Polarization Modulation-infrared Reflection-adsorption Spectroscopy Research Articles

The Role of Cholesterol in the Interaction of the Lipid Monolayer with the Endocrine Disruptor Bisphenol-A.

Among pollutants of emerging concern, endocrine disruptors (ED) have been shown to cause side effects in humans and animals. Bisphenol-A (BPA) is an ED by-product of the plastic industry and one of the chemicals with the highest volume produced yearly. Here, we studied the role of cholesterol in the BPA exposure effects over membrane models. We used Langmuir films of both neat lipid DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine) and cholesterol (Chol) and a binary mixture containing DPPC/Chol, exposing it to BPA. We evaluate changes in the π-A isotherms and the PM–IRRAS (polarization modulation–infrared reflection adsorption spectroscopy) spectra. BPA exposure induced changes in the DPPC and Chol neat monolayers, causing mean molecular area expansion and altering profiles. However, at high surface pressure, the BPA was expelled from the air–water interface. For the DPPC/Chol mixture, BPA caused expansion throughout the whole compression, indicating that BPA is present at the monolayer interface. The PM–IRRAS analysis showed that BPA interacted with the phosphate group of DPPC through hydrogen bonding, which caused the area’s expansion. Such evidence might be biologically relevant to better understand the mechanism of action of BPA in cell membranes once phosphatidylcholines and Chol are found in mammalian membranes.

Olefin-Bridged Bidentate Adsorbates for Generating Self-Assembled Monolayers on Gold

A series of custom-designed olefin-bridged bidentate adsorbates composed of an olefin group linking symmetrical hydrocarbon moieties of varying chain lengths was synthesized and used for the preparation of self-assembled monolayers (SAMs) on gold. The structures of the adsorbates are in the form Z-[CH3(CH2)m]2(C═C)[CH2SH]2 (OBCnSH) where m = 12-15 and n = m + 3 (OBC15SH, OBC16SH, OBC17SH, and OBC18SH). The influence of the olefin linker on the structural and interfacial properties of the SAMs was investigated and compared to SAMs formed from analogous n-alkanethiols. Characterization techniques included ellipsometry, X-ray photoelectron spectroscopy (XPS), polarization modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS), and contact angle measurements. The OBCnSH SAMs exhibited ellipsometric thicknesses that were similar to their monodentate counterparts, suggesting that the new olefin-bridged adsorbates pack similarly to the monodentate analogs. Characterization by PM-IRRAS revealed that the OBCnSH SAMs were as conformationally ordered as those derived from the reference n-alkanethiols with the exception of the adsorbate with the shortest chain length OBC15SH, which exhibited low coverage and a liquid-like structure. Unlike the SAMs derived from the n-alkanethiols, the OBCnSH SAMs failed to exhibit "odd-even" effects. However, the OBCnSH SAMs displayed similar hexadecane contact angles as their n-alkanethiol counterparts with the exception of OBC15SH, which exhibited markedly diminished hexadecane contact angles. The similar structural and interfacial properties of the OBCnSH SAMs, when compared to analogous n-alkanethiol SAMs, render the molecular architecture of the olefin-bridged dithiol as a robust platform for the synthesis of adsorbates with two chemically distinct tailgroups for use in the preparation and study of phase-incompatible "conflicted" interfaces.

Influence of levofloxacin and clarithromycin on the structure of DPPC monolayers

Research on lipid/drug interactions at the nanoscale underpins the emergence of synergistic mechanisms for topical drug administration. The structural understanding of bio-mimetic systems employing 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) as a lung surfactant model mixed with antibiotics, as well as their biophysical properties, is of critical importance to modulate the effectiveness of therapeutic agents released directly to the airways. In this paper, we investigate the structural details of the interaction between Levofloxacin, ‘a respiratory quinolone’, and the macrolide Clarithromycin, with DPPC monolayers at the air-water interface, using a combination of Brewster angle microscopy, polarization modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS), surface pressure isotherms and neutron reflectometry (NR) to describe the structural details of this interaction. The results allowed association of changes in the π-A isotherm profile with changes in the molecular organization and the co-localization of the antibiotics within the lipid monolayer by NR measurements. Overall, both antibiotics are able to increase the thickness of the acyl tails in DPPC monolayers with a corresponding reduction in tail tilt as well as to interact with the phospholipid headgroups as shown by PM-IRRAS experiments. The effects on the DPPC monolayers are correlated with the physical-chemical properties of each antibiotic and dependent on its concentration.

Two/three-dimensional interfacial properties of the novel peptide as a selective destroyer of biomembrane

Peptides are widely used in biomedicine field for their good biocompatibility and variable secondary structures. In this study, a novel amphiphilic peptide (amPE) was designed for antimicrobial agent. Its thermal responsiveness in solution and in liposome membrane was studied by circular dichroism (CD). Then, amPE’s adsorption and further insertion behaviors at lipid monolayer were investigated by Langmuir-Blodgett (LB) and polarization modulation infrared reflection adsorption spectroscopy (PM-IRRAS). Results showed that amPE could selectively insert into DPPG monolayer due to the electrostatic interaction and cause an increase in content of α-helix. Adsorption kinetics under different initial surface pressures showed higher surface pressure prevented peptide’s insertion. Then, experiments of dye leakage from liposomes were carried for discussing how amPE disturbed the liposome membrane. Serious dye leakage from DPPG liposome was observed and the leakage was further improved when temperature increased from 37 °C to 45 °C. The designed amPE showed its good potential as antimicrobial/antitumor agent and great superiority of thermal responsiveness.

Unsymmetrical Spiroalkanedithiols Having Mixed Fluorinated and Alkyl Tailgroups of Varying Length: Film Structure and Interfacial Properties.

A custom-designed series of unsymmetrical spiroalkanedithiols having tailgroups comprised of a terminally fluorinated chain and a hydrocarbon chain of varying lengths were synthesized and used to prepare self-assembled monolayers (SAMs) on gold substrates. The specific structure of the adsorbates was of the form [CH3(CH2)n][CF3(CF2)7(CH2)8]C[CH2SH]2, where n = 7, 9, and 15 (designated as F8H10-C10, F8H10-C12, and F8H10-C18, respectively). The influence of the length of the hydrocarbon chain in the bidentate dithiol on the structure and interfacial properties of the monolayer was explored. A structurally analogous partially fluorinated monodentate alkanethiol and the corresponding normal alkanethiols were used to generate appropriate SAMs as reference systems. Measurements of ellipsometric thickness showed an unexpectedly low film thickness for the SAMs derived from the bidentate adsorbates, possibly due to disruptions in interchain packing caused by the fluorocarbon chains (i.e., phase-incompatible fluorocarbon-hydrocarbon interactions), ultimately giving rise to loosely packed and disordered films. Analysis by X-ray photoelectron spectroscopy (XPS) were also consistent with a model in which the films were loosely packed; additionally, the XPS spectra confirmed the attachment of the sulfur headgroups of the bidentate adsorbates onto the gold substrates. Studies of the SAMs by polarization modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS) suggested that as the length of the hydrocarbon chain in the adsorbates was extended, a more ordered surface was achieved by reducing the tilt of the fluorocarbon segment. The wettability data indicated that the adsorbates with longer alkyl chains were less wettable than those with shorter alkyl chains, likely due to an increase in interchain van der Waals forces in the former.

Influence of amine and thiol modifications at the 3′ ends of single stranded DNA molecules on their adsorption on gold surface and the efficiency of their hybridization

Adsorption of molecules of DNA (deoxyribonucleic acid) or modified DNA on gold surfaces is often the first step in construction of many various biosensors, including biosensors for detection of DNA with a particular sequence. In this work we study the influence of amine and thiol modifications at the 3′ ends of single stranded DNA (ssDNA) molecules on their adsorption on the surface of gold substrates and on the efficiency of hybridization of immobilized DNA with the complementary single stranded DNA. The characterization of formed layers has been carried out using infrared spectroscopy and atomic force microscopy. As model single stranded DNA we used DNA containing 20 adenine bases, whereas the complementary DNA contained 20 thymine bases. We found that the bands in polarization modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS) spectra of layers formed from thiol-modified DNA are significantly narrower and sharper, indicating their higher regularity in the orientation of DNA on gold surface when using thiol linker. Also, hybridization of the layer of thiol-modified DNA containing 20 adenine bases with the respective DNA containing thymine bases leads to formation of much more organized structures than in the case of unmodified DNA or DNA with the amine linker. We conclude that the thiol-modified ssDNA is more promising for the preparation of biosensors, in comparison with the amine-modified or unmodified ssDNA. We have also found that the above-mentioned modifications at the 3′ end of ssDNA significantly influence the IR spectrum (and hence the structure) of polycrystalline films formed from such compounds, even though adsorbed fragments contain less than 5% of the DNA chain. This effect should be taken into account when comparing IR spectra of various polycrystalline films formed from modified and unmodified DNA.

Mixed Self‐Assembled Monolayers with Internal Urea Group on Silica Surface

AbstractIn this study, we report the successful grafting on silica surfaces by the coadsorption method, of mixed nitrobenzyl ester‐/methyl‐terminated self‐assembled monolayers (SAMs), with ratios of two coupling agents (30/70) and (10/90). We show that the preparation of mixed monolayers using two organosilanes with internal urea groups in the alkyl chain seems to be appropriate to obtain a monolayer composition similar to the molar ratio of the two silanes in the deposition solution. This behavior could be due to the presence of the polar urea groups in the molecular structure of both organosilanes which allows them to have the same ability of self‐assembly by hydrogen‐bonding and also the same affinity with the hydrophilic surface. To locate the ester functions at the surface of the mixed monolayers, we investigated the covalent immobilization of amino functionalized gold nanoparticles (GNPs) as nanoscale marker. Polarization modulation infrared reflection‐adsorption spectroscopy (PM‐IRRAS) and atomic force microscopy (AFM) were used to monitor the chemical modifications of the silica surfaces and to demonstrate the successful attachment of gold nanoparticles onto the modified surfaces. Finally, we show that the mixed SAMs were grafted with a phase separation.

Synthesis and characterization of Ag-Protoporphyrin nano structures using mixed co-polymer method

In this paper, we report the synthesis of hybrid silver nanostructures (AgNPs) based on an effective mixing of polyols with Polyvinylpyrrolidone (PVP) and Porphyrin molecules, in particular Protoporphyrin IX (PP). The combination of PVP and PP, which act as co-directing agents and favour the anisotropic growth of nanostructures, yields to very stable complexes for six months. The resulting hybrid silver nanoparticles have been further characterized by polarization modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS), UV–Visible spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM), revealing that the main role of Porphyrin molecules in the formation of silver nanostructures.

Self-assembled monolayers on gold generated from terminally perfluorinated alkanethiols bearing propyl vs. ethyl hydrocarbon spacers

This paper examines the structural and interfacial properties of terminally perfluorinated self-assembled monolayers (FSAMs) on gold generated from the adsorption of a new series of terminally perfluorinated propanethiols F(CF2)n(CH2)3SH, where n=8, 10, and 12. Analysis of these FSAMs by ellipsometry and X-ray photoelectron spectroscopy (XPS) confirmed the formation of the monolayer films. The contact angles of water and n-hexadecane on these FSAMs indicated a high degree of hydrophobicity and oleophobicity. Polarization modulation infrared reflection-adsorption spectroscopy (PM-IRRAS) analysis of the films revealed that the fluorinated chains are oriented largely perpendicular to the gold surface. In addition, the FSAMs formed from the new adsorbates were compared to known FSAMs derived from F(CF2)n(CH2)2SH, where n=8, 10, and 12, to examine the influence of the number of CH2 groups in the short alkyl spacer upon the conformational order and packing structure of the films. Analysis of the XPS spectra for the normalized peak intensity of the F 1s and S 2p binding energies for both types of films suggest a slight increase in packing density for the chains having the propyl vs. the ethyl hydrocarbon spacer. This conclusion is consistent with the observed decrease in the wetting behavior of hexadecane on the FSAMs formed from the new adsorbates. However, the preponderance of the data indicates that these two series of partially fluorinated alkanethiols form films with highly similar structure/packing characteristics with no discernible “odd-even” effect between the two series.

Rubber particle proteins, HbREF and HbSRPP, show different interactions with model membranes

The biomembrane surrounding rubber particles from the hevea latex is well known for its content of numerous allergen proteins. HbREF (Hevb1) and HbSRPP (Hevb3) are major components, linked on rubber particles, and they have been shown to be involved in rubber synthesis or quality (mass regulation), but their exact function is still to be determined. In this study we highlighted the different modes of interactions of both recombinant proteins with various membrane models (lipid monolayers, liposomes or supported bilayers, and multilamellar vesicles) to mimic the latex particle membrane. We combined various biophysical methods (polarization-modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS)/ellipsometry, attenuated-total reflectance Fourier-transform infrared (ATR-FTIR), solid-state nuclear magnetic resonance (NMR), plasmon waveguide resonance (PWR), fluorescence spectroscopy) to elucidate their interactions. Small rubber particle protein (SRPP) shows less affinity than rubber elongation factor (REF) for the membranes but displays a kind of “covering” effect on the lipid headgroups without disturbing the membrane integrity. Its structure is conserved in the presence of lipids. Contrarily, REF demonstrates higher membrane affinity with changes in its aggregation properties, the amyloid nature of REF, which we previously reported, is not favored in the presence of lipids. REF binds and inserts into membranes. The membrane integrity is highly perturbed, and we suspect that REF is even able to remove lipids from the membrane leading to the formation of mixed micelles. These two homologous proteins show affinity to all membrane models tested but neatly differ in their interacting features. This could imply differential roles on the surface of rubber particles.

Monolayer Collapse Regulating Process of Adsorption−Desorption of Palladium Nanoparticles at Fatty Acid Monolayers at the Air−Water Interface

In this paper, we investigate the affinity of palladium nanoparticles, stabilized with glucose oxidase, for fatty acid monolayers at the air-water interface, exploiting the interaction between a planar system and spheroids coming from the aqueous subphase. A decrease of the monolayer collapse pressure in the second cycle of interface compression proved that the presence of the nanoparticles causes destabilization of the monolayer in a mechanism driven by the interpenetration of the enzyme into the bilayer/multilayer structure formed during collapse, which is not immediately reversible after monolayer expansion. Surface pressure and surface potential-area isotherms, as well as infrared spectroscopy [polarization modulation infrared reflection adsorption spectroscopy (PM-IRRAS)] and deposition onto solid plates as Langmuir-Blodgett (LB) films, were employed to construct a model in which the nanoparticle has a high affinity for the hydrophobic core of the structure formed after collapse, which provides a slow desorption rate from the interface after monolayer decompression. This may have important consequences on the interaction between the metallic particles and fatty acid monolayers, which implies the regulation of the multifunctional properties of the hybrid material.

Real-Time IR Study of Ultra-Thin Film Photopolymerization of Liquid Porphyrin Monomer

By using an advanced polarization modulation infrared reflection adsorption spectroscopy (PM-IRRAS) device it is possible to study the photopolymerization of an ultrathin layer of a porphyrin monomer in real time. The method can be compared with the indirect UV/Vis method previously introduced by our group. With PM-IRRAS it is possible to analyze polymerization kinetics of photopolymerization at various temperatures to determine the activation energy of the reaction.

PM-IRRAS Assessment of the Compression-Mediated Orientation of the Nanocavity of a Monoacylated β-Cyclodextrin in Monolayers at the Air−Water Interface

The structural orientation adopted along the compression-decompression isotherm by a monoacylated beta-cyclodextrin (C16-betaCD) at the air-water interface was assessed by polarization-modulation infrared reflection-adsorption spectroscopy (PM-IRRAS). The adoption of different orientations of the cyclic oligosaccharide unit, relative to the interfacial plane, was interpreted analyzing the PM-IRRAS band intensity ratios of specific vibrations corresponding to the cyclodextrin moiety as a function of the surface pressure for successive compression/decompression cycles. The spectroscopic analysis revealed that the cyclic oligosaccharide modifies its position under compression from one in which the plane of the cavity of the monoacylated beta-cyclodextrin lies almost parallel to the interface to another in which the plane of the cavity is perpendicular to the interface. Through the PM-IRRAS analysis, it was also possible to evidence the establishment of an intermolecular hydrogen bonding network that may play an important role in the dynamic properties of the monolayer packing. The hydrogen bonding network becomes more important with the increases of surface pressure, up to a molecular packing limit, and it imparts the surface properties of the film for future compression-decompression cycles.

Action of an Antiparasitic Peptide Active against African Sleeping Sickness in Biomembrane Models

Peptides with trypanocidal activity are promising compounds for the treatment of African Sleeping Sickness, which have motivated the research into the ability of these compounds to disrupt the protozoan membrane. In this present study, we used the Langmuir monolayer technique to investigate the surface properties of an antiparasitic and zwitterionic peptide, namely S-(2,4-dinitrophenyl) glutathione di-2-propyl ester, and its interaction with a model membrane comprising a phospholipid monolayer, dipalmitoyl phosphatidyl choline (DPPC). The peptide formed a stable Langmuir monolayer, whose main feature of its surface pressure-area isotherm was the presence of a phase transition accompanied by a negative surface compressional modulus, which was attributed to the aggregation upon compression due to intermolecular bond associations of the molecules. This was inferred from surface pressure and surface potential isotherms, Brewster angle microscopy (BAM) images, Polarization modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS), and dynamic elasticity measurements by the pendant drop technique. When co-spread with dipalmitoyl phosphatidyl choline (DPPC), the drug affected both the surface pressure and the monolayer morphology, even at high surface pressures and with low amounts of the drug. The results were interpreted by assuming a repulsive, cooperative interaction between the drug and DPPC molecules. Such repulsive interaction and the large changes in fluidity arising from drug aggregation may be related to the disruption of the membrane, which is key for the parasite killing property.

A New Method for Performing Polarization Modulation Infrared Reflection-Adsorption Spectroscopy of Surfaces

A new and relatively simple polarization modulation technique is presented and tested that enables the whole spectral range to be detected between 400 and 4000 cm(-1). This experiment is conventionally carried out using a photoelastic modulator that modulates incident plane polarized light through 90 degrees . This suffers from the drawback that it enables spectra to be collected only over a relatively narrow spectral range. As an alternative, a polarizer is placed in the beam and oriented at 45 degrees to the sample normal. This produces incident radiation fluxes with identical intensities for both s- and p-polarized light. A second polarizer is then modulated through 90 degrees and the surface spectrum is then extracted in the usual manner from the difference between these signals, normalized to their sum. The method is demonstrated for a self-assembled monolayer of 11-mercapto-undecanoicacid (11-MUA) on gold on mica, and it is shown that, while the resulting spectra are extremely sensitive to optical alignment, the method yields spectra that are in excellent agreement with published data.

7-Octenyltrimethoxysilane, a model coupling molecule to study the adhesion promotion of a silicone elastomer on an Al 2024 alloy

Ultra-thin layers of 7-octenyltrimethoxysilane (7-OTMS) and of 7-OTMS mixed with n-octyltrimethoxysilane ( n-OTMS) (1/1 and 1/10 v/v) have been prepared as adhesion primers for silicone coatings on mechanically polished AA2024 aluminum alloy. The characterization of the silane grafting has been carried out by X-ray photoelectron spectroscopy (XPS), polarization modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS) and water contact angle measurements. Sylgard ®184 silicone has been spin-coated and cured on bare and modified aluminum to form 15 μm polymer films. Qualitative peel tests (ASTM D3359) and scanning electron microscopy (SEM) point to the beneficial effect of the 7-OTMS layer to the adhesion whereas mixed layers show comparatively poor adhesion.

Monolayers and mixed-layers on copper towards corrosion protection

In order to improve the protection abilities of (3-mercaptopropy)trimethoxysilane (MPTS) self-assembled monolayers on copper surfaces, mixed monolayers have been formed successfully by successive immersions in MPTS and in n-dodecanethiol (DT). A newly synthesised molecule, (11-mercaptoundecyl)trimethoxysilane (MUTS), has also been employed to form a thicker organic film on copper surfaces and, thereby, enhance the inhibitory action of the coating. The grafting has been confirmed by X-ray photoelectron spectroscopy (XPS), polarization modulation infrared reflection adsorption spectroscopy (PM-IRRAS) and water contact angle. The protective efficiency of each protective organic film has been evidenced by cyclic voltammetry (CV) and polarization curve measurements (CP). It was shown that the MUTS and unhydrolyzed MPTS/DT films exhibited significant corrosion protection properties.

Adsorption on stainless steel surfaces of biosurfactants produced by gram-negative and gram-positive bacteria: Consequence on the bioadhesive behavior of Listeria monocytogenes

The ability of adsorbed biosurfactants (Pf and Lb) obtained from gram-negative bacterium ( Pseudomonas fluorescens) or gram-positive bacterium ( Lactobacillus helveticus) to inhibit adhesion of four listerial strains to stainless steel was investigated. These metallic surfaces were characterized using the following complementary analytical techniques: contact-angle measurements (CAM), atomic force microscopy (AFM), polarization modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS) and X-ray photoelectron spectroscopy (XPS). Contact-angles with polar liquids (water and formamide) indicated that the stainless steel surface covered with adsorbed biosurfactant was more hydrophilic and electron-donating than bare stainless steel. The surface characterization by XPS and PM-IRRAS revealed that conditioning the stainless steel changes the substrate in two ways, by modifying the surface alloy composition and by leaving an thin adsorbed organic layer. AFM observations enabled to say that the layer covered entirely the surface and was probably thicker (with patches) in the case of Pf-conditioned surfaces compared to the Lb-conditioned ones, which seemed to be less homogeneous. Though the added layer was thin, significant chemical changes were observed that can account for drastic modifications in the surface adhesive properties. As a matter of fact, adhesion tests showed that both used biosurfactants were effective by decreasing strongly the level of contamination of stainless steel surfaces by the four strains of Listeria monocytogenes. The more important decrease concerned the CIP104794 and CIP103573 strains (>99.7%) on surface conditioned by L. helveticus biosurfactant. A less reduced phenomenon (75.2%) for the CIP103574 strain on stainless steel with absorbed biosurfactant from P. fluorescens was observed. Whatever the strain of L. monocytogenes and the biosurfactant used, this antiadhesive biologic coating reduced both total adhering flora and viable and cultivable adherent bacteria on stainless steel surfaces. This study confirms that biosurfactants constitute an effective strategy to prevent microbial colonization of metallic surfaces by pathogenic bacteria like the food-borne pathogen L. monocytogenes.

Monolayers of Salen Derivatives as Catalytic Planes for Alkene Oxidation in Water

Monolayers at the gas/water interface have been used as an adjustable catalytic system in which the molecular density may be modified. Mn(III)-salen complexes bearing perfluoroalkyl substituents have been organized as a Langmuir film on an aqueous subphase containing a urea/hydrogen peroxide adduct (UHP, the oxidant) and cinnamyl alcohol (the substrate). The catalytic activity of the monolayer for the epoxidation of the alkene dissolved in water has been demonstrated and the reaction kinetic investigated. For a constant area per molecule of catalyst, the reaction rate exhibits first-order dependence on oxidant concentration and zero-order dependence on alkene concentration, in agreement with the reaction orders reported for Mn(III)-salen-catalyzed epoxidation reactions carried out in solution. Furthermore, kinetic experiments suggest an enhanced activity of the catalysts assembled in a Langmuir film relative to that observed in bulk reaction. Finally, varying the molecular density of the catalyst at the gas/water interface highlights an important dependence of the catalytic activity of the layer with the mean molecular area. A strong increase of the catalytic properties of the monolayer was observed for a mean molecular area of 140-145 A2, an increase which was supposedly related to a modification of the Mn(III)-salen complex orientation at the interface upon compression. This hypothesis was supported by PM-IRRAS (polarization modulation infrared reflection adsorption spectroscopy) experiments performed in situ on the monolayer. Such results demonstrate that a soft and adjustable molecular system like a Langmuir film can be used to better understand the reactivity in various heterogeneous and/or pseudohomogeneous (such as those based on dendrimers) catalytic systems.