Minah Lee

Self-Assembled Light-Harvesting Peptide Nanotubes for Mimicking Natural Photosynthesis†

Light-harvesting peptide nanotubes are synthesized by the self-assembly of diphenylalanine with THPP and platinum nanoparticles (nPt; see picture; TEOA = triethanolamine). The light-harvesting peptide nanotubes are suitable for mimicking photosynthesis because of their structure and electrochemical properties that are similar to the ones of photosystem I in natural photosynthesis.

Carbon‐Based Nanomaterials for Tissue Engineering

Carbon-based nanomaterials such as graphene sheets and carbon nanotubes possess unique mechanical, electrical, and optical properties that present new opportunities for tissue engineering, a key field for the development of biological alternatives that repair or replace whole or a portion of tissue. Carbon nanomaterials can also provide a similar microenvironment as like a biological extracellular matrix in terms of chemical composition and physical structure, making them a potential candidate for the development of artificial scaffolds. In this review, we summarize recent research advances in the effects of carbon nanomaterial-based substrates on cellular behaviors, including cell adhesion, proliferation, and differentiation into osteo- or neural- lineages. The development of 3D scaffolds based on carbon nanomaterials (or their composites with polymers and inorganic components) is introduced, and the potential of these constructs in tissue engineering, including toxicity issues, is discussed. Future perspectives and emerging challenges are also highlighted.

Redox Cofactor from Biological Energy Transduction as Molecularly Tunable Energy-Storage Compound†

Energy transduction and storage in biological systems involve multiply coupled, stepwise reduction/oxidation of energycarrying molecules such as adenosine triphosphate (ATP), nicotinamide, and flavin cofactors. These are synthesized as a result of oxidation during citric acid cycles in mitochondria or during photosynthesis in chloroplasts, and high energies stored in their chemical bonds are consequently harnessed for many biological reactions. Phosphorylation and protonation are key underlying mechanisms that allow for reversible cycling and regulate the molecule-specific redox potential. A sequential progression of electron transfer through the redox cascades as well as continuous recycling of the redox centers enables efficient energy use in biological systems. The biological energy transductionmechanism hints at the construction of a man-made energy storage system. Since the pioneering work by Tarascon and co-workers towards a sustainable lithium rechargeable battery received significant resonance, organic materials such as carbonyl, carboxy, or quinone-based compounds have been demonstrated to be bio-inspired organic electrodes. The imitation of redoxactive plastoquinone and ubiquinone cofactors through the use of redox-active C=O functionalities in organic electrodes is a significant step forward to biomimetic energy storage. However, the biological energy transduction is based on numerous redox centers of versatile functionalities available in nature, not limited to the simple redox active C=O functionalities. Consideration of how natural energy transduction systems function at organelle or cellular levels by elucidating the basic components and their operating principles selected by evolution will enrich the biomimetic strategy for efficient and green energy storage. Flavins are one of most structurally and functionally versatile redox centers in nature, catalyzing an enormous range of biotransformations and electron-transfer reactions, which occur over a wide potential range (> 500 mV). The extraordinary versatility of flavins stems from their ability to engage in either oneor twoelectron-transfer redox processes, accompanying proton transfer at the nitrogen atoms of diazabutadiene motif. In the respiratory electron transport chain, for example, electrons from reduced flavin adenine dinucleotide (FADH2) are transported along a group of proteins located in the inner membrane of mitochondria to induce proton pumping across the membrane, as illustrated in Figure 1a (left). This process generates an electrochemical proton gradient, which results in the formation of high-energy ATP. FAD is reduced again in the citric acid cycle of mitochondria, which enables continuous recycling of flavin redox centers. A close analogy exists between the key components, facilitating respiration and battery operation (Figure 1a); charged ions (H or Li) and electrons, which are derived from flavin redox centers, are unidirectionally transported in a stoichiometric manner using separated paths. This creates chemical gradients across membranes, and finally results in the formation of highenergy species such as ATP and metallic lithium. Herein, we report on the possibility of using the energystorage mechanism of flavin redox cycling in mitochondria to lithium rechargeable batteries. According to our results, flavin electrodes were capable of reversibly storing and releasing two lithium ions and two electrons per formula unit. Redox reactions in flavin electrodes were thoroughly investigated using the combined analyses of ex situ characterizations and density functional theory (DFT)-based calculations. We found that the flavin redox reaction occurs during battery operation at the nitrogen atoms of the diazabutadiene motif in flavin molecules using two successive single-electron transfer steps, in a similar way to the proton-coupled electron transfer in flavoenzymes. Molecular tuning by chemical substitution on the isoalloxazine ring significantly improved electrochemical performances in terms of an average redox potential, a gravimetric capacity, and stability, resulting in a high-energy density comparable to that of LiFePO4, the [*] M. Lee, D. H. Nam, Prof. C. B. Park Department of Materials Science and Engineering Korea Advanced Institute of Science and Technology Daejeon 305-701 (Korea) E-mail: parkcb@kaist.ac.kr J. Hong, Dr. D.-H. Seo, Prof. K. T. Nam, Prof. K. Kang Center for Nanoparticle Research Institute for Basic Science (IBS) Department of Materials Science and Engineering Research Institute of Advanced Materials Seoul National University, Seoul 151-742 (Korea) E-mail: matlgen1@snu.ac.kr [] These authors contributed equally to this work.

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.

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.

Mussel-Inspired Plasmonic Nanohybrids for Light Harvesting

Core-shell plasmonic nanohybrids are synthesized through a simple solutionbased process utilizing mussel-inspired polydopamine (PDA). The multi-purpose PDA not only facilitates plasmonic metal formation, but also serves as a scaffold to incorporate photosensitizers around the metal cores, as well as an adhesive between the nanohybrids and the substrate. The resulting plasmonic assembly exhibits highly enhanced light absorption in photo catalytic systems to augment artificial photosynthesis.

Aluminum Nanoarrays for Plasmon-Enhanced Light Harvesting

The practical limits of coinage-metal-based plasmonic materials demand sustainable, abundant alternatives with a wide plasmonic range of the solar energy spectrum. Aluminum (Al) is an emerging alternative, but its instability in aqueous environments critically limits its applicability to various light-harvesting systems. Here, we report a design strategy to achieve a robust platform for plasmon-enhanced light harvesting using Al nanostructures. The incorporation of mussel-inspired polydopamine nanolayers in the Al nanoarrays allowed for the reliable use of Al plasmonic resonances in a highly corrosive photocatalytic redox solution and provided nanoscale arrangement of organic photosensitizers on Al surfaces. The Al-photosensitizer core-shell assemblies exhibited plasmon-enhanced light absorption, which resulted in a 300% efficiency increase in photo-to-chemical conversion. Our strategy enables stable and advanced use of aluminum for plasmonic light harvesting.

Multi-electron redox phenazine for ready-to-charge organic batteries

Organic redox compounds represent an emerging class of cathode materials in rechargeable batteries for low-cost and sustainable energy storage. However, the low operating voltage (<3 V) and necessity of using lithium-containing anodes have significantly limited their practical applicability to battery systems. Here, we introduce a new class of p-type organic redox centers based on N,N′-substituted phenazine (NSPZ) to build ready-to-charge organic batteries. In the absence of lithium-containing anodes, NSPZ cathodes facilitate reversible two-electron transfer at 3.7 and 3.1 V accompanying anion association, which results in a specific energy of 622 Wh kg−1 in dual-ion batteries.