Диэлектрофоретическое осаждение белков на серебряные подложки для повышения эффективности спектрального анализа
DOI:
https://doi.org/10.24160/0013-5380-2026-3-4-13Ключевые слова:
электрофоретическое осаждение, белок, гигантское комбинационное рассеяниеАннотация
В статье предложен подход, позволяющий повысить эффективность спектрального анализа и сочетающий электрохимическую пробоподготовку высокомолекулярного аналита в режиме переменного электрического поля (AEF) с последующей спектроскопией гигантского комбинационного рассеяния (ГКР). Предлагаемый подход имеет практическую значимость для количественного безмаркерного определения клинически значимых аналитов. В качестве модельного анализируемого вещества использован белок – сывороточный альбумин человека (HSA). Разрабатываемый метод диэлектрофоретического осаждения направлен на улучшение качества (амплитуды сигнала и соотношения сигнал-шум в измеряемых спектрах) аналитического сигнала – спектров ГКР. Диапазон определяемых концентраций при AEF составил 0,01–10 г/л. Диапазон обнаруживаемых концентраций для режима AEF был на порядок выше, чем для режима постоянного электрического поля. Показано, что осаждение сопровождается окислительно-восстановительными реакциями, приводящими к синтезу наночастиц серебра (НЧ), осаждающихся в виде сэндвич-структур НЧ Ag–HSA–Ag. Самоорганизующийся осадок на основе белка и НЧ Ag, полученный после воздействия AEF на модифицированной ГКР-подложке, с которой были измерены ГКР-спектры, показал достаточную морфологическую однородность. Это подтверждается значениями стандартного отклонения по амплитуде ГКР-спектров, которое не превышало 20 % во всем спектральном диапазоне.
Библиографические ссылки
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Работа выполнена при поддержке Министерства науки и высшего образования РФ в рамках Государственного задания FFUR-2024-0010
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2. Rygula A. et al. Raman Spectroscopy of Proteins: A Review. – Journal of Raman Spectroscopy, 2013, vol. 44, No. 8, pp. 1061–1076, DOI: 10.1002/jrs.4335.
3. Keskin S., Çulha M. Label-Free Detection of Proteins from Dried-Suspended Droplets Using Surface Enhanced Raman Scattering. – Analyst, 2012, vol. 137, No. 11, pp. 2651–2657, DOI: 10.1039/c2an16296b.
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5. Sharma B. et al. SERS: Materials, Applications, and the Future. – Materials Today, 2012, vol. 15, No. 1-2, pp. 16–25, DOI: 10.1016/S1369-7021(12)70017-2.
6. Fan M., Andrade G.F.S., Brolo A.G. A Review on the Fabrication of Substrates for Surface Enhanced Raman Spectroscopy and their Applications in Analytical Chemistry. – Analytica Chimica Acta, 2011, vol. 693, No. 1-2, pp. 7–25, DOI: 10.1016/j. aca.2011.03.002.
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21. Sharma B., Sharma A. Microfluidics: Recent Advances Toward Lab‐On‐Chip Applications in Bioanalysis. – Advanced Engineering Materials, 2022, vol. 24, No. 2, DOI: 10.1002/adem.202100738.
22. Mehta M. et al. Laboratory‐on‐a‐Chip: A Multitasking De-vice. – Miniaturized Analytical Devices: Materials and Technology, 2022, pp. 91–103, DOI: 10.1002/9783527827213.ch5.
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25. Boginskaya I.A. et al. Additional Enhancement of Surface-Enhanced Raman Scattering Spectra of Myoglobin Precipitated Under Action of Laser Irradiation on Self-Assembled Nanostructured Surface of Ag Films. – Chemosensors, 2023, vol. 11, No. 6, DOI: 10.3390/chemosensors11060321.
26. Xia X. Bioinformatics and the Cell: Modern Computational Approaches in Genomics, Proteomics and Transcriptomics. Boston, MA: Springer US, 2007, 349 p., DOI: 10.1007/978-0-387-71337-3.
27. Podoynitsyn S.N. et al. Surface-Enhanced Raman Spectroscopy in Tandem with a Gradient Electric Field from 4-Mercaptophenylboro-nic Acid on Silver Nanoparticles. – Microchimica Acta, 2020, vol. 187, No. 10, DOI: 10.1007/s00604-020-04550-x.
28. Boginskaya I. et al. SERS-Active Substrates Nanoengineering Based on E-Beam Evaporated Self-Assembled Silver Films. – Applied Sciences, 2019, vol. 9, No. 19, DOI: 10.3390/app9193988.
29. Khaydarov R.A. et al. Electrochemical Method for the Synthesis of Silver Nanoparticles. – Journal of Nanoparticle Research, 2009, vol. 11, No. 5, pp. 1193–1200, DOI: 10.1007/s11051-008-9513-x.
30. Chiotelli E., Pilosio G., Le Meste M. Effect of Sodium Chloride on the Gelatinization of Starch: A Multimeasurement Study. – Biopolymers, 2002, vol. 63, No. 1, pp. 41–58, DOI: 10.1002/bip.1061.
31. Deegan R.D. et al. Contact Line Deposits in an Evaporating Drop. – Physical review E, 2000, vol. 62, No. 1, DOI: 10.1103/Phys-RevE.62.756.
32. Synytsya A. et al. Raman Spectroscopic Study of Serum Albumins: An Effect of Proton‐ and γ‐Irradiation. – Journal of Raman Spectroscopy, 2007, vol. 38, No. 12, pp. 1646–1655, DOI: 10.1002/jrs.1884.
33. Jurasekova Z. et al. Spectroscopic and Molecular Modeling Studies on the Binding of the Flavonoid Luteolin and Human Serum Albumin. – Biopolymers, 2009, vol. 91, No. 11, pp. 917–927, DOI: 10.1002/ bip.21278.
34. Stewart S., Fredericks P.M. Surface-Enhanced Raman Spectroscopy of Amino Acids Adsorbed on an Electrochemically Prepared Silver Surface. – Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 1999, vol. 55, No. 7-8, pp. 1641–1660, DOI: 10.1016/S1386- 1425(98)00294-7.
35. Yang S. et al. Electrochemically Created Highly Surface Roughened Ag Nanoplate Arrays for SERS Biosensing Applications. – Journal of Materials Chemistry C, 2014, vol. 2, No. 39, pp. 8350–8356, DOI: 10.1039/c4tc01276c.
36. Zhou H., Kneipp J. Electrodeposition of Silver Nanostructures in Ethanol for Sensitive Electrochemical SERS Detection. – ACS Applied Nano Materials, 2024, vol. 7, No. 1, pp. 1300–1309, DOI: 10.1021/acsanm.3c05322.
37. Oriňáková R. et al. Electrochemical Deposition of SERS Active Nanostructured Silver Films. – International Journal of Electrochemical Science, 2013, vol. 8, No. 1, pp. 80–99, DOI: 10.1016/s1452-3981(23)14004-1.
38. Kim S. et al. Early and Direct Detection of Bacterial Signaling Molecules through One-Pot Au Electrodeposition onto Paper-Based 3D SERS Substrates. – Sensors and Actuators B: Chemical, 2022, vol. 358, DOI: 10.1016/j.snb.2022.131504.
39. Zhan Y. et al. Facile Electrochemical Surface-Alloying and Etching of Au Wires to Enable High-Performance Substrates for Surface Enhanced Raman Scattering. – Nano Materials Science, 2024, vol. 6, No. 3, pp. 305–311, DOI: 10.1016/j.nanoms.2023.05.002.
40. Chung C.K., Yu C.Y. Unique High-Performance Metal-Nanoparticle-Free SERS Substrate with Rapid-Fabricated Hybrid 3D-Nano-Micro-Cavities Anodic Alumina for Label-Free Detec-tion. – Applied Surface Science, 2023, vol. 635, DOI: 10.1016/j. apsusc.2023.157731.
41. Nechaeva N.L. et al. Multiscale Flaked Silver SERS-Substrate for Glycated Human Albumin Biosensing. – Analytica Chimica Acta, 2020, vol. 1100, pp. 250–257, DOI: 10.1016/j.aca.2019.11.072.
42. Rai A. et al. Hottest Hotspots from the Coldest Cold: Welcome to Nano 4.0. – ACS Applied Nano Materials, 2022, vol. 5, No. 9, pp. 12245–12264, DOI: 10.1021/acsanm.2c02556.
43. Akin M.S. et al. Large Area Uniform Deposition of Silver Nanoparticles through Bio-Inspired Polydopamine Coating on Silicon Nanowire Arrays for Practical SERS Applications. – Journal of Materials Chemistry B, 2014, vol. 2, No. 30, pp. 4894–4900, DOI: 10.1039/c4tb00616j.
44. Pérez-Jiménez A.I. et al. Surface-Enhanced Raman Spectroscopy: Benefits, Trade-Offs and Future Developments. – Chemical Science, 2020, vol. 11, No. 18, pp. 4563–4577, DOI: 10.1039/d0sc00809e.
45. Azimi S., Docoslis A. LESS is More: Achieving Sensitive Protein Detection by Combining Electric Field Effects and Surface-Enhanced Raman Scattering. – Sensors and Actuators B: Chemical, 2023, vol. 393, DOI: 10.1016/j.snb.2023.134250.
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The work was financially supported by the Ministry of Science and Higher Education of the Russian Federation within the framework of the State Assignment FFUR-2024-0010

