How does spacer length of imidazolium gemini surfactants control the fabrication of 2D-Langmuir films of silver-nanoparticles at the air-water interface?

A series of gemini surfactants based on cationic imidazolium ring as polar headgroup, abbreviated as Im-n-Im], 2Br(-) (n = 2, 5,6 and 12), was synthesized. Their ability to stabilize silver nanoparticles in aqueous media was investigated. The resulting suspensions were characterized by UV-Vis spectroscopy and transmission electron microscopy (TEM). They exhibit specific morphologies by adopting different supramolecular assemblies in aqueous media depending on the internal packing arrangements and on the number of spacer methylene units -(CH2)(n)-]. Individual colloids were extracted from the aqueous to chloroform layer and spread at the air/water interface to allow the formation of well-defined Langmuir films. By analysis of the surface pressure-area isotherms, the details about the packing behavior and orientation of the imidazolium gemini surfactant capped silver nanoparticles were obtained. Morphological features of the dynamic process of monolayer compression at the air-water interface were elucidated using Brewster angle microscopy (BAM). These monolayers were further transferred on mica sheets by the Langmuir-Blodgett technique at their associated collapse pressure and the morphology of these monolayers was investigated by atomic force microscopy (AFM). The number of spacer methylene units (CH2)(n)-] of the gemini surfactants exerted critical influence in modulating the characteristics of the resulting Langmuir films. (C) 2014 Elsevier Inc. All rights reserved.

Mono layer to Interdigitated Partial Bilayer Smectic C Transition in Thiophene-Based Spacer Mesogens: X-ray Diffraction and C-13 Nuclear Magnetic Resonance Studies

Mesophase organization of molecules built with thiophene at the center and linked via flexible spacers to rigid side arm core units and terminal alkoxy chains has been investigated. Thirty homologues realized by varying the span of the spacers as well as the length of the terminal chains have been studied. In addition to the enantiotropic nematic phase observed for all the mesogens, the increase of the spacer as well as the terminal chain lengths resulted in the smectic C phase. The molecular organization in the smectic phase as investigated by temperature dependent X-ray diffraction measurements revealed an interesting behavior that depended on the length of the spacer vis-a-vis the length of the terminal chain. Thus, a tilted interdigitated partial bilayer organization was observed for molecules with a shorter spacer length, while a tilted monolayer arrangement was observed for those with a longer spacer length. High-resolution solid state C-13 NMR studies carried out for representative mesogens indicated a U-shape for all the molecules, indicating that intermolecular interactions and molecular dynamics rather than molecular shape are responsible for the observed behavior. Models for the mesophase organization have been considered and the results understood in terms of segregation of incompatible parts of the mesogens combined with steric frustration leading to the observed lamellar order.

An infrared study on Langmuir-Blodgett films of octadecylammonium octadecanoate: FWHM and the vibrational coupling

The monolayer of the mixture of octadecanoic acid and octadecylamine with molar ratio 1: 1 has been investigated at the air-water interface. It was found that the monolayer shows a rather stable state at the surface pressure of 30 mN/m and this monolayer can be transferred onto a CaF2 plate by Langmuir-Blodgett (LB) technique. The infrared spectra of LB films indicated that octadecyl ammonium octadecanoate is formed by an intermolecular proton exchange between adjacent carboxylic and aminic groups (COO- and NH3+). In three-layer LB film, the CH2 scissoring mode of the long hydrocarbon chains of octadecyl ammonium octadecanoate shows a broad band feature at about 1468 cm(-1) while this vibrational mode of three-layer LB film of the mixture (1: 1) of deuterated stearic acid and octadecylamine (octadecylammonium octadecanoate-d35, C18H37NH3+C17D35COO-) only shows a narrow band. The broad feature of the CH2 scissoring mode in octadecylammonium octadecanoate probably originates from the coupling between the chain of stearic acid and that of octadecylamine while this kind of coupling could be completely removed in octadecylammonium octadecanoate-d35.

Luminescent Langmuir-Blodgett films based on Tiron-terbium

The luminescent ultrathin Langmuir-Blodgett (LB) films containing Tb-2(C6H3S2O8)(2) (Tiron-Tb) were successfully obtained. The modifications of compression isotherms of dimethyldioctadecylammonium bromide (DODA) have been observed when the Tiron-Tb complex was dissolved in the subphase. The effect of Tiron-Tb in the subphase on Langmuir films of DODA has been studied. Low-angle X-ray diffraction result indicates that the LB films have a good periodic layered structure. The UV and IR spectra results show the Tiron-Tb complex is incorporated into LB films layer-by-layer and the LB films are homogeneously deposited. The LB films containing Tiron-Tb can emit strong green luminescence, and the luminescence signal can be detected from a single layer. The luminescence properties of LB films have been discussed compared with those of the solutions.

Use of atomic force microscopy for imaging the initial stage of the nucleation of calcium phosphate in Langmuir-Blodgett films of stearic acid

The nucleation of calcium phosphate on the substrate of steatic acid Langmuir-blodgett film at the initial stage was investigated by atomic force microscopy. Nano-dots, nano-wires and nano-islands were observed in sequence for the first time, reflecting the nucleation of calcium phosphate and the molecular arrangement of carboxylic layer. The nucleation rates perpendicular and parallel to the carboxylic terminal group were estimated from the height and diameter of the calcium phosphate crystals, respectively. And this stage was distinct from the late explosive grown stage, in which the change of the morphology was not obvious. The approaches based on this discovery would lead to the development of new strategies in the controlled synthesis of inorganic nano-phases and the assembly of organized composite and ceramic materials.

Direct electrochemistry and surface plasmon resonance characterization of alternate layer-by-layer self-assembled DNA-myoglobin thin films on chemically modified gold surfaces

Alternate layer-by-layer (L-by-L) polyion adsorption onto gold electrodes coated with chemisorbed cysteamine gave stable, electroactive multilayer films containing calf thymus double stranded DNA (CT ds-DNA) and myoglobin (Mb). Direct, quasi-reversible electron exchange between gold electrodes and proteins involved the Mb heme Fe2+/Fe3+ redox couple. The formation of L-by-L (DNA/Mb), films was characterized by both in situ surface plasmon resonance (SPR) monitoring and cyclic voltammetry (CV). The effective thickness of DNA and Mb monolayers in the (DNA/Mb)l bilayer were 1.0 +/- 0.1 and 2.5 +/- 0.1 mn, corresponding to the surface coverage of similar to65% and similar to89% of its full packed monolayer, respectively. A linear increase of film thickness with increasing number of layers was confirmed by SPR characterizations. At pH 5.5, the electroactive Mb in films are those closest to the electrode surface; additional protein layers did not communicate with the electrode. CV studies showed that electrical communication might occur through hopping conduction via the electrode/base pair/Mb channel, thanks to the DNA-Mb interaction. After the uptake of Zn2+, a special electrochemical behavior, where MbFe(2+) acts as a DNA-binding reduction catalyst in the Zn2+-DNA/Mb assembly, takes place.

Assembly of alternating polycation and DNA multilayer films by electrostatic layer-by-layer adsorption

The assembly of alternating DNA and positively charged poly(dimethyldiallylammonium chloride) (PDDA) multilayer films by electrostatic layer-by-layer adsorption has been studied. The real-time surface plasmon resonance (BIAcore) technique was used to characterize and monitor the formation of multilayer films in solution in real time continuously. Electrochemical impedance spectroscopy (EIS) and UV-vis absorbance measurements were also used to study the film assembly, and linear film growth was observed. All the results indicate that the uniform multilayer can be obtained on the poly(ethylenimine)- (PEI-) coated substrate surface. The kinetics of the adsorption of DNA on PDDA surface was also studied by the real-time BIAcore technique; the observed rate constant was calculated using a Langmuir model (k(obs) = (1.28 +/- 0.08) x 10(-2) s(-1).

Electrostatic layer-by-layer assembly of polycation and DNA multilayer films by real-time surface plasmon resonance technique

The assembly of alternating DNA and positively charged poly(dimethyldiallylammonium chloride) (PDDA) multilayer films by electrostatic layer-by-layer adsorption has been studied. Real time surface plasmon resonance (BIAcore) technique was used to characterize and monitor the formation of multilayer films in solution in real time continuously. The results indicate that the uniform multilayer can be obtained on the poly(ethylenimine) (PEI) coated substrate surface. The kinetics of the adsorption of DNA on PDDA surface was also studied by real-time BIAcore technique, and the observed rate constant was calculated using a Langmuir model (k(obs) = (1.28 +/- 0.08) x 10(-2) s(-1)).

INVESTIGATION OF CETYLPYRIDINIUM BROMIDE ADSORPTION AT A GLASSY-CARBON ELECTRODE SURFACE BY SPECTROELECTROCHEMISTRY WITH A LONG OPTICAL-PATH LENGTH THIN-LAYER CELL

The adsorption of cationic surfactant cetylpyridinium bromide (CPB) on a glassy carbon (GC) electrode surface has been studied by spectroelectrochemistry with a long optical path length thin-layer cell (LOPTLC) for the first time. A fine adsorption isotherm of CPB molecules from an aqueous solution containing 0.10 M KBr has been obtained over the range of (1.00-8.00) x 10(-5) M. From theoretical calculation and experimental data, adsorption of CPB on the GC electrode surface shows four distinct orientations and three large orientation transitions. Compared with the ordinary isotherm, the differential isotherm is more characteristic and would be suitable for the study of orientation transitions of organic compounds. With a theoretical treatment of the adsorption isotherm, four orientations of adsorbed CPB on a GC electrode surface coincide with the Frumkin-Langmuir type. From adsorption parameters the Frumkin-Langmuir equations, the adsorption free energy and, therefore, the equilibrium constants of orientation transitions of the CPB molecule can be obtained.

INVESTIGATION OF ELECTRIC DICHROISM OF CETYLPYRIDINIUM BROMIDE BY SPECTROELECTROCHEMISTRY WITH A LONG OPTICAL-PATH LENGTH THIN-LAYER CELL

In this paper, the electric dichroism of cetylpyridinium bromide (CPB) has been found and studied by spectroelectrochemistry with a long optical path length thin-layer cell (LOPTLC) for the first time. The CPB molecule with a long carbon chain and a polar pyridinium ring is anisotropic in molecular configuration or in polarizability. In the electric field of a thin-layer cell, the CPB molecule reorientates along the direction of the electric field and exhibits electric dichroism, which results in the increase of absorbance of CPB in the UV-vis range. By use of in situ measurement of spectroelectrochemistry, the order parameters of long molecular axis (S = 0.845) and short molecular axis (D = 0.155) and the angle between the long axis direction of the CPB molecule and the direction normal to the electrode surface (theta = 18-degrees 44') have been determined. These data were used to describe the state of arrangement of the molecules in the solution. The reorientation of CPB molecules is the result of the interaction between the anisotropic molecules and electric field. The effects of the concentration of CPB and of the applied electric field on the electric dichroism have been investigated.

Langmuir-Blodgett assembly of colloidal crystals combined with controlled infiltration of conducting metal oxides

Colloidal photonic crystals (PhCs) possess a periodic dielectric structure which gives rise to a photonic band gap (PBG) and offer great potential in the ability to modify or control light at visible wavelengths. Although the refractive index contrast between the void or infill and the matrix material is paramount for photonics applications, integration into real optoelectronics devices will require a range of added functionalities such as conductivity. As such, colloidal PhCs can be used as templates to direct infiltration of other functional materials using a range of deposition strategies. The work in this thesis seeks to address two challenges; first to develop a reproducible strategy based on Langmuir-Blodgett (LB) deposition to assemble high quality colloidal PhCs based on silica with precise film thickness as most other assembly methods suffer from a lack of reproducibility thickness control. The second is to investigate the use of LBdeposited colloidal PhCs as templates for infiltration with conducting metal oxide materials using vapor phase deposition techniques. Part of this work describes the synthesis and assembly of colloidal silica spheres with different surface chemical functionalities at the air-water interface in preparation for LB deposition. Modification of surface funtionality conferred varying levels of hydrophobicity upon the particles. The behaviour of silica monolayer films at the air-water interface was characterised by Brewster Angle Microscopy and surface pressure isotherms with a view to optimising the parameters for LB deposition of multilayer colloidal PhC films. Optical characterisation of LB-fabricated colloidal PhCs indicated high quality photonic behaviour, exhibiting a pseudo PBG with a sharp Bragg diffraction peak in the visible region and reflectance intensities greater than 60%. Finally the atomic layer deposition (ALD) of nominally undoped ZnO and aluminium “doped” ZnO (Al-doped ZnO) inside the pores of a colloidal PhC assembled by the LB technique was carried out. ALD growth in this study was performed using trimethyl aluminium (TMA) and water as precursors for the alumina and diethyl zinc (DEZn) and water for the ZnO. The ZnO:Al films were grown in a laminate mode, where DEZn pulses were substituted for TMA pulses in the sequences with a Zn:Al ratio 19:1. The ALD growth of ZnO and ZnO:Al in colloidal PhCs was shown to be highly conformal, tuneable and reproducible whilst maintaining excellent photonic character. Furthermore, at high levels of infiltration the opal composite films demonstrated significant conductivity.

Exact analytical expressions for the potential of electrical double layer interactions for a sphere-plate system.

Exact, closed-form analytical expressions are presented for evaluating the potential energy of electrical double layer (EDL) interactions between a sphere and an infinite flat plate for three different types of interactions: constant potential, constant charge, and an intermediate case as given by the linear superposition approximation (LSA). By taking advantage of the simpler sphere-plate geometry, simplifying assumptions used in the original Derjaguin approximation (DA) for sphere-sphere interaction are avoided, yielding expressions that are more accurate and applicable over the full range of κa. These analytical expressions are significant improvements over the existing equations in the literature that are valid only for large κa because the new equations facilitate the modeling of EDL interactions between nanoscale particles and surfaces over a wide range of ionic strength.

On the structure of Langmuir turbulence

The Stokes drift induced by surface waves distorts turbulence in the wind-driven mixed layer of the ocean, leading to the development of streamwise vortices, or Langmuir circulations, on a wide range of scales. We investigate the structure of the resulting Langmuir turbulence, and contrast it with the structure of shear turbulence, using rapid distortion theory (RDT) and kinematic simulation of turbulence. Firstly, these linear models show clearly why elongated streamwise vortices are produced in Langmuir turbulence, when Stokes drift tilts and stretches vertical vorticity into horizontal vorticity, whereas elongated streaky structures in streamwise velocity fluctuations (u) are produced in shear turbulence, because there is a cancellation in the streamwise vorticity equation and instead it is vertical vorticity that is amplified. Secondly, we develop scaling arguments, illustrated by analysing data from LES, that indicate that Langmuir turbulence is generated when the deformation of the turbulence by mean shear is much weaker than the deformation by the Stokes drift. These scalings motivate a quantitative RDT model of Langmuir turbulence that accounts for deformation of turbulence by Stokes drift and blocking by the air–sea interface that is shown to yield profiles of the velocity variances in good agreement with LES. The physical picture that emerges, at least in the LES, is as follows. Early in the life cycle of a Langmuir eddy initial turbulent disturbances of vertical vorticity are amplified algebraically by the Stokes drift into elongated streamwise vortices, the Langmuir eddies. The turbulence is thus in a near two-component state, with suppressed and . Near the surface, over a depth of order the integral length scale of the turbulence, the vertical velocity (w) is brought to zero by blocking of the air–sea interface. Since the turbulence is nearly two-component, this vertical energy is transferred into the spanwise fluctuations, considerably enhancing at the interface. After a time of order half the eddy decorrelation time the nonlinear processes, such as distortion by the strain field of the surrounding eddies, arrest the deformation and the Langmuir eddy decays. Presumably, Langmuir turbulence then consists of a statistically steady state of such Langmuir eddies. The analysis then provides a dynamical connection between the flow structures in LES of Langmuir turbulence and the dominant balance between Stokes production and dissipation in the turbulent kinetic energy budget, found by previous authors.

Theoretical studies of the interface between water and Langmuir films of aliphatic alcohols

The interface between water and Langmuir films of long chain aliphatic molecules is investigated using accurate intermolecular potentials. The stabilities of various ice structures which could form at the interface are examined. Antiferroelectric ice is found to be the most stable, but this stability depends crucially on the first layer of water. Ferroelectric structures are found to collapse upon relaxation. Our model was not able to differentiate between the different nucleation properties of C31H63OH and C30H61OH. A better description of the alcohol–water interaction is probably required to account for this difference.

Hydrogen-bonding-driven self-assembly of PEGylated organosilica nanoparticles with poly(acrylic acid) in aqueous solutions and in layer-by-layer deposition at solid surfaces

PEGylated organosilica nanoparticles have been synthesized through self-condensation of (3-mercaptopropyl)trimethoxysilane in dimethyl sulfoxide into thiolated nanoparticles with their subsequent reaction with methoxypoly(ethylene glycol) maleimide. The PEGylated nanoparticles showed excellent colloidal stability over a wide range of pH in contrast to the parent thiolated nanoparticles, which have a tendency to aggregate irreversibly under acidic conditions (pH < 3.0). Due to the presence of a poly(ethylene glycol)-based corona, the PEGylated nanoparticles are capable of forming hydrogen-bonded interpolymer complexes with poly(acrylic acid) in aqueous solutions under acidic conditions, resulting in larger aggregates. The use of hydrogen-bonding interactions allows more efficient attachment of the nanoparticles to surfaces. The alternating deposition of PEGylated nanoparticles and poly(acrylic acid) on silicon wafer surfaces in a layer-by-layer fashion leads to multilayered coatings. The self-assembly of PEGylated nanoparticles with poly(acrylic acid) in aqueous solutions and at solid surfaces was compared to the behavior of linear poly(ethylene glycol). The nanoparticle system creates thicker layers than the poly(ethylene glycol), and a thicker layer is obtained on a poly(acrylic acid) surface than on a silica surface, because of the effects of hydrogen bonding. Some implications of these hydrogen-bonding-driven interactions between PEGylated nanoparticles and poly(acrylic acid) for pharmaceutical formulations are discussed.