DNA-Induced Restructuring of Interfacial Water and the Hydrocarbon Chain of Different Forms of Fungicide at the Water Interface: Vibrational Sum Frequency Generation Study

Abstract

Fungicides adopt different structures at the air/water interface depending on their concentration, which affects their potency against fungi. However, the nontargeted action of fungicides causes a genotoxic effect on other organisms, which is responsible for several serious diseases such as cancer, neurodegenerative disorders, and developmental problems. Hence, understanding the effect of DNA on the different structures of fungicides at the air/water interface is essential. The surface-selective vibrational sum frequency generation technique has been implemented to obtain insights into the effect of DNA on the fungicide, namely, dodine at the air/water interface. The hydrocarbon chain of dodine with an increasing concentration adopts disordered, ordered, and packed forms at the air/water interface. DNA gets closer to the positively charged head group of dodine at the air/water interface in its disordered, ordered, and packed forms by removing the interfacial water and reorganizes the hydrogen bonding of water beneath the head group of dodine. Interestingly, DNA also increases the ordering of the hydrocarbon chain of disordered and ordered dodine at the air/water interface by modulating the gauche defect and orientational ordering of the hydrocarbon chain of dodine. Unlike the disordered and ordered dodine, the addition of DNA at the packed dodine on the air/water interface does not affect the ordering of its hydrocarbon chain. The significant reorganization of the interfacial water and the hydrocarbon chain of dodine by DNA can be useful for understanding the mechanism of the nontargeted genotoxic effects of dodine.

Understanding of the interaction of biological macromolecules with lipids using vibrational sum‐frequency generation spectroscopy

“…[61] Several groups have used the C-H stretch of the lipids to characterize the local conformation as well as the ordering of the hydrocarbon chain of the lipids at the interface in the presence of different molecules as well as different conditions. [46][47][48][49][50][51][52][53][56][57][58][59][60][61][62] For example, Bonn et al have utilized the C-H stretch of the hydrocarbon chain of lipids to understand the effect of cholesterol on the packing of the lipids at different surface pressure. [58] Similarly, several other groups have utilized the C-H stretch of the hydrocarbon chain of lipids to understand the conformational change of lipid and interaction with neurotransmitter, DNA, and other biomolecules.…”

“…[58] Similarly, several other groups have utilized the C-H stretch of the hydrocarbon chain of lipids to understand the conformational change of lipid and interaction with neurotransmitter, DNA, and other biomolecules. [47][48][49][50][51][52][53]62] The interfacial water near to the different head groups of lipid has been characterized by the VSFG technique. Conventional VSFG measurements show that the intensity of the VSFG signal of the O-H stretch of water enhances in the presence of the lipids compared with the air/water interface and the enhancement of the water signal is higher at the charged lipids compared with the zwitterionic (Figure 2A).…”

“…[ 58 ] Similarly, several other groups have utilized the C–H stretch of the hydrocarbon chain of lipids to understand the conformational change of lipid and interaction with neurotransmitter, DNA, and other biomolecules. [ 47–53,62 ]…”

“…VSFG technique has the capability to understand the molecular behavior at the interface, and hence, it has been also implemented at the model membrane interfaces (consisting of lipid monolayer at air/water interface) to understand the structure of lipid and interfacial water molecules during the complex biological processes. [34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53] In this review, we have focused on the discussion of the structural change of lipid and interfacial water molecules during the fibrillation of proteins, interaction with hydrated proton, and neurotransmitter interaction related to synaptic vesicles.…”

Sixty Years of Surface-Specific Spectroscopy

“…VSFG was used to study the vibrational spectra of water at graphene oxide surfaces by Hong et al, and at ice surfaces by Sudera et al Seki et al used VSFG to record the vibrational spectra of water at charged lipid interfaces, and the presence of weakly hydrogen bonded water at lipid interfaces was detected using heterodyne-detected VSFG by Nojima and Yamaguchi . Singh and co-workers used VSFG to study how DNA changes the structure of water at the surface of cationic and zwitterionic lipid monolayers. , In many of these studies, the interpretation of the experimental data is enhanced by atomistic simulations. For instance, statistical mechanics techniques were employed to aid the interpretation of nonlinear optical responses from aqueous interfaces by Rajagopal et al who used a lattice model to obtain detailed molecular insights into cooperativity in interfacial acid–base chemistry.…”