Synthesis and spectroscopic studies of complexes containing the Schiff base 1-acetylferrocene(thio)semicarbazone

Summary [RuCl₂(CO)₂] _n reacts with the Schiff base 1-acetylferrocenethiosemicarbazone, [Fe(-Cp)(-C₅H₄MeC=NN-HCSNH₂)] to give [Fe(-Cp)(-C₅H₄MeC=NN-HCSNH₂)RuCl₂(CO)₂] and with 1-acetylferrocenesemicarbazone [Fe(-Cp)(-C₅H₄MeC=NN-HCSNH₂)] to give [Fe(-Cp)(-C₅H₄MeC=NN-HCSNH₂)RuCl₂-(CO) ₂]. Spectroscopic data indicate that the Schiff bases act as bidentate ligands and coordinate to ruthenium via the hydrazinic N and either the S or O atoms, respectively, giving stable heterobimetallic complexes, which have been characterized by i.r. and ¹H-n.m.r. spectroscopies, and elemental analyses.Part of this work was presented at the First International Conference in Chemistry and its applications in Doha, Qatar, 1993.     

Cellulose nanocrystals from bleached rice straw pulp: acidic deep eutectic solvent versus sulphuric acid hydrolyses

The present work aims to investigate the feasibility of oxalic acid-choline chloride deep eutectic solvent (OA-ChCl DES), which serves as a promising green solvent that utilized in the acidic deep eutectic solvent (DES) hydrolysis. Oxalic acid-choline chloride DES cellulose nanocrystal (OA-ChCl DES CNC) was isolated from the bleached DES treated pulp (BP) through the acidic DES hydrolysis using 1:1 molar ratio of OA-ChCl DES. The functional groups, crystallinity index, morphological structure, particle size, zeta potential, thermal stability and surface chemistry of the OA-ChCl DES CNC were compared with the sulphuric acid cellulose nanocrystal (SA-CNC) that prepared via sulphuric acid hydrolysis. The findings revealed the presence of negatively charged carboxyl groups on OA-ChCl DES CNC surface after the acidic DES hydrolysis. The physicochemical analyses verified that the OA-ChCl DES CNC was in nano-sized range with polydispersity index (PdI) of 0.56, indicating slightly monodispersed nanoparticles. A stable OA-ChCl DES CNC colloidal suspension with zeta potential value of ?52.1?±?5.2 mV was obtained. The OA-ChCl DES CNC outweighed the SA-CNC in term of thermal stability (288 °C) despite having a slightly lower crystallinity index (76.7%). In fact, the OA-ChCl DES CNC with a yield of 55.1% was achieved through the acidic DES hydrolysis, suggesting that the OA-ChCl DES was capable of promoting efficient cleavage of strong hydrogen bonds in BP.

Graphic abstract

     

Regioselectivity in Reactions of Bis‐Hydrazonoyl Halides with Some Bifunctional Heterocycles

Bis‐hydrazonoyl chloride 1 reacts regioselectively with 3‐mercapto‐1,2,4‐triazole 2a , 2,3‐dihydro‐3‐thioxo‐1,2,4‐triazin‐5(4H)‐one 2b and 2‐mercaptobenzimidazole 2c to give the hitherto unknown annelated 2,3‐bis‐(phenylhydrazono)thiazoles 6a‐c , respectively. Reactions of 1 with the methylthio derivatives of such heterocycles afforded the annelated 3,3′‐bis‐(1,2,4‐triazoles) 11a‐c , respectively. Similar reaction of 1 with 2‐phenylamino‐4(3H)‐pyrimidinones 4 gave 2,3‐bis(phenylhydrazono)imidazo[1,2‐a]pyrimidin‐5(1H)‐ones 16 . Oxidation of 6c yielded the corresponding bis(phenylazo) derivative 15 . The regiochemistry of the studied reactions is discussed.     

Spectrophotometric estimation of cobalt(II) with nitrilotriacetic acid

A convenient and efficient method for the estimation of cobalt(II) ions in the presence of other metal ions is described. Interference of metal ions such as iron(II), iron(III), nickel(II), manganese(II), and copper(II) have been investigated. Only iron(III) ions seriously affect this determination. Copper(II) and nickel(II) ions do not interfere if present in a molar-ratio less than 1:2 in the cobalt(II) ion solution. Cobalt(II)-nickel(II) and cobalt(II)-copper(II) binary mixtures can be efficiently analyzed at selective wavelengths.     

Simultaneous determination of uranium and thorium in high grade thorium ores

A routine procedure has been developed for the simultaneous determination of uranium and thorium in high concentration thorium ores. INAA is used to determine the uranium and thorium concentration. However, for very low concentrations of uranium a radiochemical procedure based on the use of NPy/benzene as an extractant has to be employed. The precision and accuracy of the method has been determined by analyzing IAEA and NBL standard thorium/uranium ores.     

Proficiency test exercise on the determination of natural levels of radionuclides in mushroom reference material

The results from a proficiency test exercise for the determination of natural levels of radionuclides in mushroom reference material carried out by laboratories in six different countries are discussed. These laboratories submitted data on seven radionuclides, namely ¹³⁴Cs, ¹³⁷Cs, ⁴⁰K, ⁹⁰Sr, ²⁴¹Am, ²²⁶Ra, and ²¹⁰Po. However, only the data received for three of these radionuclides could be statistically evaluated to obtain consensus mean values and confidence intervals (at a significance level of 0.05). The contents of ¹³⁴Cs, ¹³⁷Cs and ⁴⁰K were quantified as 4.4, 2,899 and 1,136 Bq/kg, respectively.     

Dietary evaluation of toxic elements through integrated diet

Several potentially toxic trace elements, namely, Hg, Pb, Cd, As, Sb, Br and Se have been measured by INAA in combination with AAS techniques in the integrated diet representative of the inhabitants of Gujranwala, a highly industrialized city of Pakistan. The dietary intake values for these elements have been estimated from the prevailing concentration level in the summer and winter season diets, which reveals that present intake data are well within the reported WHO values and can be considered to be safe. Posslble sources of food contamination by the toxic elements and their adverse impacts on human heaith are briefly discussed.     

Isotope shift studies in the second spectrum of neodymium in UV region

Isotope shift (IS) Δσ (142–150) have been measured in 92 spectral lines of Nd⁺ in the region 3290–3955 Å, employing recording Fabry-Perot spectrometer and highly enriched isotopic samples excited in a liquid-nitrogen cooled hollow cathode. Earlier IS measurement in UV region of Nd II spectrum is available for only a few lines, New classification has been made for several of the spectral lines studied presently. We have also revised the earlier suggested classification for some of the Nd II lines on the basis of observed isotope shifts. The transitions presently studied mostly involve high lying odd parity energy levels above 30,000 cm^?1 having neither electronic configuration assignment nor term isotope shifts (ΔT) evaluated. The present study would thus enable to evaluate ΔT values of some of these high lying odd levels, which should be helpful in suggesting possible electronic configurations.     

Kinetics and Mechanism of the Epoxidation of Alkyl-Substituted Alkenes by Hydrogen Peroxide, Catalyzed by Methylrhenium Trioxide

Epoxidations of alkyl-substituted alkenes, with hydrogen peroxide as the oxygen source, are catalyzed by CH(3)ReO(3) (MTO). The kinetics of 28 such reactions were studied in 1:1 CH(3)CN-H(2)O at pH 1 and in methanol. To accommodate the different requirements of these reactions, (1)H-NMR, spectrophotometric, and thermometric techniques were used to acquire kinetic data. High concentrations of hydrogen peroxide were used, so that diperoxorhenium complex CH(3)Re(O)(eta(2)-O(2))(2)(H(2)O), B, was the only predominant and reactive form of the catalyst. The reactions between B and the alkenes are about 1 order of magnitude more rapid in the semiaqueous solvent than in methanol. The various trends in reactivity are medium-independent. The rate constants for B with the aliphatic alkenes correlate closely with the number of alkyl groups on the olefinic carbons. The reactions become markedly slower when electron-attracting groups, such as halo, hydroxy, cyano, and carbonyl, are present. The rate constants for catalytic epoxidations with B and those reported for the stoichiometric reactions of dimethyldioxirane show very similar trends in reactivity. These findings suggest a concerted mechanism in which the electron-rich double bond of the alkene attacks a peroxidic oxygen of B. These data, combined with those reported for the epoxidation of styrene (a term intended to include related molecules with ring and/or aliphatic substituents) by B and by the monoperoxo derivative of MTO, suggest that all of the rhenium-catalyzed epoxidations occur by a common mechanism. The geometry of the system at the transition state can be inferred from these data, which suggest a spiro arrangement.