Solution self-assembly and adsorption at the air-water interface of the monorhamnose and dirhamnose rhamnolipids and their mixtures

The self-assembly in solution and adsorption at the air-water interface, measured by small-angle neutron scattering, SANS, and neutron reflectivity, NR, of the monorhamnose and dirhamnose rhamnolipids (R1, R2) and their mixtures, are discussed. The production of the deuterium-labeled rhamnolipids (required for the NR studies) from a Pseudomonas aeruginosa culture and their separation into the pure R1 and R2 components is described. At the air-water interface, R1 and R2 exhibit Langmuir-like adsorption isotherms, with saturated area/molecule values of about 60 and 75 ?(2), respectively. In R1/R2 mixtures, there is a strong partitioning of R1 to the surface and R2 competes less favorably because of the steric or packing constraints of the larger R2 dirhamnose headgroup. In dilute solution (<20 mM), R1 and R2 form small globular micelles, L(1), with aggregation numbers of about 50 and 30, respectively. At higher solution concentrations, R1 has a predominantly planar structure, L(α) (unilamellar, ULV, or bilamellar, BLV, vesicles) whereas R2 remains globular, with an aggregation number that increases with increasing surfactant concentration. For R1/R2 mixtures, solutions rich in R2 are predominantly micellar whereas solutions rich in R1 have a more planar structure. At an intermediate composition (60 to 80 mol % R1), there are mixed L(α)/L(1) and L(1)/L(α) regions. However, the higher preferred curvature associated with R2 tends to dominate the mixed R1/R2 microstructure and its associated phase behavior.     

Lagrange solution for three wavelength solitary wave clusters in nematic liquid crystals

We investigate the interaction of three optical solitary waves propagating with angular momentum in bulk nematic liquid crystals. The resulting cluster of solitary waves, or nematicons, is shown to orbit about its common centre of “mass”. An elongated isosceles triangle configuration is derived, this solution being the equivalent of the Lagrange solution of Newtonian gravitation. This triangle solution is found to be stable owing to diffractive radiation. A modulation theory explains the existence of the triangle solution as due to the non-monotonicity of an effective potential for the interaction of the solitary waves. This modulation theory also gives good agreement with numerical solutions for the trajectories of the nematicons in the three colours. Finally, it is shown that a cut-off in the shed diffractive radiation prevents the break-up of the triangle due to radiative losses.     

Microstructure and dynamics of a mesogenic diol

A number of techniques have been used to elucidate the structure and dynamics of 4,4'-bis(6-hydroxyhexyloxy)biphenyl (BHHBP) in its various phases. X-ray diffraction studies indicate that the molecules pack in a crystalline phase which melts to produce a highly ordered smectic/disordered crystal mesophase. Based on molecular models and the infrared results, the all trans conformation requires a 45°-55° tilt of the molecules in the smectic layers. Infrared spectroscopic results indicate that a predominantly trans chain conformation and hydrogen bonding of the layered crystal structure persists through the mesophase. Additionally, rotational freedom about the biphenyl linkage appears to occur only in the isotropic phase. NMR data indicate that the alkoxy chain is at or near co-planarity with the respect to the phenyl ring in the crystalline phase, with reorientational motion of the biphenyl group becoming allowed in the mesophase in the form of rapid (τ_c ∼ 3 μs at 100°C) small angle liberations and, perhaps, slower (τ_c ∼ 0·5 ms at 100°C) 180° ring flips. The alkyl chains exhibit a progressive increase in mobility with distance from the biphenyl core and achieve considerable mobility at the hydroxy end of the chain despite the fact that hydrogen bonding still occurs in the mesophase.     

Development of adaptive modeling techniques for non-linear hysteretic systems

Adaptive estimation procedures have gained significant attention by the research community to perform real-time identification of non-linear hysteretic structural systems under arbitrary dynamic excitations. Such techniques promise to provide real-time, robust tracking of system response as well as the ability to track time variation within the system being modeled. An overview of some of the authors’ previous work in this area is presented, along with a discussion of some of the emerging issues being tackled with regard to this class of problems. The trade-offs between parametric-based modeling and non-parametric modeling of non-linear hysteretic dynamic system behavior are discussed. Particular attention is given to (1) the effects of over- and under-parameterization on parameter convergence and system output tracking performance, (2) identifiability in multi-degree-of-freedom structural systems, (3) trade-offs in setting user-defined parameters for adaptive laws, and (4) the effects of noise on measurement integration. Both simulation and experimental results indicating the performance of the parametric and non-parametric methods are presented and their implications are discussed in the context of adaptive structures and structural health monitoring.     

Adsorption of sophorolipid biosurfactants on their own and mixed with sodium dodecyl benzene sulfonate, at the air/water interface

The adsorption of the lactonic (LS) and acidic (AS) forms of sophorolipid and their mixtures with the anionic surfactant sodium dodecyl benzene sulfonate (LAS) has been measured at the air/water interface by neutron reflectivity, NR. The AS and LS sophorolipids adsorb with Langmuir-like adsorption isotherms. The more hydrophobic LS is more surface active than the AS, with a lower critical micellar concentration, CMC, and stronger surface adsorption, with an area/molecule ～70 ?(2) compared with 85 ?(2) for the AS. The acidic sophorolipid shows a maximum in its adsorption at the CMC which appears to be associated with a mixture of different isomeric forms. The binary LS/AS and LS/LAS mixtures show a strong surface partitioning in favor of the more surface active and hydrophobic LS component but are nevertheless consistent with ideal mixing at the interface. In contrast, the surface composition of the AS/LAS mixture is much closer to the solution composition, but the surface mixing is nonideal and can be accounted for by regular solution theory, RST. In the AS/LS/LAS ternary mixtures, the surface adsorption is dominated by the sophorolipid, and especially the LS component, in a way that is not consistent with the observations for the binary mixtures. The extreme partitioning in favor of the sophorolipid for the LAS/LS/AS (1:2) mixtures is attributed to a reduction in the packing constraints at the surface due to the AS component. Measurements of the surface structure reveal a compact monolayer for LS and a narrow solvent region for LS, LS/AS, and LS/LAS mixtures, consistent with the more hydrophobic nature of the LS component. The results highlight the importance of the relative packing constraints on the adsorption of multicomponent mixtures, and the impact of the lactonic form of the sophorolipid on the adsorption of the sophorolipid/LAS mixtures.     

The characterisation of coumarins from selected structural classes by electrospray ionisation quadrupole time-of-flight tandem mass spectrometry

Electrospray ionisation quadrupole time-of-flight tandem mass spectrometry (ESI-QTOF-MS/MS) has been used for characterisation of a selection of naturally occurring and synthetic coumarins from different structural classes. The product ions, suggested in earlier studies by electrospray ionisation ion trap mass spectrometry (ESI-MS(n)), are unequivocally established for the representative coumarins by virtue of accurate mass measurement. Synthetic coumarins that are unsubstituted in the heterocyclic ring give rise to a major product ion by loss of CO(2), whereas those substituted in the heterocyclic ring generally undergo alternative fragmentation releasing neutral species such as ketene or methyl ketene. Naturally occurring coumarins, unsubstituted in the heterocyclic ring and substituted in the benzene ring with chains or rings of hydrocarbons and oxygen, principally fragment at the side chain releasing unsaturated hydrocarbons. The ESI-QTOF-MS/MS behaviour of some naturally occurring and synthetic quinolines which are structurally similar or fragment similarly are included where appropriate.     

Modulation theory solution for nonlinearly resonant,fifth‐order Korteweg–de Vries,nonclassical, traveling dispersive shock waves

A new class of resonant dispersive shock waves was recently identified as solutions of the Kawahara equation— a Korteweg–de Vries (KdV) type nonlinear wave equation with third‐ and fifth‐order spatial derivatives— in the regime of nonconvex, linear dispersion. Linear resonance resulting from the third‐ and fifth‐order terms in the Kawahara equation was identified as the key ingredient for nonclassical dispersive shock wave solutions. Here, nonlinear wave (Whitham) modulation theory is used to construct approximate nonclassical traveling dispersive shock wave (TDSW) solutions of the fifth‐ order KdV equation without the third derivative term, hence without any linear resonance. A self‐similar, simple wave modulation solution of the fifth order, weakly nonlinear KdV–Whitham equations is obtained that matches a constant to a heteroclinic traveling wave via a partial dispersive shock wave so that the TDSW is interpreted as a nonlinear resonance. The modulation solution is compared with full numerical solutions, exhibiting excellent agreement. The TDSW is shown to be modulationally stable in the presence of sufficiently small third‐order dispersion. The Kawahara–Whitham modulation equations transition from hyperbolic to elliptic type for sufficiently large third‐order dispersion, which provides a possible route for the TDSW to exhibit modulational instability.