Organophosphorus acid anhydrolase bio-template for the synthesis of CdS quantum dots

A direct conjugation of organophosphorus acid anhydrolase (OPAA) with CdS quantum dots was prepared via arrested precipitation within the enzyme matrix. The bio-conjugate was found not only to retain enzyme conformational structure but also to retain enzyme activity and be effective at detecting diisopropyl fluorophosphate (DFP) at the micro molar level.     

Serum albumin in 2D: A Langmuir monolayer approach

Understanding of protein interaction at the molecular level raises certain difficulties which is the reason a model membrane system such as the Langmuir monolayer technique was developed. Ubiquitous proteins such as serum albumin comprise 50% of human blood plasma protein content and are involved in many biological functions. The important nature of this class of protein demands that it be studied in detail while modifying the experimental conditions in two dimensions to observe it in all types of environments. While different from bulk colloidal solution work, the two dimensional approach allows for the observation of the interaction between molecules and subphase at the air–water interface. Compiled in this review are studies which highlight the characterization of this protein using various surroundings and also observing the types of interactions it would have when at the biomembrane interface. Free-energy changes between molecules, packing status of the bulk analyte at the interface as well as phase transitions as the monolayer forms a more organized or aggregated state are just some of the characteristics which are observed through the Langmuir technique. This unique methodology demonstrates the chemical behavior and physical behavior of this protein at the phase boundary throughout the compression of the monolayer.     

New Advances in the Synthesis of Emerging Cyclic Amidrazones to Foster Bioisosterism of Azaheterocycles

The pace and the scope of new molecules design is often constrained by limitations in synthetic chemistry. The azaheterocyclic amidrazones are of particular interest for bioisosteric considerations in drug discovery. However, the lack of efficient synthetic access has undoubtedly hampered their occurrence in the drug chemical space. Our current results describe a robust synthetic access relying on cyclization of aminohydrazine in presence of various orthoesters by either metal free- or metal-catalyzed condensations. This optimized synthetic access to cyclic amidrazones as original scaffold should inspire the chemist community and further drive innovation in the design of molecular structure for many applications (for example, drugs, materials, dyes).     

Photothermal ablation of amyloid aggregates by gold nanoparticles

Amyloid peptide (Aβ) is found in the brain and blood of both healthy and diseased individuals alike. However, upon secondary structure transformation to a β-sheet dominated conformation, the protein aggregates. These aggregates accumulate to form neuritic plaques that are implicated in the pathogenesis of Alzheimer's disease. Gold nanoparticles are excellent photon-thermal energy converters. The extinction coefficient of the surface plasmon band of gold nanoparticles is very large when compared to typical organic dyes. In this study, gold nanoparticle–Aβ conjugates were prepared and the photothermal ablation of amyloid peptide aggregates by laser irradiation was studied. Monofunctional gold nanoparticles were prepared using a recently reported solid phase modification method and then coupled to fragments of Aβ peptide, namely Aβ(31–35) and Aβ(25–35). The conjugates were then mixed with Aβ fragments in solution. The aggregated peptide formation was studied by a series of spectroscopic and microscopic techniques. The peptide aggregates were then irradiated by a continuous laser. With gold nanoparticle–Aβ conjugates present the aggregates were destroyed by photothermal ablation. Gold nanoparticles without Aβ conjugation were not incorporated into the aggregates and when irradiated did not result in photothermal ablation. With gold nanoparticle–Aβ conjugates the ablation was selective to the site of irradiation and minimal damage was observed as a result of thermal diffusion. In addition to the application of photoablation to a protein-based sample the nanoparticles and the chemistry involved provide an easily monofunctionalized photothermal material for the biological conjugation.     

Peptidolipid as binding site of acetylcholinesterase: molecular recognition of paraoxon in Langmuir films

Peptidolipid C18H35O (stearoyl)-Phe-Trp-Ser-His-Glu (peptidolipid A) was synthesized and spread at the air-water interface to study the interaction with an organophosphorus compound. Paraoxon, sodium dihydrogen phosphate, or 4-nitrophenyl phosphate disodium was added to the subphase, but only paraoxon changed the surface pressure-area (pi-A) isotherm of peptidolipid A. This indicated a specific interaction between paraoxon and peptidolipid A. To clarify which amino acid residue of peptidolipid A was responsible for the interaction, peptidolipid B, namely, C18H35O-Gly-His-Ser-Glu-Glu, was synthesized and studied as a Langmuir film. The difference between the pi-A isotherms of peptidolipid B in the absence and presence of paraoxon in the subphase was minimal; consequently, the presence of amino acids phenylalanine (Phe) and tryptophan (Trp) in peptidolipid A may explain the interaction between peptidolipid A and paraoxon. The compression-decompression cycles and kinetic studies of peptidolipid A showed that the Langmuir film was stable. The in situ optical properties of the peptidolipid A Langmuir film such as UV-vis and fluorescence spectroscopies were examined to elucidate the interaction between peptidolipid A and paraoxon. UV-vis absorption of peptidolipid A was investigated in the presence and absence of paraoxon in the subphase. The emission maximum of fluorescence of Trp in peptidolipid A was observed at 351 nm on pure water, and the band intensity decreased when the concentration of paraoxon increased in the subphase. This suggested that the Trp was involved in the molecular recognition process. Epifluorescence micrographs showed domains of peptidolipid A on the pure water subphase. In the presence of paraoxon in the subphase, the Langmuir film of peptidolipid A showed a homogeneity, which was another indication of the recognition between paraoxon and peptidolipid A.     

Numerical analysis of eigenproblem for cavities by a particular integral method with a low frequency approximation of surface admittance

In this paper, a three-dimensional boundary element method for the eigenanalysis of complex-shaped cavity is presented. A particular integral method is proposed with general absorbing boundary conditions, well suited for determination of the lower modes. In this approach, a polynomial approximation of surface admittance is used with a recent class of compactly supported radial basis function. Two common absorbent models are employed in order to demonstrate the relevance of high-order approximation of the admittance. Resulting eigenproblems of several orders (linear to cubic) are thus performed on basic geometries and a car interior. Results show significant improvements for the computed damped eigenfrequencies and the associated modal reverberation time while using an approximation polynomial matching the surface admittance variation order.