a combination of carbon paper, amino(thia)calix[4]arene, and gold nanoparticles for the determination of amitriptyline and desipramine, the working concentration range was 1 × 10–9–1 × 10–4 M, and the lower limit of detectable concentrations was (4–6) × 10–10 М. Amitriptyline and desipramine were determined by amperometric immunosensors in pharmaceutical preparations with relative standard deviation not exceeding 0.040. Comparison of the results of determination of tricyclic antidepressants by immunosensors and fluorescence polarization immunoassay in human urine with relative standard deviation not exceeding 0.085 indicates the correctness and convergence of the obtained results.
Full Text

About the authors
D. V. Brusnitsyn
Kazan (Volga region) Federal University, Alexander Butlerov Institute of Chemistry
Author for correspondence.
Email: brussman@mail.ru
Russian Federation, Kazan
A. N. Ramazanova
Kazan (Volga region) Federal University, Alexander Butlerov Institute of Chemistry
Email: brussman@mail.ru
Russian Federation, Kazan
E. P. Medyantseva
Kazan (Volga region) Federal University, Alexander Butlerov Institute of Chemistry
Email: brussman@mail.ru
Russian Federation, Kazan
E. R. Ramazanova
Kazan National Research Technological University, Institute of Petroleum, Chemistry and Nanotechnology
Email: brussman@mail.ru
Russian Federation, Kazan
A. V. Prytkova
Kazan (Volga region) Federal University, Alexander Butlerov Institute of Chemistry
Email: brussman@mail.ru
Russian Federation, Kazan
E. R. Karimova
Interregional clinical diagnostic center
Email: brussman@mail.ru
Russian Federation, Kazan
M. A. Ziganshin
Kazan (Volga region) Federal University, Alexander Butlerov Institute of Chemistry
Email: brussman@mail.ru
Russian Federation, Kazan
V. A. Burilov
Kazan (Volga region) Federal University, Alexander Butlerov Institute of Chemistry
Email: brussman@mail.ru
Russian Federation, Kazan
E. G. Makarov
Kazan (Volga region) Federal University, Alexander Butlerov Institute of Chemistry
Email: brussman@mail.ru
Russian Federation, Kazan
T. L. Khamidullin
Kazan (Volga region) Federal University, Alexander Butlerov Institute of Chemistry
Email: brussman@mail.ru
Russian Federation, Kazan
References
- Balahura L.R., Stefan-Van Staden R.I., Van Staden J.F., Aboul-Enein H.Y. Advances in immunosensors for clinical applications // J. Immunoassay Immunochem. 2019. V. 40. № 1. P. 40. https://doi.org/10.1080/15321819.2018.1543704
- Medyantseva E.P., Brusnitsyn D.V., Gazizullina E.R., Budnikov H.C. Analytical capabilities of some immunosensors for the determination of drugs / Macro, Micro, and Nano-Biosensors: Potential Applications and Possible Limitations / Eds. M. Rai, A. Reshetilov, Y. Plekhanova, A.P. Ingle. Springer, 2021. P. 177. https://doi.org/10.1007/978-3-030-55490-3_10
- Wang A., Ma K., You X., Chen Y., Liu H., Qi Y. et al. A sensitive analysis of sulfadimethoxine using an AuNPs/Ag-GO-Nf-based electrochemical immunosensor // J. Solid State Electrochem. 2022. V. 26. P. 515. https://doi.org/10.1007/s10008-021-05069-8
- Ibragimova R., Burilov V., Aimetdinov A., Mironova D., Evtugyn V., Osin Y. et al. Polycationic derivatives of p-tert-butylthiacalix[4]arene in 1,3-alternate stereoisomeric form: new DNA condensing agents // Macroheterocycles. 2016. V. 9. № 4. P. 433. https://doi.org/10.6060/mhc161180b
- Kanu A.B. Recent developments in sample preparation techniques combined with high-performance liquid chromatography: A critical review // J. Chromatogr. A. 2021. V. 1654. Article 462444. https://doi.org/10.1016/j.chroma.2021.462444
- Kasagic-Vujanovic I., Jancic-Stojanovic B. Quality by design oriented development of hydrophilic interactionliquid chromatography method for the analysis of amitriptyline and its impurities // J. Pharm. Biomed. Anal. 2019. V. 173. P. 86. https://doi.org/10.1016/j.jpba.2019.05.026
- Sajid M., Alhooshani K. Dispersive liquid-liquid microextraction based binary extraction techniques prior to chromatographic analysis: A review // Trends Anal. Chem. 2018. V. 108. P. 167. https://doi.org/10.1016/j.trac.2018.08.016
- Safari M., Shahlaei M., Yamini Y., Shakorian M., Arkan E. Magnetic framework composite as sorbent for magnetic solid phase extraction coupled with high performance liquid chromatography for simultaneous extraction and determination of tricyclic antidepressants // Anal. Chim. Acta. 2018. V. 1034. P. 204. https://doi.org/10.1016/j.aca.2018.06.023
- Karami M., Yamini Y. On-disc electromembrane extraction-dispersive liquid-liquid microextraction: A fast and effective method for extraction and determination of ionic target analytes from complex biofluids by GC/MS // Anal. Chim. Acta. 2020. V. 1105. P. 95. https://doi.org/ 10.1016/j.aca.2020.01.024
- Křesinová Z., Linhartová L., Petrů K., Krejčová L., Šrédlová K., Lhotský O. et al. Method for analysis of psychopharmaceuticals in real industrial wastewater and groundwater with suspended organic particulate matter using solid phase extraction disks extraction and ultra-high performance liquid chromatography/time-of-flight mass spectrometry // J. Chromatogr. A. 2016. V. 1440. P. 15. https://doi.org/10.1016/j.chroma.2016.02.035
- Rossmann J., Renner L.D., Oertel R., El-Armouche A. Post-column infusion of internal standard quantification for liquid chromatography-electrospray ionization-tandem mass spectrometry analysis – Pharmaceuticals in urine as example approach // J. Chromatogr. A. 2018. V. 1535. P. 80. https://doi.org/ 10.1016/j.chroma.2018.01.001
- Carasek E. Morés L., Merib J. Basic principles, recent trends and future directions of microextraction techniques for the analysis of aqueous environmental samples // Trends Anal. Chem. 2018. V. 19. Article e00060. https://doi.org/10.1016/j.teac.2018.e00060
- Oliveira F.M., Scheel G.L., Augusti R., Tarley C.R.T., Nascentes C.C. Supramolecular microextraction combined with paper spray ionization mass spectrometry for sensitive determination of tricyclic antidepressants in urine // Anal. Chim. Acta. 2020. V. 1106. P. 52. https://doi.org/10.1016/j.aca.2020.01.061
- Ocana-Gonzalez J.A., Fernandez-Torres R., Bello-Lopez M.A., Ramos-Payan M. New developments in microextraction techniques in bioanalysis. A review // Anal. Chim. Acta. 2016. V. 905. P. 8. https://doi.org/10.1016/j.aca.2015.10.041
- Mansour F.R., Khairy M.A. Pharmaceutical and biomedical applications of dispersive liquid–liquid microextraction // J. Chromatogr. B. 2017. V. 1061–1062. P. 382. https://doi.org/10.1016/j.jchromb.2017.07.055
- Yu R.B., Quirino J.P. Open-tubular admicellar electrochromatography of charged analytes // Talanta. 2020. V. 208. Article 120401. https://doi.org/10.1016/j.talanta.2019.120401
- Wu H.-F., Kailasa S.K., Yan J.-Y., Chin C.-C., Ku H.-Y. Comparison of single-drop microextraction with microvolume pipette extraction directly coupled with capillary electrophoresis for extraction and separation of tricyclic antidepressant drugs // J. Ind. Eng. Chem. 2014. V. 20. № 4. Article 2071. https://doi.org/10.1016/j.jiec.2013.09.034
- Kamari K., Taheri A. Preparation and evaluation of magnetic core–shell mesoporous molecularly imprinted polymers for selective adsorption of amitriptyline in biological samples // J. Taiwan Inst. Chem. Eng. 2018. V. 86. P. 230. https://doi.org/10.1016/j.jtice.2018.02.031
- Rutkowska M., Płotka-Wasylka J., Morrison C., Wieczorek P.P., Namiesnik J., Marc M. Application of molecularly imprinted polymers in analytical chiral separations and analysis // Trends Anal. Chem. 2018. V. 102. P. 91. https://doi.org/10.1016/j.trac.2018.01.011
- Brusnitsyn D.V., Medyantseva E.P., Varlamova R.M. Carbon nanomaterials as electrode surface modifiers in development of amperometric monoamino oxidase biosensors // Inorg. Mater. 2016. V. 52. № 14. P. 1413. https://doi.org/10.1134/S002016851614003X
- Медянцева Э.П., Брусницын Д.В., Газизуллина Э.Р., Варламова Р.М., Коновалова О.А., Будников Г.К. Гибридные нанокомпозиты как модификаторы электродов амперометрических иммуносенсоров при определении амитриптилина // Журн. аналит. химии. 2020. Т. 75. № 4. С. 360. https://doi.org/10.31857/S0044450220040118 (Medyantseva E.P., Brusnitsyn D.V., Gazizullina E.R., Varlamova R.M., Konovalova O.A., Budnikov H.C. Hybrid nanocomposites as electrode modifiers in amperometric immunosensors for the determination of amitriptyline // J. Anal. Chem. 2020. V. 75. № 4. P. 536. https://doi.org/10.1134/S1061934820040103)
- Медянцева Э.П., Газизуллина Э.Р., Брусницын Д.В., Добрынин А.Б., Брылев К.А., Мустафина А.Р., Елистратова Ю.Г. Амперометрические иммуносенсоры на основе углеродных наноматериалов и кластеров рения для определения трициклических антидепрессантов в последовательной инжекционной системе // Аналитика и контроль. 2022. Т. 26. № 4. С. 255. https://doi.org/10.15826/analitika.2022.26.4.002
- Medyantseva E.P., Brusnitsyn D.V., Varlamova R.M. Nanostructured composites based on graphene and cobalt nanoparticles in monoamine oxidase biosensors for determining antidepressants // Inorg. Mater. 2019. V. 55. № 14. P. 1390. https://doi.org/10.1134/S0020168519140103
- Медянцева Э.П., Брусницын Д.В., Газизуллина Э.Р., Бейлинсон Р.М., Еремин С.А., Кутырева М.П. и др. Наноразмерные материалы в составе биосенсоров для определения амитриптилина // Заводск. лаборатория. Диагностика материалов. 2021. Т. 87. № 9. С. 20. https://doi.org/10.26896/1028-6861-2021-87-9-20-29
- Khataee S., Dehghan G., Shaghaghi Z., Khataee A., Amini M. A novel bifunctional electrochemical nanosensor for simultaneous detection of glucose and insulin based on NiO/Co3O4@CuAl LDH-MWCNT nanocomposite-modified carbon paste electrode // Microchem. J. 2024. V. 201. Article 110644. https://doi.org/10.1016/j.microc.2024.110644
- Luo S., Wang G., Wang Y., Xu Y., Luo Y. Carbon nanomaterials enabled fiber sensors: A structure-oriented strategy for highly sensitive and versatile in situ monitoring of composite curing process // Composites. Part B. 2019. V. 166. P. 645. https://doi.org/10.1016/j.compositesb.2019.02.067
- Wang B., Duan Y., Xin Z., Yao X., Abliz D., Ziegmann G. Fabrication of an enriched graphene surface protection of carbon fiber/epoxy composites for lightning strike via a percolating-assisted resin film infusion method // Compos. Sci. Technol. 2018. V. 158. P. 51. https://doi.org/10.1016/j.compscitech.2018.01.047
- Boztepe S., Liu H., Heide D., Thostenson E.T. Novel carbon nanotube interlaminar film sensors for carbon fiber composites under uniaxial fatigue loading // Compos. Struct. 2018. V. 189. P. 340. https://doi.org/10.1016/j.compstruct.2018.01.033
- Harsini M., Widyaningrum B.A., Fitriany E., Paramita D.R.A., Farida A.N., Baktir A. et al. Electrochemical synthesis of polymelamine/gold nanoparticle modified carbon paste electrode as voltammetric sensor of dopamine // Chin. J. Anal. Chem. 2022. V. 50. № 4. Article 100052. https://doi.org/10.1016/j.cjac.2022.100052
- Zhang Y., Du X., Mao J., He S., Cao Z. Facile preparation of gold nanoparticles anchored on layered yttrium hydroxide by electrochemical methods for enhanced sensing of hydroquinone and catechol // Mater. Chem. Phys. 2024. V. 311. Article 128526. https://doi.org/10.1016/j.matchemphys.2023.128526
- Wang J., Luo Z., Lin X. An ultrafast electrochemical synthesis of Au@Ag core-shell nanoflowers as a SERS substrate for thiram detection in milk and juice // Food Chem. 2023. V. 402. P. 134433. https://doi.org/10.1016/j.foodchem.2022.134433
- Song K.-H., Chen F.-L., Xu J.-T., Wang K.-Z., Feng X.-Z., Han G.-C., Kraatz H.-B. Composites of nano-flower copper nanoparticles and well dispersed multi-walled carbon nanotubes for the voltammetric detection of moxifloxacin in pork // Microchem. J. 2024. V. 201. Article 110631. https://doi.org/10.1016/j.microc.2024.110631
- Порфирьева А.В., Шибаева К.С., Евтюгин В.Г., Якимова Л.С., Стойков И.И., Евтюгин Г.А. Электрохимический ДНК-сенсор на доксорубицин на основе полиэлектролитного комплекса и аминированного тиакаликс[4]арена // Журн. аналит. химии. 2019. Т. 74. № 7. С. 542. (Porfir’eva A.V., Shibaeva K.S., Evtyugin V.G., Yakimova L.S., Stoikov I.I., Evtyugin G.A. An electrochemical DNA sensor for doxorubicin based on a polyelectrolyte complex and aminated thiacalix[4]arene // J. Anal. Chem. 2019. V. 74. P. 707. https://doi.org/10.1134/S1061934819070086)
- Stoikov D., Ivanov A., Shafigullina I., Gavrikova M., Padnya P., Shiabiev I. et al. Flow-through amperometric biosensor system based on functionalized aryl derivative of phenothiazine and PAMAM-calix-dendrimers for the determination of uric acid // Biosensors. 2024. V. 14. № 3. P. 120. https://doi.org/10.3390/bios14030120
- Zhang C., Zhang S., Jia Y., Li Y., Wang P., Liu Q. et al. Sandwich-type electrochemical immunosensor for sensitive detection of CEA based on the enhanced effects of Ag NPs@CS spaced Hemin/rGO // Biosens. Bioelectron. 2019. V. 126. P. 785. https://doi.org/10.1016/j.bios.2018.11.039
- Zhang Z., Yang M., Wu X., Dong S., Zhu N., Gyimah E. et al. A competitive immunosensor for ultrasensitive detection of sulphonamides from environmental waters using silver nanoparticles decorated single-walled carbon nanohorns as labels // Chemosphere. 2019. V. 225. P. 282. https://doi.org/10.1016/j.chemosphere.2019.03.033
- Datta S., Neerukatti R.K., Chattopadhyay A. Buckypaper embedded self-sensing composite for real-time fatigue damage diagnosis and prognosis // Carbon. 2018. V. 139. P. 353. https://doi.org/10.1016/j.carbon.2018.06.059
- Kumar V., Sharma S., Pathak A., Singh B.P., Dhakate S.R., Yokozeki T., Okada T., Ogasawara T. Interleaved MWCNT buckypaper between CFRP laminates to improve through-thickness electrical conductivity and reducing lightning strike damage // Compos. Struct. 2019. V. 210. P. 581. https://doi.org/10.1016/j.compstruct.2018.11.088
- Cheng X., Yokozeki T., Wang H., Wu L., Sun Q.-F. Simultaneous enhancement of electrical conductivity and mechanical properties in buckypaper-reinforced polydivinylbenzene(doped polyaniline) composites // Compos. Sci. Technol. 2018. V. 161. P. 50. https://doi.org/10.1016/j.compscitech.2018.03.042
- Alanazi A.H., Jurewicz I., Alyahyawi A., Alsubaie A., Hinder S., Bañuls-Ciscar J. et al. Novel dosimetric study of the sp2 to sp3 hybridisation ratio in free–standing carbon nanotubes buckypaper // Radiat. Phys. Chem. 2019. V. 154. P. 38. https://doi.org/10.1016/j.radphyschem.2018.02.006
- Ibragimova R.R., Burilov V.A., Aimetdinov A.R., Mironova D.A., Evtugyn V.G., Osin Y.N., Solovieva S.E. and Antipin I.S. Macroheterocycles. 2016. V. 9. N 4. P. 433. https://macroheterocycles.isuct.ru/en/mhc161180b
- Zhou J., Zhang C., Chen Y., Wang Z., Lan L., Wang Y. et al. A simple immunosensor for alpha-fetoprotein determination based on gold nanoparticles-dextran-reduced graphene oxide // J. Electroanal. Chem. 2019. V. 833. P. 126. https://doi.org/10.1016/j.jelechem.2018.11.036
- Liu P., Li C., Zhang R., Tang Q., Wei J., Lu Y., Shen P. An ultrasensitive electrochemical immunosensor for procalcitonin detection based on the gold nanoparticles-enhanced tyramide signal amplification strategy // Biosens. Bioelectron. 2019. V. 126. P. 543. https://doi.org/10.1016/j.bios.2018.10.048
- Fan Y., Shi S., Ma J., Guo Y. A paper-based electrochemical immunosensor with reduced graphene oxide/thionine/gold nanoparticles nanocomposites modification for the detection of cancer antigen 125 // Biosens. Bioelectron. 2019. V. 135. P. 1. https://doi.org/10.1016/j.bios.2019.03.063
- Wang Z., Yang S., Wang Y., Feng W., Li B., Jiao J. et al. A novel oriented immunosensor based on AuNPs-thionine-CMWCNTs and staphylococcal protein A for interleukin-6 analysis in complicated biological samples // Anal. Chim. Acta. 2020. V. 1140. P. 145. https://doi.org/10.1016/j.aca.2020.10.025
- Cheng Y., Gao J., Shi Q., Li Z., Huang W. In situ electrochemical reduced Au loaded black TiO2 nanotubes for visible light photocatalysis // J. Alloys Compd. 2022. V. 901. Article 163562. https://doi.org/10.1016/j.jallcom.2021.163562
- Медянцева, Э.П., Газизуллина Э.Р., Брусницын Д.В., Федоренко С.В., Мустафина А.Р., Еремин С.А. Определение амитриптилина методом поляризационного флуоресцентного иммуноанализа // Журн. аналит. химии. 2022. Т. 77. № 9. С. 828. https://doi.org/10.31857/S0044450222070088 (Medyantseva E.P., Gazizullina E.R., Brusnitsyn D.V., Fedorenko S.V., Mustafina A.R., Eremin S.A. Determination of amitriptyline by fluorescence polarization immunoassay // J. Anal. Chem. 2022. V. 77. № 9. P. 1147. https://doi.org/10.1134/s1061934822070085)
Supplementary files
