Porphyrinic Metal-organic Framework Research Articles

Research progress of porphyrinic metal-organic frameworks based on platinum-group metals

<p indent="0mm">Being one of the most frequently found species in nature, porphyrins have been used as linkers, giving rise to porphyrinic metal-organic frameworks (PMOFs). Porphyrin ligands have good chemical stability, thermal stability and optical properties, combined with the porosity of PMOFs themselves, which endows PMOFs as a heterogeneous catalyst to exhibit distinct properties in catalytic reactions. Meanwhile, porphyrins can accommodate vairous elements in the periodic table, ranging from transition metals to main group elements, and therefore, the catalytic functionalities of MOFs can be easily realized by modulating the central atoms within the porphyrin macrocycles. Platinum-group metalloporphyrins display excellent catalytic performances in photocatalysis, carbene/nitrene transfer and small molecule activation, and the resultant PMOFs based on platinum-group metalloporphyrins can be of great potentials in the heterogeneous catalytic field. This review summarizes the synthetic strategies, structures and catalytic applications of platinum-group metals-based PMOFs.

A Fe(III)-porphyrin-oxaliplatin(IV) nanoplatform for enhanced ferroptosis and combined therapy.

Since there are several limitations in cancer treatment for traditional chemotherapy, such as side effects, poor prognosis and drug resistance, developing new combined therapy is urgently needed. In this work, a biocompatible, simple and tumor microenvironment-responsive nanotheranostics (PCN-Oxpt/PEG) was built to favor the chemotherapy/ferroptosis/immunomodulation synergism in cancer. This nanotheranostics is constructed by modifying oxaliplatin prodrug and PEG on Fe(III)-porphyrin metal-organic frameworks (PCN(Fe) MOFs). After intravenous injection, the cloak of PEG leads to long circulation, and the Fe(III)-porphyrin MOFs enables dual-model guidance with fluorescence (FL) and magnetic resonance imaging (MRI). Inside the tumor, the intracellular H2O2 would be transferred into hydroxyl radicals (•OH) by iron ions released from MOFs, which could trigger the lethal ferroptosis to cancer cells. Meanwhile, oxaliplatin(II) transformed from the loaded oxaliplatin prodrug would result in the chemotherapy, as well as immunogenic cell death (ICD), and the prodrug strategy could also avoid the occurring of liver damage by the direct administration of oxaliplatin(II). It was noticed that the ferroptosis effect was enhanced by triple-assistance during the combined therapy, as followed: (1) glutathione (GSH) would be consumed in the process of oxaliplatin(II) generation from oxaliplatin prodrug; (2) the increased CD8+ T cells induced by ICD were able to produce interferon-γ (IFN-γ), which could inhibit the transport of cystine by tumor cells, and impair the activation of glutathione peroxidase 4 (GPX4); (3) the amount of H2O2 could be increased by the internalized oxaliplatin and thus further promote the Fenton reaction and ferroptosis. Both in vivo and in vitro results revealed that tumor growing was significantly inhibited by PCN-Oxpt/PEG, taken together, the concomitant of oxaliplatin-mediated chemotherapy and ICD with triple-enhanced ferroptosis offer great prospect in the clinical treatment of cancer.

Ferric iron loaded porphyrinic zirconium MOFs on corncob for the enhancement of diuretics extraction.

Herein, corncob waste was used as a scaffold for the fabrication of effective adsorbents. Porphyrinic zirconium metal-organic frameworks (MOFs) PCN-223 and PCN-224 constructed by different numbers of Zr6 cluster nodes were grown on the surface of the corncob. Fe (Ш) ions were implanted in the porphyrin ring by post-synthesis modification. The results showed that the extraction capacity of diuretics on PCN-224@corncob containing suitable pore size was larger than that of PCN-223@corncob. The adsorption of diuretics was further enhanced because of the electrostatic effect caused by implantation of Fe (Ш) ions. PCN-224-Fe@corncob was recyclable and selective for the extraction of furosemide (Fur) and bumetanide (Bum). Coupled in-syringe solid phase extraction (IS-SPE) with ultra-performance liquid chromatography (UPLC), an efficient, sensitive, and stable method was established. With a sensitivity between 0.6 and 1.0μg/L and a recovery between 83.2% and 119.2%, it is used for the analysis of trace amounts of Fur and Bum in weight loss products and environmental water. The functionalized corncob has potential application for the adsorption of diuretics, and the metal ions implantation in MOFs provides a promising strategy for enhancing extraction capacity.

A porous Fe‐based porphyrinic metal–organic framework for highly effective removal of organic azo‐dye

With the rapid development of the global dye industry, a series of environmental problems affecting the ecosystem and human health has been perceived. In this work, a porous porphyrin catecholate iron‐based metal–organic framework (MOF) (PorphCat‐Fe) has been prepared and evaluated for the first time for adsorptive removal of azo‐dye methyl orange (MO) pollutant from aqueous media. Consequently, various MO adsorption factors using PorphCat‐Fe MOF were studied and optimized. PorphCat‐Fe was able to remove about 98% of the pollutant from the water within 20 min in the batch experiments with maximum adsorption capacity of 232.5 mg g−1. Under optimum conditions, the limit of detection (LOD) was found to be 0.8 μg L−1. The MOF could maintain its adsorption efficiency toward MO in the real samples. The combination of electrostatic attractions, hydrophobic and π–π interactions, and iron‐organic coordination bonding make PorphCat‐Fe able to show the superior MO adsorption capacity. Remarkably, the removal efficiency of MO was nearly unchanged after five regeneration sequences on PorphCat‐Fe. This effort offers the ability for application of MOFs beyond metal‐carboxylate linkers in wastewater remediation.

Dual-modes of ratiometric fluorescent and smartphone-integrated colorimetric detection of glyphosate by carbon dots encapsulated porphyrin metal–organic frameworks

Ultrasensitive, reliable and prompt pre-warning of pesticide residue is critically significant to ensure environmental and food safety. Herein, a novel nanosensor fabricated by in situ encapsulating N-doped carbon dots into a porphyrin metal–organic framework was developed to ratiometric fluorescence (RF) and smartphone-integrated portable platform colorimetric dual-mode detection of glyphosate (GLP). The sensor responded to GLP by RF in the range of 0.01–6.67 mg/L with low limit of detection of 9.06 µg/L. Besides, a noticeable color evolution from pink purple to green under nature light was observed upon addition of GLP, thus a portable smartphone-integrated colorimetric platform was fabricated for visual colorimetric detecting GLP by incorporating the sensor with a smartphone and a 3D-printed mini-device. Interestingly, the platform can detect GLP merely by virtue of a built-in flashlight of the smartphone and Color Analyser Application. Additionally, desirable recoveries of 94.0–112.5 % and 90.0–113.6 % in spiked real samples were respectively obtained for RF and colorimetric channel. Furthermore, a one-to-one colorimetric logic gate (RGB vs GLP concentrations) offered the possibility of intelligent monitoring of GLP. Summarily, the versatile sensor satisfied laboratory instrumental analysis and was further integrated as a smartphone-assisted platform to furnish a novel tactic for quick GLP monitoring, particularly for resource-constrained settings.

Silver nanoparticle-decorated 2D Co-TCPP MOF nanosheets for synergistic photodynamic and silver ion antibacterial

Two-dimensional (2D) metal organic framework (MOF) nanosheets have been demonstrated to be promising templates for preparing functional 2D composites. Herein, we report the preparation of silver nanoparticle (Ag NP)-decorated 2D porphyrinic MOF nanosheets (denoted as Ag/Co-TCPP NSs) with a high efficiency for combined antibacterial therapy. The as-prepared Ag/Co-TCPP NSs feature both the advantages of Co-TCPP NSs and Ag NPs, which exhibit excellent antibacterial properties against both Gram-positive (S. aureus) and Gram-negative (E. coli) bacteria. Under a 660 nm laser irradiation, Ag/Co-TCPP NSs locally generated singlet oxygen (1O2) and promoted Ag NPs to be partly degraded for sustained release of toxic Ag+, achieving a synergistic sterilization effect. This effective strategy for achieving 2D MOF nanosheets with in situ loaded metal nanoparticles provides a guideline to broaden the diverse applications of MOFs and contributes to the development of new intelligent metal-based antibacterial nanomaterials.

Nanoscale Porphyrin Metal-Organic Frameworks Deliver siRNA for Alleviating Early Pulmonary Fibrosis in Acute Lung Injury

Acute lung injury (ALI) has high mortality and still lacks novel and efficient therapies. Zinc finger E-box binding homeobox 1 and 2 (ZEB1/2) are highly expressed in the early stage of ALI and are positively correlated with the progression of pulmonary fibrosis. Herein, we developed a nanoscale Zr(IV)-based porphyrin metal-organic (ZPM) framework to deliver small interfering ZEB1/2 (siZEB1/2) to alleviate early pulmonary fibrosis during ALI. This pH-responsive nano-ZPM system could effectively protect siRNAs during lung delivery until after internalization and rapidly trigger siRNA release under the mildly acidic environment of the endo/lysosome (pH 4.0–6.5) for transfection and gene silencing. Furthermore, the in vivo studies confirmed that this nano-ZPM system could anchor in inflamed lungs. Moreover, the ZEB1/2 silencing led to increased E-cadherin and decreased α-SMA levels. Overall, the nano-ZPM system was an excellent non-viral vector system to deliver siRNAs to alleviate early pulmonary fibrosis during ALI.

Strategic Design of Mg-Centered Porphyrin Metal-Organic Framework for Efficient Visible Light-Promoted Fixation of CO2 under Ambient Conditions: Combined Experimental and Theoretical Investigation.

The sunlight-driven fixation of CO2 into valuable chemicals constitutes a promising approach toward environmental remediation and energy sustainability over traditional thermal-driven fixation. Consequently, in this article, we report a strategic design and utilization of Mg-centered porphyrin-based metal-organic framework (MOFs) having relevance to chlorophyll in green plants as a visible light-promoted highly recyclable catalyst for the effective fixation of CO2 into value-added cyclic carbonates under ambient conditions. Indeed, the Mg-centered porphyrin MOF showed good CO2 capture ability with a high heat of adsorption (44.5 kJ/mol) and superior catalytic activity under visible light irradiation in comparison to thermal-driven conditions. The excellent light-promoted catalytic activity of Mg-porphyrin MOF has been attributed to facile ligand-to-metal charge transfer transition from the photoexcited Mg-porphyrin unit (SBU) to the Zr6 cluster which in turn activates CO2, thereby lowering the activation barrier for its cycloaddition with epoxides. The in-depth theoretical studies further unveiled the detailed mechanistic path of the light-promoted conversion of CO2 into high-value cyclic carbonates. This study represents a rare demonstration of sunlight-promoted sustainable fixation of CO2, a greenhouse gas into value-added chemicals.

Porphyrinic MOF derived Single-atom electrocatalyst enables methanol oxidation

Electrochemical methanol oxidation reaction (MOR) serves as a key route for renewable energy technologies. However, unmet challenges remain in the preparation of low-cost, efficient and robust electrocatalysts for MOR. Herein, a porphyrinic metal–organic framework (MOF) with spatially isolated Ni centres is prepared. Upon pyrolysis, this affords a single-atom Ni implanted nitrogen-doped porous carbon (20% Ni-N-C). Integrating abundant and accessible single-atom Ni sites, hierarchical porosity, excellent conductivity with stable Ni-N4 moieties all in one, the derived ultra-stable 20% Ni-N-C exhibits high MOR activity, impressive durability and CO tolerance, thereby outperforming state-of-the-art nonprecious metal based electrocatalysts. Computational insights reveal a low energy barrier of 1.19 eV for the rate-determining step, in agreement with the experimental observations of superior MOR activity. As the first foray into improving MOR efficiency with nonprecious metal based single-atom electrocatalysts, the yet-unrealized potential for MOFs and related modular hybrids is demonstrated.

Atomic-layer Fe2O3-modified 2D porphyrinic metal-organic framework for enhanced photocatalytic disinfection through electron-withdrawing effect

In this work, an atomic-layer Fe2O3-modified two-dimensional (2D) porphyrinic metal-organic framework (MOF) was prepared (2D MOF-Fe2O3), which exhibits unique interfacial electron-withdrawing effect via charge transfer pathways from Zn2O8 and C-O bonds to Fe-O bonds. Concretely, the atomic-layer Fe2O3 is deposited on 2D porphyrinic MOF (ZnTCPP) by atomic layer deposition technique to enhance the photocatalytic performance and the subsequent bacteria-killing efficacy. After 20 min light irradiation, the photocatalytic antibacterial efficacy of 2D MOF-Fe2O3 can reach up to 99.9%. The underlying mechanism of enhanced photocatalytic activity is that the heterointerface between 2D MOF and Fe2O3 can facilitate the transfer of lots of photogenerated electrons from 2D MOF to Fe2O3, where 2D MOF and Fe2O3 act as electronic donator and receptor, respectively. This work provides an insight into developing highly effective photocatalysts by using electron-withdrawing modulator to optimize charge transfer pathway.

Ultrathin Two‐Dimensional Metal–Organic Framework Nanosheets Based on a Halogen‐Substituted Porphyrin Ligand: Synthesis and Catalytic Application in CO2 Reductive Amination

Ultrathin two-dimensional metal-organic framework nanosheets have emerged as a promising kind of heterogeneous catalysts. Herein, we report a series of 2D porphyrinic metal-organic framework nanosheets (X-PMOF, X=F, Cl, Br), which was prepared from the self-assembly of a halogen-based porphyrin ligand X-TCPP (X-TCPP=5-(4-halogenatedphenyl)-10,15,20-tris(4-carboxyphenyl)-porphyrin) and ZrCl4 in the presence of trifluoroacetic acid as the modulating reagent. The framework of X-PMOF possessed the ftw topology as in MOF-525. The lamellar X-PMOF nanosheets with the thickness of down to 4.5 nm were assembled and aggregated into a flower-like morphology. With the introduction of iridium(III) atoms into the porphyrin rings, the resultant X-PMOF(Ir) nanosheets were prepared by a similar method. Catalytic results show that Br-PMOF(Ir) nanosheets were efficient for CO2 reduction and aminolysis, giving rise to formamides in high yields under room temperature and atmospheric pressure, and can be recycled and reused for 3 runs. The total turnover number of Br-PMOF(Ir) after 3 runs was 1644 based on Ir. Mechanistic studies disclose that the high efficiency of Br-PMOF(Ir) nanosheets was ascribed to three factors, including the superior activation capability of iridium(III) porphyrin for Si-H bonds, more active sites on the external surfaces of Br-PMOF(Ir) nanosheets, and the defects caused by unsymmetrical porphyrin ligand that increased the framework's affinity towards CO2 .

Two dimensional porphyrin-based metal–organic framework constructed on K4Nb6O17 microflowers for highly efficient charge transfer and photocatalytic hydrogen generation

By constructing Co(II) meso-tetra(4-carboxyphenyl) porphyrin-metal organic frameworks (CPMOF) on K4Nb6O17 microflowers, a special K4Nb6O17-based nanocomposite (K4Nb6O17/CPMOF) was achieved. The CPMOF constructed on the K4Nb6O17 microflowers was employed as strong light-harvesting sensitizer and electron transfer carrier, and thus the light absorbance range of K4Nb6O17 microflowers could be efficiently expanded as well as relatively high separation of photo-generated charges was obtained. Only introducing 9 wt% CPMOF, the K4Nb6O17/CPMOF nanocomposite showed about 17.5 times higher photocatalytic activity than that of K4Nb6O17 microflowers. Impressively, the stability of the K4Nb6O17/CPMOF can be improved due to the protection of the K4Nb6O17 microflowers and the constructed heterostructure. The reason for the enhanced photocatalytic activity was explored in detail. This research will provide a new perspective for the rational design of oxysalt-based photocatalysts used in energy conversion.

Near-infrared light triggered photodynamic therapy and release of silver ion from CuTCPP nanosheet for synergistic Gram-positive bacteria elimination

Bacterial infection increases the risk of human morbidity and mortality. There is a significant desire for more effective bacterial treatment through the precise therapeutic method. Herein, a Gram-positive bacterial-specific antimicrobial nanoplatform (CuTCPP@AgNPs@MBA) based on the synergistic effect of near-infrared laser (NIR)-induced Ag+ release and generation of reactive oxygen species (ROS) was developed. CuTCPP@AgNPs@MBA was constructed using mercaptophenylboronic acid (MBA) functional two-dimensional (2D) copper-tetrakis-(4-carboxyphenyl)porphyrin (CuTCPP) metal-organic framework (MOF) nanosheet combined with Ag nanoparticles (Ag NPs) in situ grown on their surface. The formed CuTCPP@AgNPs@MBA possessed high specific surface area, active oxygen generation capacity, and the inherent antibacterial activity of Ag NPs. In addition, MBA molecules can improve its targeting performance and biocompatibility. Experiment results showed that CuTCPP@AgNPs@MBA was more efficacious to kill Staphylococcus aureus compared with pure CuTCPP nanosheet or MBA-unfunctional CuTCPP@AgNPs. This study provides a new strategy for antimicrobial application.

Metallated porphyrinic metal−organic frameworks for CO2 conversion to HCOOH: A computational screening and mechanistic study

Catalytic CO2 conversion is a promising and increasingly needed strategy to reduce carbon footprint, stockpile renewable energy in the form of fuels and high value-added chemicals. In recent years, porphyrinic metal-organic frameworks (PMOFs) have emerged as potential catalysts due to their isolated active sites, tunable structures and functionalities. Herein, we report a computational exploration for CO2 conversion into formic acid (HCOOH) on 9 metallated porphyrinic MOF-525(M) (M = CrIII, MnIII, FeIII, CoIII, NiII, CuII, ZnII, RhIII and IrIII) via density functional theory (DFT) calculations. The confinement effect of MOF-525(M) framework on CO2 conversion is found to be negligible. A reaction mechanism involving H2 dissociation and subsequent CO2 hydrogenation is proposed and investigated in detail, and the former is revealed to be rate-determining. From the analysis of natural bonding orbital (NBO) charges, charge transfer among different atoms is observed during H2 dissociation and the magnitude of charge is governed by the internal charge redistribution and the spin-state of metal. Moreover, d–σ* back-donation is unraveled to be significant in H2 dissociation on MOF-525(Rh) and MOF-525(Ir). Good correlations are established between the energy barriers of H2 dissociation and certain geometric/thermodynamic properties. During CO2 hydrogenation, there is significant non-covalent interaction between CO2 and dissociated H atom, and a strong attractive interaction is revealed to be favorable for hydrogenation. All the 9 MOF-525(M) are predicted to be catalytic active over the gas-phase reaction, particularly MOF-525(Rh) and MOF-525(Ir) are screened out as the best catalysts for CO2 conversion to HCOOH. This study demonstrates the capability of metallated porphyrinic MOF-525 to catalyze CO2 conversion and would assist in the future rational design of more efficient MOFs for CO2 conversion.

The Mn-modified porphyrin metal-organic framework with enhanced oxidase-like activity for sensitively colorimetric detection of glutathione

The selective detection of glutathione (GSH) has been used as important colorimetric probe for human health. Herein, we used a facile method to synthesize manganese ions modified porphyrin metal-organic framework (PCN-224-Mn) with a size of 125.7 ± 14.2 nm and zeta potential of −3.9 ± 0.5 mV. We showed that PCN-224-Mn catalyzed oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) in the absence of H2O2, resulting in a blue-colored oxidized TMB (oxTMB) that exhibits oxidase-like activity. Furthermore, a simple colorimetric detection method for GSH was developed based on the oxidase-like activity of PCN-224-Mn. This method shows wide linear detection range of 0.5–60 μM for GSH with a much lower detection limit of 0.233 μM. Finally, the recovery of colorimetric sensor of PCN-224-Mn suggests its great potential as a biosensor. As the catalytically active site, the manganese porphyrin unit plays a major role in the oxidase-like property and detection ability of PCN-224-Mn. Our data suggest that GSH detection method using PCN-224-Mn has great potential in multiple applications in the future.

3D Printing of Metal-Organic Framework-Based Ionogels: Wearable Sensors with Colorimetric and Mechanical Responses.

Soft ionotronics are emerging materials as wearable sensors for monitoring physiological signals, sensing environmental hazards, and bridging the human-machine interface. However, the next generation of wearable sensors requires multiple sensing capabilities, mechanical toughness, and 3D printability. In this study, a metal-organic framework (MOF) and three-dimensional (3D) printing were integrated for the synthesis of a tough MOF-based ionogel (MIG) for colorimetric and mechanical sensing. The ink for 3D printing contained deep eutectic solvents (DESs), cellulose nanocrystals (CNCs), MOF crystals, and acrylamide. After printing, further photopolymerization resulted in a second covalently cross-linked poly(acrylamide) network and solidification of MIG. As a porphyrinic Zr-based MOF, MOF-525 served as a functional filler to provide sharp color changes when exposed to acidic compounds. Notably, MOF-525 crystals also provided another design space to tune the printability and mechanical strength of MIG. In addition, the printed MIG exhibited high stability in the air because of the low volatility of DESs. Thereafter, wearable auxetic materials comprising MIG with negative Poisson's ratios were prepared by 3D printing for the detection of mechanical deformation. The resulting auxetic sensor exhibited high sensitivity via the change in resistance upon mechanical deformation and a conformal contact with skins to monitor various human body movements. These results demonstrate a facile strategy for the construction of multifunctional sensors and the shaping of MOF-based composite materials.

Ultrasensitive electrochemical determination of bisphenol A in food samples based on a strategy for activity enhancement of enzyme: Layer-by-layer self-assembly of tyrosinase between two-dimensional porphyrin metal–organic framework nanofilms

Bisphenol A, as an endocrine disruptor, has aroused widespread attention for its safety. Electrochemical enzyme-based biosensor is a powerful tool for the determination of bisphenol A, but the instability of enzyme limits its practical application. Assembling biomacromolecules in metal–organic frameworks (MOFs) can preserve their biological functions in harsh environments. In this work, tyrosinase (Tyr) was assembled layer-by-layer in an ultrathin copper–porphyrin MOF nanofilm (Tyr@Cu–TCPP) via a simple one-step solvothermal method, and an ultrasensitive electrochemical biosensor was fabricated for bisphenol A detection. Compared with native Tyr or a traditional surface-adsorbed structure of Tyr on Cu–TCPP nanofilm, Tyr@Cu–TCPP retained superior enzymatic activity when exposed to elevated temperatures and extreme acidity or basicity, the sensor exhibited significantly enhanced thermal and long-term storage stability, as well as acid/base tolerance. In addition, the electrochemical biosensor based on Tyr@Cu–TCPP showed significantly enhanced sensing performance, including a wide linear range of 3.5 nM–18.9 μM, with a detection limit of 1.2 nM. For the first time, the fabrication of an electrochemical biosensor relying on enzyme assembled between two-dimensional MOF nanomaterial layers has been reported. This method greatly improves the activity and stability of the biosensor, and provides a promising strategy for promoting the application of enzyme biosensors in harsh detection environments, discovering and controlling environmental pollutants and food hazards.

Temperature sensitive polyMOF hydrogel formed by in situ open-ring polymerization for infected chronic wound treatment

Chronic wounds, especially those caused by drug-resistant bacteria, remain mostly intractable to existing treatments. Photothermal therapy, apart from the additional inflammation it may cause, exhibits potent ability to efficiently destroy drug-resistant bacteria. A system capable of thermal therapy together with active regulation of the repairing process could be a potentially effective treatment for these wounds. Here we developed a highly integrated hydrogel made of curcumin loaded copper-tetrakis(4-carboxyphenyl)porphyrin metal–organic framework and poly (ethylene glycol)-poly(ε-caprolactone-co-lactide) hybrid by in situ ring-opening polymerization. It combines photothermal effect, immune modulatory, hemostasis and temperature-sensitive sol–gel transition capacity. This multifunctional polymer-metal–organic framework (polyMOF) hydrogel dressing showed the ability to completely heal drug-resistant bacteria infected wounds within 14 days and could be an effective and biocompatible material for chemo-photothermal therapy against chronic wounds. Moreover, our strategy to prepare the polyMOF hybrid may provide a universal approach for the development of multifunctional gels with great significance in clinical application.

Porphyrin NanoMetal-Organic Frameworks as Cancer Theranostic Agents.

Metal-Organic Frameworks (MOFs) are hybrid multifunctional platforms that have found remarkable applications in cancer treatment and diagnostics. Independently, these materials can be employed in cancer treatment as intelligent drug carriers in chemotherapy, photothermal therapy, and photodynamic therapy; conversely, MOFs can further be used as diagnostic tools in fluorescence imaging, magnetic resonance imaging, computed tomography imaging, and photoacoustic imaging. One essential property of these materials is their great ability to fine-tune their composition toward a specific application by way of a judicious choice of the starting building materials (metal nodes and organic ligands). Moreover, many advancements were made concerning the preparation of these materials, including the ability to downsize the crystallites yielding nanoporous porphyrin MOFs (NMOFs) which are of great interest for clinical treatment and diagnostic theranostic tools. The usage of porphyrins as ligands allows a high degree of multifunctionality. Historically these molecules are well known for their reactive oxygen species formation and strong fluorescence characteristics, and both have proved helpful in cancer treatment and diagnostic tools. The anticipation that porphyrins in MOFs could prompt the resulting materials to multifunctional theranostic platforms is a reality nowadays with a series of remarkable and ground-breaking reports available in the literature. This is particularly remarkable in the last five years, when the scientific community witnessed rapid development in porphyrin MOFs theranostic agents through the development of imaging technologies and treatment strategies for cancer. This manuscript reviews the most relevant recent results and achievements in this particular area of interest in MOF chemistry and application.

Two-photon responsive porphyrinic metal-organic framework involving Fenton-like reaction for enhanced photodynamic and sonodynamic therapy.

Designing new oxygenation nanomaterials by oxygen-generating or oxygen-carrying strategies in hypoxia-associated anti-tumor therapy is a high priority target yet challenge. In this work, we fabricated a nanoplatform involving Fenton-like reaction, Pd@MOF-525@HA, to relieve tumor hypoxia via oxygen-generating strategy for enhanced oxygen-dependent anti-tumor therapy. Thereinto, the porphyrinic MOF-525 can produce singlet oxygen (1O2) via light or ultrasonic irradiation for photodynamic and sonodynamic therapy. Notably, the well-dispersed Pd nanocubes within MOF-525 can convert H2O2 into O2 to mitigate the hypoxic environment for enhanced therapy outcome. Moreover, the two-photon activity and cancer cell specific targeting capability of Pd@MOF-525@HA gave rise to deeper tissue penetration and near-infrared light-induced fluorescence imaging to achieve precise guidance for cancer therapy. This work provides a feasible way in designing new oxygenation nanomaterials to relieve tumor hypoxia for enhanced cancer treatment.Graphical Supplementary InformationThe online version contains supplementary material available at 10.1186/s12951-022-01436-3.