Single‐walled Carbon Nanotube Strings for Biosensor Development

Strings of single‐walled carbon nanotubes (SWCNT) were prepared using an aqueous dispersion of gellan gum wrapped nanotubes and crosslinked using Ca²⁺ ions. Various formulations were evaluated to determine the parameters for successful string formation; these included 8–12 % nanotube by weight, 60–70 % gellan gum, and 20–30 % KCl. Strings showed electrical conductivity when dried between ITO electrodes. Conductivity variations were observed and potential sources of the variation identified. Proteins were attached to the carbon nanotube strings with peroxidase enzymatic activity detected following horseradish peroxidase attachment. This work provides a basis for development of electronic biosensors based on these carbon nanotube strings.     

A criterion for the planarity of a graph

In a recent paper, Carsten Thomassen [Carsten Thomassen, Planarity and duality of finite and infinite graphs. J. Combinatorial Theory Ser. B 29 (1980) 244–271] has shown that a number of criteria for the planarity of a graph can be reduced to that of Kuratowski. Here we present another criterion which, as well, is easily proved via Kuratowski's. The criterion is based on the observation that the imbedding of a graph in a plane imposes a cyclic ordering, say clockwise, on the edges incident with each vertex, and that these cyclic orderings are related.     

Transfer functions of US transducers for harmonic imaging and bubble responses

Current medical diagnostic echo systems are mostly using harmonic imaging. This means that a fundamental frequency (e.g., 2 MHz) is transmitted and the reflected and scattered higher harmonics (e.g., 4 and 6 MHz), produced by nonlinear propagation, are recorded. The signal level of these harmonics is usually low and a well-defined transfer function of the receiving transducer is required. Studying the acoustic response of a single contrast bubble, which has an amplitude in the order of a few Pascal, is another area where an optimal receive transfer function is important.

We have developed three methods to determine the absolute transfer function of a transducer. The first is based on a well-defined wave generated by a calibrated source in the far field. The receiving transducer receives the calibrated wave and from this the transfer functions can be calculated. The second and third methods are based on the reciprocity of the transducer. The second utilizes a calibrated hydrophone to measure the transmitted field. In the third method, a pulse is transmitted by the transducer, which impinges on a reflector and is received again by the same transducer. In both methods, the response combined with the transducer impedance and beam profiles enables the calculation of the transfer function.

The proposed methods are useful to select the optimal piezoelectric material (PZT, single crystal) for transducers used in reception only, such as in certain 3D scanning designs and superharmonic imaging, and for selected experiments like single bubble behavior.

We tested and compared these methods on two unfocused single element transducers, one commercially available (radius 6.35 mm, centre frequency 2.25 MHz) the other custom built (radius 0.75 mm, centre frequency 4.3 MHz). The methods were accurate to within 15%.     

Concerted Ring Opening and Cycloaddition of Chiral Epoxy Enolsilanes with Dienes

Silyl‐triflate‐catalyzed (4+3) cycloadditions of epoxy enolsilanes with dienes provide a mild and chemoselective synthetic route to seven‐membered carbocycles. Epoxy enolsilanes containing a terminal enolsilane and a single stereocenter undergo cycloaddition with almost complete conservation of enantiomeric purity, a finding that argues against the involvement of oxyallyl cation intermediates which have been previously proposed for these types of reactions. Reported are theoretical and experimental investigations of the cycloaddition mechanism. The major enantiomers of the cycloadducts are derived from S_N2‐like reactions of the silylated epoxide with the diene, in which stereospecific ring opening and formation of the two new C? C bonds occur in a single step. Calculations predict, and experiments confirm, that the observed small losses of enantiomeric purity are traced to a triflate‐mediated double S_N2 cycloaddition pathway.     

Room‐Temperature Decarboxylative Alkynylation of Carboxylic Acids Using Photoredox Catalysis and EBX Reagents

Alkynes are used as building blocks in synthetic and medicinal chemistry, chemical biology, and materials science. Therefore, efficient methods for their synthesis are the subject of intensive research. Herein, we report the direct synthesis of alkynes from readily available carboxylic acids at room temperature under visible‐light irradiation. The combination of an iridium photocatalyst with ethynylbenziodoxolone (EBX) reagents allowed the decarboxylative alkynylation of carboxylic acids in good yields under mild conditions. The method could be applied to silyl‐, aryl‐, and alkyl‐ substituted alkynes. It was particularly successful in the case of α‐amino and α‐oxo acids derived from biomass.     

Copolymer nanosphere encapsulated CdS quantum dots prepared by RAFT copolymerization: synthesis,characterization and mechanism of formation

Cadmium sulfide (CdS) quantum dots (QDs) encapsulated in block copolymer spheres were synthesized by an aqueous emulsion polymerization process. First, stable dispersions of CdS QDs in water were prepared using a polymer dispersant, either poly(acrylic acid) or a random copolymer having an average of ten acrylic acid and five butyl acrylate units. These polymer dispersants were prepared by reversible addition-fragmentation chain transfer polymerization. Then, the CdS QDs dispersed in water were encapsulated in a polystyrene shell using an emulsion polymerization process. Spectroscopic and microscopic techniques were used to characterize the resulting nanocomposites. Optical properties of QDs in polymer microspheres were investigated by UV-vis and fluorescence spectroscopic studies. Particle sizes of all CdS QD samples were calculated from absorption edges using Henglein's empirical curve. Transmission electron microscopy was used to determine the size and morphology of CdS QD samples. These observations were used to elucidate the mechanism of formation of the resulting well-defined polymer-encapsulated CdS nanoparticles.     

Electrospinning of a functional perfluorinated block copolymer as a powerful route for imparting superhydrophobicity and corrosion resistance to aluminum substrates

Superhydrophobic aluminum surfaces with excellent corrosion resistance were successfully prepared by electrospinning of a novel fluorinated diblock copolymer solution. Micro- and nanostructuration of the diblock copolymer coating was obtained by electrospinning which proved to be an easy and cheap electrospinning technology to fabricate superhydrophobic coating. The diblock copolymer is made of poly(heptadecafluorodecylacrylate-co-acrylic acid) (PFDA-co-AA) random copolymer as the first block and polyacrylonitrile (PAN) as the second one. The fluorinated block promotes hydrophobicity to the surface by reducing the surface tension, while its carboxylic acid functions anchor the polymer film onto the aluminum surface after annealing at 130 °C. The PAN block of this copolymer insures the stability of the structuration of the surface during annealing, thanks to the infusible character of PAN. It is also demonstrated that the so-formed superhydrophobic coating shows good adhesion to aluminum surfaces, resulting in excellent corrosion resistance.     

The molecular basis of pharmacological chaperoning in human α-galactosidase

Fabry disease patients show a deficiency in the activity of the lysosomal enzyme α-galactosidase (α-GAL or α-Gal A). One proposed treatment for Fabry disease is pharmacological chaperone therapy, where a small molecule stabilizes the α-GAL protein, leading to increased enzymatic activity. Using enzyme kinetics, tryptophan fluorescence, circular dichroism, and proteolysis assays, we show that the pharmacological chaperones 1-deoxygalactonojirimycin (DGJ) and galactose stabilize the human α-GAL glycoprotein. Crystal structures of complexes of α-GAL and chaperones explain the molecular basis for the higher potency of DGJ over galactose. Using site-directed mutagenesis, we show the higher potency of DGJ results from an ionic interaction with D170. We propose that protonation of D170 in acidic conditions leads to weaker binding of DGJ. The results establish a biochemical basis for pharmacological chaperone therapy applicable to other protein misfolding diseases.