Infrared imaging of a solid phase surfactant monolayer

A new method for visualizing solid phase surfactant monolayers is presented. This method utilizes infrared (IR) imaging of the surface of a warm subphase covered by the monolayer. When the subphase is deep, natural convection occurs, resulting in a complex surface temperature field that is easily visualized using an IR camera. The presence of a surfactant monolayer changes the hydrodynamic boundary condition at the interface, dramatically altering the surface temperature field, and permitting the differentiation of surfactant-covered and surfactant-free regions. In this work, solid phase monolayers are imaged using this IR method. Fractures in the monolayer are dramatically visualized because of the sudden elimination of surfactant in the region opened up by the crack. The method is demonstrated in a wind/water tunnel, where a stearic acid monolayer is deposited and a crack is created through shear on the surfactant surface, created by suddenly increasing the velocity of the air over the water.     

Enzyme-encapsulated silica monolayers for rapid functionalization of a gold surface

We report a simple and rapid method for the deposition of amorphous silica onto a gold surface. The method is based on the ability of lysozyme to mediate the formation of silica nanoparticles. A monolayer of lysozyme is deposited via non-specific binding to gold. The lysozyme then mediates the self-assembled formation of a silica monolayer. The silica formation described herein occurs on a surface plasmon resonance (SPR) gold surface and is characterized by SPR spectroscopy. The silica layer significantly increases the surface area compared to the gold substrate and is directly compatible with a detection system. The maximum surface concentration of lysozyme was found to be a monolayer of 2.6 ng/mm(2) which allowed the deposition of a silica layer of a further 2 ng/mm(2). For additional surface functionalization, the silica was also demonstrated to be a suitable matrix for immobilization of biomolecules. The encapsulation of organophosphate hydrolase (OPH) was demonstrated as a model system. The silica forms at ambient conditions in a reaction that allows the encapsulation of enzymes directly during silica formation. OPH was successfully encapsulated within the silica particles and a detection limit for the substrate, paraoxon, using the surface-encapsulated enzyme was found to be 20 microM.     

Stretching of single DNA molecules complexed with restriction endonuclease by Langmuir-Blodgett method

We have proposed a new technique for stretching single double-stranded DNA molecules on solid substrates by the Langmuir–Blodgett (LB) method. The polyion complex monolayer of a cationic amphiphile and DNA molecules formed at the air–water interface was transferred on a clean glass substrate. Vertical lifting up of the glass substrate provided the transferred monolayer consisting the stretched individual DNA molecules aligned parallel to the lifting direction on the glass. The DNA molecules complexed with the restriction endonuclease (EcoRI) were employed for stretching by using this method. Fluorescence images of the transferred monolayer showed that the EcoRI-binding DNA molecules could be stretched and immobilized on the glass substrate. A specific sequence of DNA recognized by EcoRI was detected as spatial positions of the stretched DNA molecules.     

Theoretical evaluation of nano- or microparticulate contact angle at fluid/fluid interfaces: analysis of the excluded area behavior upon compression

A novel method for the determination of the particle contact angle at the liquid/gas or liquid/liquid interface based on the excluded area concept revealed, in spite of its simplicity, some serious difficulties connected with the exact quantitative particle deposition at the interface and with changes in the particulate contact angle upon binary monolayer compression. The comprehensive theoretical consideration of the contact angle behavior made for such a system allowed considerable improvements: firstly, the prediction of direction of the particles' displacement at surface pressure increase is now possible and hence an unambiguous identification of particle hydrophobicity can be done. Secondly, the analytical relation describing the dependence of the particulate contact angle on the surface tension (surface pressure) was derived, allowing the prediction of whether or not particles of a given hydrophobicity will be expelled from the monolayer at certain surface pressure and of the area relinquished by the displaced particles. Thirdly, the transformation of this relation upon taking into consideration the initial conditions led to a linear dependence between excluded area and normalized surface tension allowing the determination of the particle contact angle and the exact number of deposited particles simultaneously and independently of each other. Finally, the application of the improved approach to the previously collected experimental data yielded reasonable values for both particle contact angle and number of deposited particles.     

Surface induced dissociation of chromium hexacarbonyl on fluorinated alkanethiolate surface in ion cyclotron resonance mass spectrometer: studies of energetics of the process using recursive internal energy distribution search method

Energy transfer in ion-surface collisional activation is characterized for 0–30 eV collisions of chromium hexacarbonyl molecular cations with a monolayer of fluorinated alkanethiolate self-assembled onto a solid gold surface. This surface was mounted on the back trapping plate of the Infinity® cell of a Bruker BioApex 7T ion cyclotron resonance mass spectrometer on the B-field axis orthogonal to the ion beam direction. Internal energy deposition was deduced from fragmentation spectra using a recursive internal energy distribution search method. The efficiency of energy transfer into the ion slowly increases with incident ion energy to a maximum value of 20% at about 23 eV collision energy. Approximate kinetic energy distributions of the fragments were measured by deducing the dependence of ion abundance on trapping potential. From the kinetic energy dependence on mass we infer that rapid decomposition of the molecular cation occurs after it recoils from the surface. Knowledge of both internal and kinetic energy distributions of collisionally activated ions enabled us to deduce the energy deposited into the self-assembled monolayer as a function of collision energy.     

Layer-by-layer assembly of thiol-capped au nanoparticles on a water surface and their deposition on H-terminated Si(001) by the Langmuir-Blodgett method

A monolayer of dodecanethiol-encapsulated Au nanoparticles when compressed laterally transforms into layer-by-layer assemblies on water surface. These layer-by-layer assemblies of Au nanoparticles have been deposited on H-terminated Si(001) substrates by using one down-up cycle (two strokes) in the Langmuir-Blodgett (LB) method. The transformation from monolayer to layer-by-layer assembly on a water surface is irreversible; i.e., if the compressed film is decompressed the layer-by-layer structure cannot regenerate the monolayer structure. Unlike layer-by-layer growth, only odd numbers of layers grow from the monolayer on the H-terminated Si(001) substrates by using different numbers of down-up cycles. Z-type LB deposition occurs only in the first down-up cycle of the hydrophobic substrate, whereas Y-type LB deposition takes place in the successive cycles. Such layer-by-layer assemblies of Au nanoparticles, which are made on bare silicon surfaces and where thickness can be controlled at the nanoscale level, are very promising for their novel applications in the field of nanoscience.     

Electrodeposition of mercury on gold from very dilute mercury(II) solution

Flameless atomic absorption spectrometry (flameless a.a.s.) was applied to study the state of mercury deposited on a gold plate electrode from very dilute mercury(II) solution by controlled-potential electrolysis. A stable monolayer is formed on the gold electrode by the electrolysis at a potential about 200 mV more positive than the reversible Nernst potential for the reduction of mercury(II) to mercury(0). After the monolayer formation, bulk mercury is deposited on the monolayer at the reversible potential and an adatom layer is also found. The difference of activation free energies between the evaporation of mercury from the monolayer and that from bulk mercury corresponds to the underpotential shift for the electrodeposition of mercury on the gold electrode.     

Configuration and photochemical reaction of a bolaamphiphilic diacid with a diazo resin in monolayers and Langmuir-Blodgett films

The monolayer formation of a bolaamphiphile, 1,18-octadecanedicarboxylic acid (ODA), on pure water and the subphase containing a positively charged photoactive 2-nitro-N-methyldiphenylamine-4-diazoniumformaldehyde resin (NDR) have been investigated by pi-A isotherms, pi-t curves, and Brewster angle microscopy (BAM) measurements. It has been revealed that although an unstable monolayer was formed by ODA alone, a stable complex monolayer between ODA and NDR could be formed at the interface through electrostatic adsorption and hydrogen bonding. It has been shown that the ODA formed a U-shaped monolayer at a lower pressure and was converted to a stretched configuration upon compression to a higher surface pressure on the subphase containing NDR. Under UV irradiation at the interface photoreaction can occur in the complex monolayer, which causes shrinkage of the monolayer. Photochemical reactions can also occur in deposited Langmuir-Blodgett films. In reactions occurring at the air/water interface, the two ends of ODA can react with NDR to form an ester containing aromatic rings. This makes the compound more hydrophobic and can easily be stretched without any phase transition upon compression. When the film with U-shaped configuration was deposited onto solid substrates, the configuration could be kept even upon photoirradiation.     

Simple solid-phase spectrophotometric method for free iron(III) determination

A simple and rapid solid-phase spectrophotometric procedure to determine free Fe(III) in environmental and biological samples is proposed. In particular, a deferoxamine (DFO) self assembled monolayer on mesoporous silica (DFO SAMMS) is developed and here applied as a sensor for iron(III). The solid product became brownish when put in contact with iron(III) solutions; so an immediate application as colorimetric sensor is considered. In order to optimize the DFO SAMMS synthesis and to obtain the best product for iron(III) sensing, a factorial experimental design is performed selecting the maximum absorption at 425 nm as response. The robustness of the spectrophotometric method is also proved.     

Molecular organization in protein-lipid film on the water surface studied by x-ray standing wave measurements under total external reflection

The x-ray standing wave method has been applied to study self-assembling processes in a protein-lipid film formed by injecting the protein-lipid mixture of alkaline phosphatase and phosphatidylinositol under the phospholipid monolayer preliminarily deposited on the water subphase by Langmuir method. X-ray standing wave measurements allowed to determine the composition of the protein-lipid film and to locate ions position in the direction normal to the film surface. The presence of trace Ni contamination incorporated in the protein-lipid film from the water subphase has been established. Numerical analysis of the X-ray standing wave fluorescence data revealed that after injection under the phospholipid monolayer, the protein-lipid mixture separated in a self-assembled manner to layered structure, molecules of alkaline phosphatase arranged themselves into a pure protein layer containing no phospholipid molecules.     

Aryl Diazonium for Biomolecules Immobilization onto SPRi Chips

A method for the immobilization of proteins at the surface of surface plasmon resonance imaging (SPRi) chips is presented. The technology, based on the electro‐deposition of a 4‐carboxymethyl aryl diazonium (CMA) monolayer is compared to a classical thioctic acid self‐assembled monolayer. SPRi live recording experiments followed by the quantification of the diazonium surface coverage demonstrate the presence of a monolayer of electro‐deposited molecules (11*10¹² molecules mm^?²). This monolayer, when activated through a classical carbodiimide route, generates a surface suitable for the protein immobilization. In the present study, protein A and BSA are immobilized as specific and control spots (150 μm id), respectively. The AFM characterization of the spots deposited onto CMA or thioctic acid modified chips prove the presence of 4.7 nm protein monolayers. Finally, the SPRi detection capabilities of the two surface chemistries are compared according to specific signal, non‐specific interaction and regeneration possibilities. Advantages are given to the CMA surface modification since no measurable non‐specific signal is obtained while reaching a higher specific signal.     

Synthesis and characterization of platinum monolayer oxygen-reduction electrocatalysts with Co–Pd core–shell nanoparticle supports

We synthesized Pt monolayer electrocatalysts for oxygen-reduction using a new method to obtain the supporting core–shell nanoparticles. They consist of a Pt monolayer deposited on carbon-supported Co–Pd core–shell nanoparticles with the diameter of 3–4 nm. The nanoparticles were made using a redox-transmetalation (electroless deposition) method involving the oxidation of Co by Pd cations, yielding a Pd shell around the Co core. The quality of the thus-formed core–shell structure was verified using transmission electron microscopy and X-ray absorption spectroscopy, while cyclic voltammetry was employed to confirm the lack of Co oxidation (dissolution). A Pt monolayer was deposited on the Co–Pd core–shell nanoparticles by the galvanic displacement of a Cu monolayer obtained by underpotential deposition. The total noble metal mass-specific activity of this Pt monolayer electrocatalyst was ca. 3-fold higher than that of commercial Pt/C electrocatalysts.     

Chemically bonded carbon nanotubes on modified gold substrate as novel unbreakable solid phase microextraction fiber

A new technique is introduced for preparation of an unbreakable fiber using gold wire as a substrate for solid phase microextraction (SPME). A gold wire is used as a solid support, onto which a first film is deposited that consists of a two-dimensional polymer obtained by hydrolysis of a self-assembled monolayer of 3-(trimethoxysilyl)-1-propanthiol. This first film is covered with a layer of 3-(triethoxysilyl)-propylamine. Next, a stationary phase of oxidized multi-walled carbon nanotubes was chemically bound to the surface. The synthetic strategy was verified by Fourier transform infrared spectroscopy and scanning electron microscopy. Thermal stability of new fiber was examined by thermogravimetric analysis. The applicability of the novel coating was verified by its employment as a SPME fiber for isolation of diazinon and fenthion, as model compounds. Parameters influencing the extraction process were optimized to result in limits of detection as low as 0.2?ng?mL^?1 for diazinon, and 0.3?ng?mL^?1 for fenthion using the time-scheduled selected ion monitoring mode. The method was successfully applied to real water, and the recoveries for spiked samples were 104% for diazinon and 97% for fenthion.

Reversible activation of diblock copolymer monolayers at the interface by pH modulation, 2: Membrane interactions at the solid/liquid interface

A monolayer of the pH-responsive poly[2-(dimethylamino)ethyl methacrylate-block-methyl methacrylate] diblock copolymer [PDMAEMA-PMMA] was transferred from the air/water interface to a silicon substrate for evaluation as a tunable interlayer between biological material and solid substrates. Specular neutron reflectivity experiments revealed that the weak polyelectrolyte PDMAEMA chains at the solid/liquid interface can be reversibly activated by pH modulation. The thickness, scattering length density, and surface roughness of the polymer film can be systematically controlled by pH titration. As a simple model of plasma membranes, a lipid bilayer was deposited onto the polymer film. The membrane-substrate interaction was characterized by neutron reflectivity experiments, demonstrating that the membrane-substrate distance could be reversibly regulated by pH titration. These results confirm the potential of stimuli-responsive polymers for precise control of cell-surface interactions.     

Preparation of Nanoparticulate [PMo11Cu(H2O)O39]5--n-C18H37NH2 Film Using Langmuir-BIodgett Method

Nanoparticulate [PMo₁₁Cu(H₂O)O₃₉]^5--(PCuMo₁₁)-n-C₁₈H₃₇NH₂ composite monolayer can be formed at the air-liquid interface using nanoparticulate PCuMo₁₁ as the subphase. The area extrapolated to π=0 is 0.27 nm² per hydrocarbon chain of the monolayer. The collapse pressure is about 3.5×10^-1 N. The composite monolayer was deposited on the solid substrate using the LB technique. The XPS characterization of the composite monolayer showed that in the film the directional alignment of PCuMo₁₁, molecules was in the direction of Cu atoms close to the amino groups of the octadecylamine moleculos.     

Recognition of sugars on surface-bound cap-shaped gold particles modified with a polymer brush

A dithiolated random copolymer with pendent phenylboronic acid residues (Cys-Poly(3-acrylamidophenylboronic acid-co-2-dimethylaminopropyl methacrylamide), Cys-Poly(APBA-co-DMAPMA)) obtained by photo-iniferter method was accumulated as a polymer brush on a cap-shaped gold particles deposited on a vacuum-evaporated gold film, and the usefulness of the polymer brush as a sensing element for glycoprotein, ovalbumin (OVA), was examined by using UV-vis spectroscopy with a help of surface plasmon resonance. A similar system was constructed with a dithiolated mannose-carrying polymer, dithiolated-poly(2-methacryloyloxyethyl-D-mannopyranoside) (DT-PMEMan), prepared by the atom transfer radical polymerization (ATRP). The brush composed of this polymer was examined as a sensing element for lectin, concanavalin A (Con A). The sensor cells modified with Cys-Poly(APBA-co-DMAPMA) and DT-PMEMan showed a concentration-dependent binding of OVA and Con A, respectively, with a comparable detection limit to those with a monolayer of polymer brush-coated gold particle deposited on a glass substrate. Using this system, it can be expected to open a new perspective to various functional polymer brushes fixed to the cap-shaped gold particle on a solid substrate.     

PITANSEMA-MAS, a solid-state NMR method to measure heteronuclear dipolar couplings under MAS

A 2D NMR method is presented for the measurement of the dipole-dipole interaction between a proton and a low-frequency nuclear spin species in the solid state under the magic angle spinning. It employs the time averaged nutation concept to dramatically reduce the required radio frequency (rf) power on the low γ nuclear channel and spin exchange at the magic angle is used to suppress (1)H-(1)H dipolar interactions and chemical shifts. The flexibility in choosing the spinning speed, rf power and the scaling factor of the pulse sequence are of considerable importance for the structural studies of biological solids. The performance of the pulse sequence has been numerically and experimentally demonstrated on several solids.     

Platinum monolayer on nonnoble metal-noble metal core-shell nanoparticle electrocatalysts for O2 reduction

We synthesized a new class of O2 electrocatalysts with a high activity and very low noble metal content. They consist of Pt monolayers deposited on the surfaces of carbon-supported nonnoble metal-noble metal core-shell nanoparticles. These core-shell nanoparticles were formed by segregating the atoms of the noble metal on to the nanoparticles' surfaces at elevated temperatures. A Pt monolayer was deposited by galvanic displacement of a Cu monolayer deposited at underpotentials. The mass activity of all the three Pt monolayer electrocatalysts investigated, viz., Pt/Au/Ni, Pt/Pd/Co, and Pt/Pt/Co, is more than order of magnitude higher than that of a state-of-the-art commercial Pt/C electrocatalyst. Geometric effects in the Pt monolayer and the effects of PtOH coverage, revealed by electrochemical data, X-ray diffraction, and X-ray absorption spectroscopy data, appear to be the source of the enhanced catalytic activity. Our results demonstrated that high-activity electrocatalysts can be devised that contain only a fractional amount of Pt and a very small amount of another noble metal.     

para‐Xylene Ultra‐selective Zeolite MFI Membranes Fabricated from Nanosheet Monolayers at the Air–Water Interface

The control of membrane morphology and microstructure is crucial to improve the separation performance of molecular‐sieve membranes. This can be enabled by making thin, dense, and uniform seed‐crystal coatings, which are then intergrown into continuous membranes. Herein, we show a novel and simple floating particle coating method can give closely packed monolayers of zeolite nanosheets on nonporous or porous supports. The zeolite nanosheet monolayer is formed at the air–water interface in a conical Teflon trough. As the water in the trough is drained, the monolayer is deposited on a support placed below. Membranes prepared by gel‐free secondary growth of the nanosheets deposited by this method show unprecedented ultra‐selective performance for separation of para‐ from ortho‐xylene (separation factor >10 000).