ABSTRACT
Anthrax bacillus is a very dangerous zoonotic pathogen that seriously endangers public health. Rapid and accurate qualitative and quantitative detection of its biomarkers, 2,6-dipicolinic acid (DPA), is crucial for the prevention and treatment of this pathogenic bacterium. In this work, a novel Cd-based MOF (TTCA-Cd) has been synthesized from a polycarboxylate ligand, [1,1':2',1â³-terphenyl]-4,4',4â³,5'-tetracarboxylic acid (H4TTCA), and further doped with Tb(III), forming a dual-emission lanthanide-functionalized MOF hybrid (TTCA-Cd@Tb). TTCA-Cd@Tb can be developed as a high-performance ratiometric fluorescent sensor toward DPA with a very low detection limit of 7.14 nM and high selectivity in a wide detection range of 0-200 µM, demonstrating a big advancement and providing a new option for the detection of DPA.
Subject(s)
Anthrax , Bacillus anthracis , Biomarkers , Fluorescent Dyes , Metal-Organic Frameworks , Picolinic Acids , Terbium , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/chemical synthesis , Terbium/chemistry , Picolinic Acids/analysis , Picolinic Acids/chemistry , Fluorescent Dyes/chemistry , Fluorescent Dyes/chemical synthesis , Biomarkers/analysis , Anthrax/diagnosis , Cadmium/chemistry , Cadmium/analysis , Molecular Structure , Limit of Detection , Spectrometry, FluorescenceABSTRACT
Although hierarchically porous zeolitic imidazolate frameworks (HPZIFs) not only inherit the intrinsic architectural and chemical stabilities of their microporous counterparts but also afford open space for the efficient mass diffusion of the macromolecules involved, their rational design and construction are still challenging. Herein, HPZIFs with tailorable pore sizes ranging from 18 to 54 nm were successfully fabricated by using a newly developed soft-template-directed strategy. Our success rooted in the fact that the screened PS81-PVP44-PEO113 triblock copolymer could effectively coordinate with the metal precursor for the directed crystallization of ZIFs along surfactant assemblies. The advantages of continuous large pores and open structures in such HPZIFs were fully taken into account to serve as a bioreactor for the efficient immunoassay. The expanded large pores provided not only a significantly vast surface area to enhance the density of capture antibodies but also enough space for accommodating multiple conjugated biomolecules in one pore channel. In combination with a cascade enzyme cycle amplification strategy, a model biomarker of prostate-specific antigen (PSA) at the femtomolar level was checked with a limit of detection of 92 fM using the developed immunosensor. Specific screening on patients with prostate cancer or even benign prostatic hyperplasia was exemplified through accurately quantifying small changes of PSA concentration in clinical serum samples, prefiguring the great potential of the developed HPZIF-8 immunosensor platform for the early monitoring and diagnostics of diseases.
Subject(s)
Imidazoles , Prostate-Specific Antigen , Zeolites , Zeolites/chemistry , Immunoassay/methods , Porosity , Imidazoles/chemistry , Humans , Prostate-Specific Antigen/blood , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/chemical synthesis , Biosensing Techniques/methods , Limit of DetectionABSTRACT
Gossypol (Gsp) and antibiotics present in water bodies become organic pollutants that are harmful to human health and the ecological environment. Accurate and effective detection of these pollutants has far-reaching significance in many fields. A new three-dimensional metal-organic framework (MOF), {[Eu3(L)2(HCOO-)(H2O)3]·2H2O·2DMF}n (Eu-MOF), was synthesized from 3,5-bis(2,4-dicarboxylphenyl)nitrobenzene (H4L) ligand and Eu3+ via the solvothermal method in this paper. The Eu-MOF demonstrates strong red fluorescence and can remain stable in different pH solutions. The MOF fluorescence probe could detect organic pollutants through the "shut-off" effect, with a fast response speed and a low detection limit [Gsp, nitrofurantoin (NFT), and nitrofurazone (NFZ) for 0.43, 0.38, and 0.41 µM, respectively]. During the testing process, Eu-MOF exhibited good selectivity and recoverability. Furthermore, the mechanism of fluorescence quenching was investigated, and the recoveries were also good in real samples. This paper introduced a deep learning model to recognize the fluorescence images, a portable intelligent logic detector designed for real-time detection of Gsp by logic gate strategy, and an anticounterfeiting mark prepared based on inkjet printing. Importantly, this work provides a new way of thinking for the detection of organic pollutants in water with high sensitivity and practicality by combining the fluorescence probe with machine learning and logical judgment.
Subject(s)
Anti-Bacterial Agents , Europium , Fluorescent Dyes , Gossypol , Metal-Organic Frameworks , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/chemical synthesis , Fluorescent Dyes/chemistry , Fluorescent Dyes/chemical synthesis , Europium/chemistry , Anti-Bacterial Agents/analysis , Anti-Bacterial Agents/chemistry , Gossypol/analysis , Gossypol/chemistry , Water Pollutants, Chemical/analysis , Nitrofurans/analysis , Spectrometry, Fluorescence , Molecular Structure , Limit of DetectionABSTRACT
Morphological modulation in covalent organic frameworks (COFs) with particular emphasis on the correlation between structure and target applications in biomedical fields, is currently in its early stage of evolution. Herein, a multifunctional rattle-architecture imine-based COF with a mobile core of gold nanoparticles (Au NPs) and an outer polydopamine (PDA) shell, tailored for cancer treatment, has been developed to effectively integrate dual responsive release capabilities with the potential for multiple therapeutic applications. The engineered COF displays outstanding crystallinity, a suitable size and precisely controlled morphological characteristics. By leveraging COF and PDA attributes, the successful co-delivery of hydrophilic doxorubicin (DOX) and hydrophobic docetaxel (DTX) within discrete compartments is achieved responsive to both pH and near-infrared triggers. Designed nanocarrier outperforms prior COFs with a superior 83.7% DOX loading capacity, thanks to its expansive internal space and porous shell. Taking advantage of the inclusion of Au core and the concurrent presence of COF and PDA outer shells, the nanocarrier exhibits a significant photothermal-conversion capability. The rattle-architecture double-shelled Au@RCOF@PDA were functionalized with poly(ethylene glycol)-folic acid (PEG-FA) to confer the system with active-targeting capability and enhanced biocompatibility. Through in vitro and in vivo evaluations, the designed system demonstrates an exceptional synergistic anti-tumor effect, along with favorable biosafety and histocompatibility. This study not only sheds light on the remarkable merits offered by regulating the morphology of COF-based systems in cancer therapy but also highlights the potential for synergistic therapeutic approaches in advancing cancer treatment strategies.
Subject(s)
Antineoplastic Agents , Docetaxel , Doxorubicin , Gold , Indoles , Metal-Organic Frameworks , Photothermal Therapy , Doxorubicin/chemistry , Doxorubicin/pharmacology , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/pharmacology , Metal-Organic Frameworks/chemical synthesis , Humans , Docetaxel/chemistry , Docetaxel/pharmacology , Gold/chemistry , Gold/pharmacology , Antineoplastic Agents/chemistry , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemical synthesis , Animals , Indoles/chemistry , Indoles/pharmacology , Polymers/chemistry , Polymers/pharmacology , Mice , Drug Screening Assays, Antitumor , Particle Size , Surface Properties , Metal Nanoparticles/chemistry , Drug Liberation , Cell Survival/drug effects , Cell Proliferation/drug effects , Drug Carriers/chemistryABSTRACT
Metal-organic frameworks (MOFs) are materials with potential applications in fields such as gas adsorption and separation, catalysis, and biomedicine. Attempts to enhance the utility of MOFs have involved the preparation of various composites, including polymer-grafted MOFs. By directly grafting polymers to the external surface of MOFs, issues of incompatibility between polymers and MOFs can be overcome. Polymer brushes grafted from the surface of MOFs can serve to stabilize the MOF while enabling particle assembly into self-assembled metal-organic framework monolayers (SAMMs) via polymer-polymer interactions. Control over the chemical composition and molecular weight of the grafted polymer can allow for tuning of the SAMM characteristics. In this work, instructions are provided on how to immobilize a chain transfer agent (CTA) onto the surface of the MOF UiO-66 (UiO = Universitetet i Oslo). The CTA serves as initiation sites for the growth of polymers. Once polymer chains are grown from the MOF surface, the formation of SAMMs is achieved through self-assembly at an air-water interface. The resulting SAMMs are characterized and shown to be freestanding by scanning electron microscopy imaging. The methods presented in this paper are expected to make the preparation of SAMMs more accessible to the research community and thereby expand their potential use as a MOF-polymer composite.
Subject(s)
Polymers , Polymers/chemistry , Organometallic Compounds/chemistry , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/chemical synthesis , Phthalic AcidsABSTRACT
The selective separation and purification of artesunate (ARU) and artemisinin (ART) using zirconium-based metal-organic frameworks (MOF), especially UiO-66 MOF, are receiving increasing attention. In this study, tunable "hydrophobic" sites of thiol (-SH) were introduced to amino-functionalized MOFs (UiO-66-NH2) to fabricate a thiol-amino bifunctional UiO-66/polyvinylidene fluoride (PVDF)-blended membrane (S1-UiO/PVDF-DPIM) via the delayed-phase-inversion method for selective separation of ARU/ART. The adsorption results indicated that the modification of UiO-66-NH2 with thiol can indeed increase the ARU adsorption. The thiol-functional MOF (S1-UiO-66-NH2) was chosen as the optimal thiol-amino bifunctional MOF, as it possessed the maximum ARU adsorption capacity (111.14 mg g-1) and the highest selective-separation factor (α = 51.84). The ATR FT-IR dynamic spectrum disclosed the recognition mechanism, indicating that incorporating thiol groups into a hydrophilic MOF as hydrophobic sites can boost adsorption efficiency. Moreover, the static-selective permeation results showed that the S1-UiO/PVDF-DPIM preferentially transfers ARU when mixed with ART, even achieving complete ARU/ART separation. The most crucial aspect was the introduction of a hydrophobic core of -SH and new spontaneously formed disulfide bonds to S1-UiO/PVDF-DPIM, creating alternated hydrogen bonds and hydrophobic interactions. This work provides an alternative strategy to prepare hydrophobic-hydrophilic MOF-based membranes for the highly efficient and selective separation of complex analogue systems.
Subject(s)
Artesunate , Hydrophobic and Hydrophilic Interactions , Metal-Organic Frameworks , Sulfhydryl Compounds , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/chemical synthesis , Sulfhydryl Compounds/chemistry , Sulfhydryl Compounds/isolation & purification , Artesunate/chemistry , Artesunate/pharmacology , Artesunate/isolation & purification , Adsorption , Polyvinyls/chemistry , Membranes, Artificial , Molecular Structure , Artemisinins/chemistry , Artemisinins/isolation & purification , Zirconium/chemistry , Surface Properties , Fluorocarbon Polymers , Phthalic AcidsABSTRACT
Antibiotic resistance is a significant global concern, necessitating the development of either new antibiotics or advanced delivery methods. With this in mind, we report on the synthesis and characterisation of a new family of Metal-Organic Frameworks (MOFs), OnG6 MOFs, designed to act as multi-drug carriers for bacterial infection treatment. OnG6 is based on the pro-drug 4,4'-azodisalicylic acid (AZDH4), which in vivo produces two equivalents of para-aminosalicylic acid (ASA), a crucial drug for M. tuberculosis treatment. X-ray and computational studies revealed that OnG6 MOFs are mesoporous MOFs with etb topology and an [M2(AZD)] formula (M = Zn, OnG6-Zn; Mg, OnG6-Mg; Cu, OnG6-Cu; and Co, OnG6-Co), featuring 1-dimensional channel type pores of 25 Å diameter. OnG6 MOFs are the first reported MOFs bearing the ligand AZDH4, joining the family of mesoporous MOFs arranged in a honeycomb pattern. They absorb isoniazid (INH) and ciprofloxacin (CIPRO) with the former being a specific antibiotic for M. tuberculosis, and the latter being a broader-spectrum antibiotic. The stability of the MOFs and their capacity for antibiotic uptake depend on the nature of the metal ion, with OnG6-Mg demonstrating the highest drug absorption. The antimicrobial activity of these species was assessed against S. aureus and E. coli, revealing that the carriers containing CIPRO displayed optimal efficacy.
Subject(s)
Drug Carriers , Metal-Organic Frameworks , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/pharmacology , Metal-Organic Frameworks/chemical synthesis , Drug Carriers/chemistry , Drug Carriers/chemical synthesis , Microbial Sensitivity Tests , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/chemical synthesis , Ciprofloxacin/pharmacology , Ciprofloxacin/chemistry , Isoniazid/chemistry , Isoniazid/pharmacology , Escherichia coli/drug effects , Mycobacterium tuberculosis/drug effects , Models, MolecularABSTRACT
Photodynamic therapy (PDT) is an emerging treatment but often restricted by the availability of oxygen. Enhancing the lifespan of singlet oxygen (1O2) by fractionated generation is an effective approach to improve the efficacy of PDT. Herein, an imine-based nanoscale COF (TpDa-COF) has been synthesized and functionalized with a pyridone-derived structure (Py) to create a 1O2-storing nanoplatform TpDa-COF@Py, which can reversibly capture and release 1O2. Under 660 nm laser exposure, Py interacts with 1O2 produced by the porphyrin motif in COF backbones to generate 1O2-enriched COF (TpDa-COF@Py + hv), followed by the release of 1O2 through retro-Diels-Alder reactions at physiological temperatures. The continuous producing and releasing of 1O2 upon laser exposure leads to an "afterglow" effect and a prolonged 1O2 lifespan. In vitro cytotoxicity assays demonstrates that TpDa-COF@Py + hv exhibits an extremely low half-maximal inhibitory concentration (IC50) of 0.54 µg/mL on 4T1 cells. Remarkably, the Py-mediated TpDa-COF@Py nanoplatform demonstrates enhanced cell-killing capability under laser exposure, attributed to the sustained 1O2 cycling, compared to TpDa-COF alone. Further in vivo assessment highlights the potential of TpDa-COF@Py + hv as a promising strategy to enhance phototheronostics and achieve effective tumor regression. Accordingly, the study supplies a generalized 1O2 "afterglow" nanoplatform to improve the effectiveness of PDT.
Subject(s)
Cell Survival , Metal-Organic Frameworks , Photochemotherapy , Photosensitizing Agents , Singlet Oxygen , Singlet Oxygen/metabolism , Singlet Oxygen/chemistry , Photosensitizing Agents/chemistry , Photosensitizing Agents/pharmacology , Photosensitizing Agents/chemical synthesis , Animals , Mice , Cell Survival/drug effects , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/pharmacology , Metal-Organic Frameworks/chemical synthesis , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Particle Size , Cell Line, Tumor , Drug Screening Assays, Antitumor , Molecular Structure , Surface Properties , Humans , Cell Proliferation/drug effects , Female , Mice, Inbred BALB CABSTRACT
Zeolitic imidazolate framework-8 (ZIF-8) encapsulating enzymatically active biomolecules has emerged as a novel biocompatible nanozyme and offers significant implications for bioanalysis of various biomarkers towards early diagnosis of severe diseases such as cancers. However, the rapid, continuous and scalable synthesis of these nanozymes still remains challenging. In this work, we proposed a novel microfluidic approach for rapid and continuous synthesis of hemin@ZIF-8 nanozyme. By employing a distinctive combination of zigzag-shaped channel and spiral channel with sudden expansion structures, we have enhanced the mixing efficiency within the chip and achieved effective encapsulation of hemin in ZIF-8. The resulting hemin@ZIF-8 nanoparticles exhibit peroxidase-like activity and are capable of detecting free H2O2 with a limit of detection (LOD) as low as 45 nM, as well as H2O2 secreted by viable cells with a detection threshold of approximately 10 cells per mL. By leveraging this method, we achieved successful detection of cancer cells and effective screening of anticancer drugs that induce oxidative stress injury in cancer cells. This innovative microfluidic strategy offers a new avenue for synthesizing functional nanocomposites to facilitate the development of next-generation diagnostic tools for early disease detection and personalized medicine.
Subject(s)
Antineoplastic Agents , Hemin , Metal-Organic Frameworks , Reactive Oxygen Species , Hemin/chemistry , Hemin/metabolism , Humans , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Reactive Oxygen Species/metabolism , Reactive Oxygen Species/analysis , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/chemical synthesis , Metal-Organic Frameworks/pharmacology , Hydrogen Peroxide/analysis , Hydrogen Peroxide/chemistry , Microfluidic Analytical Techniques/instrumentation , Drug Screening Assays, Antitumor , Lab-On-A-Chip Devices , Zeolites/chemistry , Limit of Detection , ImidazolesABSTRACT
Herein, we report a composite COF material loaded with a Pt nanoenzyme and an organic photosensitizer BODIPY, synthesized via a stepwise post-synthetic modification. The obtained Pt@COF-BDP nanoparticles can efficiently and continuously convert H2O2 to O2, thereby increasing the efficiency of single-linear oxygen production and achieving efficient tumor inhibition.
Subject(s)
Boron Compounds , Metal-Organic Frameworks , Photochemotherapy , Photosensitizing Agents , Platinum , Boron Compounds/chemistry , Boron Compounds/pharmacology , Humans , Photosensitizing Agents/chemistry , Photosensitizing Agents/pharmacology , Photosensitizing Agents/chemical synthesis , Platinum/chemistry , Platinum/pharmacology , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/pharmacology , Metal-Organic Frameworks/chemical synthesis , Animals , Antineoplastic Agents/chemistry , Antineoplastic Agents/pharmacology , Cell Line, Tumor , Mice , Nanoparticles/chemistry , Tumor Hypoxia/drug effects , Hydrogen Peroxide/chemistryABSTRACT
Cyclodextrin-based metal-organic frameworks (CD-MOFs) are gaining traction in the realm of drug delivery due to their inherent versatility and potential to amplify drug efficacy, specificity, and safety. This article explores the predominant preparation techniques for CD-MOFs, encompassing methods like vapor diffusion, microwave-assisted, and ultrasound hydrothermal approaches. Native CD-MOFs present compelling advantages in drug delivery applications. They can enhance drug loading capacity, stability, solubility, and bioavailability by engaging in diverse interactions with drugs, including host-guest, hydrogen bonding, and electrostatic interactions. Beyond their inherent properties, CD-MOFs can be customized as drug carriers through two primary strategies: co-crystallization with functional components and surface post-modifications. These tailored modifications pave the way for controlled release manners. They allow for slow and sustained drug release, as well as responsive releases triggered by various factors such as pH levels, glutathione concentrations, or specific cations. Furthermore, CD-MOFs facilitate targeted delivery strategies, like pulmonary or laryngeal delivery, enhancing drug delivery precision. Overall, the adaptability and modifiability of CD-MOFs underscore their potential as a versatile platform for drug delivery, presenting tailored solutions that cater to diverse biomedical and industrial needs.
Subject(s)
Cyclodextrins , Drug Carriers , Metal-Organic Frameworks , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/chemical synthesis , Cyclodextrins/chemistry , Humans , Drug Carriers/chemistry , Drug Delivery Systems , Drug Liberation , AnimalsABSTRACT
The integration of functional nanomaterials with tissue engineering scaffolds has emerged as a promising solution for simultaneously treating malignant bone tumors and repairing resected bone defects. However, achieving a uniform bioactive interface on 3D-printing polymer scaffolds with minimized microstructural heterogeneity remains a challenge. In this study, we report a facile metal-coordination self-assembly strategy for the surface engineering of 3D-printed polycaprolactone (PCL) scaffolds with nanostructured two-dimensional conjugated metal-organic frameworks (cMOFs) consisting of Cu ions and 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP). A tunable thickness of Cu-HHTP cMOF on PCL scaffolds was achieved via the alternative deposition of metal ions and HHTP. The resulting composite PCL@Cu-HHTP scaffolds not only demonstrated potent photothermal conversion capability for efficient OS ablation but also promoted the bone repair process by virtue of their cell-friendly hydrophilic interfaces. Therefore, the cMOF-engineered dual-functional 3D-printing scaffolds show promising potential for treating bone tumors by offering sequential anti-tumor effects and bone regeneration capabilities. This work also presents a new avenue for the interface engineering of bioactive scaffolds to meet multifaceted demands in osteosarcoma-related bone defects.
Subject(s)
Bone Neoplasms , Bone Regeneration , Osteosarcoma , Polyesters , Printing, Three-Dimensional , Tissue Scaffolds , Osteosarcoma/pathology , Osteosarcoma/drug therapy , Osteosarcoma/therapy , Bone Regeneration/drug effects , Tissue Scaffolds/chemistry , Bone Neoplasms/pathology , Bone Neoplasms/drug therapy , Bone Neoplasms/therapy , Polyesters/chemistry , Humans , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/pharmacology , Metal-Organic Frameworks/chemical synthesis , Surface Properties , Copper/chemistry , Copper/pharmacology , Hyperthermia, Induced , Tissue Engineering , Particle Size , Catalysis , Animals , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Mice , Cell Survival/drug effects , Nanostructures/chemistry , Cell Line, Tumor , Cell Proliferation/drug effectsABSTRACT
Pathogenic bacteria have consistently posed a formidable challenge to human health, creating the critical need for effective antibacterial solutions. In response, enzyme-metal-organic framework (MOF) composites have emerged as a promising class of antibacterial agents. This study focuses on the development of an enzyme-MOF composite based on HZIF-8, incorporating the advantages of simple synthesis, ZIF-8 antibacterial properties, lysozyme hydrolysis, and high biological safety. Through a one-pot method, core-shell nanoparticles (HZIF-8) were synthesized. This structure enables efficient immobilization of lysozyme and lactoferrin within the HZIF-8, resulting in the formation of the lysozyme-lactoferrin@HZIF-8 (LYZ-LF@HZIF-8) composite. Upon exposure to light irradiation, HZIF-8 itself possessed antibacterial properties. Lysozyme initiated the degradation of bacterial peptidoglycan and lactoferrin synergistically enhanced the antibacterial effect of lysozyme. All of the above ultimately contributed to comprehensive antibacterial activity. Antibacterial assessments demonstrated the efficacy of the LYZ-LF@HZIF-8 composite, effectively eradicating Staphylococcus aureus at a cell density of 1.5 × 106 CFU/mL with a low dosage of 200 µg/mL and completely inactivating Escherichia coli at 400 µg/mL with the same cell density. The enzyme-MOF composite exhibited significant and durable antibacterial efficacy, with no apparent cytotoxicity in vitro, thereby unveiling expansive prospects for applications in the medical and food industries.
Subject(s)
Anti-Bacterial Agents , Escherichia coli , Lactoferrin , Metal-Organic Frameworks , Microbial Sensitivity Tests , Muramidase , Staphylococcus aureus , Zeolites , Muramidase/pharmacology , Muramidase/chemistry , Muramidase/metabolism , Lactoferrin/chemistry , Lactoferrin/pharmacology , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/pharmacology , Metal-Organic Frameworks/chemical synthesis , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/chemical synthesis , Staphylococcus aureus/drug effects , Escherichia coli/drug effects , Zeolites/chemistry , Zeolites/pharmacology , Imidazoles/chemistry , Imidazoles/pharmacology , Imidazoles/chemical synthesis , Porosity , Surface Properties , Particle Size , Enzymes, Immobilized/chemistry , Enzymes, Immobilized/pharmacologyABSTRACT
A new quinoline-based COF (covalent organic framework), obtained by Povarov reaction, containing 2,6-diisopropylphenyl moieties as substituents over the heterocyclic ring is described for detecting Zn2+ in aqueous solution. The introduction of the mentioned bulky phenyl rings into the network favors an increase of the distance between the reticular sheets and their arrangement, obtaining a new material with an alternating AB type stacking. The new material exhibits good selectivity to detect Zn2+ by fluorescence emission in aqueous solutions up to a concentration of 1.2 × 10-4 m of the metal ion. In order to have a deeper insight into the interaction between the COF and the zinc cation, a thorough spectroscopical, microscopical, and theoretical study is also presented and discussed in this communication.
Subject(s)
Metal-Organic Frameworks , Quinolines , Spectrometry, Fluorescence , Zinc , Quinolines/chemistry , Zinc/chemistry , Zinc/analysis , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/chemical synthesis , Molecular Structure , Fluorescent Dyes/chemistry , Ions/chemistry , Ions/analysis , FluorescenceABSTRACT
Enzyme immobilization within metal-organic frameworks (MOFs) is a promising solution to avoid denaturation and thereby utilize the desirable properties of enzymes outside of their native environments. The biomimetic mineralization strategy employs biomacromolecules as nucleation agents to promote the crystallization of MOFs in water at room temperature, thus overcoming pore size limitations presented by traditional postassembly encapsulation. Most biomimetic crystallization studies reported to date have employed zeolitic imidazole frameworks (ZIFs). Herein, we expand the library of MOFs suitable for biomimetic mineralization to include zinc(II) MOFs incorporating functionalized terephthalic acid linkers and study the catalytic performance of the enzyme@MOFs. Amine functionalization of terephthalic acids is shown to accelerate the formation of crystalline MOFs enabling new enzyme@MOFs to be synthesized. The structure and morphology of the enzyme@MOFs were characterized by PXRD, FTIR, and SEM-EDX, and the catalytic potential was evaluated. Increasing the linker length while retaining the amino moiety gave rise to a family of linkers; however, MOFs generated with the 2,2'-aminoterephthalic acid linker displayed the best catalytic performance. Our data also illustrate that the pH of the reaction mixture affects the crystal structure of the MOF and that this structural transformation impacts the catalytic performance of the enzyme@MOF.
Subject(s)
Carboxylic Acids , Crystallization , Metal-Organic Frameworks , Temperature , Water , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/chemical synthesis , Carboxylic Acids/chemistry , Water/chemistry , Phthalic Acids/chemistry , Biomimetic Materials/chemistry , Biomimetic Materials/chemical synthesis , Molecular Structure , Zinc/chemistry , Enzymes, Immobilized/chemistry , Enzymes, Immobilized/metabolism , Amines/chemistry , CatalysisABSTRACT
Covalent organic frameworks (COFs) constitute a class of highly functional porous materials composed of lightweight elements interconnected by covalent bonds, characterized by structural order, high crystallinity, and large specific surface area. The integration of naturally occurring porphyrin molecules, renowned for their inherent rigidity and conjugate planarity, as building blocks in COFs has garnered significant attention. This strategic incorporation addresses the limitations associated with free-standing porphyrins, resulting in the creation of well-organized porous crystal structures with molecular-level directional arrangements. The unique optical, electrical, and biochemical properties inherent to porphyrin molecules endow these COFs with diversified applications, particularly in the realm of biology. This review comprehensively explores the synthesis and modulation strategies employed in the development of porphyrin-based COFs and delves into their multifaceted applications in biological contexts. A chronological depiction of the evolution from design to application is presented, accompanied by an analysis of the existing challenges. Furthermore, this review offers directional guidance for the structural design of porphyrin-based COFs and underscores their promising prospects in the field of biology.
Subject(s)
Metal-Organic Frameworks , Porphyrins , Porphyrins/chemistry , Porphyrins/chemical synthesis , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/chemical synthesis , Humans , Porosity , AnimalsABSTRACT
Metal-organic frameworks (MOFs) are porous materials with potential in biomedical applications such as sensing, drug delivery, and radiosensitization. However, how to tune the properties of the MOFs for such applications remains challenging. Herein, we synthesized two MOFs, Zr-PEB and Hf-PEB. Zr-PEB can be classified as porous interpenetrated zirconium frameworks (PIZOFs) and Hf-PEB is its analogue. We controlled their sizes while maintaining their crystal structure by employing a coordination modulation strategy. They were designed to serve as sensitizer for X-ray therapy and as potential drug carriers. Comprehensive characterizations of the MOFs' properties have been conducted, and the in vitro biological impacts have been studied. Since viability assay showed that Hf-PEB was more biocompatible compared to Zr-PEB, the cellular uptake of Hf-PEB by cells was evaluated using both fluorescence microscopy and soft X-ray tomography (SXT), and the three-dimensional structure of Hf-PEB in cells was observed. The results revealed the potential of Zr-PEB and Hf-PEB as nanomaterials for biomedical applications and demonstrated that SXT is an effective tool to assist the development of such materials.
Subject(s)
Metal-Organic Frameworks , Zirconium , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/chemical synthesis , Zirconium/chemistry , Humans , Tomography, X-Ray , Porosity , Cell Survival/drug effects , Hafnium/chemistry , Particle Size , Surface Properties , Biocompatible Materials/chemistry , Biocompatible Materials/chemical synthesis , Biocompatible Materials/pharmacologyABSTRACT
Reactive oxygen species (ROS)-driven chemodynamic therapy has emerged as a promising anti-tumor strategy. However, the insufficient hydrogen peroxide (H2O2) supply in tumor microenvironment results in a low Fenton reaction rate and subsequently poor ROS production and therapeutic efficacy. Herein, we report on a new nanocomposite MIL-53@ZIF-67/S loaded with doxorubicin and glucose oxidase, which is decomposed under the acidic tumor microenvironment to release Fe3+, Co3+, glucose oxidase, and doxorubicin. The released content leads to synergistic anti-tumor effect through the following manners: 1) doxorubicin is directly used for chemotherapy; 2) Fe3+and Co3+ result in glutathione depletion and Fenton reaction activation through Fe2+ and Co2+ generation to achieve chemodynamic therapy; 3) glucose oxidase continuously catalyzes glucose consumption to induce starvation of the cancer cells, and 4) at the same time the produced gluconic acid and H2O2 significantly promote Fenton reaction and further boost chemodynamic therapy. This work not only demonstrates the high anti-tumor effect of the new nanocomposite, but also provides an innovative strategy for the development of a multi-in-one nanoplatform for cancer therapy.
Subject(s)
Cobalt , Doxorubicin , Iron , Metal-Organic Frameworks , Nanocomposites , Nanocomposites/chemistry , Cobalt/chemistry , Cobalt/pharmacology , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/pharmacology , Metal-Organic Frameworks/chemical synthesis , Iron/chemistry , Humans , Doxorubicin/pharmacology , Doxorubicin/chemistry , Catalysis , Animals , Mice , Hydrogen Peroxide/chemistry , Glucose Oxidase/metabolism , Glucose Oxidase/chemistry , Tumor Microenvironment/drug effects , Cell Line, Tumor , Reactive Oxygen Species/metabolism , Cell Survival/drug effects , Cell Proliferation/drug effects , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Surface Properties , Particle Size , Drug Screening Assays, AntitumorABSTRACT
With the rapid advancement of nanotechnology, stimuli-responsive nanomaterials have emerged as a feasible choice for the designing of controlled drug delivery systems. Zeolitic imidazolates frameworks are a subclass of Metal-organic frameworks (MOFs) that are recognized by their excellent porosity, structural tunability and chemical modifications make them promising materials for loading targeted molecules and therapeutics agents. The biomedical industry uses these porous materials extensively as nano-carriers in drug delivery systems. These MOFs not only possess excellent targeted imaging ability but also cause the death of tumor cells drawing considerable attention in the current framework of anticancer drug delivery systems. In this review, the outline of stability, porosity, mechanism of encapsulation and release of anticancer drug have been reported extensively. In the end, we also discuss a brief outline of current challenges and future perspectives of ZIFs in the biomedical world.
Subject(s)
Antineoplastic Agents , Drug Carriers , Imidazoles , Metal-Organic Frameworks , Zeolites , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Antineoplastic Agents/chemical synthesis , Zeolites/chemistry , Zeolites/pharmacology , Humans , Imidazoles/chemistry , Imidazoles/pharmacology , Imidazoles/chemical synthesis , Drug Carriers/chemistry , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/pharmacology , Metal-Organic Frameworks/chemical synthesis , Neoplasms/drug therapy , Neoplasms/pathology , Drug Delivery Systems , Animals , PorosityABSTRACT
Gefitinib (GET) is a revolutionary targeted treatment inhibiting the epidermal growth factor receptor's tyrosine kinase action by competitively inhibiting the ATP binding site. In preclinical trials, several lung cancer cell lines and xenografts have demonstrated potential activity with GET. Response rates neared 25% in preclinical trials for non-small cell lung cancer. Here, we describe the one-pot synthesis of GET@ZIF-8 nanocomposites (NCs) in pure water, encapsulating zeolitic imidazolate framework 8 (ZIF-8). This method developed NCs with consistent morphology and a loading efficiency of 9%, resulting in a loading capacity of 20 wt%. Cell proliferation assay assessed the anticancer effect of GET@ZIF-8 NCs on A549 and H1299 cells. The different biochemical staining (Calcein-AM and PI and 4',6-Diamidino-2-phenylindole nuclear staining) assays assessed the cell death and morphological examination. Additionally, the mode of apoptosis was evaluated by mitochondrial membrane potential (∆ψm) and reactive oxygen species. Therefore, the study concludes that GET@ZIF-8 NCs are pledged to treat lung cancer cells.