Molecular Ordering of Layer-by-Layer Polyelectrolyte Films Studied by Sum-Frequency Vibrational Spectroscopy

The molecular arrangement in organic thin films is crucial for their increasing technological applications. Here, we use vibrational spectroscopy by sum-frequency generation (SFG) to study the ordering of polyelectrolyte layers adsorbed on silica for all steps of layer-by-layer (LbL) self-assembly. In situ measurements during adsorption and rinsing showed that the adsorbed polymer has a disordered conformation and confirmed surface charge overcompensation upon polyelectrolyte adsorption by probing the interfacial electric field. In dry films, the polymer chains acquired a net orientational ordering, which was affected, however, by the adsorption of subsequent layers. Such a detailed characterization may allow the control of LbL film structure and functionality with unprecedented power.

Molecular Ordering in Layer-by-Layer Polyelectrolyte Films Studied by Sum-Frequency Vibrational Spectroscopy: The Effects of Drying Procedures

Sum-Frequency Vibrational Spectroscopy (SFVS) has been used to investigate the effect of nitrogen-flow drying on the molecular ordering of Layer-by-Layer (LbL) films of poly(allylamine hydrochloride) (PAH) alternated with poly(styrene sulfonate) (PSS). We find that films dried by spontaneous water evaporation are more ordered and homogeneous than films dried by nitrogen flow. The latter are quite inhomogeneous and may have regions with highly disordered polymer conformation. We propose that drying by spontaneous water evaporation reduces the effect of drag by the drying front, while during nitrogen-flow drying the fast evaporation of water ""freezes"" the disordered conformation of adsorbed polyelectrolyte molecules. These findings are important for many applications of LbL films, since device performance usually depends on film morphology and its molecular structure.

Dodecyltrimethylammonium chloride adsorption at the silica/water interface studied by Sum Frequency Generation

La génération des fréquences somme (SFG), une technique spectroscopique spécifique aux interfaces, a été utilisée pour caractériser les changements de la structure macromoléculaire du surfactant cationique chlorure de dodécyltriméthylammonium (DTAC) à l’interface silice/eau dans une plage de pH variant entre 3 et 11. Les conditions expérimentales ont été choisies pour imiter les conditions les plus communes trouvées pendant les opérations de récupération assistée du pétrole. Particulièrement, la silice a été étudiée, car elle est un des composantes des surfaces minérales des réservoirs de grès, et l’adsorption du surfactant a été étudiée avec une force ionique pertinente pour les fluides de la fracturation hydraulique. Les spectres SFG ont présenté des pics détectables avec une amplitude croissante dans la région des étirements des groupes méthylène et méthyle lorsque le pH est diminué jusqu’à 3 ou augmenté jusqu’à 11, ce qui suggère des changements de la structure des agrégats de surfactant à l’interface silice/eau à une concentration de DTAC au-delà de la concentration micellaire critique. De plus, des changements dans l’intensité SFG ont été observés pour le spectre de l’eau quand la concentration de DTAC augmente de 0,2 à 50 mM dans les conditions acide, neutre et alcaline. À pH 3, près du point de charge zéro de la surface de silice, l’excès de charge positive en raison de l’adsorption du surfactant cationique crée un champ électrostatique qui oriente les molécules d’eau à l’interface. À pH 7 et 11, ce qui sont des valeurs au-dessus du point de charge zéro de la surface de silice, le champ électrostatique négatif à l’interface silice/eau diminue par un ordre de grandeur avec l’adsorption du surfactant comme résultat de la compensation de la charge négative à la surface par la charge positive du DTAC. Les résultats SFG ont été corrélés avec des mesures de l’angle de contact et de la tension interfaciale à pH 3, 7 et 11.

Dodecyltrimethylammonium chloride adsorption at the silica/water interface studied by Sum Frequency Generation

La génération des fréquences somme (SFG), une technique spectroscopique spécifique aux interfaces, a été utilisée pour caractériser les changements de la structure macromoléculaire du surfactant cationique chlorure de dodécyltriméthylammonium (DTAC) à l’interface silice/eau dans une plage de pH variant entre 3 et 11. Les conditions expérimentales ont été choisies pour imiter les conditions les plus communes trouvées pendant les opérations de récupération assistée du pétrole. Particulièrement, la silice a été étudiée, car elle est un des composantes des surfaces minérales des réservoirs de grès, et l’adsorption du surfactant a été étudiée avec une force ionique pertinente pour les fluides de la fracturation hydraulique. Les spectres SFG ont présenté des pics détectables avec une amplitude croissante dans la région des étirements des groupes méthylène et méthyle lorsque le pH est diminué jusqu’à 3 ou augmenté jusqu’à 11, ce qui suggère des changements de la structure des agrégats de surfactant à l’interface silice/eau à une concentration de DTAC au-delà de la concentration micellaire critique. De plus, des changements dans l’intensité SFG ont été observés pour le spectre de l’eau quand la concentration de DTAC augmente de 0,2 à 50 mM dans les conditions acide, neutre et alcaline. À pH 3, près du point de charge zéro de la surface de silice, l’excès de charge positive en raison de l’adsorption du surfactant cationique crée un champ électrostatique qui oriente les molécules d’eau à l’interface. À pH 7 et 11, ce qui sont des valeurs au-dessus du point de charge zéro de la surface de silice, le champ électrostatique négatif à l’interface silice/eau diminue par un ordre de grandeur avec l’adsorption du surfactant comme résultat de la compensation de la charge négative à la surface par la charge positive du DTAC. Les résultats SFG ont été corrélés avec des mesures de l’angle de contact et de la tension interfaciale à pH 3, 7 et 11.

Filmes ultrafinos de ésteres de celulose: preparo, caracterização e imobilização de proteínas

In this study cellulose acetate butyrate (CAB) and carboxymehtylcellulose acetate butyrate (CMCAB) films adsorbed onto silicon wafers were characterized by means of ellipsometry, atomic force microscopy (AFM), sum frequency generation spectroscopy (SFG) and contact angle measurements. The adsorption behavior of lysozyme (LIS) or bovine serum albumin (BSA) onto CAB and CMCAB films was investigated. The amounts of adsorbed LIS or BSA onto CMCAB films were more pronounced than those onto CAB films due to the presence of carboxymethyl group in the CMCAB structure. Besides, the adsorption of BSA molecules on CMCAB films was more favored than that of LIS molecules. Antimicrobial effect of LIS bound to CAB or CMCAB layers was evaluated using Micrococcus luteus as substrate.

On molecular chirality within naturally occurring secondary organic aerosol particles from the central Amazon Basin

In this perspectives article, we reflect upon the existence of chirality in atmospheric aerosol particles. We then show that organic particles collected at a field site in the central Amazon Basin under pristine background conditions during the wet and dry seasons consist of chiral secondary organic material. We show how the chiral response from the aerosol particles can be imaged directly without the need for sample dissolution, solvent extraction, or sample preconcentration. By comparing the chiral-response images with optical images, we show that chiral responses always originate from particles on the filter, but not all aerosol particles produce chiral signals. The intensity of the chiral signal produced by the size resolved particles strongly indicates the presence of chiral secondary organic material in the particle. Finally, we discuss the implications of our findings on chiral atmospheric aerosol particles in terms of climate-related properties and source apportionment.

Novel solitons in parametric amplifiers and atom lasers

We review recent developments in quantum and classical soliton theory, leading to the possibility of observing both classical and quantum parametric solitons in higher-dimensional environments. In particular, we consider the theory of three bosonic fields interacting via both parametric (cubic) and quartic couplings. In the case of photonic fields in a nonlinear optical medium this corresponds to the process of sum frequency generation (via chi((2)) nonlinearity) modified by the chi((3)) nonlinearity. Potential applications include an ultrafast photonic AND-gate. The simplest quantum solitons or energy eigenstates (bound-state solutions) of the interacting field Hamiltonian are obtained exactly in three space dimensions. They have a point-like structure-even though the corresponding classical theory is nonsingular. We show that the solutions can be regularized with the imposition of a momentum cut-off on the nonlinear couplings. The case of three-dimensional matter-wave solitons in coupled atomic/molecular Bose-Einstein condensates is discussed.

Molecular View of the Interaction between iota-Carrageenan and a Phospholipid Film and Its Role in Enzyme Immobilization

Proteins incorporated into phospholipid Langmuir-Blodgett (LB) films are a good model system for biomembranes and enzyme immobilization studies. The specific fluidity of biomembranes, an important requisite for enzymatic activity, is naturally controlled by varying phospholipid compositions. In a model system, instead, LB film fluidity may be varied by covering the top layer with different substances able to interact simultaneously with the phospholipid and the protein to be immobilized. In this study, we immobilized a carbohydrate rich Neurospora crassa alkaline phosphatase (NCAP) in monolayers of the sodium salt of dihexadecylphosphoric acid (DHP), a synthetic phospholipid that provides very condensed Langmuir films. The binding of NCAP to DHP Langmuir-Blodgett (LB) films was mediated by the anionic polysaccharide iota-carrageenan (iota-car). Combining results from surface isotherms and the quartz crystal microbalance technique, we concluded that the polysaccharide was essential to promote the interaction between DHP and NCAP and also to increase the fluidity of the film. An estimate of DHP:iota-car ratio within the film also revealed that the polysaccharide binds to DHP LB film in an extended conformation. Furthermore, the investigation of the polysaccharide conformation at molecular level, using sum-frequency vibrational spectroscopy (SFG), indicated a preferential conformation of the carrageenan molecules with the sulfate groups oriented toward the phospholipid monolayer, and both the hydroxyl and ether groups interacting preferentially with the protein. These results demonstrate how interfacial electric fields can reorient and induce conformational changes in macromolecules, which may significantly affect intermolecular interactions at interfaces. This detailed knowledge of the interaction mechanism between the enzyme and the LB film is relevant to design strategies for enzyme immobilization when orientation and fluidity properties of the film provided by the matrix are important to improve enzymatic activity.

Design of surface forces apparatus for tribology studies combined with nonlinear optical spectroscopy

We describe the design, calibration, and performance of surface forces apparatus with the capability of illumination of the contact interface for spectroscopic investigation using optical techniques. The apparatus can be placed in the path of a Nd-YAG laser for studies of the linear response or the second harmonic and sum-frequency generation from a material confined between the two surfaces. In addition to the standard fringes of equal chromatic order technique, which we have digitized for accurate and fast analysis, the distance of separation can be measured with a fiber-optic interferometer during spectroscopic measurements (2 Å resolution and 10 ms response time). The sample approach is accomplished through application of a motor drive, piezoelectric actuator, or electromagnetic lever deflection for variable degrees of range, sensitivity, and response time. To demonstrate the operation of the instrument, the stepwise expulsion of discrete layers of octamethylcyclotetrasiloxane from the contact is shown. Lateral forces may also be studied by using piezoelectric bimorphs to induce and direct the motion of one surface.

Filmes ultrafinos de ésteres de celulose: preparo, caracterização e imobilização de proteínas

In this study cellulose acetate butyrate (CAB) and carboxymehtylcellulose acetate butyrate (CMCAB) films adsorbed onto silicon wafers were characterized by means of ellipsometry, atomic force microscopy (AFM), sum frequency generation spectroscopy (SFG) and contact angle measurements. The adsorption behavior of lysozyme (LIS) or bovine serum albumin (BSA) onto CAB and CMCAB films was investigated. The amounts of adsorbed LIS or BSA onto CMCAB films were more pronounced than those onto CAB films due to the presence of carboxymethyl group in the CMCAB structure. Besides, the adsorption of BSA molecules on CMCAB films was more favored than that of LIS molecules. Antimicrobial effect of LIS bound to CAB or CMCAB layers was evaluated using Micrococcus luteus as substrate.

Neue redoxfunktionalisierte Schwefel-Tripodliganden für selbstassemblierende monomolekulare Filme auf Goldoberflächen

Für die Entwicklung selbstorganisierter Monoschichten (SAMs) auf Gold(111)-Oberflächen wurden neue, redox-funktionalisierte Schwefel-Tripodliganden synthetisiert. Um die tripodale Struktur zu realisieren, wurde Adamantan als vierbindiges Zentrum eingesetzt. Die Anbindung an die Goldoberfläche wurde durch Thioethereinheiten ermöglicht, eventuelle laterale Wechselwirkungen durch Alkylseitenketten an den Thioethereinheiten, sowie durch lineare, rigide Spacereinheiten wurden untersucht. Als redoxaktive, funktionelle Einheit wurde ein Ferrocenylrest an den Liganden eingeführt. Gebildete monomolekulare Filme der Liganden auf Gold wurden mit Hilfe von Röntgenphotoelektronenspektroskopie (XPS), Nahkanten-Reflexions-Röntgenabsorptionsspektroskopie (NEXAFS) und Sum-Frequency-Generation (SFG) charakterisiert, um die Filmqualität, die Bindung ans Substrat und Orientierungsordnung im Film zu ermitteln.

Solution behavior and surface properties of carboxymethylcellulose acetate butyrate

Solution behavior of carboxymethylcellulose acetate butyrate (CMCAB) in acetone and ethyl acetate has been investigated by small-angle X-ray scattering (SAXS) and capillary viscometry and correlated with the characteristics of CMCAB films. Viscosity and SAXS measurements showed that ethyl acetate is a better solvent than acetone for CMCAB. Thin films of CMCAB were deposited onto silicon wafers (Si/SiO(2)) by spin coating. AFM images revealed that CMCAB spin coated films from solutions prepared in ethyl acetate were homogeneous and flat. However, films obtained from solutions in acetone were very rough. Contact angle measurements with polar and apolar test liquids characterized CMCAB surfaces as hydrophobic and allowed estimating the surface energy of CMCAB. Sum frequency generation vibrational spectroscopy was used to understand the role played by solvents and to gain insight about molecular orientation at Si/SiO(2)/CMCAB interface.

Cholesterol Mediates Chitosan Activity on Phospholipid Monolayers and Langmuir-Blodgett Films

The polysaccharide chitosan has been largely used in many biological applications as a fat and cholesterol reducer, bactericide agent, and wound healing material. While the efficacy for some of such uses is proven, little is known about the molecular-level interactions involved in these applications. In this study, we employ mixed Langmuir and Langmuir-Blodgett (LB) films of negatively charged dimyristoyl phosphatidic acid (DMPA) anti cholesterol as cell membrane models to investigate the role of cholesterol in the molecular-level action of chitosan. Chitosan does not remove cholesterol froth the monolayer. The interaction with chitosan tends to expand the DMPA monolayer due to its interpenetration within the film. On the other hand, cholesterol induces condensation of the DMPA monolayer. The competing effects cause the surface pressure isotherms of mixed DMPA-cholesterol films on a chitosan subphase to be unaffected by the cholesterol mole fraction, due to distinct degrees of chitosan penetration into the film in the presence of cholesterol. By combining polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS) and sum-frequency generation spectroscopy (SFG), we showed that chitosan induces order into negatively charged phospholipid layers, whereas the opposite occurs for cholesterol. In conclusion, chitosan has its penetration in the film modulated by cholesterol, and electrostatic interactions with negatively charged phospholipids, such as DMPA, are crucial for the action of chitosan.

Stability and interface properties of thin cellulose ester films adsorbed from acetone and ethyl acetate solutions

Stability and interface properties of cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB) films adsorbed from acetone or ethyl acetate onto Si wafers have been investigated by means of contact angle measurements and atomic force microscopy (AFM). Surface energy (gamma(total)(S)) values determined for CAP adsorbed from acetone are larger than those from ethyl acetate. In the case of CAB films adsorbed from ethyl acetate and acetone were similar. Dewetting was observed by AFM only for CAP films prepared from ethyl acetate. Positive values of effective Hamaker constant (A(eff)) were found only for CAP prepared from ethyl acetate, corroborating with dewetting phenomena observed by AFM. Oil the contrary, negative values of A(eff) were determined for CAP and CAB prepared from acetone and for CAB prepared from ethyl acetate, Corroborating with experimental observations. Sum frequency generation (SFG) vibrational spectra indicated that CAP and CAB films prepared from ethyl acetate present more alkyl groups oriented perpendicularly to the polymer-air interface than those films prepared from acetone. Such preferential orientation corroborates with macroscopic contact angle measurements. Moreover, SFG spectra showed that acetone hinds strongly to Si wafers, creating a new surface for CAP and CAB films. (C) 2008 Elsevier Inc. All rights reserved.

Vibrational spectroscopy for probing molecular-level interactions in organic films mimicking biointerfaces

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)