DFT Study of Nitroxide Radicals. 1. Effects of solvent on structural and electronic characteristics of 4-amino-2,2,5,5-tetramethyl-3-imidazoline-N-oxyl

Imidazoline-based nitroxide radicals are often used as spin probes for medium acidity and polarity in different systems. In this work, using the density functional theory (DFT) approach, we have studied how physico-chemical characteristics (geometry, atomic charges and electron spin density distribution) of pH-sensitive spin label 4-amino-2,2,5,5-tetramethyl-3-imidazoline-N-oxyl (ATI) depend on protonation and aqueous surroundings. Our calculations demonstrate that ATI protonation should occur at the nitrogen atom of the imidazoline ring rather than at the amino group. Protonation of ATI leads to a decrease in a spin density on the nitrogen atom of the nitroxide fragment >N-O. For simulation of ATI hydration effects, we have constructed a water shell around a spin label molecule by means of gradual (step-by-step) surrounding of ATI with water molecules (n = 2-41). Calculated spin density on the nitrogen atom of the nitroxide fragment increased with an extension of a water shell around ATI. Both protonation and hydration of ATI caused certain changes in calculated geometric parameters (bond lengths and valence angles). Investigating how structural and energy parameters of a system ATI-(H2O)n depend on a number of surrounding water molecules, we came to the conclusion that a hydrogen-bonded cluster of n ≥ 41 water molecules could be considered as an appropriate model for simulation of ATI hydration effects.Comment: 30 pages, 11 figures, 6 table

Raman Study of Block Copolymers of Methyl Ethylene Phosphate with Caprolactone and L-lactide

We present an in-depth analysis of Raman spectra of novel block copolymers of methyl ethylene phosphate (MeOEP) with caprolactone (CL) and L-lactide (LA), recorded with the excitation wavelengths of 532 and 785 nm. The experimental peak positions, relative intensities and profiles of the poly(methyl ethylene phosphate) (PMeOEP), polycaprolactone (PCL) and poly(L-lactide) (PLA) bands in the spectra of the copolymers and in the spectra of the PMeOEP, PCL and PLA homopolymers turn out to be very similar. This clearly indicates the similarity between the conformational and phase compositions of PMeOEP, PCL and PLA parts in molecules of the copolymers and in the PMeOEP, PCL and PLA homopolymers. Experimental ratios of the peak intensities of PMeOEP bands at 737 and 2963 cm−1 and the PCL bands at 1109, 1724 and 2918 cm−1 can be used for the estimation of the PCL—b—PMeOEP copolymers chemical composition. Even though only one sample of the PMeOEP—b—PLA copolymers was experimentally studied in this work, we assume that the ratios of the peak intensities of PLA bands at 402, 874 and 1768 cm−1 and the PMeOEP band at 737 cm−1 can be used to characterize the copolymer chemical composition

Raman Spectroscopy Study of Structurally Uniform Hydrogenated Oligomers of α-Olefins

The expansion of the range of physico-chemical methods in the study of industrially significant α-olefin oligomers and polymers is of particular interest. In our article, we present a comparative Raman study of structurally uniform hydrogenated dimers, trimers, tetramers, and pentamers of 1-hexene and 1-octene, that are attractive as bases for freeze-resistant engine oils and lubricants. We found out that the joint monitoring of the disorder longitudinal acoustic mode (D-LAM) and symmetric C–C stretching modes allows the quantitative characterization of the number and length of alkyl chains (i.e., two structural characteristics), upon which the pour point and viscosity of the hydrocarbons depend, and to distinguish these compounds from both each other and linear alkanes. We demonstrated that the ratio of the contents of CH2 and CH3 groups in these hydrocarbons can be determined by using the intensities of the bands in the spectra, related to the asymmetric stretching vibrations of these groups. The density functional theory (DFT) calculations were applied to reveal the relations between the wavenumber and bandshape of the symmetric C–C stretching mode and a conformation arrangement of the 1-hexene and 1-octene dimers. We found that the branched double-chain conformation results in the splitting of the C–C mode into two components with the wavenumbers, which can be used as a measure of the length of branches. This conformation is preferable to the extended-chain conformation for hydrogenated 1-hexene and 1-octene dimers