Thionicotinamide SAM on Gold: Adsorption Studies and Electroactivity

STM and impedance results of the self‐assembled monolayer (SAM) formed with thionicotinamide (TNA) on gold indicate the presence of defects that increase with the immersion time of the electrode in the TNA solution affecting the SAM electroactivity toward the electron transfer reaction of the cytochrome c metalloprotein and [Fe(CN)₆]^4? and [Ru(NH₃)₆]³⁺ complexes. It was observed that this electroactivity was also affected by the pH of the electrolyte solution. SERS and STM data indicate sulfur coordination to the surface with contribution of the NH₂ group. From the dependence of the TNA surface coverage on the temperature and concentration in solution, thermodynamic parameters of adsorption were determined.     

Photodegradation of the pharmaceuticals amoxicillin, bezafibrate and paracetamol by the photo-Fenton process—Application to sewage treatment plant effluent

Photodegradation of the pharmaceuticals amoxicillin (AMX), bezafibrate (BZF) and paracetamol (PCT) in aqueous solutions via the photo-Fenton process was investigated under black-light and solar irradiation. The influences of iron source, initial H₂O₂ concentration and matrix (distilled water and sewage treatment plant effluent) on degradation efficiency were discussed in detail. The results showed that (i) the degradation of the drugs was favored in the presence of potassium ferrioxalate (FeOx) in comparison to Fe(NO₃)₃; (ii) the increase of the H₂O₂ concentration improved the efficiency of AMX and BZF oxidation; however, the same was not observed for PCT; (iii) the influence of the matrix was observed for the degradation of BZF and PCT; (iv) under solar irradiation, the oxidation of the BZF and PCT is faster than under black-light irradiation. All these pharmaceuticals can be efficiently degraded employing the process evaluated.     

Surface pressure‐area curves compression isotherm of sericin Langmuir monolayer

The Langmuir monolayer of sericin protein was studied by means of surface pressure (π)—molecular area (A) isotherms at different pH subphase. The monolayer of sericin exhibits typical phase transition phenomena at pH 2, pH 4.8, pH 7 and pH 11, respectively, including from gas state to gas‐liquid state and finally to condensed solid state. However, the monolayer of sericin on pH 11 subphase appears to be solid state. Copyright © 2007 John Wiley & Sons, Ltd.     

In situ PM‐IRRAS studies of organothiols and organosilane monolayers–ZnO interfaces at high water activities

In situ photoelastic‐modulated Fourier transform infrared reflection absorption spectroscopy has been applied for the investigation of interfacial stability of organothiol and organosilane monolayer films on nanocrystalline zinc oxide thin films. It has been shown that for octadecyltriethoxysilane films, exposure to high water activities results in physisorption of water in the cross‐linked film. This high water activity at the interface leads to a reversible wet de‐adhesion of the interfacial silanol groups from the ZnO surface. However, the organothiol seems to form a denser monolayer and a stable by S–Zn bond that is resistant to the competition with adsorbed water. The reversible attachment for cross‐linked organosilanol films has been demonstrated for the first time by means of an in situ spectroscopic method on model ZnO surfaces. Copyright © 2016 John Wiley & Sons, Ltd.     

Liquid crystal-gold nanoparticle composite-modified indium tin oxide (ITO) substrates and their electrochemical characterisation

A simple efficient strategy for the simultaneous synthesis and anchoring of liquid crystal (LC)-stabilised gold nanoparticles (NPs) on indium tin oxide (ITO) substrate is described. A monolayer of 3-mercaptopropyltrimethoxy silane (MPS) compound was formed on ITO and quality of the monolayer was assessed using electrochemical techniques namely cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Gold NP preparation was carried out on this monolayer-modified substrate (and on bare ITO), in a single-step reaction, simply by drop-casting a solution containing an appropriate amount of chloroauric acid and a LC compound possessing a terminal amino group, on the MPS monolayer-modified substrate and heating (70degree) for 2-3 min.. The LC compound served as a reducing agent as well as a capping ligand. LC-capped NPs were chemically anchored onto the ITO substrate through bonding to thiol moiety of the MPS. The CV and EIS analysis of the MPS monolayer showed a complete blocking behaviour for the electron transfer across the electrode/electrolyte interface confirming the formation of a high-quality dense compact monolayer. On the other hand, upon immobilisation of LC-gold NP composite on self-assembled monolayer-modified ITO substrates, both CV and impedance studies showed a small current indicating the gold NP-mediated electron transfer, thus confirming the successful immobilisation of NPs.     

Langmuir–Blodgett films of stearic acid deposited on substrates at different orientations relative to compression direction: alignment layer for nematic liquid crystal

The Langmuir monolayer at an air–water interface shows remarkably different surface pressure (π)–area (A) isotherm, when measured with the surface normal of a Wilhelmy plate parallel or perpendicular to the direction of compression of the monolayer. Such difference arises due to difference in stress exerted by the monolayer on the plate in different direction. In this article, we report the effect of changing the direction of substrate normal with respect to the compression of the monolayer during Langmuir–Blodgett (LB) film deposition on the morphology of the films. The morphology of the LB film of stearic acid is studied using an atomic force microscope. The morphology of the LB films is found to be different due to difference in the stress in different directions. The role of such surface morphology on the alignment of a nematic liquid crystal (LC) in LC cells is studied. The granular texture of LB films of stearic acid supports the homogeneous alignment of the LC whereas the uniform texture supports the homeotropic alignment of the LC.     

Construction of a simple optical sensor based on air stable lipid film with incorporated urease for the rapid detection of urea in milk

This work describes the construction of a simple optical sensor for the rapid, selective and sensitive detection of urea in milk using air stable lipid films with incorporated urease. The lipid film is stabilized on a glass filter by polymerization using UV (ultra-violet) radiation prior its use. Methacrylic acid was the functional monomer, ethylene glycol dimethacrylate was the crosslinker and 2,2′-azobis-(2-methylpropionitrile) was the initiator. Urease is incorporated within this mixture prior to the polymerization. The presence of the enzyme in these films quenched this fluorescence and the colour became similar to that of the filters without the lipid films. A drop of aqueous solution of urea provided a “switching on” of the fluorescence which allows the rapid detection of this compound at the levels of 10⁻⁸ M concentrations. The investigation of the effect of potent interferences included a wide range of compounds usually found in foods and also of proteins and lipids. These lipid membranes were used for the rapid detection of urea in milk.     

Electrochemical Characterization of Gold 6‐Amino‐2‐mercaptobenzothiazole Self‐Assembled Monolayer for Dopamine Detection in Pharmaceutical Samples

A new sensor, gold‐6‐amino‐2‐mercaptobenzothiazole (6A2MBT), was fabricated via a self‐assembly procedure. Electrochemical properties of the monolayer were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The modified electrode showed excellent antifouling property against the oxidation products of DA, allowed us to construct a dynamic calibration curve with two linear parts, 1.00×10^?6 to 3.72×10^?4 and 3.72×10^?4 to 6.42×10^?4 M DA, with correlation coefficients of 0.997 and 0.992 and a detection limit of 1.57×10^?7 M DA by using differential pulse voltammetry (DPV), respectively. Finally, the performance of the Au‐6A2MBT modified electrode was successfully tested for electrochemical detection of DA in a pharmaceutical sample.     

Precise and global identification of phospholipid molecular species by an Orbitrap mass spectrometer and automated search engine Lipid Search

In the present research, we have established a new lipidomics approach for the comprehensive and precise identification of molecular species in a crude lipid mixture using a LTQ Orbitrap mass spectrometer (MS) and reverse-phase liquid chromatography (RPLC) combination with our newly developed lipid search engine “Lipid Search”. LTQ Orbitrap provides high mass accuracy MS spectra by Fourier-transform (FT) mass spectrometer mode and can perform rapid MSⁿ by ion trap (IT) mass spectrometer mode. In this study, the negative ion mode was selected to detect fragment ions from phospholipids, such as fatty acid anions, by MS2 or MS3. We selected the specific detection approach by neutral loss survey-dependent MS3, for the identification of molecular species of phosphatidylcholine, sphingomyelin and phosphatidylserine. Identification of molecular species was performed by using both the high mass accuracy of the mass spectrometric data obtained from FT mode and structural data obtained from fragments in IT mode. Some alkylacyl and alkenylacyl species have the same m/z value as molecular-related ions and fragment ions, thus, direct acid hydrolysis analysis was performed to identify alkylacyl and alkenylacyl species, and then the RPLC–LTQ Orbitrap method was applied. As a result, 290 species from mouse liver and 248 species from mouse brain were identified within six different classes of phospholipid, only those in manually detected and confirmed. Most of all manually detected mass peaks were also automatically detected by “Lipid Search”. Adding to differences in molecular species in different classes of phospholipids, many characteristic differences in molecular species were detected in mouse liver and brain. More variable number of saturated and monounsaturated fatty acid-containing molecular species were detected in mouse brain than liver.     

A level set projection model of lipid vesicles in general flows

A new numerical method to model the dynamic behavior of lipid vesicles under general flows is presented. A gradient-augmented level set method is used to model the membrane motion. To enforce the volume- and surface-incompressibility constraints a four-step projection method is developed to integrate the full Navier–Stokes equations. This scheme is implemented on an adaptive non-graded Cartesian grid. Convergence results are presented, along with sample two-dimensional results of vesicles under various flow conditions.