Kuk-Youn Ju

Bioinspired Polymerization of Dopamine to Generate Melanin-Like Nanoparticles Having an Excellent Free-Radical-Scavenging Property

Melanin-like nanoparticles were synthesized with size control through neutralization of dopamine hydrochloride with NaOH, followed by spontaneous air oxidation of dopamine. Although the particle characteristic of natural melanins was understood to be significantly affected by the biological and structural environment, melanin-lke nanoparticles can be realized through the chemical reactions only. Melanin-like nanoparticles that are <100 nm showed excellent dispersion stability in water as well as biological media and good biocompatibility to HeLa cells after the appropriate surface modification with thiol-terminated methoxy-poly(ethylene glycol) (mPEG-SH). Furthermore, the demonstrated ability of melanin-like nanoparticles to reduce 2,2-diphenyl-1-picrylhydrazyl (DPPH) suggests free radical scavenging activity of the material.

Bio-inspired, melanin-like nanoparticles as a highly efficient contrast agent for T1-weighted magnetic resonance imaging.

The development of nontoxic and biocompatible imaging agents will create new opportunities for potential applications in clinical MRI diagnosis. Synthetic melanin-like nanoparticles (MelNPs), analogous to natural sepia melanin (a major component of the cuttlefish ink), can be used as contrast agent for MRI. MelNPs complexed with paramagnetic Fe(3+) ions show much higher relaxivity values than existing MRI T1 contrast agents based on gadolinium (Gd) or manganese (Mn); MelNP values at 3T were r1 = 17 and r2 = 18 mM(-1) s(-1) (r2/r1 value of 1.1). With significant enhancement to MRI contrast, this biomimetic approach using MelNPs functionalized with paramagnetic Fe(3+) ions and surface-modified with biocompatible poly(ethylene glycol) units, could provide new insight into how melanin-based bioresponsive and therapeutic imaging probes integrate with their various biological functions.

Stable Biomimetic Superhydrophobic Surfaces Fabricated by Polymer Replication Method from Hierarchically Structured Surfaces of Al Templates

We have developed a simple, efficient, and highly reproducible method to fabricate the large-area biomimetic superhydrophobic polymer surfaces having hierarchical structures of micrometer-sized irregular steps and nanometer-sized fibrils. Commercial Al plates (99.0%) were etched using Becks dislocation etchant (mixture of HCl and HF) for different time periods in order to alter the structure of the etched Al surfaces from micrometer-sized to highly rough nanometer-sized irregular steps. These hierarchical structures could be easily replicated onto the surface of various thermoplastic polymer plates from the etched Al templates by applying heat and pressure; many polymer replicas without any significant deviations from each other could be duplicated from the same etched Al master templates. All of thermoplastic polymer replicas having hierarchical structures exhibited superhydrophobic properties with water contact angles of larger than 150 degrees. Especially, the surfaces of the high-density polyethylene (HDPE) replicas having nanometer-sized curled strands exhibited superhydrophobicity with a static water contact angle of approximately 160 degrees and a sliding angle of less than 2 degrees. These superhydrophobic HDPE replicas having nanometer-sized curled strands showed excellent stability after being exposed to various organic solvents and aqueous solutions of various pH.

Bio‐inspired Development of a Dual‐Mode Nanoprobe for MRI and Raman Imaging

New generation dual-mode imaging probes for MRI and Raman imaging techniques are developed, inspired by the hyper intense contrast enhancing capability in T1 -weighted MRI and characteristic Raman signal of natural melanin. MDA-MB-231cells labeled with dual-mode imaging probe are successfully detected in both T1-weighted MRI and Raman imaging.

Clue to Understanding the Janus Behavior of Eumelanin: Investigating the Relationship between Hierarchical Assembly Structure of Eumelanin and Its Photophysical Properties

The contradictory biological function of eumelanin (photoprotection vs photosensitization) has long been a topic of debate in a wide range of disciplines such as chemistry, physics and biology. For understanding full spectrum of eumelanins photobiological aspect, revealing how eumelanins complex structural organization dictates its photophysical properties is critical step. Here, we report a practical approach to controlling the hierarchically assembled structure of natural eumelanin, which leads to disassembly of its structure into subunits and oxidized subunits, respectively. Based on the well-characterized model system, it was possible to systematically determine how the photophysical properties of eumelanin are ruled by its hierarchical assembly organization. Particularly, our experiments reveal that the chemical oxidation of eumelanins subunits, which leads to delamination of their stacked layer structure, is critical to significantly increase their photochemical reactivity to generate ROS under UV irradiation. This result provides clear experimental evidence that oxidative degradation of eumelanin, which might be induced by phagosomal enzymatic activity in the process of melanomagenesis, is responsible for triggering the negative photobiological role of eumelanin such as ROS source needed for development of malignant melanoma.

Artificial pheomelanin nanoparticles and their photo-sensitization properties

Pheomelanin-type nanoparticles (PMNPs) were synthesized through a simple oxidative polymerization of 3,4-dihydroxyphenylalanine (DOPA) in the presence of cysteine by KMnO4. The synthesized PMNPs had a diameter of approximately 100nm, exhibited high dispersion stability in neutral water and various culture media and possessed similar morphology to naturally occurring pheomelanins. The efficiency of photoinduced generation of hydroxyl radicals from PMNPs was determined and related in vitro cell experiments that were carried out, with data being compared to those from eumelanin-type nanoparticles (EMNPs) and natural sepia melanin nanoparticles. Endocytosed PMNPs showed the highest phototoxicity (~50% viability) to UV-irradiated HeLa cells, confirming the direct relationship between phototoxic efficiency and the generation of hydroxyl radicals through the complex processes of the O2 sensitization.