Release Of Iron Ions Research Articles

3D‐Printed Biomimetic Ceramic Scaffolds with Photothermal/Chemodynamic Effects and Ionic Microenvironment for Preventing Tumor Recurrence and Promoting Vascularized Bone Reconstruction

AbstractOsteosarcoma is an aggressive malignant bone tumor predominantly affecting adolescents and young adults, characterized by a high mortality rate. A significant challenge in treatment is the presence of residual tumor cells and associated bone defects. Here, a novel functionalized biomimetic ceramic scaffold is presented, which combines photothermal and chemodynamic therapies to effectively target bone tumors while promoting vascularized bone regeneration through an optimized ionic microenvironment. The scaffold consists of a 3D‐printed zinc‐doped β‐tricalcium phosphate ceramic matrix and a biomimetic dopamine‐modified hyaluronic acid hydrogel membrane loaded with Ti3C2 MXene and iron ions. In the tumor microenvironment, the hydrogel membrane degrades rapidly, releasing iron ions that lead to glutathione depletion and downregulation of glutathione peroxidase 4. When exposed to near‐infrared light, Ti3C2 enhances local temperature and catalyzes the redox cycling of iron ions, leading to the generation of hydroxyl radicals through Fenton reactions. This process results in lipid peroxidation and induces ferroptosis of tumor cells. Following the clearance of residual tumor cells, the gradual release of iron and zinc ions encourages osteogenic differentiation and vascularization, facilitating vascularized bone regeneration. Therefore, the biomimetic ceramic scaffold exhibits effective anti‐osteosarcoma properties while supports bone repair, presenting a promising treatment option for osteosarcoma‐associated bone defects.

Tracing the electron transfer behavior driven by hydrophyte-derived carbon materials empowered autotrophic denitrification in iron-based constructed wetlands: Efficacy and enhancement mechanism.

Iron-based constructed wetlands (ICWs) displayed great potential in deep nitrogen elimination for low-polluted wastewater. However, the unsatisfactory denitrification performance caused by the limited solubility and sluggish activity of iron substrates needs to be improved in an eco-effective manner. To fill this gap, the bioavailability of iron substrates (iron scraps) affected by wetland biomass-derived carbon materials with potential conductivity were explored. Results indicated that the cumulative removal of TN in biochar-added ICW (BC-ICW) and activated carbon-added ICW (AC-ICW) increased by 29.04 % and 22.96 %, respectively. The carbon matrix of AC played the geo-conductor role to facilitate the rapid release of iron ions, as indicated by the higher TN removal efficiency of AC-ICW (45.36 ± 1.45 %) at the early stage, while the reduced conductivity of AC negatively impacted the nitrogen removal. BC-ICW exhibited intensified denitrification potential, with higher TN removal capacity (52.08 ± 3.04 %) and effluent Fe2+ concentration. Electroactive bacteria (EB) (Geobacter, Desulfovibrio, Shewanella, etc.) associated with extracellular electron transfer were enriched in BC-ICW, as well as the expanded niches breadth and improved microbial community diversity. The electron-shuttling effect of BC was mainly attributed to its oxygenated functional groups (quinone/phenolic moieties), which supported the electron transfer from EB to extracellular iron oxides, as evidenced by the increased Fe(III)(hydro)oxides bioavailability. Besides, biochar concurrently up-regulated the gene expression of electron transport chains/mediators and denitrification reductases, suggesting that BC boosted the active iron cycle and iron-mediated autotrophic denitrification in ICWs by accelerating intracellular and extracellular electron transfer. This work explored the electron transfer behavior of biomass-derived carbon materials coupled with ICWs to enhance denitrification, providing insights into the sustainable application of biomass derived carbon-assisted ICWs in tertiary treatment.

A novel bio-microcapsule with high mechanical strength for sustained release of carbon sources and iron ions to enhance nitrogen removal in low-carbon sewage

A novel bio-microcapsule with high mechanical strength for sustained release of carbon sources and iron ions to enhance nitrogen removal in low-carbon sewage

Mild Magnetothermal Immunotherapy for Malignant Pleural Effusion.

Malignant pleural effusion (MPE) is one of the most difficult complications of cancer to cure, usually indicating poor prognosis in late-stage cancer patients. Due to the presence of a large number of tumor-associated immune cells with the tumor promoting phenotype in MPE and pleural tumors, current clinical therapy offers limited effectiveness. Here, a mild magnetothermal regulation strategy is proposed based on a magnetic nanocatlytic nanoplatform ZCMF@PEG-AF (ZCMF-AF)constructed by surface-modifying anti-F4/80 antibody (AF) on ZnCoFe2O4@ZnMnFe2O4 magnetic nanoparticles (ZCMF) to target and polarize tumor-associated macrophages. Under alternating magnetic field-induced hyperthermia (41-42°C), ZCMF-AF exhibits in situ nanocatalytic production of hydroxyl radicals via released iron ions under acidic cellular environment, which induces repolarization from the immunosuppressed M2 phenotype to the M1 phenotype. More importantly, the tumor cell damage induced by M1 macrophages and magnetic hyperthermia promote the maturation of dendritic cells, which subsequently awakens cytotoxic T lymphocytes to combat tumor cells. The integrated innate and adaptive immunity activations based on ZCMF-AF nano-immunomedicine through intrapleural administration elicit substantially regulated immune microenvironment of MPE and pleural tumors. Moreover, the interpleural magnetic nanoparticle-based immunotherapy effectively reduced the MPE volume and inhibited tumor growth in the pleural cavity, significantly prolonging the survival of the MPE-bearing mice.

Nebulized Immunotherapy of Orthotopic Lung Cancer by Mild Magnetothermal–Based Innate Immunity Activations

AbstractAdvances in adaptive immunity have greatly contributed to the development of cancer immunotherapy. However, its over‐low efficacy and insufficient invasion of immune cells in the tumor tissue, and safety problems caused by cytokine storm, have seriously impeded further clinical application for solid tumor immunotherapy. Notably, the immune microenvironment of the lungs is naturally enriched with alveolar macrophages (AMs). Herein, we introduce a novel nebulized magnetothermal immunotherapy strategy to treat orthotopic lung cancer by using magnetothermal nanomaterial (Zn−CoFe2O4@Zn−MnFe2O4−PEG, named ZCMP), which can release iron ions via an acid/thermal‐catalytic reaction to maximize the use of lung‘s immune environment through the cascade activations of AMs and natural killer (NK) cells. Nebulized administration greatly enhance drug bioavailability by localized drug accumulation at the lesion site. Upon mild magnetic hyperthermia, the released iron ions catalyze endogenous H2O2 decomposition to produce reactive oxygen species (ROS), which triggers the M1 polarization of AMs, and the resultant inflammatory cytokine IFN‐β, IL‐1β and IL‐15 releases to activate c‐Jun, STAT5 and GZMB related signaling pathways, promoting NK cells proliferation and activation. This innovative strategy optimally utilizes the lung‘s immune environment and shows excellent immunotherapeutic outcomes against orthotopic lung cancer.

Nebulized Immunotherapy of Orthotopic Lung Cancer by Mild Magnetothermal-Based Innate Immunity Activations.

Advances in adaptive immunity have greatly contributed to the development of cancer immunotherapy. However, its over-low efficacy and insufficient invasion of immune cells in the tumor tissue, and safety problems caused by cytokine storm, have seriously impeded further clinical application for solid tumor immunotherapy. Notably, the immune microenvironment of the lungs is naturally enriched with alveolar macrophages (AMs). Herein, we introduce a novel nebulized magnetothermal immunotherapy strategy to treat orthotopic lung cancer by using magnetothermal nanomaterial (Zn-CoFe2O4@Zn-MnFe2O4-PEG, named ZCMP), which can release iron ions via an acid/thermal-catalytic reaction to maximize the use of lung's immune environment through the cascade activations of AMs and natural killer (NK) cells. Nebulized administration greatly enhance drug bioavailability by localized drug accumulation at the lesion site. Upon mild magnetic hyperthermia, the released iron ions catalyze endogenous H2O2 decomposition to produce reactive oxygen species (ROS), which triggers the M1 polarization of AMs, and the resultant inflammatory cytokine IFN-β, IL-1β and IL-15 releases to activate c-Jun, STAT5 and GZMB related signaling pathways, promoting NK cells proliferation and activation. This innovative strategy optimally utilizes the lung's immune environment and shows excellent immunotherapeutic outcomes against orthotopic lung cancer.

Differential interaction modes of As(III)/As(V) with microbial cell membrane induces opposite effects on organic contaminant biodegradation in groundwater

Arsenic, a widespread toxic metalloid in groundwater, derives both from natural geological environment and industrial discharge, is extensively detected to be coexisting with organic contaminants, such as 2,4,6-trichlorophenol (TCP), a prior concerned pollutant. During biological remediation of groundwater, arsenic potentially intervenes microbial behaviors. This study found an opposite interference of arsenic in its two different valences (III and V) on the degradation of TCP by the functional bacteria, Sphingomonas fennica K101. As(III) inhibited TCP degradation in a concentration-dependent manner (from 0.1-10 mg/L), with a maximum inhibition rate of 35.5%, whereas As(V) exhibited promoting effects by 13.8% and 33.2% at 1 mg/L and 10 mg/L, respectively. Employing field emission transmission electron microscopy, quantum chemical calculations, fourier-transform ion cyclotron resonance mass spectrometry and metabolomic analysis, we unveil distinct interactions between cell membranes and arsenic in two valence states. Exposure to As(III) led to significant accumulation of As(III) in the cytoplasm, followed by interaction with intracellular ferritin (ferritin heavy chain 1), releasing iron ions and generating ROS. Subsequently, it induced ferroptosis and disrupted bacterial basal metabolism, thereby inhibiting TCP biodegradation. Oppositely, As(V) bound to a critical component sphingosine and triggered sphingosine polymerization, increasing membrane permeability, which was evidenced by measuring lactate dehydrogenase release. This process facilitated TCP transmembrane permeation by reducing membrane or extracellular secretion resistance. As(V) concurrently upregulated energy metabolism and accelerated TCP degradation. Our study elucidates the influence of prevalent arsenic on biodegradation efficacy, particularly amidst changing redox conditions associated with varying arsenic valences.

Designed magnetic nanoparticles for ferroptosis: Release of iron ions from metal-organic frameworks modified with iron oxides

The unique chemical properties of the catalytic and biocompatible metal organic framework MIL88b allow for considering it as prooxidant agent. The authors hypothesize whether additional modification of the MIL88b with an additional iron source as Fe3O4 nanoparticles can increase both pro-oxidant activity and provide magnetic properties contributing to target delivery. The prooxidant activity of the Fe3O4-MOF was studied using electron paramagnetic resonance spectroscopy and methylene blue degradation reactions in the presence of hydrogen peroxide. To understand the reaction mechanism, the authors studied the released iron ions, as well as the surface composition using the X-ray photoelectron spectroscopy method. The addition of iron oxide leads to a more prolonged release of iron ions and the production of hydroxyl radicals within 24 h. The native MIL88b demonstrates the highest Fenton reaction rate due to "sacrificial" behavior (despite lower concentration of iron ions in the composition and on the surface compared to the modified sample) and the blocking of the active centers of MIL88b by Fe3O4 on the surface.

Biomimetic Scaffolds Regulating the Iron Homeostasis for Remolding Infected Osteogenic Microenvironment.

The treatment of infected bone defects (IBDs) needs simultaneous elimination of infection and acceleration of bone regeneration. One mechanism that hinders the regeneration of IBDs is the iron competition between pathogens and host cells, leading to an iron deficient microenvironment that impairs the innate immune responses. In this work, an in situ modification strategy is proposed for printing iron-active multifunctional scaffolds with iron homeostasis regulation ability for treating IBDs. As a proof-of-concept, ultralong hydroxyapatite (HA) nanowires are modified through in situ growth of a layer of iron gallate (FeGA) followed by incorporation in the poly(lactic-co-glycolic acid) (PLGA) matrix to print biomimetic PLGA based composite scaffolds containing FeGA modified HA nanowires (FeGA-HA@PLGA). The photothermal effect of FeGA endows the scaffolds with excellent antibacterial activity. The released iron ions from the FeGA-HA@PLGA help restore the iron homeostasis microenvironment, thereby promoting anti-inflammatory, angiogenesis and osteogenic differentiation. The transcriptomic analysis shows that FeGA-HA@PLGA scaffolds exert anti-inflammatory and pro-osteogenic differentiation by activating NF-κB, MAPK and PI3K-AKT signaling pathways. Animal experiments confirm the excellent bone repair performance of FeGA-HA@PLGA scaffolds for IBDs, suggesting the promising prospect of iron homeostasis regulation therapy in future clinical applications.

Tailoring Iron-Ion Release of Cellulose-Based Aerogel-Coated Iron Foam for Long-Term High-Power Microbial Fuel Cells

Tailoring Iron-Ion Release of Cellulose-Based Aerogel-Coated Iron Foam for Long-Term High-Power Microbial Fuel Cells

Mechanistic insights into Fe3O4-mediated inhibition of H2S gas production in sludge anaerobic digestion

The addition of iron-based conductive materials has been extensively validated as a highly effective approach to augment methane generation from anaerobic digestion (AD) process. In this work, it was additionally discovered that Fe3O4 notably suppressed the production of hazardous H2S gas during sludge AD. As the addition of Fe3O4 increased from 0 to 20 g/L, the accumulative H2S yields decreased by 89.2 % while the content of element sulfur and acid volatile sulfide (AVS) respectively increased by 55.0 % and 30.4 %. Mechanism analyses showed that the added Fe3O4 facilitated sludge conductive capacity, and boosted the efficiency of extracellular electron transfer, which accelerated the bioprocess of sulfide oxidation. Although Fe3O4 can chemically oxidize sulfide to elemental sulfur, microbial oxidation plays a major role in reducing H2S accumulation. Moreover, the released iron ions reacted with soluble sulfide, which promoted the chemical equilibrium of sulfide species from H2S to metal sulfide. Microbial analysis showed that some SRBs (i.e., Desulfomicrobium and Defluviicoccus) and SOB (i.e., Sulfuritalea) changed into keystone taxa (i.e., connectors and module hubs) in the reactor with Fe3O4 addition, showing that the functions of sulfate reduction and sulfur oxidation may play important roles in Fe3O4-present system. Fe3O4 presence also increased the content of functional genes encoding sulfide quinone reductase and flavocytochrome c sulfidedehydrogenase (e.g., Sqr and Fcc) that could oxidize sulfide to sulfur. The impact of other iron-based conductive material (i.e., zero-valent iron) was also verified, and the results showed that it could also significantly reduce H2S production. These findings provide new insights into the effect of iron-based conductive materials on anaerobic process, especially sulfur conversion.

Syndepositional and diagenetic processes in the pigmentation of Middle Ordovician carbonate red beds in South China

Marine red beds (MRBs) are often attributed to specific redox environments during syndepositional and early diagenetic phases. During the Middle Ordovician, a succession of reddish, deeper-water nodular argillaceous limestones (i.e., Zitai and Kuniutan formations) were deposited along the margin of Yangtze Platform in South China. However, the origin of their color remains enigmatic. In this study, we investigated the Middle Ordovician MRBs from a borehole core newly drilled in the Lower Yangtze area of South China whose stratigraphy frameworks are constrained by carbon isotope and biostratigraphy. This study investigates the pigmentation of these MRBs by integrating petrographic observations, elemental geochemistry, diffusive reflectance spectrometry (DRS), and scanning electron microscope (SEM) coupled with energy dispersive X-ray spectrometry (EDS). DRS results show that the red pigment is caused by hematite particles in submicron- to micron-level size. SEM demonstrates that the hematite grains are either detrital grains with traces of physical transport from terrestrial source, or flaky amorphous hematite aggregates situated within the calcite crystal interstices, implicating both syndepositional and early diagenetic origins, respectively. In terms of the geochemical result of the bulk rocks, the close positive correlation between Al2O3 and Fe2O3 indicates that the iron pigment materials may mainly originate from terrestrial Fe-bearing phyllosilicates. These observations are also consistent with the distribution patterns of rare earth elements (REEs) in carbonate leachates. The MRB limestones are characterized by MREE-bulged patterns and close to ~1 Ce anomalies, suggesting active reductive dissolution and subsequent reprecipitation of iron oxides during diagenesis in pore systems. This study proposes that the coloration of Middle Ordovician MRBs in Lower Yangtze Platform was linked to the enhanced input of terrestrial clay minerals rich in iron. The reductive dissolution released iron ions from terrestrial detrital and allowed subsequent reprecipitation of iron-oxides in pore water system during the fluid-buffered diagenesis. In this light, hematites formed during both the syndepositional and diagenetic processes thus could have involved the coloration of the Middle Ordovician carbonate red beds in this case.

The Effects of Air Abrasive Polishing on the Release of Iron Ions from Various Orthodontic Arch Wires (Stainless Steel and Nickel Titanium)

Orthodontic treatment with has been increasingly demanded. However, when using fixed appliances for orthodontic treatment, oral hygiene is compromised, and there is a higher chance of developing dental stains, plaque-related diseases, and corrosion-related problems. Air abrasive polishing had a superior effect over the conventional method in removing dental deposits, however, its effect on corrosion process was not investigated thoroughly in details. This study designed to assess the effects of air polishing onion release and surface micromorphology of stainless steel and Nickel titanium arch wires. A total of 288 ( stainless-steel , coated stainless steel , Nickel titanium and coated Nickel titanium rectangular arch wires ) of one brand ( The Ultimate Wire) ™ From IOS (International Orthodontic Services, Stafford, USA), (0.016 * 0.022 ) were subjected to varying air abrasion polishing periods (5, 10, and 20 seconds), after which they were immersed in artificial saliva with a pH of 6.75 and incubated at 37°C for 28 days. Ion release was measured using an atomic absorption spectrophotometer at 7 days, 14 days, and 28 days. The cumulative effect was then calculated. After polishing the chosen sample, corrosion and surface changes were evaluated using a scanning electron microscope (SEM). The significant difference between the analysed groups was found using an analysis of variance (ANOVA) and the LSD test, with a significance level of p 0.05. The results revealed that all types of arch wire showed a significant amount of release in the tested ions and the amounts of nickel and iron ions released was higher than chromium ion. Additionally, the longer the polishing time the higher the number of ions release that’s yields the level of significance, air abrasion polishing increased surface roughness and surface pits and crevices.It may be concluded that the air polishing method enhanced the amount of ion release to a subtoxic level and could be employed in adult patients with a lengthy time between visits.This study was performed to:1. Evaluate the effect of calcium carbonate airborne particles abrasion with different polishing times 5, 10 and 20 seconds on (Fe) ions release from orthodontic arch wires. 2. Assess the surface micromorphology of orthodontic arch wires after air polishing procedure.

Intranasal Delivery of Near-Infrared and Magnetic Dual-Response Nanospheres to Rapidly Produce Antidepressant-Like and Cognitive Enhancement Effects.

Restricted by synaptic plasticity, dopamine receptor (DR) upregulation takes a long time to work. Moreover, the impact of the blood-brain barrier (BBB) on delivery efficiency restricts the development of drugs. Taking inspiration from snuff bottles, a convenient, fast-acting, and nonaddictive nasal drug delivery system has been developed to rapidly reshape the balance of synaptic transmitters. This optical and magnetic response system called CFs@DP, comprised of carbonized MIL-100 (Fe) frameworks (CFs) and domperidone (DP), which can enter the brain via nasal administration. Under dual stimulation of near-infrared (NIR) irradiation and catecholamine-induced complexation, CFs@DP disintegrates to release iron ions and DP, causing upregulation of the dopamine type 1 (D1), type 2 (D2) receptors, and brain-derived neurotrophic factor (BDNF) to achieve a therapeutic effect. In vivo experiments demonstrate that the DR density of mice (postnatal day 50-60) increased in the prefrontal cortex (PFC) and the hippocampus (HPC) after 10 days of therapy, resulting in antidepressant-like and cognitive enhancement effects. Interestingly, the cognitive enhancement effect of CFs@DP is even working in noniron deficiency (normal fed) mice, making it a promising candidate for application in enhancing learning ability.

The iron(III) coordinating properties of citrate and α-hydroxycarboxylate containing siderophores.

The iron(III) binding properties of citrate and rhizoferrin, a citrate containing siderophore, are compared. Citrate forms many oligonuclear complexes, whereas rhizoferrin forms a single mononuclear complex. The α-hydroxycarboxylate functional group, which is present in both citrate, and rhizoferrin, has a high affinity and selectivity for iron(III) under most biological conditions. The nature of the toxic form of iron found in the blood of patients suffering from many haemoglobinopathies and haemochromatosis is identified as a mixture of iron(III)citrate complexes. The significance of the presence of this iron pool to patients suffering from systemic iron overload is discussed. The wide utilisation of the α-hydroxycarboxylate functional group in siderophore structures is described, as is their photo-induced decarboxylation leading to the release of iron(II) ions. The importance of this facile dissociation to algal iron uptake is discussed.

Reactive Oxygen Species Activate a Ferritin-Linked TRPV4 Channel under a Static Magnetic Field.

Magnetogenetics has shown great potential for cell function and neuromodulation using heat or force effects under different magnetic fields; however, there is still a contradiction between experimental effects and underlying mechanisms by theoretical computation. In this study, we aimed to investigate the role of reactive oxygen species (ROS) in mechanical force-dependent regulation from a physicochemical perspective. The transient receptor potential vanilloid 4 (TRPV4) cation channels fused to ferritin (T4F) were overexpressed in HEK293T cells and exposed to static magnetic fields (sMF, 1.4-5.0 mT; gradient: 1.62 mT/cm). An elevation of ROS levels was found under sMF in T4F-overexpressing cells, which could lead to lipid oxidation. Compared with the overexpression of TRPV4, ferritin in T4F promoted the generation of ROS under the stimulation of sMF, probably related to the release of iron ions from ferritin. Then, the resulting ROS regulated the opening of the TRPV4 channel, which was attenuated by the direct addition of ROS inhibitors or an iron ion chelator, highlighting a close relationship among iron release, ROS production, and TRPV4 channel activation. Taken together, these findings indicate that the produced ROS under sMF act on the TRPV4 channel, regulating the influx of calcium ions. The study would provide a scientific basis for the application of magnetic regulation in cellular or neural regulation and disease treatment and contribute to the development of the more sensitive regulatory technology.

Effects of water-induced aging on iron (oxyhydr)oxides nanoparticles: linking crystal structure, iron ion release, and toxicity

Effects of water-induced aging on iron (oxyhydr)oxides nanoparticles: linking crystal structure, iron ion release, and toxicity

Activation of iron oxide minerals in an aquifer by humic acid to promote adsorption of organic molecules

In aquifers, the sequestration and transformation of organic carbon are closely associated with soil iron oxides and can facilitate the release of iron ions from iron oxide minerals. There is a strong interaction between dissolved organic matter (DOM) and iron oxide minerals in aquifers, but the extent to which iron is activated by DOM exposure to active iron minerals in natural aquifers, the microscopic distribution of minerals on the surface, and the mechanisms involved in DOM molecular transformation are currently unclear. This study investigated the nonbiological reduction transformation and coupled adsorption of iron oxide minerals in aquifers containing DOM from both macro- and micro perspectives. The results of macroscopic dynamics experiments indicate that DOM can mediate soluble iron release during the reduction of iron oxide minerals, that pH strongly affects DOM removal, and that DOM is more efficiently degraded at low rather than high pH values, suggesting that a low pH is conducive to DOM adsorption and oxidation. Spherical aberration-corrected scanning transmission electron microscopy (SACTS) indicates that the reacted mineral surfaces are covered with large amounts of carbon and that dynamic agglomeration of iron, carbon, and oxygen occurs. At the nanoscale, three forms of DOM are found in the mineral surface agglomerates (on the surfaces, inside the surface agglomerates, and in the polymer pores). The microscopic organic carbon and iron mineral reaction patterns can form through oxidation reactions and selective adsorption effects. Fourier transform ion cyclotron resonance mass spectra indicate that both synergistic and antagonistic reactions occur between DOM and the minerals, that the release of iron is accompanied by DOM decomposition and humification, that large oxygen- and carbon-containing molecules are broken down into smaller oxygen- and carbon-containing compounds and that more molecules are produced through oxidation under acidic rather than alkaline conditions. These molecules provide adsorption sites for sediment, meaning that more iron can be released. Microscopic evidence for the release of iron was acquired. These results improve the understanding of the geochemical processes affecting iron in groundwater, the nonbiological transformation mechanisms that occur at the interfaces between natural iron minerals and organic matter, groundwater pollution control, and the environmental behavior of pollutants.

A Cancer Nanovaccine Based on an FeAl-Layered Double Hydroxide Framework for Reactive Oxygen Species-Augmented Metalloimmunotherapy.

The complexity and heterogeneity of individual tumors have hindered the efficacy of existing therapeutic cancer vaccines, sparking intensive interest in the development of more effective in situ vaccines. Herein, we introduce a cancer nanovaccine for reactive oxygen species-augmented metalloimmunotherapy in which FeAl-layered double hydroxide (LDH) is used as a delivery vehicle with dihydroartemisinin (DHA) as cargo. The LDH framework is acid-labile and can be degraded in the tumor microenvironment, releasing iron ions, aluminum ions, and DHA. The iron ions contribute to aggravated intratumoral oxidative stress injury by the synergistic Fenton reaction and DHA activation, causing apoptosis, ferroptosis, and immunogenic cell death in cancer cells. The subsequently released tumor-associated antigens with the aluminum adjuvant form a cancer nanovaccine to generate robust and long-term immune responses against cancer recurrence and metastasis. Moreover, Fe ion-enabled T1-weighted magnetic resonance imaging can facilitate real-time tumor therapy monitoring. This cancer-nanovaccine-mediated metalloimmunotherapy strategy has the potential for revolutionizing the precision immunotherapy landscape.

Dramatic change in the properties of magnetite-modified MOF particles depending on the synthesis approach

Iron-containing metal–organic frameworks are promising Fenton catalysts. However, the absence of additional modifiers has proven difficult due to the low reaction rates and the inability to manipulate the catalysts. We hypothesize that the production of iron oxide NPs in the presence of a metal-organic framework will increase the rate of the Fenton reaction and lead to the production of particles that can be magnetically manipulated without changing the structure of the components. A comprehensive approach lead to a metal organic framework using the example of MIL-88b (Materials of Institute Lavoisier) modified with iron oxides NPs: formulation of iron oxide in the presence of MIL-88b and vice versa. The synthesis of MIL-88b consists of preparing a complexation compound with the respective structure and addition of terephthalic acid. The synthesis of MIL-88b facilitates to control the topology of the resulting material. Both methods for composite formulation lead to the preservation of the structure of iron oxide, however, a more technologically complex approach to obtaining MIL-88b in the presence of Fe3O4 suddenly turned out to be the more efficient for the release of iron ions.