Small-Angle Neutron-Scattering Studies of Mixed Micellar Structures Made of Dimeric Surfactants Having Imidazolium and Ammonium Headgroups

Planar imidazolium cation based gemini surfactants 16-Im-n-Im-16], 2Br(-) (where n = 2, 3, 4, 5, 6, 8, 10, and 12), exhibit different morphologies and internal packing arrangements by adopting different supramolecular assemblies in aqueous media depending on their number of spacer methylene units (CH2)(n). Detailed measurements of the small-angle neutron-scattering (SANS) cross sections from different imidazolium-based surfactant micelles in aqueous media (D2O) are reported. The SANS data, containing the information of aggregation behavior of such surfactants in the molecular level, have been analyzed on the basis of the Hayter and Penfold model for the macro ion solution to compute the interparticle structure factor S(Q) taking into account the screened Coulomb interactions between the dimeric surfactant micelles. The characteristic changes in the SANS spectra of the dimeric surfactant with n = 4 due to variation of temperature have also been investigated. These data are then compared with the SANS characterization data of the corresponding gemini micelles containing tetrahedral ammonium ion based polar headgroups. The critical micellar concentration of each surfactant micelle (cmc) has been determined using pyrene as an extrinsic fluorescence probe. The variation of cmc as a function of spacer chain length has been explained in terms of conformational variation and progressive looping of the spacer into the micellar interior upon increasing the n values. Small-angle neutron-scattering (SANS) cross sections from different mixed micelles composed of surfactants with ammonium headgroups, 16-A(0), 16-Am-n-Am-16], 2Br(-) (where n = 4), 16-I-0, and 16-Im-n-Im-16], 2Br(-) (where n = 4), in aqueous media (D2O) have also been analyzed. The aggregate composition matches with that predicted from the ideal mixing model.

Sharp tips from crumples and capillary bridges

We describe two techniques to create sharp tips. The first involves the buckling of thin metal films deposited on soft, stretchable substrates. The second involves the formation of narrow necked capillary bridges.

Organophotocatalysis in nanostructured soft gel materials as tunable reaction vessels: comparison with homogeneous and micellar solutions

Riboflavin tetraacetate-catalyzed aerobic photooxidation of 1-(4-methoxyphenyl)ethanol was investigated as a model reaction under blue visible light in different soft gel materials, aiming to establish their potential as reaction vessels for photochemical transformations. Three strategies involving different degrees of organization of the catalyst within the gel network were explored, and the results compared to those obtained in homogeneous and micellar solutions. In general, physical entrapment of both the catalyst and the substrate under optimized concentrations into several hydrogel matrices (including low-molecular-weight and biopolymer-based gels) allowed the photooxidation with conversions between 55 and 100% within 120 min (TOF similar to 0.045-0.08 min(-1); k(obs) similar to 0.011-0.028 min(-1)), albeit with first-order rates ca. 1-3-fold lower than in solution under comparable non-stirred conditions. Remarkably, the organogel made of a cyclohexane-based bisamide gelator in CH3CN not only prevented the photodegradation of the catalyst but also afforded full conversion in less than 60 min (TOF similar to 0.167 min(-1); k(obs) similar to 0.073 min(-1)) without the need of additional proton transfer mediators (e. g., thiourea) as it occurs in CH3CN solutions. In general, the gelators could be recycled without detriment to their gelation ability and reaction rates. Moreover, kinetics could be fine-tuned according to the characteristics of the gel media. For instance, entangled fibrillar networks with relatively high mechanical strength were usually associated with lower reaction rates, whereas wrinkled laminated morphologies seemed to favor the reaction. In addition, the kinetics results showed in most cases a good correlation with the aeration efficiency of the gel media.

Yielding and large deviations in micellar gels: a model

We present a simple model that can be used to account for the rheological behaviour observed in recent experiments on micellar gels. The model combines attachment detachment kinetics with stretching due to shear, and shows well-defined jammed and flowing states. The large-deviation function (LDF) for the coarse-grained velocity becomes increasingly non-quadratic as the applied force F is increased, in a range near the yield threshold. The power fluctuations are found to obey a steady-state fluctuation relation (FR) at small F. However, the FR is violated when F is near the transition from the flowing to the jammed state although the LDF still exists; the antisymmetric part of the LDF is found to be nonlinear in its argument. Our approach suggests that large fluctuations and motion in a direction opposite to an imposed force are likely to occur in a wider class of systems near yielding.

Ratiometric, reversible, and parts per billion level detection of multiple toxic transition metal ions using a single probe in micellar media

We present the selective sensing of multiple transition metal ions in water using a synthetic single probe. The probe is made up of pyrene and pyridine as signaling and interacting moiety, respectively. The sensor showed different responses toward metal ions just by varying the medium of detection. In organic solvent (acetonitrile), the probe showed selective detection of Hg2+ ion. In water, the fluorescence quenching was observed with three metal ions, Cu2+, Hg2+, and Ni2+. Further, just by varying the surface charge on the micellar aggregates, the probe could detect and discriminate the above-mentioned three different toxic metal ions appropriately. In neutral micelles (Brij 58), the probe showed a selective interaction with Hg2+ ion as observed in acetonitrile medium. However, in anionic micellar medium (sodium dodecyl sulfate, SDS), the probe showed changes with both Cu2+ and Ni2+. under UV-vis absorption spectroscopy. The discrimination between these two ions was achieved by recording their emission spectra, where it showed selective quenching with Cu2+.

Rapid determination of main constituents of packed juices by reverse phase-high performance liquid chromatography: an insight in to commercial fruit drinks

The present work reports the compositional analysis of thirteen different packed fruit juices using high performance liquid chromatography (HPLC). Vitamin C, organic acids (citric and malic) and sugars (fructose, glucose and sucrose) were separated, analyzed and quantified using different reverse phase methods. A new rapid reverse phase HPLC method was developed for routine analysis of vitamin C in fruit juices. The precision results of the methods showed that the relative standard deviations of the repeatability and reproducibility were < 0.05 and < 0.1 respectively. Correlation coefficient of the calibration models developed was found to be higher than 0.99 in each case. It has been found that the content of Vitamin C was less variable amongst different varieties involved in the study. It is also observed that in comparison to fresh juices, the packed juices contain lesser amounts of vitamin C. Citric acid was found as the major organic acids present in packed juices while maximum portion of sugars was of sucrose. Comparison of the amount of vitamin C, organic acids and sugars in same fruit juice of different commercial brands is also reported.

Nonlinear viscoelasticity of entangled wormlike micellar fluid under large-amplitude oscillatory shear: Role of elastic Taylor-Couette instability

The role of elastic Taylor-Couette flow instabilities in the dynamic nonlinear viscoelastic response of an entangled wormlike micellar fluid is studied by large-amplitude oscillatory shear (LAOS) rheology and in situ polarized light scattering over a wide range of strain and angular frequency values, both above and below the linear crossover point. Well inside the nonlinear regime, higher harmonic decomposition of the resulting stress signal reveals that the normalized third harmonic I-3/I-1 shows a power-law behavior with strain amplitude. In addition, I-3/I-1 and the elastic component of stress amplitude sigma(E)(0) show a very prominent maximum at the strain value where the number density (n(v)) of the Taylor vortices is maximum. A subsequent increase in applied strain (gamma) results in the distortions of the vortices and a concomitant decrease in n(v), accompanied by a sharp drop in I-3 and sigma(E)(0). The peak position of the spatial correlation function of the scattered intensity along the vorticity direction also captures the crossover. Lissajous plots indicate an intracycle strain hardening for the values of gamma corresponding to the peak of I-3, similar to that observed for hard-sphere glasses.

A Probe for the Selective and Parts-per-Billion-Level Detection of Copper(II) and Mercury(II) using a Micellar Medium and Its Utility in Cell Imaging

A novel colorimetric probe 1 based on the picolyl moiety has been designed and synthesized. Probe 1 is composed of a pyrene and a bispicolyl amine (BPA) unit, in which the BPA moiety acts as a binding unit and the binding phenomenon is sensed from the changes in the signaling subunit. The probe detects Cu2+ specifically in water and both Cu2+ and Hg2+ efficiently in neutral Brij-58 micellar media. The probe shows a color change visible to the naked eye upon addition of metal ions. Notably, in a micellar medium, probe 1 can detect both the Cu2+ and Hg2+ ions even at parts-per-billion levels. Furthermore, the probe shows ratiometric detection of both the metal ions making the sensing quantitative. The two metal ions could be discriminated both visibly under a UV lamp and with the use of fluorescence spectroscopy. The probe could be also used in biological cell lines for the detection of both Hg2+ and Cu2+ ions.

Experimental study on evaporation of pentane from a heated capillary slot

An experimental investigation of evaporation of a pentane meniscus from a heated capillary slot is presented. A novel aspect of this study is that both the wicking height and steady state evaporation mass flow rate are measured simultaneously. Based on a macroscopic force balance, the apparent contact angle of the evaporating meniscus is experimentally estimated from the wicking height and mass flow rate. This is compared with the results obtained using evaporating thin-film theory. The experimentally estimated contact angle is slightly larger than that obtained from the thin-film model but both show similar trends. Further, it is found that the reduction in the meniscus height is primarily due to an increase in the apparent contact angle. The liquid and vapor pressure drops in the capillary are insignificant relative to the capillary pressure. (C) 2015 Elsevier Ltd. All rights reserved.