Shou-Tian Zheng

Cancer immunotherapy is limited by insufficient immunomodulatory efficacy and systemic toxicity. This study reports a giant silver cluster‐incorporated polyoxoniobate (PONb), K ₆ Na ₂₁ H ₃₉ {Ag ₃₀ Cl ₄ (SeO ₃ ) ₄ @(SiNb ₁₈ O ₅₄ ) ₆ }·96H ₂ O ( 1 ), as a potent immunotherapeutic agent. 1 features a unique core‐shell architecture, comprising a silver cluster core [Ag ₃₀ Cl ₄ (SeO ₃ ) ₄ ] ¹⁸⁺ and a shell of six [SiNb ₁₈ O ₅₄ ] ¹⁴⁻ polyanions. Notably, 1 contains the largest silver cluster (30 Ag ⁺ ) in a molecular PONb with solubility and biocompatibility under physiological conditions to date. In vitro, 1 exhibits potent cytotoxicity against mouse colorectal carcinoma cells with an IC ₅₀ of 0.11 µM, triggering immunogenic cell death (ICD). Additionally, it induces polarization of macrophages to the antitumor M1‐phenotype. In vivo, it outperforms doxorubicin (DOX) in suppressing tumor growth, with 1 achieving 90.63% tumor inhibition at 5 mg/kg (0.23 µmol/kg). Unlike DOX‐induced immunosuppression and hepatic toxicity, 1 robustly activates antitumor immune response via an ROS‐dependent mechanism by promoting T cell priming in the tumor‐draining lymph node and effector T cell infiltration into tumors, without impairing organ functions. Moreover, 1 converts tumor‐associated macrophages (TAMs) from the protumorogenic M2‐phenotype to the antitumor M1‐phenotype, further reprogramming the immune microenvironment in tumor tissues. This study validates PONbs as a promising class of immunotherapeutics, bridging structural innovation in inorganic chemistry with improved cancer immunotherapy.

Cancer immunotherapy is limited by insufficient immunomodulatory efficacy and systemic toxicity. This study reports a giant silver cluster‐incorporated polyoxoniobate (PONb), K ₆ Na ₂₁ H ₃₉ {Ag ₃₀ Cl ₄ (SeO ₃ ) ₄ @(SiNb ₁₈ O ₅₄ ) ₆ }·96H ₂ O ( 1 ), as a potent immunotherapeutic agent. 1 features a unique core‐shell architecture, comprising a silver cluster core [Ag ₃₀ Cl ₄ (SeO ₃ ) ₄ ] ¹⁸⁺ and a shell of six [SiNb ₁₈ O ₅₄ ] ¹⁴⁻ polyanions. Notably, 1 contains the largest silver cluster (30 Ag ⁺ ) in a molecular PONb with solubility and biocompatibility under physiological conditions to date. In vitro, 1 exhibits potent cytotoxicity against mouse colorectal carcinoma cells with an IC ₅₀ of 0.11 µM, triggering immunogenic cell death (ICD). Additionally, it induces polarization of macrophages to the antitumor M1‐phenotype. In vivo, it outperforms doxorubicin (DOX) in suppressing tumor growth, with 1 achieving 90.63% tumor inhibition at 5 mg/kg (0.23 µmol/kg). Unlike DOX‐induced immunosuppression and hepatic toxicity, 1 robustly activates antitumor immune response via an ROS‐dependent mechanism by promoting T cell priming in the tumor‐draining lymph node and effector T cell infiltration into tumors, without impairing organ functions. Moreover, 1 converts tumor‐associated macrophages (TAMs) from the protumorogenic M2‐phenotype to the antitumor M1‐phenotype, further reprogramming the immune microenvironment in tumor tissues. This study validates PONbs as a promising class of immunotherapeutics, bridging structural innovation in inorganic chemistry with improved cancer immunotherapy.

Reversing the sign of photoconductivity in a single material has long been a formidable challenge, yet achieving this goal could open the door to a new generation of adaptive optoelectronics. Here, we report the first case of an inorganic‐organic hybrid polyoxometalate (POM), [Ni(BTP)] ₄ [Nb ₁₀ O ₂₆ ]·35H ₂ O ( 1 , BTP = Bis‐tris propane), capable of fully reversible switching between positive photoconductivity (PPC) and negative photoconductivity (NPC). This switching is dually controlled by excitation wavelength and relative humidity. Short‐wavelength excitation and low humidity give conventional PPC, whereas long‐wavelength excitation and high humidity induce NPC. This anomalous polarity inversion stems from the competition between two coexisting mechanisms: one is the photoelectric effect, which generates charge carriers within the POM; the other is the light‐induced water desorption process, which suppresses the electron donation from adsorbed H ₂ O molecules, thereby reducing the carrier density. Resonant microcantilever measurements directly confirm the light‐induced water desorption process, and systematic wavelength/humidity‐dependent photoconductivity mapping reveals a well‐defined phase boundary that governs reversible PPC–NPC interconversion. This work represents a rare polarity‐switchable photoconductive material, expanding POM applications in optoelectronics.

Efficient solar‐driven interfacial evaporation requires precise coordination of heat and mass transport, yet achieving such synergy within conventional molecular systems remains challenging. Here, we address this limitation using an atomically precise polyoxoniobate (PONb)‐based molecular heterojunction, [Te ₅ Cu _0.2 Nb ₁₅ O ₅₇ H _5.6 ][(CuL) ₇ (OH)]·21H ₂ O (PONb‐CuL, L = 2,2′‐bipyridine), in which hydrophilic PONb clusters are covalently integrated with photothermal organocopper CuL units. This Janus molecular architecture couples broadband solar absorption with interfacial water‐cluster regulation within a single framework. Under one‐sun irradiation, a two‐dimensional PONb‐CuL evaporator delivers an evaporation rate of 2.87 kg m ⁻² h ⁻¹ . Incorporation into a three‐dimensional aerogel architecture further boosts the evaporation rate to 5.34 kg m ⁻² h ⁻¹ , affording a freshwater yield of 29.25 L m ⁻² under outdoor operation. Ab initio molecular dynamics simulations reveal that the PONb domain promotes hydrogen‐bonded water‐cluster formation, whereas the organocopper domain reduces the energy barrier for interfacial water transport and vapor escape. This work introduces polyoxometalate‐based molecular heterojunction engineering as a strategy for orchestrating coupled heat and mass transport, offering critical insights into the rational design of efficient solar‐to‐vapor conversion systems.

The development of efficient and sustainable strategies for imine synthesis remains highly desirable, as conventional approaches often suffer from harsh reaction conditions and limited selectivity. Herein, we report an electrocatalytic strategy that utilizes reproducible electricity to drive the selective oxidative coupling of benzylamine (BA) into imines under mild conditions. A series of disubstituted Keggin polyoxometalates (POMs), M₂PW₁₀O₃₈ (M = Fe-Zn), were assembled at the gas-liquid interface into well-defined two-dimensional nanosheet superstructures. Structural characterizations reveal a uniform nanosheet morphology, featuring single-cluster assembly and highly ordered arrangements of POM units. Among these, the Fe₂PW₁₀ NS exhibits outstanding electrocatalytic performance for BA oxidation, achieving >99% conversion, 99% yield of the target imine, and a Faradaic efficiency of 81.8%, along with excellent cycling stability. Comparative studies highlight the advantages of the cluster-assembled superstructure arising from the high density of accessible active sites and the synergistic effects of the ordered superstructure. Furthermore, substrate scope investigations demonstrate the broad applicability toward diverse amine substrates. This work provides a viable platform for the green and efficient synthesis of value-added imines and offers valuable insights into the design of advanced POM-based electrocatalysts.

The direct C–H bond amination represents one of the most straightforward and efficient strategies for C–N bond construction. However, conventional transition metal catalytic systems suffer from critical drawbacks, such as dependence on stoichiometric bases, high reaction temperatures, stringent inert atmosphere requirements, and poor catalyst recyclability. Herein, we report the development of an integrated heterogeneous polyoxoniobate (PONb) catalyst, Cu/FZU-1, achieved via the precise anchoring of catalytically active Cu sites onto an alkaline Nb-oxo cluster. The Cu/FZU-1 exhibited remarkable catalytic performance and recyclability in the direct amination of C–H bonds under mild conditions, achieving excellent yields up to 94% and an outstanding turnover number (TON) of 78. Its remarkable catalytic performance arises from the synergistic interplay of two key components within the integrated catalyst: Nb-oxo polyoxoanions provide Brønsted basicity and anchoring Cu²⁺ ions at the dangling sites serve as active sites for C–H bond activation. This integrated catalyst not only overcomes the bottleneck of low efficiency in the reaction interface, but also provides a new paradigm for precisely identifying active sites at the atomic level in complex catalytic systems.

This work investigates the first one‐dimensional (1D) silver cluster‐mediated polyoxotantalate molecular heterostructures of ‐[Ag ₉ ‐Ta ₆ ] _n ‐ ( 1g , 1y , and 1r ), combining silver clusters as versatile emitting units and polyoxotantalate as light propagation units. Its ultra‐low waveguiding loss coefficient of (1.03 ∼ 1.63 × 10 ⁻³ dB/µm) demonstrates this assembly of silver clusters and polyoxotantalate as an efficient platform in designing active optical waveguides. The solvent‐affected luminescent emission of silver clusters within this heterostructure enables the construction of emission‐tunable (green, yellow, and red) waveguides. Furthermore, the local photoluminescent (PL) behaviors of a single crystal could be changed via local thermal treatment, leading to the formation of an optical heterojunction. Spatially PL resolved spectra also confirm heterojunction microrods exhibit an obvious optical waveguide effect with a low waveguide loss coefficient (2.22 ∼ 2.93 × 10 ⁻³ dB/µm) during propagation. This study not only represents the first example following the function decomposition discipline but also establishes new types of silver cluster‐mediated polyoxotantalate‐based low‐dimensional ultralow‐loss optical waveguides for advanced optical communication and information coding.

This work investigates the first one‐dimensional (1D) silver cluster‐mediated polyoxotantalate molecular heterostructures of ‐[Ag ₉ ‐Ta ₆ ] _n ‐ ( 1g , 1y , and 1r ), combining silver clusters as versatile emitting units and polyoxotantalate as light propagation units. Its ultra‐low waveguiding loss coefficient of (1.03 ∼ 1.63 × 10 ⁻³ dB/µm) demonstrates this assembly of silver clusters and polyoxotantalate as an efficient platform in designing active optical waveguides. The solvent‐affected luminescent emission of silver clusters within this heterostructure enables the construction of emission‐tunable (green, yellow, and red) waveguides. Furthermore, the local photoluminescent (PL) behaviors of a single crystal could be changed via local thermal treatment, leading to the formation of an optical heterojunction. Spatially PL resolved spectra also confirm heterojunction microrods exhibit an obvious optical waveguide effect with a low waveguide loss coefficient (2.22 ∼ 2.93 × 10 ⁻³ dB/µm) during propagation. This study not only represents the first example following the function decomposition discipline but also establishes new types of silver cluster‐mediated polyoxotantalate‐based low‐dimensional ultralow‐loss optical waveguides for advanced optical communication and information coding.