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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 eumelanin's photobiological aspect, revealing how eumelanin's 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 eumelanin's 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. [ABSTRACT FROM AUTHOR]

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 Beck’s 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°. Especially, the surfaces of the high-density polyethylene (HDPE) replicas having nanometer-sized curled strands exhibited superhydrophobicity with a static water contact angle of ∼160° and a sliding angle of less than 2°. 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. [ABSTRACT FROM AUTHOR]