Jungki Ryu

General functionalization route for cell adhesion on non-wetting surfaces

We present a versatile route for promoting cell adhesion and viability on various non-wetting surfaces, inspired by mussel adhesion mechanism. The oxidative polymerization of dopamine, a small designer molecule of the DOPA-K motif found in mussels, results in the formation of a poly(dopamine) ad-layer on any material surface. We found that the poly(dopamine) coating can promote cell adhesion on any type of material surfaces including the well-known anti-adhesive substrate, poly(tetrafluoroethylene). According to our results, mammalian cells well adhered and underwent general cell adhesion processes (i.e., attachment to substrate, spreading, and cytoskeleton development) on poly(dopamine)-modified surfaces, while they barely adhered and spread on unmodified non-wetting surfaces. The mussel-inspired surface functionalization strategy is extremely useful because it does not require the time-consuming synthesis of complex linkers and the process is solvent-free and non-toxic. Therefore, it can be a powerful route for converting a variety of bioinert substrates into bioactive ones.

High stability of self‐assembled peptide nanowires against thermal, chemical, and proteolytic attacks

Understanding the self‐assembly of peptides into ordered nanostructures is recently getting much attention since it can provide an alternative route for fabricating novel bio‐inspired materials. In order to realize the potential of the peptide‐based nanofabrication technology, however, more information is needed regarding the integrity or stability of peptide nanostructures under the process conditions encountered in their applications. In this study, we investigated the stability of self‐assembled peptide nanowires (PNWs) and nanotubes (PNTs) against thermal, chemical, proteolytic attacks, and their conformational changes upon heat treatment. PNWs and PNTs were grown by the self‐assembly of diphenylalanine (Phe–Phe), a peptide building block, on solid substrates at different chemical atmospheres and temperatures. The incubation of diphenylalanine under aniline vapor at 150°C led to the formation of PNWs, while its incubation with water vapor at 25°C produced PNTs. We analyzed the stability of peptide nanostructures using multiple tools, such as electron microscopy, thermal analysis tools, circular dichroism, and Fourier‐transform infrared spectroscopy. Our results show that PNWs are highly stable up to 200°C and remain unchanged when incubated in aqueous solutions (from pH 1 to 14) or in various chemical solvents (from polar to non‐polar). In contrast, PNTs started to disintegrate even at 100°C and underwent a conformational change at an elevated temperature. When we further studied their resistance to a proteolytic environment, we discovered that PNWs kept their initial structure while PNTs fully disintegrated. We found that the high stability of PNWs originates from their predominant β‐sheet conformation and the conformational change of diphenylalanine nanostructures. Our study suggests that self‐assembled PNWs are suitable for future nano‐scale applications requiring harsh processing conditions. Biotechnol. Bioeng. 2010; 105: 221–230.

Synthesis of Diphenylalanine/Cobalt Oxide Hybrid Nanowires and Their Application to Energy Storage

We report the synthesis of novel diphenylalanine/cobalt(II,III) oxide (Co(3)O(4)) composite nanowires by peptide self-assembly. Peptide nanowires were prepared by treating amorphous diphenylalanine film with aniline vapor at an elevated temperature. They were hybridized with Co(3)O(4) nanocrystals through the reduction of cobalt ions in an aqueous solution using sodium borohydride (NaBH(4)) without any complex processes such as heat treatment. The formation of peptide/Co(3)O(4) composite nanowires was characterized using multiple tools, such as electron microscopies and elemental analysis, and their potential application as a negative electrode for Li-ion batteries was explored by constructing Swagelok-type cells with hybrid nanowires as a working electrode and examining their charge/discharge behavior. The present study provides a useful approach for the synthesis of functional metal oxide nanomaterials by demonstrating the feasibility of peptide/Co(3)O(4) hybrid nanowires as an energy storage material.

Rational Design and Engineering of Quantum‐Dot‐Sensitized TiO2 Nanotube Arrays for Artificial Photosynthesis

Redox enzymes can catalyze complex synthesis reactions under mild conditions but conventional catalysts rarely accomplish this task. Despite the high potential of redox enzymes for the synthesis of valuable compounds (e.g., chiral alcohols and drug intermediates), [ 1–5 ] their application is hampered by the high cost of enzyme-specifi c cofactors that are required as a redox equivalent, such as nicotinamide adenine dinucleotide (NAD(P) H) and fl avin adenine dinucleotide (FADH). Thus, numerous efforts have been made over the past decades to accomplish in situ cofactor regeneration from their oxidized counterpart. [ 6–9 ]

Mineralization of Self‐assembled Peptide Nanofibers for Rechargeable Lithium Ion Batteries

S.-W.K and J. R. contributed equally to this work. This study was supported by grants from the National Research Foundation (NRF) National Research Laboratory (R0A-2008-000-20041-0; C. B. P.), Engineering Research Center (2008-0062205; C. B. P.), Converging Research Center (2009-0082276; C. B. P.), and WCU (31-2008-000-10055-0; K. K.) programs. This research was supported by Energy Resource Technology RD K. K.) funded by the Ministry of Knowledge Economy, Republic of Korea. This work was also supported by the National Research Foundation (NRF) Grant funded by the Korean Government (MEST) (NRF-2009-0094219; K. K.).

Synthesis of Diphenylalanine/Polyaniline Core/Shell Conducting Nanowires by Peptide Self-Assembly†

Breaking the mold: Self-assembled peptide nanowires were used as a template for the synthesis of hollow polyaniline (PANI) nanotubes (see scanning electron microscopy images). The thickness and the morphology of the PANI nanostructures could be controlled readily either by varying the reaction time or by applying multiple PANI coatings.

Self-assembled, photoluminescent peptide hydrogel as a versatile platform for enzyme-based optical biosensors

A self-assembled peptide hydrogel consisting of Fmoc-diphenylalanine has been employed as a biosensing platform through the encapsulation of enzyme bioreceptors (e.g., glucose oxidase or horseradish peroxidase) and fluorescent reporters (e.g., CdTe and CdSe quantum dots). Enzymes and quantum dots (QDs) were physically immobilized within the hydrogel matrix in situ in a single step by simply mixing aqueous solution containing QDs and enzymes with monomeric peptide (Fmoc-diphenylalanine) solution. By using atomic force microscopy and scanning transmission electron microscopy, we observed that the self-assembled peptide hydrogel had a three-dimensional network of nanofibers (with a diameter of approximately 70-90 nm) that physically hybridized with QDs and encapsulated enzyme bioreceptors with a minimal leakage. We successfully applied the peptide hydrogel to the detection of analytes such as glucose and toxic phenolic compounds by using a photoluminescence quenching of the hybridized QDs. The Michaelis-Menten constant (K(M)) of the photoluminescent peptide hydrogel was found to be 3.12 mM (GOx for glucose) and 0.82 mM (HRP for hydroquinone), respectively, which were much lower than those of conventional gel materials. These results suggest that the peptide hydrogel is an alternative optical biosensing platform with practical advantages such as simple fabrication via self-assembly, efficient diffusion of target analytes, and high encapsulation efficiencies for fluorescent reporters and bioreceptors.

Mussel-inspired functionalization of carbon nanotubes for hydroxyapatite mineralization

Hydroxyapatite (HAp)/carbon nanotubes (CNTs) hybrid composite materials are successfully synthesized via a biomineralization process that employs poly(dopamine) (PDA), a synthetic mimic of mussel adhesive proteins. Creating bio-inorganic composites for regenerative medicine requires appropriate fillers to enhance their mechanical robustness; for example, natural bones are composed mainly of HAp supported by collagen fibers. In this regard, many efforts have been made to harness HAp as a bone substitute through its integration with reinforcing fibrous materials such as CNTs. We found that the formation of a PDA ad-layer on the surface of CNTs changed the hydrophobic CNTs to become bioactive. This enabled efficient interaction between the CNTs and mineral ions (e.g., Ca2+), which facilitated the mineralization of HAp. CNTs functionalized with PDA (CNT-PDA) highly accelerated the formation of HAp when incubated in a simulated body fluid and exhibited a minimal cytotoxic effect on bone osteoblast cells compared to pristine or carboxylated CNTs. Our results show the potential of CNT-PDA as a scaffold material for bone tissue regeneration and implantation.

Bio-inspired fabrication of superhydrophobic surfaces through peptide self-assembly

A vertically aligned peptide nanowire film, prepared by the self-assembly of diphenylalanine upon exposure to fluorinated aniline vapor at high temperature, exhibits a superhydrophobic property due to its nanoscale roughness and low surface free energy. We fabricated a self-cleaning, superhydrophobic surface by hierarchically re-organizing peptide nanowires into a hill-and-valley-like structure using capillary force induced by solvent-evaporation. Our approach provides an alternative way of nanofabrication for superhydrophobic materials, which should broaden the spectrum of applications for peptide self-assembly.

Bone-like peptide/hydroxyapatite nanocomposites assembled with multi-level hierarchical structures

Inspired by natures strategy for creating organic/inorganic hybrid composite materials, we developed a simple but powerful method to synthesize bone-like peptide/hydroxyapatite nanocomposites using a mussel-mimetic adhesive, polydopamine. We found that polydopamine was uniformly coated in a graphite-like layered structure on the surface of self-assembled diphenylalanine (Phe-Phe, FF) nanowires and enabled the epitaxial growth of c-axis-oriented hydroxyapatite nanocrystals along the nanowires, which is similar to mineralized collagen nanofibers of natural bone. The mineralized peptide nanowires were further organized in relation to each other and then readily hybridized with osteoblastic cells, resulting in the formation of multi-level hierarchical structures. They were found to be nontoxic and enabled efficient adhesion and proliferation of osteoblastic cells by guiding filopoidal extension.