Polymeric membrane sodium-selective electrodes based on calix[4]arene ionophores

Six kinds of tetra alkylester type calix[4]arene derivatives, (R₁=R₂=CH₃1, C₂H₅2, C₃H₇3,n-C₄H₉4,t-C₄H₉5,n-C₁₀H₂₁6), a diethyl-didecyl mixed ester type (R₁=C₂H₅, R₂ =C₁₀H₂₁7), and three kinds of lower rim bridged types (R₁=C₂H₅, R₂–R₂=(CH₂)₁₀8, (CH₂)₁₂9, (CH₂)₂(OCH₂CH₂)₃10) were characterized by electrochemical measurement to elucidate the effect of the length of the alkyl group of alkoxycarbonyl substituents on Na⁺ selectivity. To obtain excellent Na⁺ selective ionophores, introduction of short chain alkyl groups rather than long chain ones, such as a decyl group, and maintenance of sufficient solubility of the calix[4]arene derivatives in the membrane solvent are required concurrently. Among the calix[4]arenes tested, 25,26,27,28-tetrakis[(ethoxycarbonyl)methoxy]-p-tert-butylcalix[4]arene2, and the diethyl-didecyl mixed ester type derivative7 are the best ionophores for a Na⁺ selective electrode. On the other hand, sodium selectivity of the bridged type derivative9 is comparable or even superior to that of the known bis(12-crown-4).This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.     

Micro reversed phase liquid chromatography of Cd-, Ni-, Zn-, Cu-, Co-, Hg-diethyldithiocarbamates at picogram level

Summary The use of micro reversed phase columns (Polygosil C18) for the separation of metal DDTC chelates was investigated and applied to drinking water analysis.Three different eluents have been tested [702010 (MeOH H₂OCHCl₃); 8020 (MeOHH₂O); 7030 (MeOHH₂O)] at flow rates of 7 to 28gml/min. Eluent composition showed strong influence onk of Co(DDTC)₂.The linear working curves fitted at least 3 decades with detection limit of 40–500 pg. Monitoring at _max instead of 254 nm decreases the detection limits. The consume of eluent is 10 to 20 times less than with analytical columnes.Results of micro LC have been compared with predictible data of theoretical considerations.

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Mikro-Umkehrphasen-Flüssigkeitschromatographie der Cd-, Ni-, Zn-, Cu-, Co-, Hg-Diethyldithiocarbamatchelate im Picogrammbereich

Zusammenfassung Die Anwendung von Mikro-RP-Säulen (Polygosil C18) für die Trennung von Metall-DDTC-Chelaten wurde untersucht und auf die Analyse von Trinkwasser angewendet. Drei verschiedene Eluentien [702010 (MeOH H₂OCHCl₃); 8020 (MeOHH₃O); 7030 (MeOHH₂O)] bei Fließraten von 7 bis 28gml/min wurden untersucht,k von Co(DDTC)₂ wird von der Eluenszusammensetzung erheblich beeinflußt. Der lineare Meßbereich betrug mindestens 3 Dekaden mit einer Nachweisgrenze von 40–500 pg, die durch Detektion bei _max statt bei 254 nm noch weiter gesenkt werden kann.Der Verbrauch an Eluens ist 10–20mal geringer als bei analytischen Säulen.Die Ergebnisse der Mikro-LC wurden anhand theoretischer Überlegungen mit den vorhersagbaren Daten verglichen.

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Presented in parts at 9th International Symposium on Microchemical Techniques, Amsterdam 1983.     

Phthalocyaninartige Bor-Komplexe

Zusammenfassung Aus Halogenboranen und Organohalogenboranen (RBX ₂R=C₆H₅, Cl, Br;X=F, Cl, Br) sowie aus Organoboranen oder Thioboranen entstehen mit Phthalodinitril Triisoindolo-[1,2,3-cd1,2,3-gh1,2,3-kl][2,3a,5,6a,8,9a,9b]-hexaazaboraphenalene von denen die B–Cl- und B–F-Verbindungen näher charakterisiert werden.Dekaboran(14), Diboran(6) oder Boranaddukte von Stickstoffbasen liefern hingegen mit Phthalodinitril metallfreies Phthalocyanin.

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Triisoindolo[1,2,3-cd1,2,3-gh1,2,3-kl][2,3a,5,6a,8,9a,9b]-hexa-azaboraphenalene

Triisoindolo[1,2,3-cd1,2,3-gh1,2,3-kl][2,3a,5,6a,8, 9a,9b]-hexaazaboraphenalenes are obtained from the reactions of haloboranes and organohaloboranes (RBX ₂R=C₆H₅, Cl, Br;X=F, Cl, Br) as well as from organoboranes or thioboranes with phthalodinitrile. The B–Cl and B–F compound have been characterized by analyses, i.r.-, u.v.- and mass-spectrometry.Diborane(6), dekaborane(14) and amine-boranes, however, upon reaction with phthalodinitrile lead to high yields of metal free phthalocyanine.

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Herrn Prof. Dr.M. Pailer zum 60. Geburtstag gewidmet.     

Determination ofFe 2+ content of NiZnCo iron-excess ferrites by thermogravimetry

Experimental results are reported on the determination by thermogravimetry of the iron(II) content of the NiZnCo ferrite with the molar ratio Fe₂O₃NiOZnOCoO=59.019.520.51.0.     

Aktivierungsanalytische Bestimmung sehr kleiner Iridiumgehalte in Uranoxid

Zusammenfassung Es wird über die dünnschichtchromatographische Trennung und Reinheitsprüfung von 12 Naphthylaminmonosulfonsäuren berichtet. Für das Laufmittel n-Butanol-n-Propanol-Wasser-konz. Ammoniak (10541) werden die R_f-Werte ermittelt und ihre Standardabweichungen berechnet. Für die rechnerische Bestimmung der R_f-Werte aus den Dipolmomenten der Säuren wird eine quadratische Gleichung angegeben.

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Summary A report is presented on the thin-layer chromatographic separation and purity control of 12 naphthylaminemonosulphonic acids. R_f-values and standard deviations are determined for the solvent-mixture n-butanol-n-propanol-waterconc. ammonia (10541). A quadratic equation is given for the calculation of the R_f-values from the dipole moments of the acids.

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Für die Durchführung dieser Arbeit wurden dankenswerterweise Forschungsmittel aus dem ERP-Sondervermögen bereitgestellt.Dem Verbande der Chemischen Industrie und der Deutschen Forschungsgemeinschaft, die diese Arbeit unterstützt haben, danken wir bestens.     

Untersuchungen über die diamagnetische Suszeptibilität einiger Organo (imino-oxy)silane

Diamagnetic susceptibilities of trimethyl(imino-oxy)silanes,Me ₃SiON CMeR, and dimethyldi(imino-oxy)silanes,Me ₂Si(ON CMeR)₂, containing Si–O bonds are reported. _M of these silicon compounds has been calculated theoretically from the method ofBaudet et al. and a good agreement has been obtained between the observed _M values and the corresponding calculated values. _Si in these compounds has been calculated graphically and the lower values have been explained on the basis of back-bonding to the silicon atom from the oxygen lone pair.     

Metallographische Untersuchungen über das System Ag2Te x Se1−x

Zusammenfassung Das System Ag₂Te _x Se_1–x wurde im Bereich 0<x<1 mit x=0,1 metallographisch untersucht. Zur Entwicklung der Mikrostruktur ist ein Ätzmittel mit der Zusammensetzung HNO₃CH₃COOHH₂O=213 vorgeschlagen worden; auch die Mikrohärte der Proben wurde ermittelt. Auf Grund der Ergebnisse der Röntgen-Phasenanalyse, der Mikrostruktur und Mikrohärte wird bei 120°C die Anwesenheit einer diskontinuierlichen festen Lösung angenommen.

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Metallographic investigation of the system Ag₂Te _x Se_1–x

The system Ag₂Te _x Se_1–x has metallographically been investigated forx from 0 to 1 and x=0.1. For developing the micro-structure, an etching mixture of composition HNO₃CH₃COOHH₂O=213 is proposed. Micro-hardness of the samples also has been established. On the basis of the results from the X-ray-phase-analysis, the micro-structure and micro-hardness, the presence of a discontinous solid solution is assumed at 120°C.

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Mit 3 Abbildungen     

Discrimination of active sites for ethylene homologation and ethylene metathesis on molybdena silica catalyst

Active sites for ethylene homologation (3C₂H₄2C₃H₆) and ethylene metathesis (C₂H₄–¹²C₂+C₂H₄–¹³C₂2C₂H₄–¹³C₁) were discriminated by adding platinum to a reduced molybdena silica catalyst, and the former was presumed to be composed of several molybdenum species, while the latter was presumed to be composed of one molybdenum species.

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(3C₂H₄2C₃H₆) (C₂H₄–¹²C₂+C₂H₄–¹³C₂2C₂H₄–¹³C₁) . , , .

     

Some effective solvents for rapid and reliable characterization of phenylthiohydantoin-amino acids

Summary One-dimensional chromatography with internal standards permits reliable identification of the phenylthiohydantoins from all the common amino acids with the following TLC systems: silica gel — chloroform/n-butyl acetate (9010), di-isopropylether/ethanol (955), dichloromethane/ethanol/acetic acid (9082) ortrans-dichloroethylene/ethanol/acetic acid (88102); and cellulose with 25% formic acid — heptane/isobutanol/75% fromic acid (40309) or silica gel — chloroform/ ethanol/acetic acid/water (50470.52.5).Abbreviations: PTH=phenylthiohydantoin, TLC=thin-layer chromatography, HPTLC=high-performance TLC; other abbreviations: see end of text. Proportions in solvent mixtures are v/v except where otherwise indicated.     

Schiff base complexes of dioxouranium(VI), III. Commun.: Dioxouranium(VI) complexes of bibasic tetradentateSchiff bases

Bibasic tetradentateSchiff bases having the donor system OH–NX–NX–OH have been shown to form UO₂(NO₃)₂(SBH₂) type of derivatives [SBH₂ is the molecule of the bibasic tetradentateSchiff bases such as HOC₆H₄C(R) N(CH₂) _n NC(R)C₆H₄OH (where R=H or CH₃ andn=2 or 3) and HOC(R)CHC(CH₃)N(CH₂) _n NC(CH₃)CH C(R)OH (where R=CH₃ or C₆H₅ andn=2 or 3)]. The 11 stoichiometry of these complexes is shown by elemental analysis and conductometric titrations. The molar conductence values in nitrobenzene indicate the non-electrolytic behaviour and the magnetic susceptibility measurements by the Gouy method show these complexes to be diamagnetic.With 1 Figure     

A versatile solvent system for the paper chromatography of inorganic cations

Summary The paper chromatographic resolution potentiality of the solvent system chloroform-acetone-iso-amyl alcohol-11N HCl (1 1 1 0.5v/v) for the metal cations has been tested. Successful results with various multiconstituent mixtures are presented andR _f values of the common metal ions are tabulated.

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Zusammenfassung Das papierchromatographische Trennungsvermögen des Lösungsmittel Systems Chloroform—Aceton—i-Amylalkohol—11-n Salzsäure (1 1 1 0,5v/v) für Metallkationen wurde geprüft. Mit verschiedenen, aus einer Mehrzahl Komponenten bestehenden Gemischen wurden gute Ergebnisse erhalten. DieR _f -Werte der üblichen Kationen wurden angegeben.

     

Komplexbildung im System Ni2+—o-Methylbenzamidoxim

Zusammenfassung Die Komplexe des Ni²⁺ mit o-Methylbenzamidoxim wurden in neutraler und in alkalischer Lösung spektrophotometrisch untersucht. Die Bildungskonstanten sindK ₁=40 für 11 undK ₂=1,7·10² für 12 in neutraler Lösung und ₁ = =(3,92 ±0,2) · 10⁴für 11 und lgK = lg ₁ + lg ₂ = 3,45 ± ±0,15 für 12 bei 25° und =1 in alkalischer Lösung.

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Complex formation in the systemeNi ²⁺—o-methylbenzamide oxime

The complexes of Ni²⁺ with o-methylbenzamide oxime were investigated spectrophotometrically in neutral as well as in alkaline solution. The formation constants areK ₁=40 for 11 andK ₂=1.7·10² for 12 in the neutral solution and ₁ = =(3.92 ±0.2) · 10⁴ for 11 and lgK = lg ₁ + lg ₂ = 3.45 ± ±0.15 for 12 at 25° and =1 for the alkaline solution. *** DIRECT SUPPORT *** A3615139 00007

     

Hydrogen peroxide yields in methanol-water mixtures gamma-irradiated at room temperature and 77 K

Hydrogen peroxide yields in air-saturated methanol-water mixtures with methanol: water volume ratios varying from 199 to 1000, produced by⁶⁰Co gamma-irradiation boith at room temperature and at 77 K have been determined. At room temperature, G(H₂O₂) values are almost constant over the entire range of methanol: water ratios. However, for irradiations at 77 K, G(H₂O₂) values increase with increasing methanol concentration up to the volume ratio of 982.     

Sintering of supported palladium

Sintering results of Pd supported on carbon black at 723–973 K, in water vapor, in H₂ and under high vacuum are reported. They are compared with sintering data of Pd on other supports. The observed sequences are: SiO₂C>sepioliteAl₂O₃>AlPO₄ and H₂O>high vacuum>H₂.

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Pd 723–973 , , H₂ . Pd . : SiO₂Al₂O₃>AlPO₄ H₂O> >H₂.

     

Haematein as a reagent for thorium, zirconium and uranium

Summary Haematein gives violet colored complexes with thorium and uranium and an orange colored complex with zirconium of the stoichiometric ratios 16, 13, and 11 respectively of the metal and the reagent (Job's method). The reagent and the complexes of thorium, uranium and zirconium show absorption maxima at 520–540 m, 520–540 m 500–520 m respectively. In observations at 540 m in 60 percent aqueous acetone 0.05 mg of thoria (a 12 fold excess of cerite earths has no influence), 0.029 mg U₃O₈ and 0.025 mg of zirconia may be determined. The spectral characteristics of the complexes indicate a similarity in character in spite of differences in stoichiometric composition.     

μSr studies of free radicals in the gas phase

Muonium (Mu=₊+e^-) is the bound state of a positive muon and an electron. Since the positive muon has a mass about 1/9 of the proton, Mu can be regarded as an ultra light isotope of hydrogen with unusually large mass ratios (MuHDT=1/9123). The muon spin rotation technique (SR) relies on the facts that (1) the muon produced in pion decay, ^{+ +} + , is 100% spin polarized and (2) the positron from muon decay is emitted preferentially along the instantaneous muon spin direction at the time of the muon decay.In transverse field SR (TF-SR), the precession of the muon spin in muonium substituted radicals is directly observed by detecting decay positrons time differentially. From observed radical frequencies, the hyperfine coupling constants (A ) of C₂H₄Mu, C₂D₄Mu,¹³C₂H₄Mu, C₂F₄Mu, and C₂H₃FMu are determined. In the longitudinal field avoided level crossing (LF-ALC) technique, one observes the resonant loss of the muon spin polarization caused by the crossing of hyperfine levels at particular magnetic fields. The LF-ALC method together with the information onA obtained from TF-SR allows one to determine the magnitude and sign of the nuclear hyperfine constants at - and -positions. Results are compared with hydrogen substituted ethyl-radicals and isotope effects are discussed.     

Chromatographie sur couche mince des acides aliphatiques non volatils. Partie I. Nouveaux solvants mobiles contenant un acide volatil. Observations préliminaires

Résumé De nouveaux solvants mobiles contenant un acide volatil sont proposés pour la séparation des acides aliphatiques non volatils du métabolisme et des fermentations et des diacides aliphatiques à chaîne droite. Les solvants les plus efficaces du point de vue séparation, sont ceux qui contiennent des éthers. Les meilleurs chromatogrammes sont ceux pour lesquels les frontières d'autochromatographie des produits issus des liants de la couche et des composants du solvant ont une très faible mobilitè. D'excellentes séparations sont obtenues par chromatographie sur couche mince de poudre de cellulose. Les solvants mobiles les plus intéressants sont:Eucalyptol/acide formique 98%/eau (65025075) Ether di-n-butylique/acide formique 98%/eau (65025022)Ether di-isopropylique/acide formique 98%/eau (650250100) Ether di-isoamylique/acide formique 98%/eau (6502505,5)Benzène/acide propionique/eau (47047057) Toluène/acide propionique/eau (47047049)Par suite des propriétés adsorbantes et échangeuses d'ions du gel de silice, les résultats obtenus sur ces couches minces sont décevants pour la plupart des acides aliphatiques lorsqu'on les chromatographie dans un solvant mobile alcalin. Il en est de même pour les acides oxalique et malonique, les hydroxyacides et les acides aliphatiques du métabolisme et des fermentations lorsqu'on les chromatographie dans un solvant mobile acide.

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Thin-layer chromatography of non-volatile aliphatic acids. Part I. New mobile phases containing a volatile acid. Preliminary observations

Summary New mobile phases containing a volatile acid are proposed for the separation of non-volatile aliphatic acids (metabolic acids or acids produced in fermentation) and of straight-chain aliphatic diacids. From the point of view of separations, solvents containing ethers are the most efficient. Best results are obtained when impurities in the binder and the components of the solvent are of very low mobility. Excellent separations are obtained by chromatography on cellulose powder thin layers.The most interesting mobile solvents are: Eucalyptol/98% formic acid/water (65025075) n-Dibutyl-ether/98% formic acid/water (65025022). Diisopropyl-ether/98% formic acid/water (650250100). Diisoamyl-ether/98% formic acid/water (6502505.5). Benzene/propionic acid/water (47047057). Toluene/propionic acid/water (47047049).Because of its adsorbent and ion-exchange properties, results obtained with thin layers of silica gel are disappointing for most aliphatic acids when chromatographed using an alkaline mobile phase, and for oxalic and malonic acids, hydroxyacids, aliphatic metabolic acids and aliphatic acids produced during fermentation when chromatographed using an acid mobile phase.