Orientation-selected 15N-HYSCORE detection of weakly coupled nitrogens around the archaeal rieske [2Fe-2S] center

The weakly coupled 15N atoms around a reduced Rieske [2Fe-2S] cluster of the uniformly 15N-labeled, hyperthermostable archaeal Rieske protein appear to produce readily observable cross-peaks in the HYSCORE spectra, with the well-resolved couplings of 0.3-0.4 MHz for the Nepsilon and 1.1 MHz for the peptide backbone nitrogens, in addition to the contributions from the coordinated Ndelta atoms. These features can be used for structure-mechanism studies of the biological redox protein system involving the weakly coupled nitrogens in coupled electron-proton transfer reactions.     

Copper (II) complexes of sterically hindered o-diphenol derivatives: synthesis, characterization and microbiological studies

Cu (II) complexes with the sterically hindered diphenol derivatives 3,5-di(tert-butyl)-1,2-benzenediol (I), 4,6-di(tert-butyl)-1,2,3-benzenetriol (II) and the sulfur-containing 4,6-di(tert-butyl)-3-(2-hydroxyethylsulfanyl)-1,2-benzenediol (III) and 2-[4,6-di(tert-butyl)-2,3-dihydroxyphenylsulfanyl]acetic acid (IV) have been synthesized and characterized by elemental analysis, TG/DTA, FT-IR, ESR, XPS, XPD and conductivity measurements. Compounds I–III can coordinate in their singly deprotonated forms and act as bidentate ligands. These compounds yield Cu (II) complexes of the stoichiometry Cu(L)₂, which have square planar geometry (g_| > g_⊥ > g_e). Unlike them, compound IV behaves as a terdentate ligand, and its complex Cu(L^IV)₂ has distorted octahedral geometry. According to ESR data, only the Cu(L^II)₂ complex contains a very small amount of phenoxyl radicals. Antimicrobial activities of these ligands and their respective Cu (II) complexes have been determined with respect to Gram-positive and Gram-negative bacteria, as well as on yeasts. Their phytotoxic properties against Chlorella vulgaris 157 were also examined.     

Acylation through Ketene Intermediates

Carboxylic acids possessing a strong electron-withdrawing group in the alpha-position undergo facile dehydration upon reaction with carbodiimides to form the corresponding substituted ketenes that can react in situ with alcohols providing esters in a high yield. The ketene formed by the treatment of ethyl 2-methylmalonate with DCC was trapped in situ by a [4+2] cycloaddition with a second DCC molecule. The chemoselectivity of the acylation through the ketene intermediates was found to be substantially different from that of conventional acylation reagents showing a very low sensitivity toward the steric bulk of alcohols. A comparison of the sensitivity of the acylation to the steric bulk of alcohols supports the presence of a pseudopericyclic pathway for the nucleophilic addition of alcohols to ketenes derived from ethyl malonic and diethylphosphonoacetic acid.     

Decacyclene Radical Anions Showing Strong Low‐energy Intramolecular Absorption and Magnetic Coupling of Spins in a Hexagonal Network

Two salts of the aromatic hydrocarbon decacyclene, {cryptand[2.2.2](Cs⁺)} (decacyclene^.?) ( 1 ) and {Bu₃MeP⁺}(decacyclene^.?) ( 2 ), were obtained. In both salts, decacyclene^.? radical anions formed channels occupied by cations. However, corrugated hexagonal decacyclene^.? layers could be outlined in the crystal structure of 1 with several side‐by‐side C???C approaches. The decacyclene^.? radical anions showed strong distortion in both salts, deviating from the C₃ symmetry owing to the repulsion of closely arranged hydrogen atoms and the Jahn‐Teller effect. Radical anions showed intense unusually low energy absorption in the IR‐range, with maxima at 4800 and 6000 cm^?1. According to the carculations, these bands can originate from the SOMO‐LUMO+1 and SOMO‐LUMO+2 transitions, respectively. Radical anions exhibited a S=1/2 spin state, with an effective magnetic moment of 1.72 μ_B at 300 K. The decacyclene^.? spin antiferromagnetically coupled with a Weiss temperature of ?11 K. Spin ordering was not observed down to 1.9 K owing to spin frustration in the hexagonal decacyclene^.? layers.     

Monocyclic and Fused 4-Imino(4-Oxo)-1,3,2-Diazaphospholanes and - Phosphorinanes. Synthesis and Some Properties

Abstract

In contrast to the great variety of well known phosphorus heterocycles with exocyclic C=O double bond the number of ones containing exocyclic C=N bond is unusually modest. We elaborated the convenient method of preparation of various N,P,N-heterocycles with exocyclic C=N bond (1–4) from the readily available corresponding amino acid amidines and appropriated dichlorides or diamides of phosphorus (III) acids. Rings' 1–3 with P(III) are easily converted into (thio)phosphoryl derivatives, while the direct phosphorylation of amino amidines by RP(Y)Cl₂ is unusually ineffective. Tricycles 4 - derivatives of 2-(2-amino pheny1)imidazoline - mainly exist in the more conjugated hydrophosphazo tautomeric form 4b (>90 %).     

Poly(vinyl alcohol)/heteropolyacid nanocomposites as new materials for radiochromic dosimetry in radiation processing

Radiochromic films composed of polymer matrices and organic dyes are widely used for routine dosimetry purposes in operation of various radiation facilities—gamma and X-ray-irradiation, electron accelerators, and so on. However, the sensitivity of these films rapidly decreases at doses exceeding 30–50 kGy due to a saturation of their optical response, making them unsuitable for accurate dosimetry in radiation processing of polymers and composites where doses up to 200 kGy are typically employed. To overcome this limitation, the use of inorganic substances as the coloring agents of polymer-based radiochromic films was proposed in this paper, specifically, heteropolyacidacid H₃PW₁₂O₄₀ (tungstophosphoric acid) in the matrix of poly(vinyl alcohol) (PVA). Nanocomposite PVA/H₃PW₁₂O₄₀ films were prepared by solution casting and their optical responses toward ⁶⁰Co gamma radiation and beams of 6 MeV electrons for a dose range of 10–200 kGy were investigated. It was established that upon exposure to gamma rays and electron beams, the films turn blue and a broad absorption band at 750 nm appears in their spectra. Importantly, the radiation-induced optical absorption increases in a linear fashion up to the dose of 150 kGy and only slightly deviates from linearity at 200 kGy. Moreover, it was found that the PVA/H₃PW₁₂O₄₀ films have a long shelf life, are dose-rate independent within a wide range, and color-stable after irradiation. All these features make the nanocomposite PVA/H₃PW₁₂O₄₀ films promising for use as routine dosimeters and dose labels in a much wider range of high doses as compared to radiochromic films based on organic dyes.