Effect of N-glycinylmaleamic acid on microstructural characteristics and solubilization properties of sodium dodecyl sulfate micellar assemblies

The cosurfactant activity of N-glycinylmaleamic acid (NGMA) in sodium dodecyl sulfate (SDS) micelles has been demonstrated. The complementary techniques of electron spin resonance (ESR) and fluorescence spectroscopy have been used to draw information on hydration index (H), microviscosity (eta), and aggregation number (N) of micellar assemblies. The estimate of the critical micelle concentration of SDS in the presence of NGMA suggests a synergistic effect of NGMA. The enhanced solubilization of butyl propionate in the presence of NGMA in SDS micelles is explained on the basis of availability of larger interfacial area calculated from a simple spherical geometric model, combined with a low hydrophilicity index as estimated from ESR. Thus, addition of NGMA contributes to an increase of about 50% in ratio of area of polar shell (AP)/volume of hydration (Vh) ratio. The decrease in H accompanied by a decrease in eta with the incorporation of butyl propionate probably arises from solubilization of a butyl component inside the core with the adsorption of propionate ester on the interface.     

Specific heat studies on pristine and oxygenated iron tellurides

Specific heat studies carried out on Fe_1.1Te and oxygenated Fe_1.1Te and FeTe₂ in the range 77-300 K exhibit interesting behavior. The specific heat of the pristine sample reveals a well known structural transition associated with antiferromagnetic ordering near 67 K with a small thermal hysteresis of ∼1 K. Contrastingly, the oxygenated samples exhibit a phase transition with a very large thermal hysteresis of ∼100 K. The specific heat transition observed at the 150 and 260 K regions in the oxygenated Fe_1.1Te sample could not be captured by the magnetization measurements indicating that specific heat transitions seen in oxygenated samples may not be of magnetic origin.     

Molecular modeling of 3,4-pyridinedicarbonitrile dye sensitizer for solar cells using quantum chemical calculations

The geometries, electronic structures, polarizabilities, and hyperpolarizabilities of organic dye sensitizer 3,4-pyridinedicarbonitrile was studied based on Hartree–Fock (HF) and density functional theory (DFT) using the hybrid functional B3LYP. Ultraviolet–visible (UV–Vis) spectrum was investigated by time dependent DFT (TD-DFT). Features of the electronic absorption spectrum in the visible and near-UV regions were assigned based on TD-DFT calculations. The absorption bands are assigned to π → π1 transitions. Calculated results suggest that the three lowest energy excited states are due to photoinduced electron transfer processes. The interfacial electron transfer between semiconductor TiO₂ electrode and 3,4-pyridinedicarbonitrile is due to electron injection process from excited dye to the semiconductor’s conduction band. The role of cyanine in 3,4-pyridinedicarbonitrile in geometries, electronic structures, and spectral properties were analyzed.     

High-quality single crystals for neutron experiments

To make headway on any problem in physics, high-quality single crystals are required. In this talk, special emphasis will be placed on the crystal growth of various oxides (superconductors and magnetic materials), borides and carbides using the image furnaces at Warwick. The floating zone method of crystal growth used in these furnaces produces crystals of superior quality, circumventing many of the problems associated with, for example, flux growth from the melt. This method enables the growth of large volumes of crystal, a prerequisite especially for experiments using neutron beams. Some examples of experimental results from crystals grown at Warwick, selected from numerous in-house studies and our collaborative research projects with other UK and international groups will be discussed.      

Self-organization at the interface and in aqueous solution of a cationic gemini surfactant from the dioctyl ester of cystine

The cationic surfactant, dioctyl ester of cystine hydrochloride (DOEC), was characterized for interfacial adsorption and aggregation behavior in water. The cmc of DOEC was measured as 1.42±0.27×10(-5) mol dm(-3) using the techniques of tensiometry, conductivity and fluorimetry. From specific conductivity measurements, the degree of dissociation (α) of the amine hydrochloride was measured as 0.612. The standard free energy change of micellization (ΔG(m)(°)) and adsorption (ΔG(a)(°)) were calculated to be -25.07 and -44.37 kJ mol(-1), respectively. The aggregated structures provide non-polar microdomains as inferred from the I(3)/I(1) emission intensity ratio of 1.05 of pyrene fluoroprobe and also a blue shift of fluorescence emission wave length (λ(emi.)) maximum down to 470 nm with enhanced intensity of ANS probe in micellar solutions. From Langmuir film balance experiments, it is shown that DOEC forms stable viscoelastic films at the interface with A(0) at 0.69 nm(2)molecule(-1) that agree with the result from surface tension measurements. Molecular modeling suggests the tilted orientation of DOEC at the interface. A large packing parameter (P) of 0.58 and the fibril structures as observed from microscopy studies demonstrate that DOEC favors one-dimensional growth to form elongated micelles.     

High performance controlled reactors from micellar assemblies of aromatic amino acid amphiphiles for nanoparticle synthesis

The micellar assemblies of lauryl esters of tyrosine (LET) and phenylalanine (LEP) show extraordinary emulsification properties. The structural similarity in respect of the aromatic ring between the dispersed phase, styrene, and the surfactants facilitates solubilization of styrene up to four times the weight of LEP and 11 times that of LET. We propose that the solubilization site varies between core in the LEP and shell in the LET micelles. LET affords double emulsions, water in oil in water (w/o/w) over a narrow phase composition, for example at R=7.15, where R represents ratio of weight of styrene to LET. A schematic model depicting the solubilization site of styrene at different regions in LET and LEP micelles has been proposed. On polymerization, the emulsions with LET and LEP micelles generated high molecular weight polymer nanoparticles of size 12-49 nm with low polydispersity index (P(d)). This demonstrates that micellar assemblies act as templating controlled reactors for the polymerization reaction. We demonstrate that PS nanoparticle dispersion of size 49 nm with polymer weight fraction as high as 42.80% could be produced from emulsions with the LET surfactant, in contrast to LEP that is 50% less efficient. Polymerization of these emulsions occurs predominantly through a micellar nucleation mechanism. It is significant to note that under the same conditions, the control experiments with sodium dodecylsulfate (SDS) micelles resulted in polymers with broad distribution, P(d)>3.0 in molecular weight.     

Formation of self-aggregated structures of different types in water of chiral polymerizable amphiphiles from L-tyrosine and L-phenylalanine

Sodium salts of maleamic acid derivatives from lauryl esters of L-tyrosine (MTNa) and L-phenylalanine (MPNa) were synthesized and characterized. The aggregated structures of MTNa and MPNa in water were investigated, employing several independent methods. MPNa showed secondary aggregated structures in contrast to MTNa at concentrations of >1 × 10(-3) M. The results from dynamic light scattering, transmittance, conductivity, and viscosity measurements suggested the formation of aggregated structures of different types in MTNa and MPNa solutions. The measured fluorescence anisotropy (r) at 0.180 of the fluoroprobe, 1,6-diphenyl-1,3,5-hexatriene (DPH), and the d spacing of 38 ? from small-angle X-ray diffraction (SAXD) experiments confirmed the bilayer structures in MPNa. Scanning electron microscope (SEM) images provided the morphological features. The emulsion produced using MPNa solution was more stable. The confocal fluorescence microscopy image of the emulsion from MPNa confirmed the entrapment of water-soluble dye, rhodamine. The models of MTNa and MPNa molecules and the aggregated structures are presented.     

Relativistic calculations of ground and excited states of LiYb molecule for ultracold photoassociation spectroscopy studies

We report a series of quantum-chemical calculations for the ground and some of the low-lying excited states of an isolated LiYb molecule by the spin-orbit multistate complete active space second-order perturbation theory (SO-MS-CASPT2). Potential energy curves, spectroscopic constants, and transition dipole moments (TDMs) at both spin-free and spin-orbit levels are obtained. Large spin-orbit effects especially in the TDMs of the molecular states dissociating to Yb((3)P(0,1,2)) excited states are found. To ensure the reliability of our calculations, we test five types of incremental basis sets and study their effect on the equilibrium distance and dissociation energy of the ground state. We also compare CASPT2 and CCSD(T) results for the ground state spectroscopic constants at the spin-free relativistic level. The discrepancies between the CASPT2 and CCSD(T) results are only 0.01 ? in equilibrium bond distance (R(e)) and 200 cm(-1) in dissociation energy (D(e)). Our CASPT2 calculation in the supermolecular state (R=100 a.u.) with the largest basis set reproduces experimental atomic excitation energies within 3% error. Transition dipole moments of the super molecular state (R=100 a.u.) dissociating to Li((2)P) excited states are quite close to experimental atomic TDMs as compared to the Yb((3)P) and Yb((1)P) excited states. The information obtained from this work would be useful for ultracold photoassociation experiments on LiYb.     

Investigations of the dissociation behavior and interfacial adsorption characteristics of polyelectrolytes from poly(acrylamido‐2‐methyl‐1‐propane sulfonic acid) with an octadecyl side chain

Water‐soluble polymeric amphiphiles derived from acrylamido‐2‐methyl‐1‐propane sulfonic acid (AMPS) and octadecyl monomers in which the linker groups vary among acryloyl [octadecyl methacrylate (ODMAc)], maleate [octadecyl maleate ester (ODME)], and maleamic acid [octadecyl maleamic acid (ODMA)] have been synthesized. The dissociation behavior in water from potentiometric titration suggests that these polymers show resistance to neutralization. This might arise from coil structures, which effect the destabilization of sulfonate ions because of a proximity effect. The effect of the ? COOH group in modifying the dissociation behavior in the copolymers AMPS–ODME and AMPS–ODMA is indicated. The ratio of the intensities of the third vibronic peak (I₃) to the first vibronic peak (I₁) of the fluoroprobe pyrene in the presence of polymer solutions shows negligible changes as a function of pH, and this suggests the retention of micropolarity. The high I₃/I₁ value observed in the presence of the ODMAc polymer suggests intermolecular association. The reduction in the reduced viscosity with the concentration of the polymers suggests the polyelectrolyte behavior of all the copolymers. The progressive decrease in the reduced viscosity from 120 to 95 mL/g when the degree of ionization increases from 0.5 to 1 for the ODME polymer suggests changes in the solution structure. AMPS–ODMA and AMPS–ODME polymers exhibit significant adsorption at the interface and exhibit equilibrium surface tensions of 58.8 and 56.3 mN/m, respectively. The lower surface activity and higher reduced viscosity of ODMAc polymer solutions further support the formation of intermolecular associated or network structures. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 314–324, 2006