An array of aligned carbon nanotubes (CNTs) was incorporated across a polymer film to form a well-ordered nanoporous membrane structure. This membrane structure was confirmed by electron microscopy, anisotropic electrical conductivity, gas flow, and ionic transport studies. The measured nitrogen permeance was consistent with the flux calculated by Knudsen diffusion through nanometer-scale tubes of the observed microstructure. Data on Ru(NH3)6(3+) transport across the membrane in aqueous solution also indicated transport through aligned CNT cores of the observed microstructure. The lengths of the nanotubes within the polymer film were reduced by selective electrochemical oxidation, allowing for tunable pore lengths. Oxidative trimming processes resulted in carboxylate end groups that were readily functionalized at the entrance to each CNT inner core. Membranes with CNT tips that were functionalized with biotin showed a reduction in Ru(NH3)6(3+) flux by a factor of 15 when bound with streptavidin, thereby demonstrating the ability to gate molecular transport through CNT cores for potential applications in chemical separations and sensing.
This paper describes a new class of composite materials designed by combining multiwall carbon nanotubes (MWNTs) and sol−gels. These
materials provide new capabilities for the development of electrochemical devices by taking advantage of the favorable electrochemical
characteristics of MWNTs. Further, variations in the silane precursors used and in the carbon nanotube content of the composites results in
materials with a range of capacitance, electron-transfer rates, and potential to control selectivity.
Synthetic nanopore membranes can be used to mimic ion channels provided that molecular transport
through membranes is precisely gated with selective and reversible chemical interactions. Aligned
nanotubes of carbon or other inorganic materials can be assembled to construct higher-order supramolecular
architectures using polymer films to force chemical flux through hollow cores. Open tips of carbon
nanotubes (CNT) can be activated to have carboxylic groups, which can be easily derivatized with a
molecule that binds to a bulky receptor that can open/close the pore entrance. In particular, the core
entrances of an aligned CNT membrane were functionalized with a desthiobiotin derivative that binds
reversibly to streptavidin, thereby enabling a reversible closing/opening of the core entrance. Ionic flux
through the CNT membrane was monitored using optically absorbing charged marker molecules. The
flux is reduced by a factor of 24 when the desthiobiotin on the CNT is coordinated with streptavidin;
release of streptavidin increases the flux, demonstrating a reversible ion-channel flow. Analysis of solutions
of released streptavidin shows approximately 16 bound streptavidin molecules per CNT tip.
Hybrid alumina nanoparticles with pepsin were prepared in a controlled and efficient manner. Phosphorylated pepsin can be coupled to alumina through the interaction between phosphoserine on pepsin and the alumina surface in an orientation-specific manner. A comparison of data obtained with nanoparticles and microsized alumina particles reveals that the conjugated pepsin retained much higher enzymatic activity when it was immobilized on nanoparticles mainly because of the lack of diffusion limitations of the substrate. Additionally, upon attachment to the alumina nanoparticles, the thermal stability of pepsin is enhanced. The coupled enzyme can be quantitatively released by simply incubating the hybrid nanoparticles with phosphate buffer.Introduction. Nanotechnology has emerged as a powerful tool in the fabrication of materials having superior and often unique properties. 1-4 The incorporation of biological molecules into these materials should expand the range of potential applications to include nanoscale biosensors and biocatalysts. 5 Previous studies on the conjugation of nanoparticles with biomolecules such as proteins and DNA used mainly gold-, silver-, silica-, and nickel-based nanoparticles as well as quantum dots. 6 Several methods have been employed for the attachment of biomolecules on nanoparticles including binding through a thiol group to gold 7,8 and maleimido-modified fullerenes, 9 through amino groups to carboxyl-functionalized paricles, 10 through a polyhistidine tag to nickel, 11 or through electrostatic interactions to charged nanoparticles. 12 Herein, we report a new class of hybrid nanoparticles composed of nanosized alumina functionalized with an enzyme. We demonstrate, using pepsin as a model enzyme, an orientation-specific, efficient, and reversible means to couple phosphorylated proteins to alumina nanoparticles through the interaction between the phosphoryl group and the alumina surface. When alumina nanoparticles are used in this manner, the decrease in enzymatic activity is minimal. A unique property of these hybrid nanoparticles is the ability to release the coupled pepsin quantitatively (98%) in a controlled manner.Pepsin is an enzyme essential to the digestion process in animals. The optimal pH for its activity is 2.0, which is compatible with that of alumina. The enzyme has a total of
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