Covalent organic frameworks have recently gained increasing attention in photocatalytic hydrogen generation from water. However, their structure-property-activity relationship, which should be ...beneficial for the structural design, is still far-away explored. Herein, we report the designed synthesis of four isostructural porphyrinic two-dimensional covalent organic frameworks (MPor-DETH-COF, M = H
, Co, Ni, Zn) and their photocatalytic activity in hydrogen generation. Our results clearly show that all four covalent organic frameworks adopt AA stacking structures, with high crystallinity and large surface area. Interestingly, the incorporation of different transition metals into the porphyrin rings can rationally tune the photocatalytic hydrogen evolution rate of corresponding covalent organic frameworks, with the order of CoPor-DETH-COF < H
Por-DETH-COF < NiPor-DETH-COF < ZnPor-DETH-COF. Based on the detailed experiments and calculations, this tunable performance can be mainly explained by their tailored charge-carrier dynamics via molecular engineering. This study not only represents a simple and effective way for efficient tuning of the photocatalytic hydrogen evolution activities of covalent organic frameworks at molecular level, but also provides valuable insight on the structure design of covalent organic frameworks for better photocatalysis.
Here, a label-free perovskite-based photoelectrochemical (PEC) aptasensor was rationally designed for the displacement assay of dibutyl phthalate (DBP), a well-known endocrine disruptor, with the aid ...of cetyltrimethylammonium bromide (CTAB). In this method, CTAB significantly enhanced the PEC response and humidity resistance of the CH3NH3PbI3 perovskite by forming a protecting layer and passivating the X- and A-sites vacancies of CH3NH3PbI3. In addition, CTAB facilitated the immobilization of an aptamer through van der Waals and hydrophobicity forces, as well as the electrostatic interactions between the phosphate group of the aptamer and the cationic group of CTAB. When exposed to DBP in the affinity solution, the DBP aptamer was released from the electrode because the affinity between DBP and its aptamer competes with the interaction of the aptamer and CTAB. The displacement of the aptamer from the perovskite surface relieves the block effect and thus enhances the photoelectric signal of perovskite. By virtue of the good photoelectrochemical characters of CH3NH3PbI3 and the specific recognition ability of aptamer, the linear range of the PEC sensor was 1.0 × 10–13 to 1.0 × 10–8 M and the detection and quantification limits were down to 2.5 × 10–14 and 8.2 × 10–14 M (S/N = 3), respectively. This work offers a novel strategy for designing aptasensors for the detection of various targets and exhibits the marvelous potential of organic–inorganic perovskite in the field of PEC analysis.
Metastasis‐associated protein 2 (MTA2) is frequently amplified in many types of cancers; however, the role and underlying molecular mechanism of MTA2 in esophageal squamous cell carcinoma (ESCC) ...remain unknown. Here, we reported that MTA2 is highly expressed in ESCC tissue and cells, and is closely related to the malignant characteristics and poor prognosis of patients with ESCC. Through in vitro and in vivo experiments, we demonstrated that MTA2 significantly promoted ESCC growth, metastasis, and epithelial‐mesenchymal transition (EMT) progression. This integrative analysis combined with expression microarray showed that MTA2 could interact with eukaryotic initiation factor 4E (EIF4E), which positively regulates the expression of Twist, known as a master regulator of EMT. Moreover, the results of chromatin immunoprecipitation revealed that MTA2 was recruited to the E‐cadherin promoter by Twist, which reduced the acetylation level of the promoter region and thus inhibited expression of E‐cadherin, and subsequently promoted the aggressive progression of ESCC. Collectively, our study provided novel evidence that MTA2 plays an aggressive role in ESCC metastasis by a novel EIF4E‐Twist positive feedback loop, which may provide a potential therapeutic target for the management of ESCC.
We demonstrated that the upregulation of MTA2 in ESCC was significantly correlated with malignant characteristics and poor survival probability of patients. The abnormal expression of MTA2 in ESCC contributed to the proliferation, metastasis, and EMT phenotype of ESCC cells through a novel EIF4E‐Twist positive feedback loop.
(
) is the natural enemy of many aphid species. Traditional manual release of
adults requires substantial manpower, and release efficiency is low. Automatic mechanical devices can improve the ...efficiency of delivery. Based on
adults' morphological size, a prototype release system for
was designed, which considered the adhesion characteristics of
adults. According to the measured physical characteristics of
adults, the structural parameters of the mechanical system for the release of the
adults were determined. The relationship of the quantity of release, the impeller rotating speed, and the time for the release of
adults were constructed. The mechanism can quantitatively adjust the number of
adults to meet a certain
-aphids ratio. Combining the image processing technology with the camera function of a mobile phone, the maximum cross-sectional area method was used to count the
adults in the designated area. Results showed that the impeller rotating speed had a significant effect on the survival rate of the
adults. When the airflow velocities were 29.5 m/s and 38.3 m/s, the survival rates of the
adults were 93.8% and 94.5% at 4.2 rpm. The adhesion rate of the
adults was 2.5%-4.6%. This work will provide technical support for the research of biological control.
Herein we demonstrate the protocol of a biocatalytic precipitation (BCP)-based sandwich photoelectrochemical (PEC) horseradish peroxidase (HRP)-linked immunoassay on the basis of their synergy effect ...for the ultrasensitive detection of mouse IgG (antigen, Ag) as a model protein. The hybrid film consisting of oppositely charged polyelectrolytes and CdS quantum dots (QDs) is developed by the classic layer by layer (LbL) method and then employed as the photoactive antibody (Ab) immobilization matrix for the subsequent sandwich-type Ab-Ag affinity interactions. Improved sensitivity is achieved through using the bioconjugates of HRP-secondary antibodies (Ab2). In addition to the much enhanced steric hindrance compared with the original one, the presence of HRP would further stimulate the BCP onto the electrode surface for signal amplification, concomitant to a competitive nonproductive absorption that lowers the photocurrent intensity. As a result of the multisignal amplification in this HRP catalyzed BCP-based PEC immunoassay, it possesses excellent analytical performance. The antigen could be detected from 0.5 pg/mL to 5.0 ng/mL with a detection limit of 0.5 pg/mL.
Diabetes mellitus (DM) can lead to diabetic ulcers (DUs), which are the most severe complications. Due to the need for more accurate patient classifications and diagnostic models, treatment and ...management strategies for DU patients still need improvement. The difficulty of diabetic wound healing is caused closely related to biological metabolism and immune chemotaxis reaction dysfunction. Therefore, the purpose of our study is to identify metabolic biomarkers in patients with DU and construct a molecular subtype-specific prognostic model that is highly accurate and robust. RNA-sequencing data for DU samples were obtained from the Gene Expression Omnibus (GEO) database. DU patients and normal individuals were compared regarding the expression of metabolism-related genes (MRGs). Then, a novel diagnostic model based on MRGs was constructed with the random forest algorithm, and classification performance was evaluated utilizing receiver operating characteristic (ROC) analysis. The biological functions of MRGs-based subtypes were investigated using consensus clustering analysis. A principal component analysis (PCA) was conducted to determine whether MRGs could distinguish between subtypes. We also examined the correlation between MRGs and immune infiltration. Lastly, qRT-PCR was utilized to validate the expression of the hub MRGs with clinical validations and animal experimentations. Firstly, 8 metabolism-related hub genes were obtained by random forest algorithm, which could distinguish the DUs from normal samples validated by the ROC curves. Secondly, DU samples could be consensus clustered into three molecular classifications by MRGs, verified by PCA analysis. Thirdly, associations between MRGs and immune infiltration were confirmed, with LYN and Type 1 helper cell significantly positively correlated; RHOH and TGF-β family remarkably negatively correlated. Finally, clinical validations and animal experiments of DU skin tissue samples showed that the expressions of metabolic hub genes in the DU groups were considerably upregulated, including GLDC, GALNT6, RHOH, XDH, MMP12, KLK6, LYN, and CFB. The current study proposed an auxiliary MRGs-based DUs model while proposing MRGs-based molecular clustering and confirmed the association with immune infiltration, facilitating the diagnosis and management of DU patients and designing individualized treatment plans.
Femoral neck fractures are one of the problems in clinical treatment. The prognosis is uncertain. Currently, No internal fixation method is superior to other internal fixation methods in the ...treatment of femoral neck fractures. Therefore, the internal fixation system needs to be further explored. The aim of this study was to compare clinical outcomes of femoral neck dynamic compression locking system (DCLS) and multiple cannulated compression screws(MCCS) in the treatment of femoral neck fractures.
A prospective analysis of 54 cases of femoral neck fractures treated with either a DCLS (n = 28) or MCCS (n = 26) was conducted between December 2015 and November 2017 in authors' hospitals. The perioperative and postoperative parameters of the two groups were recorded and evaluated.
Fifty-four patients were followed up for 24-47 months. The etiology was caused by a fall. There was no significant difference in follow-up time, operation time, incision length, surgical blood loss, the incidence of perioperative and postoperative healing complications, and mobility in the two groups (all P > 0.05). The Harris score, fracture healing time, femoral neck shortening, partial weight-bearing time and complete weight-bearing time were significantly better in the DCLS group than in the MCCS group (all P < 0.05). The fracture healing rate in the DCLS group was higher than that in the MCCS group.
The DCLS and MCCS might be equally effective in terms of operation time, incision length, surgical blood loss, the incidence of perioperative and postoperative healing complications, and mobility in the treatment of femoral neck fractures. However, the DCLS is superior to the MCCS in Harris score, fracture healing time, femoral neck shortening, weight-bearing time and fracture healing rate. So, DCLS deserves further study.
Here, we developed a self-powered bipolar electrode (SP-BPE) based dual-mode sensor with electrochromic (EC) and photoelectrochemical (PEC) techniques for the visualized and sensitive detection of ...bisphenol A (BPA). An open BPE with the molecularly imprinted polymers (MIPs) modified electron injection area and the Prussian blue (PB) coated electrochromic area was fabricated on an indium tin oxide (ITO) glass. A kind of Zr-based metal-organic framework (UiO-66) coated TiO2 heterojunction (TiO2@UiO-66) was used for aptamer (Apt) immobilization and electron generation. BPA was selectively accumulated by MIPs, and subsequently recognized TiO2@UiO-66-Apt quantitatively, resulting in the formation of MIPs/BPA/Apt-TiO2@UiO-66 “sandwich” structure. Under UV-light, electrons were generated from the captured TiO2@UiO-66. For EC visualization measurements, electrons were injected into the PB film, causing a color change without an external power source. The extent of color change was proportional to the number of generated electrons, which correlated with the amount of captured BPA within a concentration range of 10−6–10−11 M. This allowed for the semi-quantification of BPA by naked eyes. For PEC detection, the BPE was used as the working electrode in a three-electrode system. The generated photocurrents signals could be digitally output for BPA with the concentrations ranging from 10−5 to 10−11 M. The SP-BPE sensors showed low background signal, improved selectivity and anti-interference abilities, and have demonstrated excellent performance in quantitative BPA analysis in water samples. They are particularly useful in scenarios where traditional power sources are limited or unavailable, and they offer opportunities for sustainable and environmentally friendly target detection.
•An autonomous and sustainable sensing devices was developed based on self-powered open bipolar electrode.•Sandwich-type recognition model based on the dual-recognition of MIP and aptamer.•The visual and digital dual-mode enhanced flexibility, reliability, and user-friendliness.
Metal-organic framework (MOF) has great potential in the field of supercapacitors as electrode material due to its high specific surface area and unique structure. Herein, a series of nickel MOFs ...(Ni-MOFs) were fabricated by one-pot solvothermal method at different experimental conditions. The electrochemical properties of the Ni-MOFs as electrode materials can be tuned by adjusting the experimental conditions to regulate the structures. The result indicates that a novel moss-like three-dimensional (3D) Ni-MOF had the maximum specific capacity of 638 C g-1 at a current density of 0.5 A g-1. The asymmetric supercapacitor (ASC) assembled by using moss-like 3D Ni-MOF as the positive electrode and active carbon as the negative electrode exhibited a high energy density of 30.4 Wh kg-1 at power density of 407.4 W kg-1.
The moss-like 3D Ni-MOF was synthesized by one-pot solvothermal method utilizing Ni(NO3)2·6H2O to provide metal central ions and PTA as the organic ligand. PTA in the solution had a large number of carboxyl groups, which could adsorb free Ni2+ by coordination bonds to promote the growth of Ni-MOF during the solvothermal reaction, and further fabricated a novel moss-like 3D Ni-MOF by self-assembly. Display omitted
•A novel moss-like 3D Ni-MOF was synthesized by one-pot solvothermal method.•The moss-like 3D Ni-MOF possessed a high specific capacity of 638 C g-1.•The asymmetric moss-like 3D Ni-MOF.||AC device exhibited a high energy density of 30.4 Wh kg-1 at power density of 407.3 W kg-1.
Volvocales forms a species‐rich clade with wide morphological variety and is regarded as an ideal model for tracing the evolutionary transitions in multicellularity. The phylogenetic relationships ...among the colonial volvocine algae and its relatives are important for investigating the origin of multicellularity in the clade Reinhardtinia. Therefore, a robust phylogenetic framework of the unicellular and colonial volvocine algae with broad taxon and gene sampling is essential for illuminating the evolution of multicellularity. Recent chloroplast phylogenomic studies have uncovered five major orders in the Chlorophyceae, but the family‐level relationships within Sphaeropleales and Volvocales remain elusive due to the uncertain positions of some incertae sedis taxa. In this study, we contributed six newly sequenced chloroplast genomes in the Volvocales and analyzed a dataset with 91 chlorophycean taxa and 58 protein‐coding genes. Conflicting phylogenetic signals were detected among chloroplast genes that resulted in discordant tree topologies among different analyses. We compared the phylogenetic trees inferred from original nucleotide, RY‐coding, codon‐degenerate, and amino acid datasets, and improved the robustness of phylogenetic inference in the Chlorophyceae by reducing base compositional bias. Our analyses indicate that the unicellular Chlamydomonas and Vitreochlamys are close to or nested within the colonial taxa, and all the incertae sedis taxa are nested within the monophyletic Sphaeropleales s.l. We propose that the colonial taxa in the Reinhardtinia are paraphyletic and multicellularity evolved once in the volvocine green algae and might be lost in Chlamydomonas and Vitreochlamys.
We assessed base compositional bias among 91 volvocine algae in the nt dataset and each of the three codon positions, and the percentage GC content of each species was plotted to visualize compositional heterogeneity. We compared the phylogenies inferred from different datasets with decreasing compositional biases (original nucleotide, RY‐coding, codon‐degenerate and amino acid datasets) and Robinson–Foulds (RF) algorithm was used for tree distance calculations. Conflicting phylogenetic signals among 58 plastid genes were detected and quantified through the calculation of genewise log‐likelihood support, which resulted in discordant tree topologies at key nodes among different datasets. We hypothesize that the colonial taxa in the Reinhardtinia are paraphyletic and multicellularity has evolved once in the colonial clade, but was subsequently lost in Vitreochlamys and Chlamydomonas based on the phylogeny and ancestral state reconstruction analysis. We supplemented the chloroplast genomes and improved the robustness of phylogenetic inference in the Volvocales, which are crucial for studying the fundamental processes that shaped the initial advent of multicellularity.
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