Влияние наномасштабного конфайнмента водной среды на кривую подвода в сканирующей микроскопии ионной проводимости

Исследованы особенности на зависимости ионного тока от расстояния при сближении стеклянной нанопипетки с диаметром апертуры ~100 нм к поверхности твердого диэлектрика в сканирующем микроскопе ионной проводимости. При положительном смещении потенциала электрода, расположенного в нанопипетке, относительно электрода, расположенного в чашке происходит монотонное снижение тока, однако при отрицательном смещении на кривой подвода наблюдается характерный пик. Для объяснения этого необычного поведения предложена модель, учитывающая перекрытие электрических двойных слоев и явление конфайнмента водной среды в наноканалах и нанозазорах. Модель демонстрирует хорошее согласие с экспериментальными данными и обеспечивает основу для количественной оценки поверхностного заряда на границе раздела электролит–твердое тело с наномасштабной пространственной чувствительностью.

1. Hansma P.K., Drake B., Marti O., Gould S.A., Prater C.B. The scanning ion-conductance microscope. Science, 1989, 243 (4891), P. 641–643.

2. Korchev Y.E., Bashford C.L., Milovanovic M., Vodyanoy I., Lab M.J. Scanning ion conductance microscopy of living cells. Biophys. J., 1997, 73 (2), P. 653–658.

3. Klenerman D., Korchev Y.E., Davis S.J. Imaging and characterisation of the surface of live cells. Curr. Opin. Chem. Biol., 2011, 15 (5), P. 696–703.

4. Rheinlaender J., Geisse N.A., Proksch R., Schaffer T.E. Comparison of scanning ion conductance microscopy with atomic force microscopy for ¨ cell imaging. Langmuir, 2011, 27 (2), P. 697–704.

5. Pleskova S.N., Bezrukova N.A., Gorshkova E.N., Bobyk S.Z., Lazarenko E.V. A study of EA.hy926 endothelial cells using atomic force and scanning ion conductance microscopy. Cell Tissue Biol., 2024, 18 (1), P. 36–44.

6. Gorelik J., Shevchuk A., Ramalho M., Elliott M., Lei C., Higgins C.F., et al. Scanning surface confocal microscopy for simultaneous topographical and fluorescence imaging: application to single virus-like particle entry into a cell. Proc. Natl. Acad. Sci. U.S.A., 2002, 99 (25), P. 16018–16023.

7. Gu C., et al. Scanning ion conductance microscopy of living renal epithelial cells. Kidney Int., 2002, 61 (3), P. 1250–1255.

8. Shevchuk A.I., et al. Imaging proteins in membranes of living cells by high-resolution scanning ion conductance microscopy. Angew. Chem. Int. Ed., 2006, 45 (14), P. 2212–2216.

9. Muhammed Y., De Sabatino M., Lazenby R.A. The heterogeneity in the response of A549 cells to toyocamycin observed using hopping scanning ion conductance microscopy. J. Phys. Chem. B, 2025, 129 (20), P. 4904–4916.

10. Pastre D., Iwamoto H., Liu J., Szabo G., Shao Z. Characterization of AC mode scanning ion-conductance microscopy. Ultramicroscopy, 2001, 90, P. 13–19.

11. Novak P., Li C., Shevchuk A.I., Stepanyan R., Caldwell M., Hughes S., et al. Nanoscale live-cell imaging using hopping probe ion conductance microscopy. Nat. Methods, 2009, 6 (4), P. 279–281.

12. Page A., Perry D., Unwin P.R. Multifunctional scanning ion conductance microscopy. Proc. R. Soc. A., 2017, 473, 20160889.

13. Wang X.-F., Duan Y.-F., Zhu Y.-Q., Liu Z.-J., Wu Y.-C., Liu T.-H., Zhang L., Wei J.-F., Liu G.-C. An insulin-modified pH-responsive nanopipette based on ion current rectification. Sensors, 2024, 24 (13), 4264.

14. Yingfei M., Rujia L., Xiaoyue S., Dengchao W. Quantification of asymmetric ion transport in glass nanopipettes near charged substrates. ChemElectroChem, 2021, 8, 3917.

15. Clarke R.W., Zhukov A., Richards O., Johnson N., Ostanin V., Klenerman D. Pipette–surface interaction: current enhancement and intrinsic force. J. Am. Chem. Soc., 2013, 135, 322.

16. Ushiki T., Ishizaki K., Mizutani Y., Nakajima M., Iwata F. Scanning ion conductance microscopy of isolated metaphase chromosomes in a liquid environment. Chromosome Res., 2021, 29 (1), P. 95–106.

17. Sa N., Lan W.J., Shi W., Baker L.A. Rectification of ion current in nanopipettes by external substrates. ACS Nano, 2013, 7, 272.

18. McKelvey K., Kinnear S.L., Perry D., Momotenko D., Unwin P.R. Surface charge mapping with a nanopipette. J. Am. Chem. Soc., 2014, 136, 13.

19. Lukashenko S.Yu., Gorbenko O.M., Felshtyn M.L., Sapozhnikov I.D., Kirilenko D.A., Stepan V.P., Zhukov M.V., Golubok A.O. Ionic conductivity in nanopipettes: experiment and model. Nanosyst.: Phys. Chem. Math., 2025, 16 (4), P. 441–449.

20. Tao D., Jiang L., Jin M. A method of preparation of Ag/AgCl chloride selective electrode. J. Wuhan Univ. Technol., Mater. Sci. Ed., 2018, 33, P. 767–771.

21. Cervera J., Schiedt B., Ramirez P. A Poisson/Nernst-Planck model for ionic transport through synthetic conical nanopores. Europhys. Lett., 2005, 71, 35.

22. Apel P., Korchev Y.E., Siwy Z., Spohr R., Yoshida M. Diode-like single-ion track membrane prepared by electro-stopping. Nucl. Instrum. Methods Phys. Res., Sect. B., 2001, 184, 337.

23. Rabinowitz J., Edwards M.A., Whittier E., Jayant K., Shepard K.L. Nanoscale fluid vortices and nonlinear electroosmotic flow drive ion current rectification in the presence of concentration gradients. J. Phys. Chem. A, 2019, 123 (38), P. 8285–8293.

24. Nitz H., Kamp J., Fuchs H. A combined scanning ion-conductance and shear-force microscope. Probe Microsc., 1998, 1, P. 187–200.

25. Laurance N. Self-diffusion of the chlorine ion in sodium chloride. Phys. Rev., 1960, 120, P. 57–62.

26. Alvarez-Quintana S., Carmona F.J., Palacio L., Hern ´ andez A., Pr ´ adanos P. Water viscosity in confined nanoporous media and flow through ´ nanofiltration membranes. Microporous Mesoporous Mater., 2020, 300, 110176.

27. Bowen W.R., Welfoot J.S. Modelling the performance of membrane nanofiltration—critical assessment and model development. Chem. Eng. Sci., 2002, 57, P. 1121–1137.

28. Wesolowska K., Koter S., Bodzek M. Modelling of nanofiltration in softening water. Desalination, 2004, 162, P. 137–151.

29. Deißenbeck F., Freysoldt C., Todorova M., Neugebauer J., Wippermann S. Dielectric properties of nanoconfined water: a canonical thermopotentiostat approach. Phys. Rev. Lett., 2021, 126 (13), 136803.

30. Fumagalli L., Esfandiar A., Fabregas R., Hu S., Ares P., Janardanan A., Yang Q., Radha B., Taniguchi T., Watanabe K., Gomila G., Novoselov K.S., Geim A.K. Anomalously low dielectric constant of confined water. Science, 2018, 360 (6395), P. 1339–1342.

31. Girault H.H. Analytical and Physical Electrochemistry. EPFL Press: New York, 2004.

32. Perry D., Momotenko D., Lazenby R.A., Kang M., Unwin P.R. Characterization of nanopipettes. Anal. Chem., 2016, 88, P. 5523–5530.

33. Wright M.R. An Introduction to Aqueous Electrolyte Solutions. John Wiley & Sons: Chichester, UK, 2007.

34. Kolmogorov V.S., Erofeev A.S., Woodcock E., Efremov Y.M., Iakovlev A.P., Savin N.A., et al. Mapping mechanical properties of living cells at nanoscale using intrinsic nanopipette–sample force interactions. Nanoscale, 2021, 13 (13), P. 6558–6568.

35. Amadu M., Miadonye A. Determination of the point of zero charge pH of borosilicate glass surface using capillary imbibition method. Int. J. Chem., 2017, 9, P. 67–84.

36. Perry D., Al Botros R., Momotenko D., Kinnear S.L., Unwin P.R. Simultaneous nanoscale surface charge and topographical mapping. ACS Nano, 2015, 9, P. 7266–7276.

37. Meyers G.F., DeKoven B.M., Seitz J.T. Is the molecular surface of polystyrene really glassy? Langmuir, 1992, 8 (9), P. 2330–2335.