Nanostructured Spinel Oxides as Bi-functional Electrocatalysts for Rechargeable Metal-Air Batteries

Due to continuously increasing energy demands, particularly with the emergence of electric vehicles (EV), smart energy grids, and portable electronics, advanced energy conversion and storage systems such as fuel-cells and metal-air batteries have drawn tremendous research and industrial attention. Even though the lithium-ion battery technology is the most developed and widely distributed energy device for a wide range of applications, some researchers view its energy density insufficient for fulfilling the ultimate requirements of highly energy intensive applications such as EVs. Recently, zinc-air batteries have re-gained research attention since the initial development in the 1970s due to their remarkably highly energy density and the potential to be electrically rechargeable. However, some technological hurdles such as low charge/discharge energy efficiency, and insufficient cycle stability have hampered commercialization and introduction of rechargeable zinc-air batteries to the market. The mentioned hurdles are currently the main challenges of rechargeable zinc-air battery developed, and they stem from the fact that the reaction kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are intrinsically very sluggish. The two are the main electrochemical reactions that govern the charge and discharge processes of a rechargeable metal-air battery at the air electrode, and these oxygen reactions must be facilitated by active electrocatalysts in order to progress them at practically viable and stable rates. Currently, the best known catalysts for ORR and OER are carbon supported platinum (Pt/C) and iridium (Ir/C), respectively. However, the use of these precious metal based catalysts for large scale applications like EVs and energy storage systems is prohibitively expensive. Additionally, the durability of these catalysts have been reported to be insufficient for long-term usage under normal device operating conditions. Perhaps most importantly, the precious metal based catalysts are strongly active towards only one of the two oxygen reactions required for rechargeable applications. For example, Pt/C is a strong ORR active catalyst, while Ir/C is a strong OER active catalyst. Recently in the literature, a simple physical mixture of these two catalysts have been used to render bi-functionality, but this method is very rudimentary and still requires two separate syntheses for each catalyst. This suggests that future bi-functionally active catalysts must not only be non-precious (inexpensive), but also a single active material capable of catalyzing both ORR and OER over the same active surface. Having said above, non-precious catalyst research, specifically for bi-functional ORR and OER electrocatalyses, has increased dramatically beginning in the 90’s with a very popular and positive belief in the energy community that rechargeable lithium-air batteries could potentially replace lithium-ion batteries. This wave of interest has also picked up research in rechargeable zinc-air batteries since the electrochemical oxygen reactions that take place at the air electrodes are fundamentally very similar. Additionally, the use of zinc metal as the anode, which is one of Earth’s most abundant elements, and the water-based (aqueous) solutions as the electrolyte (as opposed to organic ones) made the rechargeable zinc-air battery development very attractive and seemingly easy to scale-up. Moreover, primary (non-rechargeable) zinc-air batteries have already been commercialized and are available in the market as hearing aid batteries, leading many researchers to believe that a simple tuning of the current technology would lead to a successful secondary (rechargeable) zinc-air battery development. However, there are a set of technical difficulties specific to rechargeable zinc-air batteries that have slowed the development for the past few decades. Therefore, the work presented in this thesis aims to address the challenges of rechargeable zinc-air batteries particularly from the active bi-functional electrocatalyst standpoint to make them as commercially viable as possible. In the first study, a facile hydrothermal materials synthesis technique has been employed to synthesize a non-precious metal cobalt oxide bi-functional catalyst. Microscopic characterizations have revealed the morphology of this material to be mesoporous hexagonal nanodisks, a high surface area catalyst compared to simple granular nanoparticles which enhances active site exposure and transport of reactants during the electrochemical reactions. This unique nanostructure has been made possible with the addition of surface-active agents that played a role of capping agent, binding to specific crystal faces and allowing growth of cobalt oxide only in certain directions. Additionally, the adsorbed capping agent has been found to leave mesopores on the nanodisks as it decomposes during the heat treatment following the hydrothermal process. Compared to randomly shaped nanoparticle catalyst of the same atomic composition, the mesoporous nanodisks greatly outperformed in terms of both charge and discharge performance of a rechargeable zinc-air battery. In the second study, the bi-functional capabilities of the cobalt oxide catalyst towards the ORR and OER in the first study have been improved by introducing nickel metal substituents into the spinel crystal lattice, as well as adapting a highly conductive nano-structured carbon support. The bi-functional activity enhancements have been attributed to an increase in electrical conductivity of spinel cobalt oxide with the insertion of nickel atoms into specific interstitial sites of the spinel lattice, as well as the high surface area nano-carbon support which helped to disperse the active spinel oxide catalyst and facilitate charge transfer during the electrochemical reactions. In the third study, the effect of nickel and manganese insertion into the spinel cobalt oxide lattice on the bi-functional catalytic activity has been studied more in detail. Spinel oxide catalysts with different atomic compositions, including cobalt oxide (un-doped), nickel cobalt oxide, and manganese cobalt oxide, have been synthesized as nanocrystals that self-assembled into high surface area porous spheres. Based on the electrochemical evaluation, the best overall bi-functional catalytic activity has been observed with nickel-substituted cobalt oxide, while the least has been observed with manganese cobalt oxide, with pristine cobalt oxide in the middle. Interestingly, computational modelling of these catalysts has resulted in the same activity trend, confirming the importance of choosing an appropriate metal substituent depending on the level of bi-functional activity required. In the last study, the knowledge gained from the high surface area nanostructured spinel oxide catalysts has been transferred to the fabrication of active catalyst/current collector assemblies. Specifically, cobalt oxide nanowire array has been directly grown on stainless steel mesh, a typical current collector used for zinc-air batteries. This unique active electrode assembly design greatly simplified battery architecture and the preparation steps required to produce a rechargeable air electrode, which usually involve physical deposition techniques such as spray-coating to deposit as-synthesized catalysts on gas diffusion layers. During this step, catalyst is mixed with ancillary materials such as carbon black and polymer ionomer, which corrode during battery charging. The direct coupling of active cobalt oxide catalyst onto the current collector completely eliminated the use of any additional material, and a gas diffusion layer was simply attached to the active assembly to form a rechargeable air electrode. Without any corrosion, the advanced electrode has demonstrated a remarkable durability during rechargeable zinc-air battery testing, lasting over 600 hours of operation, which has never been reported in the literature. There are still a plenty of opportunities to further leverage the knowledge and experience gained from this thesis work to improve the performance of electrically rechargeable zinc-air batteries. For example, the cobalt oxide nanowire arrays can be doped with other metals such as nickel and manganese to precisely tune the bi-functional catalytic activity depending on specific requirements for the battery application. Also, the idea of high surface area nano-carbon support can be used to fabricate an interfacial layer between the cobalt oxide array and stainless steel mesh to improve charge transfer during the reactions. Graphitized carbon, such as graphene nanosheets and carbon nanotubes, that are stable in rechargeable zinc-air battery conditions are great candidates for this purpose and is likely to significantly improve both the activities of ORR and OER

BlindHarmony: "Blind" Harmonization for MR Images via Flow model

In MRI, images of the same contrast (e.g., T$_1$) from the same subject can exhibit noticeable differences when acquired using different hardware, sequences, or scan parameters. These differences in images create a domain gap that needs to be bridged by a step called image harmonization, to process the images successfully using conventional or deep learning-based image analysis (e.g., segmentation). Several methods, including deep learning-based approaches, have been proposed to achieve image harmonization. However, they often require datasets from multiple domains for deep learning training and may still be unsuccessful when applied to images from unseen domains. To address this limitation, we propose a novel concept called `Blind Harmonization', which utilizes only target domain data for training but still has the capability to harmonize images from unseen domains. For the implementation of blind harmonization, we developed BlindHarmony using an unconditional flow model trained on target domain data. The harmonized image is optimized to have a correlation with the input source domain image while ensuring that the latent vector of the flow model is close to the center of the Gaussian distribution. BlindHarmony was evaluated on both simulated and real datasets and compared to conventional methods. BlindHarmony demonstrated noticeable performance on both datasets, highlighting its potential for future use in clinical settings. The source code is available at: https://github.com/SNU-LIST/BlindHarmonyComment: ICCV 2023 accepted. 9 pages and 5 Figures for manuscipt, supplementary include

Differential profiling of breast cancer plasma proteome by isotope-coded affinity tagging method reveals biotinidase as a breast cancer biomarker

<p>Abstract</p> <p>Background</p> <p>Breast cancer is one of the leading causes of women's death worldwide. It is important to discover a reliable biomarker for the detection of breast cancer. Plasma is the most ideal source for cancer biomarker discovery since many cells cross-communicate through the secretion of soluble proteins into blood.</p> <p>Methods</p> <p>Plasma proteomes obtained from 6 breast cancer patients and 6 normal healthy women were analyzed by using the isotope-coded affinity tag (ICAT) labeling approach and tandem mass spectrometry. All the plasma samples used were depleted of highly abundant 6 plasma proteins by immune-affinity column chromatography before ICAT labeling. Several proteins showing differential abundance level were selected based on literature searches and their specificity to the commercially available antibodies, and then verified by immunoblot assays.</p> <p>Results</p> <p>A total of 155 proteins were identified and quantified by ICAT method. Among them, 33 proteins showed abundance changes by more than 1.5-fold between the plasmas of breast cancer patients and healthy women. We chose 5 proteins for the follow-up confirmation in the individual plasma samples using immunoblot assay. Four proteins, α1-acid glycoprotein 2, monocyte differentiation antigen CD14, biotinidase (BTD), and glutathione peroxidase 3, showed similar abundance ratio to ICAT result. Using a blind set of plasmas obtained from 21 breast cancer patients and 21 normal healthy controls, we confirmed that BTD was significantly down-regulated in breast cancer plasma (Wilcoxon rank-sum test, <it>p </it>= 0.002). BTD levels were lowered in all cancer grades (I-IV) except cancer grade zero. The area under the receiver operating characteristic curve of BTD was 0.78. Estrogen receptor status (<it>p </it>= 0.940) and progesterone receptor status (<it>p </it>= 0.440) were not associated with the plasma BTD levels.</p> <p>Conclusions</p> <p>Our study suggests that BTD is a potential serological biomarker for the detection of breast cancer.</p

Picture Quality and Sound Quality of OLED TVs

Unlike the past when cathode-ray tube (CRT) dominated display industry, many different types of flat panel displays (FPDs) are now leading the industry. Of these, organic light-emitting diode (OLED) display has recently become a next-generation display since this display is recognised as having advantages over other competing technologies in picture quality and form factor. With major attributes of picture quality considered, a series of evaluations based on objective measures was performed with an OLED TV compared to an LCD TV. OLED TV outperformed LCD TV 100 times in black, 20 times in colour contrast, 30% in dynamic range coverage, 50 times in local contrast and 20 times in viewing angle. In addition, sound quality of the OLED TV was assessed using both objective and subjective evaluation methods compared to conventional TV speakers since OLED panel speaker technology was recently commercialised. The OLED panel speaker showed better performance both in objective and subjective methods

Novel epitheliomesenchymal biphasic stomach tumour (gastroblastoma) in a 9-year-old: morphological, usltrastructural and immunohistochemical findings

Gastroblastoma is a rare gastric epitheliomesenchymal biphasic tumour composed of spindle and epithelial cells, reported by Miettinen et al in a series of three cases in 2009. All those cases arose in stomachs of young adults. Neither the epithelial nor the mesenchymal component displayed sufficient atypia to diagnose a carcinosarcoma or other malignancy. On immunohistochemistry, the epithelial component expressed cytokeratin, and the mesenchymal component was positive for vimentin and CD10. Miettinen et al designated these neoplasms as gastroblastomas based on their similarities with other childhood blastomas such as pleuropulmonary blastoma and nephroblastoma. This report describes a probable fourth case of this unique type of neoplasm. The present case arose in the gastric antrum of a 9-year-old boy. While similarities were evident with the other cases, there were some differences. The epithelial component was more predominant and showed more mature morphology. Immunohistochemically, the epithelial component showed immunolabelling for c-KIT and CD56. The mesenchymal component was only focally positive for CD10. Ultrastructually, desmosomes and microvilli were found supporting a truly epithelial lesion

Genome-wide association study to identify novel loci and genes for Fusarium root rot resistance in sweet potato using genotyping-by-sequencing

Fusarium root rot, caused by Fusarium solani, is a major post-harvest disease in sweet potatoes (Ipomoea batatas (L.) Lam.). An effective strategy for controlling this disease is the development of resistant varieties. In this study, a genome-wide association study (GWAS) was conducted on 96 sweet potato genotypes to identify novel candidate loci and dissect the genetic basis of Fusarium root rot resistance. Genotyping was performed using genotyping-by-sequencing (GBS), and 44,255 SNPs were identified after filtering. The genotypes (n = 96) were evaluated through resistance tests in 2021 and 2022, separately and combined. The GWAS identified two significant SNP markers (LG3_22903756 and LG4_2449919) on chromosomes 3 and 4 associated with Fusarium root rot resistance, respectively. Lesion length showed significant differences between homozygous A and G alleles of LG3_22903756, which can potentially be used to develop molecular markers for selecting accessions resistant to Fusarium root rot. Expression analysis of 11 putative genes flanking the significant SNPs revealed the alteration in the expression of nine genes, indicating their possible involvement in Fusarium root rot resistance. The results of this study will aid in the marker-assisted selection and functional analysis of candidate genes for Fusarium root rot resistance in sweet potatoes

Construction of a DNA Chip for Screening of Genetic Hearing Loss

ObjectivesHearing loss is the most common sensory disorder in humans and genetic causes are estimated to cause more than 50% of all incidents of congenital hearing loss. To develop an efficient method for a genetic diagnosis of hearing loss, we have developed and validated a genetic hearing loss DNA chip that allows the simultaneous analysis of 7 different mutations in the GJB2, SLC26A4, and the mtDNA 12S rRNA genes in Koreans.MethodsA genotyping microarray, based on the allele-specific primer extension (ASPE) method, was used and preliminary validation was examined from the five patients and five controls that were already known their genotypes by DNA sequencing analysis.ResultsThe cutoff Genotyping index (GI) of genotyping for each mutation was set up and validated to discriminate among the genotypes. The result of the DNA chip assay was identical to those of previous results.ConclusionWe successfully designed the genetic hearing loss DNA chip for the first time in Korea and it would be useful for a clinical genetic diagnosis of hearing loss. Further consideration will be needed in order to examine the accuracy of this DNA chip with much larger patient sample numbers