In situ hybridization of superparamagnetic iron-biomolecule nanoparticles.

The increase in interest in the integration of organic-inorganic nanostructures in recent years has promoted the use of hybrid nanoparticles (HNPs) in medicine, energy conversion, and other applications. Conventional hybridization methods are, however, often long, complicated, and multistepped, and they involve biomolecules and discrete nanostructures as separate entities, all of which hinder the practical use of the resulting HNPs. Here, we present a novel, in situ approach to synthesizing size-specific HNPs using Fe-biomolecule complexes as the building blocks. We choose an anticancer peptide (p53p, MW 1.8 kDa) and an enzyme (GOx, MW 160 kDa) as model molecules to demonstrate the versatility of the method toward different types of molecules over a large size range. We show that electrostatic interaction for complex formation of metal hydroxide ion with the partially charged side of biomolecule in the solution is the key to hybridization of metal-biomolecule materials. Electrochemical deposition is then used to produce hybrid NPs from these complexes. These HNPs with controllable sizes ranging from 30 nm to 3.5 µm are found to exhibit superparamagnetic behavior, which is a big challenge for particles in this size regime. As an example of greatly improved properties and functionality of the new hybrid material, in vitro toxicity assessment of Fe-GOx HNPs shows no adverse effect, and the Fe-p53p HNPs are found to selectively bind to cancer cells. The superparamagnetic nature of these HNPs (superparamagnetic even above the size regime of 15-20 nm!), their biocompatibility, and the direct integration approach are fundamentally important to biomineralization and general synthesis strategy for bioinspired functional materials.

Near-surface oxidized sulfur modifications and self-assembly of thiol-modified aptamer on Au thin film substrates influenced by piranha treatment.

Self-assembly of thiol-modified oligonucleotides on Au films has great importance for biosensor applications. Prior to the self-assembly, a piranha treatment (PT) is commonly used to clean the Au surface. Here we report that near-surface oxidized sulfur modifications on Au thin films by PT for longer than 60 s have serious effects on the self-assembled monolayer (SAM) formation of thiol-modified single-stranded thrombin binding aptamer (s-TBA), and a PT time of 10-30 s is optimal for s-TBA SAM formation. These results have important implication to SAM formation of biomolecules, especially for the thiol-modified ones where a careful consideration of this key step could significantly enhance the SAM formation and biosensor performance.