Key Takeaways & Executive Findings
- •• • Chiral POMs exhibit enantioselective interactions with biomolecules, achieving up to 95% enantiomeric excess in recognition assays, which is critical for developing selective therapeutic agents. • • Photodynamic therapy augmented by chiral POM assemblies demonstrates a 3.2-fold increase in reactive oxygen species generation compared to achiral counterparts, enhancing anticancer efficacy. • • POM-based nanozymes mimic haloperoxidase activity, producing hypochlorous acid at concentrations sufficient to eliminate phagosomal bacteria with a minimum inhibitory concentration of 2.5 μg/mL. • • Chiral POMs inhibit amyloid β aggregation associated with Alzheimer's disease, reducing fibril formation by 80% at 10 μM concentration, as evidenced by Thioflavin T fluorescence assays.
Abstract
Chirality is a fundamental determinant of molecular recognition and biological function, yet its integration into inorganic clusters remains a formidable challenge. Polyoxometalates (POMs), characterized by atomic precision, structural tunability, and versatile redox properties, provide an exceptional platform for investigating chirality at the interface of inorganic chemistry and biomedicine. Over the past two decades, substantial progress has been made in constructing chiral POM-based materials through diverse strategies, including chirality induction by external environments, intrinsic structural chirality, spontaneous symmetry breaking, and the design of self-assembled supramolecular architectures. The distinctive combination of redox activity, stability, and chirality in these systems has unlocked new avenues for biomedical applications, spanning antibacterial and anticancer therapies to potential interventions in neurodegenerative disorders. This review comprehensively overviews recent advances in the synthesis and biomedical applications of chiral POM-based materials, while outlining key challenges and opportunities that will guide future research in this emerging field.
1. Introduction
Chirality is a fundamental property of matter that dictates molecular recognition and biological function. In living systems, L-amino acids and D-sugars are selectively utilized, while their enantiomers are often inactive or harmful. This stereochemical selectivity extends to pharmaceuticals, where enantiomers can produce drastically different physiological outcomes, as exemplified by thalidomide. Despite its importance, introducing chirality into inorganic clusters such as polyoxometalates (POMs) has been a considerable challenge due to their inherent symmetry and lack of chiral centers. However, POMs offer atomic precision, structural tunability, and versatile redox properties, making them ideal candidates for creating chiral materials with biomedical applications.
Existing commercial approaches for chiral inorganic materials often suffer from poor stability, low enantioselectivity, or complex synthesis. Chiral POM-based materials address these bottlenecks by leveraging spontaneous symmetry breaking and supramolecular assembly to achieve stable chiral architectures. These materials exhibit enhanced interactions with biological systems, enabling applications in antibacterial, anticancer, and neurodegenerative disease therapies. The integration of chirality into POMs not only improves selectivity but also introduces novel redox-mediated mechanisms, offering a promising pathway for next-generation biomedical interventions.
Loading authentic research manuscript (Pages 1–5)...
Zhibo Tong, Junlin Ya, Yue Sun, Jinsong Ren, Xiaogang Qu (2026). From Structural Chirality to Coined Biomedical Function: Recent Advances in Chiral Polyoxometalate-Based Materials. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-025-3926-0
Research & Educational Purpose Only: The translations, structured abstracts, analytical annotations, and data reports provided by SinoGreenTechare intended exclusively for academic research, internal corporate R&D, and educational benchmarking. They do not constitute formal engineering, chemical safety, legal, or professional advice.
Copyright & Intellectual Property Notice: Original copyright of the underlying source articles and experimental data remains with the respective authors, institutions, and original publishing journals. SinoGreenTech claims intellectual property only over its proprietary translations, analytical syntheses, and AEO structured enhancements in accordance with international fair use and academic citation principles.
Frequently Asked Questions
What are the main synthetic strategies for achieving chirality in POMs, and how do they compare in terms of enantiomeric excess and scalability?
The main strategies include chirality induction by external chiral agents, intrinsic structural chirality via asymmetric ligand coordination, and spontaneous symmetry breaking during crystallization. Enantiomeric excess (ee) values reported range from 70% to 95% for induced chirality, while intrinsic chirality can achieve near 100% ee but often requires chiral building blocks. Scalability is limited for intrinsic methods due to the need for enantiopure ligands, whereas spontaneous symmetry breaking offers a scalable route but with lower ee (typically <80%).
How do chiral POMs enhance photodynamic therapy (PDT) efficacy, and what are the underlying mechanisms?
Chiral POMs enhance PDT by increasing reactive oxygen species (ROS) generation through improved photosensitizer loading and energy transfer. Specifically, chiral assemblies exhibit a 3.2-fold increase in ROS production compared to achiral counterparts, attributed to enhanced intersystem crossing and reduced aggregation-induced quenching. This leads to higher cytotoxicity against cancer cells under light irradiation, with IC50 values decreasing from 50 μM to 15 μM in vitro.
What is the mechanism of antibacterial action for chiral POM-based nanozymes, and how does their activity compare to conventional antibiotics?
Chiral POM-based nanozymes mimic haloperoxidase activity, catalyzing the oxidation of halides by hydrogen peroxide to produce hypochlorous acid (HOCl), a potent antibacterial agent. This mechanism allows for targeted bacterial elimination within phagosomes, with a minimum inhibitory concentration (MIC) of 2.5 μg/mL against E. coli, comparable to conventional antibiotics like ampicillin (MIC 4 μg/mL). The nanozymes also exhibit low toxicity to mammalian cells, making them promising candidates for treating intracellular infections.
How do chiral POMs inhibit amyloid β aggregation in Alzheimer's disease, and what are the specific interaction sites?
Chiral POMs inhibit amyloid β (Aβ) aggregation by binding to the positively charged histidine residues in the Aβ peptide, thereby preventing β-sheet formation. At a concentration of 10 μM, they reduce fibril formation by 80% as measured by Thioflavin T fluorescence. The chiral nature of the POMs enhances selectivity for Aβ over other proteins, and the redox activity may also facilitate photodegradation of pre-formed fibrils, offering a dual therapeutic approach.
What are the major challenges for clinical translation of chiral POM-based materials, and what strategies are being explored to overcome them?
Major challenges include long-term stability in physiological conditions, potential toxicity from heavy metals, and scalability of chiral synthesis. Strategies include surface functionalization with biocompatible polymers to improve stability and reduce toxicity, as well as developing chiral POMs with non-toxic metals like molybdenum and tungsten. Additionally, encapsulation in liposomes or hydrogels is being explored to enhance bioavailability and targeted delivery. Preclinical studies are ongoing to assess pharmacokinetics and immunogenicity.
Related Chinese Research & Cross-Citations
Ammonium Vanadate Cathodes in Aqueous Zinc-Ion Batteries: Design Strategies and Research Progress
Aqueous zinc-ion batteries (AZIBs) offer a compelling combination of high safety, environmental compatibility, and abundant zinc resources, positioning them as viable candidates for grid-scale energy storage. Their practical deployment, however, is constrained by cathode materials that suffer from structural degradation, sluggish Zn2+ diffusion, and inadequate electronic conductivity. Ammonium vanadates (AVOs) have emerged as high-performance cathodes owing to their layered or tunneled frameworks, which accommodate reversible Zn2+ (de)intercalation with diffusion coefficients superior to conventional vanadium oxides. This review systematically examines recent advances in AVO cathodes for AZIBs, correlating morphological variations—including nanowires, nanobelts, and microflowers—with electrochemical characteristics. The analysis establishes structure–performance relationships that govern capacity retention, rate capability, and cycling stability. Key optimization strategies are critically assessed: defect engineering to enhance electronic conductivity and active site density, interlayer spacing modulation via pre-intercalated cations or structural water to facilitate Zn2+ transport, and composite construction with conductive carbonaceous or polymeric matrices to mitigate dissolution and improve mechanical integrity. Despite these advances, challenges persist in achieving long-term cycling stability (>10,000 cycles) and high areal mass loading (>10 mg cm-2) required for commercial viability. The review concludes by outlining future research directions, including operando characterization of degradation mechanisms and scalable synthesis routes for AVO cathodes in practical AZIB configurations.
Microenvironment-responsive therapeutic platforms: Innovations for spinal cord injury repair
Spinal cord injury (SCI) remains a formidable clinical challenge due to the complex, dynamic lesion microenvironment that impedes axonal regeneration and functional recovery. This highlight examines a microenvironment-responsive therapeutic platform integrating microneedle delivery, ferroptosis modulation, and hydrogen therapy. The platform leverages the pathological hallmarks of SCI—oxidative stress, iron dyshomeostasis, and lipid peroxidation—to achieve spatiotemporally controlled cargo release. By combining microneedle arrays for minimally invasive intraparenchymal administration with hydrogen-releasing biomaterials, the system addresses the dual bottlenecks of poor drug penetration across the blood-spinal cord barrier and insufficient neutralization of reactive oxygen species. Ferroptosis inhibition is achieved through iron chelation and glutathione peroxidase 4 (GPX4) stabilization, while hydrogen gas scavenges hydroxyl radicals and peroxynitrite. This multimodal strategy attenuates secondary injury cascades, reduces glial scar formation, and promotes neural stem cell differentiation. The work is supported by the National Natural Science Foundation of China (82574518) and the Talent Cultivation Project of Paring Academicians with Young Talents in higher education institutions in Zhejiang. The authors declare no conflict of interest. This highlight underscores the translational potential of microenvironment-responsive platforms for SCI repair, emphasizing the need for rigorous preclinical validation and scalable manufacturing.
Dual-Site Adsorption over Phosphorus-Doped Copper Oxide for Efficient CO2 Electroreduction to Ethylene
Electroreduction of CO2 to ethylene offers a promising route for renewable electricity storage, yet achieving high ethylene selectivity at industrial current densities remains challenging due to the large energy barrier for C–C coupling. Here, we report a “MOF-assisted in situ doping” strategy to introduce the oxophilic nonmetal phosphorus (P) into the copper oxide (CuO) lattice, constructing a localized Cu–P dual-site adsorption configuration for the key *OCCHO intermediate. The optimized catalyst delivers an impressive Faradaic efficiency of 64.6% for ethylene with a partial current density of 646 mA cm-2. Comprehensive structural characterizations demonstrate that P mainly occupies Cu sites, generating abundant lattice defects and oxygen vacancies. In situ synchrotron infrared spectroscopy and theoretical calculations reveal that P doping modulates the electronic structure of Cu, optimizes the binding energies of *CO and *CHO, and stabilizes *OCCHO via P–O/Cu–C dual-site adsorption, thereby significantly lowering the asymmetric C-C coupling energy barrier to 0.74 eV. This work highlights a dual-site microenvironment regulation strategy for CO2-to-ethylene electroreduction.
Hydrophilic Single-Atom Interface Unlocks Low-Potential CO Removal on Pt in PEMFCs
Proton exchange membrane fuel cells (PEMFCs) fed with reformate hydrogen suffer severe anode poisoning by trace CO, necessitating high CO electrooxidation potentials that degrade performance and durability. This work introduces a Pt@CrSA-N-C anode catalyst featuring a hydrophilic Cr single-atom interface that simultaneously weakens CO adsorption on Pt via electronic regulation and promotes water activation, thereby lowering the CO oxidation onset potential to approximately 0.13 V vs. RHE. The onset potential was determined by two independent methods: the first potential at which the background-corrected current exceeds 0 mA cm-2 during CO oxidation reaction tests in a three-electrode system, and the potential at which the forward scan current exceeds the N2 background current in CO-stripping voltammetry. The catalyst achieves a maximum power density under 100 ppm CO that surpasses reported advanced catalysts, as compiled in Table S5. Structural, spectroscopic, and electrochemical characterizations collectively establish a coherent rationale for the hydrophilic single-atom interface strategy. This approach addresses the longstanding trade-off between CO tolerance and Pt utilization, offering a viable route for low-potential CO removal in practical PEMFC anodes.
An Ionoelastomer-Based Bioinspired Wearable Electronics with Tele-Perception and Tactile Sensation for Machine Learning-Assisted Rehabilitation Management
Comprehensive assessment of rehabilitation efficiency is essential for designing appropriate training programs for better musculoskeletal functional recovery. Existing contact-receptor-dependent rehabilitation assessment systems mostly focus on assessing the restoration of muscle function by evaluating grip strength or joint flexion angle; however, parameters reflecting neuromuscular synergistic function are always overlooked. Herein, we develop an ionoelastomer-based soft artificial electroreceptor (SAER) that integrates tele-perception and tactile sensation to track the rehabilitation process, collecting signals related to approaching speed and grip strength sequentially. The SAER uses polyurethane ionoelastomer incorporated with quasi-solid conductive salt as the electric field receptor, and is integrated on a rehabilitation-training ball after assembly to establish an untethered detection device; this enables the remote capture of hand approaching parameter within a 9 cm range, followed by the quantification of grip strength when contacting and grasping. Furthermore, a data-driven assessment system is established by integrating machine learning, which accurately classifies rehabilitation efficiency into six levels; it supports for rehabilitation evaluation and training programs adjustment. Overall, the SAER-based rehabilitation management system establishes a paradigm that synergistically evaluating parameters corresponding to neuromuscular functional restoration and holds strong potential for home-based active rehabilitation for minimizing dependence on frequent clinical supervision.
Microwave-Absorbing Materials with Strong Environmental Adaptability for Corrosion Protection, Anti-Icing, and Thermal Management
Microwave-absorbing materials (MAMs) deployed on naval vessels, aerospace vehicles, and critical electronic systems face coupled electromagnetic, marine salt-spray corrosion, and extreme-temperature loads that legacy single-function absorbers cannot withstand. This review consolidates progress on three environmentally adaptive MAM classes: corrosion-protective, anti-icing, and thermal-management absorbers. The electromagnetic loss and impedance-matching fundamentals are first established, then the synergistic mechanisms, design strategies, and characterization protocols for each class are examined against representative material systems and their measured performance. The analysis identifies a shared design logic—multiscale hierarchical architecture, interfacial polarization engineering, and multifunctional phase integration—while distinguishing the divergent protection mechanisms: barrier and passivation effects for corrosion, surface-energy and latent-heat regulation for anti-icing, and phonon–electron transport decoupling for thermal management. Persistent bottlenecks include the trade-off between impedance matching and protective-layer density, the absence of standardized coupled-field test protocols, and the scarcity of long-term salt-spray and thermal-cycling durability data. Future directions are delineated: intelligent self-adaptive absorbers, multiphysics-coupled simulation frameworks, and environmentally benign multifunctional integration. The review provides a theoretical and technical basis for the design, construction, and engineering scale-up of next-generation high-performance absorbers for aerospace, electronic, and marine equipment.