Porous adsorbents with high capacity and selectivity are recognized as promising alternatives for energy-efficient gas separation, but the inherent trade-off between the two metrics hinders their industrial application. Herein, we synthesize a multivariate Al-based metal–organic framework (MOF), namely MOF-303/MIL-160, for CO2/CH4 separation under the guidance of reticular chemistry. The obtained MOF-303/MIL-160 contains both 3,5-pyrazoledicarboxylic acid, the ligand of MOF-303, and 2,5-furandicarboxylic acid, the ligand of MIL-160, in a ratio of 1 : 0.51. MOF-303 exhibits high capacity but low selectivity, whereas MIL-160 shows the opposite. Multivariate MOF-303/MIL-160 draws upon their respective strong points, realizing the balance of trade-off between capacity and selectivity in CO2/CH4 separation.
{"title":"Multivariate MOF-303/MIL-160 balancing the trade-off between capacity and selectivity in CO2/CH4 separation","authors":"Mingming Xu, Xiaokang Wang, Jingjing Chen, Meng Sun, Xueyan Zhang, Weidong Fan, Tingyi Wang, Daofeng Sun","doi":"10.1039/d6dt00085a","DOIUrl":"https://doi.org/10.1039/d6dt00085a","url":null,"abstract":"Porous adsorbents with high capacity and selectivity are recognized as promising alternatives for energy-efficient gas separation, but the inherent trade-off between the two metrics hinders their industrial application. Herein, we synthesize a multivariate Al-based metal–organic framework (MOF), namely MOF-303/MIL-160, for CO<small><sub>2</sub></small>/CH<small><sub>4</sub></small> separation under the guidance of reticular chemistry. The obtained MOF-303/MIL-160 contains both 3,5-pyrazoledicarboxylic acid, the ligand of MOF-303, and 2,5-furandicarboxylic acid, the ligand of MIL-160, in a ratio of 1 : 0.51. MOF-303 exhibits high capacity but low selectivity, whereas MIL-160 shows the opposite. Multivariate MOF-303/MIL-160 draws upon their respective strong points, realizing the balance of trade-off between capacity and selectivity in CO<small><sub>2</sub></small>/CH<small><sub>4</sub></small> separation.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"159 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122350","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Alejandro Cervantes Reyes, Ricardo Malpica-Calderón, Hugo Valdes, David Morales-Morales
Caffeine and other purine bases are naturally occurring, inexpensive, and readily available heterocycles composed of a fused imidazole–pyrimidine framework, whose five–membered imidazole core corresponds to a N–heterocyclic carbene (NHC) precursor. These features make purine scaffolds ideal precursors for the design of metal–NHC ligands that combine biological relevance, structural diversity, and tunable electronic properties. Over the past two decades (2004–2025), an expanding family of purine–derived NHC complexes has been developed across the periodic table—including those Ru, Ir, Rh, Ni, Pd, Pt, Cu, Ag and Au—revealing distinctive coordination modes, redox behaviors, and catalytic activities. This review provides a comprehensive overview of their synthetic strategies, structural features, and catalytic applications, emphasizing how the intrinsic anisotropy and multifunctionality of the purine framework enable unique metal–ligand interactions and reactivity patterns relevant to sustainable catalysis, photophysics, and bio–organometallic chemistry.
{"title":"Purine–Derived N–Heterocyclic Carbene Metal Complexes: Catalytic Applications and Reactivity","authors":"Alejandro Cervantes Reyes, Ricardo Malpica-Calderón, Hugo Valdes, David Morales-Morales","doi":"10.1039/d6dt00012f","DOIUrl":"https://doi.org/10.1039/d6dt00012f","url":null,"abstract":"Caffeine and other purine bases are naturally occurring, inexpensive, and readily available heterocycles composed of a fused imidazole–pyrimidine framework, whose five–membered imidazole core corresponds to a N–heterocyclic carbene (NHC) precursor. These features make purine scaffolds ideal precursors for the design of metal–NHC ligands that combine biological relevance, structural diversity, and tunable electronic properties. Over the past two decades (2004–2025), an expanding family of purine–derived NHC complexes has been developed across the periodic table—including those Ru, Ir, Rh, Ni, Pd, Pt, Cu, Ag and Au—revealing distinctive coordination modes, redox behaviors, and catalytic activities. This review provides a comprehensive overview of their synthetic strategies, structural features, and catalytic applications, emphasizing how the intrinsic anisotropy and multifunctionality of the purine framework enable unique metal–ligand interactions and reactivity patterns relevant to sustainable catalysis, photophysics, and bio–organometallic chemistry.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"51 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122429","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rhodium alkene complexes with η5-pyrrolyl ligands are successfully synthesized and fully characterized by X-ray analyses and NMR spectra. The dynamics of pyrrolyl and alkene coordination as well as combined σ- and π-ligation ability of pyrrolyl is demonstrated in the reactions of these half-sandwich complexes with isocyanide, organic azide and Lewis acid
{"title":"Half-Sandwich η5-Pyrrolyl Rhodium(I) Complexes with Alkene Coordination: Synthesis and Reactivity Exploration","authors":"Jiayu Yan, Jian Sun, Shuangliu Zhou","doi":"10.1039/d6dt00024j","DOIUrl":"https://doi.org/10.1039/d6dt00024j","url":null,"abstract":"Rhodium alkene complexes with η5-pyrrolyl ligands are successfully synthesized and fully characterized by X-ray analyses and NMR spectra. The dynamics of pyrrolyl and alkene coordination as well as combined σ- and π-ligation ability of pyrrolyl is demonstrated in the reactions of these half-sandwich complexes with isocyanide, organic azide and Lewis acid","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"12 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135443","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
hydroxymethylfurfural (HMF) serves as a key platform compound for the production of value-added chemicals from biomass. Consequently, its catalytic oxidation to 2,5-furandicarboxylic acid (FDCA), a highly promising renewable monomer substance, is of particular importance. But this process entails a complex dehydroxylation reaction, which can lead to numerous competing side reactions. Therefore, developing highly selective catalysts for this transformation remains a critical challenge. This study pioneers the use of a polyoxoniobate (PONb) incorporating vanadium and copper amine complexes, Nb12V3Cu, for the catalytic oxidation of HMF. Unlike conventional polyoxometalates (POMs), this PONbs-based catalyst exhibits superior stability under alkaline reaction conditions. Comparative experiments reveal that incorporating hetero-metallic components into PONb anions promotes the catalytic centers at the terminal or bridging oxygen atoms.These sites demonstrate enhanced synergistic catalysis towards both the hydroxyl and adjacent methylene groups in HMF, thereby facilitating the dehydrogenation and oxidation processes. Under optimized conditions, the Nb12V3Cu catalyst achieved 90.3% HMF conversion with 81.4% FDCA yield, outperforming most reported counterparts, and maintained its activity over five consecutive cycles. This research presents a novel hetero-metallic incorporation approach for the design of polyoxometalate-based catalysts specifically customized for biomass conversion in alkaline media, establishing a robust pathway for cutting-edge research on the selective oxidation of HMF to produce its derived platform chemicals.
{"title":"Heterometallic incorporation to promote catalytic activity of polyoxoniobate toward selective oxidation of 5-hydroxymethylfurfural","authors":"Lixiao Song, Ziwei Cai, Caili Lv, Long-Fei Chao, Yun-Dong Cao, Wenjing Xu, Hong Liu, Chun-Hui Zhang, Guanggang Gao","doi":"10.1039/d5dt03085d","DOIUrl":"https://doi.org/10.1039/d5dt03085d","url":null,"abstract":"hydroxymethylfurfural (HMF) serves as a key platform compound for the production of value-added chemicals from biomass. Consequently, its catalytic oxidation to 2,5-furandicarboxylic acid (FDCA), a highly promising renewable monomer substance, is of particular importance. But this process entails a complex dehydroxylation reaction, which can lead to numerous competing side reactions. Therefore, developing highly selective catalysts for this transformation remains a critical challenge. This study pioneers the use of a polyoxoniobate (PONb) incorporating vanadium and copper amine complexes, Nb12V3Cu, for the catalytic oxidation of HMF. Unlike conventional polyoxometalates (POMs), this PONbs-based catalyst exhibits superior stability under alkaline reaction conditions. Comparative experiments reveal that incorporating hetero-metallic components into PONb anions promotes the catalytic centers at the terminal or bridging oxygen atoms.These sites demonstrate enhanced synergistic catalysis towards both the hydroxyl and adjacent methylene groups in HMF, thereby facilitating the dehydrogenation and oxidation processes. Under optimized conditions, the Nb12V3Cu catalyst achieved 90.3% HMF conversion with 81.4% FDCA yield, outperforming most reported counterparts, and maintained its activity over five consecutive cycles. This research presents a novel hetero-metallic incorporation approach for the design of polyoxometalate-based catalysts specifically customized for biomass conversion in alkaline media, establishing a robust pathway for cutting-edge research on the selective oxidation of HMF to produce its derived platform chemicals.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"83 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122348","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Guorui Song, Jinke Ji, Changying Li, Jinlong Zhao, Bo Zhang
Photodynamic therapy (PDT) has shown good therapeutic results in recent years, but the efficacy is limited by the hypoxic environment within cancer cells. At present, most of the research studies on overcoming PDT hypoxia focus on providing exogenous oxygen, but the effect is not outstanding. This work shows an unconventional source of free radicals, compared with the traditional PDT strategy of generating reactive oxygen species, using a radical polymerization initiator (2,2'-azobis (2,4-dimethylvaleronitrile), ABVN) to generate alkyl radicals, which is free from the limitation of oxygen, is simpler and more efficient, and has obvious therapeutic effects. By synthesizing hollow mesoporous manganese dioxide (MnO2) as a carrier, the nanoparticles are loaded with ABVN and encapsulated with PEG, which have excellent photothermal properties, can quickly heat up to the thermal decomposition temperature of ABVN under laser irradiation, can degrade and release ABVN in GSH and acidic environments, and generate a large number of alkyl radicals in a short period of time, with excellent treatment efficiency. This study breaks through the limitation of PDT caused by hypoxia in cancer cells and provides a promising research strategy for PDT treatment.
{"title":"A pMnO<sub>2</sub>@ABVN nanoparticle with dual pH/GSH response for the production of alkyl radicals for the treatment of osteosarcoma.","authors":"Guorui Song, Jinke Ji, Changying Li, Jinlong Zhao, Bo Zhang","doi":"10.1039/d5dt02532j","DOIUrl":"https://doi.org/10.1039/d5dt02532j","url":null,"abstract":"<p><p>Photodynamic therapy (PDT) has shown good therapeutic results in recent years, but the efficacy is limited by the hypoxic environment within cancer cells. At present, most of the research studies on overcoming PDT hypoxia focus on providing exogenous oxygen, but the effect is not outstanding. This work shows an unconventional source of free radicals, compared with the traditional PDT strategy of generating reactive oxygen species, using a radical polymerization initiator (2,2'-azobis (2,4-dimethylvaleronitrile), ABVN) to generate alkyl radicals, which is free from the limitation of oxygen, is simpler and more efficient, and has obvious therapeutic effects. By synthesizing hollow mesoporous manganese dioxide (MnO<sub>2</sub>) as a carrier, the nanoparticles are loaded with ABVN and encapsulated with PEG, which have excellent photothermal properties, can quickly heat up to the thermal decomposition temperature of ABVN under laser irradiation, can degrade and release ABVN in GSH and acidic environments, and generate a large number of alkyl radicals in a short period of time, with excellent treatment efficiency. This study breaks through the limitation of PDT caused by hypoxia in cancer cells and provides a promising research strategy for PDT treatment.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146123258","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Herein, we are reporting bis-heteroleptic ruthenium(II) complex 1[PF6]2 carrying two o-Phenylenediamine groups (OPD) connected to the 4,7- position of a 1,10-phenanthroline ligand. Compound 1[PF6]2 shows aggregation-induced emission enhancement (AIEE) property through the restriction of intramolecular motion (RIM), which is a known phenomenon where the luminescent intensity of compounds is enhanced in the aggregated state. 1[PF6]2 was used as a highly sensitive (<2 min) luminescent turn-on phosgene-responsive probe and showed high selectivity over other competitive reactive toxic analytes with a low detection limit (72 nM). The −NH− and –NH2 groups in the OPD group provide two active reaction sites for coupling with electrophilic phosgene. It was envisioned that phosgene would simultaneously couple with the −NH− and –NH2 groups in the chemosensor to form a five-membered imidazolone ring. FTIR, ESI−HRMS analysis, and extensive 1H NMR titration established the detailed reaction mechanism. The probe 1[PF6]2 is non-luminescent due to the OPD group present in the analyte targeting σ-donor ligand L1, and nonradiative decay occurs from 3MC excited states. The phosgene reacted with the cyclized ligand become a strong π-acceptor, and also the intramolecular rotation around the C-N bond was restricted due to the steric hindrance of ligand L1. Consequently, the 3MLCTRu(d)→L(π*) state becomes responsible for the bright red emission of phosgene-reacted product through the shifting of the population from 3MC to 3MLCT state. Finally, 1[PF6]2 coated solid-state paper strip was utilized for practical applications to detect the different concentrations of phosgene vapor without any interference from other competitive analytes.
{"title":"A Dual-Phase Luminescent Phosgene Sensor Based on an AIE-Active Ruthenium(II) Polypyridine Complex","authors":"Snehadrinarayan Khatua, Sumit Kumar Patra, Jogat Gogoi, Monosh Rabha","doi":"10.1039/d5dt03001c","DOIUrl":"https://doi.org/10.1039/d5dt03001c","url":null,"abstract":"Herein, we are reporting bis-heteroleptic ruthenium(II) complex 1[PF6]2 carrying two o-Phenylenediamine groups (OPD) connected to the 4,7- position of a 1,10-phenanthroline ligand. Compound 1[PF6]2 shows aggregation-induced emission enhancement (AIEE) property through the restriction of intramolecular motion (RIM), which is a known phenomenon where the luminescent intensity of compounds is enhanced in the aggregated state. 1[PF6]2 was used as a highly sensitive (<2 min) luminescent turn-on phosgene-responsive probe and showed high selectivity over other competitive reactive toxic analytes with a low detection limit (72 nM). The −NH− and –NH2 groups in the OPD group provide two active reaction sites for coupling with electrophilic phosgene. It was envisioned that phosgene would simultaneously couple with the −NH− and –NH2 groups in the chemosensor to form a five-membered imidazolone ring. FTIR, ESI−HRMS analysis, and extensive 1H NMR titration established the detailed reaction mechanism. The probe 1[PF6]2 is non-luminescent due to the OPD group present in the analyte targeting σ-donor ligand L1, and nonradiative decay occurs from 3MC excited states. The phosgene reacted with the cyclized ligand become a strong π-acceptor, and also the intramolecular rotation around the C-N bond was restricted due to the steric hindrance of ligand L1. Consequently, the 3MLCTRu(d)→L(π*) state becomes responsible for the bright red emission of phosgene-reacted product through the shifting of the population from 3MC to 3MLCT state. Finally, 1[PF6]2 coated solid-state paper strip was utilized for practical applications to detect the different concentrations of phosgene vapor without any interference from other competitive analytes.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"23 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135444","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Patrick Schmidt, Fabian Strauß, Marcus Scheele, Carl P. Romao, Hans-Jürgen Meyer
We explore the cationic intercalation of tungsten ditelluride (WTe2) with potassium (K), rubidium (Rb), and cesium (Cs), yielding intercalation compounds of the form A0.5WTe2 (A = K, Rb, Cs). Structural characterization was performed using powder X-ray diffraction (PXRD), while diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and temperature-dependent conductivity measurements were employed to investigate the electronic properties. Density functional theory (DFT) calculations were carried out to support the experimental findings and to provide insight into the intercalation mechanisms and the resulting material characteristics. All synthesized compounds display semiconducting behavior with narrow band gaps, emphasizing the influence of alkali metal intercalation on the electronic structure and transport properties of WTe2. These results advance the fundamental understanding of property modulation in transition-metal dichalcogenides (TMDCs) and highlight their potential for electronic device applications.
{"title":"Intercalation of alkali metal into WTe2, the crystal structure of A0.5WTe2 and observation of a metal-to-semiconductor transition","authors":"Patrick Schmidt, Fabian Strauß, Marcus Scheele, Carl P. Romao, Hans-Jürgen Meyer","doi":"10.1039/d5dt02775f","DOIUrl":"https://doi.org/10.1039/d5dt02775f","url":null,"abstract":"We explore the cationic intercalation of tungsten ditelluride (WTe<small><sub>2</sub></small>) with potassium (K), rubidium (Rb), and cesium (Cs), yielding intercalation compounds of the form <em>A</em><small><sub>0.5</sub></small>WTe<small><sub>2</sub></small> (<em>A</em> = K, Rb, Cs). Structural characterization was performed using powder X-ray diffraction (PXRD), while diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and temperature-dependent conductivity measurements were employed to investigate the electronic properties. Density functional theory (DFT) calculations were carried out to support the experimental findings and to provide insight into the intercalation mechanisms and the resulting material characteristics. All synthesized compounds display semiconducting behavior with narrow band gaps, emphasizing the influence of alkali metal intercalation on the electronic structure and transport properties of WTe<small><sub>2</sub></small>. These results advance the fundamental understanding of property modulation in transition-metal dichalcogenides (TMDCs) and highlight their potential for electronic device applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"19 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116151","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The redox reaction of K3Sb and Ru3(CO)12 in the ethylenediamine (en) of 2,2,2-cryptand to produce the deeply reduced [Ru6(μ6-Sb)(μ2-CO)2(CO)16]3- (1) wherein the unprecedented boat-like Ru6 cluster unit is embedded with μ6-Sb for the first time. Structural and bonding evolution from the reported electroneutral {Ru6(μ5-Sb)(μ2-H)3(CO)18SbPh3} (2) to the negatively charged 1 have been discussed.
{"title":"[Ru6(μ6-Sb)(CO)18]3-: Deeply Reduced Metal Carbonyl Cluster Embedded with Naked μ6-Sb","authors":"Cheng Ding, Xian Xu, qian qin, Jingen Ding, Li Xu","doi":"10.1039/d6dt00002a","DOIUrl":"https://doi.org/10.1039/d6dt00002a","url":null,"abstract":"The redox reaction of K3Sb and Ru3(CO)12 in the ethylenediamine (en) of 2,2,2-cryptand to produce the deeply reduced [Ru6(μ6-Sb)(μ2-CO)2(CO)16]3- (1) wherein the unprecedented boat-like Ru6 cluster unit is embedded with μ6-Sb for the first time. Structural and bonding evolution from the reported electroneutral {Ru6(μ5-Sb)(μ2-H)3(CO)18SbPh3} (2) to the negatively charged 1 have been discussed.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"17 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116144","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Alzheimer’s disease (AD), marked by the misfolding/aggregation of β-amyloid (Aβ), is a major global health challenge. Polyoxometalates (POMs), as anionic therapeutic agents, exhibit potential in depolymerizing Aβ fibrils, inhibiting Aβ fibrillation, and photocatalyst. To achieve targeted reactive oxygen species (ROS) amplification, we developed a chitosan-modified near-infrared (NIR)-responsive upconversion nanoplatform, UCNPs(Tm/Er)@SiO2@GPS@CH, as a targeted carrier for POMs. The nanoplatform was constructed by sequentially modifying upconversion nanoparticles (UCNPs) with a silica layer, 3-glycidoxypropyltrimethoxysilane (GPS, as a linker), and chitosan (CH, a cationic biomacromolecule). The cationic CH layer enabled efficient loading of anionic POMs through electrostatic interactions with an optimal POMs loading capacity of 415.41 μg/mg that positively correlated with CH modification levels. Under NIR irradiation, the nanoplatform triggered a photodynamic effect with abundant ROS. Notably, compared with the control group and Aβ monomer group, the ROS generation in the Aβ fibril group was approximately doubled, which further enhanced the targeted therapeutic efficacy of system. By integrating NIR responsiveness, cationic chitosan, targeted ROS generation, and low systemic toxicity, the nanoplatform provides a novel strategy for the photooxidative treatment of AD and offers insights into the design of chitosan-modified upconversion nanoparticles-based drug carrier systems.
{"title":"NIR-Responsive Upconversion Nanoplatforms: an Anionic Drug Carrier for ROS Amplification Induced by β-amyloid Fibrils","authors":"Xiaofeng Jia, Yijia Guan, Weijie Cao, Xiaoshuo Zhang, Huazhen Duan, Hui Guo, Huichang Chen, Binbin Wang, Tao Li, Jianguo Liao","doi":"10.1039/d5dt03121d","DOIUrl":"https://doi.org/10.1039/d5dt03121d","url":null,"abstract":"Alzheimer’s disease (AD), marked by the misfolding/aggregation of β-amyloid (Aβ), is a major global health challenge. Polyoxometalates (POMs), as anionic therapeutic agents, exhibit potential in depolymerizing Aβ fibrils, inhibiting Aβ fibrillation, and photocatalyst. To achieve targeted reactive oxygen species (ROS) amplification, we developed a chitosan-modified near-infrared (NIR)-responsive upconversion nanoplatform, UCNPs(Tm/Er)@SiO2@GPS@CH, as a targeted carrier for POMs. The nanoplatform was constructed by sequentially modifying upconversion nanoparticles (UCNPs) with a silica layer, 3-glycidoxypropyltrimethoxysilane (GPS, as a linker), and chitosan (CH, a cationic biomacromolecule). The cationic CH layer enabled efficient loading of anionic POMs through electrostatic interactions with an optimal POMs loading capacity of 415.41 μg/mg that positively correlated with CH modification levels. Under NIR irradiation, the nanoplatform triggered a photodynamic effect with abundant ROS. Notably, compared with the control group and Aβ monomer group, the ROS generation in the Aβ fibril group was approximately doubled, which further enhanced the targeted therapeutic efficacy of system. By integrating NIR responsiveness, cationic chitosan, targeted ROS generation, and low systemic toxicity, the nanoplatform provides a novel strategy for the photooxidative treatment of AD and offers insights into the design of chitosan-modified upconversion nanoparticles-based drug carrier systems.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"1 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116128","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
D. Kuzman, V. Damjanović, J. Toplak, G. Medak, I. Halasz, T. Hrenar, M. Cindrić, V. Vrdoljak
Eight heteropolyoxomolybdates were synthesized and characterized, comprising three Anderson-type compounds [Co(ox)(NH<small><sub>3</sub></small>)<small><sub>4</sub></small>]<small><sub>3</sub></small>[AlMo<small><sub>6</sub></small>(OH)<small><sub>6</sub></small>O<small><sub>18</sub></small>]·7H<small><sub>2</sub></small>O (<strong>1</strong>), [Co(ox)(NH<small><sub>3</sub></small>)<small><sub>4</sub></small>]<small><sub>6</sub></small>[TeMo<small><sub>6</sub></small>O<small><sub>24</sub></small>]·16H<small><sub>2</sub></small>O (<strong>2</strong>), and Na<small><sub>2</sub></small>[Co(ox)(en)<small><sub>2</sub></small>]<small><sub>4</sub></small>[TeMo<small><sub>6</sub></small>O<small><sub>24</sub></small>]·16H<small><sub>2</sub></small>O (<strong>3</strong>), four Keggin-type compounds [Co(ox)(NH<small><sub>3</sub></small>)<small><sub>4</sub></small>]<small><sub>4</sub></small>[GeMo<small><sub>12</sub></small>O<small><sub>40</sub></small>]·6H<small><sub>2</sub></small>O (<strong>4</strong>), [Co(ox)(NH<small><sub>3</sub></small>)<small><sub>4</sub></small>]<small><sub>4</sub></small>[SiMo<small><sub>12</sub></small>O<small><sub>40</sub></small>]·6H<small><sub>2</sub></small>O (<strong>5</strong>), [Co(ox)(en)<small><sub>2</sub></small>]<small><sub>4</sub></small>[GeMo<small><sub>12</sub></small>O<small><sub>40</sub></small>]·12H<small><sub>2</sub></small>O (<strong>6</strong>), and [Co(ox)(en)<small><sub>2</sub></small>]<small><sub>4</sub></small>[SiMo<small><sub>12</sub></small>O<small><sub>40</sub></small>]·12H<small><sub>2</sub></small>O (<strong>7</strong>), as well as one coordination polymer Na<small><sub>4</sub></small>[Co(ox)(NH<small><sub>3</sub></small>)<small><sub>4</sub></small>]<small><sub>3</sub></small>[GeMo<small><sub>6</sub></small>O<small><sub>22</sub></small>(Hmal)<small><sub>3</sub></small>]·7.75H<small><sub>2</sub></small>O (<strong>8</strong>) featuring an extensive three-dimensional coordination framework. Additionally, two reaction intermediates, [{Co(ox)(NH<small><sub>3</sub></small>)<small><sub>4</sub></small>}<small><sub>2</sub></small>Na<small><sub>2</sub></small>(H<small><sub>2</sub></small>O)<small><sub>6</sub></small>{H<small><sub>4</sub></small>Mo<small><sub>8</sub></small>O<small><sub>28</sub></small>}]·4H<small><sub>2</sub></small>O (<strong>1a</strong>) and [Co(ox)(NH<small><sub>3</sub></small>)<small><sub>4</sub></small>]<small><sub>2</sub></small>[Al(mal)<small><sub>2</sub></small>(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>]·Hmal·2H<small><sub>2</sub></small>O (<strong>1b</strong>), were also isolated. Compounds [Co(NH<small><sub>3</sub></small>)<small><sub>6</sub></small>][Al(mal)<small><sub>2</sub></small>(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>](NO<small><sub>3</sub></small>)<small><sub>2</sub></small>·H<small><sub>2</sub></small>O (<strong>9</strong>) and [Co(en)<small><sub>3</sub></small>]<small><sub>2</sub></small>[Mo<small><sub>8</sub></small>O<small><sub>26</sub></sm
{"title":"Synthesis, structural characterization and properties of a series of heteropolyoxomolybdates: [AlMo6(OH)6O18]3−, [GeMo12O40]4−, [GeMo6O22(Hmal)3]7−, [SiMo12O40]4−, and [TeMo6O24]6−","authors":"D. Kuzman, V. Damjanović, J. Toplak, G. Medak, I. Halasz, T. Hrenar, M. Cindrić, V. Vrdoljak","doi":"10.1039/d5dt03064a","DOIUrl":"https://doi.org/10.1039/d5dt03064a","url":null,"abstract":"Eight heteropolyoxomolybdates were synthesized and characterized, comprising three Anderson-type compounds [Co(ox)(NH<small><sub>3</sub></small>)<small><sub>4</sub></small>]<small><sub>3</sub></small>[AlMo<small><sub>6</sub></small>(OH)<small><sub>6</sub></small>O<small><sub>18</sub></small>]·7H<small><sub>2</sub></small>O (<strong>1</strong>), [Co(ox)(NH<small><sub>3</sub></small>)<small><sub>4</sub></small>]<small><sub>6</sub></small>[TeMo<small><sub>6</sub></small>O<small><sub>24</sub></small>]·16H<small><sub>2</sub></small>O (<strong>2</strong>), and Na<small><sub>2</sub></small>[Co(ox)(en)<small><sub>2</sub></small>]<small><sub>4</sub></small>[TeMo<small><sub>6</sub></small>O<small><sub>24</sub></small>]·16H<small><sub>2</sub></small>O (<strong>3</strong>), four Keggin-type compounds [Co(ox)(NH<small><sub>3</sub></small>)<small><sub>4</sub></small>]<small><sub>4</sub></small>[GeMo<small><sub>12</sub></small>O<small><sub>40</sub></small>]·6H<small><sub>2</sub></small>O (<strong>4</strong>), [Co(ox)(NH<small><sub>3</sub></small>)<small><sub>4</sub></small>]<small><sub>4</sub></small>[SiMo<small><sub>12</sub></small>O<small><sub>40</sub></small>]·6H<small><sub>2</sub></small>O (<strong>5</strong>), [Co(ox)(en)<small><sub>2</sub></small>]<small><sub>4</sub></small>[GeMo<small><sub>12</sub></small>O<small><sub>40</sub></small>]·12H<small><sub>2</sub></small>O (<strong>6</strong>), and [Co(ox)(en)<small><sub>2</sub></small>]<small><sub>4</sub></small>[SiMo<small><sub>12</sub></small>O<small><sub>40</sub></small>]·12H<small><sub>2</sub></small>O (<strong>7</strong>), as well as one coordination polymer Na<small><sub>4</sub></small>[Co(ox)(NH<small><sub>3</sub></small>)<small><sub>4</sub></small>]<small><sub>3</sub></small>[GeMo<small><sub>6</sub></small>O<small><sub>22</sub></small>(Hmal)<small><sub>3</sub></small>]·7.75H<small><sub>2</sub></small>O (<strong>8</strong>) featuring an extensive three-dimensional coordination framework. Additionally, two reaction intermediates, [{Co(ox)(NH<small><sub>3</sub></small>)<small><sub>4</sub></small>}<small><sub>2</sub></small>Na<small><sub>2</sub></small>(H<small><sub>2</sub></small>O)<small><sub>6</sub></small>{H<small><sub>4</sub></small>Mo<small><sub>8</sub></small>O<small><sub>28</sub></small>}]·4H<small><sub>2</sub></small>O (<strong>1a</strong>) and [Co(ox)(NH<small><sub>3</sub></small>)<small><sub>4</sub></small>]<small><sub>2</sub></small>[Al(mal)<small><sub>2</sub></small>(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>]·Hmal·2H<small><sub>2</sub></small>O (<strong>1b</strong>), were also isolated. Compounds [Co(NH<small><sub>3</sub></small>)<small><sub>6</sub></small>][Al(mal)<small><sub>2</sub></small>(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>](NO<small><sub>3</sub></small>)<small><sub>2</sub></small>·H<small><sub>2</sub></small>O (<strong>9</strong>) and [Co(en)<small><sub>3</sub></small>]<small><sub>2</sub></small>[Mo<small><sub>8</sub></small>O<small><sub>26</sub></sm","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"46 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116061","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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