Precise Modulation of Triple-Phase Boundaries towards a Highly Functional Exsolved Catalyst for Dry Reforming of Methane under a Dilution-Free System

Dry reforming of methane (DRM) has been emerging as a viable solution to achieving carbon neutrality enhanced by the Paris Agreement as it converts the greenhouse gases of CO2 and CH4 into industrially useful syngas. However, there have been limited studies on the DRM catalyst under mild operating conditions with a high dilution gas ratio due to their deactivation from carbon coking and metal sintering. Herein, we apply the triple-phase boundary (TPB) concept to DRM catalyst via exsolution phenomenon that can secure elongated TPB by controlling the Fe-doping ratio in perovskite oxide. Remarkably, the exsolved catalyst with prolongated TPB shows exceptional CO2 and CH4 conversion rates of 95.9 % and 91.6 %, respectively, stable for 1000 hours under a dilution-free system. DFT calculations confirm that the Lewis acid of support and Lewis base of metal at the TPB promote the adsorption of reactants, resulting in lowering the overall CO2 dissociation and CH4 dehydrogenation energy

Unveiling the key factor for the phase reconstruction and exsolved metallic particle distribution in perovskites

To significantly increase the amount of exsolved particles, the complete phase reconstruction from simple perovskite to Ruddlesden-Popper (R-P) perovskite is greatly desirable. However, a comprehensive understanding of key parameters affecting the phase reconstruction to R-P perovskite is still unexplored. Herein, we propose the Gibbs free energy for oxygen vacancy formation in Pr-0.5(Ba/Sr)(0.5)TO3-delta (T = Mn, Fe, Co, and Ni) as the important factor in determining the type of phase reconstruction. Furthermore, using in-situ temperature & environment-controlled X-ray diffraction measurements, we report the phase diagram and optimum 'x' range required for the complete phase reconstruction to R-P perovskite in Pr0.5Ba0.5-xSrxFeO3-delta system. Among the Pr0.5Ba0.5-xSrxFeO3-delta, (Pr0.5Ba0.2Sr0.3)(2)FeO4+delta - Fe metal demonstrates the smallest size of exsolved Fe metal particles when the phase reconstruction occurs under reducing condition. The exsolved nano-Fe metal particles exhibit high particle density and are well-distributed on the perovskite surface, showing great catalytic activity in fuel cell and syngas production. The complete phase reconstruction to Ruddlesden-Popper perovskite is greatly desirable to increase the exsolved particle distribution. Here, the authors report a key factor for the complete phase reconstruction in perovskites, leading to good catalytic activity in fuel cell and syngas production

Early Growth Response 1-Dependent Downregulation of Matrix Metalloproteinase 9 and Mouse Double Minute 2 Attenuates Head and Neck Squamous Cell Carcinoma Metastasis

Background/Aims: The functional relevance of early growth response-1 (EGR1) on cancer invasion remains controversial. The effect of EGR1 on the expression of MMP9, which is important for HNSCC invasion, is still disputed. There is no previous data showing the effect of EGR1 on mouse double minute 2 (MDM2), an enhancer of matrix metalloproteinase 9 (MMP9) expression. Our aim is to clarify the negative correlation between EGR1 expression and head and neck squamous cell carcinoma (HNSCC) metastasis. Methods: EGR1 mRNA and protein expressions were compared in normal and HNSCC tissues using The Cancer Genome Atlas (TCGA) dataset analysis or immunohistochemistry (IHC), respectively. In vitro cell invasion was evaluated Matrigel invasion assay. EGR1-dependent inhibition of MDM2 transcription was assessed by promoter–luciferase assay and chromatin immunoprecipitation (ChIP). Results: TCGA data showed that EGR1 mRNA levels are significantly higher in normal oral tissues as compared with HNSCC tumor tissues (adjusted P = 1.64x10-16). In addition, nonmetastatic HNSCC tissues showed significantly higher EGR1 mRNA levels as compared with metastatic tissues (adjusted P = 0.023). IHC analysis showed that primary tumor tissues expressed significantly higher levels of nuclear EGR1 compared with paired metastatic lymph node tissues (P < 0.05). EGR1 overexpression downregulated MMP9 and MDM2 protein expression. Consistent with these observations, TCGA data analysis found significantly fewer metastatic patients among a subgroup of population presenting higher EGR1 expressions with lower MMP9 and/or MDM2. Conclusion: Our data suggests that EGR1 prevents HNSCC metastasis through downregulation of MMP9 and MDM2. EGR1 might be a potential candidate to attenuate HNSCC metastasis

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School of Energy and Chemical Engineering (Energy Engineering)With an increasing demand for carbon emission reduction and hydrogen society sparked by the Paris agreement, dry reforming of methane (DRM) has brought into the spotlight more than ever as it converts greenhouse gases of CO2 and CH4 to syngas (a mixture of H2 and CO). Heterogeneous catalysts have been studied as an effective breakthrough to promote the industrialization of DRM. Especially, exsolution phenomena can be a promising platform in designing size-controlled and uniformly distributed catalysts, resulting in high catalytic performance and stability. Exsolution induces partially segregated nanoparticles which are in situ grown from the bulk lattice of perovskite oxide under reducing conditions. Such embedded morphology of the exsolved nanoparticles strengthens the interaction between metal and support oxide, leading to the enhanced durability of the catalyst. There have been numerous studies conducted on the origin of the enhanced catalytic performance of exsolution. However, most of the studies have been limitedly focused on controlling the parameters related to metal given that metal is the active site for DRM reaction. Since exsolved nanoparticles form a unique interface with the support oxide, the influence of the interface on the reaction should be taken into account, in contrast to the conventional supported catalysts where metal is the almost only active site as it forms a shallow interface. This thesis begins with the basic and theoretical explanation of DRM and exsolution phenomena. In chapter 2, precise modulation of triple-phase boundaries towards highly functional exsolved catalyst for dry reforming of methane under dilution-free system is discussed.clos

Associations between weekend catch-up sleep and health-related quality of life with focusing on gender differences

Abstract This study investigated associations between weekend catch-up sleep (WCUS) and health-related quality of life (HRQoL) in 15,837 participants from the 7th (2016–2018) Korea National Health and Nutrition Examination Survey. We categorized WCUS durations into four groups: none (≤ 0 h [h]), short (> 0 h, ≤ 1 h), medium (> 1 h, ≤ 2 h), and long (> 2 h), and performed complex samples logistic regression and likelihood ratio χ2 test. The study found significant associations in women for the European Quality of Life-5 Dimensions (EQ-5D) index and three EQ-5D subdomains (self-care, usual activities, and anxiety/depression) with the WCUS durations, but no significant association in men. Compared to the non-WCUS, the short or medium WCUS was positively associated with the EQ-5D index and EQ-5D subdomains (usual activities and anxiety/depression) in women, while the long WCUS significantly reduced the quality of life in the self-care domain. In an additional subgroup analysis by age, middle-aged and elderly women had a more noticeable effect of WCUS on HRQoL than young women, and the short or medium WCUS improved HRQoL in middle-aged and elderly women in general. Therefore, we recommend appropriate WCUS durations to improve HRQoL, considering both gender and age

Luteolin Synergistically Enhances Antitumor Activity of Oxaliplatin in Colorectal Carcinoma via AMPK Inhibition

Luteolin is a naturally-occurring polyphenolic compound that is known to have antioxidative and antitumor activities in vitro. This study aimed to examine the in vivo anticancer efficacy of luteolin in conjunction with oxaliplatin treatment using a colorectal carcinoma xenograft mouse model. HCT116 human colorectal carcinoma cells were subcutaneously implanted into BALB/c nude mice, followed by the intraperitoneal administration of luteolin at a dose of 50 mg/kg body weight (BW)/day with or without oxaliplatin at a dose of 10 mg/kg BW/day three times per week for a total of 3 weeks. The combined luteolin and oxaliplatin treatment resulted in the synergistic suppression of the growth of HCT116 xenograft tumors when compared to treatment with luteolin or oxaliplatin alone. In addition, the combined treatment significantly increased the expression of cleaved PARP and p53 in the xenograft tumors compared with the vehicle control, but only marginally affected the level of heme oxygenase-1 (HO-1). These results indicated that luteolin treatment retarded oxaliplatin-induced tumor growth by facilitating apoptotic cell death and inhibiting HO-1-mediated cytoprotection. Therefore, these findings suggest the synergistic potential of dietary luteolin in conjunction with conventional chemotherapy for the treatment of colorectal cancer

NGFI-A Binding Protein 2 Promotes EGF-Dependent HNSCC Cell Invasion

NGFI-A binding protein 2 (NAB2) represses the transcriptional activation of early growth response protein-1 (EGR1), a tumor-suppressor. However, Epidermal Growth Factor (EGF) promotes tumor progression even with significant EGR1 upregulation. The molecular mechanism through which NAB2 is involved in cancer is largely unknown. Therefore, we evaluated how the NAB2-mediated suppression of EGR1 facilitates head and neck squamous cell carcinoma (HNSCC) cancer progression, in association with Sp1, which competes with EGR1 as a transcriptional regulator. The effect of NAB2 on EGR1/SP1 binding to the consensus promoter sequences of MMP2 and MMP9 was evaluated by chromatin immunoprecipitation (ChIP) and promoter luciferase assay. The correlation between EGR1-NAB2 expression and metastatic status was investigated using The Cancer Genome Atlas (TCGA) for HNSCC patients. Our data showed that NAB2 knockdown in FaDu and YD-10B HNSCC cells alleviated EGF-dependent increase of Matrigel invasion. In addition, NAB2 upregulation in EGF-treated FaDu cell diminishes EGR1 transcriptional activity, resulting in the upregulation of Sp1-dependent tumor-promoting genes. TCGA data analysis of 483 HNSCC tumors showed that higher levels of both EGR1 and NAB2 mRNA were significantly associated with metastasis, corresponding to in vitro results. Our data suggest that NAB2 upregulation facilitates EGF-mediated cancer cell invasion through the transactivation of Sp1-dependent tumor-promoting genes. These results provide insight into the paradoxical roles of EGF-EGR1 in cancer progression

NAB 2-Expressing Cancer-Associated Fibroblast Promotes HNSCC Progression

Cancer-associated fibroblast (CAF)-specific proteins serve as both prognostic biomarkers and targets for anticancer drugs. In this study, we investigated the role of NGFI-A-binding protein (NAB)2 derived from CAFs in the progression of head and neck squamous cell carcinoma (HNSCC). Patient-derived HNSCC and paired metastatic lymph node tissues were examined for NAB2 expression by immunohistochemistry. Primary CAF cultures were established from HNSCC patient tissue, with paired non-tumor fibroblasts (NTFs) serving as a control. CAF or NTF was used to evaluate the effect of NAB2 on HNSCC progression using FaDu cell spheroids and an in vivo mouse xenograft model. NAB2 was detected in interstitial CAFs in primary and metastatic lymph node tissues of HNSCC patients. NAB2 mRNA and protein levels were higher in CAFs as compared to paired NTFs. Conditioned medium (CM) of NAB2-overexpressing CAFs increased the invasion of FaDu spheroids in the Matrigel invasion assay as compared to CM of NTF. Co-injection of NAB2-overexpressing CAFs with FaDu spheroids into mice enhanced the growth of tumors. These data suggest that NAB2-overexpressing CAFs promotes HNSCC progression and is a potential therapeutic target for preventing HNSCC metastasis