Fluoride-selective polymeric membrane electrodes based on Zr(IV)- and Al(III)-salen ionophores of various structures

Al(III)- and Zr(IV)-salophens of novel structures were tested as anion-selective ionophores. It was shown that these compounds are highly selective to fluoride and give selectivity greatly deviating from classical Hofmeister pattern, when doped into the polymeric membrane of ion-selective electrode (ISE). The following selectivity sequence has been recorded for both ionophores: F⁻ > ClO₄⁻ > SCN⁻ > NO₃⁻ ≈ Br⁻ ≈ Cl⁻. The results of potentiometric and spectrophotometric measurements allow to conclude that the nature and structure of salophen ligands influence stability of ISE working parameters. An increase in salophen ligands lipophilicity results in prolongation of the ISE lifetime, most likely due to slower ionophore decomposition caused by the hydrolysis of imine bonds in salophen structure. Ion-selective electrodes (ISEs) with the most successful Al(III)-salophen exhibited a stable, fast and near-Nernstian fluoride response and a functional lifetime near 3 weeks and selectivity coefficients with as follows: −2.8 (Y⁻ = Br⁻), −2.7 (Cl⁻), −2.8 (NO₃⁻), −1.5 (SCN⁻), −1.3 (ClO₄⁻), which is better than for other ones based on Zr(IV)- and Al(III)-salophens and salens described to date.     

Dynamic Light Scattering and NMR Studies of Napin

We analyze the structure of napin (BngNAP1), a storage protein (m.w. 14.5 kDa) from Brassica napus. On the basis of the results of ¹H NMR spectroscopy and dynamic light scattering (DLS) studies, the overall shape and secondary structure of the molecule are estimated.     

Synthesis of unsymmetrical alkyl acetals via addition of primary alcohols to allyl ethers mediated by ruthenium complexes

Abstract  

Ru-catalyzed synthesis of mixed alkyl–alkyl acetals via addition of primary alcohols to allyl ethers has been extended to include long-chain and/or functionalized substrates. The catalytic systems for these reactions were generated from RuCl₂(PPh₃)₃ and [RuCl₂(1,5-COD)]_x and phosphines [PPh₃ or P(p-chlorophenyl)₃] or SbPh₃. Of particular importance is the almost quantitative elimination of transacetalization. The addition proceeds through allyl complexes, not via isomerization of allyl ethers––subsequent addition of ROH to vinyl ethers.     

The role of Mg<Subscript>2</Subscript>FeH<Subscript>6</Subscript> formation on the hydrogenation properties of MgH<Subscript>2</Subscript>-FeF<Subscript>x</Subscript> composites

The hydrogenation properties of magnesium hydride mechanically milled with iron fluorides (FeF₂ and FeF₃), were investigated by Temperature Programmed Desorption (TPD) and volumetric methods using a Sieverts-type apparatus, as prepared upon dehydrogenation and finally upon subsequent hydrogenation. The activation energy of hydrogen desorption (E_a), calculated from the Kissinger formula using TPD measurements obtained with different heating rates, showed significant decreases of Ea in comparison to that of milled MgH₂ without any dopants. Moreover, the influence of these metal fluorides on the thermodynamics of the decomposition process was also examined. In the case of the FeF₂ dopant, rehydrogenation following desorption caused the complete decomposition of the iron fluoride to BCC iron and the formation of a predominant MgH₂ phase. In contrast to FeF₂, the addition of FeF₃ led to the formation of β-MgH₂ as a major phase coexisting with Mg₂FeH₆ and MgF₂ compounds. The presence of pure Fe in the MgH₂+FeF₂ composite, as opposed to MgH₂+FeF₃ containing Mg₂FeH₆ and MgF₂, did not cause any significant influence on the sorption properties of MgH₂. Moreover, the original material doped with FeF₃ predominantly showed iron in the Mg₂FeH₆ compound, while the FeF₂ dopant iron mostly showed the nearly pure BCC metallic phase      

Synthesis of the four enantiomers of diethyl 1,2-di(N-Boc-amino)propylphosphonates

A simple and efficient synthetic strategy to all four enantiomerically pure diethyl 1,2-di(N-Boc-amino)propylphosphonates has been elaborated starting from the corresponding N-[(R)-(1-phenylethyl)]aziridine-(2S)- and N-[(S)-(1-phenylethyl)]aziridine-(2R)-carboxaldehydes, employing a one-pot three-components Kabachnik-Fields reaction followed by the hydrogenolytic removal of the chiral auxiliary and aziridine ring opening with simultaneous protection of the amino groups as the N-Boc derivatives.     

Lipase-catalyzed kinetic resolution approach toward enantiomerically enriched 1-(β-hydroxypropyl)indoles

In a route towards enantiomerically enriched 1-(β-hydroxypropyl)indoles, which are potentially useful building blocks for high value-added chemicals synthesis, a kinetic resolution approach by means of lipase-catalyzed enantioselective acylation as well as hydrolysis/methanolysis has been elaborated for the first time. The enzymatic resolution of chiral N-substituted indole-based sec-alcohols was successfully accomplished, yielding both enantiomeric forms of the employed derivatives with up to >99% enantiomeric purity via an enantioselective transesterification under mild reaction conditions. The most selective resolutions were obtained using fungal (CAL-B and TLL) and bacterial (PFL and BCL) lipases and vinyl acetate as the acyl?group donor. The synthetic protocol described herein is very simple, user-friendly and efficient, thus paving the way for future access towards more complex compounds of this type. The absolute configurations of novel enantiomeric derivatives, and thus stereoselectivity of the described enzymatic reactions were confirmed by application of CDA-based NMR methodology and single-crystal X-ray diffraction analysis.     

Development of zinc alkyl/air systems as radical initiators for organic reactions

This paper reports a series of comparative experiments on the activity of carbon- and oxygen-centred radical species in a model reaction of the radical addition of THF to imines mediated by a series of zinc alkyl/air reaction systems. The study strongly contradicts the notion that generally R˙ radicals are the initiating species in organic reactions mediated by R_nM/air systems, and simultaneously demonstrates that oxygen-centred radical species are the key intermediates responsible for the initiation process. In addition, a new efficient RZn(L)/air initiating system for radical organic reactions exampled by a model reaction of radical addition of THF to imines is developed. Moreover, the isolation and structural characterization of the first zinc alkylperoxide supported by a carboxylate ligand, [Zn₄(μ₃-OOtBu)₃(μ₄-O)(O₂CEt)₃]₂, as well as the novel octanuclear zinc oxo(alkoxide) aggregate with entrapped O–THF species, [Zn₄(μ₄-O)(μ₃-2-O–THF)(O₂CEt)₅]₂, provide clear mechanistic signatures for the mode of function of the RZn(O₂CR′)/air system.