Four highly porous covalent organic frameworks (COFs) containing pyrene units were prepared and explored for photocatalytic H2O2 production. The experimental studies are complemented by density ...functional theory calculations, proving that the pyrene unit is more active for H2O2 production than the bipyridine and (diarylamino)benzene units reported previously. H2O2 decomposition experiments verified that the distribution of pyrene units over a large surface area of COFs plays an important role in catalytic performance. The Py‐Py‐COF though contains more pyrene units than other COFs which induces a high H2O2 decomposition due to a dense concentration of pyrene in close proximity over a limited surface area. Therefore, a two‐phase reaction system (water‐benzyl alcohol) was employed to inhibit H2O2 decomposition. This is the first report on applying pyrene‐based COFs in a two‐phase system for photocatalytic H2O2 generation.
Four highly porous pyrene‐based covalent organic frameworks (COFs) were prepared for photocatalytic H2O2 generation. The reported findings highlight that the presence of pyrene active sites in very close proximity leads to unwanted H2O2 decomposition. Accordingly, a biphasic system (benzyl alcohol and water) was employed to inhibit H2O2 decomposition.
To analyze the risk factors affecting psychiatric behavior and study the psychobehavioral conditions of children with epilepsy.
We randomly selected and enrolled 294 children with epilepsy who ...visited and were hospitalized in the pediatric clinic of Hebei General Hospital between January 2017 and January 2022, as the study participants. We comprehensively assessed their cognitive functions using the Gesell development schedule or Wechsler Intelligence Scales. The participants were divided into the study group (n = 123) with cognitive impairment and the control group (n = 171) with normal cognitive functions, for analysis.
There were statistically significant differences between the two groups in disease course, frequency of epilepsy, status epilepticus, and the number of antiseizure medications (ASMs) used (P < 0.05), while there were no statistically significant differences in age, gender, age of onset, form of onset, interictal epileptiform discharge, history of febrile convulsion, and the time from onset to initial visit (P > 0.05). Based on multivariate logistic regression analysis, the course of disease, frequency of onset, status epilepticus and number of ASMs used were identified as high-risk factors for cognitive impairment in children with epilepsy. Similarly, early onset, long course of disease, known etiology, and combination of multiple drugs have a negative impact on behavioral problems, school education, and social adaptability.
The course of disease, the frequency of onset, status epilepticus, and the number of ASMs used are high-risk factors for cognitive impairment in children with epilepsy, which can be prevented and controlled early. When selecting ASMs, their advantages and disadvantages should be weighed. Moreover, the availability of alternative treatment options must be considered. With the help of genomic technology, the causes of epilepsy should be identified as early as possible, and precision medicine and gene therapy for children with epilepsy should be actively developed.
Display omitted
•Highly dispersed Ni2P catalyst was prepared from nickel phyllosilicate precursor.•Nickel phyllosilicate facilitated the formation of nanosized Ni2P particles.•(201) plane of Ni2P ...gave more coordinately-unsaturated active sites.•Ni2P/SiO2-DP exhibited high performance in hydrodesulfurization of 4,6-DMDBT.•Highly dispersed Ni2P catalysts were obtained on MCM-41, S-1, and TS-1.
Highly dispersed Ni2P catalysts were prepared from nickel phyllosilicate precursor, which was generated on the support by the deposition–precipitation (DP) method. Si-containing materials, including SiO2, MCM-41, S-1, and TS-1, were used as the supports. The strong interaction between Ni and Si species in nickel phyllosilicate effectively suppressed the agglomeration of nickel species. Highly dispersed Ni2P catalyst (Ni2P/SiO2-DP) was obtained by subsequent temperature-programmed hydrogen reduction, and the size of Ni2P crystallites was smaller than that of Ni2P/SiO2-IM prepared from conventional impregnation precursor (7.7 nm vs 14.2 nm). HRTEM observation demonstrated that a large fraction of (201) planes were present in Ni2P/SiO2-DP whereas (111) planes were predominant in Ni2P/SiO2-IM. The strong metal-support interaction and the smaller particle size, along with the higher degree of coordinately unsaturated sites facilitated the hydrogen spillover and the hydrogenation activity. As a result, Ni2P/SiO2-DP exhibited significantly higher performance than Ni2P/SiO2-IM in hydrodesulfurization of 4,6-dimethyldibenzothiophene. Similarly, highly dispersed Ni2P catalysts supported on Si-containing molecular sieves (MCM-41, S-1, and TS-1) were obtained from the in situ generated nickel phyllosilicate as well. It seems that the strong interaction between Ni and Si species in nickel phyllosilicate precursor played a decisive role in the formation of highly dispersed and (201) plane-exposed Ni2P catalysts.
The exploration of an efficient photocatalyst for H2 evolution directly from water splitting is highly desirable due to the current environmental and energy situation. The present work successfully ...used a solvothermal method to synthesize organic-inorganic CdS-diethylenetriamine (CdS-D) nanorods (NRs). The amine-modified CdS-D@ZIF-8 nanocomposite materials were prepared using the self-assembly method with different ZIF-8 nanocrystals (NCs) weight ratios. At λ ≥ 420 nm wavelength, the optimized CdS-D@ZIF-8 (CZ-2) nanocomposite with 5.0 wt% loading of ZIF-8 NCs showed the highest performance of 2293.9 μmol g−1 h−1 H2 evolution and an apparent quantum yield (AQY) of 4.95%. The CZ-2 nanocomposite's activity was 114.69, 5.25, and 1.32 times higher than that of ZIF-8 NCs (20.0 μmol g−1 h−1), CdS-D NRs (436.4 μmol g−1 h−1) and 1.0 wt% Pt/CdS-D (1737.3 μmol g−1 h−1), respectively. The cyclic photostability of the prepared CZ-2 nanocomposite remained unchanged after six consecutive cycles. The UV-DRS, electrochemical measurements, and Mott-Schottky (MS) analysis were performed to explain the band edge positions for CdS-D NRs and ZIF-8 NCs. The detailed S-scheme charge transfer mechanism of the as-prepared catalysts was also studied using the density functional theory (DFT). This work provides vital information for the controllable synthesis of ZIF-8-modified S-scheme nanocomposites for solar energy utilization.
Display omitted
•Novel amine-modified CdS-D@ZIF-8 nanocomposites were built using a self-assembly approach.•The prepared CdS-D@ZIF-8 (5.0 wt% ZIF-8) nanocomposite showed excellent photocatalytic H2 evolution.•The CZ-2 nanocomposite showed excellent cyclic stability and recyclability.•UV-DRS, EIS, and Mott-Schottky analysis were performed to determine the band edge position.•The charge transfer mechanism for enhanced photocatalytic H2 evolution was proposed.
A Pd/UiO-66 catalyst was synthesized with well-dispersed Pd nanoparticles. The obtained catalyst was tested in the hydrogenation of furfural to tetrahydrofurfuryl alcohol in various solvents, Water ...was found to be the most suitable solvent. Pd/UiO-66 exhibited much higher activity than Pd/SiO2 and Pd/γ-Al2O3, completely converting furfural to tetrahydrofurfuryl alcohol with 100% selectivity under mild conditions. The hydrogenation of CO moiety in tetrahydrofurfural was rate-determining step. Static adsorption measurement indicated that the adsorption of furfural on UiO-66 was significantly stronger than that on SiO2 or γ-Al2O3, suggesting that the adsorption play an important role in the gas-liquid-solid furfural hydrogenation reaction.
Display omitted
•A Pd/UiO-66 catalyst was prepared with average Pd particle size of 2–3 nm.•100% selectivity to tetrahydrofurfuryl alcohol was achieved by Pd/UiO-66.•Hydrogenation of CO moiety in tetrahydrofurfural was the rate-determining step.
Abstract
Aberrant activation of EGFR due to overexpression or mutation is associated with poor prognosis in many types of tumors. Here we show that blocking the sorting system that directs EGFR to ...plasma membrane is a potent strategy to treat EGFR-dependent tumors. We find that EGFR palmitoylation by DHHC13 is critical for its plasma membrane localization and identify ARF6 as a key factor in this process. N-myristoylated ARF6 recognizes palmitoylated EGFR via lipid-lipid interaction, recruits the exocyst complex to promote EGFR budding from Golgi, and facilitates EGFR transporting to plasma membrane in a GTP-bound form. To evaluate the therapeutic potential of this sorting system, we design a cell-permeable peptide, N-myristoylated GKVL-TAT, and find it effectively disrupts plasma membrane localization of EGFR and significantly inhibits progression of EGFR-dependent tumors. Our findings shed lights on the underlying mechanism of how palmitoylation directs protein sorting and provide an potential strategy to manage EGFR-dependent tumors.
Display omitted
•A highly dispersed Ni3P/HZSM-5 catalyst was prepared by modified electroless plating method.•Both deposition precipitation and electroless plating take place in aqueous solution, ...facilitating the formation of nano-sized Ni3P.•Bifunctional Ni3P/HZSM-5 exhibited high performance in hydrodeoxygenation of phenolic compounds.
A highly dispersed Ni3P/HZSM-5 catalyst was prepared by deposition-precipitation of Ni species followed by electroless plating and thermal treatment, and characterized by means of XRD, ICP, N2 physical adsorption, TEM, XPS, NH3-TPD, and CO chemisorption. Electroless plating reaction takes place in an aqueous solution under mild conditions, facilitating the high dispersion of the formed Ni3P particles. XRD measurements illustrated the lamellar nickel phyllosilicate was produced at the first step of deposition-precipitation, amorphous Ni-P was formed in the subsequent electroless plating, and highly dispersed Ni3P crystallites were generated in thermal treatment. TEM observation demonstrated that the average particle size of Ni3P crystallites in the prepared Ni3P/HZSM-5 catalyst was 4.3 nm. Bifunctional Ni3P/HZSM-5 was investigated in hydrodeoxygenation (HDO) of phenolic compounds, including phenol, m-cresol, and guaiacol. Ni3P/HZSM-5 exhibited high catalytic performance in HDO with enhanced hydrogenation and dehydration pathway.
The hybrid materials that are created by supporting or incorporating polyoxometalates (POMs) into/onto metal–organic frameworks (MOFs) have a unique set of properties. They combine the strong ...acidity, oxygen-rich surface, and redox capability of POMs, while overcoming their drawbacks, such as difficult handling, a low surface area, and a high solubility. MOFs are ideal hosts because of their high surface area, long-range ordered structure, and high tunability in terms of the pore size and channels. In some cases, MOFs add an extra dimension to the functionality of hybrids. This review summarizes the recent developments in the field of POM@MOF hybrids. The most common applied synthesis strategies are discussed, together with major applications, such as their use in catalysis (organocatalysis, electrocatalysis, and photocatalysis). The more than 100 papers on this topic have been systematically summarized in a handy table, which covers almost all of the work conducted in this field up to now.
ZIF-8-templated ZnIn2S4 (ZIS) crystals with different morphologies have been synthesized solvothermally by varying the organic solvents, while thioacetamide (TAA) and L-cysteine (L‐cyst) were used as ...sulfur precursors. It is found that solvothermal properties, including ions coordination, dielectric constant, and atomic chain length, influence the nucleation and growth of ZIS composites. The differences in morphology and composition of the prepared ZIS crystals strongly affect their photophysical properties and photocatalytic hydrogen evolution reactions (PHER). The hydrogen evolution rates for ZIS composites decrease in the following order: Leaf‐like (EG, TAA) > nanorods (EtOH, TAA) > nanoflowers (EG, L‐cyst) > nanosheets (Gly, TAA) > irregular particles (EDA, TAA) > plate‐like (DETA, TAA). The leaf‐like ZIS‐EG composite prepared using TAA as a sulfur precursor and ethylene glycol (EG) as a solvent shows an excellent PHER performance of 5208 μmol g−1 h−1 (44.91 μmol) with an apparent quantum yield (AQY) of 4.80% at 420 nm. The ZIS‐EG composites with different ZIF‐8 contents (50, 100, 150, and 200 mg) were also investigated for the PHER activity with mixed Na2S/Na2SO3 sacrificial agent at λ ≥ 420 nm. It shows that the nature of solvents and sulfur precursors had a significant influence on the morphology, photoabsorption, electrochemical properties, and PHER performance of ZIF‐8‐templated ZIS composites, which complements the knowledge of designing efficient and perspective photocatalysts with enhanced visible‐light‐driven PHER performance.
Display omitted
•Novel morphology-dependent MOF-templated ZIS composites were prepared using a solvothermal approach.•Solvents and sulfur precursors influencing morphology and photocatalytic H2-evolution of ZIS composites.•The highest photocatalytic H2-evolution was observed for ZIS-EG composite with leaf-like morphology.•The ZIS-EG composite showed long-term cyclic stability and recyclability.•The charge transfer mechanism for enhanced photocatalytic H2 evolution was proposed.
PDF
