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Conformers of Piperazine on air-water interface studied by VSFG spectroscopy

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Abstract

Piperazine is a saturated six-membered heterocyclic compound that is used for commercial CO2 removal for carbon capture and storage. In this work, we have investigated piperazine conformers' structure and orientation at an aqueous solution's surface using surface-specific vibrational sum-frequency generation (VSFG) spectroscopy. It is found that though piperazine molecules exist majorly as centrosymmetric conformers in gas-phase and crystalline states, they can have a substantial population of non-centrosymmetric conformers on the air-water interface with net polar orientation. The VSFG signal varies slightly with concentration, indicating some changes in the conformational distribution and orientation of the interfacial molecules. In the presence of HCl, VSFG spectra of piperazine aqueous solution change considerably with the extent of protonation. The VSFG signal in the C-H stretching region, even from completely protonated piperazine cations, and its similarity with the peak positions of unprotonated piperazine, establishes the presence of non-centrosymmetric conformers at the air-water interface for piperazine and its cations. From the O-H stretching VSFG spectra, it is found that on increasing the concentration of piperazine up to 800 mM, there is an increase in the orientational order of the interfacial water molecules, and disorderliness sets in at higher concentrations and in acidic conditions.

Graphical abstract

The structure and orientation of piperazine conformers at the surface of an aqueous solution are investigated. Piperazine molecules which exist majorly as centrosymmetric conformers in gas-phase and crystalline states are found to have a substantial population of non-centrosymmetric conformers on the air-water interface with net polar orientation. VSFG signal in the C-H stretching region even from completely protonated piperazine cations and its similarity with the peak positions of unprotonated piperazine establishes the presence of non-centrosymmetric conformers on air-water interface, for piperazine and its cations.

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Acknowledgments

The authors acknowledge the financial support from Bhabha Atomic Research Centre, Mumbai, India. The authors also acknowledge support and encouragement from Dr. P.D. Naik and Dr. A.K. Tyagi.

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Authors and Affiliations

  1. Radiation and Photochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai, 400085, India

    Ankur Saha, Sumana Sengupta, Anmol Virmani & Awadhesh Kumar

  2. Homi Bhabha National Institute (HBNI), Training School Complex, Anushaktinagar, Mumbai, 400 094, India

    Ankur Saha, Sumana Sengupta & Awadhesh Kumar

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  1. Ankur Saha
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  2. Sumana Sengupta
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Correspondence to Sumana Sengupta or Awadhesh Kumar.

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Saha, A., Sengupta, S., Virmani, A. et al. Conformers of Piperazine on air-water interface studied by VSFG spectroscopy. J Chem Sci 134, 98 (2022). https://doi.org/10.1007/s12039-022-02093-7

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  • DOI: https://doi.org/10.1007/s12039-022-02093-7

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