Investigating the Adsorption of the Thyroid Stimulating Hormones Molecules on Graphene Sheets by the Density Functional Theory for Possible Nano-Biosensor Applications

Document Type : Research Paper


1 Department of Biotechnology, Faculty of Biological Science, Alzahra University, Tehran, Iran.

2 Chemical Engineering, University of Tehran, Tehran, Iran

3 Computational Materials Science Laboratory, Nano Research and Training Center, NRTC, Iran

4 Computational Materials Science Laboratory, Nano Research and Training Center, NRTC, Iran.


In this paper, the electronic effects of the adsorption of thyroid stimulating hormones (TSH) on two-dimensional structures of graphene and ψ-graphene are theoretically investigated by means of the density functional theory (DFT). Initially, the binding energies of TSH molecules on graphene (both the zigzag and armchair structures) and ψ-graphene are computed at different spatial orientations using the Siesta code. The most stable orientations had the following binding energies: –1.04 eV for triiodothyronine on graphene, –1.25 eV for thyroxine on graphene, –0.97 eV for triiodothyronine on ψ-graphene, and –0.95 eV for thyroxine on ψ-graphene. Subsequent to identifying the most stable orientations, the current-voltage characteristics of graphene and ψ-graphene monolayers, before and after the adsorption of TSH molecules are calculated by the TranSiesta computational software package, using the non-equilibrium Green’s function approach. The adsorption of the TSH molecules on the both graphene structures reduced the passing electric current significantly. The findings show that graphene sheets can be used to synthesize fast responding TSH nano-biosensors.


  1. Toft AD. Subclinical hyperthyroidism. New England Journal of Medicine. 2001;345(7):512-6.
  2. Wu K, Ji X, Fei J, Hu S. The fabrication of a carbon nanotube film on a glassy carbon electrode and its application to determining thyroxine. Nanotechnology. 2003;15(3):287.
  3. Wang H, Dong P, Di D, Wang C, Liu Y, Chen J, et al. Interdigitated microelectrodes biosensor with nanodot arrays for thyroid-stimulating hormone detection. Micro & Nano Letters. 2013;8(1):11-4.
  4. Chou H-T, Fu C-Y, Lee C-Y, Tai N-H, Chang H-Y. An ultrasensitive sandwich type electrochemiluminescence immunosensor for triiodothyronine detection using silver nanoparticle-decorated graphene oxide as a nanocarrier. Biosensors and Bioelectronics. 2015;71:476-82.
  5. Elstner M, Frauenheim T, Suhai S. An approximate DFT method for QM/MM simulations of biological structures and processes. Journal of Molecular Structure: THEOCHEM. 2003;632(1-3):29-41.
  6. Salihović M, Huseinović S, Špirtović-Halilović S, Osmanović A, Dedić A, Ašimović Z, et al. DFT study and biological activity of some methylxanthines. Bulletin of the Chemists and Technologists of Bosnia and Herzegovina. 2014;42:31-6.
  7. Mirzaei M, Gulseren O, Rafienia M, Zare A. Nanocarbon-assisted biosensor for diagnosis of exhaled biomarkers of lung cancer: DFT approach. Eurasian Chemical Communications. 2021;3(3):154-61.
  8. Al‐Mahayni H, Wang X, Harvey JP, Patience GS, Seifitokaldani A. Experimental methods in chemical engineering: Density functional theory—DFT. The Canadian Journal of Chemical Engineering.
  9. Bain A, Languri E, Padmanabhan V, Davidson J, Kerns D, editors. Thermal Conductance of Nanoparticles: A Study of Phonon Transport in Functionalized Nanodiamond Suspensions. ASME International Mechanical Engineering Congress and Exposition; 2020: American Society of Mechanical Engineers.
  10. Khan S, Choi H, Kim D, Lee SY, Zhu Q, Zhang J, et al. Self-assembled heterojunction of metal sulfides for improved photocatalysis. Chemical Engineering Journal. 2020;395:125092.
  11. Ślusarski T, Brzostowski B, Tomecka DM, Kamieniarz G. Application of the package SIESTA to linear models of a molecular chromium-based ring. Acta Physica Polonica A. 2010;118(5):967-8.
  12. Sutton JE, Panagiotopoulou P, Verykios XE, Vlachos DG. Combined DFT, microkinetic, and experimental study of ethanol steam reforming on Pt. The Journal of Physical Chemistry C. 2013;117(9):4691-706.
  13. García A, Papior N, Akhtar A, Artacho E, Blum V, Bosoni E, et al. Siesta: Recent developments and applications. The Journal of chemical physics. 2020;152(20):204108.
  14. Khatir NM, Ahmadi A, Taghizade N, Faghihnasiri M. Electronic transport properties of nanoribbons of graphene and ψ-graphene-based lactate nanobiosensor. Superlattices and Microstructures. 2020;145:106603.
  15. Perdew JP, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Physical review letters. 1996;77(18):3865.
  16. Gerrits N, Smeets EW, Vuckovic S, Powell AD, Doblhoff-Dier K, Kroes G-J. Density functional theory for molecule–metal surface reactions: When does the generalized gradient approximation get it right, and what to do if it does not. The journal of physical chemistry letters. 2020;11(24):10552-60.
  17. Patra A, Patra B, Constantin LA, Samal P. Electronic band structure of layers within meta generalized gradient approximation of density functionals. Physical Review B. 2020;102(4):045135.
  18. Troullier N, Martins JL. Efficient pseudopotentials for plane-wave calculations. Physical review B. 1991;43(3):1993.
  19. Papior N, Lorente N, Frederiksen T, García A, Brandbyge M. Improvements on non-equilibrium and transport Green function techniques: The next-generation transiesta. Computer Physics Communications. 2017;212:8-24.
Volume 55, Issue 2
December 2021
Pages 385-392
  • Receive Date: 29 June 2020
  • Revise Date: 08 July 2021
  • Accept Date: 31 October 2021
  • First Publish Date: 24 November 2021