Oxidation of cis-Diamminediacetato PtII with Hydrogen Peroxide Can Give Rise to Two Isomeric PtIV Products

The oxidation of cis-[Pt(NH₃)₂(OAc)₂] with H₂O₂ yields a mixture of two isomers: ctc-[Pt(NH₃)₂(OH)₂(OAc)₂] and ctc-[Pt(NH₃)₂(OH)(OAc)(OH)(OAc)]. Following modification with 4-phenylbutyric (PhB) anhydride, two isomers were separated and characterized; the symmetric ctc-[Pt(NH₃)₂(PhB)₂(OAc)₂] ( 1 ) and the nonsymmetric ctc-[Pt(NH₃)₂(PhB)(OAc)(PhB)(OAc)] ( 2 ). They differ in their log P values and despite having similar cellular uptake and similar DNA platination levels, the symmetric ctc-[Pt(NH₃)₂(OH)₂(OAc)₂] is more than 4-fold more potent than the nonsymmetric isomer in a panel of 4 cancer cell lines.     

Tosic Acid-on-Silica Gel: A Cheap and Eco-friendly Catalyst for a Convenient One-pot Synthesis of Substituted Benzimidazoles

Summary. 2-Substituted and 1,2-disubstited benzimidazoles were prepared efficiently from o-phenylenediamines and aryl aldehydes using p-toluenesulphonic acid (5 mol%)-on-silica gel as a cheap and environmentally benign catalyst.     

Numerical modelling of a direct current non-transferred thermal plasma torch for optimal performance

A laminar steady-state 2D axisymmetric model of a direct current (DC) thermal plasma torch using a magneto-hydrodynamic approach has been developed. The model takes into account the entire torch system comprising the plasma gas injection, the inner region of the torch, and the jet exiting into the ambient environment. Numerical results are obtained for two different power inputs chosen from published experimental data. The temperature predictions at the torch exit are found in good agreement with experimental results. Velocity analysis of the plasma jet has been presented and the impact of electromagnetic force on jet velocity is analysed. The Lorentz force arising due to the coupling of fluid motion and electromagnetic forces shoots up the jet velocity to significantly high values near the cathode tip. Temperature and velocity profiles are in good agreement with the characteristics of a long laminar plasma jet. An operating value of heat transfer coefficient (h) has been suggested for optimal torch operation, thus ensuring a low anode erosion rate and acceptable thermal efficiency. The argon torch has the maximum temperature and longest jet length among the plasma gases considered.     

Mechanistic aspects of ligand substitution on <Emphasis Type="Italic">cis</Emphasis>-diaqua(<Emphasis Type="Italic">cis</Emphasis>-1,2-diaminocyclohexane)platinum(II) by Glycine-<Emphasis Type="SmallCaps">l</Emphasis>-Leucine

The kinetics of the interaction of glycine-l-leucine (Glyleu) with cis-[Pt(cis-dach)(OH₂)₂]²⁺ (dach = 1,2-diaminocyclohexane) has been studied spectrophotometrically as a function of [cis-[Pt(cis-dach)(OH₂)₂]²⁺], [Glyleu] and temperature at pH 4.0, where the complex exists predominantly as the diaqua species and Glyleu as a zwitterion. The substitution reaction shows two consecutive steps: the first is the ligand-assisted anation and the second is the chelation step. The activation parameters for both the steps were evaluated using Eyring’s equation. The low ∆H₁^≠ (51.9 ± 2.8 kJmol⁻¹) and large negative value of ∆S₁^≠ (−152 ± 8 JK⁻¹mol⁻¹) as well as ∆H₂^≠ (54.4 ± 1.7 kJmol⁻¹) and ∆S₂^≠ (−162 ± 5 JK⁻¹mol⁻¹) indicate an associative mode of activation for both the aqua ligand substitution processes.     

Kinetics and mechanism of the reaction of hydroxopentaaquarhodium(III) ion with <Emphasis Type="SmallCaps">l</Emphasis>-Arginine in aqueous solution

The kinetics of the aqua ligand substitution from hydroxopentaaquarhodium(III) ion, [Rh(H₂O)₅(OH)]²⁺, by l-Arginine has been studied spectrophotometrically as a function of Arginine concentration, and temperature, at pH 4.3. The reaction proceeds via a rapid outer sphere association complex formation step followed by two consecutive steps. The first of these involves ligand-assisted anation, while the second involves chelation as the second aqua ligand is displaced. The association equilibrium constant for the outer sphere complex formation has been evaluated together with the rate constants for the two subsequent steps. The activation parameters for both steps have been evaluated using Eyring’s equation. Thermodynamic parameters calculated from the temperature dependence of the outer sphere association equilibrium constants are also consistent with an associative mode of activation. The product of the reaction has been characterized by conductivity measurement and IR spectroscopic analysis.     

Kinetic and mechanistic studies on the reaction of thiosemicarbazide with [(H<Subscript>2</Subscript>O)(tap)<Subscript>2</Subscript>RuORu(tap)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)]<Superscript>2+</Superscript> {tap = 2-(m-tolylazo)pyridine}

The interaction of thiosemicarbazide with the title complex has been studied spectrophotometrically in aqueous medium as a function of [complex], [thiosemicarbazide], pH and temperature at constant ionic strength. At pH 7.4, the reaction shows two distinct paths; both of which are [thiosemicarbazide] dependent. A parallel reaction scheme fits well with the experimental findings. An associative interchange mechanism is proposed for both the paths; the activation parameters calculated from Eyring plots are ΔH₁^≠ = 14.2 ± 0.8 kJ mol⁻¹, ΔS₁^≠ = −241 ± 2 JK⁻¹ mol⁻¹, ΔH₂^≠ = 30.8 ± 1.4 kJ mol⁻¹ and ΔS₂^≠ = −236 ± 4 JK⁻¹ mol⁻¹. From the temperature dependence of the outer sphere association complex equilibrium constants, the thermodynamic parameters calculated are ΔH₁^° = 34.25 ± 1.9 kJ mol⁻¹, ΔS₁^° = 146 ± 6 J K⁻¹ mol⁻¹ and ΔH₂^° = 9.4 ± 1.1 kJ mol⁻¹, ΔS₂^° = 71 ± 3 JK⁻¹ mol⁻¹, which gives a negative ΔG° at all temperatures studied, supporting the spontaneous formation of an outer sphere association complex.     

Switchable Cucurbituril–Bipyridine Beacons

4‐Aminobipyridine derivatives form strong inclusion complexes with cucurbit[6]uril, exhibiting remarkably large enhancements in fluorescence intensity and quantum yields. The remarkable complexation‐induced pK_a shift (ΔpK_a=3.3) highlights the strong charge–dipole interaction upon binding. The reversible binding phenomenon can be used for the design of switchable beacons that can be incorporated into cascades of binding networks. This concept is demonstrated herein by three different applications: 1) a switchable fluorescent beacon for chemical sensing of transition metals and other ligands; 2) direct measurement of binding constants between cucurbit[6]uril and various nonfluorescent guest molecules; and 3) quantitative monitoring of biocatalytic reactions and determination of their kinetic parameters. The latter application is illustrated by the hydrolysis of an amide catalyzed by penicillin G acylase and by the elimination reaction of a β‐cabamoyloxy ketone catalyzed by aldolase antibody 38C2.     

Experimental lifetime of some level belonging to the 5p46d configuration of XeII

Lifetimes of eight levels belonging to the 5p⁴6d configuration of singly ionized xenon have been measured by high frequency deflection technique with a delayed coincidence single photon counting arrangement. The results have been compared with other experimental and theoretical values. The lifetimes of the 6d ²F_3/2 and 6d ⁴F_3/2 levels have been measured for the first time.     

K2PdCl4 catalyzed efficient multicomponent synthesis of α-aminonitriles in aqueous media

An efficient, mild and environmentally friendly method has been developed for the Strecker reaction to synthesize α-aminonitriles in the presence of K₂PdCl₄ as a catalyst. The three-component one-pot condensation of an aldehyde, amine and trimethylsilyl cyanide proceeded smoothly in water to afford the corresponding product in high yield with short reaction times.     

Surface plasmon resonance in nano-gold antimony glass–ceramic dichroic nanocomposites: One-step synthesis and enhanced fluorescence application

A single-step melt-quench in situ thermochemical reduction technique has been used to synthesize a new series of Au° nanoparticles embedded antimony glass–ceramic (K₂O–B₂O₃–Sb₂O₃–ZnO) dichroic nanocomposites. X-ray and selected area electron diffractions manifest growth of Au° nanoparticles along (2 0 0) planes. The particle sizes obtained from X-ray diffraction patterns are found to vary in the range 4–21 nm. Dichroic behavior is attributed to the elliptical shape gold nanoparticles having aspect ratio 1.2, as observed from the transmission electron microscopy (TEM) images. The Au° nanoparticles exhibit surface plasmon resonance band (SPR) around 600 nm, which experiences red-shifts with increasing Au concentration. These nanocomposites when co-doped with Sm₂O₃ and excited at 949 nm, exhibit 2-fold intensification of 636 nm red emission transition (⁴G_5/2 → ⁶H_9/2) due to SPR induced local field enhancement of Au° nanoparticles and are promising materials for display applications.