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Nanomaterials Mimicking Natural Enzymes with Superior Catalytic Activity and Selectivity for Detecting Acetylcholine
(Professor Jinwoo Lee from the Department of Chemical and Biomolecular Engineering) A KAIST research team doped nitrogen and boron into graphene to selectively increase peroxidase-like activity and succeeded in synthesizing a peroxidase-mimicking nanozyme with a low cost and superior catalytic activity. These nanomaterials can be applied for early diagnosis of Alzheimer’s disease. Enzymes are the main catalysts in our body and are widely used in bioassays. In particular, peroxidase, which oxidizes transparent colorimetric substrates to become a colored product in the presence of hydrogen peroxide, is the most common enzyme that is used in colorimetric bioassays. However, natural enzymes consisting of proteins are unstable against temperature and pH, hard to synthesize, and costly. Nanozymes, on the other hand, do not consist of proteins, meaning the disadvantages of enzymes can be overcome with their robustness and high productivity. In contrast, most nanonzymes do not have selectivity; for example, peroxidase-mimicking nanozymes demonstrate oxidase-like activity that oxidizes colorimetric substrates in the absence of hydrogen peroxide, which keeps them away from precisely detecting the target materials, such as hydrogen peroxide. Professor Jinwoo Lee from the Department of Chemical and Biomolecular Engineering and his team were able to synthesize a peroxidase-mimicking nanozyme with superior catalytic activity and selectivity toward hydrogen peroxide. Co-doping of nitrogen and boron into graphene, which has negligible peroxidase-like activity, selectively increased the peroxidase-like activity without oxidase-like activity to accurately mimic the nature peroxidase and has become a powerful candidate to replace the peroxidase. The experimental results were also verified with computational chemistry. The nitrogen and boron co-doped graphene was also applied to the colorimetric detection of acetylcholine, which is an important neurotransmitter and successfully detected the acetylcholine even better than the nature peroxidase. Professor Lee said, “We began to study nanozymes due to their potential for replacing existing enzymes. Through this study, we have secured core technologies to synthesize nanozymes that have high enzyme activity along with selectivity. We believe that they can be applied to effectively detect acetylcholine for quickly diagnosing Alzheimer’s disease. This research, led by PhD Min Su Kim, was published in ACS Nano (10.1021/acsnano.8b09519) on March 25, 2019. Figure 1. Comparison of the catalytic activities of various nanozymes and horseradish peroxidase (HRP) toward TMB and H₂O₂ Figure 2. Schematic illustration of NB-rGO Reactions in Bioassays
Hierarchical Porous Titanium Nitride Synthesized by Multiscale Phase Separation for LSBs
(from left: Professor Jinwoo Lee and PhD candidate Won-Gwang Lim) A KAIST research team developed ultra-stable, high-rate lithium-sulfur batteries (LSBs) by using hierarchical porous titanium nitride as a sulfur host, and achieved superior cycle stability and high rate performance for LSBs. The control of large amounts of energy is required for use in an electric vehicle or smart grid system. In this sense, the development of next-generation secondary batteries is in high demand. Theoretically, LSBs have an energy density seven times higher than commercial lithium ion batteries (LIBs). Also, their production cost can be reduced dramatically since sulfur can be obtained at a low price. Despite these positive aspects, there have been several issues impeding the commercialization of LSBs, such as the low electric conductivity of sulfur, the dissolution of active materials during operation, and sluggish conversion reactions. These issues decrease the cycle stability and rate capability of batteries. To tackle those issues, Professor Jinwoo Lee from the Department of Chemical and Biomolecular Engineering and his team synthesized a well-developed hierarchical macro/mesoporous titanium nitride as a host material for sulfur. The titanium nitride has a high chemical affinity for sulfur and high electrical conductivity. As a result, it prevents the dissolution of active materials and facilitates the charge transfer. Moreover, the synergistic effect of macropore and mesopore structures allows the stable accommodation of large amounts of sulfur and facilitates the electrolyte penetration. Previously reported polar inorganic materials have a high affinity for sulfur, but it was challenging to control the porous architecture suitable to the sulfur host. This work breaks such limitations by developing a synthetic route to easily control the porous architecture of inorganic materials, which led to obtaining superior cycle stability and high rate capabilities. Professor Lee said, “Some problems still remain in commercializing LSBs as next-generation batteries. Hence, there should be a continued research on this matter to solve the issues. Through this research, we secured a key technology for ultrastable, high-rate LSBs.” This research was led by PhD candidate Won-Gwang Lim and collaborated on by Jeong Woo Han from POSTECH. It was chosen as the cover article of Advanced Materials on January 15, 2019. Figure 1. Schematic illustration for the synthetic route of co-continuous h-TiN Figure 2. The hierarchical multiscale porous structure is still retained without any collapse after the conversion to h-TiN. The good retention of the porous structure is attributed to the thick pore wall of the h-TiO₂derived from the block copolymer self-assembly Figure 3. The cover page of Advanced Materials
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