Incorporation conditions guiding the aggregation of a glycosylphosphatidyl inositol (GPI)-anchored protein in Langmuir monolayers

This work investigates the process of incorporation of a glycosylphosphatidyl inositol (GPI)-anchored alkaline phosphatase into Langmuir monolayers of dimyristoyl phosphatidic acid (DMPA). Three different methods of protein incorporation were assayed. When the protein solution was injected below the air–water interface after formation of the lipid monolayer a micro-heterogeneous distribution of alkaline phosphatase throughout the interface was observed. Adsorption kinetics studied by fluorescence microscopy, associated with surface pressure measurements, led to the proposition of a model in which the protein penetration is modulated by the surface packing of the monolayer and intermolecular interactions occurring between the phospholipid and the protein. At initial surface pressures higher than 20 mN m⁻¹, the protein is quickly adsorbed on the interface and the lateral diffusion drives the alkyl chains to turn towards the air phase while the polypeptide moiety faces the aqueous subphase.     

A peroxidase-tetrathiafulvalene biosensor based on self-assembled monolayer modified Au electrodes for the flow-injection determination of hydrogen peroxide

The construction and performance under flow-injection conditions of an integrated amperometric biosensor for hydrogen peroxide is reported. The design of the bioelectrode is based on a mercaptopropionic acid (MPA) self-assembled monolayer (SAM) modified gold disk electrode on which horseradish peroxidase (HRP, 24.3 U) was immobilized by cross-linking with glutaraldehyde together with the mediator tetrathiafulvalene (TTF, 1 μmol), which was entrapped in the three-dimensional aggregate formed.

The amperometric biosensor allows the obtention of reproducible flow injection amperometric responses at an applied potential of 0.00 V in 0.05 mol L⁻¹ phosphate buffer, pH 7.0 (flow rate: 1.40 mL min⁻¹, injection volume: 150 μL), with a range of linearity for hydrogen peroxide within the 2.0 × 10⁻⁷–1.0 × 10⁻⁴ mol L⁻¹ concentration range (slope: (2.33 ± 0.02) × 10⁻² A mol⁻¹ L, r = 0.999). A detection limit of 6.9 × 10⁻⁸ mol L⁻¹ was obtained together with a R.S.D. (n = 50) of 2.7% for a hydrogen peroxide concentration level of 5.0 × 10⁻⁵ mol L⁻¹. The immobilization method showed a good reproducibility with a R.S.D. of 5.3% for five different electrodes. Moreover, the useful lifetime of one single biosensor was estimated in 13 days.

The SAM-based biosensor was applied for the determination of hydrogen peroxide in rainwater and in a hair dye. The results obtained were validated by comparison with those obtained with a spectrophotometric reference method. In addition, the recovery of hydrogen peroxide in sterilised milk was tested.     

Controlled Activity Polymers. IV. Copolymers of 2-(1-Naphthylacetyl)Ethyl Acrylate With Hydrophilic Comonomers: Synthesis and Characterization

2-(1-Naphthylacetyl)ethyl acrylate (NAEA) was synthesized by esterification of 1-naphthylacetic acid (NAA) and 2-hydroxyethyl acrylate (HEA) and then polymerized to obtain the polymer-bound auxin NAA. The resulting polymer is potentially useful as a plant growth regulator through hydrolytic release of NAA. Copolymers of NAEA with hydrophilic comonomers were prepared by solution polymerization. The copolymer compositions were determined from elemental analysis, ¹³C-NMR, and UV spectroscopy. The copolymer microstructure was predicted from the reactivity ratios in order to investigate the influence on the behavior of controlled release. These model structures will be utilized for assessment of structure/hydrolysis relationships in a subsequent paper.     

pH-Dependent Slipping and Exfoliation of Layered Covalent Organic Framework

Layered/two-dimensional covalent organic frameworks (2D COF) are crystalline porous materials composed of light elements linked by strong covalent bonds. Interlayer force is one of the main factors directing the formation of a stacked layer structure, which plays a vital role in the stability, crystallinity, and porosity of layered COFs. The as-developed new way to modulate the interlayer force of imine-linked 2D TAPB-PDA-COF (TAPB = 1,3,5-tris(4-aminophenyl)benzene, PDA = terephthaldehyde) by only adjusting the pH of the solution. At alkaline and neutral pH, the pore size of the COF decreases from 34 Å due to the turbostratic effect. Under highly acidic conditions (pH 1), TAPB-PDA-COF shows a faster and stronger turbostratic effect, thus causing the 2D structure to exfoliate. This yields bulk quantities of an exfoliated few/single-layer 2D COF, which was well dispersed and displayed a clear Tyndall effect (TE). Furthermore, nanopipette-based electrochemical testing also confirms the slipping of layers with increase towards acidic pH. A model of pH-dependent layer slipping of TAPB-PDA-COF was proposed. This controllable pH-dependent change in the layer structure may open a new door for potential applications in controlled gas adsorption/desorption and drug loading/releasing.     

Oriented Crystallization on Organic Monolayers to Control Concomitant Polymorphism

Nucleation events and crystal growth can be guided by molecular recognition at interfaces through intermolecular interactions. The short-acting antimicrobial sulfa drug sulfathiazole is known for its concomitant crystallization, which has five known polymorphs, due to conformational flexibility and hydrogen-bond synthon variation. In its development stage of a drug the issue of concomitant crystallization needs to be addressed with respect to patent litigation, including legal actions to protect patents against infringement. A functional self-assembled monolayer (SAM) of organic thiol on a gold surface has been employed as an efficient approach to control concomitant nucleation of such flexible drugs. The crystallization on a SAM surface is mostly kinetically driven and often leads to the nucleation of novel metastable forms. Spectroscopic, thermal analysis and X-ray diffraction studies reveal that a previously unknown, sixth form of the drug nucleates on the designed SAM surface.     

Langmuir wave phase-mixing in warm electron-positron-dusty plasmas

An analytical study on nonlinear evolution of Langmuir waves in warm electron-positron-dusty plasmas is presented. The massive dust grains of either positively or negatively charged are assumed to form a fixed charge neutralizing background. A perturbative analysis of the fluid-Maxwell's equations confirms that the excited Langmuir waves phase-mix and eventually break, even at arbitrarily low amplitudes. It is shown that the nature of the dust-charge as well as the amount of dust grains can significantly influence the Langmuir wave phase-mixing process. The phase-mixing time is also found to increase with the temperature.     

Adsorption of a cationic water-soluble dye onto cationic Langmuir–Blodgett films via nano clay platelets: An efficient approach to control the H-dimer

This communication reports the successful adsorption of a water-soluble cationic fluorescent dye Acridine Orange (AO) onto Langmuir–Blodgett (LB) films of a cationic amphiphile octadecylamine (ODA) in the presence of nano-clay platelets hectorite. Acridine orange (AO) has been widely used as a stainer for the characterization of biopolymers. But AO has a tendency to form non-florescent H-dimer even in the aqueous solution. Anionic nano-clay platelets hectorite played an important role in controlling the H-dimer formation of AO in the hybrid film. Effects of various parameters in the adsorption process were investigated in detail.