• google scholor

  • Views: 717

  • PDF Downloads: 5

Photoacid as an Efficient ICT Probe for Understanding the Ground State Proton Transfer (GSPT) Process from Solute to Solvents

Anas D Fazal , Trupti D Solanky , Abhishek R Patel and Sumit K Panja*

1Tarsadia Institute of Chemical Science, Uka Tarsadia University, Maliba Campus, Gopal Vidyanagar, Bardoli, Mahuva Road, Surat, Gujarat India .

Corresponding author Email: sumitkpanja@gmail.com

DOI: http://dx.doi.org/10.13005/OJPS08.02.01

Copy the following to cite this article:

Fazal A. D, Solanky T. D, Patel A. R, Panja S. K. Photoacid as an Efficient ICT Probe for Understanding the Ground State Proton Transfer (GSPT) Process from Solute to Solvents. Oriental Jornal of Physical Sciences 2023; 8(2).
  DOI:http://dx.doi.org/10.13005/OJPS08.02.01

Copy the following to cite this URL:

Fazal A. D, Solanky T. D, Patel A. R, Panja S. K. Photoacid as an Efficient ICT Probe for Understanding the Ground State Proton Transfer (GSPT) Process from Solute to Solvents. Oriental Jornal of Physical Sciences 2023; 8(2). Available here:https://bit.ly/3Fs1T2C

Download article (pdf)
Citation Manager
Publish History

Article Publishing History

Received: 14-08-2023
Accepted: 20-10-2023

Intermolecular interactions play a crucial role for the generation of physiologically active compounds, novel functional materials, and mechanisms for chemical and biological recognition and rational drug design.1-2 The creation of useful novel materials and enhanced understanding of mechanism of formation of cluster in solution depend greatly upon the research of fundamental intermolecular interactions.2 The intermolecular interaction between solvent & solute can be described by intermolecular H-bonding interaction at ground and excited state.3-4 Excited state intermolecular proton transfer (ESPT) process of photoacid has been comprehensively examined so far.5-7 However ground state proton transfer (GSPT) process from solute to solvents are infrequently pragmatic. Photoacid have unique characteristic feature to exhibit microsolvation behavior with protic solvent via intermolecular H-bonding interactions.8-9

Upon electronic excitation, photoacids has shown significant changes of their acidity and exhibit distinct pKa values in ground & excited state.10 Solute-Solvent interaction via intermolecular H-bonding interaction & degree of photoacidity of photoacids are responsible for efficiently GSPT transfer process from solute to solvent.11-12 The microsolvation behavior of  photoacid in protic solvents depends upon strength of intermolecular H-bonding interaction & degree of photoacidity at ground and excited state. It is also pragmatic that electron withdrawing group enhances photoacidity of photoacid in solutions and makes photoacids as ICT probe for GSPT and ESPT process from solute to solvents.8-9

Microsolvation is a key phenomenon and has been widely studied in protic solvents, especially in water.13 The microsolvation of photoacids provides better understanding for proton transfer phenomena from solute to solvents, considering solute molecule enclosed by solvent molecule.13-14 Photoacid is an important class of molecule used as molecular probe for determining structural transitions of proteins & water accessibility in biological surfaces.15-16 Electronic structure of hydrated cluster has been calculated to provide  molecular level understanding about hydration process of photoacid.17-18 Phenol is considered as simplest photoacid and also works as chromophore in aromatic amino acid in biological system.19-20 The interaction between phenol & solvent molecule is considered as model system for understanding the molecular level microsolvation behavious of phenol clusters.14, 21-22 In neutral condition, phenol behaves as weak ICT probe but in basic solutions, it shows strong ICT probe due to the enhancement of intermolecular charge transfer (ICT) process in solution.23 In homogeneous clusters such as water/aliphatic alcohol, water/aromatic alcohol, aliphatic alcohol/aromatic alcohol and other similar complicated systems are also inspected via UV and IR spectroscopic methods.12 Precise disturbance of the clusters can lead to red shift of O-H vibrational stretching by alternation of H-bonding interaction which happens between solute & solvent in solution.24

Recent studies indicate that microsolvation of photoacids can have a considerable impact on solute in the ground state proton transfer in solution.25 Photoacid has a great importance in different chemical, pharmaceutical and fragrant industries etc. It can also be used for the conformational changes of complex biological systems and in many complex reactions. Further, degree of photoacid related to efficient ICT probe to investigate GSPT from solute to solvent & impact of electron withdrawing group on photoacidity should be studied further applications in complex chemical, pharmaceutical and biological systems.

References

  1. E. A. Meyer, R. K. Castellano, F. Diederich. Interactions with aromatic rings in chemical    and biological recognition. Angew. Chem. Int. Ed. 42 (2003) 1210-1250.
    CrossRef
  2. K. S. Kim, P. Tarakeshwar, J. Y. Lee. Molecular clusters of π-systems: theoretical studies of structures, spectra, and origin of interaction energies. Chem. Rev. 100 (2000) 4145-4186.
    CrossRef
  3. S. K. Panja, S. Verma, S. Saha. Probing phenol dimer in molecular complex: role of nitro group and stabilizing agent. J. Mol. Struct. 1193 (2019) 103-109.
    CrossRef
  4. P. Song, F.-C. Ma. Intermolecular hydrogen-bonding effects on photophysics and photochemistry. Annu. Rev. Phys. Chem. 32 (2013) 589-609.
    CrossRef
  5. J. F. Joung, S. Kim, S. Park. Effect of NaCl Salts on the Activation Energy of Excited-State Proton Transfer Reaction of Coumarin 18. J. Phys. Chem. B 50 (2015) 15509-15515.
    CrossRef
  6. O. Gajst, L. P. da Silva, J. C. G. Esteves da Silva, and D. Huppert. Excited-State Proton Transfer from the Photoacid 2-Naphthol-8-sulfonate to Acetonitrile/Water Mixtures. J. Phys. Chem. A, 30 (2018) 6166–6175.
    CrossRef
  7. N. Sülzner, B. Geissler, A. Grandjean, G. Jung, P. Nuernberger. Excited-State Proton Transfer Dynamics of a Super-Photoacid in Acetone-Water Mixtures. ChemPhotoChem 6 (2022) e202200041
    CrossRef
  8. K. M. Solntsev, D. Huppert, N. Agmon. Photochemistry of “Super”-Photoacids. Solvent Effects. J. Phys. Chem. A 103 (1999) 6984–6997.
    CrossRef
  9. L. M. Tolbert, K. M. Solntsev. Excited-State Proton Transfer:  From Constrained Systems to “Super” Photoacids to Superfast Proton Transfer. Acc. Chem. Res. 35(2002) 19-27.
    CrossRef
  10. O. Gajst, L. P. da Silva, J.C.G.E. da Silva, D. Huppert, Excited-state proton transfer from the photoacid 2-Naphthol-8-sulfonate to acetonitrile/water mixtures. J. Phys. Chem. A 122 (2018) 6166–6175.
    CrossRef
  11. L. M. Oltrogge, Q. Wang, S. G. Boxer. Ground-State Proton Transfer Kinetics in Green Fluorescent Protein. Biochemistry 53 (2014) 5947–5957.
    CrossRef
  12. R. Knochenmuss, O. Cheshnovsky, S. Leutwyler, Proton transfer reactions in neutral gas-phase clusters: 1-Naphthol with H2O, D2O, CH3OH, NH3 and piperidine. Chem. Phys. Lett. 144 (1988) 317–323.
    CrossRef
  13. T. Sawamura, A. Fujii, S. Sato, T. Ebata, N. Mikami, Size dependence of intracluster proton transfer of phenol-(H2O)n (n = 1−4) Cations. J. Phys. Chem. 100 (1996) 8131–8138.
  14. P. Krishnakumar, R. Kar, D. K. Maity. Microhydration of 2-Naphthol at Ground, First Excited Triplet, and First Excited Singlet States: A Case Study on Photo Acids. J. Phys. Chem. A 122 (2018) 929–936
    CrossRef
  15. G. J. Zhao, K. Li Han, Hydrogen Bonding in the Electronic Excited State. Acc. Chem. Res. 45 (2012) 404–413.
    CrossRef
  16. N. Amdursky, Photoacids as a new fluorescence tool for tracking structural transitions of proteins: following the concentration-induced transition of bovine serum albumin. Phys. Chem. Chem. Phys. 17 (2015) 32023–32032.
    CrossRef
  17. J. L. Perez-Lustres, F. Rodriguez-Prieto, M. Mosquera, T.A. Senyushkina, N.P. Ernsting, S.A. Kovalenko, Ultrafast Proton Transfer to Solvent:  Molecularity and Intermediates from Solvation- and Diffusion-Controlled Regimes. J. Am. Chem. Soc. 129 (2007) 5408–5418.
    CrossRef
  18. D. K. Deb, B. Sarkar, Theoretical investigation of gas-phase molecular complex formation between 2-hydroxy thiophenol and a water molecule. Phys. Chem. Chem. Phys. 19 (2017) 2466–2478.
    CrossRef
  19. S. K. Panja, S. Saha, Temperature Sensor Probe Based on Intramolecular Charge Transfer (ICT) & Reversible Solute-Solvent Interaction in Solution. Spectrochimica Acta Part A 212 (2019) 128–131.
    CrossRef
  20. A. Nilsen-Moe, C. R. Reinhardt, S. D. Glover, L. Liang, S. Hammes-Schiffer, L. Hammarström, C. Tommos. Proton-Coupled Electron Transfer from Tyrosine in the Interior of a de novo Protein: Mechanisms and Primary Proton Acceptor. J. Am. Chem. Soc. 142 (2020) 11550–11559.
    CrossRef
  21. B. Brutschy, The Structure of Microsolvated Benzene Derivatives and the Role of Aromatic Substituents. Chem. Rev. 100 (2000) 3891–3920.
    CrossRef
  22. S. K Panja. Photoacid as ICT Probe for Ground State Proton Transfer Process from Solute to Solvents. J. Mol. Liq., 299 (2020) 112194-112201
    CrossRef
  23. S. K. Panja, N. Dwivedi, S. Saha, Manipulating the proton transfer process in molecular complexes: synthesis and spectroscopic studies. Phys. Chem. Chem. Phys. 18 (2016) 21600–21609.
    CrossRef
  24. M. Prémont-Schwarz, D. Xiao, V. S. Batista, E. T. J. Nibbering, The O–H Stretching Mode of a Prototypical Photoacid as a Local Dielectric Probe, J. Phys. Chem. A 115 (2011) 10511–10516.
    CrossRef
  25. A. Shabashini, S. K Panja, A. Biswas, S. Bera, G. C. Nandi, ICT based photoacid probe for microsolvation and H-bonding assisted proton transfer process from solute to solvents, J. Photochem. Photobio. A, 432 (2022) 114087-114092
    CrossRef
Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 International License.