RESUMO
Ultrasensitive photoelectric detection of nitrogen dioxide (NO2) with PHI under visible light irradiation at room temperature (RT) remains an ongoing challenge due to the low charge separation and scarce adsorption sites. In this work, a dimensionally matched ultrathin CoNiHHTP MOF/PHI Z-scheme heterojunction is successfully constructed by taking advantage of the π-π interactions existing between the CoNiHHTP MOF and PHI. The amount-optimized heterojunction possesses a record detection limit of 1 ppb (response = 15.6%) for NO2 under 405 nm irradiation at RT, with reduced responsive (3.6 min) and recovery (2.7 min) times, good selectivity and reversibility, and long-time stability (150 days) compared with PHI, even superior to others reported at RT. Based on the time-resolved photoluminescence spectra, in situ X-ray photoelectron spectra, and diffuse reflectance infrared Fourier transform spectroscopy results, the resulting sensing performance is attributed to the favorable Z-scheme charge transfer and separation. Moreover, the Ni nodes favorably present in adjacent metal sites between the lamellae contribute to charge transfer and redistribution, whereas Co nodes could act as selective centers for promoted adsorption of NO2. Interestingly, it is confirmed that the CoNiHHTP MOF/PHI heterojunction could effectively reduce the influence of O2 in the gas-sensitive reaction due to their unique bimetallic (Co and Ni) nodes, which is also favorable for the improved sensing performances for NO2. This work provides a feasible strategy to develop promising PHI-based optoelectronic gas sensors at RT.
Assuntos
Estruturas Metalorgânicas , Dióxido de Nitrogênio , Dióxido de Nitrogênio/análise , Dióxido de Nitrogênio/química , Estruturas Metalorgânicas/química , Estruturas Metalorgânicas/efeitos da radiação , Luz , Limite de Detecção , TemperaturaRESUMO
High-Z metal-based nanoscale metal-organic frameworks (nMOFs) with photosensitizing ligands can enhance radiation damage to tumors via a unique radiotherapy-radiodynamic therapy (RT-RDT) process. Here we report Monte Carlo (MC) simulation-guided design of a Th-based nMOF built from Th6 -oxo secondary building units and 5,15-di(p-benzoato)porphyrin (DBP) ligands, Th-DBP, for enhanced RT-RDT. MC simulations revealed that the Th-lattice outperformed the Hf-lattice in radiation dose enhancement owing to its higher mass attenuation coefficient. Upon X-ray or γ-ray radiation, Th-DBP enhanced energy deposition, generated more reactive oxygen species, and induced significantly higher cytotoxicity to cancer cells over the previously reported Hf-DBP nMOF. With low-dose X-ray irradiation, Th-DBP suppressed tumor growth by 88 % in a colon cancer and 97 % in a pancreatic cancer mouse model.
Assuntos
Neoplasias do Colo , Estruturas Metalorgânicas , Nanoestruturas , Camundongos , Animais , Estruturas Metalorgânicas/uso terapêutico , Estruturas Metalorgânicas/efeitos da radiação , Tório , Método de Monte Carlo , Ligantes , Nanoestruturas/uso terapêutico , Neoplasias do Colo/tratamento farmacológicoRESUMO
Although organic artificial enzymes have been reported as biomimetic oxidation catalysts and are widely used for colorimetric biosensors, developing organic artificial enzymes with high enzymatic activity is still a challenge. Two-dimensional (2D) covalent organic frameworks (COFs) have shown superior potential in biocatalysts because of their periodic π-π arrays, tunable pore size and structure, large surface area, and thermal stability. The interconnection of electron acceptor and donor building blocks in the 2D conjugated COF skeleton can lead to narrower band gaps and efficient charge separation and transportation and thus is helpful to improve catalytic activity. Herein, a donor-acceptor 2D COF was synthesized using tetrakis(4-aminophenyl)pyrene (Py) as an electron donor and thieno[3,2-b]thiophene-2,5-dicarbaldehyde (TT) as an electron acceptor. Under visible light irradiation, the donor-acceptor 2D COF exhibited superior enzymatic catalytic activity, which could catalyze the oxidation of chromogenic substrates such as 3,3',5,5'-tetramethylbenzidine (TMB) by the formation of superoxide radicals and holes. Based on the above property, the photoactivated donor-acceptor 2D COF with enzyme-like catalytic properties was designed as a robust colorimetric probe for cheap, highly sensitive, and rapid colorimetric detection of glutathione (GSH); the corresponding linear range of GSH was 0.4-60 µM, and the limit of detection was 0.225 µM. This study not only presents the construction of COF-based light-activated nanozymes for environmentally friendly colorimetric detection of GSH but also provides a smart strategy for improving nanozyme activity.
Assuntos
Glutationa/sangue , Estruturas Metalorgânicas/química , Nanoestruturas/química , Benzidinas/química , Catálise/efeitos da radiação , Compostos Cromogênicos/química , Colorimetria/métodos , Teoria da Densidade Funcional , Glutationa/química , Humanos , Luz , Limite de Detecção , Estruturas Metalorgânicas/síntese química , Estruturas Metalorgânicas/efeitos da radiação , Modelos Químicos , Nanoestruturas/efeitos da radiação , Oxirredução , Pirenos/síntese química , Pirenos/química , Pirenos/efeitos da radiação , Tiofenos/síntese química , Tiofenos/química , Tiofenos/efeitos da radiaçãoRESUMO
The excessive colonization of Propionibacterium acnes (P. acnes) is responsible for the genesis of acne vulgaris, a common inflammatory disease of skin. However, the conventional anti-acne therapies are always limited by various side effects, drug resistance, and poor skin permeability. Microneedles (MNs) are emerging topical drug delivery systems capable of noninvasively breaking through the skin stratum corneum barrier to efficiently enhance the transdermal drug penetration. Herein, MNs loaded with intelligent pH-sensitive nanoplatforms were constructed for amplified chemo-photodynamic therapy against acne vulgaris, jointly exerting antimicrobial and anti-inflammatory effects. The photosensitizer indocyanine green (ICG) was loaded into the zeolitic imidazolate framework-8 (ZIF-8) to improve its photostability, which would be triggered by 808 nm laser irradiation to generate cytotoxic reactive oxygen species (ROS) to result in oxidative damage and disturbed metabolic activities of P. acnes. In addition to the efficient drug delivery, the ZIF-8 carrier could selectively degrade in response to the acidic microenvironment of acne lesions, and the released Zn2+ also exhibited a potent antimicrobial activity. The fabricated ZIF-8-ICG@MNs presented an outstanding synergistic anti-acne efficiency both in vitro and in vivo. This bioresponsive microneedle patch is expected to be readily adapted as a generalized, modular strategy for noninvasive therapeutics delivery against superficial skin diseases.
Assuntos
Acne Vulgar/tratamento farmacológico , Antibacterianos/uso terapêutico , Anti-Inflamatórios/uso terapêutico , Imidazóis/uso terapêutico , Verde de Indocianina/uso terapêutico , Estruturas Metalorgânicas/uso terapêutico , Fármacos Fotossensibilizantes/uso terapêutico , Acne Vulgar/patologia , Animais , Antibacterianos/química , Antibacterianos/efeitos da radiação , Antibacterianos/toxicidade , Anti-Inflamatórios/química , Anti-Inflamatórios/efeitos da radiação , Anti-Inflamatórios/toxicidade , Células HEK293 , Humanos , Imidazóis/química , Imidazóis/efeitos da radiação , Imidazóis/toxicidade , Verde de Indocianina/química , Verde de Indocianina/efeitos da radiação , Verde de Indocianina/toxicidade , Raios Infravermelhos , Masculino , Estruturas Metalorgânicas/química , Estruturas Metalorgânicas/efeitos da radiação , Estruturas Metalorgânicas/toxicidade , Camundongos Endogâmicos BALB C , Fotoquimioterapia , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/efeitos da radiação , Fármacos Fotossensibilizantes/toxicidade , Propionibacterium acnes/efeitos dos fármacos , Ratos , Pele/efeitos dos fármacos , Pele/patologia , Suínos , Zinco/química , Zinco/efeitos da radiação , Zinco/uso terapêutico , Zinco/toxicidadeRESUMO
Black phosphorus (BP) nanosheet is easily oxidized by oxygen and water under ambient environment, thus, reliable BP passivation techniques for biomedical applications is urgently needed. A simple and applicable passivation strategy for biomedical applications was established by encapsulating BP nanosheet into zeolitic imidazole framework-8 (ZIF-8). The resulted BP nanosheet in ZIF-8 (BP@ZIF-8) shows not only satisfied chemical stability in both water and phosphate buffered saline (PBS), but also excellent biocompatibility. Notably, BP nanosheet endows the prepared BP@ZIF-8 with prominent photothermal conversion efficiency (31.90%). Besides passivation BP, ZIF-8 provides the BP@ZIF-8 with high drug loading amount (1353.3 mg g-1). Moreover, the loaded drug can be controlled release by pH stimuli. Both in vitro and in vivo researches verified the resulted BP@ZIF-8 an ideal candidate for tumor multimodal treatments.
Assuntos
Antineoplásicos/uso terapêutico , Portadores de Fármacos/química , Estruturas Metalorgânicas/química , Nanoestruturas/química , Neoplasias/tratamento farmacológico , Fósforo/química , Animais , Antineoplásicos/química , Linhagem Celular Tumoral , Terapia Combinada , Doxorrubicina/química , Doxorrubicina/uso terapêutico , Portadores de Fármacos/efeitos da radiação , Portadores de Fármacos/toxicidade , Liberação Controlada de Fármacos , Tratamento Farmacológico , Feminino , Humanos , Concentração de Íons de Hidrogênio , Raios Infravermelhos , Estruturas Metalorgânicas/efeitos da radiação , Estruturas Metalorgânicas/toxicidade , Camundongos , Nanoestruturas/efeitos da radiação , Nanoestruturas/toxicidade , Fósforo/efeitos da radiação , Fósforo/toxicidade , Terapia FototérmicaRESUMO
HKUST-1 MOFs and its derivative HKUST-CuO were coupled with TiO2 nanoparticles to form the heterogeneous composites of HKUST-1/TiO2 and HKUST-CuO/TiO2 based on their well-suitable bandgap energies (Eg). Compared with mono-component HKUST-1 or HKUST-CuO, the prepared composites displayed photoelectrochemical (PEC) response due to the synergistic effect from their heterogeneous structure. Higher photocurrent response was obtained on HKUST-CuO/TiO2-modified ITO electrode (HKUST-CuO/TiO2/ITO), which could be attributed to the hollow structure with a thin shell of HKUST-CuO greatly enhancing visible spectra harvesting. The CuO component in HKUST-CuO not only could accelerate electron transfer on the heterojunction interface but also effectively separate the photo-generated charge carriers (e-1/h+). Based on the excellent PEC performance of prepared photoactive composite material, under visible-light excitation (λ ≥ 420 nm) and with a working potential of 0 V (vs. Ag/AgCl), the S1 (probe DNA)/HKUST-CuO/TiO2/ITO PEC platform was successfully fabricated for colitoxin DNA detection without using ascorbic acid (AA) as an electron donor. Compared with the analysis results on S1/HKUST-1/TiO2/ITO electrode, S1/HKUST-CuO/TiO2/ITO displayed a wider linear response range from 1.0 × 10-6 to 4.0 × 10-1 nM with a lower detection limit of 3.73 × 10-7 nM (S/N = 3), the linear regression equation was ΔI (10-6 A) =0.5549-0.1858 log (CS2/M), which confirmed the HKUST-CuO could improve sensitivity because of its prominent PEC property. The relative standard deviation (RSD) of the PEC sensor for target DNA detection of 2.0 × 10-4 nM was 7.4%. The proposed DNA biosensor also possessed good specificity and stability. Hence, this reported work was a promising strategy for molecular diagnosis in the bio-analysis field. (A) Schematic illustration of the preparation process of the proposed PEC biosensors for colitoxin DNA detection. (B) The preparation process of HKUST-1 and HKUST-CuO.
Assuntos
Técnicas Biossensoriais/métodos , Cobre/química , DNA/análise , Técnicas Eletroquímicas/métodos , Estruturas Metalorgânicas/química , Titânio/química , Toxinas Bacterianas/genética , Técnicas Biossensoriais/instrumentação , Cobre/efeitos da radiação , Sondas de DNA/química , Técnicas Eletroquímicas/instrumentação , Eletrodos , Escherichia coli/química , Proteínas de Escherichia coli/genética , Ácidos Nucleicos Imobilizados/química , Luz , Limite de Detecção , Nanopartículas Metálicas/química , Nanopartículas Metálicas/efeitos da radiação , Estruturas Metalorgânicas/efeitos da radiação , Processos Fotoquímicos , Titânio/efeitos da radiaçãoRESUMO
Light-driven polymerization, such as photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization, enables biological benign conditions and versatile functional polymer structure design, which is readily used in protein-polymer bioconjugates. However, conventional metalloporphyrinic homogeneous catalysts for PET-RAFT polymerization suffer from limited aqueous solubility and tedious purification. Here we demonstrate the design of PET-RAFT photocatalyst from the reticular assembled Zr-porphyrinic metal-organic frameworks (MOFs), along with a biomacromolecule-based chain transfer agent, as efficient bioconjugation tools in water. Our methodology offers manufacturing advantages on bioconjugates under mild conditions such that MTT (3-[4,5-dimethylthiazol-2-yl]-2,5 diphenyl tetrazolium bromide) and cytotoxicity assays have shown the preservation of the protein integrity, bioactivity, and high cell viability after PET-RAFT polymerization. We find that the fast kinetics are benefiting from the ultrahigh loading of metalloporphyrins in MOF-525-Zn. This heterogeneous catalyst also allows us to maintain living characteristics to incorporate myriads of monomers into block copolymers. Other advantages like easy postreaction purification, reusability, and high oxygen tolerance even in an open system are demonstrated. This study provides a tool of highly efficient heterogeneous photocatalysts for polymer-protein bioconjugation in aqueous media and paves the road for biological applications.
Assuntos
Acrilamidas/química , Estruturas Metalorgânicas/química , Soroalbumina Bovina/química , Acrilamidas/síntese química , Animais , Catálise/efeitos da radiação , Bovinos , Luz , Estruturas Metalorgânicas/efeitos da radiação , Metaloporfirinas/química , Metaloporfirinas/efeitos da radiação , Polimerização , Zircônio/química , Zircônio/efeitos da radiaçãoRESUMO
Chronic wound healing, impeded by bacterial infections and drug resistance, poses a threat to global human health. Antibacterial phototherapy is an effective way to fight microbial infection without causing drug resistance. Covalent organic frameworks (COFs) are a class of highly crystalline functional porous carbon-based materials composed of light atoms (e.g., carbon, nitrogen, oxygen, and borane), showing potential applications in the biomedical field. Herein, we constructed porphyrin-based COF nanosheets (TP-Por CON) for synergizing photodynamic and photothermal therapy under red light irradiation (e.g., 635 nm). Moreover, a nitric oxide (NO) donor molecule, BNN6, was encapsulated into the pore volume of the crystalline porous framework structure to moderately release NO triggered by red light irradiation for realizing gaseous therapy. Therefore, we successfully synthesized a novel TP-Por CON@BNN6-integrated heterojunction for thoroughly killing Gram-negative bacteria Escherichia coli and Gram-positive bacteria Staphylococcus aureus in vitro. Our research identified that TP-Por CON@BNN6 has favorable biocompatibility and biodegradability, low phototoxicity, anti-inflammatory properties, and excellent mice wound healing ability in vivo. This study indicates that the TP-Por CON@BNN6-integrated heterojunction with multifunctional properties provides a potential strategy for COF-based gaseous therapy and microorganism-infected chronic wound healing.
Assuntos
Anti-Inflamatórios/uso terapêutico , Estruturas Metalorgânicas/uso terapêutico , Doadores de Óxido Nítrico/uso terapêutico , Fármacos Fotossensibilizantes/uso terapêutico , Infecções Cutâneas Estafilocócicas/tratamento farmacológico , Cicatrização/efeitos dos fármacos , Animais , Anti-Inflamatórios/efeitos da radiação , Anti-Inflamatórios/toxicidade , Linhagem Celular , Escherichia coli/efeitos dos fármacos , Luz , Estruturas Metalorgânicas/efeitos da radiação , Estruturas Metalorgânicas/toxicidade , Camundongos Endogâmicos BALB C , Doadores de Óxido Nítrico/efeitos da radiação , Doadores de Óxido Nítrico/toxicidade , Fármacos Fotossensibilizantes/efeitos da radiação , Fármacos Fotossensibilizantes/toxicidade , Porfirinas/efeitos da radiação , Porfirinas/uso terapêutico , Porfirinas/toxicidade , Staphylococcus aureus/efeitos dos fármacosRESUMO
The development of modern agriculture has prompted the greater input of herbicides, insecticides, and fertilizers. However, precision release and targeted delivery of these agrochemicals still remain a challenge. Here, a pesticide-fertilizer all-in-one combination (PFAC) strategy and deep learning are employed to form a system for controlled and targeted delivery of agrochemicals. This system mainly consists of three components: (1) hollow mesoporous silica (HMS), to encapsulate herbicides and phase-change material; (2) polydopamine (PDA) coating, to provide a photothermal effect; and (3) a zeolitic imidazolate framework (ZIF8), to provide micronutrient Zn2+ and encapsulate insecticides. Results show that the PFAC at concentration of 5 mg mL-1 reaches the phase transition temperature of 1-tetradecanol (37.5 °C) after 5 min of near-infrared (NIR) irradiation (800 nm, 0.5 W cm-2). The data of corn and weed are collected and relayed to deep learning algorithms for model building to realize object detection and further targeted weeding. In-field treatment results indicated that the growth of chicory herb was significantly inhibited when treated with the PFAC compared with the blank group after 24 h under NIR irradiation for 2 h. This system combines agrochemical innovation and artificial intelligence technology, achieves synergistic effects of weeding and insecticide and nutrient supply, and will potentially achieve precision and sustainable agriculture.
Assuntos
Portadores de Fármacos/química , Fertilizantes , Herbicidas/química , Inseticidas/química , Nanopartículas/química , Ácido 2,4-Diclorofenoxiacético/química , Ácido 2,4-Diclorofenoxiacético/toxicidade , Animais , Cichorium intybus/efeitos dos fármacos , Aprendizado Profundo , Portadores de Fármacos/efeitos da radiação , Liberação Controlada de Fármacos , Álcoois Graxos/química , Álcoois Graxos/efeitos da radiação , Guanidinas/química , Guanidinas/toxicidade , Herbicidas/toxicidade , Indóis/química , Indóis/efeitos da radiação , Raios Infravermelhos , Insetos/efeitos dos fármacos , Inseticidas/toxicidade , Estruturas Metalorgânicas/química , Estruturas Metalorgânicas/efeitos da radiação , Nanopartículas/efeitos da radiação , Neonicotinoides/química , Neonicotinoides/toxicidade , Nitrocompostos/química , Nitrocompostos/toxicidade , Polímeros/química , Polímeros/efeitos da radiaçãoRESUMO
Phototherapy holds great promise in the treatment of bacterial infections, especially the multidrug resistant bacterial infections. However, most therapeutic agents are based on the integration of individual photothermal agents and photosensitizers, always in the activated state, and generally lack bacterial specificity, resulting in uncertain pharmacokinetics and serious nonspecific damage to normal tissues. Herein, we report a pH-responsive nanoplatform with synergistic chemo-phototherapy function for smart fluorescence imaging-guided precision sterilization. pH reversible activated symmetric cyanine was designed and prepared as a bacterial-specific imaging unit and PTT/PDT-in-one agent. Meanwhile, a guanidinium-based covalent organic framework (COF) was employed as a nanocarrier and chemotherapy agent to build the intelligent nanoplatform via electrostatic self-assembly. The self-assembly of the PTT/PDT-in-one agent and the COF greatly improves the stability and blood circulation of the PTT/PDT-in-one agent and provides charge-reversed intelligent targeting ability. The developed smart nanoplatform not only enables bacterial-targeted imaging but also possesses chemo/PTT/PDT synergetic high-efficiency bactericidal effects with little side effects, showing great potential in practical applications.
Assuntos
Antibacterianos/uso terapêutico , Corantes Fluorescentes/uso terapêutico , Estruturas Metalorgânicas/uso terapêutico , Fármacos Fotossensibilizantes/uso terapêutico , Infecções Estafilocócicas/diagnóstico por imagem , Infecções Estafilocócicas/tratamento farmacológico , Animais , Antibacterianos/química , Antibacterianos/efeitos da radiação , Escherichia coli/efeitos dos fármacos , Feminino , Corantes Fluorescentes/química , Corantes Fluorescentes/efeitos da radiação , Gadolínio/química , Gadolínio/efeitos da radiação , Indóis/química , Indóis/efeitos da radiação , Raios Infravermelhos , Estruturas Metalorgânicas/química , Estruturas Metalorgânicas/efeitos da radiação , Camundongos Endogâmicos BALB C , Testes de Sensibilidade Microbiana , Fotoquimioterapia , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/efeitos da radiação , Terapia Fototérmica , Medicina de Precisão/métodos , Oxigênio Singlete/metabolismo , Staphylococcus aureus/efeitos dos fármacosRESUMO
2D metal-organic framework (MOF) film as the active layer show promising application prospects in various fields including sensors, catalysis, and electronic devices. However, exploring the application of 2D MOF film in the field of artificial synapses has not been implemented yet. In this work, we fabricated a novel 2D MOF film (Cu-THPP, THPP=5,10,15,20-Tetrakis(4-hydroxyphenyl)-21H,23H-porphine), and further used it as an active layer to explore the application in the simulation of human brain synapses. It shows excellent light-stimulated synaptic plasticity properties, and exhibits the foundation function of synapses such as long-term plasticity (LTP), short-term plasticity (STP), and the conversion of STP to LTP. Most critically, the MOF based artificial synaptic device exhibits an excellent stability in atmosphere. This work opens the door for the application of 2D MOF film in the simulation of human brain synapses.
Assuntos
Materiais Biomiméticos/química , Membranas Artificiais , Estruturas Metalorgânicas/química , Materiais Biomiméticos/efeitos da radiação , Biomimética/métodos , Cobre/química , Cobre/efeitos da radiação , Luz , Estruturas Metalorgânicas/efeitos da radiação , Plasticidade Neuronal , Porfirinas/química , Porfirinas/efeitos da radiação , Sinapses/químicaRESUMO
The exploitation of effective strategies to develop materials bearing deep tissue focal fluorescence imaging capacity and excellent reactive oxygen species (ROS) generation ability is of great interest to address the high-priority demand of photodynamic therapy (PDT). Therefore, we use a rational strategy to fabricate a two-photon-active metal-organic framework via a click reaction (PCN-58-Ps). Moreover, PCN-58-Ps is capped with hyaluronic acid through coordination to obtain cancer cell-specific targeting properties. As a result, the optimized composite PCN-58-Ps-HA exhibits considerable two-photon activity (upon laser excitation at a wavelength of 910 nm) and excellent light-triggered ROS (1O2 and O2â¢-) generation ability. In summary, the interplay of these two critical factors within the PCN-58-Ps-HA framework gives rise to near-infrared light-activated two-photon PDT for deep tissue cancer imaging and treatment, which has great potential for future clinical applications.
Assuntos
Antineoplásicos/farmacologia , Estruturas Metalorgânicas/farmacologia , Fármacos Fotossensibilizantes/farmacologia , Antineoplásicos/síntese química , Antineoplásicos/efeitos da radiação , Apoptose/efeitos dos fármacos , Benzotiazóis/síntese química , Benzotiazóis/farmacologia , Benzotiazóis/efeitos da radiação , Química Click , Células HEK293 , Células HeLa , Humanos , Ácido Hialurônico/análogos & derivados , Ácido Hialurônico/farmacologia , Ácido Hialurônico/efeitos da radiação , Raios Infravermelhos , Estruturas Metalorgânicas/síntese química , Estruturas Metalorgânicas/efeitos da radiação , Fotoquimioterapia , Fótons , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/efeitos da radiação , Espécies Reativas de Oxigênio/metabolismoRESUMO
A new photo-electrochemical sensor based on MIL-101(Cr) MOF/carbon black (CB) is fabricated and characterized. By using differential pulse voltammetry, dopamine (DA) can be effectively detected using a photo-electrochemical MIL-101(Cr)/CB sensor under visible light. The CB acts as the electron bridge to combine with the large specific surface area and photo-catalytic feature of MOF, which contribute to the improvements of sensitivity of DA detection. The concentration of the catalyst, pH value, accumulation potential, and accumulation time were also optimized. Furthermore, the electrochemical performances of MIL-101(Cr)/CB sensor was investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scan rate, electrochemically active surface area (ECSA), and amperometric responses. A detection limit of 0.38 nM (LOD = 3 sb/S, sb = 0.028) and a working range of 1 nM to 2.22 µM has been achieved. The MIL-101(Cr)/CB sensor exhibits excellent reproducibility, stability, and selectivity and also has satisfactory recovery rate for the analysis of real samples including calf serum and human urine. Graphical abstract.
Assuntos
Dopamina/sangue , Dopamina/urina , Técnicas Eletroquímicas/métodos , Estruturas Metalorgânicas/química , Fuligem/química , Animais , Catálise/efeitos da radiação , Bovinos , Técnicas Eletroquímicas/instrumentação , Eletrodos , Humanos , Luz , Limite de Detecção , Estruturas Metalorgânicas/efeitos da radiação , Processos Fotoquímicos , Reprodutibilidade dos TestesRESUMO
Here, ferric oxide-loaded metal-organic framework (FeTCPP/Fe2O3 MOF) nanorice was designed and constructed by the liquid diffusion method. The introduction of iron metal nodes and the loading of Fe2O3 can effectively catalyze the Fenton reaction to produce hydroxyl radicals (â¢OH) and overcome the hypoxic environment of tumor tissue by generating oxygen. The monodispersity and porosity of the porphyrin photosensitizers in the MOF structure exposed more active sites, which promoted energy exchange between porphyrin molecules and oxygen molecules for photodynamic therapy (PDT) treatment. Therefore, the generated hydroxyl radicals and singlet oxygen (1O2) can synergistically act on tumor cells to achieve the purpose of improving tumor therapy. Then the erythrocyte membrane was camouflaged to enhance blood circulation and tissue residence time in the body, and finally, the targeted molecule AS1411 aptamer was modified to achieve the high enrichment of MOF photosensitizers on a tumor domain. As a result, the MOF nanorice camouflaged by the erythrocyte membrane can effectively reduce side effects and improve the therapeutic effect of PDT and chemo-dynamic therapy (CDT). The study not only improved the efficacy of PDT and CDT in essence from the MOF nanorice but also used the camouflage method to further concentrate FeTCPP/Fe2O3 on the tumor sites, achieving the goal of multiple gains. These results will provide theoretical and practical directions for the development of tumor-targeted MOF nanomaterials.
Assuntos
Aptâmeros de Nucleotídeos/química , Membrana Eritrocítica/química , Estruturas Metalorgânicas/uso terapêutico , Neoplasias/tratamento farmacológico , Fármacos Fotossensibilizantes/uso terapêutico , Animais , Apoptose/efeitos dos fármacos , Linhagem Celular Tumoral , Compostos Férricos/química , Compostos Férricos/efeitos da radiação , Compostos Férricos/uso terapêutico , Estruturas Metalorgânicas/química , Estruturas Metalorgânicas/efeitos da radiação , Camundongos , Nanopartículas/química , Nanopartículas/efeitos da radiação , Nanopartículas/uso terapêutico , Necrose/induzido quimicamente , Neoplasias/patologia , Oligodesoxirribonucleotídeos/química , Fotoquimioterapia/métodos , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/efeitos da radiação , Porfirinas/química , Porfirinas/efeitos da radiação , Porfirinas/uso terapêutico , Espécies Reativas de Oxigênio/metabolismoRESUMO
The high reactive oxygen species (ROS) generation ability and simple construction of sonosensitizer systems remain challenging in sonodynamic therapy against the hypoxic tumor. In this work, we rationally prepared MOF-derived double-layer hollow manganese silicate nanoparticle (DHMS) with highly effective ROS yield under ultrasound irradiation for multimodal imaging-guided sonodynamic therapy (SDT). The presence of Mn in DHMS increased ROS generation efficiency because it could be oxidized by holes to improve the electron-hole separation. Moreover, DHMS could produce oxygen in the tumor microenvironment, which helps overcome the hypoxia of the solid tumor and thus enhance the treatment efficiency. Inâ vivo experiments demonstrated efficient tumor inhibition in DHMS-mediated SDT guided by ultrasound and magnetic resonance imaging. This work presents a MOF-derived nanoparticle with sonosensitive and oxygen generating ability, which provides a promising strategy for tumor hypoxia in SDT.
Assuntos
Antineoplásicos/uso terapêutico , Estruturas Metalorgânicas/uso terapêutico , Nanopartículas/uso terapêutico , Neoplasias/tratamento farmacológico , Oxigênio/uso terapêutico , Animais , Antineoplásicos/efeitos da radiação , Antineoplásicos/toxicidade , Linhagem Celular Tumoral , Compostos de Manganês/efeitos da radiação , Compostos de Manganês/uso terapêutico , Estruturas Metalorgânicas/efeitos da radiação , Estruturas Metalorgânicas/toxicidade , Camundongos , Imagem Multimodal , Nanopartículas/efeitos da radiação , Oxigênio/química , Espécies Reativas de Oxigênio/metabolismo , Silicatos/efeitos da radiação , Silicatos/uso terapêutico , Silicatos/toxicidade , Hipóxia Tumoral/efeitos dos fármacos , Microambiente Tumoral/efeitos dos fármacos , Ondas UltrassônicasRESUMO
Small interfering RNA (siRNA)-induced gene therapy has been recognized as a promising avenue for effective cancer treatment, while easy enzymatic degradation, poor transfection efficiency, nonspecific biodistribution, and uncontrolled release hinder its extensive clinical applications. Zeolitic imidazolate frameworks-8 (ZIF-8) have emerged as promising drug carriers without an in-depth exploration in programmable siRNA delivery. Herein, we report a multifunctional PDAs-ZIF-8 (PZ) nanoplatform for delivering siRNA with combined photothermal therapy (PTT) and gene therapy (GT) via the noninvasive guidance of photoacoustic (PA)/near-infrared (IR) dual-modal imaging. The ingenious PZ nanocarriers mediated the tumor-specific accumulation of therapeutic siRNA without undesired degradation and preleakage. The pH-responsive ZIF-8 decomposed in an acidic tumor microenvironment that was accompanied by the release of siRNA payloads for cleaving target mRNA in gene silencing therapy. Meanwhile, the polydopamine nanoparticles (PDAs) could simultaneously serve as a powerful noninvasive PA/IR imaging contrast agent and versatile photothermal agent for diagnosis-guided photogenetherapy. The systematic in vitro and in vivo experimental explorations demonstrated that our PDAs-siRNA-ZIF-8 (PSZ) could greatly enhance the therapeutic efficiency as compared with the corresponding PTT or GT monotherapy. This work holds great potential to advance the development of more intelligent diagnosis and therapeutic strategies, thus supplying promising smart nanomedicines in the near future.
Assuntos
Antineoplásicos/uso terapêutico , Meios de Contraste/química , Portadores de Fármacos/química , Nanopartículas/química , Neoplasias/tratamento farmacológico , RNA Interferente Pequeno/uso terapêutico , Animais , Terapia Combinada/métodos , Meios de Contraste/efeitos da radiação , Portadores de Fármacos/efeitos da radiação , Inativação Gênica/efeitos dos fármacos , Terapia Genética , Hipertermia Induzida/métodos , Indóis/química , Indóis/efeitos da radiação , Raios Infravermelhos , Estruturas Metalorgânicas/química , Estruturas Metalorgânicas/efeitos da radiação , Camundongos Endogâmicos BALB C , Nanopartículas/efeitos da radiação , Fototerapia/métodos , Polímeros/química , Polímeros/efeitos da radiação , Ensaios Antitumorais Modelo de XenoenxertoRESUMO
Supramolecular coordination is an efficient strategy to construct supramolecular coordination frameworks with predesigned structures, assembled shapes, and specific function. In this work, we report the synthesis, structural characterization, and photophysical property of two tetraphenylethene-based supramolecular coordination frameworks 1a and 1b formed from 1,1,2,2-tetrakis(4-(pyridin-4-yl)phenyl)ethene (2a) or 1,1,2,2-tetrakis(4-((E)-2-(pyridin-4-yl)vinyl)phenyl)ethene (2b) and a linear difunctional platinum(II) ligand (3a) via coordination-driven self-assembly. Controlled by the specific angularity and geometry of tetraphenylethene (with 60° and 120°) and difunctional Pt(II) linker (with 180°), these supramolecular coordination frameworks possess a well-defined and two-dimensional (2D) rhombic network-type topology with good periodicity and porosity. Given the aggregation-induced emission (AIE) property of tetraphenylethene units and the porosity of frameworks, 1a and 1b have been successfully used as fluorescent platforms and energy donors to fabricate efficient artificial light-harvesting materials with two fluorescent acceptors (Nile Red and Sulforhodamine 101) via noncovalent interactions in aqueous solution. Furthermore, these light-harvesting materials have been applied for promoting cancer cell imaging with a full shift of imaging channels from blue/green channels to the red channel. Thus, this study provides an effective approach to fabricate functional frameworks as fluorescent platforms for developing more fluorescent materials.
Assuntos
Compostos de Benzilideno/química , Complexos de Coordenação/química , Corantes Fluorescentes/química , Estruturas Metalorgânicas/química , Compostos de Benzilideno/efeitos da radiação , Complexos de Coordenação/efeitos da radiação , Células HeLa , Humanos , Ligantes , Luz , Estruturas Metalorgânicas/efeitos da radiação , Microscopia Confocal , Microscopia de Fluorescência , Neoplasias/diagnóstico por imagem , Oxazinas/química , Platina/química , Platina/efeitos da radiação , Rodaminas/químicaRESUMO
Biological ion channels and ion pumps with sub-nanometer sizes modulate ion transport in response to external stimuli. Realizing such functions with sub-nanometer solid-state nanopores has been an important topic with wide practical applications. Herein, we demonstrate a biomimetic photoresponsive ion channel and photodriven ion pump using a porphyrin-based metal-organic framework membrane with pore sizes comparable to hydrated ions. We show that the molecular-size pores enable precise and robust optoelectronic ion transport modulation in a broad range of concentrations, unparalleled with conventional solid-state nanopores. Upon decoration with platinum nanoparticles to form a Schottky barrier photodiode, photovoltage across the membrane is generated with "uphill" ion transport from low concentration to high concentration. These results may spark applications in energy conversion, ion sieving, and artificial photosynthesis.
Assuntos
Materiais Biomiméticos/química , Estruturas Metalorgânicas/química , Nanoporos , Materiais Biomiméticos/efeitos da radiação , Canais Iônicos/química , Luz , Nanopartículas Metálicas/química , Estruturas Metalorgânicas/efeitos da radiação , Platina/química , Porfirinas/química , Porfirinas/efeitos da radiaçãoRESUMO
Covalent organic frameworks (COFs), as one of the most significant members of the porous organic frameworks, have been well used in the photocatalysis owing to their outspread π-conjugated framework, high crystallinity and regular pore structure. Herein, after reducing the labile imine-linked COF-300 to the more stable amine-linked COF-300-AR, we for the first time demonstrated that COF-300-AR was the light-responsive oxidase mimic. COF-300-AR exhibited excellent oxidase-mimicking activity under purple light stimulation (λ = 400 nm), which can catalyze the oxidation of classical substrates such as 3,3',5,5'-tetramethylbenzydine (TMB) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) by the formation of â¢OH and O2â¢- free radicals in the presence of dissolved oxygen. The COF-300-AR oxidase mimic has outstanding advantages of easy light control, high stability, good reusability, and highly catalytic oxidation capacity and has been applied to detect glutathione (GSH) levels in HL60 cells with good selectivity and high sensitivity. This study will broaden the sensing applications of COFs and offer a promising build block for the construction of artificial enzymes.
Assuntos
Glutationa/análise , Estruturas Metalorgânicas/química , Benzidinas/química , Benzotiazóis/química , Catálise/efeitos da radiação , Glutationa/química , Células HL-60 , Humanos , Luz , Estruturas Metalorgânicas/efeitos da radiação , Oxirredução/efeitos da radiação , Espécies Reativas de Oxigênio/química , Espectrofotometria/métodos , Ácidos Sulfônicos/químicaRESUMO
Herein we report the design of a bacteriochlorin-based nanoscale metal-organic framework, Zr-TBB, for highly effective photodynamic therapy via both type I and type II mechanisms. The framework of Zr-TBB stabilizes 5,10,15,20-tetra(p-benzoato)bacteriochlorin (TBB) ligands toward oxygen and light via geometrical constraint. Upon 740 nm light irradiation, Zr-TBB efficiently generates various reactive oxygen species, including singlet oxygen, superoxide anion, hydrogen peroxide, and hydroxyl radicals, to afford superb antitumor efficacy on mouse models of breast and colon cancers, with cure rates of 40% and 60%, respectively.