Lewis Superacidic Divalent Bis(m-terphenyl)element Cations [(2,6-Mes2C6H3)2E]+ of Group 13 Revisited and Extended (E=B,Al, Ga,In, Tl)

In a combined experimental and computational study, the molecular and electronic structures of the divalent bis(m-terphenyl)element cations [(2,6-Mes₂C₆H₃)₂E]⁺ of group 13 ( 1 , E=B; 2 , E=Al; 3 , E=Ga; 4 , E=In; 5 , E=Tl) were investigated. The preparation and characterization of 2 , 3 and 5 were previously reported by Wehmschulte's (Organometallics 2004 , 23, 1965–1967; J. Am. Chem. Soc. 2003 , 125, 1470–1471) and our groups (Organometallics 2009 , 28, 6893–6901). The indinium ion 4 was prepared and fully characterized for the first time. Attempts to prepare the borinium ion 1 by fluoride or hydride abstraction were unsuccessful. The electronic structures of 1 – 5 and the stabilization by the bulky m-terphenyl substituents were analyzed using quantum chemical calculations and compared to the divalent bis(m-terphenyl)pnictogenium ions [(2,6-Mes₂C₆H₃)₂E]⁺ of group 15 ( 6 , E=P; 7 , E=As; 8 , E=Sb; 9 , E=Bi) previously investigated by our group (Angew. Chem. Int. Ed. 2018 , 57, 10080–10084). The calculated fluoride ion affinities (FIA) of 1–9 are higher than that of SbF₅, which classifies them as Lewis superacids.     

Photodegradation of soil organic matter and its effect on gram-negative bacterial growth

To learn more about the role of the reactive oxygen species (ROS) in the production of bioavailable products of the dissolved organic matter, we investigate here the effect of the photolysis (lambda(exc) > 320 nm) of a soil extract (SE) on the growth of bacteria isolated from the same soil as used for obtaining the extract. Comparative experiments with Aldrich humic acid (AHA) as substrate were performed. The photodegradation of the SE was evaluated with different techniques-UV-visible absorption spectroscopy, fluorescence excitation emission matrices (EEM) and Fourier transform infrared spectroscopy (FTIR). Known ROS scavengers were employed to study the effect of photochemically produced ROS on the photodegradation of the substrates. To evaluate the effect of irradiation on the bioavailability of the SE and AHA, photolyzed and nonphotolyzed substrates were added to different culture media and the growth of Pseudomonas sp. isolated from the soil and a strain of Escherichia coli were studied. The different results obtained were assigned to the dissimilar metabolisms of both bacteria.     

Bidirectional asymmetric allylboration. A convenient asymmetric synthesis of C(2)-symmetric 3-methylenepentane-1,5-diols and rapid access to C(2)-symmetric spiroketals

The double allylboration of aldehydes using 1, 3-bis(diisopinocampheylboryl)-2-methylenepropanes (R,R)-3 and (S, S)-3 under Brown's salt-free conditions provides C(2)-symmetric 3-methylenepentane-1,5-diols 1 in excellent enantiomeric excess. The absolute stereochemistry of the products was confirmed by a single-crystal X-ray study of bis-Mosher ester 6g. Desymmetrization and further functionalization of diol 1a were achieved by treatment of the bis-BOC carbonate 13 with IBr in toluene at -80 degrees C to give cyclic iodocarbonate 14 as a single diastereomer. This methodology is also applicable in natural product synthesis; enantiomerically pure spiroketals 1,7-dioxaspiro[5.5]undecanes 18 and 25, the latter representing an expedient synthesis of the AB ring system of the spongistatins 20, were easily accessed from simple starting materials in excellent yields and selectivities.     

Synthesis of New Symmetric Disubstituted Dithioether Dithiols

Abstract

The β,β′-dihydroxydithioethers, derived from oxirane, have been converted into dithioethers dithiols in good yields. A colloidal solution of gold nanoparticles (AuNPs) with 5,8-dithiadodecane-3,10-dithiol was prepared and showed a good stability from tight binding offered by the thiol group on the Au surfaces.     

Thinking wants to be organized

Can the describable complexity of test problems concerning mathematical thinking and the empirical results of their dealing with be put into a relation? Can graded test problems be constructed which lead to results which can basically be predicted? Empirical studies give interesting and helpful answers which lead to didactically important consequences, just like the evaluation of the PISA results.     

Universal Algorithm for Simulating and Evaluating Cyclic Voltammetry at Macroporous Electrodes by Considering Random Arrays of Microelectrodes

An algorithm for the simulation and evaluation of cyclic voltammetry (CV) at macroporous electrodes such as felts, foams, and layered structures is presented. By considering 1D, 2D, and 3D arrays of electrode sheets, cylindrical microelectrodes, hollow-cylindrical microelectrodes, and hollow-spherical microelectrodes the internal diffusion domains of the macroporous structures are approximated. A universal algorithm providing the time-dependent surface concentrations of the electrochemically active species, required for simulating cyclic voltammetry responses of the individual planar, cylindrical, and spherical microelectrodes, is presented as well. An essential ingredient of the algorithm, which is based on Laplace integral transformation techniques, is the use of a modified Talbot contour for the inverse Laplace transformation. It is demonstrated that first-order homogeneous chemical kinetics preceding and/or following the electrochemical reaction and electrochemically active species with non-equal diffusion coefficients can be included in all diffusion models as well. The proposed theory is supported by experimental data acquired for a reference reaction, the oxidation of [Fe(CN)₆]⁴⁻ at platinum electrodes as well as for a technically relevant reaction, the oxidation of VO₂⁺ at carbon felt electrodes. Based on our calculation strategy, we provide a powerful open source tool for simulating and evaluating CV data implemented into a Python graphical user interface (GUI).     

Zeaxanthin Production by Novel Marine Isolates from Coastal sand of India and its Antioxidant Properties

Zeaxanthin carotenoids are class of commercially important natural products and diverse biomolecules produced by plants and many microorganisms. Bacteria often produce a cocktail of polar and nonpolar carotenoids limiting their industrial applications. Marine members of the family Flavobacteriaceae are known to produce potential carotenoids such as astaxanthin and zeaxanthin. A few bacterial species have been reported for the predominant production zeaxanthin. Here, we report the molecular identification of the zeaxanthin as a major carotenoid produced by two novel bacteria (YUAB-SO-11 and YUAB-SO-45) isolated from sandy beaches of South West Coast of India and the effect of carbon sources on the production of zeaxanthin. The strains were identified based on the 16S rRNA gene sequencing as a member of genus Muricauda. The closest relatives of YUAB-SO-11 and YUAB-SO-45 were Muricauda aquimarina (JCM 11811^T) (98.9 %) and Muricauda olearia (JCM 15563^T) (99.2 %), respectively, indicating that both of these strains might represent a novel species. The highest level of zeaxanthin production was achieved (YUAB-SO-11, 1.20?±?0.11 mg g^?1) and (YUAB-SO-45, 1.02?±?0.13 mg g^?1) when cultivated in marine broth supplemented with 2 % NaCl (pH 7) and incubated at 30 °C. Addition of 0.1 M glutamic acid, an intermediate of citric acid cycle, enhanced the zeaxanthin production as 18 and 14 % by the strains YUAB-SO-11 and YUAB-SO-45 respectively. The zeaxanthin showed in vitro nitric oxide scavenging, inhibition of lipid peroxidation, and 2,2-diphenyl-1-picryl hydrazyl scavenging activities higher than the commercial zeaxanthin. The results of this study suggest that two novel strains YUAB-SO-11 and YUAB-SO-45 belonging to genus Muricauda produce zeaxanthin as a predominant carotenoid, and higher production of zeaxanthin was achieved on glutamic acid supplementation. The pigment showed good in vitro antioxidant activity, which can be exploited further for commercial applications.