A Simple Additive Potential Model for Simulating Hydrogen Peroxide in Chemical and Biological Systems

Abstract

Hydrogen peroxide (HO) has numerous industrial, environmental, medical, cosmetic, and biological applications. Given its importance, we provide a simple model as an alternative to experiment for studying the properties of pure liquid HO and its concentrated aqueous solutions, which are hazardous, and for understanding the biological roles of HO at the molecular level. A four-site additive model is calibrated for HO based on the ab initio and experimental properties of the gaseous monomer and the density and heat of vaporization of liquid HO at 0 °C. Our model together with the TIP3P water model reproduce the ab initio binding energies of (HO) , HO· nHO, and nHO·HO clusters ( m = 2, 3 and n = 1, 2) calculated at the MP2 level using the 6-311++G(d,p) or the 6-311++G(3df,3pd) basis set. It yields structure, the self-diffusion coefficient, heat capacity, and densities at temperatures up to 200 °C of the pure liquid in good agreement with experiment. The model correctly predicts the hydration free energy of HO and reproduces the experimental density of aqueous HO solutions at 0-96 °C. Investigation of the solvation of HO and HO in aqueous HO solutions reveals that, as in the gas phase, HO is a better H-bond donor but poorer acceptor than HO and the bonding stability follows the order O-H···O > O-H···O ≥ O-H···O > O-H···O. Stronger H-bonding in HO/HO mixtures than in the pure liquids is consistent with exothermic heats of mixing and explains why the observed density and vapor pressure of the aqueous solutions are higher and lower, respectively, than expected from ideal mixing. Results also show that HO adopts a skewed equilibrium geometry in gas and liquid phases but more polar cis and nonpolar trans conformations also are accessible and will stabilize HO in environments of different polarity. In sum, our simple model presents a reliable tool for simulating HO in chemistry and biology.

The Possibility of Blocking the Process of DNA Base Pairs Opening by Hydrogen Peroxide

“…The values of charges on the atoms of H 2 O 2 molecule are in good agreement with charges obtained by quantum-chemical calculations in the work [23]. Also the same charge values are used in recently developed force field for hydrogen peroxide molecule [24].…”

Modeling Shows that Rotation about the Peroxide O–O Bond Assists Protein and Lipid Functional Groups in Discriminating between H2O2 and H2O

“…Our MM model for H 2 O 2 reproduces the ab initio properties of all complexes except those containing sulfur. Thus, rigid potential energy curves (PECs) were generated for H 2 O 2 –CH 3 SH, H 2 O 2 –CH 3 S – , and H 2 O 2 –(CH 3 ) 2 S by scanning the r S···H H-bond distance from 1.5 to 10.0 Å, in 0.1 Å increments.…”

“…However, to enable future computer simulations of H 2 O 2 in actual proteins and membranes, we now examine the performance of our MM model in computing the ab initio properties of the gaseous H 2 O 2 complexes using the CHARMM36 force field for the analogs . The results reveal that, after force-field calibration for the S-containing analogs, our model delivers a reliable MM description of the structure and stability of all the H 2 O 2 –protein/lipid interactions investigated, thus demonstrating its transferability to biological systems. Additionally, we show that the TIP3P model for H 2 O , yields a reliable MM description of H 2 O–protein/lipid interactions.…”

“…We have recently published a simple four-site nonpolarizable molecular mechanics (MM) model for H 2 O 2 . This MM model accurately reproduces the energetics of gaseous H 2 O 2 and H 2 O 2 –H 2 O clusters as well as the properties of pure liquid H 2 O 2 plus its aqueous solutions under a range of thermodynamic conditions of industrial interest . We did not previously report any interactions of H 2 O 2 with functional groups found in biomolecules such as the analogs listed above.…”

Assessment of Hydrate Formation, Storage Capacity, and Transport Properties of Methane and Carbon Dioxide through Functionalized Carbon Nanotube Membranes

“…The interaction between particles is defined by the Lennard-Jones potential parameters. The Lennard-Jones parameters corresponding to −CONH 2 , −COOH, and −H 2 O 2 were taken from the literature. − Table lists the Lennard-Jones parameters for molecules used in this study. The Lennard-Jones parameters for the interaction of different atoms are defined using the Lorentz–Berthelot mixing rules, where and ε ij = (ε i ·ε j ) 0.5 , where ε and σ are the well depth and collision diameter, respectively.…”