https://scholarworks.unist.ac.kr/handle/201301/13 2026-04-17T06:27:20Z https://scholarworks.unist.ac.kr/handle/201301/91355 Title: Predictive Synthesis of Reticular Materials in the Era of Physical AI Author(s): Choe, Wonyoung 2026-04-08T15:00:00Z https://scholarworks.unist.ac.kr/handle/201301/91342 Title: Unveiling an {FeNO}6 Intermediate: A Sequential Mechanistic Investigation of Nitrite Reduction in a Mononuclear Iron(II) Complex Author(s): Sun, Seungwon; Jeon, Youngjin; Lee, Youngseob; Kim, Hyokyung; Kang, Vom; Hwang, Seung Jun; Cho, Kyung-Bin; Cho, Jaeheung Abstract: The reduction of nitrite (NO2 -) to nitric oxide (NO center dot) is a fundamental transformation within both the global nitrogen cycle and enzymatic signaling pathways. Although extensively investigated, the elusive {FeNO}6 intermediate implicated in the 2H+/1e- reduction pathway has rarely been observed or isolated due to the inherent instability. Here, we present a comprehensive mechanistic investigation of nitrite reduction by a mononuclear iron(II)-nitrite complex, [FeII(TBDAP)(NO2)(CH3CN)]+ (1) (TBDAP = N,N '-di-tert-butyl-2,11-diaza[3.3](2,6)-pyridinophane). Treatment of 1 with 2.5 equiv of triflic acid (HOTf) affords the {FeNO}6 (2) intermediate, which was characterized using a combination of various physicochemical techniques and DFT calculations. Isotopic labeling using Na15NO2 confirmed the formation of 2 via heterolytic N-O bond cleavage. Kinetic studies revealed a HOTf-independent rate constant and a markedly negative value of activation entropy for the formation of 2, suggesting that the rate-determining step involves an associative reaction between Fe(II) and NO+. Electrochemical analysis showed a reversible redox couple for 2, and subsequent one-electron reduction by ferrocene released NO center dot. The generation of NO center dot was confirmed through trapping experiments using [Co(TPP)], resulting in the formation of [Co(TPP)(NO)]. The experimental findings establish {FeNO}6 as an isolable and reactive intermediate, offering new insight into the mechanistic landscape of nitrite reduction. 2026-02-28T15:00:00Z https://scholarworks.unist.ac.kr/handle/201301/91314 Title: Dual Enzyme-Responsive Zwitterionic Peptide for High Cancer Selectivity via Intralysosomal Self-Assembly Author(s): Kim, Dohyun; Jang, Jiwon; Jin, Seongeon; Lee, Jaemo; Jana, Batakrishna; Ryu, Ja-Hyoung Abstract: The major challenges in cancer chemotherapy are the severe side effects of the chemotherapeutic drugs due to their off-target toxicity to normal cells. Peptide amphiphiles capable of enzyme-instructed intracellular self-assembly have emerged as biocompatible alternatives, yet achieving high cancer selectivity remains challenging. Herein, we reported a dual enzyme-responsive zwitterionic peptide assembly, which undergoes matrix metalloproteinase induced-disassembly and cathepsin B instructed-assembly to form the fiber in the cancerous lysosome. This sequential enzymatic process induces lysosomal membrane permeabilization and cancer cell death at low micromolar concentrations while remaining inactive in normal cells lacking these enzymes. As a result, very high cancer selectivity (cancer selectivity index of 64.1) is achieved with our designed peptide amphiphiles. The peptide amphiphile also shows significant tumor regression with low doses and no in vivo toxicity tested in the human colorectal adenocarcinoma cell line (HT-29) xenograft tumor model. 2026-01-31T15:00:00Z https://scholarworks.unist.ac.kr/handle/201301/91313 Title: Dynamic Microinterfacial Polymerization Enables Scalable Synthesis of Two-Dimensional Polymer Sheets for Quasi-Solid-State Electrolytes in Sodium-Metal Batteries Author(s): Ji, Xiaolei; Ma, Jiaying; Wang, Zhongli; Shi, Xiang; Wang, Jiamin; Meng, Xiaodong; Bielawski, Christopher W.; Geng, Jianxin Abstract: Organic two-dimensional (2D) materials hold great potential in a broad range of applications. However, their practical utility is constrained by limited structural diversity and a lack of synthetic strategies. Herein, we report that simply stirring immiscible solutions of poly(propylene glycol)bis(2-aminopropyl ether) and 1,3,5-benzenetricarbonyl trichloride results in a dynamic microinterfacial polymerization that affords novel 2D polymer sheets (designated as PEO-BTA). These sheets can be transformed to Na-ion conducting materials via treatment with sodium hydride, followed by incorporation of a prototypical MOF, HKUST-1, to obtain composite sheets (MOF@PEO-BTA-Na) that retain the structural integrity of the original 2D polymer sheets. The 2D composite sheets can be assembled into self-supporting membranes and used as a quasi-solid-state electrolyte (QSSE) with a remarkably high ionic conductivity value of 2.80 x 10-3 S cm-1 and a Na+ transference number of 0.95. Consequently, the QSSE facilitates uniform Na plating in Na//Na and Na//Cu cells. Na//NaTi2(PO4)3 cells containing MOF@PEO-BTA-Na QSSE exhibit a high initial specific capacity (129.1 mAh g-1 at 0.5 C), superior rate capability (60.0 mAh g-1 at 20 C), and high-capacity retention (92% after 1000 cycles at 1 C). This work establishes a new, scalable approach for synthesizing 2D organic sheets with promising applications in energy-related areas. 2026-01-31T15:00:00Z