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Control of the interfacial structures of ionic liquids (ILs) at charged interfaces is important to many of their applications, including in energy storage solutions, sensors and advanced lubrication technologies utilising electric fields. In the case of the latter, there is an increasing demand for the study of non-halogenated ILs, as many fluorinated anions have been found to produce corrosive and toxic halides under tribological conditions. Here, the interfacial structuring of a series of four imidazolium ILs ([C(n)C(1)Im]) of varying alkyl chain lengths (n = 5, 6, 7, 10), with a non-halogenated borate-based anion ([BOB]), have been studied at charged interfaces using sum frequency generation (SFG) spectroscopy and neutron reflectivity (NR). For all alkyl chain lengths, the SFG spectra show that the cation imidazolium ring responds to the surface charge by modifying its orientation with respect to the surface normal. In addition, the combination of SFG spectra with electrochemical NR measurements reveals that the longest alkyl chain length (n = 10) forms a bilayer structure at all charged interfaces, independent of the ring orientation. These results demonstrate the tunability of IL interfacial layers through the use of surface charge, as well as effect of the cation alkyl chain length, and provide valuable insight into the charge compensation mechanisms of ILs.

The rheological behavior of different precursor poly(p-phenylene vinylene) (prec-PPV) monolayers at the air-water interface was investigated using an interfacial stress rheometer (ISR). This device nicely reveals a transition of the precursor poly(2,5-dimethoxy-1,4 phenylene vinylene) (prec-DMePPV) monolayer from Newtonian to elastic behavior with increasing surface pressure. The transition is accompanied by an increase in the modulus. This behavior coincides with the coagulation of different 21) condensed domains as revealed by Brewster angle microscopy (BAM). However, partly converted prec-DMePPV monolayers show elastic behavior even at low surface pressures, although a sudden increase of the moduli does occur. This phenomenon is attributed to enhanced hydrophobic interactions between the conjugated moieties in the partly converted polymers. The latter also explains the stretching behavior of the partly converted prec-DMePPV upon transfer in Langmuir-Blodgett-type vertical dipping. The increase of the moduli which is observed is much more gradual in the precursor poly(2,5-dibutoxy-1,4-phenylene vinylene), prec-DBuPPV, a monolayer which is in agreement with the expected expanded state of the latter monolayer.

In the present communication one monolayer Langmuir-Blodgett (LB) films of cadmium arachidate (CdA), lead arachidate (PbA), calcium arachidate (CaA), zinc arachidate (ZnA) and barium arachidate (BaA) have been investigated using core level loss spectroscopy, electron energy loss spectroscopy (EELS) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS), The core level loss spectra and electron energy loss spectra of all the films were largely similar. This has been attributed to the similarity of the band structure of these films. which depends on the hydrocarbon chains rather than the cation incorporated. The NEXAFS spectra show a large angular dependence for the PbA film and barely any angular dependence for BaA. A possible explanation for this observation has been offered on the basis of electronegativities of the cations. (C) 1998

We report on the second-order nonlinear optical susceptibility chi(2)(2omega,omega,omega) of dye-doped Langmuir-Blodgett monolayers. Chi(2) is found to exhibit a nonlinear dependence on surface density, which is attributed to microscopic local-fields. In order to calculate the microscopic local-field for the disordered systems, a novel Monte-Carlo type of calculation is described, in which the tilt angle of the dye unit is a sensitive parameter. It is shown also that the tilt angle of rod-shaped chromophores in Langmuir-Blodgett films can be measured by angular-dependent absorption measurements.

The azimuthal helix orientation of the rigid-rod amphiphilic diblock copolypeptides (PLGA-b-PMLGSLGs) of poly(alpha-L-glutamic acid) (PLGA) and poly(gamma-methyl-L-glutamate-ran-gamma-stearyl-L-glutamate) with 30 mol % of stearyl substituents (PMLGSLG) in Langmuir-Blodgett (LB) monolayers was investigated using polarized transmission Fourier transform infrared spectroscopy. The relative position of dipping with respect to the previous transfer position can be used to manipulate the azimuthal orientation of the helices parallel to or tilted by an angle of 450 with respect to the dipping direction in the transferred films. The study of the azimuthal order for the LB monolayers of PLGA-b-PMLGSLGs of various block lengths revealed that the observed effect arises mainly from the deformation of the PMLGSLG top brush layer, induced by the flow Orientation around the transfer region. In those cases where the PMLGSLG block is tilted by a sufficiently large angle with respect to the surface normal, high azimuthal order parameters of 0.5-0.75 were obtained.

The synthesis of amphiphilic diblock copolypeptides consisting of poly(alpha-L-glutamic acid) (PLGA) and poly(gamma-methyl-L-glutamate-ran-gamma-stearyl-L-glutamate) with 30 mol % of stearyl substituents (PMLGSLG) and their monolayer behavior at the air-water interface have been studied. PLGA-b-PMLGSLG was synthesized via a diblock copolymer precursor consisting of poly(gamma-tert-butyl-L-glutamate) (PtBuLG) and PMLGSLG blocks, with the tert-butyl group as a mild acid-labile protecting group for the carboxylic acid. The polymerization conditions were found to influence the alpha-helix to beta-sheet content ratio and can be tuned to significantly enhance the cliblock copolypeptide helicity. Purely alpha-helical PtBuLG-b-PMLGSLG diblock copolymers were successfully prepared. After removal of the tert-butyl group, the study of the PLGA-b-PMLGSLG amphiphilic cliblock copolymers in Langmuir monolayers; and Langmuir-Blodgett films demonstrated the formation of a stable alpha-helical double-brush structure, with the helices tilted away from the substrate surface. These double-brush monolayers combine the unique properties arising from the unidirectionally aligned helix macrodipole and the liquid-like features of the side chain mantle of the PMLGSLG block. Such systems are promising for thin film applications requiring incorporation and orientation of bio- and optical molecules. (C) 2010 Elsevier Ltd. All rights reserved.

The surface potentials and effective dipole moments of alpha-helical amphiphilic diblock copolypeptides during monolayer compression at the air water interface are reported. Amphiphilic diblock copolypeptides (PLGA-b-PM LGSLGs) of poly(alpha-L-glutamic acid) (PLGA) and poly(gamma-methyl-L-glutamate-ran-gamma-stearyl-L-glutamate) with 30 mol% of stearyl substituents (PMLGSLG) of various block lengths were studied during the double-brush formation process at the water surface. Upon monolayer spreading of PLGA-b-PMLGSLGs, surface potentials of hundreds of millivolts were recorded, attributed to the dipole moments of water molecules reorienting due to interactions with the monolayers. Upon compression, the effective dipole moments derived from the surface potentials of the PLGA-b-PMLGSLG monolayers decrease gradually, most likely as a result of the immersion of the hydrophilic block in water and cancellation of the interactions between the hydrophobic block and the underlying water molecules. The polypeptide macrodipole moment immersed in water was apparently effectively screened out. The remaining effective dipole moment of the monolayer contributes mainly to the hydrophobic block, and upon tilting away from the water surface toward the surface no it was found to increase with the hydrophobic block length, indicating the gradual formation of unidirectional aligned polypeptide molecules in the double-brush monolayer.

We measured NEXAFS spectra on both C and N K-edges of an ordered monolayer of lead phthalocyanine adsorbed onto an InSb(001) 4 × 2/c(8 × 2) substrate. We compared the spectra with the calculated density of unoccupied states of an isolated molecule. We demonstrate that molecules lay flat on the surface, determine the energy position of the lowest excited state, and show that it is site dependent. Finally, we compare the core exciton structure with the valence exciton structure previously measured by two different valence spectroscopic techniques and discuss their differences in terms of electron−nuclear and electron−hole Coulomb interactions.

The effect of chain length on the helix orientation of alpha-helical diblock copolypeptides in Langmuir and Langmuir-Blodgett monolayers is reported for the first time. Amphiphilic diblock copolypeptides (PLGA-b-PMLGSLGs) of poly(alpha-L-glutamic acid) (PLGA) and poly(gamma-methyl-L-glutamate-ran-gamma-stearyl-L-glutamate) with 30 mol% of stearyl substituents (PMLGSLG) of various block lengths were studied. The tilt angle between the helices and the substrate-normal decreases upon increasing the transfer pressure coincident with "double brush" formation. The hydrophobic block length strongly affects the maximum surface chain density and thereby the helix orientation of the diblock copolypeptides. Increasing the degree of polymerization of the hydrophobic block (DP(PMLGSLG)) results in an increase in the helix tilt angle tentatively attributed to the off-axis interactions of the unscreened peptide dipoles between the parallel aligned alpha-helices. In those cases where the alkyl side chains surround the PMLGSLG helices, the smallest helix tilt angle of 29 degrees for the PMLGSLG block and 67 degrees for the PLGA block were obtained for the diblock copolymer of DP(PLGA) 37 and DP(PMLGSLG) 24. For smaller DP values of the hydrophobic block, in particular the diblock copolymer having DP(PMLGSLG) 11, the long alkyl side chains are partially expelled from the brush layer and the alpha-helices of the PMLGSLG block are oriented nearly perpendicular to the interface.

Detailed measurements of the macroscopic second-order optical nonlinearity chi(2) (2-omega,omega,omega) of Langmuir-Blodgett dye-doped monolayers are reported. The observed deviations from a linear behavior of chi-(2) with increasing surface density are shown to be due to local-field effects. In order to calculate these local-field factors for disordered systems, a novel Monte Carlo type calculation is introduced. This calculation not only accounts for density variations in the monolayers but also incorporates the effect of off-diagonal elements of the (microscopic) linear susceptibility tensor. Quantitative agreement is found between the calculations and the experimental results using only the molecular hyperpolarizability as a free parameter. A method is presented to determine the tilt angle of the chromophores in Langmuir-Blodgett monolayers from the anisotropy of the linear absorption. The tilt angle determined this way is in excellent agreement with a determination by second-harmonic generation.