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Simple Molecular Reagents to Treat Alzheimer’s Disease
- Researchers report minimalistic principles for designing small molecules with multiple reactivities against dementia. - Sometimes the most complex problems actually have very simple solutions. A group of South Korean researchers reported an efficient and effective redox-based strategy for incorporating multiple functions into simple molecular reagents against neurodegenerative disorders. The team developed redox-active aromatic molecular reagents with a simple structural composition that can simultaneously target and modulate various pathogenic factors in complex neurodegenerative disorders such as Alzheimer’s disease. Alzheimer’s disease is one of the most prevalent neurodegenerative disorders, affecting one in ten people over the age of 65. Early-onset dementia also increasingly affects younger people. A number of pathogenic elements such as reactive oxygen species, amyloid-beta, and metal ions have been suggested as potential causes of Alzheimer’s disease. Each element itself can lead to Alzheimer’s disease, but interactions between them may also aggravate the patient’s condition or interfere with the appropriate clinical care. For example, when interacting with amyloid-beta, metal ions foster the aggregation and accumulation of amyloid-beta peptides that can induce oxidative stress and toxicity in the brain and lead to neurodegeneration. Because these pathogenic factors of Alzheimer’s disease are intertwined, developing therapeutic agents that are capable of simultaneously regulating metal ion dyshomeostasis, amyloid-beta agglutination, and oxidative stress responses remains a key to halting the progression of the disease. A research team led by Professor Mi Hee Lim from the Department of Chemistry at KAIST demonstrated the feasibility of structure-mechanism-based molecular design for controlling a molecule’s chemical reactivity toward the various pathological factors of Alzheimer’s disease by tuning the redox properties of the molecule. This study, featured as the ‘ACS Editors’ Choice’ in the May 6th issue of the Journal of the American Chemical Society (JACS), was conducted in conjunction with KAIST Professor Mu-Hyun Baik’s group and Professor Joo-Young Lee’s group at the Asan Medical Center. Professor Lim and her collaborators rationally designed and generated 10 compact aromatic molecules presenting a range of redox potentials by adjusting the electronic distribution of the phenyl, phenylene, or pyridyl moiety to impart redox-dependent reactivities against the multiple pathogenic factors in Alzheimer’s disease. During the team’s biochemical and biophysical studies, these designed molecular reagents displayed redox-dependent reactivities against numerous desirable targets that are associated with Alzheimer’s disease such as free radicals, metal-free amyloid-beta, and metal-bound amyloid-beta. Further mechanistic results revealed that the redox properties of these designed molecular reagents were essential for their function. The team demonstrated that these reagents engaged in oxidative reactions with metal-free and metal-bound amyloid-beta and led to chemical modifications. The products of such oxidative transformations were observed to form covalent adducts with amyloid-beta and alter its aggregation. Moreover, the administration of the most promising candidate molecule significantly attenuated the amyloid pathology in the brains of Alzheimer’s disease transgenic mice and improved their cognitive defects. Professor Lim said, “This strategy is straightforward, time-saving, and cost-effective, and its effect is significant. We are excited to help enable the advancement of new therapeutic agents for neurodegenerative disorders, which can improve the lives of so many patients.” This work was supported by the National Research Foundation (NRF) of Korea, the Institute for Basic Science (IBS), and the Asan Institute for Life Sciences. Image credit: Professor Mi Hee Lim, KAIST Image usage restrictions: News organizations may use or redistribute this image, with proper attribution, as part of the news coverage of this paper only. Publication: Kim, M. et al. (2020) ‘Minimalistic Principles for Designing Small Molecules with Multiple Reactivities against Pathological Factors in Dementia.’ Journal of the American Chemical Society (JACS), Volume 142, Issue 18, pp.8183-8193. Available online at https://doi.org/10.1021/jacs.9b13100 Profile: Mi Hee Lim Professor email@example.com http://sites.google.com/site/miheelimlab Lim Laboratory Department of Chemistry KAIST Profile: Mu-Hyun Baik Professor firstname.lastname@example.org https://baik-laboratory.com/ Baik Laboratory Department of Chemistry KAIST Profile: Joo-Yong Lee Professor email@example.com Asan Institute for Life Sciences Asan Medical Center (END)
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
Wafer-Scale Multilayer Fabrication of Silk Fibroin-Based Microelectronics
A KAIST research team developed a novel fabrication method for the multilayer processing of silk-based microelectronics. This technology for creating a biodegradable silk fibroin film allows microfabrication with polymer or metal structures manufactured from photolithography. It can be a key technology in the implementation of silk fibroin-based biodegradable electronic devices or localized drug delivery through silk fibroin patterns. Silk fibroins are biocompatible, biodegradable, transparent, and flexible, which makes them excellent candidates for implantable biomedical devices, and they have also been used as biodegradable films and functional microstructures in biomedical applications. However, conventional microfabrication processes require strong etching solutions and solvents to modify the structure of silk fibroins. To prevent the silk fibroin from being damaged during the process, Professor Hyunjoo J. Lee from the School of Electrical Engineering and her team came up with a novel process, named aluminum hard mask on silk fibroin (AMoS), which is capable of micropatterning multiple layers composed of both fibroin and inorganic materials, such as metal and dielectrics with high-precision microscale alignment. The AMoS process can make silk fibroin patterns on devices, or make patterns on silk fibroin thin films with other materials by using photolithography, which is a core technology in the current microfabrication process. The team successfully cultured primary neurons on the processed silk fibroin micro-patterns, and confirmed that silk fibroin has excellent biocompatibility before and after the fabrication process and that it also can be applied to implanted biological devices. Through this technology, the team realized the multilayer micropatterning of fibroin films on a silk fibroin substrate and fabricated a biodegradable microelectric circuit consisting of resistors and silk fibroin dielectric capacitors in a silicon wafer with large areas. They also used this technology to position the micro-pattern of the silk fibroin thin film closer to the flexible polymer-based brain electrode, and confirmed the dye molecules mounted on the silk fibroin were transferred successfully from the micropatterns. Professor Lee said, “This technology facilitates wafer-scale, large-area processing of sensitive materials. We expect it to be applied to a wide range of biomedical devices in the future. Using the silk fibroin with micro-patterned brain electrodes can open up many new possibilities in research on brain circuits by mounting drugs that restrict or promote brain cell activities.” This research, in collaboration with Dr. Nakwon Choi from KIST and led by PhD candidate Geon Kook, was published in ACS AMI (10.1021/acsami.8b13170) on January 16, 2019. Figure 1. The cover page of ACS AMI Figure 2. Fibroin microstructures and metal patterns on a fibroin produced by using the AMoS mask. Figure 3. Biocompatibility assessment of the AMoS Process. Top: Schematics image of a) fibroin-coated silicon b) fibroin-pattered silicon and c) gold-patterned fibroin. Bottom: Representative confocal microscopy images of live (green) and dead (red) primary cortical neurons cultured on the substrates.
KAIST Develops Analog Memristive Synapses for Neuromorphic Chips
(Professor Sung-Yool Choi from the School of Electrical Engineering) A KAIST research team developed a technology that makes a transition of the operation mode of flexible memristors to synaptic analog switching by reducing the size of the formed filament. Through this technology, memristors can extend their role to memristive synapses for neuromorphic chips, which will lead to developing soft neuromorphic intelligent systems. Brain-inspired neuromorphic chips have been gaining a great deal of attention for reducing the power consumption and integrating data processing, compared to conventional semiconductor chips. Similarly, memristors are known to be the most suitable candidate for making a crossbar array which is the most efficient architecture for realizing hardware-based artificial neural network (ANN) inside a neuromorphic chip. A hardware-based ANN consists of a neuron circuit and synapse elements, the connecting pieces. In the neuromorphic system, the synaptic weight, which represents the connection strength between neurons, should be stored and updated as the type of analog data at each synapse. However, most memristors have digital characteristics suitable for nonvolatile memory. These characteristics put a limitation on the analog operation of the memristors, which makes it difficult to apply them to synaptic devices. Professor Sung-Yool Choi from the School of Electrical Engineering and his team fabricated a flexible polymer memristor on a plastic substrate, and found that changing the size of the conductive metal filaments formed inside the device on the scale of metal atoms can make a transition of the memristor behavior from digital to analog. Using this phenomenon, the team developed flexible memristor-based electronic synapses, which can continuously and linearly update synaptic weight, and operate under mechanical deformations such as bending. The team confirmed that the ANN based on these memristor synapses can effectively classify person’s facial images even when they were damaged. This research demonstrated the possibility of a neuromorphic chip that can efficiently recognize faces, numbers, and objects. Professor Choi said, “We found the principles underlying the transition from digital to analog operation of the memristors. I believe that this research paves the way for applying various memristors to either digital memory or electronic synapses, and will accelerate the development of a high-performing neuromorphic chip.” In a joint research project with Professor Sung Gap Im (KAIST) and Professor V. P. Dravid (Northwestern University), this study was led by Dr. Byung Chul Jang (Samsung Electronics), Dr. Sungkyu Kim (Northwestern University) and Dr. Sang Yoon Yang (KAIST), and was published online in Nano Letters (10.1021/acs.nanolett.8b04023) on January 4, 2019. Figure 1. a) Schematic illustration of a flexible pV3D3 memristor-based electronic synapse array. b) Cross-sectional TEM image of the flexible pV3D3 memristor
Stretchable Multi-functional Fiber for Energy Harvesting and Strain Sensing
(from left: Professor Steve Park, Jeongjae Ryu and Professor Seungbum Hong) Fiber-based electronics are expected to play a vital role in next-generation wearable electronics. Woven into textiles, they can provide higher durability, comfort, and integrated multi-functionality. A KAIST team has developed a stretchable multi-functional fiber (SMF) that can harvest energy and detect strain, which can be applied to future wearable electronics. With wearable electronics, health and physical conditions can be assessed by analyzing biological signals from the human body, such as pulse and muscle movements. Fibers are highly suitable for future wearable electronics because they can be easily integrated into textiles, which are designed to be conformable to curvilinear surfaces and comfortable to wear. Moreover, their weave structures offer support that makes them resistant to fatigue. Many research groups have developed fiber-based strain sensors to sense external biological signals. However, their sensitivities were relatively low. The applicability of wearable devices is currently limited by their power source, as the size, weight, and lifetime of the battery lessens their versatility. Harvesting mechanical energy from the human body is a promising solution to overcome such limitations by utilizing various types of motions like bending, stretching, and pressing. However, previously reported, fiber-based energy harvesters were not stretchable and could not fully harvest the available mechanical energy. Professor Seungbum Hong and Professor Steve Park from the Department of Materials Science and Engineering and their team fabricated a stretchable fiber by using a ferroelectric layer composed of P(VDF-TrFE)/PDMS sandwiched between stretchable electrodes composed of a composite of multi-walled carbon nanotubes (MWCNT) and poly 3,4-ethylenedioxythiophene polystyrenesulfonate (PEDOT:PSS). Cracks formed in MWCNT/PEDOT:PSS layer help the fiber show high sensitivity compared to the previously reported fiber strain sensors. Furthermore, the new fiber can harvest mechanical energy under various mechanical stimuli such as stretching, tapping, and injecting water into the fiber using the piezoelectric effect of the P(VDF-TrFE)/PDMS layer. Professor Hong said, “This new fiber has various functionalities and makes the device simple and compact. It is a core technology for developing wearable devices with energy harvesting and strain sensing capabilities.” This article, led by PhD candidate Jeongjae Ryu, was published in the January 2019 issue of Nano Energy. Figure 1.Schematic illustration of an SMF fiber and its piezoelectric voltage output and response to strain. Figure 2. Photographs of a stretchable multi-functional fiber being stretched by 100%, bent, and twisted.
Fabrication of Shape-conformable Batteries with 3D-Printing
(from left: Dr. Bok Yeop Ahn, Dr. Chanhoon Kim, Professor Il-Doo Kim and Professor Jennifer A. Lewis) Flexible, wireless electronic devices are rapidly emerging and have reached the level of commercialization; nevertheless, most of battery shapes are limited to either spherical and/or rectangular structures, which results in inefficient space use. Professor Il-Doo Kim’s team from the Department of Materials Science at KAIST has successfully developed technology to significantly enhance the variability of battery design through collaboration research with Professor Jennifer A. Lewis and her team from the School of Engineering and Applied Sciences at Harvard University. Most of the battery shapes today are optimized for coin cell and/or pouch cells. Since the battery as an energy storage device occupies most of the space in microelectronic devices with different designs, new technology to freely change the shape of the battery is required. The KAIST-Harvard research collaboration team has successfully manufactured various kinds of battery shapes, such as ring-type, H, and U shape, using 3D printing technology. And through the research collaboration with Dr. Youngmin Choi at the Korea Research Institute of Chemical Technology (KRICT), 3D-printed batteries were applied to small-scale wearable electronic devices (wearable light sensor rings). The research group has adopted environmentally friendly aqueous Zn-ion batteries to make customized battery packs. This system, which uses Zn2+ instead of Li+ as charge carriers, is much safer compared with the conventional lithium rechargeable batteries that use highly inflammable organic electrolytes. Moreover, the processing conditions of lithium-ion batteries are very complicated because organic solvents can ignite upon exposure to moisture and oxygen. As the aqueous Zn-ion batteries adopted by the research team are stable upon contact with atmospheric moisture and oxygen, they can be fabricated in the ambient air condition, and have advantages in packaging since packaged plastic does not dissolve in water even when plastic packaging is applied using a 3D printer. To fabricate a stable cathode that can be modulated in various forms and allows high charge-discharge, the research team fabricated a carbon fiber current collector using electrospinning process and uniformly coated electrochemically active polyaniline conductive polymer on the surface of carbon fiber for a current collector-active layer integrated cathode. The cathode, based on conductive polyaniline consisting of a 3D structure, exhibits very fast charging speeds (50% of the charge in two minutes) and can be fabricated without the detachment of active cathode materials, so various battery forms with high mechanical stability can be manufactured. Prof. Kim said, “Zn-ion batteries employing aqueous electrolytes have the advantage of fabrication under ambient conditions, so it is easy to fabricate the customized battery packs using 3D printing.” “3D-printed batteries can be easily applied for niche applications such as wearable, personalized, miniaturized micro-robots, and implantable medical devices or microelectronic storage devices with unique designs,” added Professor Lewis. With Dr. Chanhoon Kim in the Department of Materials Science and Engineering at KAIST and Dr. Bok Yeop Ahn School of Engineering and Applied Sciences at Harvard University participating as equally contributing first authors, this work was published in the December issue of ACS Nano. This work was financially supported by the Global Research Laboratory (NRF-2015K1A1A2029679) and Wearable Platform Materials Technology Center (2016R1A5A1009926). Figure 1.Fabrication of shape-conformable batteries based on 3D-printing technology and the application of polyaniline carbon nanofiber cathodes and wearable electronic devices Figure 2.Fabricated shape-conformable batteries based on a 3D-printing method Meanwhile, Professor Il-Doo Kim was recently appointed as an Associate Editor of ACS Nano, a highly renowned journal in the field of nanoscience. Professor Kim said, “It is my great honor to be an Associate Editor of the highly renowned journal ACS Nano, which has an impact factor reaching 13.709 with 134,596 citations as of 2017. Through the editorial activities in the fields of energy, I will dedicate myself to improving the prominence of KAIST and expanding the scope of Korea’s science and technology. I will also contribute to carrying out more international collaborations with world-leading research groups.” (Associate Editor of ACS Nano Professor Il-Doo Kim)
Spray Coated Tactile Sensor on a 3-D Surface for Robotic Skin
Robots will be able to conduct a wide variety of tasks as well as humans if they can be given tactile sensing capabilities. A KAIST research team has reported a stretchable pressure insensitive strain sensor by using an all solution-based process. The solution-based process is easily scalable to accommodate for large areas and can be coated as a thin-film on 3-dimensional irregularly shaped objects via spray coating. These conditions make their processing technique unique and highly suitable for robotic electronic skin or wearable electronic applications. The making of electronic skin to mimic the tactile sensing properties of human skin is an active area of research for various applications such as wearable electronics, robotics, and prosthetics. One of the major challenges in electronic skin research is differentiating various external stimuli, particularly between strain and pressure. Another issue is uniformly depositing electrical skin on 3-dimensional irregularly shaped objects. To overcome these issues, the research team led by Professor Steve Park from the Department of Materials Science and Engineering and Professor Jung Kim from the Department of Mechanical Engineering developed electronic skin that can be uniformly coated on 3-dimensional surfaces and distinguish mechanical stimuli. The new electronic skin can also distinguish mechanical stimuli analogous to human skin. The structure of the electronic skin was designed to respond differently under applied pressure and strain. Under applied strain, conducting pathways undergo significant conformational changes, considerably changing the resistance. On the other hand, under applied pressure, negligible conformational change in the conducting pathway occurs; e-skin is therefore non-responsive to pressure. The research team is currently working on strain insensitive pressure sensors to use with the developed strain sensors. The research team also spatially mapped the local strain without the use of patterned electrode arrays utilizing electrical impedance tomography (EIT). By using EIT, it is possible to minimize the number of electrodes, increase durability, and enable facile fabrication onto 3-dimensional surfaces. Professor Park said, “Our electronic skin can be mass produced at a low cost and can easily be coated onto complex 3-dimensional surfaces. It is a key technology that can bring us closer to the commercialization of electronic skin for various applications in the near future.” The result of this work entitled “Pressure Insensitive Strain Sensor with Facile Solution-based Process for Tactile Sensing Applications” was published in the August issue of ACS Nano as a cover article. (Figure: Detecting mechanical stimuli using electrical impedance tomography.)
KAIST Develops VRFB with Longer Durability
(from left: PhD candidate Soohyun Kim, Professor Hee-Tak Kim and PhD candidate Junghoon Choi) There has been growing demand for large-scale storage for energy produced from renewable energy sources in an efficient and stable way. To meet this demand, a KAIST research team developed a new vanadium redox-flow battery (VRFB) with 15 times greater capacity retention and five times longer durability. This VRFB battery can be an excellent candidate for a large-scale rechargeable battery with no risk of explosion. The VRFB has received much attention for its high efficiency and reliability with the absence of cross-contamination. However, it has the limitation of having insufficient charge and discharge efficiency and a low capacity retention rate because its perfluorinated membrane is very permeable to any active materials. To minimize energy loss, it needs a membrane that has low vanadium ion permeability and high ion conductivity. Hence, there was an attempt to incorporate a hydrocarbon membrane that has low cost and high ion selectivity but it turned out that the VO₂+ caused chemical degradation, which led to shortening the battery life drastically. To develop a membrane with pore sizes smaller than the hydrated size of vanadium ions yet larger than that of the protons, a research team co-led by Professor Hee-Tae Jung and Professor Hee-Tak Kim from the Department of Chemical and Biomolecular Engineering implemented a graphene-oxide framework (GOF) membrane by cross-linking graphene oxide nanosheets. They believed that GOF, having strong ion selectivity, would be a good candidate for the membrane component for the VRFB. The interlayer spacing between the GO sheets limited moisture expansion and provided selective ion permeation. The GOF membrane increased the capacity retention of the VRFB, which showed a 15 times higher rate than that of perfluorinated membranes. Its cycling stability was also enhanced up to five times, compared to conventional hydrocarbon membranes. These pore-sized-tuned graphene oxide frameworks will allow pore-sized tuning of membranes and will be applicable to electrochemical systems that utilize ions of various sizes, such as rechargeable batteries and sensors. Professor Kim said, “Developing a membrane that prevents the mixing of positive and negative active materials has been a chronic issue in the field of redox-flow batteries. Through this research, we showed that nanotechnology can prevent this crossover issue and membrane degradation. I believe that this technology can be applied to various rechargeable batteries requiring large-scale storage.” This research was published in Nano Letters on May 3. Figure 1. Electrochemical performances of the VRFBs with Nafion 115, SPAES (sulfonated poly), and GOF/SPAES: discharge capacity Figure 2. Schematic of the selective ion transfer of hydrated vanadium ions and protons in the GOF membrane and the molecular structure of the GOF membrane, showing that the GO nanosheets are cross-linked with EDA (ethylenediamine)
Transfering Nanowires onto a Flexible Substrate
(from left: PhD Min-Ho Seo and Professor Jun-Bo Yoon) Boasting excellent physical and chemical properties, nanowires (NWs) are suitable for fabricating flexible electronics; therefore, technology to transfer well-aligned wires plays a crucial role in enhancing performance of the devices. A KAIST research team succeeded in developing NW-transfer technology that is expected to enhance the existing chemical reaction-based NW fabrication technology that has this far showed low performance in applicability and productivity. NWs, one of the most well-known nanomaterials, have the structural advantage of being small and lightweight. Hence, NW-transfer technology has drawn attention because it can fabricate high-performance, flexible nanodevices with high simplicity and throughput. A conventional nanowire-fabrication method generally has an irregularity issue since it mixes chemically synthesized nanowires in a solution and randomly distributes the NWs onto flexible substrates. Hence, numerous nanofabrication processes have emerged, and one of them is master-mold-based, which enables the fabrication of highly ordered NW arrays embedded onto substrates in a simple and cost-effective manner, but its employment is limited to only some materials because of its chemistry-based NW-transfer mechanism, which is complex and time consuming. For the successful transfer, it requires that adequate chemicals controlling the chemical interfacial adhesion between the master mold, NWs, and flexible substrate be present. Here, Professor Jun-Bo Yoon and his team from the School of Electrical Engineering introduced a material-independent mechanical-interlocking-based nanowire-transfer (MINT) method to fabricate ultralong and fully aligned NWs on a large flexible substrate in a highly robust manner. This method involves sequentially forming a nanosacrificial layer and NWs on a nanograting substrate that becomes the master mold for the transfer, then weakening the structure of the nanosacrificial layer through a dry etching process. The nanosacrificial layer very weakly holds the nanowires on the master mold. Therefore, when using a flexible substrate material, the nanowires are very easily transferred from the master mold to the substrate, just like a piece of tape lifting dust off a carpet. This technology uses common physical vapor deposition and does not rely on NW materials, making it easy to fabricate NWs onto the flexible substrates. Using this technology, the team was able to fabricate a variety of metal and metal-oxide NWs, including gold, platinum, and copper – all perfectly aligned on a flexible substrate. They also confirmed that it can be applied to creating stable and applicable devices in everyday life by successfully applying it to flexible heaters and gas sensors. PhD Min-Ho Seo who led this research said, “We have successfully aligned various metals and semiconductor NWs with excellent physical properties onto flexible substrates and applied them to fabricated devices. As a platform-technology, it will contribute to developing high-performing and stable electronic devices.” This research was published in ACS Nano on May 24. Figure 1. Photograph of the fabricated wafer-scale fully aligned and ultralong Au nanowire array on a flexible substrate
Rh Ensemble Catalyst for Effective Automobile Exhaust Treatment
(from left: Professor Hyunjoo Lee and PhD candidate Hojin Jeong) A KAIST research team has developed a fully dispersed Rh ensemble catalyst (ENS) that shows better performance than commercial diesel oxidation catalyst (DOC). This newly developed ENSs could improve low-temperature automobile exhaust treatment. Precious metals have been used for various heterogeneous reactions, but it is crucial to maximize efficiency of catalysts due to their high cost. Single-atom catalysts (SACs) have received much attention because it is possible for all of the metal atoms to be used for reactions, yet they do not show catalytic activity for reactions that require ensemble sites. Meanwhile, hydrocarbons, such as propylene (C3H6) and propane (C3H8) are typical automobile exhaust gas pollutants and must be converted to carbon dioxide (CO2) and water (H2O) before they are released as exhaust. Since the hydrocarbon oxidation reaction proceeds only during carbon-carbon (C-C) or carbon-hydrogen (C-H) bond cleavage, it is essential to secure the metal ensemble site for the catalytic reaction. Therefore, precious metal catalysts with high dispersion and ensemble sites are greatly needed. To solve this issue, Professor Hyunjoo Lee from the Department of Chemical and Biomolecular Engineering and Professor Jeong Woo Han from POSTECH developed an Rh ensemble catalyst with 100% dispersion, and applied it to automobile after-treatment. Having a 100% dispersion means that every metal atom is used for the reaction since it is exposed on the surface. SACs also have 100% dispersion, but the difference is that ENSs have the unique advantage of having an ensemble site with two or more atoms. As a result of the experiment, the ENSs showed excellent catalytic performance in CO, NO, propylene, and propane oxidation at low temperatures. This complements the disadvantage of nanoparticle catalyst (NPs) that perform catalysis poorly at low temperatures due to low metal dispersion, or SACs without hydrocarbon oxidation. In particular, the ENSs have superior low-temperature activity even better than commercial DOC, hence they are expected to be applied to automobile exhaust treatment. Professor Lee said, “I believe that the ENSs have given academic contribution for proposing a new concept of metal catalysts, differentiating from conventional SACs and NPs. At the same time, they are of great value in the industry of exhaust treatment catalysts.” This research, led by PhD candidate Hojin Jeong, was published in the Journal of the American Chemical Society on July 5. Figure 1. Concept of Rh ensemble catalyst for automobile exhaust treatment Figure 2. Structure and performance comparison of single-atom catalyst and ensemble catalyst Figure 3. Energy-dispersive X-ray spectroscopy (EDS) mapping images for SAC, ENS, and NP, respectively (green, Eh; red, Ce)
Levitating 2D Semiconductor for Better Performance
(from top: Professor Yeon Sik Jung and PhD candidate Soomin Yim) Atomically thin 2D semiconductors have been drawing attention for their superior physical properties over silicon semiconductors; nevertheless, they are not the most appealing materials due to their structural instability and costly manufacturing process. To shed some light on these limitations, a KAIST research team suspended a 2D semiconductor on a dome-shaped nanostructure to produce a highly efficient semiconductor at a low cost. 2D semiconducting materials have emerged as alternatives for silicon-based semiconductors because of their inherent flexibility, high transparency, and excellent carrier transport properties, which are the important characteristics for flexible electronics. Despite their outstanding physical and chemical properties, they are oversensitive to their environment due to their extremely thin nature. Hence, any irregularities in the supporting surface can affect the properties of 2D semiconductors and make it more difficult to produce reliable and well performing devices. In particular, it can result in serious degradation of charge-carrier mobility or light-emission yield. To solve this problem, there have been continued efforts to fundamentally block the substrate effects. One way is to suspend a 2D semiconductor; however, this method will degrade mechanical durability due to the absence of a supporter underneath the 2D semiconducting materials. Professor Yeon Sik Jung from the Department of Materials Science and Engineering and his team came up with a new strategy based on the insertion of high-density topographic patterns as a nanogap-containing supporter between 2D materials and the substrate in order to mitigate their contact and to block the substrate-induced unwanted effects. More than 90% of the dome-shaped supporter is simply an empty space because of its nanometer scale size. Placing a 2D semiconductor on this structure creates a similar effect to levitating the layer. Hence, this method secures the mechanical durability of the device while minimizing the undesired effects from the substrate. By applying this method to the 2D semiconductor, the charge-carrier mobility was more than doubled, showing a significant improvement of the performance of the 2D semiconductor. Additionally, the team reduced the price of manufacturing the semiconductor. In general, constructing an ultra-fine dome structure on a surface generally involves costly equipment to create individual patterns on the surface. However, the team employed a method of self-assembling nanopatterns in which molecules assemble themselves to form a nanostructure. This method led to reducing production costs and showed good compatibility with conventional semiconductor manufacturing processes. Professor Jung said, “This research can be applied to improve devices using various 2D semiconducting materials as well as devices using graphene, a metallic 2D material. It will be useful in a broad range of applications, such as the material for the high speed transistor channels for next-generation flexible displays or for the active layer in light detectors.” This research, led by PhD candidate Soomin Yim, was published in Nano Letters in April. Figure 1. Image of a 2D semiconductor using dome structures
Platinum Catalyst Has Price Lowed and Durability Doubled
(Professor Cho in the Department of Materials Science and Engineering) Professor EunAe Cho in the Department of Materials Science and Engineering reported a fuel cell catalyst that shows 12 times higher performance and twice the durability than previously used platinum catalyst. Fuel cells, eco-friendly power generators, are said to be running air purifiers. A hydrogen vehicle powered by fuel cells can allegedly purify more than 98 percent of the particulate matter and ultrafine particles from the amount of air that 70 adults breathe. Despite this peculiarity, the high price of platinum, which is used as an electrode catalyst, remains a big challenge to accelerating commercialization. In addition, recently developed ‘nano-structured platinum catalysts’ have not yet commercialized due to its meager oxygen reduction reaction and durability in fuel cell. Addressing all those challenges, Professor Cho’s team reported a platinum catalyst costing 30 percent less but boasting 12 times higher performance. The research team, to this end, combined the platinum with nickel, then applied various metallic elements for making the most efficient performance. Among others, they found that the addition of gallium can modulate the oxygen intermediate binding energy, leading to enhanced catalytic activity of the oxygen reduction reaction. They made octahedron nanoparticle platinum-nickel alloy and could efficiently achieve 12-times high performance with the platinum catalyst by adding gallium to the surface of octahedron. Existing fuel cell catalysts have issues in practical fuel cell applications. However, Professor Cho’s team experimentally proved the high performance of the catalyst even in the fuel cell, and is expected to be practically applied to the existing procedure. First author JeongHoon Lim said their work demonstrates the gallium-added octahedral nanoparticles can be utilized as a highly active and durable oxygen reduction reaction catalyst in practical fuel cell applications. It will make it feasible for the mass production of the catalysts. Professor Cho also said, “Our study realized the two main goals: an affordable price and increased performance of fuel cells. We hope this will make a contribution to the market competitiveness of fuel cell electric vehicles.” This research was described in Nano Letters in April and was supported by the Korea Institute of Energy Technology Evaluation and Planning (KETEP), the National Research Foundation (NRF), and the Agency for Defense Development (ADD). (Figure: HAADF STEM images with EDX analyses and line scanning profiles of (a) Ga-PtNi/C and (b) PtNi/C during the voltage-cycling tests. The composition changes of Ni, Pt, and Ga atoms in the nanoparticles were determined by EDX (inset in the EDX mapping results)).
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