Spectroscopic study of vinylidene chloride—Vinyl chloride copolymers

Summary Deuteration technique was applied to study the micro structures of copolymer series VDC/VC by infrared spectroscopy and high resolution NMR. The CH₂ bending modes of chlorine atom containing polymers assigned as follows; –CCl₂CH₂CCl₂– 1405 cm^–1 (cryst.) and 1410 cm^–1 (amorph.), –CHClCH₂CCl₂– 1422 cm^–1, –CHClCH₂CHCl– 1428 cm^–1 (cryst.) and 1432 cm^–1 (amorph.) –CHClCH₂CH₂CHCl– 1445 cm^–1 and –CCl₂CH₂CH₂CCl₂– 1448 cm^–1. This infrared interpretation shows that only the head to tail addition occurs in the copolymerisation. Nine peaks of the methylene protons were observed clearly in the NMR spectra of the copolymers. The study of the deuterated copolymers revealed that the effects of the chemical groups until the third at both sides from the marked methylene and the stereo configuration of long VC part should be considered to assign the NMR spectra. The CCl₂ group made the chemical shift of the methylene proton to appear at lower magnetic field and the CHCl group gave the opposite behavior.

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Zusammenfassung Mit deuterierten Monomeren wurde die Mikrostruktur der Copolymerenserie Vinyliden-Chlorid/Vinyl-Chlorid im Infraroten und mit hochauflösender Kernresonanz untersucht. Für die Biegeschwingung der Chloratome enthaltenden Polymeren der Methylengruppe ergeben sich folgende Werte: –CCl₂CH₂CCl₂– 1405 cm^–1 (krist.) und 1410 cm^–1 (amorph.), –CHClCH₂CCl₂– 1422 cm^–1, –CHClCH₂CHCl– 1428 cm^–1 (krist.) und 1432 cm^–1 (amorph.), –CHClCH₂CH₂CHCl– 1445 cm^–1 und –CCl₂CH₂CH₂CCl₂– 1448 cm^–1.Diese Interpretation des Infraroten zeigt, daß nur die Kopf-Schwanz-Addition bei der Copolymerisation stattfindet. Neun Maxima des Methylenprotons wurden deutlich in den NMR-Spektren der Copolymeren beobachtet. Die Untersuchungen an den deuterierten Copolymeren zeigen, daß die Effekte der chemischen Gruppen bis zur dritten nach beiden Seiten vom markierten Methylen und die Stereokonfiguration von langen Vinyl-Chlorid-Anteilen betrachtet werden müssen, um die NMR-Spektren zu beschreiben. Die CCl₂-Gruppe läßt die chemische Verschiebung des Methylen-protons bei geringeren magnetischen Feldern und die CHCl-Gruppe bei höheren erscheinen.

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With 5 figures in 13 details and 4 tables     

Multiple fluorescences. Different triplets from N-methyl-2-N-phenylamino-6-naphthalenesulfonate and its C-protonated form by laser pulse photolysis

The triplets generated by laser pulse excitation of N-methyl-2-N-phenylamino-6-naphthalenesulfonate (1M) and its C-protonated form, the N-methyl betaine of 6-sulfonato-3β-tetralenone N-phenylimine (2M) are distinct and apparently do not interconvert at 25°C either in dioxane-water or in glycerol, for which single pulses must be used to avoid conversion of 1M to 2M. Some parallel results are reported for the N-hydroxyethyl derivatives (1HEand2HE).     

Recognition of polarized lipid bilayers by p-oligophenyl ion channels: from push-pull rods to push-pull barrels

Design, synthesis, and evaluation of 14-methoxy-84-methylsulfonyl-22,33,42,53,62,73-hexa(Gla-Leu-Lys-Leu-NH2)-p-octiphenyl (1) and 14,84-bismethoxy-22,33,42,53,62,73-hexa(Gla-Leu-Lys-Leu-NH2)-p-octiphenyl (2) are described (Gla = -OCH2CO-). Nanomolar concentrations of push-pull rod 1 are found to suffice to selectively form ion channels in polarized spherical bilayer membranes composed of egg yolk phosphatidylcholine. Exponential dependence of the ion-channel activity on membrane polarization reveals a gating charge of 0.85/channel. Independence of the activity of push-push rod 2 on membrane potential demonstrates that cell membrane recognition originates from the axial dipole in push-pull rod 1. Nonlinear concentration dependence of activity at -180 mV indicates parallel self-assembly of push-pull rod 1 into a tetrameric barrel-stave supramolecule.     

Synthesis of protoheme IX derivatives with a covalently linked proximal base and their human serum albumin hybrids as artificial hemoprotein

The simple one-pot reaction of protoporphyrin IX and omega-(N-imidazolyl)alkylamine or O-methyl-L-histidyl-glycine with benzotriazol-1-yl-oxytris(dimethylamino)phosphonium hexafluorophosphate at room temperature produced a series of protoporphyrin IX species with a covalently linked proximal base at the propionate side-chain. The central iron was inserted by the general FeCl2 method, converting the free-base porphyrins to the corresponding protoheme IX derivatives. Mesoporphyrin IX and diacetyldeuteroporphyrin IX analogues were also prepared by the same procedure. The Fe(II) complexes formed dioxygen (O2) adducts in dimethylformamide at 25 degrees C. Some of them were incorporated into the hydrophobic domain of recombinant human serum albumin (rHSA), providing albumin-heme hybrids (rHSA-heme), which can bind and release O2 in aqueous media (pH 7.3, 25 degrees C). The oxidation process of converting the dioxygenated heme in rHSA to the inactive Fe(III) state obeyed first-order kinetics, indicating that the mu-oxo dimer formation was prevented by the immobilization of heme in the albumin scaffold. The rHSA-heme, in which the histidylglycil tail coordinates to the Fe(II) center, showed the most stable O2 adduct complexes.     

Multitracer screening for in vivo element-element interrelations

Radioactive multitracer technique was applied to study the screening of in vivo interrelations between radioactive tracers (⁴⁶Sc, ⁵⁹Fe, ⁵⁸Co, ⁶⁵Zn, ⁷⁵Se, ⁸³Rb, ⁸⁵Sr and ⁸⁸Zr) and stable Mn species. Comparative uptake rates were examined in the blood, 9 organs (thymus, lung, cardiac muscle, spleen, pancreas, kidney, liver, testes and bone) and 8 brain regions (cerebral cortex, striatum, hippocampus, thalamus and hypothalamus, midbrain, cerebellum, pons and medulla, olfactory bulb) using the 3-weeks-old mice fed the Mn-deficient, -adequate or -excessive diets with Mn concentration from 0.4 to 300.4 ppm. Significant diet-related differences were found for ⁶⁵Zn uptake in some organs. The dietary Mn-deficient state induced increase Zn absorption in thymus and lung in short-time span (during 48 hours after injection). On the other hand, no significant diet-related differences were observed in any brain regional uptake rates except for ⁵⁴Mn uptake rate. The screening results are expected to give us new findings concerning the diet-related element-element interrelations in living bodies.