Phosphorenes as a New Material for Surface-Enhanced Infrared Spectroscopy of Cell Membranes

Authors

DOI:

https://doi.org/10.15407/ujpe71.4.349

Keywords:

phosphorenes, spectral markers, model membranes, surface-enhanced infrared absorption

Abstract

Phosphorene is a promising two-dimensional (2D) material consisting of a single-layer phosphorus artificially created from layered black phosphorus, which is known to be the most stable allotrope of phosphorus. Phosphorene, similar to graphene-based substrates used in surfaceenhanced infrared spectroscopy (SEIRA), is expected to exhibit similar behavior. The results of a SEIRA experiment with a model biological cell membrane, formed on the basis of dioleoylphosphatidylcholine (DOPC) lipids, and deposited onto the surface of several phosphorene layers are presented. The enhancement of the absorption factor by up to 2–4 times was observed without changing the positions of the absorption frequencies of the bands corresponding to the main spectral markers of liposomes, which is comparable to that observed for metallic silver particles. Density functional theory (DFT) calculations of the DOPC-phosphorene system indicate a high reactivity of multilayer phosphorene and a possibility of the rapid, often reversible oxidation and reduction processes depending on the pH of the medium. Taking into account that the optical signal from the membrane is insignificant, this technique can be recommended for the use of two-dimensional phosphorene as SEIRA and SERS substrates for membrane studies.

References

1. A.H. Khan, S. Ghosh, B. Pradhan, A. Dalui, L.K. Shrestha, S. Acharya, K. Ariga. Two-dimensional (2D) nanomaterials towards electrochemical nanoarchitectonics in energy-related applications. Bull. Chem. Soc. Jpn. 90, 627 (2017).

https://doi.org/10.1246/bcsj.20170043

2. A.V. Terebilenko, M.V. Olenchuk, D.O. Mazur, A.S. Nikolenko, V.I. Popenko, G.I. Dovbeshko, O. Bezkrovnyi, T. Sabov, B.M. Romanyuk, V.N. Poroshin, S.V. Ryabukhin, D.M. Volochnyuk, S.V. Kolotilov. Influence of formation temperature on the morphology of MoS2 and its catalytic properties in the hydrogenation of isomeric bromoquinolines to bromo-1,2,3,4-tetrahydroquinolines. Dalton Trans. 54, 13057 (2025).

https://doi.org/10.1039/D5DT00065C

3. M.V. Olenchuk, U.K. Afonina, O.P. Gnatyuk, V.V. Strelchuk, A.S. Nikolenko, G.I. Dovbeshko. Heat annealing influences the optical properties of 2D-MoS2 nanoparticles. Mol. Cryst. Liq. Cryst. 749, 1 (2022).

https://doi.org/10.1080/15421406.2022.2067669

4. G.I. Dovbeshko, U.K. Afonina, M.V. Olenchuk, I.M. Kupchak, O.P. Gnatyuk, G.P. Monastyrskyi, A.S. Nikolenko, H.V. Shevliakova, A.N. Morozovska. Effect of 2D-WS2 nanoparticles on a local electrical field at a membrane vicinity: Vibrational spectroscopy data. J. Phys. Chem. C 128, 1131 (2024).

https://doi.org/10.1021/acs.jpcc.3c05693

5. V. Sorkin, Y. Cai, Z. Ong, G. Zhang, Y.W. Zhang. Recent advances in the study of phosphorene and its nanostructures. Crit. Rev. Solid State Mater. Sci. 42, 1 (2017).

https://doi.org/10.1080/10408436.2016.1182469

6. S.M. Tan, M. Pumera. Two-dimensional materials on the rocks: Positive and negative role of dopants and impurities in electrochemistry. ACS Nano 13, 2681 (2019).

https://doi.org/10.1021/acsnano.8b07795

7. J. Chao, M. Zou, C. Zhang, H. Sun, D. Pan, H. Pei, S. Su, L. Yuwen, C. Fan, L.A. Wang. A MoS2-based system for efficient immobilization of hemoglobin and biosensing applications. Nanotechnology 26, 274005 (2015).

https://doi.org/10.1088/0957-4484/26/27/274005

8. C.I. Idumah. Phosphorene polymeric nanocomposites for biomedical applications: A review. Int. J. Polym. Mater. Polym. Biomater. 73, 292 (2024).

https://doi.org/10.1080/00914037.2022.2158333

9. K.H. Min, K.H. Kim, S.P. Pack. Two-dimensional materials for biosensing: Emerging bio-converged strategies for wearable and implantable platforms. Chemosensors 13, 209 (2025).

https://doi.org/10.3390/chemosensors13060209

10. J. Ko, C. Ock, H. Gim, K. Hong, Y. Lee, K.C. Kwon. Twodimensional materials for artificial sensory devices: Advancing neuromorphic sensing technology. npj 2D Mater. Appl. 9, 35 (2025).

https://doi.org/10.1038/s41699-025-00556-2

11. R. Gusm˜ao, Z. Sofer, M. Pumera. Black phosphorus rediscovered: From bulk material to monolayers. Angew. Chem. Int. Ed. Engl. 56, 8052 (2017).

https://doi.org/10.1002/anie.201610512

12. R.K. Mishra, J. Sarkar, I. Chianella, S. Goel, H.Y. Nezhad. Black phosphorus: The rise of phosphorene in 2D materials applications. Next Materials 4, 100217 (2024).

https://doi.org/10.1016/j.nxmate.2024.100217

13. A. Chalechale, R. Melnik, Z.L. Miˇskovic. Modeling of anisotropy effects in phosphorene devices. Phys. Rev. Appl. 23, 064031 (2025).

https://doi.org/10.1103/y75r-txww

14. M.S. Islam, M.T. Islam, M.R. Hossain. Phosphorene: A novel nanomaterial revolutionizing biomedicine. JCIS Open 16, 100123 (2024).

https://doi.org/10.1016/j.jciso.2024.100124

15. A. Jain, A. McGaughey. Strongly anisotropic in-plane thermal transport in single-layer black phosphorene. Sci. Rep. 5, 8501 (2015).

https://doi.org/10.1038/srep08501

16. X. Zhang, Q. Li, B. Xu, B. Wan, J. Yin, X.G. Wan. Tuning carrier mobility of phosphorene nanoribbons by edge passivation and strain. Phys. Lett. A 380, 614 (2016).

https://doi.org/10.1016/j.physleta.2015.11.019

17. L. Kou, C. Chen, S.C. Smith. Phosphorene: fabrication, properties, and applications. J. Phys. Chem. Lett. 6, 2794 (2015).

https://doi.org/10.1021/acs.jpclett.5b01094

18. N.M. Latiff, C.C. Mayorga-Martinez, Z. Sofer, A.C. Fisher, M. Pumera. Cytotoxicity of phosphorus allotropes (black, violet, red). Appl. Mater. Today 13, 310 (2018).

https://doi.org/10.1016/j.apmt.2018.09.010

19. M. Qiu, A. Singh, D.Wang, J. Qu, M. Swihart, H. Zhang, P.N. Prasad. Biocompatible and biodegradable inorganic nanostructures for nanomedicine: Silicon and black phosphorus. Nano Today 25, 135 (2019).

https://doi.org/10.1016/j.nantod.2019.02.012

20. J. Ouyang, Y. Deng, W. Chen, Q. Xu, L. Wang, Z. Liu, F. Tang, L. Deng, Y.N. Liu. Marriage of artificial catalase and black phosphorus nanosheets for reinforced photodynamic antitumor therapy. J. Mater. Chem. B 6, 2057 (2018).

https://doi.org/10.1039/C8TB00371H

21. J. Liu, P. Du, T. Liu, B.J. C'ordova Wong, W. Wang, H. Ju, J. Lei. A black phosphorus/manganese dioxide nanoplatform: Oxygen self-supply monitoring, photodynamic therapy enhancement and feedback. Biomaterials 192, 179 (2019).

https://doi.org/10.1016/j.biomaterials.2018.10.018

22. J. Xie, T. Fan, J.H. Kim, Y. Xu, Y. Wang, W. Liang, L. Qiao, Z. Wu, Q. Liu, W. Hu, N. Yin, L. Yang, L. Liu, J.S. Kim, H. Zhang. Large-area flexible organic solar cells with a robust silver nanowire-polymer composite as transparent top electrode. Adv. Funct. Mater. 30, 1 (2020).

23. G. Yang, X. Wan, Z. Gu, X. Zeng, J. Tang. Near infrared photothermal-responsive poly(vinyl alcohol)/black phosphorus composite hydrogels with excellent on-demand drug release capacity. J. Mater. Chem. B 6, 1622 (2018).

https://doi.org/10.1039/C7TB03090H

24. M.A. Buabeid, E.S.A. Arafa, G. Murtaza, Emerging prospects for nanoparticle-enabled cancer immunotherapy. J. Immunol. Res. 2020, 9624532 (2020).

https://doi.org/10.1155/2020/9624532

25. X. Shou, Y. Liu, D. Wu, H. Zhang, Y. Zhao, W. Sun, X. Shen. Black phosphorus quantum dots doped multifunctional hydrogel particles for cancer immunotherapy. Chem. Eng. J. 408, 127349 (2021).

https://doi.org/10.1016/j.cej.2020.127349

26. Z.L. Shaw, S. Kuriakose, S. Cheeseman, E.L.H. Mayes, A. Murali, Z.Y. Oo, T. Ahmed, N. Tran, K. Boyce, J. Chapman, C.F. McConville, R.J. Crawford, P.D. Taylor, A.J. Christofferson, V.K. Truong, M.J.S. Spencer, A. Elbourne, S. Walia. Broad-spectrum solvent-free layered black phosphorus as a rapid action antimicrobial. ACS Appl. Mater. Interfaces 13, 17340 (2021).

https://doi.org/10.1021/acsami.1c01739

27. P. Zhang, B. Sun, F. Wu, Q. Zhang, X. Chu, M. Ge, N. Zhou, J. Shen. Wound healing acceleration by antibacterial biodegradable black phosphorus nanosheets loaded with cationic carbon dots. J. Mater. Sci. 56, 6411 (2021).

https://doi.org/10.1007/s10853-020-05766-1

28. Ying Teng Yew, Z. Sofer, C.C. Mayorga Martinez, M. Pumera. Black phosphorus nanoparticles as a novel fluorescent sensing platform for nucleic acid detection. Mater. Chem. Front. 1, 1130 (2017).

https://doi.org/10.1039/C6QM00341A

29. V. Kumar, J.R. Brent, M. Shorie, H. Kaur, G. Chadha, A.G. Thomas et al. Nanostructured aptamer-functionalized black phosphorus sensing platform for label-free detection of myoglobin, a cardiovascular disease biomarker. ACS Appl. Mater. Interfaces 8, 22860 (2016).

https://doi.org/10.1021/acsami.6b06488

30. W. Chen, J. Ouyang, H. Liu, M. Chen, K. Zeng, J. Sheng, Z. Liu, Y. Han, L. Wang, J. Li, L. Deng, Y.-N. Liu, S. Guo. Black phosphorus nanosheet-based drug delivery system for synergistic photodynamic/photothermal/chemotherapy of cancer. Adv. Mater. 29, 1603864 (2017).

https://doi.org/10.1002/adma.201603864

31. E. Kovalska, J. Luxa, T. Hartman, N. Antonatos, P. Shaban, E. Oparin, M. Zhukova, Z. Sofer. Non-aqueous solution-processed phosphorene by controlled low-potential electrochemical exfoliation and thin film preparation. Nanoscale 12, 2638 (2020).

https://doi.org/10.1039/C9NR10257D

32. P. Yasaei, B. Kumar, T. Foroozan, C. Wang, M. Asadi, D. Tuschel, J.E. Indacochea, R.F. Klie, A. Salehi-Khojin. High-quality black phosphorus atomic layers by liquidphase exfoliation. Adv. Mater. 27, 1887 (2015).

https://doi.org/10.1002/adma.201405150

33. M. Bogdanov, K. Pyrshev, S. Yesylevskyy, S. Ryabichko, V. Boiko, P. Ivanchenko, R. Kiyamova, Z. Guan, C. Ramseyer, W. Dowhan. Phospholipid distribution in the cytoplasmic membrane of Gram-negative bacteria is highly asymmetric, dynamic, and cell shape-dependent. Sci. Adv. 6, eaaz6333 (2020).

https://doi.org/10.1126/sciadv.aaz6333

34. G.I. Dovbeshko, U.K. Afonina, M.V. Olenchuk, I.M. Kupchak, O.P. Gnatyuk, G.P. Monastyrskyi, A.S. Nikolenko, H.V. Shevliakova, A.N. Morozovska. Effect of 2D-WS2 nanoparticles on a local electrical field at a membrane vicinity: Vibrational spectroscopy data. J. Phys. Chem. C 128, 1131 (2023).

https://doi.org/10.1021/acs.jpcc.3c05693

35. G. Monastyrskyi, O. Gnatyuk, I. Gubareni, G. Levchenko, A. Nikolenko, M. Olenchuk, A. Tolochko, I. Kupchak, G. Dovbeshko. MoS2 2D nanoparticles as inducers of changes in liposomes formation and their spectroscopic properties. Low Temp. Phys. 51, 261 (2025).

https://doi.org/10.1063/10.0035414

36. M. Olenchuk, G. Monastyrskyi, Yu.M. Barabash, O. Gnatyuk, Ie. Gubareni, G. Levchenko, A. Nikolenko, A. Tolochko, I. Kupchak, G. Dovbeshko. The influence of 2DWS2 nanoparticles on the liposomes formation, morphology and spectral properties. J. Molecul. Struct. 1352, Part 1, 144277 (2025).

https://doi.org/10.1016/j.molstruc.2025.144277

37. Z. Guo, H. Zhang, S. Lu, Z. Wang, S. Tang, J. Shao, Z. Sun, H. Xie, H. Wang, X.-F. Yu, P.K. Chu. From black phosphorus to phosphorene: Basic solvent exfoliation, evolution of raman scattering, and applications to ultrafast photonics. Adv. Funct. Mater. 25, 6996 (2015).

https://doi.org/10.1002/adfm.201502902

38. J. G'omez-P'erez, B. Barna, I.Y. T'oth, Z. K'onya, 'A. kos Kukovecz. Quantitative tracking of the oxidation of black phosphorus in the few-layer regime. ACS Omega 3, 12482 (2018).

https://doi.org/10.1021/acsomega.8b01989

39. GAMESS-US, version 15 JUL 2024 (R2 Patch 1).

https://doi.org/10.1109/SoutheastCon52093.2024.10500126

40. G.M.J. Barca, C. Bertoni, L. Carrington et al. Recent developments in the general atomic and molecular electronic structure system. J. Chem. Phys. 152, 154102 (2020).

https://doi.org/10.1063/5.0005188

41. P.J. Stephens, F.J. Devlin, C.F. Chabalowski, M.J. Frisch. Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields. J. Phys. Chem. 98, 11623 (1994).

https://doi.org/10.1021/j100096a001

42. P.J. Hay, W.R. Wadt. Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg. J. Chem. Phys. 82, 270 (1985).

https://doi.org/10.1063/1.448799

43. W.R. Wadt, P.J. Hay. Ab initio effective core potentials for molecular calculations. Potentials for main group elements Na to Bi. J. Chem. Phys. 82, 284 (1985).

https://doi.org/10.1063/1.448800

44. P.J. Hay, W.R. Wadt. Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals. J. Chem. Phys. 82, 299 (1985).

https://doi.org/10.1063/1.448975

45. S. Grimme, J. Antony, S. Ehrlich, H. Krieg. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104 (2010).

https://doi.org/10.1063/1.3382344

Published

2026-04-21

Issue

Section

Contents

How to Cite

Phosphorenes as a New Material for Surface-Enhanced Infrared Spectroscopy of Cell Membranes. (2026). Ukrainian Journal of Physics, 71(4), 349. https://doi.org/10.15407/ujpe71.4.349

Most read articles by the same author(s)