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81.
Kalina Kostova Vladimir Dimitrov Svetlana Simova Manfred Hesse 《Helvetica chimica acta》1999,82(9):1385-1399
The allylic and homoallylic alcohols 1 – 8 , prepared from (+)-camphor and (−)-fenchone, were ozonized in Et2O at −78° and treated with Et3N or LiAlH4 to give the chiral hydroxy carbonyl compounds 9 – 16 and the diols 17 – 24 , respectively (Scheme 1). In the case of the diols 19 and 24 , the formation of new chiral centers proceeded with high diastereoselectivity. These diols were prepared highly diastereoselectively also by LiAlH4 reduction of the hydroxy carbonyl compounds 11 and 16a , respectively (Scheme 2). The absolute configuration of the new chiral centers in 19 and 24 was determined by X-ray and NMR methods. The ozonization of compounds 2 , 3 , 7 , and 8 provided the relatively stable hydroxy-substituted 1,2,4-trioxolane derivatives (ozonides) 37 – 40 (Scheme 5) which were characterized by 1H- and 13C-NMR spectra, ESI-MS, and natural-abundance 17O-NMR spectra. 相似文献
82.
Electrochemical properties and radical anions of carbocycle‐fluorinated quinoxalines and their substituted derivatives
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Leonid A. Shundrin Irina G. Irtegova Nadezhda V. Vasilieva Pavel A. Avrorov Natalia Yu. Selikhova Arkady G. Makarov Alexander Yu. Makarov Yuri G. Slizhov Andrey V. Zibarev 《Journal of Physical Organic Chemistry》2017,30(8)
Electrochemical reduction (ECR) and oxidation (ECO) of 5,6,7,8‐tetrafluoroquinoxaline ( 1 ) and its derivatives bearing various substituents R (7‐H ( 2 ), 7,8‐H2 (3 ), 6‐CF3 ( 4 ), 6‐Cl ( 5 ), 5,7‐Cl2 ( 6 ), 5‐NH2 ( 7 ), 6‐OCH3 ( 8 ), 6,7‐(OCH3)2 ( 9 ), 6,7,8‐(OCH3)3 ( 10 ), 5,6,7,8‐(OCH3)4 ( 11 ), 6‐OCH3,7‐N(CH3)2 ( 12 ), 6‐N(CH3)2 ( 13 ), 6,7‐(N(CH3)2)2 ( 14 ), 5,6,7‐(N(CH3)2)3 ( 15 ), and 7,8‐cyclo‐(=CF‐CF = CF‐CF=) ( 16 )) in the carbocycle have been studied by cyclic voltammetry in MeCN. For 1 – 4 and 7 – 15 , the first reduction peaks have been found to be 1‐electron and reversible, thus corresponding to the formation of their radical anions (RAs), which are long lived at 295 K except those of 4 – 6 and 15 , 16 . Irreversible hydrodechlorination has been observed for 5 and 6 at the first step of their ECR confirmed by EPR detection of corresponding RAs of 2 and 5,7‐H2 derivative of 1 ( 17 ) at the next steps. Electrochemically generated RAs of 1 – 3 , 7 – 14 , and 17 have been characterized in MeCN by EPR spectroscopy together with DFT calculations at the (U)B3LYP/6‐31 + G(d) level of theory using PCM to describe the solvent. A noticeable alternation of spin density on the –NCCN– moiety of quinoxaline has been observed for all RAs possessing R‐substitution asymmetry. The comparative electron‐accepting ability of 1 – 15 has been analyzed in terms of their experimental reduction peak potentials and the (U)B3LYP/6‐31 + G(d)‐calculated gas‐phase first adiabatic electron affinities (EAs). The differences in electron transfer solvation energies for 1 – 15 have been evaluated on the basis of ECR peaks' potentials and calculated gas‐phase EAs. The ECO of 1 – 5 and 7 – 14 has been found to be irreversible. 相似文献
83.
84.
Nadezhda V. Dokhlikova Maxim V. Grishin Sergey V. Doronin 《International journal of quantum chemistry》2024,124(1):e27242
Calculations showed that hydrogen adsorption into subsurface sites is most likely to occur on Au (110) and (211) faces. The presence of low-coordinated Au atoms on significantly reduces the barrier of subsurface adsorption of H. The barriers of H surface diffusion increase in the following Au series: (110) < (111) < (100) < (211). An analysis of the dependence of the surface diffusion barriers on the electronic structure of gold atoms on the respective faces revealed a U-shaped dependence of the centers of the s- and d-bands. This dependence is the result of the filling of the s- and d-bands on different faces of the gold. The results obtained suggest that it is possible to use band centers to determine surface diffusion barriers. 相似文献
85.
Japaridze NJ Okuneva VG Qsovreli MG Surmava AG Lordkipanidze TG Kiladze MT Zhvania MG 《Micron (Oxford, England : 1993)》2012,43(9):948-953
Porosomes are the universal secretory machinery in cells, where membrane-bound secretory vesicles transiently dock and fuse to release intravesicular contents to the outside of the cell during cell secretion. Studies using atomic force microscopy, electron microscopy, electron density and 3D contour mapping, provided rich nanoscale information on the structure and assembly of proteins within the neuronal porosome complex in normal brain. However it remains uncertain whether pathological conditions that alter process of neurotransmission, provoke alterations in the porosome structure also. To determine if porosomes are altered in disease states, the current study was undertaken for first time using high resolution electron microscope. One of pathologies that produce subtle alteration at the presynaptic terminals has been demonstrated to be hypokinetic stress. The central nucleus of amygdale is the brain region, where such alterations are mostly expressed. We have examined the width and depth of the neuronal porosome complex and their alterations provoked by chronic hypokinetic stress in above mentioned limbic region. Specifically, we have demonstrated that despite alterations in the presynaptic terminals and synaptic transmission provoked by this pathological condition in this region, the final step/structure in neurosecretion--the porosome--remains unaffected: the morphometric analysis of the depth and diameter of this cup-shaped structure at the presynaptic membrane point out to the heterogeneity of porosome dimensions, but with unchanged fluctuation in norm and pathology. 相似文献
86.
D. Kostova 《Russian Journal of Inorganic Chemistry》2012,57(12):1593-1598
The system manganese(VII)-3,7-bis(dimethylamino)-phenothiazin-5-ium chloride (MB)-water-1,2-dichloroethane has been studied using UV-spectrophotometry. The molar absorptivity of the complex is (3.86 ± 0.06) × 104 L mol?1 cm?1 at 290 nm and the system obeys Beer??s law in the range 0.1?C0.99 ??g mL?1 Mn(VII). The detection limit (DL) and quantitation limit (QL) of Mn(VII) determination were found to be 0.0146 and 0.049 ??g mL?1, respectively. The composition of the complex is established as MB: MnO 4 ? = 1: 1. Extraction investigations of the system discussed were carried out. The characteristic values for the extraction equilibrium and the equilibrium in the aqueous phase was determined: extraction constant Kex = (1.12 ± 0.05) × 105, distribution constant KD = 75.61 ± 0.1 and association constant ?? = (1.48 ± 0.08) × 103. A new method has been developed for the microdetermination of manganese(VII) in plants and steels. 相似文献
87.
Iosif V. Gofman Ivan V. Abalov Svetlana V. Gladchenko Nadezhda V. Afanas'eva 《先进技术聚合物》2012,23(3):408-413
The mechanical characteristics and thermal properties of composite films based on the thermally stable aromatic polyimide (PI) (PMDA‐ODA) and carbon nanocones/discs (CNC) were studied. The introduction of CNC to PMDA‐ODA leads to the substantial increase of film stiffness. The Young's modulus values of the composite films are somewhat higher than those of the previously characterized composite films of this PI filled with nanoclay, carbon nanofibers, and asbestos‐like hydrosilicate nanotubes. The introduction of CNC into PMDA‐ODA (concentrations of CNC were up to 15 vol%) does not cause any marked aggregation of nanoparticles. The presence of CNC in the PI matrix does not affect the glass transition temperature of the polymer but hinders chain mobility at temperatures above Tg. This behavior makes it possible to increase the working temperature range of the composite films containing more than 5 vol% of CNCs, up to the temperature of thermal decomposition. The introduction of CNC into PMDA‐ODA leads to dramatic (~12 orders of magnitude) increase of active electrical conductivity of the material. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
88.
Alexander N. Titov Ingrid Bryntse Svetlana G. Titova Nadezhda V. Toporova 《Solid State Ionics》2001,140(3-4):293-300
The reaction between metallic Ag and PbS1.18(TiS2)n, n=1, 2, misfit layer compounds has been investigated by electrochemical technique, X-ray powder analysis and transmission electron microscopy. It was found that silver intercalation is possible only in the compound with n=2. The thermodynamic behavior and location of phase boundaries were studied in the temperature range 400–650 K. DC-conductivity and magnetic-susceptibility measurements were performed, and the data can be interpreted as an appearance of small polarons during silver insertion. 相似文献
89.
Nadezhda Rangelova Lachezar Radev Sanchi Nenkova Isabel M. Miranda Salvado Maria H. Vas Fernandes Michael Herzog 《Central European Journal of Chemistry》2011,9(1):112-118
Methylcellulose (MC) / SiO2 organic / inorganic hybrid materials have been prepared from MC and methyltriethoxysilane or ethyltrimethoxysilane, and characterized
by XRD, FTIR and AFM. XRD showed peak shifts. FTIR shows intermolecular hydrogen bonding between MC and SiO2. AFM depicts surface roughness which depends on the silica precursor and MC content.
相似文献
90.
Polina Angelova Kalina Kostova Karsten Hinrichs Dimiter Tsankov 《Central European Journal of Chemistry》2005,3(4):658-667
New 4-substituted benzyl esters of 16-mercaptohexadecanoic acid were prepared by developing a practicable synthetic procedure
and using readily available staring materials. The compounds synthesized have been characterized by NMR, MS, IR spectra and
elemental analysis. The mercapto derivatives are precursors for the formation of self-assembled monolayers on metal substrates.
Dedicated to Professor Dr. Manfred Hesse on the occasion of his 70
th
birthday 相似文献