Spin Crossover [Fe(qsal)2]X (X = Cl, SCN, CF3SO3) Complexes: EPR and DFT Study

The compounds [Fe(qsal)2]X (X = Cl, SCN, CF3SO3) were synthesized and investigated by electron paramagnetic resonance (EPR). The dependence of the Fe(III) spin state on the type of counterion X and on the temperature was established. On the basis of the density functional calculations, the geometrical parameters of compounds in high- and low-spin states were optimized and the difference in their internal energies was calculated. A correlation between the experimental EPR data and the theoretically calculated energy difference between the high-spin and the low-spin states of the compounds with different anions was obtained. © 2010 Springer-Verlag

The current status of orbital experiments for UHECR studies

Two types of orbital detectors of extreme energy cosmic rays are being developed nowadays: (i) TUS and KLYPVE with reflecting optical systems (mirrors) and (ii) JEM-EUSO with high-transmittance Fresnel lenses. They will cover much larger areas than existing ground-based arrays and almost uniformly monitor the celestial sphere. The TUS detector is the pioneering mission developed in SINP MSU in cooperation with several Russian and foreign institutions. It has relatively small field of view (+/-4.5 deg), which corresponds to a ground area of 6.4x10^3 sq.km. The telescope consists of a Fresnel-type mirror-concentrator (~2 sq.m) and a photo receiver (a matrix of 16x16 photomultiplier tubes). It is to be deployed on the Lomonosov satellite, and is currently at the final stage of preflight tests. Recently, SINP MSU began the KLYPVE project to be installed on board of the Russian segment of the ISS. The optical system of this detector contains a larger primary mirror (10 sq.m), which allows decreasing the energy threshold. The total effective field of view will be at least +/-14 degrees to exceed the annual exposure of the existing ground-based experiments. Several configurations of the detector are being currently considered. Finally, JEM-EUSO is a wide field of view (+/-30 deg) detector. The optics is composed of two curved double-sided Fresnel lenses with 2.65 m external diameter, a precision diffractive middle lens and a pupil. The ultraviolet photons are focused onto the focal surface, which consists of nearly 5000 multi-anode photomultipliers. It is developed by a large international collaboration. All three orbital detectors have multi-purpose character due to continuous monitoring of various atmospheric phenomena. The present status of development of the TUS and KLYPVE missions is reported, and a brief comparison of the projects with JEM-EUSO is given.Comment: 18 pages; based on the rapporteur talk given by M.I. Panasyuk at ECRS-2014; v2: a few minor language issues fixed thanks to the editor; to be published in the proceeding

Time-resolved EPR study of radicals from 2,2-dimethoxy-2-phenylacetophenone in ethylene glycol after flash photolysis

The dynamic behaviour of transient free radicals generated by laser pulse photolysis (with λ = 351 nm) of 2,2-dimethoxy-2-phenylacetophenone (DMPA) in ethylene glycol solutions have been studied by time-resolved EPR at room temperature. A main result of the study is a suitable evaluation method for radical systems with CIDEP in the case of very close hyperfine lines and hence with a overlap of several signals. The evaluation of single EPR time-profile signals requires in this case to take in account also the influence of the near resonance positions, what successfully has been done. The formation and decay of the two spin polarized radicals, 7,7-dimethoxy-benzyl (R1) and benzoyl radical (R2), has been observed. For R1 the relaxation time T2 was determined with a good accuracy and the rate constants k1 and k2 were estimated by fitting the time evolution of the EPR signal at resonance and near resonance positions of the field using the Bloch equations and direct Fourier transform analysis. Radicals from DMPA in the high viscous solvent ethylene glycol have been proved to be an excellent model system for this study however the treatment is applicable also for other systems. © 2002 Elsevier Science B.V. All rights reserved

Complexation and ligand exchange in aqueous of Cu(II) and Ni(II) with hydrazides of some aromatic acids

Solvation and complexation of Cu(II) and Ni(II) with benzoic (L′), p-methoxybenzoic (L″), and isonicotinic (L) acid hydrazides in aqueous-ethanol solutions (ethanol mole fraction 0.07-0.68) were studied by pH-metry, spectrophotometry, and nuclear magnetic relaxation. The formation constants of the species M(L′)2+, M(L′) 2 2+ , M(L″)2+, M(L″) 2 2+ , M(LH)3+, M(L)2+, M(L)(LH)3+, and M(L) 2 2+ , where M = Cu2+ and Ni2+, were determined. With isonicotinic acid hydrazide, a change in the coordination mode was observed in an isomer of Cu(L) 2 2+ , with one of the ligands coordinating in the bidentate fashion, and the other, in the monodentate fashion via the pyridine nitrogen atom. The suggested structures were confirmed by analysis of the parameters of the ESR and electronic absorption spectra of the complexes. The rate constants of ligand exchange and formation of the complexes Cu(L′)2+, Cu(L′) 2 2+ , Cu(L″)2+, and Cu(L″) 2 2+ in aqueous solutions were determined from nuclear magnetic relaxation measurements; the reactions occur by the associative mechanism. A cyclic process of reduction of Cu(II) to colloidal copper in the presence of L″ and atmospheric oxygen is described. © Pleiades Publishing, Inc., 2006

Accelerated Recovery Protocol in Extended Combined and Single-Stage Surgery for Pelvic Cancer

Introduction. The study aimed to evaluate a routine accelerated recovery management in patients with extended combined pelvic surgery.Materials and methods. We surveyed the records and outcomes in various oncological patients following the accelerated recovery protocol after a routine extended combined pelvic surgery at the Moscow City Oncology Hospital No. 1 during 2018–2020.Results and discussion. Locally advanced tumours comprised 37 (75.5 %) cases, and the remaining 12 (24.5 %) were nonpelvic resections due to metastasis. Radical surgery was achieved in 41 (83.7 %) cases, while the other 8 (16.3 %) were symptomatic due to the emerged complications of intestinal permeability disruption, bleeding, urinary obstruction, paracancrotic abscess, internal fistulae or pain syndrome. Postoperative complications were evaluated in the Clavien-Dindo classification.Conclusion. The results obtained suggest the feasibility of an accelerated recovery protocol-based practice in extended combined pelvic surgery

Seasonal changes of free-radical initiated processes in cyprinids from the middle Volga river basin

The purpose of this research was to study the free radical induced lipid oxidation in the commonest fish species inhabiting the Volga river, in the Middle Volga region of the Russian Federation, de-pending on the seasons of the year. The commonest fish species in the Volga river basin: European carp Cyprinus carpio (L., 1758), sabrefish Pelecus cultratus (L., 1758), common bream Abramis brama (L., 1758), tench Tinca tinca (L., 1758), and common roach Rutilus rutilus (L., 1758) were studied. The level of malondialdehyde and the activity of catalase were investigated in gills, liver, muscles and gonads. The values of molecular oxidative biomarkers in the studied fish species were significantly higher in the summer, suggestinga more active lipid peroxidation. The increase in cata-lase activity in the studied organs may indicate activation of the antioxidant defense system that can positively affect the growth and development of fish

Time-resolved ESR studies on transient radicals photogenerated in solutions of melamine in ethylene glycol

Chemically Induced Dynamic Electron Polarization (CIDEP) spectra of transient radicals generated by laser pulse with λ = 248 nm in solutions of melamine in ethylene glycol have been studied by means of time-resolved (TR) ESR at room temperature. The main products are radicals of the solvent molecules formed through abstraction of hydrogen from ethylene glycol by excited melamine molecules and a melamine radical with attached hydrogen atom on melamine. Parameters obtained from well resolved TR ESR spectra coincide with parameters of radical of ethylene glycol HOC{radical dot}HCH2OH and methylol {radical dot}CH2OH, and an unresolved ESR spectrum was attributed to the melamine radical. The electron spin polarization results from the radical pair mechanism (RPM) involving S-T0 mixing (ST0M) and additionally from a small part of triplet mechanism (TM). In order to establish the possible structure and nature of melamine radical quantum-chemical calculations by the DFT B3LYP method using several different basis sets have been done. The reaction pathway and mechanisms of alcohol and melamine radicals formation are proposed and supported by DFT calculations within B3LYP and CIS(D) methods. Melamine and ethylene glycol free radicals relaxation time T2 was estimated as 1.5 and 0.5 μs, respectively. © 2005 Elsevier B.V. All rights reserved

Electron spin resonance study of radicals generated in cellulose/N- methylmorpholine solutions after flash photolysis at 77 K

The processes of radical formation in N-methylmorpholine-N-oxide monohydrate (NMMO) and cellulose/NMMO solutions were studied by ESR at 77 K under high-power UV (λ = 248 nm) excimer laser flash photolysis. Radicals mainly generated were attributed to the nitroxide type radicals -CH 2-NO.-CH2- and -CH2-NO .-CH3 at the first step and methyl .CH 3 and formyl .CHO radicals at the second step of the photoreaction. Kinetic studies of these radicals revealed that formation and recombination rates of the radicals depend on the cellulose concentration in cellulose/NMMO solutions and the concentration of additional ingredients, e.g. Fe(II) and propyl gallate. Even at frozen state temperature, acceleration or quenching of radical reaction processes was found. The proposed scheme of UV light-induced NMMO degradation during irradiation based on ESR data correlates well with independently obtained results based on high-performance liquid chromatography (HPLC). The analysis of degradation products by HPLC, e.g. aminoethanol and acetaldehyde, supports the assumption concerning a radical-initiated ring opening of NMMO. Copyright © 2006 John Wiley & Sons, Ltd

Coordination diversity of N-phosphoryl-N′-phenylthiourea (LH) towards CoII, NiII and PdII cations: Crystal structure of ML2-N,S and ML2-O,S chelates

Thiourea, PhNHC(S)NHP(O)(OPri)2 (LH) chelates of CoII, NiII, and PdII ions have been obtained and investigated by single-crystal X-ray diffraction, UV, IR, NMR spectroscopy, and EI mass-spectrometry. The unusual 1,3-N,S-coordination via sulfur and NP(O) nitrogen atoms has been found in the trans-square-planar NiL2 and PdL2 complexes, whereas the 1,5-O,S-coordination is realized in the tetrahedral CoL2 complex. DFT calculations have revealed significant stabilization of the 1,3-N,S-structures due to stronger crystal field and the NH-O{double bond, long}P hydrogen bonds. © 2006 Elsevier B.V. All rights reserved