Coordinatively Unsaturated Lanthanide(III) Helicates: Luminescence Sensors for Adenosine Monophosphate in Aqueous Media

Coordinatively unsaturated double‐stranded helicates [(H₂L)₂Eu₂(NO₃)₂(H₂O)₄](NO₃)₄, [(H₂L)₂Tb₂(H₂O)₆](NO₃)₆, and [(H₂L)₂Tb₂(H₂O)₆]Cl₆ (H₂L=butanedioicacid‐1,4‐bis[2‐(2‐pyridinylmethylene)hydrazide]) are easily obtained by self‐assembly from the ligand and the corresponding lanthanide(III) salts. The complexes are characterized by X‐ray crystallography showing the helical arrangement of the ligands. Co‐ligands at the metal ions can be easily substituted by appropriate anions. A specific luminescence response of AMP in presence of ADP, ATP, and other anions is observed. Specificity is assigned to the perfect size match of AMP to bridge the two metal centers and to replace quenching co‐ligands in the coordination sphere.     

Hexabromide salt of a tiny octaazacryptand as a receptor for encapsulation of lower homolog halides: structural evidence on halide selectivity inside the tiny cage

Tiny azacryptand 1,4,7,10,13,16,21,24-octaazabicyclo[8.8.8]hexacosane (L) upon reaction with 48% hydrobromic acid (containing <0.05% chloride contamination) forms hexabromide salt (1). Single crystal X-ray crystallographic investigation of the hexaprotonated bromide (1) shows no guest encapsulation inside the tiny cage. This bromide salt 1 with an empty proton cage has been utilized as the receptor for encapsulation of chloride (2) and fluoride (3). Crystallographic results of mixed chloride/bromide (2) and fluoride/bromide (3) complexes of L are examined, which show monotopic recognition of chloride in the case of 2 and fluoride in the case of 3 inside the proton cage with five bromide and three water molecules outside the cavity. Single crystals obtained from an experiment on mixed anionic system (chloride and fluoride), 1 shows selective encapsulation of fluoride, which supports the formation of complex 3 and crystals obtained upon treatment of 2 with tetrabutyl ammonium fluoride also yields complex 3. In a separate reaction between L and 49% hydrobromic acid containing higher chloride contamination (<0.2%) forms chloride/bromide salt (2). ¹H NMR studies of 1 with sodium chloride and fluoride support the encapsulation of the respective anions inside the proton cage.     

Trace element analysis of high purity arsenic through vapour phase dissolution and ICP-QMS

Vapour phase dissolution (VPD) has been used for the dissolution of high purity arsenic through acid vapours generated by aquaregia mixture, prior to trace element characterization. Trace impurities in As were determined by employing ion-exchange and volatilization methodologies for quantitative separation of the As matrix. After dissolving the As matrix through VPD procedure, sample solution in 0.1 M HF medium was loaded on Dowex-50WX8. The sorbed elements were then eluted first with a 20 ml aliquot of 4 M HNO₃ followed by another 10 ml of 6 M HNO₃ for the elution of REE (La, Ce, Gd and Lu). In the volatilization procedure, arsenic was removed from H₂SO₄ medium as volatile bromide by three successive additions of HBr at a temperature of about 220 °C. The trace element determinations were carried out by ICP-QMS. In both the matrix separation procedures namely on Dowex-50WX8 in 0.1 M HF medium and volatilization from H₂SO₄+HBr medium showed that the removal of arsenic matrix was nearly quantitative (>99.99%). The recoveries of trace elements were found to be >95%. Good agreement was obtained for many elements in both the procedures. The VPD approach provides considerable reduction of the process blank levels for all the elements when compared with conventional open dissolution approach. The subsequent ion-exchange or volatilization steps, contribute more to the overall process blanks.     

Metallosurfactants of Chromium(III) Coordination Complexes. Synthesis, Characterization and Determination of CMC Values

A number of mixed ligand chromium(III)–surfactant coordination complexes, of the type cis-[Cr(en)₂(A)X]²⁺ and cis-α-[Cr(trien)(A)X]²⁺ (A = Dodecyl or Cetylamine; X = F⁻, Cl⁻, Br⁻) were synthesized from the corresponding dihalogeno complexes by ligand substitution. These compounds form foam in aqueous solution when shaken. The critical micelle concentration (CMC) values of these surfactant metal complexes in aqueous solution were obtained from conductance measurements. Specific conductivity data (at 303, 308 and 313 K) served for evaluation of the temperature-dependent critical micelle concentration (cmc) and the thermodynamics of micellization (Δ G_m⁰, Δ H_m⁰ and Δ S_m⁰).     

A new hexaaza bicyclic cyclophane with dual binding sites

A new C3-symmetric drum-shaped homoditopic haxaamino bicyclic cyclophane and its hexachloride and hexaiodide complexes have been synthesized and characterized and dual recognition of guests has been demonstrated. Single-crystal X-ray analysis illustrates that bicyclic cyclophane has a cavity and side pockets for acetone molecules. The hexaprotonated state of this bicycle shows encapsulation of an iodide inside its cavity, and in hexachloride complex, chloride is recognized as Cl(-)...H2O in each of the three side pockets which are in extensive hydrogen bonding interactions with the water and chlorides. (1)H NMR experiments have also been carried out on hexatosylated cyclophane with the halides to study solution state binding.     

Determination of trace phosphorus in zirconium-niobium alloy and Zircaloy by UV-vis spectrophotometry

A spectrophotometric method has been developed for the determination of traces of phosphorus in zirconium based alloys (Zr-2.5Nb and Zircaloy). It is achieved by selective fluoride complexation controlled by boric acid. The samples were dissolved in HF and fluoro-complexes of the matrices were formed by maintaining the concentration of HF while the excess HF was controlled by boric acid. After the formation of phosphomolybdate, extracted into n-butyl acetate, ion-associated with crystal violet and the absorbance was measured at 582 nm. The results obtained by this procedure were in close agreement with the certified reference material (CRM) values and further these values were compared with the values determined by Glow Discharge-Quadrupole Mass Spectrometry (GD-QMS). The potential interferences like fluoride, silicon, arsenic(V), niobium, titanium, tantalum, etc., were tolerable to large level. LOD (3 s) was found to be 0.055 mg kg(-1) with a precision (R.S.D.) of 2-3% and molar absorptivity was 2.7x10(5) L mol(-1) cm(-1).     

Kinetics and the Mechanism of Iron(II) Reduction of cis-α-halogeno(cetylamine) (triethylenetetramine)cobalt(III) Complex Ion in Aqueous Acid Medium

The kinetics and mechanism of iron(II) reduction of cis- α-chloro/bromo(cetylamine)(triethylenetetramine) cobalt(III) surfactant complex ions were studied spectrophotometrically in an aqueous acid medium by following the disappearance of Co^III using an excess of the reductant under pseudo-first-order conditions: [Fe^II = 0.25 mol dm⁻³, [H⁺ = 0.1 mol dm⁻³, [μ = 1.0 mol dm⁻³ ionic strength in a nitrogen atmosphere at 303, 308 and 313 K. The reaction was found to be second order and showed acid independence in the range [H⁺ = 0.05−0.25 mol dm⁻³. The second order rate constant increased with Co^III concentration and the presence of aggregation of the complex itself altered the reaction rate. The effects of [Fe^II], [H⁺] and [ μ] on the rate were determined. Activation and thermodynamic parameters were computed. It is suggested that the reaction of Fe²⁺(aq) with Co^III complex proceeds by an inner-sphere mechanism.     

Mechanism of (Salen)manganese(III)‐Catalyzed Oxidation of Aryl Phenyl Sulfides with Sodium Hypochlorite

The oxidation of 4‐substituted phenyl phenyl sulfides was carried out with several oxo(salen)manganese(V) complexes in MeCN/H₂O 9 : 1. The kinetic data show that the reaction is first‐order each in the oxidant and sulfide. Electron‐attracting substituents in the sulfides and electron‐releasing substituents in salen of the oxo(salen)manganese(V) complexes reduce the rate of oxidation. A Hammett analysis of the rate constants for the oxidation of 4‐substituted phenyl phenyl sulfides gives a negative ρ value (ρ=?2.16) indicating an electron‐deficient transition state. The log k₂ values observed in the oxidation of each 4‐substituted phenyl phenyl sulfide by substituted oxo(salen)manganese(V) complexes also correlate with Hammett σ constants, giving a positive ρ value. The substituent‐, acid‐, and solvent‐effect studies indicate direct O‐atom transfer from the oxidant to the substrate in the rate‐determining step.