Calcium-selective electrodes based on calcium tetra(4-chlorophenyl)borate complexes of macrocyclic polyether diamides

The preparation of macrocyclic 7,19-dibenzyl-7,19-diaza-1,4,10,13,16-pentaoxa-cycloheneicosane-6, 20-diones substituted in positions 2 and 3 with methyl groups, and their properties in PVC membranes as calcium sensors are described. Complexes of these polyether diamides (PEDA) with calcium and tetra(4-chlorophenyl)borate (TClPB) ions having the composition 2PEDA·Ca·2TClPB were prepared. Calcium electrodes based on these complexes have selectivity coefficients for calcium over barium up to 10³, and over alkali metals up to 3 × 10⁴.     

Preparation and NMR spectra of substituted 2-phenyl-5,5-dialkylimidazolinones

Eighteen substituted 2-phenyl-5,5-dialkylimidazolinones 2 have been prepared by cyclizations of substituted 2-(N-benzoylamino)alkanamides 1. The cyclization of methylamides 1 proceeds at room temperature whereas primary amides are cyclized on boiling. The ¹H and ¹³C nmr spectra of the imidazolinones are presented and the changes in their spectra connected with their protonation in hexadeuteriodimethyl sulfoxide-trifluoroacetic acid mixtures are discussed.     

Perturbation theory for open-shell systems: Simulation of the UHF states by means of the perturbed RHF wave functions

Second-, third-, and selected fourth-order contributions to the correlation energy were calculated for a series of simple open-shell systems by means of the previously developed double-perturbation theory in the restricted MO formalism. It was found possible to assign some of the diagrams to self-consistency effects and to approximate in this way the E – E energy difference. A comparison is made with a more rigorous approach, in which the UHF ground-state wave function is expressed as a first-order perturbation expansion based on the RHF reference wave function. Distinguishing between “self-consistency” and “correlation” diagrams for open-shell systems in the RHF formulation represents a special case of a more general problem met in any double-perturbation treatment, such as, e.g., treatments of systems in the external field or perturbation expansions with noncanonical orbitals.     

Asymmetric synthesis of [7]helicene-like molecules

[reaction: see text] A new approach to nonracemic [7]helicene-like molecules has been developed. Stereoselective Co(I)-mediated [2 + 2 + 2] cycloisomerization of aromatic triynes containing an asymmetric carbon atom produces [7]helicene-like scaffolds in diastereomeric ratios up to 100:0. This central-to-helical chirality transfer can be controlled by the absolute configuration at the asymmetric center and by the presence of carbon substituents.     

Synthesis of protected peptides from the human IgG1 hinge region on PEG support using disulfide bond synthons and alkaline or enzymatic detachment

Peptides from the hinge region of human IgG1 are potential defined carriers of synthetic immunogens. Their synthesis was carried out on the soluble support—PEG-OMe 2000 using disulfide bond synthons. The loading capacity of the polymer was increased twofold by anchoring the lysine as a simple branching unit. The amino acid leucine was used as an enzymatically cleavable linker. Peptide detachment from the polymer was performed either by classical ester bond saponification or newly by peptide bond cleavage catalyzed by thermolysin in water.     

Chronoamperometric stripping analysis following biocatalytic preconcentration

Electrodes containing glucose oxidase or xanthine oxidase adsorbed on modified glassy carbon electrodes or on conductive complexes, accumulate charge in the presence of substrates, the discharge of which gives the chronoamperometric stripping current. This current is 15 times higher than the stationary current after preconcentration for 8 min. A ten-fold increase in sensitivity of the determination of glucose or hypoxanthine is observed. The stripping current of electrodes based on cytochrome b₂ adsorbed on a graphite electrode is 25 times higher than the stationary current. The electrode is useful for lactate determinations for more than 7 days.     

Structural basis for recognition of bacterial cell wall teichoic acid by pseudo-symmetric SH3b-like repeats of a viral peptidoglycan hydrolase

Endolysins are bacteriophage-encoded peptidoglycan hydrolases targeting the cell wall of host bacteria via their cell wall-binding domains (CBDs). The molecular basis for selective recognition of surface carbohydrate ligands by CBDs remains elusive. Here, we describe, in atomic detail, the interaction between the Listeria phage endolysin domain CBD500 and its cell wall teichoic acid (WTA) ligands. We show that 3′O-acetylated GlcNAc residues integrated into the WTA polymer chain are the key epitope recognized by a CBD binding cavity located at the interface of tandem copies of beta-barrel, pseudo-symmetric SH3b-like repeats. This cavity consists of multiple aromatic residues making extensive interactions with two GlcNAc acetyl groups via hydrogen bonds and van der Waals contacts, while permitting the docking of the diastereomorphic ligands. Our multidisciplinary approach tackled an extremely challenging protein–glycopolymer complex and delineated a previously unknown recognition mechanism by which a phage endolysin specifically recognizes and targets WTA, suggesting an adaptable model for regulation of endolysin specificity.

Combining genetic, biochemical and computational approaches, we elucidated the molecular mechanisms underlying the recognition of Listeria wall teichoic acid by bacteriophage-encoded SH3b repeats.     

Influence of γ-radiation on the properties of Langmuir-Blodgett films of poly (3-hexadecylthiophene) in interaction with selected environment-polluting gases

The influence of -radiation on the electric properties of Langmuir-Blodgett (LB) films of partially iodine-doped poly-(3-hexadecylthiophene) and stearic acid in interaction with selected environment-polluting gases has been studied. CO₂, CO and NO₂ increase the LB films conductivity and NO has a tendency to decrease the electric conductivity. The influence of -radiation was expressive onyl in the case of CO₂, whereas NO₂ brought about degradation of the conductive polymer.     

Template evaporation method for controlling anatase nanocrystal size in ordered macroporous TiO2

The importance of pure-phase titanium oxide materials as catalysts, sensors, and photonic band-gap materials has been growing steadily. Recently, more attention has been focused on nanostructured titanium oxide showing controlled and periodic porosity on a nanometric scale. The nanocrystal size control of porous nanostructured titanium oxide in an anatase form is a crucial step for the organic template method. Simple template removal by evaporation in an inert atmosphere is reported in this article and compared with the calcination technique usually reported in the literature. The proposed method allows the formation of a double-porous (macro and meso) anatase phase. We demonstrate that it highly preserves the macropore order into a titanium oxide material and induces narrowly dispersed mesopores by controlling the nano-crystal size that is kept around 6 nm. For the proposed method, polystyrene beads are particularly suitable as templates, being evaporated in the temperature range of anatase existence. The final high surface area makes the materials appealing for applications as photocatalysts or sensors.     

Mercury(II) complex with terpyridine: structure of the 2∶1 solvate of [Hg(terpy)2](CF3SO3)2 with acetone

[Hg(terpy)₂](CF₃SO₃)₂·0.5(CH₃)₂CO crystallizes in the triclinic space group witha=14.631(6),b=15.258(4),c=18.785(7) Å, =69.66(2), =70.72(1), =88.55(1)°. The crystal structure consists of two independent [Hg(terpy)₂]²⁺ cations, four trifluoromethanesulfonate anions and an acetone molecule in the asymmetric unit. Each mercury atom is coordinated by two tridentate terpyridine ligands forming an irregular six-coordination polyhedron. The Hg–N bond lengths range from 2.27(2) to 2.53(2) Å.