Design of molecularly imprinted polymer grafts with embedded gold nanoparticles through the interfacial chemistry of aryl diazonium salts

A novel strategy is described for the preparation of highly sensitive molecularly imprinted (MIPs) sensors for dopamine. It combines mercaptobenzene diazonium salt as a coupling agent for immobilizing gold nanoparticles to gold electrodes and benzoyl benzene diazonium salt as photoinitiator of radical polymerization at the said gold nanoparticle-decorated gold electrodes. The MIP films were prepared by surface-initiated photopolymerization (SIPP) of methacrylic acid (MAA) as functional monomer (F) for dopamine (DA) the template molecule (T), and ethylene glycol dimethacrylate (EGDMA), the crosslinker (C). Dimethylaniline was employed as a hydrogen donor. The specificity and selectivity were demonstrated by square wave voltammetry (SWV). The detection limit was 0.35 nmol L^-1 (0.054 ng mL⁻¹). The sensor layers are stable and adherent to the surface through aryl layers. The originality and advantage of the process lie in the use of aryl diazonium salt as coupling agents for anchroring nanoparticles and MIP layers to the electrode surface in a simple and efficient way which ensures high sensing performance together with good surface-MIP adhesion. The same strategy can be extended to a broad range of templates.     

A single active site mutation inverts stereoselectivity of 16-hydroxylation of testosterone catalyzed by engineered cytochrome P450 BM3

Inversion of stereoselectivity: screening of a minimal mutant library revealed a cytochrome P450?BM3 variant M01?A82W?S72I capable of producing 16?α-OH-testosterone. Remarkably, a single active site mutation S72I in M01?A82W inverted the stereoselectivity of hydroxylation from 16?β to 16?α. Introduction of S72I mutation in another 16?β-OH-selective variant M11?V87I, also resulted in similar inversion of stereoselectivity.     

Controlled reversible debundling of single-walled carbon nanotubes by photo-switchable dendritic surfactants

Stimulus responsive surfactants based on dendritic glycerol azobenzene conjugates were used to solubilize and debundle single-walled carbon nanotubes in aqueous media. Their debundling property as well as their reaggregation behavior upon irradiation with light was examined and light triggered reversible bundling and precipitation are shown.     

Evolutionary Interactions Between Visual and Chemical Signals: Chemosignals Compensate for the Loss of a Visual Signal in Male <Emphasis Type="Italic">Sceloporus</Emphasis> Lizards

Animals rely on multimodal signals to obtain information from conspecifics through alternative sensory systems, and the evolutionary loss of a signal in one modality may lead to compensation through increased use of signals in an alternative modality. We investigated associations between chemical signaling and evolutionary loss of abdominal color patches in males of four species (two plain-bellied and two colorful-bellied) of Sceloporus lizards. We conducted field trials to compare behavioral responses of male lizards to swabs with femoral gland (FG) secretions from conspecific males and control swabs (clean paper). We also analyzed the volatile organic compound (VOC) composition of male FG secretions by stir bar extraction and gas chromatography-mass spectrometry (GC-MS) to test the hypothesis that loss of the visual signal is associated with elaboration of the chemical signal. Males of plain-bellied, but not colorful-bellied species exhibited different rates of visual displays when exposed to swabs of conspecific FG secretions relative to control swabs. The VOC composition of male Sceloporus FG secretions was similar across all four species, and no clear association between relative abundances of VOCs and evolutionary loss of abdominal color patches was observed. The emerging pattern is that behavioral responses to conspecific chemical signals are species- and context-specific in male Sceloporus, and compensatory changes in receivers, but not signalers may be involved in mediating increased responsiveness to chemical signals in males of plain-bellied species.     

ION-SELECTIVE POLYMER-SUPPORTED REAGENTS

ABSTRACT

The design and synthesis of polymer-supported reagents that can selectively complex targeted metal ions from multi-component solutions will continue to be an important area of research into the 21^st century. Environmental remediation and sensor technology are only two of a number of areas in which such polymers can be applied. This paper reviews the recent literature with an emphasis on the key ligands that have been immobilized in order to better understand where this research is heading in the near future.     

Kinetics of Isothermal Crystallization of Hydrogenated Castor Oil-in-Water Emulsions

Kinetics of isothermal crystallization of hydrogenated castor oil in water emulsions exhibiting multiple crystal morphologies have been studied experimentally by DSC and polarized light microscopy. The induction time of nucleation increases with the increase of the isothermal temperature under which crystallization occurred. Crystal growth has been observed by microscopy showing that both crystal morphologies, fibers and rosettes, grow linearly at the initial stage of crystallization and then slow down to reach a plateau value. The Avrami model, which has been widely used in kinetics studies of triacylglycerol systems, was employed to fit experimental results at different isothermal temperatures. It was found that experimental trends could be captured by introducing the volume fraction of each type of morphology into three-dimensional and one-dimensional full Avrami models.     

Modular construction of P3HT/PCBM planar-heterojunction solar cells by lamination allows elucidation of processing–structure–function relationships

Contrary to polymer solar cells with bulk-heterojunction active layers, devices with planar-heterojunction active layers allow the decoupling of active layer phase separation from constituent crystallization, and their relative influence on device performance. We fabricated planar-heterojunction devices by first processing the electron donor and electron acceptor in isolation; they were subsequently laminated across the donor–acceptor interface to establish electrical contact. Thermal annealing was intentionally avoided after lamination to maintain the pristine charge transfer interface. Lamination thus obviates the need for solvent orthogonality; more importantly, it provides independent process tuning of individual organic semiconductor layers, ultimately allowing control over constituent structural development. We found the short-circuit current density of planar-heterojunction solar cells comprising poly(3-hexyl thiophene), P3HT, and [6,6]-phenyl-C₆₁-butyric acid methyl ester, PCBM, as the electron donor and acceptor, respectively, to be generally independent of the annealing history of P3HT. On the contrary, thermal annealing PCBM prior to lamination mainly led to a reduction in short-circuit current density. This deterioration is correlated with the development of preferentially oriented PCBM crystals that hinders electron transport in the vertical direction.     

Structure,Protein Interactions and In Vitro Protease Accessibility of Extruded and Pressurized Full-Fat Soybean Flakes

The objectives of the present study were to determine how extrusion (barrel temperature of 100 °C) and high-pressure processing (HPP, 200 and 500 MPa, 15 min, 25 °C) of full-fat soybean flakes (FFSF) modified the structure of soybean cotyledon cells, the protein interactions and the in vitro protease accessibility. Cellular disruption of the cotyledon cells was only observed for extruded FFSF. Extrusion and HPP at 500 MPa favored formation of insoluble protein aggregates, in which oil was entrapped. High pressure size exclusion chromatography (HPSEC) and extraction methods using buffers containing SDS and 2-mercaptoethanol suggested that noncovalent interactions were the main forces in protein aggregate formation during HPP 500 MPa and extrusion. Intermolecular cross-linking by disulfide bonding was also involved in insoluble aggregates, but at a lesser extent than noncovalent interactions. Extrusion and HPP 500-MPa treatment enhanced the proteolytic attack, while treatment at 200 MPa had no impact. Drastic changes in the peptide profile of the extracted proteins were, however, only observed for the enzyme-treated 500-MPa FFSF. Optimal oil and protein extraction yields required cellular disruption of cotyledon cells and hydrolysis of protein aggregates, which were obtained with enzyme-assisted aqueous extraction of extruded FFSF.     

Purification and identification of a novel cutinase from Coprinopsis cinerea by adsorptive bubble separation

A novel extracellular esterase was separated from culture supernatants of the basidiomycete Coprinopsis cinerea by means of foam fractionation. The parameters pH value, gas flow rate, addition of detergents, and the column design were varied to optimise the transport of the active enzyme into the foam phase. On the 70-mL scale, a recovery of activity of 79% with an enrichment factor of 10.5 was obtained at pH 7 and 20 mL air min⁻¹ within 15 min. The enriched enzyme was characterized biochemically by semi-native SDS-PAGE and IEF electrophoresis with activity staining. Peptide sequencing was performed after tryptic digestion by electrospray tandem mass spectrometry. Homology searches revealed significant similarities to cutinases of various ascomycetes and to C. cinerea genome data recently annotated as cutinases.