Computational Modeling and Experimental Approaches for Understanding the Mechanisms of [FeFe]-Hydrogenase Chang-Ah Kim, Jiabin Wu, Jun Zhu, Huaiguang Li, Zhihai Ke Advanced Science, 2025 Learning from nature has emerged as a promising strategy for catalyst development, wherein the remarkable performance of catalysts selected by nature over billions of years of evolution serves as a basis for the creative design of high-performance catalysts. Hydrogenases, with their exceptional catalytic activity in hydrogen oxidation and production, have been employed as prototypes for human learning to achieve better catalyst design. A comprehensive understanding of hydrogenases' structures and catalytic mechanisms is crucial to replicate and exceed their performance. Computational modeling has proven to be a powerful tool for elucidating the reduction chemistry of [FeFe]-hydrogenases. This review overviews recent computational and experimental efforts, focusing on density functional theory (DFT) calculations applied to [FeFe] hydrogenases. It summarizes current knowledge on identifying active sites in [FeFe] hydrogenases and the reaction cycles involved in hydrogen metabolism.
Undercoordinated Two-Dimensional Pt Nanoring Stabilized by a Ring-on-Sheet Nanoheterostructure for Highly Efficient Alkaline Hydrogen Evolution Reaction Chen Ma, Weiwei Chen, Yanjie Wu, Wenbin Wang, Lei Xu, et al. Nano Letters, 2025 Platinum (Pt) is a state-of-the-art electrocatalyst for green hydrogen production in alkaline electrolytes. The delicate design and fabrication of two-dimensional (2D) Pt nanocatalysts can significantly enhance atomic utilization efficiency, while further improving intrinsic catalytic performance by modulating the density of surface active sites. However, the high surface energy and morphology complexity of 2D nanostructures often result in poor structural stability under the working conditions. Here, we report the synthesis of a 2D ring-on-sheet nanoheterostructure featuring abundant low-coordination Pt sites in which a defect-rich Pt nanoring is stabilized by an ultrathin 2D rhodium (Rh) support. The Rh@Pt nanoring exhibits remarkably enhanced activity and stability in an electrocatalytic hydrogen evolution reaction in alkaline media compared to defect-free Rh@Pt core-shell nanoplates and commercial Pt/C. This work provides new insights for the design and synthesis of 2D nanoheterostructures with abundant surface active sites for efficient and durable electrocatalysis.
Ultrasound-activated erythrocyte membrane-camouflaged Pt (II) layered double hydroxide enhances PD-1 inhibitor efficacy in triple-negative breast cancer through cGAS-STING pathway-mediated immunogenic cell death Yanjie Wu, Zhiyu Zhao, Mengli Ma, Weijin Zhang, Wei Liu, et al. Theranostics, 2025 Rationale: Immunogenic cell death (ICD) offers a promising avenue for the treatment of triple-negative breast cancer (TNBC). However, optimizing immune responses remains a formidable challenge. This study presents the design of RBCm@Pt-CoNi layered double hydroxide (RmPLH), an innovative sonosensitizer for sonodynamic therapy (SDT), aimed at enhancing the efficacy of programmed cell death protein 1 (PD-1) inhibitors by inducing robust ICD responses. Methods: Pt-CoNi layered double hydroxide (LDH) nanocages were synthesized using a two-step method, followed by functionalization with red blood cell membranes to prepare RmPLH. The in vitro assessments included evaluations of cell toxicity, cellular uptake, and sonodynamic effects of RmPLH. Key mechanisms—such as oxidative stress, DNA damage, pyroptosis, cGAS/STING pathway activation, and inhibition of cellular migration and invasion—were explored under varying treatment conditions in 4T1 cells. Tumor-bearing mice were employed to evaluate tumor-targeting capabilities and the synergistic tumor-suppressive effects of RmPLH combined with PD-1 inhibitors. Comprehensive safety evaluations, including blood tests, biochemical analyses, and histopathological examinations, were also conducted. Results: The synthesized Pt-CoNi LDH exhibited a uniform rhombic dodecahedral nanocage morphology with an average particle size of approximately 231 nm. Encapsulation with red blood cell membranes conferred prolonged systemic circulation, enhanced tumor targeting, and reduced immune clearance for RmPLH. Upon ultrasound (US) stimulation, the LDH released substantial levels of reactive oxygen species (ROS) and platinum ions. The ROS effectively induced endoplasmic reticulum stress and ferroptosis, while platinum ions facilitated DNA crosslinking, triggering significant DNA damage. ROS-induced pyroptosis released inflammatory mediators and damage-associated molecular patterns (DAMPs), which activated the cGAS/STING pathway and reinforced ICD. Combining RmPLH with PD-1 inhibitors significantly enhanced therapeutic efficacy against TNBC. Furthermore, safety assessments confirmed the excellent biocompatibility and biosafety of RmPLH. Conclusion: The integration of RmPLH with PD-1 inhibitors substantially amplifies ICD, fostering robust antigen-specific T cell immunity and offering a promising therapeutic strategy for TNBC. This study represents a pioneering application of Pt (II)-based LDH nanocages in oncology, laying a foundation for future innovations in tumor immunotherapy.
Strategies for the Preparation of Single-Atom Catalysts Using Low-Dimensional Metal–Organic Frameworks Yi Lu, Zhihai Ke Small, 2024 As single‐atom catalysts are important energy materials, their preparation and synthesis methods have become particularly important. The unique structures of low‐dimensional metal‐organic frameworks and their derivatives provide various strategies for preparing single‐atom catalysts. This paper summarizes various strategies for the preparation of single‐atom catalysts based on low‐dimensional metal‐organic frameworks and their derivatives.
Visible and selective gel assembly via covalent click chemistry Yinglin Zheng, Zhihai Ke Smartmat, 2024 This study marks the birth of visible and selective click covalent assembly. It is achieved by amplifying orthogonal alkyne−azide click chemistry through interfacial multisite interactions between azide/alkyne functionalized polymer hydrogels. Macroscopic assembly of hydrogels via host−guest chemistry or noncovalent interactions such as electrostatic interactions has been reported. Unlike macroscopic supramolecular assembly, here we report visible and selective “click” covalent assembly of hydrogels at the macroscale. LEGO‐like hydrogels modified with alkyne and azide groups, respectively, can click together via the formation of covalent bonds. Monomer concentration‐dependent assembly and selective covalent assembly have been studied. Notably, macroscopic gel assembly clearly elucidates click preferences and component selectivity not observed in the solution reactions of competing monomers.
Electrostatically assembled MnO2 nanoflower-pillared Ti3C2Tx MXene heterostructures for flexible, high-sensitivity electrochemical sensors S Jing, S Zhao, C Ruan, Z Ke Materials Today Nano 34, 100831 , 2026 2026
Autotandem Chalcogen-Bonding Catalysis: Oxaselenolium-Catalyzed Cascade Povarov–Hydrogen-Transfer Reaction Q Zhang, M Zhang, Z Ke ACS Catalysis 15 (18), 15910-15919 , 2025 2025 Citations: 1
Computational Modeling and Experimental Approaches for Understanding the Mechanisms of [FeFe]‐Hydrogenase CA Kim, J Wu, J Zhu, H Li, Z Ke Advanced Science 12 (21), 2408297 , 2025 2025
Zwitterionic Dual Halogen Bond-Catalyzed Electrophilic Bromination of Electron-Deficient Arenes under Mild Conditions M Zhang, Z Ke ACS Catalysis 15 (5), 4270-4279 , 2025 2025 Citations: 9
Undercoordinated two-dimensional Pt nanoring stabilized by a ring-on-sheet nanoheterostructure for highly efficient alkaline hydrogen evolution reaction C Ma, W Chen, Y Wu, W Wang, L Xu, C Chen, L Zheng, G Wang, P Han, ... Nano Letters 25 (8), 3212-3220 , 2025 2025 Citations: 8
Ultrasound-activated erythrocyte membrane-camouflaged Pt (II) layered double hydroxide enhances PD-1 inhibitor efficacy in triple-negative breast cancer through cGAS-STING … Y Wu, Z Zhao, M Ma, W Zhang, W Liu, X Liang, T Zhao, Y Luo, Y Wang, ... Theranostics 15 (4), 1456 , 2025 2025 Citations: 22
Phase-engineered zirconium MOF-based titanium single-atom catalysts: phase-dependent properties and applications in biodiesel synthesis Y Wu, J He, X Li, Y Chen, Z Ke Journal of Materials Chemistry A 13 (5), 3849-3857 , 2025 2025 Citations: 6
Strategies for the Preparation of Single‐Atom Catalysts Using Low‐Dimensional Metal–Organic Frameworks Y Lu, Z Ke Small 20 (42), 2403767 , 2024 2024 Citations: 16
Epitaxial Growth of Unconventional 2H Noble Metals and Crystal Phase-Dependent Selectivity of Pt in Hydrogenation Catalysis L Zheng, Y Wu, KK Li, G Wang, C Ma, C Chen, P Han, Y Zhu, Z Ke, ... ACS Materials Letters 6 (9), 4149-4157 , 2024 2024 Citations: 6
Visible and selective gel assembly via covalent click chemistry Y Zheng, Z Ke SmartMat 5 (2), e1251 , 2024 2024 Citations: 2
Sonodynamic therapy of NRP2 monoclonal antibody‐guided MOFs@ COF targeted disruption of mitochondrial and endoplasmic reticulum homeostasis to induce autophagy‐dependent … Z Zhao, Y Wu, X Liang, J Liu, Y Luo, Y Zhang, T Li, C Liu, X Luo, J Chen, ... Advanced Science 10 (30), 2303872 , 2023 2023 Citations: 77
Metal–Organic Frameworks/Graphdiyne/Copper Foam Composite Membranes for Catalytic Applications Y Wu, Y Yang, Z Ke ACS Applied Materials & Interfaces 15 (34), 40933-40941 , 2023 2023 Citations: 7
Visible covalent click chemistry via macroscopic gel assembly Y Zheng, Z Ke 2023
Zwitterionic catalysts for (trans) esterification: application in fluoroindole-derivatives and biodiesel synthesis YY YEUNG, LAM Ying-Pong, KE Zhihai, W Xinyan, F Tan, NG Wing-Hin, ... US Patent 11,583,842 , 2023 2023
Applications of the DIB–BBr 3 Protocol in Bromination Reactions L Pan, KM Lee, YY Chan, Z Ke, YY Yeung Organic Letters 25 (1), 53-57 , 2023 2023 Citations: 12
A mechanochemical, catalyst‐free cascade synthesis of 1, 3‐diols and 1, 4‐iodoalcohols using styrenes and hypervalent iodine reagents L Pan, L Zheng, Y Chen, Z Ke, YY Yeung Angewandte Chemie International Edition 61 (36), e202207926 , 2022 2022 Citations: 14
Hypervalent chalcogenonium⋅⋅⋅ π bonding catalysis Q Zhang, YY Chan, M Zhang, YY Yeung, Z Ke Angewandte Chemie International Edition 61 (35), e202208009 , 2022 2022 Citations: 50
Amphiphilic Indoles as Efficient Phase‐Transfer Catalysts for Bromination in Water Q Zhang, Y Xu, X Liang, Z Ke ChemSusChem 15 (12), e202200574 , 2022 2022 Citations: 7
Novel Cu-doped zeolitic imidazolate framework-8 membranes supported on copper foam for highly efficient catalytic wet peroxide oxidation of phenol Y Wu, Z Ke Materials Today Chemistry 24, 100787 , 2022 2022 Citations: 10
Zwitterion-ruthenium complex for catalytic aerobic oxidation reactions RB Hu, LAM Ying-Pong, NG Wing-Hin, YY YEUNG, KE Zhihai US Patent 11,298,694 , 2022 2022
MOST CITED SCHOLAR PUBLICATIONS
Catalytic Asymmetric Bromoetherification and Desymmetrization of Olefinic 1,3-Diols with C 2 -Symmetric Sulfides Z Ke, CK Tan, F Chen, YY Yeung Journal of the American Chemical Society 136 (15), 5627-5630 , 2014 2014 Citations: 198
Applications of selenonium cations as lewis acids in organocatalytic reactions X He, X Wang, YL Tse, Z Ke, YY Yeung Angewandte Chemie International Edition 57 (39), 12869-12873 , 2018 2018 Citations: 131
Design, synthesis and crystallographic analysis of nitrile-based broad-spectrum peptidomimetic inhibitors for coronavirus 3C-like proteases CP Chuck, C Chen, Z Ke, DCC Wan, HF Chow, KB Wong European journal of medicinal chemistry 59, 1-6 , 2013 2013 Citations: 124
A Platinum(II) Terpyridine Metallogel with an L ‐Valine‐Modified Alkynyl Ligand: Interplay of Pt⋅⋅⋅Pt, π–π and Hydrogen‐Bonding Interactions C Po, Z Ke, AYY Tam, HF Chow, VWW Yam Chemistry–A European Journal 19 (46), 15735-15744 , 2013 2013 Citations: 111
Desymmetrizing enantio-and diastereoselective selenoetherification through supramolecular catalysis JY See, H Yang, Y Zhao, MW Wong, Z Ke, YY Yeung ACS Catalysis 8 (2), 850-858 , 2018 2018 Citations: 95
Lewis base catalyzed stereo‐and regioselective bromocyclization MH Gieuw, Z Ke, YY Yeung The Chemical Record 17 (3), 287-311 , 2017 2017 Citations: 92
Conformational and supramolecular properties of main chain and cyclic click oligotriazoles and polytriazoles HF Chow, KN Lau, Z Ke, Y Liang, CM Lo Chemical Communications 46 (20), 3437-3453 , 2010 2010 Citations: 90
Electrochemical self-assembly of ZnO nanoporous structures GR Li, CR Dawa, Q Bu, XH Lu, ZH Ke, HE Hong, FL Zheng, CZ Yao, ... The Journal of Physical Chemistry C 111 (5), 1919-1923 , 2007 2007 Citations: 81
Sonodynamic therapy of NRP2 monoclonal antibody‐guided MOFs@ COF targeted disruption of mitochondrial and endoplasmic reticulum homeostasis to induce autophagy‐dependent … Z Zhao, Y Wu, X Liang, J Liu, Y Luo, Y Zhang, T Li, C Liu, X Luo, J Chen, ... Advanced Science 10 (30), 2303872 , 2023 2023 Citations: 77
Bis-selenonium cations as bidentate chalcogen bond donors in catalysis X He, X Wang, YLS Tse, Z Ke, YY Yeung ACS Catalysis 11 (20), 12632-12642 , 2021 2021 Citations: 66
Lewis Base‐Promoted Ring‐Opening 1, 3‐Dioxygenation of Unactivated Cyclopropanes Using a Hypervalent Iodine Reagent MH Gieuw, Z Ke, YY Yeung Angewandte Chemie 130 (14), 3844-3848 , 2018 2018 Citations: 61
Electrochemical synthesis of orientation-ordered ZnO nanorod bundles GR Li, CR Dawa, Q Bu, F Zhen, XH Lu, ZH Ke, HE Hong, CZ Yao, P Liu, ... Electrochemistry Communications 9 (5), 863-868 , 2007 2007 Citations: 60
Lewis basic sulfide catalyzed electrophilic bromocyclization of cyclopropylmethyl amide YC Wong, Z Ke, YY Yeung Organic letters 17 (20), 4944-4947 , 2015 2015 Citations: 51
Hypervalent chalcogenonium⋅⋅⋅ π bonding catalysis Q Zhang, YY Chan, M Zhang, YY Yeung, Z Ke Angewandte Chemie International Edition 61 (35), e202208009 , 2022 2022 Citations: 50
Head-to-tail dimerization and organogelating properties of click peptidomimetics Z Ke, HF Chow, MC Chan, Z Liu, KH Sze Organic letters 14 (1), 394-397 , 2012 2012 Citations: 48
Catalytic and enantioselective bromoetherification of olefinic 1, 3-diols: mechanistic insight Z Ke, CK Tan, Y Liu, KGZ Lee, YY Yeung Tetrahedron 72 (21), 2683-2689 , 2016 2016 Citations: 40
Environmentally benign indole-catalyzed position-selective halogenation of thioarenes and other aromatics Y Shi, Z Ke, YY Yeung Green Chemistry 20 (19), 4448-4452 , 2018 2018 Citations: 37
Electrophilic bromolactonization of cyclopropyl carboxylic acids using Lewis basic sulfide catalyst Z Ke, YC Wong, JY See, YY Yeung Advanced Synthesis & Catalysis 358 (11), 1719-1724 , 2016 2016 Citations: 37
Electrophilic bromolactonization of cyclopropyl diesters using Lewis basic chalcogenide catalysts MH Gieuw, VMY Leung, Z Ke, YY Yeung Advanced Synthesis & Catalysis 360 (22), 4306-4311 , 2018 2018 Citations: 32
Investigating the enantiodetermining step of a chiral lewis base catalyzed bromocycloetherification of privileged alkenes D Böse, SE Denmark Synlett 29 (04), 433-439 , 2018 2018 Citations: 32