title: NMR investigations of self-aggregation characteristics of SDS in a model assembled tri-block copolymer solution.
abstract: The present work was undertaken with a view to understand the influence of a model non-ionic tri-block copolymer PEO-PPO-PEO (poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)) with molecular weight 5800 i.e., P123 [(EO)(20)-(PO)(70)-(EO)(20)] on the self-aggregation characteristics of the anionic surfactant sodium dodecylsulfate (SDS) in aqueous solution (D(2)O) using NMR chemical shift, self-diffusion and nuclear spin-relaxation as suitable experimental probes. In addition, polymer diffusion has been monitored as a function of SDS concentration. The concentration-dependent chemical shift, diffusion data and relaxation data indicated the significant interaction of polymeric micelles with SDS monomers and micelles at lower and intermediate concentrations of SDS, whereas the weak interaction of the polymer with SDS micelles at higher concentrations of SDS. It has been observed that SDS starts aggregating on the polymer at a lower concentration i.e., critical aggregation concentration (cac=1.94 mM) compared to polymer-free situation, and the onset of secondary micelle concentration (C(2)=27.16 mM) points out the saturation of the 0.2 wt% polymer or free SDS monomers/micelles at higher concentrations of SDS. It has also been observed that the parameter cac is almost independent in the polymer concentrations of study. The TMS (tetramethylsilane) has been used as a solubilizate to measure the bound diffusion coefficient of SDS-polymer mixed system. The self-diffusion data were analyzed using two-site exchange model and the obtained information on aggregation dynamics was commensurate with that inferred from chemical shift and relaxation data. The information on slow motions of polymer-SDS system was also extracted using spin-spin and spin-lattice relaxation rate measurements. The relaxation data points out the disintegration of polymer network at higher concentrations of SDS. The present NMR investigations have been well corroborated by surface tension and conductivity measurements.
authors.affiliation: Council of Scientific and Industrial Research (CSIR)-Central Leather Research Institute (CLRI), Chemical Physics Laboratory, Adyar, Chennai, India. bvnphani@gmail.com
authors.forename: B V N Phani
authors.initials: BV
authors.lastname: Kumar
authors.forename: S Umayal
authors.initials: SU
authors.lastname: Priyadharsini
authors.forename: G K S
authors.initials: GK
authors.lastname: Prameela
authors.forename: Asit Baran
authors.initials: AB
authors.lastname: Mandal
mesh_terms: D004553:Electric Conductivity; D009682:Magnetic Resonance Spectroscopy / Q000592:standards; D008958:Models, Molecular; D011092:Polyethylene Glycols / Q000138:chemical synthesis / Q000737:chemistry*; D011409:Propylene Glycols / Q000138:chemical synthesis / Q000737:chemistry*; D012015:Reference Standards; D012967:Sodium Dodecyl Sulfate / Q000138:chemical synthesis* / Q000737:chemistry*; D012996:Solutions; D014867:Water / Q000737:chemistry
chemical_list: C116176:PEO-PPO-PEO; D011409:Propylene Glycols; D012996:Solutions; D014867:Water; D012967:Sodium Dodecyl Sulfate; D011092:Polyethylene Glycols