Ion-selective electrodes in organic functional group analysis: Microdetermination of hydrazines with the copper electrode

Summary A simple micromethod is described for the determination of hydrazines using the copper ion-selective electrode. The method is based on direct potentiometric titration of the sample in ammoniacal solution of pH 9.5±0.2 with copper(II) ions at room temperature. N-Shaped curves with well-defined inflections at 11 and 12 molar ratios are obtained. This is probably due to the formation of copper monohydrazinate and copper dihydrazinate complexes. Various alkyl and aryl hydrazines and hydrazine salts have been satisfactorily analyzed with an average recovery of 99.4% and a relative standard deviation of ±0.4%. The reaction of hydrazines with Fehling's solution followed by measuring the copper(I) oxide formed using the copper ion-selective electrode also has been investigated.

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Zusammenfassung Eine einfache Mikromethode zur Bestimmung von Hydrazinen mit einer kupferionen-selektiven Elektrode wurde beschrieben. Sie beruht auf der direkten potentiometrischen Titration in ammoniakalischer Lösung mit Cu(II)ionen bei pH 9,5±0,2 bei Zimmertemperatur. N-förmige Kurven mit gut ausgebildeten Spitzen bei Molverhältnissen 11 und 12 wurden erhalten, wahrscheinlich auf Grund der Bildung von Mono- bzw. Dihydrazinatkomplexen des Kupfers. Verschiedene Alkyl- und Arylhydrazine und deren Salze wurden zu 99,4% mit einer Standardabweichung von ±0,4% wiedergefunden. Die Reaktion der Hydrazine mit Fehlingscher Lösung wurde ebenfalls durch Messung des entstandenen Cu(I) mit der erwähnten Elektrode untersucht.

     

Polyoxyalkylenated amines for breaking water-in-oil emulsions: effect of structural variations on the demulsification efficiency

In the present work, different aliphatic and aromatic amines were ethoxylated after a previous propoxylation (PPPEA) with different degrees of propoxylation and ethoxylation in order to obtain polymeric surfactants having different hydrophilic–lipophilic balance (HLB) values. The influence of the structural variations in the prepared PPPEA on their efficiency as demulsifiers for water-in-oil emulsions was investigated. Synthetic water-in-benzene emulsions stabilized by petroleum asphaltenes was utilized for the completion of this study. The actual propylene oxide (PO)–ethylene oxide (EO) ratios of the PPPEA under investigation was elucidated via ¹H NMR spectroscopy. It was found that each demulsifier practices a maximum demulsification efficiency at an optimum concentration. At this concentration, the demulsifiers’ molecules were believed to form a monolayer by adsorbance at the benzene–water interface. The influences of the number of aromatic rings in the molecule, the degree of substitution in the aromatic rings, the number of amine groups, the number of PO–EO chains and HLB on the demulsification efficiency were accomplished. © 1998 John Wiley & Sons, Ltd.     

A Generalized Spatial Modulation System Using Massive MIMO Space Time Coding Antenna Grouping

Massive multiple input multiple output (MIMO), also known as a very large-scale MIMO, is an emerging technology in wireless communications that increases capacity compared to MIMO systems. The massive MIMO communication technique is currently forming a major part of ongoing research. The main issue for massive MIMO improvements depends on the number of transmitting antennas to increase the data rate and minimize bit error rate (BER). To enhance the data rate and BER, new coding and modulation techniques are required. In this paper, a generalized spatial modulation (GSM) with antenna grouping space time coding technique (STC) is proposed. The proposed GSM-STC technique is based on space time coding of two successive GSM-modulated data symbols on two subgroups of antennas to improve data rate and to minimize BER. Moreover, the proposed GSM-STC system can offer spatial diversity gains and can also increase the reliability of the wireless channel by providing replicas of the received signal. The simulation results show that GSM-STC achieves better performance compared to conventional GSM techniques in terms of data rate and BER, leading to good potential for massive MIMO by using subgroups of antennas.     

Reactions of Benzoyl Isothiocyanate with Active Methylene Reagents: A Novel Synthesis of Thiophene,Thiazoline and Thieno[2,3-d]Pyrimidine Derivatives

Various derivatives of thiophene, thiazoline and thienopyrimidine have been synthesized via the reaction of active methylene reagents (la-j) with benzoyl isothiocyanate in the presence of potassium hydroxide, followed by the subsequent treatment of the potassium salt intermediates 2a-j with phenacyl bromide or ethyl chloroacetate. The stability of the formed adducts 3 and 12 or their selective cyclization depends on both the nature of the active methylene reagent and the α-halocarbonyl compounds.     

Particularization of alpha contamination using CR-39 track detectors

Solid-state nuclear track detectors have found wide use in various domains of science and technology, e.g. in environmental experiments. The measurement of alpha activity on sources in an environment, such as air is not easy because of short penetration range of alpha particles. Furthermore, measurement of alpha activity by most gas ionization detectors suffers from high background induced by the accompanying gamma radiation. Solid state nuclear track detectors (SSNTDs) have been used successfully as detecting devices and as a passive system to detect alpha contamination on different surfaces. This work presents the response of CR-39 (for two types) to alpha particles from two sources, ²³⁸Pu with energy 5 MeV and ²⁴¹Am with energy 5.4 MeV. The methods of etching and counting are investigated, along with the achievable linearity, efficiency and reproducibility. The sensitivity to low activity and energy resolution are studied.      

Determination of penicillins by desulphurization with lead and edta titration

A new, simple, accurate and rapid method is described for the determination of total penicillins in pharmaceutical preparations. The method is based on desulphurization with potassium plumbite whereby one mole of lead sulphide is formed per mole of penicillin. The excess of lead ions is titrated with EDTA at pH 4.5, with use of the lead ion-selective electrode. Results are reproducible within +/- 0.5% and compare favourably with those obtained by the procedures of the United States and British Pharmacopoeias.     

Separation of Cesium from Intermediate Level Waste Solutions Using Zirconyl Tungstate Ceramic-Supported Membranes

Zirconyl tungstate ceramic-supported membranes were developed and characterized. The transport process of Cs(I), Sr(II) and La(III) from the anode compartment to the cathode was investigated. The cationic fluxes for Cs(I), Sr(II) and La(III) were found to be 9·10^–10, 2.7·10^–9 and 2.4·10^–9 g·eq·cm^–2·s^–1, respectively. The transport numbers of these cations were found to be 0.12, 0.07 and 0.09, respectively. Separation of Cs(I), Sr(II) and La(III) was achieved using EDTA as a chelating agent in the anode compartment. Cs(I) was successfully separated with a decontamination factor of 97% from simulated intermediate level liquid waste (ILLW) containing Cs(I) and Sr(II).     

Efficient synthesis,reactions, and biological activities of new thieno and furopyrazolo[3,4-b]pyrazines and their related heterocycles

In the present investigation, a simple and straightforward methodology for the preparation of novel bifunctional thienopyrazolopyrazines 4a–d has been reported. Synthesis of thieno or furopyrazolopyrazines 5a , b , e , f was achieved by the reaction of o-amino-esters 4a , b , e , f with 2,5-dimethoxytetrahydrofuran. The latter pyrrolyl derivatives 5a , b , e , f were used as starting intermediates for the synthesis of new pyrimido, pyrido, and pyrazino heterocycles fused to the thieno or furopyrazolopyrazine moiety. Furthermore, alkaline hydrolysis of the o-amino-ester 4a followed by acidification afforded the corresponding o-amino carboxylic acid 15 , which was used as a versatile precursor for the synthesis of other heterocyclic compounds fused to the thienopyrazolopyrazine ring system, namely: pyrimidine, oxazine, oxazepine, and pyridine derivatives 16–23 . The chemical structures of the synthesized compounds were confirmed on the basis of elemental and spectral analyses (Fourier-transform infrared spectroscopy [FT-IR], ¹H nuclear magnetic resonance [NMR], and mass spectroscopy [MS] in addition to ¹³C NMR for some of them). Moreover, from the biological screening, we found that most of the tested compounds exhibited promising antifungal, antibacterial, and anti-inflammatory activities compared with the corresponding reference drugs.