XVIth International Workshop on
Quantum Systems in
Chemistry and Physics
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Hydrogen Bond Dynamics and Computational Vibrational Spectroscopy in Aqueous Solution: The Case Study of Histamine Monocation
Robert Vianello, Janez Mavri
National Institute of Chemistry, Hajdrihova 19, SI1000 Ljubljana, Slovenia. Email: vianello@irb.hr
Histamine is a biogenic amine playing important roles in molecular biology and medicine, which under physiological conditions assumes the monocationic form (Figure 1). It participates in complex processes related to intercellular communication, defence and cell proliferation in mammals. Its signalling pathways are involved in conditions such as depression, schizophrenia and Alzheimer's disease. Consequently, processes involving histamine transport and binding to macromolecules through hydrogen bonding have a significant biological relevance.

The nature of interactions of histamine with solvent water molecules is experimentally reflected in the NH vibrational stretching frequencies. Assignment of the experimental spectra[1] (Figure 2) reveals a broad feature between 3350 and 2300 cm1, which includes a mixed contribution from the ring and the aminoethyl NH stretching vibrations.

Computational analysis[1] was performed by applying an a posteriori quantization of particular nuclear motions to snapshot structures obtained after CarParrinello MD simulations (Figure 3). It showed that the ring amino group absorbs at higher frequencies than the remaining three amino NH protons. In this way, these results complemented the experiment that cannot distinguish between the two sets of protons. The effects of deuteration were also considered. Calculated spectra are in very good agreement with the experiment. The presented methodology is of general applicability to strongly correlated systems and it is particularly tuned to provide computational support to vibrational spectroscopy.










Figure 1. The structure of the histamine monocation.

Figure 2. Experimental vibrational spectra of histamine monocation recorded in H2O (left) and in D2O (right).

Figure 3. Calculated NH (full black line) and ND (dashed black line) stretching envelopes, arising from freeamino (red lines) and ring amino (blue lines) groups.


[1] J. Stare, J. Mavri, J. Grdadolnik, J. Zidar, Z. B. Maksić, R. Vianello, J. Phys. Chem. B 2011, 115(19), pp5999-6010.


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