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1.
ACS Appl Mater Interfaces ; 13(41): 49482-49489, 2021 Oct 20.
Artigo em Inglês | MEDLINE | ID: mdl-34636536

RESUMO

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 radiação
2.
ACS Appl Mater Interfaces ; 13(28): 32690-32702, 2021 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-34229434

RESUMO

The synergistic nanotheranostics of reactive oxygen species (ROS) augment or phototherapy has been a promising method within synergistic oncotherapy. However, it is still hindered by sophisticated design and fabrication, lack of a multimodal synergistic effect, and hypoxia-associated poor photodynamic therapy (PDT) efficacy. Herein, a kind of porous shuttle-shape platinum (IV) methylene blue (Mb) coordination polymer nanotheranostics-loaded 10-hydroxycamptothecin (CPT) is fabricated to address the abovementioned limitations. Our nanoreactors possess spatiotemporally controlled O2 self-supply, self-sufficient singlet oxygen (1O2), and outstanding photothermal effect. Once they are taken up by tumor cells, nanoreactors as a cascade catalyst can efficiently catalyze degradation of the endogenous hydrogen peroxide (H2O2) into O2 to alleviate tumor hypoxia. The production of O2 can ensure enhanced PDT. Subsequently, under both stimuli of external red light irradiation and internal lysosomal acidity, nanoreactors can achieve the on-demand release of CPT to augment in situ mitochondrial ROS and highly efficient tumor ablation via phototherapy. Moreover, under the guidance of near-infrared (NIR) fluorescent imaging, our nanoreactors exhibit strongly synergistic potency for treatment of hypoxic tumors while reducing damages against normal tissues and organs. Collectively, shuttle-shape platinum-coordinated nanoreactors with augmented ROS capacity and enhanced phototherapy efficiency can be regarded as a novel tumor theranostic agent and further promote the research of synergistic oncotherapy.


Assuntos
Antineoplásicos/uso terapêutico , Camptotecina/análogos & derivados , Portadores de Fármacos/química , Nanoestruturas/química , Neoplasias/tratamento farmacológico , Hipóxia Tumoral/efeitos dos fármacos , Animais , Antineoplásicos/química , Camptotecina/química , Camptotecina/uso terapêutico , Catálise/efeitos da radiação , Linhagem Celular Tumoral , Portadores de Fármacos/efeitos da radiação , Liberação Controlada de Fármacos , Feminino , Humanos , Peróxido de Hidrogênio/química , Peróxido de Hidrogênio/metabolismo , Luz , Azul de Metileno/análogos & derivados , Azul de Metileno/efeitos da radiação , Camundongos Endogâmicos BALB C , Nanoestruturas/efeitos da radiação , Neoplasias/metabolismo , Oxigênio/metabolismo , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/uso terapêutico , Terapia Fototérmica , Platina/química , Platina/efeitos da radiação , Polímeros/síntese química , Polímeros/química , Polímeros/efeitos da radiação , Porosidade , Oxigênio Singlete/metabolismo , Nanomedicina Teranóstica
3.
ACS Appl Mater Interfaces ; 13(30): 35328-35341, 2021 Aug 04.
Artigo em Inglês | MEDLINE | ID: mdl-34291912

RESUMO

The multifunctional combined nanoplatform has a wide application prospect in the synergistic treatment of cancer. Nevertheless, the traditional treatment of phototherapy is limited by the catalytic nanomaterial itself, so the effect is not satisfactory. Here, the arris of the anisotropic truncated octahedral Au (TOh Au) was coated with noble metal Pt to form a spatial separation structure, which enhanced the local surface plasmonic resonance and thus boosted the photocatalytic effect. In this system, the highly efficient photocatalysis provides a strong guarantee for oncotherapy. On the one hand, the structure of arris deposition adequately improves the efficiency of photothermal conversion, which substantially improves the effectiveness of photothermal therapy. On the other hand, in situ oxygen production of Pt ameliorates tumor hypoxia, and through the O2 self-production and sales mode, the growth and development of tumor were inhibited. Meanwhile, under the enhanced photocatalysis, more O2 were produced, which greatly evolved the treatment effect of photodynamic therapy. In the end, the addition of hyaluronic acid can specifically target osteosarcoma cells while improving the retention time and biocompatibility of the material in the body. Thus, the nanocomposite shows superexcellent synergistic enhancement of photothermal conversion efficiency and photodynamic capability in vitro and in vivo, which provides a potential possibility for osteosarcoma cure.


Assuntos
Antineoplásicos/uso terapêutico , Nanopartículas Metálicas/uso terapêutico , Osteossarcoma/tratamento farmacológico , Fármacos Fotossensibilizantes/uso terapêutico , Animais , Anisotropia , Antineoplásicos/química , Antineoplásicos/efeitos da radiação , Antineoplásicos/toxicidade , Catálise/efeitos da radiação , Clorofilídeos , Ouro/química , Ouro/toxicidade , Ácido Hialurônico/química , Ácido Hialurônico/toxicidade , Raios Infravermelhos , Nanopartículas Metálicas/química , Nanopartículas Metálicas/efeitos da radiação , Nanopartículas Metálicas/toxicidade , Camundongos Nus , Osteossarcoma/metabolismo , Oxigênio/metabolismo , Fotoquimioterapia , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/efeitos da radiação , Fármacos Fotossensibilizantes/toxicidade , Terapia Fototérmica , Platina/química , Platina/toxicidade , Polietilenoglicóis/química , Polietilenoglicóis/toxicidade , Porfirinas/química , Porfirinas/efeitos da radiação , Porfirinas/uso terapêutico , Espécies Reativas de Oxigênio/metabolismo , Ressonância de Plasmônio de Superfície
4.
ACS Appl Mater Interfaces ; 13(24): 28650-28661, 2021 Jun 23.
Artigo em Inglês | MEDLINE | ID: mdl-34124895

RESUMO

Novel and effective radiosensitizers that can enhance radiosensitivity of tumor tissues and increase the local radiation dose are highly desirable. In this work, templated by bovine serum albumin (BSA), Bi2Se3-MnO2 nanocomposites (Bi2Se3-MnO2@BSA) were fabricated via biomineralization, while Bi2Se3 nanodots act as radiosensitizers to increase the local radiation dosage because of their strong X-ray attenuation ability, and MnO2 with catalase-like activity can increase the oxygen concentration in tumors by triggering the decomposition of tumor endogenous H2O2 so as to improve the hypoxia-associated radioresistance of tumors. Owing to the interaction of the two components in the interface, Bi2Se3-MnO2@BSA showed promoted catalytic activity compared to MnO2@BSA, favoring tumor radiotherapy (RT) sensitization. BSA templating enabled the nanocomposites with high colloidal stability and biocompatibility as well as satisfactory tumor targeting both in vitro and in vivo; thus, an enhanced RT efficacy was obtained. Moreover, the proposed Bi2Se3-MnO2@BSA exhibited excellent performances in computerized tomography and magnetic resonance imaging. Thus, this work provides a tumor microenvironment-responsive multifunctional theranostic nanoagent with an improved performance for imaging-guided tumor RT sensitization.


Assuntos
Antineoplásicos/uso terapêutico , Bismuto/uso terapêutico , Compostos de Manganês/uso terapêutico , Nanocompostos/uso terapêutico , Neoplasias/tratamento farmacológico , Óxidos/uso terapêutico , Radiossensibilizantes/uso terapêutico , Compostos de Selênio/uso terapêutico , Animais , Antineoplásicos/síntese química , Antineoplásicos/efeitos da radiação , Bismuto/química , Catálise/efeitos da radiação , Bovinos , Linhagem Celular Tumoral , Meios de Contraste/síntese química , Meios de Contraste/efeitos da radiação , Meios de Contraste/uso terapêutico , Feminino , Células Endoteliais da Veia Umbilical Humana , Humanos , Peróxido de Hidrogênio/química , Peróxido de Hidrogênio/metabolismo , Compostos de Manganês/química , Compostos de Manganês/efeitos da radiação , Camundongos Endogâmicos BALB C , Nanocompostos/química , Nanocompostos/efeitos da radiação , Neoplasias/diagnóstico por imagem , Óxidos/química , Óxidos/efeitos da radiação , Oxigênio/metabolismo , Medicina de Precisão , Radiossensibilizantes/síntese química , Radiossensibilizantes/efeitos da radiação , Compostos de Selênio/química , Compostos de Selênio/efeitos da radiação
5.
Nat Commun ; 12(1): 1345, 2021 03 01.
Artigo em Inglês | MEDLINE | ID: mdl-33649319

RESUMO

Drug therapy unavoidably brings toxic side effects and drug content-limited therapeutic efficacy although many nanocarriers have been developed to improve them to a certain extent. In this work, a concept of drug-free therapeutics is proposed and defined as a therapeutic methodology without the use of traditional toxic drugs, without the consumption of therapeutic agents during treatment but with the inexhaustible therapeutic capability to maximize the benefit of treatment, and a Z-scheme SnS1.68-WO2.41 nanocatalyst is developed to achieve near infrared (NIR)-photocatalytic generation of oxidative holes and hydrogen molecules for realizing combined hole/hydrogen therapy by the drug-free therapeutic strategy. Without the need of any drug and other therapeutic agent assistance, the nanocatalyst oxidizes/consumes intratumoral over-expressed glutathione (GSH) by holes and simultaneously generates hydrogen molecules in a lasting and controllable way under NIR irradiation. Mechanistically, generated hydrogen molecules and GSH consumption inhibit cancer cell energy and destroy intratumoral redox balance, respectively, to synergistically damage DNA and induce tumor cell apoptosis. High efficacy and biosafety of combined hole/hydrogen therapy of tumors are achieved by the nanocatalyst. The proposed catalysis-based drug-free therapeutic strategy breaks a pathway to realize high efficacy and low toxicity of cancer treatment.


Assuntos
Antineoplásicos/uso terapêutico , Neoplasias/tratamento farmacológico , Neoplasias/radioterapia , Fototerapia , Animais , Catálise/efeitos da radiação , Linhagem Celular Tumoral , Glutationa/química , Humanos , Hidrogênio/química , Raios Infravermelhos , Antígeno Ki-67/metabolismo , Camundongos , Nanopartículas/ultraestrutura , Tamanho da Partícula , Análise Espectral , Carga Tumoral , Microambiente Tumoral
6.
Org Biomol Chem ; 19(10): 2177-2181, 2021 03 18.
Artigo em Inglês | MEDLINE | ID: mdl-33630007

RESUMO

Eosin Y was assessed for its ability to induce a thiol-ene dependent protein-protein reaction in a metal-free, oxygen-tolerant, visible light mediated system. Protein-protein coupling efficiency under these mild conditions was comparable to previously reported UV-dependent conditions. The desired thiol-ene reaction was however limited within more complex biological systems.


Assuntos
Cisteína Endopeptidases/química , Enzimas Desubiquitinantes/química , Amarelo de Eosina-(YS)/química , Sondas Moleculares/química , Alcenos/química , Catálise/efeitos da radiação , Cisteína/química , Amarelo de Eosina-(YS)/efeitos da radiação , Células HEK293 , Humanos , Luz , Sondas Moleculares/efeitos da radiação
7.
ACS Appl Mater Interfaces ; 13(8): 9604-9619, 2021 Mar 03.
Artigo em Inglês | MEDLINE | ID: mdl-33605733

RESUMO

Hypoxia in a tumor microenvironment (TME) has inhibited the photodynamic therapy (PDT) efficacy. Here, Ni3S2/Cu1.8S nanoheterostructures were synthesized as a new photosensitizer, which also realizes the intracellular photocatalytic O2 evolution to relieve hypoxia in TME and enhance PDT as well. With the narrow band gap (below 1.5 eV), the near infrared (NIR) (808 nm) can stimulate their separation of the electron-hole. The novel Z-scheme nanoheterostructures, testified by experimental data and density functional theory (DFT) calculation, possess a higher redox ability, endowing the photoexited holes with sufficient potential to oxide H2O into O2, directly. Meanwhile, the photostimulated electrons can capture the dissolved O2 to form a toxic reactive oxygen species (ROS). Moreover, Ni3S2/Cu1.8S nanocomposites also possess the catalase-/peroxidase-like activity to convert the endogenous H2O2 into ·OH and O2, which not only cause chemodynamic therapy (CDT) but also alleviate hypoxia to assist the PDT as well. In addition, owing to the narrow band gap, they possess a high NIR harvest and great photothermal conversion efficiency (49.5%). It is noted that the nanocomposites also exhibit novel biodegradation and can be metabolized and eliminated via feces and urine within 2 weeks. The present single electrons in Ni/Cu ions induce the magnetic resonance imaging (MRI) ability for Ni3S2/Cu1.8S. To make sure that the cancer cells were specifically targeted, hyaluronic acid (HA) was grafted outside and Ni3S2/Cu1.8S@HA integrated photodynamic therapy (PDT), chemodynamic therapy (CDT), and photothermal therapy (PTT) to exhibit the great anticancer efficiency for hypoxic tumor elimination.


Assuntos
Antineoplásicos/uso terapêutico , Ácido Hialurônico/química , Nanocompostos/uso terapêutico , Neoplasias/tratamento farmacológico , Oxigênio/metabolismo , Fármacos Fotossensibilizantes/uso terapêutico , Animais , Antineoplásicos/química , Antineoplásicos/efeitos da radiação , Catálise/efeitos da radiação , Linhagem Celular Tumoral , Cobre/química , Cobre/efeitos da radiação , Cobre/uso terapêutico , Feminino , Humanos , Hipóxia/tratamento farmacológico , Hipóxia/etiologia , Raios Infravermelhos , Camundongos , Nanocompostos/química , Nanocompostos/efeitos da radiação , Neoplasias/complicações , Neoplasias/diagnóstico por imagem , Níquel/química , Níquel/efeitos da radiação , Níquel/uso terapêutico , Oxigênio/química , Fotoquimioterapia , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/efeitos da radiação , Fototerapia , Espécies Reativas de Oxigênio/química , Espécies Reativas de Oxigênio/metabolismo
8.
Proc Natl Acad Sci U S A ; 118(5)2021 02 02.
Artigo em Inglês | MEDLINE | ID: mdl-33495326

RESUMO

Adaptation to different forms of environmental stress is crucial for maintaining essential cellular functions and survival. The nucleolus plays a decisive role as a signaling hub for coordinating cellular responses to various extrinsic and intrinsic cues. p53 levels are normally kept low in unstressed cells, mainly due to E3 ubiquitin ligase MDM2-mediated degradation. Under stress, nucleophosmin (NPM) relocates from the nucleolus to the nucleoplasm and binds MDM2, thereby preventing degradation of p53 and allowing cell-cycle arrest and DNA repair. Here, we demonstrate that the mammalian sirtuin SIRT7 is an essential component for the regulation of p53 stability during stress responses induced by ultraviolet (UV) irradiation. The catalytic activity of SIRT7 is substantially increased upon UV irradiation through ataxia telangiectasia mutated and Rad3 related (ATR)-mediated phosphorylation, which promotes efficient deacetylation of the SIRT7 target NPM. Deacetylation is required for stress-dependent relocation of NPM into the nucleoplasm and MDM2 binding, thereby preventing ubiquitination and degradation of p53. In the absence of SIRT7, stress-dependent stabilization of p53 is abrogated, both in vitro and in vivo, impairing cellular stress responses. The study uncovers an essential SIRT7-dependent mechanism for stabilization of the tumor suppressor p53 in response to genotoxic stress.


Assuntos
Dano ao DNA , Proteínas Nucleares/metabolismo , Sirtuínas/metabolismo , Proteína Supressora de Tumor p53/metabolismo , Raios Ultravioleta , Acetilação/efeitos da radiação , Animais , Proteínas Mutadas de Ataxia Telangiectasia/metabolismo , Catálise/efeitos da radiação , Linhagem Celular Tumoral , Nucléolo Celular/metabolismo , Nucléolo Celular/efeitos da radiação , Humanos , Lisina/metabolismo , Camundongos , Camundongos Endogâmicos C57BL , Nucleofosmina , Fosforilação/efeitos da radiação , Estabilidade Proteica/efeitos da radiação , Proteínas Proto-Oncogênicas c-mdm2/metabolismo , Transcrição Gênica/efeitos da radiação , Ubiquitinação/efeitos da radiação
9.
Mikrochim Acta ; 187(9): 526, 2020 08 28.
Artigo em Inglês | MEDLINE | ID: mdl-32860113

RESUMO

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 Testes
10.
ACS Appl Mater Interfaces ; 12(23): 25572-25580, 2020 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-32412741

RESUMO

Reactive oxygen species-mediated tumor chemodynamic therapy and photodynamic therapy have captured extensive attention in practical cancer combination therapies. However, the severe treatment conditions and the hypoxic microenvironment of solid tumors significantly limit the efficacy of these therapies. This work demonstrates the design and fabrication of a multifunctional persistent luminescence nanoplatform (PHFI, refers to PLNP-HSA-Fe3+-IR780) for cancer multimodal imaging and effective photoenhanced combination therapy. The near-infrared-emitted persistent luminescence nanoparticles (PLNP) was modified with human serum albumin (HSA) combined with an IR780 probe and Fe3+. The synthesized PHFI possesses high longitudinal relaxivity, obvious photoacoustic contrast signals, and long-lasting persistent luminescence, indicating that PHFI can be used for cancer magnetic resonance imaging, photoacoustic imaging, and persistent luminescence multimodal imaging. PHFI shows intrinsic photoenhanced Fenton-like catalytic activities as well as photodynamic and photothermal effects and thereby can effectively overcome severe treatment conditions for killing tumor cells. It is worth noting that PHFI serving as a rechargeable internal light source for photoenhanced combination therapy was first disclosed. We believe that our work shows the great potential of PHFI for cancer theranostics and will advance the development of PLNP-based nanoplatforms in tumor catalytic therapy.


Assuntos
Substâncias Luminescentes/uso terapêutico , Nanopartículas/uso terapêutico , Neoplasias/diagnóstico por imagem , Neoplasias/tratamento farmacológico , Animais , Benzidinas/química , Catálise/efeitos da radiação , Linhagem Celular Tumoral , Compostos Cromogênicos/química , Humanos , Peróxido de Hidrogênio/química , Hipotermia Induzida/métodos , Raios Infravermelhos , Ferro/química , Substâncias Luminescentes/química , Substâncias Luminescentes/efeitos da radiação , Camundongos Endogâmicos BALB C , Nanopartículas/química , Nanopartículas/efeitos da radiação , Fotoquimioterapia/métodos , Medicina de Precisão/métodos , Espécies Reativas de Oxigênio/metabolismo , Albumina Sérica Humana/química
11.
Mikrochim Acta ; 187(6): 349, 2020 05 27.
Artigo em Inglês | MEDLINE | ID: mdl-32462256

RESUMO

A peptide (Li5-025)-modified gold nanoparticle (AuNP)/(titania (TiO2) + 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-porphine (TAPP))/glassy carbon electrode (GCE) was developed for lipopolysaccharide (LPS) determination. This electrode not only performs well in the electrochemical impedance determination of LPS in serum but can also be easily regenerated under light irradiation. Using Fe(CN)63-/4- as a redox probe, LPS recognition can be indicated by the significantly increased electron-transfer resistance (Ret) as a result of the coaction of the increased steric hindrance from the peptide-LPS complex and the electrostatic repulsion between LPS and Fe(CN)63-/4-. The impedimetric signal was acquired in the frequency range 0.1 Hz ~ 100 kHz with an initial voltage of 174 mV and an amplitude of 10 mV. The resistance changes (ΔRet) are linearly related to the LPS concentrations in a broad range (0.1 pg mL-1 ~ 100 ng mL-1) with a low detection limit (0.08 pg mL-1). Importantly, the electrode shows high selectivity to LPS from Escherichia coli O55:B5 compared to other bacterial sources and considerable anti-interference to 0.1% fetal calf serum, demonstrating its potential application in clinically relevant samples. Another highlight is that the AuNP/(TiO2 + TAPP)/GCE surface can be photocatalytically regenerated under light irradiation (50 mW cm-2, 300-2500 nm) without any obvious damage to the electrode microstructure. After simple peptide re-immobilization, the regenerated electrode demonstrates LPS response similar to the peptide less one, and the deviation is only 2.89% after 5-cycle reuse. Graphical abstract A peptide (Li5-025)-modified AuNP/(TiO2 + TAPP porphine)/GCE was proposed, which not only has excellent electrochemical analytical performances for LPS assay in serum but also can be reused after light irradiation and subsequent peptide re-immobilization.


Assuntos
Proteínas Imobilizadas/química , Lipopolissacarídeos/sangue , Peptídeos/química , Sequência de Aminoácidos , Animais , Carbono/química , Catálise/efeitos da radiação , Bovinos , Espectroscopia Dielétrica/instrumentação , Espectroscopia Dielétrica/métodos , Eletrodos , Escherichia coli/química , Ouro/química , Ouro/efeitos da radiação , Luz , Limite de Detecção , Nanopartículas Metálicas/química , Nanopartículas Metálicas/efeitos da radiação , Porfirinas/química , Porfirinas/efeitos da radiação , Titânio/química , Titânio/efeitos da radiação
12.
J Colloid Interface Sci ; 574: 61-73, 2020 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-32305729

RESUMO

Herein, a novel oxygen vacancy-rich amorphous TiO2-BiOBr-sepiolite composite was synthesized through a facile one-pot solvothermal method. Under visible light, it exhibited enhanced adsorption and photocatalytic removal activity towards gaseous formaldehyde, whose reaction rate constant is nearly 11.75, 3.44, 1.69, 2.18 and 6.27 times higher than those of amorphous TiO2, BiOBr, TiO2-BiOBr, oxygen vacancy-poor composite and P25, respectively. Moreover, it also displayed significantly improved photodegradation performance towards oxytetracycline under visible light. The improved photocatalytic activity is mainly ascribed to the synergy between the ternary heterogeneous structure and introduced oxygen vacancy, leading to the superior adsorption performance, extended visible-light adsorption scope and faster carriers' separation rate. The photogenerated holes are the dominant active species during the reaction process. Additionally, a plausible photocatalytic degradation pathway for oxytetracycline was also proposed. In general, this work provides a viable strategy of visible-light-driven photocatalyst for practical environmental remediation of indoor volatile organic compounds (VOCs) and pharmaceuticals and personal care products (PPCPs).


Assuntos
Bismuto/química , Formaldeído/química , Luz , Oxigênio/química , Oxitetraciclina/química , Titânio/química , Catálise/efeitos da radiação , Tamanho da Partícula , Processos Fotoquímicos/efeitos da radiação , Propriedades de Superfície
13.
ACS Appl Mater Interfaces ; 12(18): 20414-20422, 2020 May 06.
Artigo em Inglês | MEDLINE | ID: mdl-32283916

RESUMO

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 •OH and O2•- 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/química
14.
J Colloid Interface Sci ; 574: 364-376, 2020 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-32339819

RESUMO

Iron-based metal-organic frameworks (MOFs) with low cost and excellent photocatalytic potential are extremely attractive in the field of energy utilization and environmental remediation. In this study, a novel In2S3/MIL-100(Fe) photocatalyst was successfully synthesized by a facile solvothermal method for the first time. Several technologies (such as X-ray diffraction, scanning electron microscope, transmission electron microscope, and X-ray photoelectron spectroscopy) were used to characterize the as-obtained samples and demonstrate the successful combination of MIL-100(Fe) and In2S3. Experimental results showed that 18% of tetracycline (TC) was adsorbed under dark condition and another 70% of TC was degraded under visible-light irradiation when treating 100 mL of TC solution (10 mg/L) with 30 mg of In2S3/MIL-100(Fe) composites. The corresponding TC removal efficiency was almost 1.9 and 1.6 times higher than that of pure MIL-100(Fe) and In2S3, respectively. The mechanism investigations revealed that the heterojunction composite exhibited superior charge transfer than either MIL-100(Fe) or In2S3, and this caused more efficient separation of electron-hole pairs. As a result, more radicals and holes were generated in the composite, leading to better photocatalytic performance. This work highlights the powerful combination of MOFs and semiconductor, which is a promising approach to fabricate heterojunction photocatalyst for wastewater purification.


Assuntos
Ferro/química , Luz , Dietilamida do Ácido Lisérgico/análogos & derivados , Estruturas Metalorgânicas/química , Processos Fotoquímicos/efeitos da radiação , Tetraciclina/química , Catálise/efeitos da radiação , Dietilamida do Ácido Lisérgico/química , Tamanho da Partícula , Propriedades de Superfície
15.
J Hazard Mater ; 389: 122148, 2020 05 05.
Artigo em Inglês | MEDLINE | ID: mdl-32004844

RESUMO

In present work, we studied a novel Fe/C nanomaterial fabricated using Fe-based metal organic frameworks (MOFs) as precursors through thermal pyrolysis to catalyze gamma irradiation-induced degradation of antibiotics, cephalosporin C (CEP-C) and sulfamethazine (SMT) in aqueous solution. The MOFs-derived Fe/C nanomaterials (DMOFs) had the regular octahedrons structure of MOFs and contained element C, Fe and O, while Fe° with a fraction of Fe3O4 and Fe2O3 were identified. Results showed that DMOFs addition could accelerate the generation of OH during gamma irradiation, while the intermediates of bonds cleavages of antibiotic molecules and OH addition were identified. DMOFs were more effective to improve the decomposition of antibiotic having the higher adsorption capacity like SMT. The degradation rate of CEP-C and SMT increased by 1.3 times and 1.8 times, and TOC reduction at 1.0 kGy reached 42 % and 51 %, respectively by gamma/DMOFs treatment, while only 20.2 % (CEP-C) and 4.5 % (SMT) of TOC reduction were obtained by γ-irradiation alone. The crystal structure, functional groups and magnetism of DMOFs changed slightly after gamma irradiation, which made it possible to be reused. DMOFs were promising to enhance the degradation of antibiotics during gamma irradiation.


Assuntos
Antibacterianos/química , Estruturas Metalorgânicas/química , Nanoestruturas/química , Poluentes Químicos da Água/química , Adsorção , Carbono/química , Carbono/efeitos da radiação , Catálise/efeitos da radiação , Cefalosporinas/química , Ferro/química , Ferro/efeitos da radiação , Estruturas Metalorgânicas/efeitos da radiação , Nanoestruturas/efeitos da radiação , Radiação Ionizante , Sulfametazina/química , Purificação da Água/métodos
16.
Molecules ; 25(3)2020 Feb 08.
Artigo em Inglês | MEDLINE | ID: mdl-32046303

RESUMO

Iron-containing particulate catalysts of 0.1-1 µm size were prepared by wet and ball-milling procedures from common salts and characterized by FTIR, TGA, UV-Vis, PXRD, FEG-SEM, and XPS analyses. It was found that when the wet method was used, semi-spherical magnetic nanoparticles were formed, whereas the mechanochemical method resulted in the formation of nonmagnetic microscale needles and rectangles. Catalytic activity of the prepared materials in the oxidation of 1-phenylethanol to acetophenone was assessed under conventional heating, microwave (MW) irradiation, ultrasound (US), and oscillating magnetic field of high frequency (induction heating). In general, the catalysts obtained by wet methods exhibit lower activities, whereas the materials prepared by ball milling afford better acetophenone yields (up to 83%). A significant increase in yield (up to 4 times) was observed under the induction heating if compared to conventional heating. The study demonstrated that MW, US irradiations, and induction heating may have great potential as alternative ways to activate the catalytic system for alcohol oxidation. The possibility of the synthesized material to be magnetically recoverable has been also verified.


Assuntos
Acetofenonas/química , Álcoois Benzílicos/química , Ferro/química , Nanopartículas de Magnetita/química , Catálise/efeitos da radiação , Calefação , Micro-Ondas , Oxirredução , Termodinâmica , Ondas Ultrassônicas
17.
Nat Commun ; 10(1): 3549, 2019 08 07.
Artigo em Inglês | MEDLINE | ID: mdl-31391466

RESUMO

The asymmetric cross-coupling reaction is developed as a straightforward strategy toward 1,1-diaryl alkanes, which are a key skeleton in a series of natural products and bioactive molecules in recent years. Here we report an enantioselective benzylic C(sp3)-H bond arylation via photoredox/nickel dual catalysis. Sterically hindered chiral biimidazoline ligands are designed for this asymmetric cross-coupling reaction. Readily available alkyl benzenes and aryl bromides with various functional groups tolerance can be easily and directly transferred to useful chiral 1,1-diaryl alkanes including pharmaceutical intermediates and bioactive molecules. This reaction proceeds smoothly under mild conditions without the use of external redox reagents.


Assuntos
Alcanos/química , Produtos Biológicos/química , Níquel/química , Processos Fotoquímicos , Brometos/química , Catálise/efeitos da radiação , Elétrons , Luz , Oxirredução , Estereoisomerismo
18.
Chem Commun (Camb) ; 55(62): 9108-9111, 2019 Aug 11.
Artigo em Inglês | MEDLINE | ID: mdl-31298230

RESUMO

Inhibition of myostatin is an attractive treatment for muscular dystrophy and other amyotrophic diseases. A myostatin-binding peptide was functionalized by equipped with an on/off switchable photo-oxygenation catalyst. This peptide induces a selective oxygenation of myostatin under near-infrared light, resulting in inactivation of myostatin. This peptide shows several orders of magnitude greater inhibitory effect than the original peptide.


Assuntos
Miostatina/efeitos dos fármacos , Miostatina/efeitos da radiação , Oxigênio/química , Oxigênio/efeitos da radiação , Peptídeos/farmacologia , Processos Fotoquímicos/efeitos da radiação , Catálise/efeitos dos fármacos , Catálise/efeitos da radiação , Humanos , Raios Infravermelhos , Modelos Moleculares , Estrutura Molecular , Miostatina/metabolismo , Peptídeos/química
19.
Molecules ; 24(10)2019 May 16.
Artigo em Inglês | MEDLINE | ID: mdl-31100775

RESUMO

We present two as-synthesized Fe(II)-based molecular catalysts with 1,10-phenanthroline (phen) ligands; Fe(phen)3Cl2 (1) and [Fe(phen)2(CH3CH2OH)Cl]Cl (2), and their robust catalytic properties for the conversion of CO2 to CO in DMF/TEOA (DMF = N,N'-dimethylformamide; TEOA = triethanolamine) solution containing Ru(bpy)32+ and BIH (1,3-dimethyl-2-phenyl-2,3- dihydro-1H-benzo-[d]-imidazole). High turnover numbers (TONs) of 19,376 were achieved with turnover frequencies (TOFs) of 3.07 s-1 for complex 1 (1.5 × 10-7 M). A quantum efficiency of 0.38% was observed after 5 h irradiated by 450 nm monochromatic light. The generation rate of CO2 and H2 were tuned by optimizing the experimental conditions, resulting in a high CO selectivity of 90%. The remarkable contribution of the photosensitizer to the total TONCO was found being 19.2% (as shown by tests under similar conditions without catalysts) when BIH was employed as a sacrificial electron donor. The product selectivity in complex 2 reached 95%, and the corresponding TONCO and TOFCO were 33,167 and 4.61 s-1 in the same concentration with complex 1 used as catalyst; respectively. This work provides guidance for future designs of simple, highly efficient and selective molecular catalytic systems that facilitate carbon-neutral solar-to-fuel conversion processes.


Assuntos
Dióxido de Carbono/metabolismo , Monóxido de Carbono/metabolismo , Ferro/metabolismo , Luz , Catálise/efeitos da radiação , Hidrogênio/metabolismo , Marcação por Isótopo , Redes e Vias Metabólicas , Processos Fotoquímicos , Fatores de Tempo
20.
Colloids Surf B Biointerfaces ; 177: 470-478, 2019 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-30807961

RESUMO

Recently, nanomaterial mediated degradation of water polluting industrial pollutant and dyes has become a topic of great interest. This study demonstrates enrichment, isolation, screening and molecular identification of iron tolerant Bacillus species for biosynthesis of iron oxide magnetic nanoparticles (IOMNPs). Synthesis parameters such as 5 mM FeCl3, 7 days of static incubation at 37 °C and slightly alkaline pH range of 7-7.5 were the most optimum conditions. The spectroscopic and imaging studies demonstrated inverse spinel face-centered cubic structure of magnetite with average size of 81.3 nm, polydispersity of 0.343 and zeta potential of -42.49 mV. The specific saturation magnetization value and coercivity Hc of hysteresis loop of 28.1 emu/g and 5.8 Oe respectively confirmed the super-paramagnetic nature of IOMNPs. The comparison of phtotocatalytic activities under UV and visible light irradiation for degrdation of methyl violet, methylene blue, and rhodamine-B indicated that IOMNPs were visible light active photocatalysts. The study of effects of various reaction parameters indicated that catalyst loadings of 500-600 µg/mL, pH 7 and 20 µg/mL initial dye concetration were optimum conditions and reactions at these parameters were also observed to follow pseudo first order kinetics. This study successfully demonstrated the use of iron tolerant bacterium for visible light active, photocatalyst synthesis.


Assuntos
Bacillus/metabolismo , Óxido Ferroso-Férrico/metabolismo , Ferro/metabolismo , Luz , Catálise/efeitos da radiação , Tamanho da Partícula , Propriedades de Superfície
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