ESR spectra of copper(ii) complexes with 2-hydroxy-5-methyl- and 5-chloro-2-hydroxyacetophenone acyldihydrazones

ESR spectra of binuclear copper(ii) complexes with 2-hydroxy-5-methyl- and 5-chloro-2-hydroxyacetophenone acyldihydrazones (H₄L) [Cu₂L·2Py], in which the coordination polyhedra are linked by the polymethylene chain with different lengths (from one to five units), were studied. The spectra of the complexes based on acyldihydrazones of malonic, succinic, glutaric, and adipic acids exhibit weak exchange interactions between the paramagnetic sites. These interactions induce seven HFS lines from two equivalent copper nuclei with the constant 40·10^–4 cm^–1 in the ESR spectra of liquid solutions. An increase in the polymethylene chain length to five units prevents the exchange interactions, and the ESR spectrum of the complex based on heptadioic acyldihydrazone contains the signal of four HFS lines with the constant 72·10^–4 cm^–1, which is common for the copper(ii) monomeric compounds.     

Radical-anions in the vicarious C-amination reactions of N-substituted nitrotriazoles

The vicarious nucleophilic substitution of hydrogen in symmetrical and vicinal nitrotriazoles by 1,1,1-trimethylhydrazinium iodide in t-BuOK/DMSO was studied by ESR. In the ESR monitoring of the reactions the primary radical-anions of 4-nitro-2-phenyl-1,2,3-triazole and 1-methyl-3-nitro-1,2,4-triazole were detected and characterized. It was shown by NMR that the amination of 4-nitro-2-phenyl-1,2,3-triazole takes place exclusively in the triazole ring with the formation of 5-amino-4-nitro-2-phenyl-1,2,3-triazole. 1-Methyl-3-nitro-1,2,4-triazole, like 3-nitro-1,2,4-triazole, does not form amination products. A possible mechanism for the vicarious C-amination of nitrotriazoles and the formation of the radical-anions of the substrates is discussed. Dedicated to Academician M. G. Voronkov on his 85th birthday. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1662–1670, November, 2006.     

Thermal degradation of the polymer obtained by oxidation of C60 fullerene by oleum

Degradation of (C₆₀) _n polymer and the C₁₂₀ and C₁₂₀O dimers at different temperatures was studied by IR and ESR spectroscopy. The formation of C₆₀ was revealed. The polymer stability was found to be higher than the stability of the dimers. Peculiar features of the IR spectra of three-dimensional hyper-crosslinked polymers obtained by liquid-phase polymerization of C₆₀ are discussed.     

ESR study of free radicals formed upon UV irradiation of nitropentafluoroacetone in various solvents

The formation of CF₃C(O)CF₂N(O^.)O₂CF₂C(O)CF₃ free radicals upon the UV irradiation of nitropentafluoroacetone (1) in toluene and mesitylene is established by ESR. The most likely cause of their formation is the one-electron oxidation of the solvents by photoexcited1 followed by decay of the radical anion formed from1 with the expulsion of an NO₂ anion and attachment of the radical to a molecule of original1. The irradiation of 1 in triethylsilane results in the elimination of a fluoride ion and fixation of a CF₃COCFN(O^–)O' radical. UV irradiation of ketone1 in pentane results in the abstraction of a hydrogen atom from the solvent and the formation of a CF₃COCF₂N(OH)O ' radical.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 512–514, March, 1993.     

High pressure treatment of pharmaceutical drug delivery and related systems

Abstract

Solids like layer silicates (kaolinite and montmorillonite) as well as ZnO are in use in pharmacy. They are pressure treated and subsequently analyzed by means of ESR spectroscopy. The structural changes indicated by Fe³⁺ ions and paramagnetic defects are reponsible for the enhanced chemical activity of the pressurized systems.

Especially active Fe-O-species are formed which can react with intercacalated organic molecules. The most probable first step of such reactions will be a solid state single electron transfer. Spin probes and spin traps were used to prove this statements. The activation of the drug delivery systems by mechanical treatments is of importance for the stability of the drugs incorporated.     

Single‐pulse pulsed laser polymerization–electron paramagnetic resonance investigations into the termination kinetics of n‐butyl acrylate macromonomers

The termination of model mid‐chain radicals (MCRs), which mimic radicals that occur in acrylate polymerization over a broad range of reaction conditions, has been studied by single‐pulse pulsed laser polymerization (SP‐PLP) in conjunction with electron paramagnetic resonance spectroscopy. The model radicals were generated by initiator‐fragment addition to acrylic macromonomers that were preformed prior to the kinetic experiments, thus enabling separation of termination from the propagation reaction, for these model radicals propagate sparingly, if at all, on the timescale of SP‐PLP experiments. Termination rate coefficients of the MCRs were determined in the temperature range of 0–60°C in acetonitrile and butyl propionate solution as well as in bulk macromonomer over the range of 0–100 °C. Termination rate coefficients slightly below those of the corresponding secondary radicals were deduced, demonstrating the relatively high termination activity of this species, even when undergoing MCR–MCR termination. For chain length of 10, a reduction by a factor of 6 is observed. Unusually high activation energies were found for the termination rate coefficient in these systems, with 35 kJ mol^?1 being determined for bulk macromonomer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Role of radicals in UV‐initiated postplasma grafting of poly‐ε‐caprolactone: An electron paramagnetic resonance study

Electron paramagnetic resonance (EPR) measurements were performed on poly‐ε‐caprolactone (PCL) films at different stages of the postplasma‐grafting process. PCL films prepared by solvent casting (SC) or electrospinning (ESP) yield very similar EPR spectra after Ar‐plasma treatment and subsequent exposure to air, but the EPR signal is much stronger in the PCL‐ESP films. The free radicals appear to be mainly, and possibly exclusively, oxygen centered. The radicals generated by UV irradiation in PCL‐ESP films were studied in situ with EPR, using a UV‐LED (λ = (285 ± 5) nm). Their EPR spectrum is distinctly different from the plasma‐induced signal, indicative of carbon‐centered radicals, and appears to be independent of the plasma pretreatment. UV‐induced homolytic splitting of (hydro)peroxide bonds was not observed. Both the plasma‐ and UV‐induced radicals decay at room temperature (RT), even in an inert atmosphere. This study demonstrates the potential of electrospun films and UV‐LEDs for the study of plasma‐ and UV‐generated free radicals with EPR in polyesters, and raises questions with respect to the validity of some generally accepted molecular mechanisms underpinning the postplasma grafting technique for polyesters. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Humic-based bionanocomposites containing stable paramagnetic gold nanoparticles for prospective use in pharmaceuticals

Structural peculiarities and supramolecular organization of medicinally promising nanocomposites, synthesized from humic substances, which essentially differ depending on decomposition degree, have been studied using electron spin resonance, transmission electron, and confocal laser scanning microscopy techniques and some other modern physical–chemical methods. It is shown that stable zero-valent gold nanoparticle of about 10–17?nm in size are formed in a natural macromolecular matrix. The nanocomposites obtained turn out to be stable in aggregative state for a long time and preserve their properties that are extremely important for prospective medicinal substances.     

Dosimetric and kinetic characteristics of watch glass sample

This paper reports the Electron Spin Resonance (ESR) and Thermoluminescence (TL) dosimetric and kinetic characteristics of commercial watch glass. Both of the ESR and TL response of the watch glass sample yielded linear behavior in the 0.5–135 Gy gamma dose range. ESR dosimetric properties of watch glass sample like dose-rate dependence, signal reproducibility and fading behavior have also been studied in detail. Kinetic behavior and activation energy of the radiation induced free radicals responsible from the ESR spectra of watch glass sample were determined. The TL kinetic parameters such as activation energy (E), frequency factor (s), order of kinetics (b) were also calculated by applying the methods of initial rise (IR), isothermal decay (ID), variable heating rate (VHR) and de-convolution.     

Evaluation of a Novel Dechlorination Reaction as an Analytically Useful Derivatization Reaction Part 1. Stoichiometry,Mechanism and Yield Optimization

Abstract

A novel reaction for the dechlorination of polychlorinated biphenyls (PCBs) as well as most other chlorinated aromatic and aliphatic compounds is evaluated and discussed in terms of its potential for analytical purposes. The active dechlorinating agent is prepared through the reaction of molten sodium or potassium with polyethylene glycols (MW >200), in the absence of oxygen, to form the corresponding alkali metal glycolate, a powerful nucleophilic agent. Special emphasis is given to the mechanistic aspects of the reaction and their importance in terms of achieving high and reproducible yields with analytical quantities of substrate, in short periods of time. The contribution of the techniques: ESR, NMR, IR, UV, MS, GC-ECD, LC-EC, CIDNP-NMR, conductimetry and chloride analysis (amperometric) in elucidating the reaction mechanism and providing valuable kinetic data is illustrated. This reaction can potentially be applied to the determination of PCBs in waste oils.