Complexation of Macrocyclic Compounds with Silver Ions in Surfactant Media

This paper is a report on the complexation studies of silverions with certain water soluble crown ethers viz., 15-crown-5,18-crown-6, cyclam, diaza 15-crown-5 and certain water insolublecrown ethers viz., benzo 15-crown-5, dibenzodiaza 15-crown-4,dibenzyldiaza 18-crown-6 in some nonionic surfactants viz.,polyoxyethylated alkyl phenol (TX 100), polyoxyethylene (20)sorbiton monolaurate (Tween 20), polyoxyethylene (20) sorbitonmonoleate (Tween 80) and polyoxyethylated glyco monolaurylether (Brij 35) by potentiometry. In addition, conductometry wasalso used to study the complexation of oxa crown ethers to comparethe results obtained by potentiometry, which were found to be ingood agreement with each other. The complexation studies indicate1:1 complex formation between the silver ion and macrocycle, thelog_ML ⁿ⁺ values being in the range 1 to 9.     

Head-group-influenced mixed micellization of sodium deoxycholate with conventional hydrocarbon surfactants of identical hydrocarbon tails

Conductivity, viscosity, turbidity, and NMR measurements were performed over most of the mole fraction range for sodium deoxycholate (SDC) with hexadecyltrimethylammonium bromide (HTAB), hexadecylpyridinium bromide (HPyBr), and hexadecylpyridinium chloride (HPyCl). All studies demonstrate that the mixed-micelle formation is more favorable in SDC plus HTAB rather than SDC plus HPyBr or SDC plus HPyCl mixtures. The results showed that the bulky pyridinium head groups of HPyBr or HPyCl create steric incompatibility with rigid SDC monomers in the mixed state.     

Order and chaos in soft condensed matter

Soft matter, like colloidal suspensions and surfactant gels, exhibit strong response to modest external perturbations. This paper reviews our recent experiments on the nonlinear flow behaviour of surfactant worm-like micellar gels. A rich dynamic behaviour exhibiting regular, quasi-periodic, intermittency and chaos is observed. In particular, we have shown experimentally that the route to chaos is via Type-II intermittency in shear thinning worm-like micellar solution of cetyltrimethylammonium tosylate where the strength of flow-concentration coupling is tuned by the addition of sodium chloride. A Poincaré first return map of the time series and the probability distribution of laminar length between burst events show that our data are consistent with Type-II intermittency. The existence of a ‘Butterfly’ intensity pattern in small angle light scattering (SALS) measurements performed simultaneously with the rheological measurements confirms the coupling of flow to concentration fluctuations in the system under study. The scattered depolarised intensity in SALS, sensitive to orientational order fluctuations, shows the same time-dependence (like intermittency) as that of shear stress.     

Studies in oxidation-reduction reactions: Oxidation with chloramine-b indirect determinations

Chloramine-B has been used as an oxidizing agent in hydrochloric acid medium for the indirect volumetric estimations of hydrogen peroxide, lead dioxide, manganese dioxide, selenium dioxide, sodium formate, sodium sulphide, sodium metavanadate, potassium iodate and copper sulphate using iodine monochloride as a catalyst and pre-oxidiser. Chloroform is used as an indicator. It is coloured pink owing to the liberation of iodine during the titration and becomes light pale yellow at the end-point because of the formation of iodine monochloride.     

Structure, reactivity and aromaticity of acenes and their BN analogues: a density functional and electrostatic investigation

Density functional calculations have been carried out on a series of linearly annelated acenes and their BN analogues. Even though borazine shows aromatic and reactivity behavior parallel with that of benzene, its condensed derivatives show patterns different from those of their hydrocarbon analogues. Nucleus independent chemical shift (NICS) values in acenes suggest that the aromaticity of the inner rings is more than that of benzene, whereas in BN-acenes there is no substantial change in the aromaticity of the individual rings. Molecular electrostatic potential (MESP) is employed to obtain further insights into the bonding and reactivity trends for these systems. The MESP topography patterns of acenes and BN-acenes are substantially different, with BN-acenes showing more localized pi electron features compared to those of acenes. The MESP values at the critical points (CPs) indicate overall lowering of aromaticity in these annelated systems. However, this change is gradual among the BN-acenes.     

Forensic classification of ballpoint pen inks using high performance liquid chromatography and infrared spectroscopy with principal components analysis and linear discriminant analysis

Several varieties of blue ballpoint pen inks were analyzed by high performance liquid chromatography (HPLC) and infrared spectroscopy (IR). The chromatographic data extracted at four wavelengths (254, 279, 370 and 400 nm) was analyzed individually and at a combination of these wavelengths by the soft independent modeling of class analogies (SIMCA) technique using principal components analysis (PCA) to estimate the separation between the pen samples. Linear discriminant analysis (LDA) measured the probability with which an observation could be assigned to a pen class. The best resolution was obtained by HPLC using data from all four wavelengths together, differentiating 96.4% pen pairs successfully using PCA and 97.9% pen samples by LDA. PCA separated 60.7% of the pen pairs and LDA provided a correct classification of 62.5% of the pens analyzed by IR. The results of this study indicate that HPLC coupled with chemometrics provided a better discrimination of ballpoint pen inks compared to IR. The need to develop a suitable IR method for analysing blue ballpoint pen inks has been emphasized and it is hoped that the development of such a method would indeed provide a valuable tool for the non-destructive analysis of blue ballpoint pen ink samples for forensic purposes.