Can multivalency be expressed kinetically? The answer is yes

Inspired by the concept of multivalency and in pursuit of ever more intricate artificial molecular machines, we investigated the strict self-assembly of a triply threaded two-component superbundle, starting from a tritopic receptor in which three benzo[24]crown-8 macrorings are fused onto a triphenylene core and a trifurcated trication wherein three bipyridinium units are linked 1,3,5 to a central benzenoid core. The result of the investigation was quite unexpected and surprising. It transpired that the rapid formation of a doubly threaded two-component complex was followed by an extremely slow conversion (a week at 253 K in CD3COCD3 to reach equilibrium) of this kinetically controlled product into a thermodynamically controlled one, namely a triply threaded two-component superbundle. This intriguing observation begs the question: are there instances in nature where multivalency is expressed as a kinetically controlled process, prior to an equilibrium state being reached, and if so, what are the biological implications, if any?     

Metal contents in tench otoliths: relationships to the aquatic environment

A monitoring of the quality of waters was attempted determining metal accumulation in target organs as otoliths of freshwater fish. Tenchs of age ranging between 2 and 10 years were sampled in three different canals receiving wastewater from industrial, agricultural and urban activities. Metal contents were determined in both lapilli and asterisci otoliths, using inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Analytical data are reported for minor metals and for some trace metals. Al, Fe and Zn have contents depending on the environment where the fish has lived, while Na, K, Ca and Sr contents are insensitive to the different aquatic habitat. Considering the two types of otolith separately, lapilli display a different affinity for trace metals (Al, Fe and Zn), while in asterisci this affinity is matched only for zinc. The high affinity of zinc for both types of otoliths suggests using this metal for discriminating the fresh waters by checking its accumulation in otoliths, as well as correlating this accumulation with age of the fish: a negative power curve equation is proposed. Since highest concentrations are found in individuals of 2-3 yr., it is advisable to use this fish for such environmental studies.     

Precipitation separation of lead and calcium,strontium, barium from acidic solutions using crown ether and tungstosilicic acid

It was found that lead reacts with 18-crown-6 (L) and tungstosilicic acid (H₄A) in acidic solutions and a compound with low solubility is formed what was confirmed by radiometric titration methods. Coprecipitation of complexion cation of PbL²⁺ with similar complexion cations of calcium, strontium and barium was studied. Formation of low soluble salts was utilized for separation of Pb from Ca, Sr and Ba from 1 mol·dm^–3 HNO₃. The ratio of Pb/Ca, Pb/Sr and Pb/Ba in the precipitation or separation factors S_pb/M undoubted depends on the ratio of the stability constants of lead and metals with 18C6 (_Pb/_M), what can be used for determination of more precise constant stability _M.     

Synthesis and fluorescent properties of some new unsymmetricbis-benzothiazolyl furans and thiophenes

Summary Some newmono- andbis-benzothiazolyl compounds with furan or thiophene nuclei were synthesized by multistep reactions from the corresponding furan and thiophene aldehydes. The data obtained from emission spectra show a large influence of the benzothiazole rings on the relative quantum efficiency of the compounds under investigation.

---

Synthese und Fluoreszenzeigenschaften von neuen unsymmetrischenbis-Benzothiazolylfuranen und thiophenen

Zusammenfassung Einige neuebis-Benzothiazolylverbindungen mit einem Furan- bzw. Thiophenenring wurden in einer mehrstufigen Reaktion dargestellt. Die Fluoreszenzdaten der untersuchten Verbindungen zeigen einen großen Einfluß der Benzothiazolringe auf die relative Fluoreszenzquantenausbeute.

     

Thermal decomposition of mineral zircon by alkali metal hydroxides

Thermal decomposition of zircon mineral was studied in the presence of sodium and potassium hydroxides and in the presence of a waste mixture of hydroxides containing NaOH and KOH in a weight ratio of 23. The process was controlled in such a way that the decomposition products might contain the minimum possible amount of alkali and could thus be applied for the syntheses of zircon pigments without any further exacting treatment.

---

Zusammenfassung Es wurde die thermische Zersetzung eines Zirkonminerals in Gegenwart von Natrium- und Kaliumhydroxid-sowie in Gegenwart einer Altlauge mit einem Gehalt an NaOH und KOH im Verhältnis zwei zu drei untersucht. Der Prozeß wird derart gesteuert, daß die Zersetzungsprodukte einen möglichst geringen Anteil an Lauge besitzen und so ohne weitere arbeitsaufwändige Behandlungen zur Synthese von Zirkonpigmenten verwendet werden können.

---

, 23. , , , - .

     

Sulfide ion electrooxidation catalysed by cobalt phthalocyanine microcrystals

Electrooxidation of sulfide ion catalysed by microcrystals of cobalt phthalocyanine was investigated by cyclic voltammetry in 0.5M KNO₃ at pH 9.22. Traces of catalyst were immobilized at the surface of a paraffin-impregnated graphite electrode by the mechanical transfer of its powder. The electro-oxidation of HS^– proceeds in two irreversible steps, with the first peak between 0 V and –0.12 V and the second at 0.17 V. The first step is second order in HS^– and its product is the adsorbed disulfide, which may further dissociate to give adsorbed sulfur atoms. The reduction of sulfur occurs at –0.1 V.     

Photocatalytic TiO2 Coatings: Effect of Substrate and Template

Summary. Transparent TiO₂ films with a high photodegradation activity towards an azo dye in aqueous solution were prepared by sol–gel processing. Films on soda–lime glass supports protected with a thin silica barrier layer exhibited better crystallization and monodisperse nanoparticles, higher absorption of light below 370 nm, and higher photocatalytic activity than those films deposited on bare glass supports proving the detrimental effect of interdiffused sodium ions on the development of the anatase nanostructure. The effect of substrate was more pronounced in thinner films (300 nm) than in thicker ones (1200 nm), which were achieved by adding a template (i.e. Pluronic F127) to the sol.     

Sorption of radionuclides on inorganic sorbents

Inorganic sorbents are often used in separation of metals and radionuclides in radioanalytical application and they were also used in technological scale for separation of radionuclides in cleanup of Three Mile Island NPP. Inorganic sorbents become popular in the last years because no problem with organic contamination, there are stable against radiation, sorption efficiency can be tailor made for selective separation of chosen metal. Contrary to the organic sorbents they have usually lower capacity and chemical stability is limited to narrower pH. Nevertheless of some problems, many good properties of inorganic sorbents make them very attractive for sorption study.     

Correlation between Lipophilicity of the Ligands and the Hepatobiliary Properties of the Radiopharmaceuticals: Approach to the Development of New IDA Derivatives

The partition coefficient (log P) for n-octanol/water system was calculated applying PACO program for various theoretically possible mono and dihalogenated IDA derivatives. Some of the synthesized ligands (SOLCOIODIDA, IODIDA and DIIODIDA) were labeled with the technetium-99m. The biodistribution and influence of bilirubin on their biokinetics were investigated in rats. The correlation between partition coefficients of ligands increase (log P) and better hepatobiliary properties of ^99mTc-IDA derivatives was determined. The values of log P increase from 1.16 for SOLCOIODIDA, 3.11 for IODIDA to 3.47 for DIIODIDA. In correlation with these results, biliary excretion decreased for 59% for ^99mTc-SOLCOIODIDA and 11% for ^99mTc-IODIDA and ^99mTc-DIIODIDA under hyperbilirubinemia (3.5 min after injection) and 45%, 11% and 0.38% respectively (15 min after injection). The highest biliary excretion had ^99mTc-DIIODIDA (55.4% for 3.5 min). Considering the correlation between hepatobiliary properties and log P, the evaluation of biological properties for various trifluoromethyl mono and dihalogenated IDA derivatives was performed on the basis of the calculated log P in order to synthetize a new radiopharmaceutical for hepatobiliary scintigraphy.     

Coulometrische Wismutometrie

Zusammenfassung Durch elektrolytische Oxydation einer Bi-Anode in gesättigter NaCl-Lösung können Bi³⁺-Ionen in Lösung gebracht werden. Dieser Prozeß ermöglicht die coulometrische Bestimmung anwesender Anionen, die schwerlösliche Bi-Verbindungen bilden.Es wurden Semimikro- und Mikrobestimmungen von Phosphationen durch elektrolytisch erzeugte Bi³⁺-Ionen bei konstanter Stromstärke ausgeführt. Die Endpunktbestimmung erfolgte amperometrisch bei konstantem Potential mit einer Indikatorelektrode — tropfende Quecksilberelektrode — und mit einer gesättigten Kalomelelektrode als Bezugselektrode. Die coulometrische Wismutometrie bietet eine weitere Möglichkeit der coulometrischen Eichung volumetrischer Lösungen im Sinne des seinerzeitigen Vorschlags vonTutundi.

---

Summary Bi³⁺ ions can be brought into solution through electrolytic oxidation of a Bi-anode in saturated NaCl solution. This process makes possible the coulometric determination of the anions present that yield difficulty soluble bismuth compounds.Semimicro- and micro-determinations of phosphate ions were made via Bi³⁺-ions produced electrolytically at constant current strength. The endpoint was determined amperometrically at constant potential with an indicator electrode-dropping mercury electrode-and with a saturated calomel electrode as reference electrode. The coulometric bismuthometry affords a further possibility of the coulometric standardization of volumetric solutions in the sense of the proposal previously advanced byTutundi.

---

Résumé On peut utiliser les ions Bi³⁺ en solution par oxydation électrolytique d'une anode en bismuth, en solution de chlorure de sodium saturée. Ce procédé permet le dosage coulométrique des anions présents qui forment des composés peu solubles avec le bismuth.On a mis au point le dosage semimicro et micro des ions phosphates par les ions Bi³⁺ formés électrolytiquement sous intensité constante. On détermine par ampérométrie le point équivalent à potentiel constant à l'aide d'une électrode indicatrice — électrode de mercure à goutte pendante —et avec une électrode au calomel saturée comme électrode de référence. La «bismuthométrie» coulométrique offre de grandes possibilités pour l'étalonnage coulométrique de solutions volumétriques, suivant l'idée queTutundi a émise en son temps.

---

---

Vorgetragen beim Symposium für analytische Chemie in Graz, 29. September bis 1. Oktober 1965.

---

Wir danken Herrn Dipl.-Ing.Vladimir Pantovi für seine Hilfe bei unserer experimentellen Arbeit.