Polarization Modulation Infrared Reflection Adsorption 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.

Electropolymerized-molecularly imprinted polymers (E-MIPS) as sensing elements for the detection of dengue infection.

A straightforward in situ detection method for dengue infection was demonstrated through the molecular imprinting of a dengue nonstructural protein 1 (NS1) epitope into an electropolymerized molecularly imprinted polyterthiophene (E-MIP) film sensor. The key enabling step in the sensor fabrication is based on an epitope imprinting strategy, in which short peptide sequences derived from the original target molecules were employed as the main template for detection and analysis. The formation of the E-MIP sensor films was facilitated using cyclic voltammetry (CV) and monitored in situ by electrochemical quartz crystal microbalance (EC-QCM). Surface properties were analyzed using different techniques including atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and polarization modulation-infrared reflection-adsorption (PM-IRRAS). The standard calibration curve (R = 0.9830) was generated for the detection of the epitope, Ac-VHTWTEQYKFQ-NH2, with a linear range of 0.2 to 30μg/mL and detection limit of 0.073μg/mL. A separate calibration curve (R = 0.9786) was obtained using spiked buffered solutions of dengue NS1 protein, which resulted in a linear range of 0.2 to 10μg/mL and a detection limit of 0.056μg/mL. The fabricated E-MIP sensor exhibited long-term stability, high sensitivity, and good selectivity towards the targeted molecules. These results indicated that the formation of the exact and stable cavity imprints in terms of size, shape, and functionalities was successful. In our future work, we aim to use our E-MIP sensors for NS1 detection in real-life samples such as serum and blood.

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.

Disruption of Tumor Cells Using a pH-Activated and Thermosensitive Antitumor Lipopeptide Containing a Leucine Zipper Structure.

Antitumor peptides may potentially alleviate the problem of chemoresistance but do not yet target tumor cells and would be cytotoxic to normal cells. Here, we designed a pH-activated and thermosensitive lipopeptide (C6-Pep) containing a leucine zipper and an alkyl chain and assessed the ability of C6-Pep to kill cancer cells. Pep, the same sequence without the N-terminal hexanoic acid moiety, was generated as a less hydrophobic control. First, lipopeptide adsorption into lipid monolayers was studied using Langmuir-Blodgett and polarization modulation infrared reflection adsorption spectroscopy. Under weakly acid conditions, electrostatic interactions between C6-Pep and negatively charged phospholipids increased the adsorption/insertion of C6-Pep (vs Pep) into lipid monolayers. Cargo leakage from liposomes was assayed to model lipopeptide-induced lipid membrane disruption. The ability of C6-Pep to disrupt liposomes depended on the peptide molecular structure/hydrophobicity, solution pH, and temperature-induced uncoiling of the zipper structure; the greatest cargo leakage from the liposome with negative charge was observed for C6-Pep at pH 5.5 under mildly hyperthermic conditions (45 °C). In vitro, C6-Pep was significantly more cytotoxic toward HeLa cells at pH 5.5 under hyperthermic conditions than at pH 7.4 and/or 37 °C. Overall, this study demonstrates that amphipathic C6-Pep can insert into cell membranes in the low-pH tumor microenvironment, whereas the application of heat promotes the uncoiling of the zipper structure, leading to the disruption of tumor cell membranes and cell death. pH-activated and thermosensitive C6-Pep represents a promising tool to kill cancer cells via a strategy that does not invoke chemoresistance and may have low side effects.

Epoxy-terminated self-assembled monolayers containing internal urea or amide groups.

We report the synthesis of new coupling agents with internal amide or urea groups possessing an epoxy-terminal group and trimethoxysilyl-anchoring group. The structural characterizations of the corresponding self-assembled monolayers (SAMs) were performed by polarization modulation infrared reflection adsorption spectroscopy (PM-IRRAS). The molecular assembly is mainly based on the intermolecular hydrogen-bonding between adjacent amide or urea groups in the monolayers. Because of the steric hindrance of amide or urea groups, the distance between the alkyl chains is too large to establish van der Waals interactions, inducing their disorder. The reactivity of the epoxy-terminal groups was successfully investigated through reaction with a fluorescent probe. We show that SAMs containing internal urea or amide groups exhibited a higher density of accessible epoxide groups than the corresponding long-chain (C22) glycidyl-terminated SAM.

Preparation and characterization of alkylphosphonic acid self-assembled monolayers on titanium alloy by chemisorption and electrochemical deposition.

Ti-6Al-4V alloy is the most commonly used alloy for dental and orthopedic implants. In order to improve osseointegration, different surface modification methods are usually employed, including self-assembled monolayers (SAMs). This study presents an investigation of both active (electroassisted) and passive (adsorption) approaches for the modification of Ti-6Al-4V using alkylphosphonic acid. The monolayers were characterized by cyclic voltammetry, double-layer capacitance, contact angle measurements, X-ray photoelectron spectroscopy, polarization modulation infrared reflection adsorption spectroscopy, electrochemical impedance spectroscopy, and corrosion potentiodynamic polarization measurements. It is shown that the electrochemically assisted monolayers, which are assembled faster, exhibit better control over surface properties, a superior degree of order, and a somewhat higher packing density. The electrosorbed SAMs also exhibit better blockage of electron transfer across the interface and thus have better corrosion resistance.

Self-Assembled Monolayers on Gold of β-Cyclodextrin Adsorbates with Different Anchoring Groups

We designed multivalent β-cyclodextrin-based adsorbates bearing different anchoring groups aiming to yield stable monolayers with improved packing and close contact of the cavity to the gold surface. Toward this end the primary rim of the β-cyclodextrin was decorated with several functional groups, namely iodide, nitrile, amine, isothiocyanate, methyl sulfide, and isocyanide. Monolayers formed by these adsorbates were characterized by contact angle measurements, surface plasmon resonance spectroscopy, polarization modulation infrared reflection adsorption spectroscopy, X-ray photoelectron spectroscopy, and electrochemistry. The nature of the anchoring group influenced the adsorption kinetics, thickness, layer stability, number of anchoring groups bounded to the surface, and packing in the resulting monolayers. Therefore, chemical manipulation of multivalent adsorbates can be used to modify the properties of their monolayers.

On the Stability of Fullerene C60 in Aqueous Medium

Fullerene C60 was dissolved in toluene-water mixture under sonochemical activation, and after toluene evaporation a stable aqueous solution remained. The problem of C60 stability in aqueous medium was studied by means of polarization modulation infrared reflection adsorption spectroscopy (PM IRRAS), time-of-flight secondary ion mass spectrometry (TOF SIMS) and atomic force microscopy/scanning tunneling microscopy (AFM/STM) techniques. It was found that C60 clusters are in the aqueous solution stabilized by the presence of thin layer of methylbenzoate produced during sonication.

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.

Differentiating Oxicam Nonsteroidal Anti-Inflammatory Drugs in Phosphoglyceride Monolayers

Meloxicam, piroxicam, and tenoxicam belong to a highly potent oxicam group of nonsteroidal anti-inflammatory drugs. Whereas the structurally similar oxicams have different pharmacokinetics, treatment efficiency, and adverse effects, their common mechanism of action is the inhibition of a membrane enzyme, cyclooxygenase. Because the prerequisite for accessing the cyclooxygenase by the drugs is interaction with the membrane, the focus of the current study was a comparison of how meloxicam, piroxicam, and tenoxicam interact with lipid monolayers used as models of biological membranes. The monolayers were formed with 1,2-dipalmitoyl-sn-glycero-3-phospho-rac-(1-glycerol), 1,2-dipalmitoyl-sn-glycero-3-phospho-l-serine, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine, 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine, 1,2-myristoyl-sn-glycero-3-phosphoethanolamine, and 1,2-dilauroyl-sn-glycero-3-phosphoethanolamine. These systems were examined via surface pressure and surface electrical potential measurements, polarization modulation infrared reflection adsorption spectra, and Brewster angle microscopy. The three oxicams are differentiated in the monolayers; meloxicam shows the highest ability to modify membrane fluidity and surface potential, followed by piroxicam and tenoxicam. The dissimilarity of the biological activity of the oxicams may be linked to different interaction with the membrane, as revealed by the present study.

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.

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.

Molecularly Specific Studies of the Frictional Properties of Monolayer Films: A Systematic Comparison of CF3-, (CH3)2CH-, and CH3-Terminated Films

The origin of frictional forces in self-assembled monolayers (SAMs) was investigated through systematic correlation of the frictional properties with the chemical structure/composition of the films. Atomic force microscopy was used to probe the frictional properties of the SAMs formed by the adsorption of methyl-, isopropyl-, and trifluoromethyl-terminated alkanethiols on Au(111) surfaces. The frictional properties of mixed monolayers composed of varying concentrations of the methyl- and trifluoromethyl-terminated thiols were also studied. Polarization modulation infrared reflection adsorption spectroscopy was used to measure the vibrational spectra of each of these monolayers and in turn to determine that each was characterized by a well-packed backbone structure. For these films, which differed only in the nature of the outermost chemical functionality, a substantial enhancement in the frictional response was observed for films with isopropyl- and trifluoromethyl-terminal groups and for mixed monolayers containing small concentrations of the trifluoromethyl-terminated component. These results strongly support the model that the difference in friction in such systems arises predominantly from the difference in the size of the terminal groups. Larger terminal groups in films of the same lattice spacing give rise to increased steric interactions that provide pathways for energy dissipation during sliding.