Reaction Mechanism of Covalent Modification of Phosphatidylethanolamine Lipids by Reactive Aldehydes 4-Hydroxy-2-nonenal and 4-Oxo-2-nonenal.

4-Hydroxy-2-nonenal (HNE) and 4-oxo-2-nonenal (ONE) are biologically important reactive aldehydes formed during oxidative stress in phospholipid bilayers. They are highly reactive species due to presence of several reaction centers and can react with amino acids in peptides and proteins, as well as phosphoethanolamine (PE) lipids, thus modifying their biological activity. The aim of this work is to study in a molecular detail the reactivity of HNE and ONE toward PE lipids in a simplified system containing only lipids and reactive aldehydes in dichloromethane as an inert solvent.

Electronic states of Myricetin. UV-Vis polarization spectroscopy and quantum chemical calculations.

Myricetin (3,3',4',5,5',7'-hexahydroxyflavone) was investigated by linear dichroism spectroscopy on molecular samples partially aligned in stretched poly(vinyl alcohol) (PVA). At least five electronic transitions in the range 40,000-20,000cm were characterized with respect to their wavenumbers, relative intensities, and transition moment directions. The observed bands were assigned to electronic transitions predicted with TD-B3LYP/6-31+G(d,p).

Ligand-Dependent Nanoparticle Clustering within Lipid Membranes Induced by Surrounding Medium.

The interactions between hydrophobic or semihydrophobic gold and silver nanoparticles (NPs) and a dimyristoylphosphatidylcholine (DMPC) bilayer as a model cell membrane in two ionic solutions result in the structural reorganization within the bilayer manifested as locally increased nanomechanical compaction in the vicinity of NP clusters as well as changed overall thermotropic properties. The effects of NP surface charge and hydrophobicity were examined using AFM imaging, force spectroscopy and IR spectroscopy. The NP clustering occurred during hydration process of dry films containing both the DMPC molecules and the NPs by the mechanism in which the number of bilayer deformations was reduced by NP clustering.

The exploration of hydrogen bonding properties of 2,6- and 3,5-diethynylpyridine by IR spectroscopy.

Hydrogen bonding properties of 2,6- and 3,5-diethynylpyridine were analyzed by exploring of their interactions with trimethylphosphate, as hydrogen bond acceptor, or phenol, as hydrogen bond donor, in tetrachloroethene C2Cl4. The employment of IR spectroscopy enabled unravelling of their interaction pattern as well as the determination of their association constants (Kc) and standard reaction enthalpies (ΔrH(⦵)). The association of diethynylpyridines with trimethylphosphate in stoichiometry 1:1 is established through CH⋯O hydrogen bond, accompanied by the secondary interaction between CC moiety and CH3 group of trimethylphosphate.

Ionic strength and composition govern the elasticity of biological membranes. A study of model DMPC bilayers by force- and transmission IR spectroscopy.

Infrared (IR) spectroscopy was used to quantify the ion mixture effect of seawater (SW), particularly the contribution of Mg(2+) and Ca(2+) as dominant divalent cations, on the thermotropic phase behaviour of 1,2-dimyristoyl-sn-glycero-3-posphocholine (DMPC) bilayers. The changed character of the main transition at 24 °C from sharp to gradual in films and the 1 °C shift of the main transition temperature in dispersions reflect the interactions of lipid headgroups with the ions in SW. Force spectroscopy was used to quantify the nanomechanical hardness of a DMPC supported lipid bilayer (SLB).

The study of secondary effects in vibrational and hydrogen bonding properties of 2- and 3-ethynylpyridine and ethynylbenzene by IR spectroscopy.

Weak hydrogen bonds formed by 2- and 3-ethynylpyridine and ethynylbenzene with trimethylphosphate and phenol were characterized by IR spectroscopy and DFT calculations (B3LYP/6-311++G(d, p)). The structure and stability of ethynylpyridines and ethynylbenzene in the gas phase and in the complexes with trimethylphosphate and phenol are discussed in terms of geometry and electronic charge redistribution. Anharmonic effects are taken into account when calculating vibrational wavenumbers of these systems what lead to partial improvement of agreement with experiment.

The study of hydrogen bonding and π⋯π interactions in phenol⋯ethynylbenzene complex by IR spectroscopy.

Weak hydrogen bonds between phenol and ethynylbenzene in tetrachloroethene were explored by using FTIR spectroscopy. Association constants (Kc) were determined by high dilution method at two temperatures, 20°C and 26°C, and they are, respectively, 0.54±0.

Characterization of intramolecular hydrogen bonds by atomic charges and charge fluxes.

The electronic charge redistribution and the infrared intensities of the two types of intramolecular hydrogen bonds, O-H···O and O-H···π, of o-hydroxy- and o-ethynylphenol, respectively, together with a set of related intermolecular hydrogen bond complexes are described in terms of atomic charges and charge fluxes derived from atomic polar tensors calculated at the B3LYP/cc-pVTZ level of theory. The polarizable continuum model shows that both the atomic charges and charge fluxes are strongly dependent on solvent. It is shown that their values for the OH bond in an intramolecular hydrogen bond are not much different from those for the "free" OH bond, but the changes are toward the values found for an intermolecular hydrogen bond.