ABSTRACT Lysosomal iron overload, resulting from dysregulated ferritinophagy, is a significant early event in the progression of Parkinson's disease (PD). This condition causes iron accumulation within cells, triggering oxidative stress and ferroptosis, along with mitochondrial dysfunction and α‐synuclein (α‐syn) aggregation, ultimately damaging dopaminergic neurons irreversibly. However, tools for real‐time monitoring of Fe 3+ dynamics in vivo are limited. In this study, we introduce TPE‐4B/4Q[7], a supramolecular fluorescent probe designed for selective and stable tracking of Fe 3+ changes within lysosomes. This probe exhibits excellent photostability, low cytotoxicity, and a detection limit of 1.23 × 10⁻⁶ M. In cellular models of PD, TPE‐4B/4Q[7] effectively monitors lysosomal ferritinophagy‐induced Fe 3+ overload, allowing for the assessment of oxidative stress, mitochondrial function, and the levels of key biomarkers such as α‐syn and tyrosine hydroxylase. Additionally, this probe can track iron accumulation linked to neurodegenerative lesions in Caenorhabditis elegans and MPTP‐induced PD mouse models, with signal changes correlating closely with neurodegenerative phenotypes and molecular pathology. Notably, TPE‐4B/4Q[7] enables non‐invasive brain imaging via nasal delivery. TPE‐4B/4Q[7] is a sensitive molecular indicator for early risk assessment and monitoring of PD progression. It is anticipated to be an effective instrument for the early diagnosis of PD.
Black phosphorus (BP) is a novel two-dimensional (2D) material with remarkable potential for use in environmental remediation and energy conversion. However, the practical application of BP is significantly limited by its low catalytic efficiency and poor structural stability. In this study, a Z-scheme BP/BiOBr 2D/2D heterojunction was fabricated using a simple solution reaction method at room temperature. The BP/BiOBr heterojunction exhibited significantly enhanced photocatalytic performance in the degradation of various organic pollutants and the production of hydrogen under visible light irradiation. This improved activity can be attributed to the efficient separation of photogenerated charges and the extended lifetime of charge carriers within the heterojunction. The durability and structural stability of the BiP-10 heterojunction were demonstrated through cycling tests, which maintained high photocatalytic efficiency over multiple uses. This study presents a promising approach to the development of BP-based photocatalytic materials for sustainable environmental and energy applications.
Black phosphorus (BP) is an innovative two-dimensional (2D) material that exhibits remarkable potential for applications in environmental remediation and energy conversion. However, the practical utilization of BP is significantly hindered by its low catalytic efficiency and insufficient structural stability. In this study, BP nanosheets were combined with Bi5O7I nanoparticles, which possess abundant oxygen vacancies (DBOI), to form a BP/Bi5O7I (BOIP) heterojunction. The BOIP-5 variant, which contains 5 mg of BP in 100 mg of DBOI, demonstrated the highest photocatalytic performance for the degradation of oxytetracycline (OTC) and levofloxacin (LVX), as well as for the production of H2 and H2O2, compared to pristine DBOI. The active species generated, including h+, & sdot;OH, and & sdot;O2-, are primarily responsible for the degradation of OTC. The Z-scheme charge transfer mechanism enhances the spatial separation of photogenerated charge carriers and maintains high redox potentials of the electrons and holes within the BOIP heterojunction. The results suggest that the construction of this heterojunction can effectively improve photocatalytic performance, making BP-based heterojunctions promising candidates for environmental remediation and energy applications.
Fenton oxidation technology utilizing hydrogen peroxide is recognized as an effective method for producing reactive oxygen species (ROS) to facilitate the degradation of antibiotics. However, the requirement for strongly acidic conditions during this process significantly restricts its broader applicability. In this study, we synthesized black phosphorus (BP) nanosheets by exposing the {010} crystal planes and then constructed a 0D/2D BP/Bi2MoO6 (PBMO) heterojunction to function as a Fenton catalyst. The PBMO-75 heterojunction exhibited a remarkable increase in photo-Fenton catalytic activity towards oxytetracycline (OTC) under neutral conditions, achieving catalytic efficiencies that were 20 and 8 times greater than those of BP and Bi2MoO6 (BMO), respectively. This can be attributed to its strong absorption of visible light, the establishment of an internal electric field (IEF) at the interface, and the implementation of a Z-scheme catalytic mechanism. Additionally, the photo-Fenton system was further improved in OTC degradation through the continuous conversion of Mo6+/Mo5+ under visible light irradiation in conjunction with H2O2. Based on ERS, XPS, and active species trapping experiments, we propose a Z-scheme charge transfer mechanism for PBMO. This research offers compelling evidence that 0D/2D Z-scheme heterojunctions are promising candidates for the photo-Fenton treatment of antibiotic contaminants.
Although evidence indicates that the abnormal accumulation of α-synuclein (α-syn) in dopamine neurons of the substantia nigra is the main pathological feature of Parkinson's disease (PD), no compounds that have both α-syn antiaggregation and α-syn degradation functions have been successful in treating the disease in the clinic. Here, it is shown that black phosphorus nanosheets (BPNSs) interact directly with α-syn fibrils to trigger their disaggregation for PD treatment. Moreover, BPNSs have a specific affinity for α-syn through van der Waals forces. And BPNSs are found to activate autophagy to maintain α-syn homeostasis, improve mitochondrial dysfunction, reduce reactive oxygen species levels, and rescue neuronal death and synaptic loss in PC12 cells. It is also observed that BPNSs penetrate the blood-brain barrier and protect against dopamine neuron loss, alleviating behavioral disorders in 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP) induced mouse model and hA53T α-syn transgenic mice. Together, the study reveals that BPNSs have the potential as a novel integrated nanomedicine for clinical diagnosis and treatment of neurological diseases.
To promote the spatial separation of photogenerated charge carriers is a critical challenge in the practical application of photocatalytic reaction. Surface oxygen vacancies (OVs) of catalysts have been confirmed to play a significant role for boosting photocatalytic quantum efficiency. Herein, Bi5O7I nanoparticles with abundant oxygen vacancies (DBOI) were prepared via a facile solution method. STEM-HAADF, HRTEM, low temperature EPR, XPS and PAS measurements were adopted to demonstrate the surface OVs. DFT calculations confirmed a DOS appeared in the forbidden band and the band gap of DBOI was consequently reduced. The surface OVs make DBOI have more coordinately unsaturated sites and defect states, functioning as the traps to capture charge carriers and reactants and thus effectively accelerate photocatalytic reaction. The optimal production rate of H2, O2 and H2O2 without cocatalyst over DBOI was respectively 1.18, 106.7 and 3.05 mmol h-1 g � 1, which manifested significant improvement than Bi5O7I with less OVs. This work presented that surface OVs can endow Bi5O7I nanoparticles with efficient charge separation to acquire superior photocatalytic overall water splitting activity.
The low separation efficiency of photogenerated charge carriers is the main impediment to the practical application of photocatalysis. Herein, Bi5O7I nanoparticles with abundant oxygen vacancies (DBOI) were deposited on Bi3O4Br nanosheets (BOBr) to create a novel 0D/2D DBOI/BOBr heterojunction (DBOI-Br) using a facile solution method. The structure of surface oxygen vacancies (SOVs) was demonstrated using HRTEM, lowtemperature EPR, and XPS. The effective interface contact between DBOI and BOBr resulted in the establishment of an internal electric field (IEF) and band bending. The photogenerated charge transfer mechanism was validated through in situ irradiated XPS, work function calculation, and ERS measurement. The synergistic effect of IEF, band bending, and SOVs efficiently suppressed the recombination of photogenerated charge carriers, enhancing the photocatalytic activity. Almost 100 % of tetracycline, oxytetracycline, levofloxacin, ciprofloxacin, methylene blue, and rhodamine B, as well as 92.3 % of phenol, could be decomposed using DBOI-Br under visible light irradiation. The average production rates of H2, O2, and H2O2 were 805, 3800, and 562 mu mol h- 1 g- 1 over 4 h, corresponding to quantum efficiencies of 3.67 %, 10.4 %, and 5.26 % at 420 nm, respectively. This study introduces a new promising DBOI-Br heterojunction photocatalyst with rich SOVs to enhance the charge separation efficiency for various photocatalytic applications.
Photocatalytic technology has been recently conducted to remove microbial contamination due to its unique features of nontoxic by-products, low cost, negligible microbial resistance and broad-spectrum elimination capacity. Herein, a novel two dimensional (2D) g-C3N4/Bi(OH)3 (CNB) heterojunction was fabricated byincorporating Bi(OH)3 (BOH) nanoparticles with g-C3N4 (CN) nanosheets. This CNB heterojunction exhibited high photocatalytic antibacterial efficiency (99.3%) against Escherichia coli (E. coli) under visible light irradiation, which was 4.3 and 3.4 times that of BOH (23.0%) and CN (28.0%), respectively. The increase in specific surface area, ultra-thin layered structure, construction of a heterojunction and enhancement of visible light absorption were conducive to facilitating the separation and transfer of photoinduced charge carriers. Live/dead cell staining, sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) assays and scanning electron microscopy (SEM) have been implemented to investigate the damage to the cell membrane and the leakage of the intracellular protein in the photocatalytic antibacterial process. The e−, h+ and O2•− were the active species involved in this process. This study proposed an appropriate photocatalyst for efficient treatment of bacterial contamination.
A novel Ag@Bi5O7I/Bi(OH)3 (AB) heterojunction was prepared and the enhanced photocatalytic antibacterial activity against Escherichia coli (E. coli) under visible light excitation was exhibited. 3 %AB (containing 3 wt% of Ag) presented best photocatalytic performance, and all of E. coli cells were inactivated within 5 min under natural solar light irradiation. The photocatalytic antibacterial mechanism of AB heterojunction was corrobo-rated by SEM, live/dead cell staining and SDS-PAGE assay. The destruction of the cell membrane, the leakage of the intracellular protein and the decomposition of the protein were considered as the events occurred in the antibacterial process. The radical capture experiment confirmed that center dot O2- and e- played the dominant role in the destruction of the cell membrane and the decomposition of the protein. The improvement of the photocatalytic activity can be mainly ascribe to the construction of heterojunction, SPR effect resulted from Ag deposition, enhanced visible light absorption and more surface oxygen vacancies. These factors are advantageous to the generation of the photogenerated electrons and holes, and improve the spatial separation efficiency of the photogenerated charge. This study presented a promising Ag@Bi5O7I/Bi(OH)3 heterojunction as the photo-catalyst for the potential application in the treatment of the bacterial contamination.
The design and synthesis of visible light-responsive heterogeneous catalysts for the effective removal of contaminants are critical areas of research in the environmental catalysis. In this study, DyFeO3/g-C3N4 p-n heterojunctions (DFCs) were successfully synthesized. TEM, HRTEM, SEM, FTIR and XPS results clarified the successful formation of DFCs and their ultra-thin and porous structure. DRS and XPS VB spectra revealed that the DFCs were type II heterojunctions with strong visible light absorption. TPC, EIS, PL and PL decay spectra confirmed the increase of the separation efficiency and the inhibition of the recombination of the photogenerated charge carriers in DFCs. DFC-2 (containing 2 wt% of DyFeO3) exhibited the best photo -Fenton degradation performance. The highest degradation efficiency was 99.1%, 100%, and 99.6% on DFC-2 for oxytetracycline, methylene blue, and rhodamine B, respectively. The photo-Fenton antibacterial effi-ciency was over 99% after 15 min of visible light irradiation. Moreover, the antibacterial effect was 4 times and 2.7 times that of photocatalytic or Fenton antibacterial processes. The internal electric field generated at the interface between DyFeO3 and g-C3N4 ameliorated the spatial separation and transfer features of charge carriers. In addition, the accelerated transfer of the electrons facilitated the reduction of Fe3+ to regenerate Fe2+, which further enhanced the photo-Fenton degradation and antibacterial activity. In a radical scavenger experiment, ESR and HPLC-MS were employed to identify the major active species and intermediates in the photo-Fenton degradation of oxytetracycline. The degradation pathways and mechanism were reasonably inferred. This study proposes promising DFCs with p-n heterostructures for the effective photo-Fenton removal of oxytetracycline and antibacterial activity.(c) 2023 Elsevier B.V. All rights reserved.
Exploring effective approach to boost the removal efficiency has always been a critical challenge in the field of environmental contaminant treatment. In this study, p-n heterojunctions were precisely fabricated by incorpo-rating perovskite ErFeO3 nanoparticles on porous g-C3N4 nanosheets and employed to degrade oxytetracycline and tetracycline through visible light assisted heterogeneous photo-Fenton technology. The built-in electric field at the interface of ErFeO3 and g-C3N4 provided an additional driving force for the separation of photoinduced electron-hole pairs, which accelerated the generation of e-, h+ and ROS. The addition of H2O2 and the present of Fe-based ErFeO3 induced the photo-Fenton reaction. Under visible light irradiation, 99.7% of oxytetracycline and 98.5% of tetracycline could be decomposed over ErFeO3/g-C3N4 p-n heterojunctions. The apparent rate constant of photo-Fenton degradation for oxytetracycline was about 194 times of photocatalytic degradation and 53 times of Fenton degradation, respectively. The ErFeO3/g-C3N4 p-n heterojunctions also had exceptional stability and adaptability. The structures of degradation intermediates, possible photo-Fenton degradation mechanism and pathways of oxytetracycline were proposed according to the HPLC-MS, ESR and free radical quenching exper-iments. This study provided an effective approach for effective treatment of refractory pollutant.
Sc2VO5-δ /g-C3N4 heterojunctions (SVCs) with abundant oxygen vacancies (OVs) were synthesized by ultrasonic exfoliation combined with the thermal etching method. The structures, OVs and spatial separation of the photogenerated carriers were systematically characterized. The results manifested that the SVCs were successfully constructed via the strong interaction between g-C3N4 (CN) and Sc2VO5-δ (SV). The SVCs possessed a higher concentration of OVs than that of pristine CN and SV. The formation of the SVC heterostructures and the optimization of the OVs were the two major factors to accelerate the separation of the charge carriers and finally to improve the photocatalysis performance. The as-prepared 10%SVC (containing 10 wt% of SV) catalyst exhibited the highest OV concentration and the best photocatalytic performance. The levofloxacin (LVX) photodegradation activity showed a positive correlation with the OV concentration. The photocatalytic degradation efficiencies were 89.1, 98.8 and 99.0% on 10%SVC for LVX, methylene blue (MB) and rhodamine B (RhB), respectively. These photodegradation processes followed the pseudo first order kinetic equation. The apparent rate constant (kapp) of LVX degradation on 10%SVC was 11.0 and 7.5 times that of CN and SV. The h+, ˙OH and ˙O2- were the major reactive species in the photodegradation process.
The technology integrating adsorption and photocatalysis is regarded as the most promising strategy for the elimination of low concentration antibiotic contaminant. In this study, we firstly prepared the mesoporous g-C3N4 nanosheets (CN) with the thickness of 4-5 nm by the thermal etching and ultrasonic techniques. Then perovskite ErFeO3 nanoparticles (EF) were incorporated into CN to construct the3/g-C3N4 (EFC) heterojunction. The heterojunction with EF content of 2 wt% (2-EFC) had the optimal adsorption and photocatalytic performance. 87.8% of ciprofloxacin (CIP) was eliminated via the adsorption-photocatalysis synergistic process over 2-EFC. The CIP adsorption capability of 2-EFC was 11.7 times that of CN, and the zero-order degradation reaction rate constant (k0) was 25.2 times of CN. The ultrathin and porous structure of CN increased the specific surface area and reaction active sites, shorten the diffusion distance of photoinduced charge carriers. And the construction of EFC heterojunction further accelerated the separation of charge carriers and inhibited its recombination. These two strategies ameliorated the adsorption and photocatalytic activity of EFC in removal of CIP. The CIP adsorption on the samples followed pseudo second order kinetics model, and the adsorption isotherm data complied with Langmuir isotherm model. The photocatalytic degradation process of CIP on 2-EFC could be divided into two phases. Due to the CIP concentration change in the degradation solution, the kinetics curve followed the zero order rate equation at 0 to 40 min. After that, it deferred to the first order rate equation. The h+ , center dot OH and center dot O-2 were involved in the photocatalytic degradation process. The structures of degradation intermediates and possible degradation pathways of CIP were proposed according to the HPLC-MS results. This research provided an alternative with high efficient synergetic effect of adsorption and photocatalytic degradation for the treatment of antibiotic wastewater. (c) 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Cu2V2O7/Cu3V2O8/g-C3N4 heterojunctions (CVCs) were prepared successfully by the reheating synthesis method. The thermal etching process increased the specific surface area. The formation of heterojunctions enhanced the visible light absorption and improved the separation efficiency of photoinduced charge carriers. Therefore, CVCs exhibited superior adsorption capacity and photocatalytic performance in comparison with pristine g-C3N4 (CN). CVC-2 (containing 2 wt% of Cu2V2O7/Cu3V2O8) possessed the best synergistic removal efficiency for removal of dyes and antibiotics, in which 96.2% of methylene blue (MB), 97.3% of rhodamine B (RhB), 83.0% of ciprofloxacin (CIP), 86.0% of tetracycline (TC) and 80.5% of oxytetracycline (OTC) were eliminated by the adsorption and photocatalysis synergistic effect under visible light irradiation. The pseudo first order rate constants of MB and RhB photocatalytic degradation on CVC-2 were 3 times and 10 times that of pristine CN. For photocatalytic degradation of CIP, TC and OTC, it was 3.6, 1.8 and 6.1 times that of CN. DRS, XPS VB and ESR results suggested that CVCs had the characteristics of a Z-scheme photocatalytic system. This study provides a reliable reference for the treatment of real wastewater by the adsorption and photocatalysis synergistic process.
In this study, we first manufactured ultrathin g-C3N4 (CN) nanosheets by thermal etching and ultrasonic techniques. Then, EuVO4 (EV) nanoparticles were loaded onto CN nanosheets to form EuVO4/g-C3N4 heterojunctions (EVCs). The ultrathin and porous structure of the EVCs increased the specific surface area and reaction active sites. The formation of the heterostructure extended visible light absorption and accelerated the separation of charge carriers. These two factors were advantageous to promote the synergistic effect of adsorption and photocatalysis, and ultimately enhanced the adsorption capability and photocatalytic removal efficiency of methylene blue (MB). EVC-2 (2 wt% of EV) exhibited the highest adsorption and photocatalytic performance. Almost 100% of MB was eliminated via the adsorption–photocatalysis synergistic process over EVC-2. The MB adsorption capability of EVC-2 was 6.2 times that of CN, and the zero-orderreaction rate constant was 5 times that of CN. The MB adsorption on EVC-2 followed the pseudo second-order kinetics model and the adsorption isotherm data complied with the Langmuir isotherm model. The photocatalytic degradation data of MB on EVC-2 obeyed the zero-order kinetics equation in 0–10 min and abided by the first-order kinetics equation for10–30 min. This study provided a promising EVC heterojunctions with superior synergetic effect of adsorption and photocatalysis for the potential application in wastewater treatment.
Mitochondrial damage mediated by reactive oxygen species (ROS) is a major contributory factor to Parkinson's disease (PD) pathogenesis. The use of hemin-based nanomaterials to control ROS production can protect against neurological damage. Here, we report the rational design of a uniform and water-soluble artificial nanozyme based on an ultrathin graphitic carbon nitride (g-C3N4) nanosheet with loaded hemin to reduce ROS and treat PD. The g-C(3)N(4)4 not only acted as a scaffold for hemin loading but also improved the stability, cytotoxicity, and catalytic action of hemin. The integration of g-C3N4 increased hemin's peroxidase activity by 31.7%, promoting effective oxidation of the substrate 3,3 & PRIME;,5,5 & PRIME;-tetramethybenzichne (TMB) in the presence of H2O2 to a blue colored solution after 10 min' incubation at room temperature. Moreover, CN-hemin exhibited good biocompatibility and could effectively scavenge intracellular ROS and reduce cytotoxicity induced by H2O2 and 6hydroxydopamine (6-OHDA). In vivo animal studies using nematode transgenic hus111 strain and 6-OHDA pretreated C. elegans wild-type Bristol (N2) as models further showed that CN-hemin extended their lifespan and restored dopamine-dependent behaviors such as area-restricted searching, ethanol avoidance, and the basal slowing response by reducing ROS-mediated neurotoxicity. Nanomaterials using CN-hemin enzyme mimicry have potential biomedical applications, including the treatment of PD and disorders related to ROS metabolism.
以配体菲咯啉取代苷脲(L),分别与CoCl2·6H2O、CuCl2·2H2O进行配位反应,得到2个配合物{[Co(L)(H2O)3]Cl2·2H2O}n(1)和[Cu2(L)2Cl4]· 3C2H5OH(2).并用元素分析、FTIR和X-射线单晶衍射进行了表征.晶体结构表明:配合物1属于正交晶系,P212121空间群,每个Co(Ⅱ)的配位环境为扭曲的八面体,分别与1个配体上菲咯啉单元的2个氮原子、另外1个配体的羰基氧原子和3个水分子配位,配合物中每个配体L表现为三齿配体分别与2个co(Ⅱ)离子配位桥联形成一维链状结构.配合物2属于单斜晶系,P21/n空间群,Cu(Ⅱ)的配位环境为扭曲的四方锥形,分别与配体上菲咯啉单元的2个氮原子和3个氯原子配位,3个氯原子中有2个氯原子同时和2个Cu(Ⅱ)离子配位,从而使配合物2形成双核配合物.