Nitrogen bridgehead compounds part 21. Preparation of new quaternary 2,3a,6a-triazaphenalenium salts

The first representatives of a new ring system, the 2,3a,6a-triazaphenalenium quaternary salts are prepared by the cycloaddition of tetrahydro-4H-pyrido[1,2-a] pyrimidin-4-ones containing an α-chloroenamine moiety with azomethines.     

Heterocyclic Spiro-naphthalenones. Part III. Synthesis and reactions of some spiro [naphthalene-1,2′-pyrrolidin]-2-ones and spiro [naphthalene-2,2′-pyrrolidin]-1-ones

The spironaphthalen-2-ones 2, 10 and 18 were prepared by N-bromosuccinimide (NBS) oxidation of 1, 9 and 17 respectively, whereas spironaphthalen-1-ones 24 and 25 were obtained by treating 23 with NBS. The stereoisomeric reduction products 29, 30 and 32 obtained from 24 and 25 , gave the pentacyclic compound 33 on treatment with polyphosphoric acid.     

Use of thenoyltrifluoroacetone for the determination of manganese by activation analysis

A new procedure for the substoichiometric extraction of bivalent manganese by thenoyltrifluoroacetone into ethyl acetate has been developed and used in activation analysis. The value of the extraction constant has been found to be 3.1 x 10(-6); the pH range in which the extraction can be performed is 7.8-9.2. The influence of oxalate, citrate, tartrate, fluoride and cyanide ions has been studied. A selective substoichiometric extraction of manganese in the presence of Zr, Hf, Nb, Th, Fe and Sc is possible at pH 8-8.5, tartrate and fluoride being used as masking agents. Copper and cobalt can be screened by ammonia and cyanide respectively. The method has been used for the determination of manganese in biological materials, potassium fluoride and zirconium.     

Dilute solutions of nylon 12—II. Relationship between intrinsic viscosity and molecular weight

Samples of poly(12-dodecanelactam) (polylaurolactam, nylon 12) with $\text{M}$_n 1 × 10³?33 × 10³ were prepared. Polymerizations initiated with water or with lauric acid proceeded under conditions for minimum changes in end-group concentration. Values of $\text{M}$_n were calculated from the end-group content and $\text{M}$_n from light scattering in the mixture m-cresol/60 vol% of 2.2,3,3-tetrafluoropropanol. From measurements of intrinsic viscosity in m-cresol, the relationship [n] ? $\text{M}$_n was established in the given range of $\text{M}$_n. The relationship [n] ? $\text{M}$_w for $\text{M}$_w from 3.3 × 10³ to 125 × 10³ has been established.     

Die Bildungswärmen von MnSi1,73, MnSi,Mn5Si3 und Mn3Si

By means of vapor pressure measurements using theTorker method (Torsion-Knudsen Effusion Recoil) as well as theKnudsen tanspiration technique in connection with a mass spectrometer, the heats of formation of the following compounds were found to be –6.5±0.7 kcal/g atom (Mn_0.366Si_0.634), –7.8±0.6 kcal/g atom (Mn_0.50Si_0.50), –7.3±0.6 kcal/g atom (Mn_0.625Si_0.375), and –6.6±0.6 kcal/g atom (Mn_0.75Si_0.25).

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Mit 7 Abbildungen     

Bestimmung von Ascorbinsäure auf Grund ihrer in einem Landolt-System ausgeübten reduzierenden Wirkung

Zusammenfassung Im Bromat-Jodid-Ascorbinsäure-System hängt die Zeit, die bis zur Jodausscheidung vergeht, von der Konzentration der Ascorbinsäure ab. Unter entsprechenden Versuchsbedingungen ist die Reaktionszeit proportional der Ascorbinsäurekonzentration. Danach kann die Ascorbinsäure sowohl mit Hilfe der Simultankomparationsmethode, als auch chronometrisch bestimmt werden. Die Genauigkeit ist ± 3% im Bereich von 5 bis 300g/5 ml. Die Grenzen der Bestimmung sind 1g bzw. 1000g Ascorbinsäure in 5 ml.

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Determination of ascorbic acid on the basis of its reducing action in a landolt system

Summary In the bromate-iodide-ascorbic acid system, the time that elapses until the iodine appears is dependent on the concentration of the ascorbic acid. Under appropriate experimental conditions, the reaction time is proportional to the ascorbic acid concentration. Accordingly, the ascorbic acid may be determined with the aid not only of the simultaneous comparison method but also chronometrically. The precision is ± 3% in the 5–300g/5 ml range. The limits of the determination are 1g and 1000g ascorbic acid in 5 ml respectively.

     

The detection of formaldehyde in textiles using interdigitated microelectrode array diffusion layer titration with electrogenerated hypobromite

An interdigitated microelectrode array (IDA) was applied to the determination of formaldehyde released from textiles produced in industry. The proposed method is based on formaldehyde reaction with hypobromite which is formed in weakly basic media by control current electrooxidation of bromide on the generator segment of the IDA array. The unreacted hypobromite diffuses through the gap between individually polarisable IDA segments and it is amperometrically detected on the collector segment of the IDA. The efficiency of this nonconvective transfer process in the absence of formaldehyde was substantially higher (78%) in comparison with that when using the rotating ring disc electrode. The influence of the added formaldehyde on the transfer process can be utilised to develop a simple and sensitive analytical procedure for formaldehyde detection with a detection limit of 4×10⁻⁶ mol dm⁻³.     

Facilitated transport of Hg(II) through novel activated composite membranes

The results presented in this work deal with the prime application of activated composite membranes (ACMs) for the transport of Hg(II) ions in a continuous extraction–re-extraction system using di-(2-ethylhexyl)dithiophosphoric acid (DTPA) as carrier. The effects of variables such as the pH, the nature of the acid and the concentration of the casting solutions on the transport of Hg(II) are also investigated. When the ACM was prepared with a 0.5 M DTPA solution and when the feed solution contained 2.5×10^–4 M Hg(II) in 0.1 M HCl, the amount of mercury extracted was greater than 76%. The re-extracted mercury was subsequently recovered by means of a stripping phase comprising 0.3 M thiourea solution in 2 M H₂SO₄, yielding 54% of the initial amount of mercury after transport had taken place for 180 min.     

Multicommutation as an environmentally friendly analytical tool in the hydride generation atomic fluorescence determination of tellurium in milk

The aim of this study is to show the advantages of the emerging multicommutation methodology based on the use of solenoid valves for Te determination in milk by hydride generation atomic fluorescence spectrometry (HG-AFS). The delivery of a series of alternating sequential insertions of small volumes of samples and reagents gives rise to new hydrodynamic processes and exciting analytical potentials by controlling the time of flow through the on/off-switched solenoid valves. This drastically reduces the reagent consumption by a factor of 4 and the generation of effluents (590 mL h^–1 instead of 750 mL h^–1 generated by the continuous-mode measurement) and also provides an improvement in the laboratory productivity by an increase of the sample throughput (85 h^–1 compared to 20 h^–1 found in the continuous mode). So, multicommutation is an environmentally and economically sustainable alternative to the methodology based on continuous measurements. The multicommutation-based method developed was applied to tellurium determination in commercially available milk samples; a calibration range of 0.0–0.5 ng mL^–1 and a detection limit of 0.20 ng L^–1 with average relative standard deviation of 2.1% were found. Comparable results were obtained for a series of samples using both continuous and multicommutation HG-AFS modes.     

Photodynamic actinometry using microspheres: concept, development and responsivity

Photodynamic therapy (PDT) relies on three main ingredients, oxygen, light and photoactivating compounds, although the PDT response is definitively contingent on the site and level of reactive oxygen species (ROS) generation. This study describes the development of a novel, fluorescent-based actinometer microsphere system as a means of discerning spatially resolved dosimetry of total fluence and ROS production. Providing a high resolution, localized, in situ measurement of fluence and ROS generation is critical for developing in vivo PDT protocols. Alginate-poly-L-lysine-alginate microspheres were produced using ionotropic gelation of sodium alginate droplets, ranging from 80 to 200 microm in diameter, incorporating two dyes, ADS680WS (ADS) and Rhodophyta-phycoerythrin (RPE), attached to the spheres' inside and outside layers, respectively. To test the responsivity and dynamic range of RPE for ROS detection, the production of ROS was initiated either chemically using increasing concentrations of potassium perchromate or photochemically using aluminum tetrasulphonated phthalocyanine. The generation of singlet oxygen was confirmed by phosphorescence at 1270 nm. The resulting photodegradation and decrease in fluorescence of RPE was found to correlate with increased perchromate or PDT treatment fluence, respectively. This effect was independent of pH (6.5-8) and could be inhibited using sodium azide. RPE was not susceptible to photobleaching with light alone (670 nm; 150 Jcm(-2)). ADS, which absorbs light between 600 and 750 nm, showed a direct correlation between radiant exposure (670 nm; 0-100 Jcm(-2)) and diminished fluorescence. Photobleaching was independent of irradiance (10-40 mW cm(-2)). We propose that actinometer microspheres may provide a means for obtaining high spatial resolution information regarding delivered PDT dose within model systems during investigational PDT development and dosimetric information for clinical extracorporeal PDT as in the case of ex vivo bone marrow purging.