Biosynthesis of zinc oxide nanoparticles using Euphorbia milii leaf constituents: Characterization and improved photocatalytic degradation of methylene blue dye under natural sunlight

A facile biosynthesis route was followed to prepare zinc oxide nanoparticles (ZnO NPs) using Euphorbia milii (E. milii) leaf constituents. The SEM images exhibited presence of spherical ZnO NPs and the corresponding TEM images disclosed monodisperse nature of the ZnO NPs with diameter ranges between 12 and 20 nm. The Brunauer–Emmett–Teller (BET) analysis revealed that the ZnO NPs have specific surface area of 20.46 m²/g with pore diameter of 2 nm–10 nm and pore volume of 0.908 cm³/g. The EDAX spectrum exemplified the existence of Zn and O elements and non-appearance of impurities that confirmed pristine nature of the ZnO NPs. The XRD pattern indicated crystalline peaks corresponding to hexagonal wurtzite structured ZnO with an average crystallite size of 16.11 nm. The FTIR spectrum displayed strong absorption bands at 512 and 534 cm^?1 related to ZnO. The photocatalytic action of ZnO NPs exhibited noteworthy degradation of methylene blue dye under natural sunlight illumination. The maximum degradation efficiency achieved was 98.17% at an illumination period of 50 min. The reusability study proved considerable photostability of the ZnO NPs during photocatalytic experiments. These findings suggest that the E. milii leaf constituents can be utilized as suitable biological source to synthesis ZnO NPs for photocatalytic applications.     

Hitherto-Unexplored Photodynamic Therapy of Ag2S and Enhanced Regulation Based on Polydopamine In Vitro and Vivo

Given their superior penetration depths, photosensitizers with longer absorption wavelengths present broader application prospects in photodynamic therapy (PDT). Herein, Ag₂S quantum dots were discovered, for the first time, to be capable of killing tumor cells through the photodynamic route by near-infrared light irradiation, which means relatively less excitation of the probe compared with traditional photosensitizers absorbing short wavelengths. On modification with polydopamine (PDA), PDA-Ag₂S was obtained, which showed outstanding capacity for inducing reactive oxygen species (increased by 1.69 times). With the addition of PDA, Ag₂S had more opportunities to react with surrounding O₂, which was demonstrated by typical triplet electron spin resonance (ESR) analysis. Furthermore, the PDT effects of Ag₂S and PDA-Ag₂S achieved at longer wavelengths were almost identical to the effects produced at 660 nm, which was proved by studies in vitro. PDA-Ag₂S showed distinctly better therapeutic effects than Ag₂S in experiments in vivo, which further validated the enhanced regulatory effect of PDA. Altogether, a new photosensitizer with longer absorption wavelength was developed by using the hitherto-unexplored photodynamic function of Ag₂S quantum dots, which extended and enhanced the regulatory effect originating from PDA.     

A General Catalyst Based on Cobalt Core–Shell Nanoparticles for the Hydrogenation of N-Heteroarenes Including Pyridines

Herein, we report the synthesis of specific silica-supported Co/Co₃O₄ core–shell based nanoparticles prepared by template synthesis of cobalt-pyromellitic acid on silica and subsequent pyrolysis. The optimal catalyst material allows for general and selective hydrogenation of pyridines, quinolines, and other heteroarenes including acridine, phenanthroline, naphthyridine, quinoxaline, imidazo[1,2-a]pyridine, and indole under comparably mild reaction conditions. In addition, recycling of these Co nanoparticles and their ability for dehydrogenation catalysis are showcased.     

Synthesis and characterization of VO–vanillin complex immobilized on MCM-41 and its facile catalytic application in the sulfoxidation reaction,and synthesis of 2,3-dihydroquinazolin-4(1H)-ones and disulfides in green media

In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance.     

A DFT study on mechanisms of CO2 coupling with propargylic alcohols using alkali carbonates

The mechanisms of CO₂ coupling with the propargylic alcohol using alkali carbonates M₂CO₃ (M = Li, Na, K, Cs) have been investigated by means of density functional theory calculations. The calculations reveal that the target product tetronic acid (TA) is yielded through two stages: (a) the formation of the α-alkylidene cyclic carbonate (αACC) intermediate via Cs₂CO₃-mediated carboxylative cyclization of the propargylic alcohol with CO₂, and (b) the conversion of the αACC intermediate with Cs₂CO₃ to produce the cesium salt of the TA. Since the overall kinetic barriers for the two stages are comparable and affordable, the excellent chemoselectivity to the TA should be primarily originated from the high thermodynamic stability of the cesium salt of the TA. Moreover, relative to the TA, the possibility to yield the by-product acyclic carbonate can be excluded due to the both kinetics and thermodynamic inferiority. This result is different from the organic base-mediated reaction. Alternatively, our calculations predict that CsHCO₃ together generated with the cesium salt of the TA might also be an available mediating reagent for the incorporation of CO₂ with the propargylic alcohol. Compared to other alkali carbonates M₂CO₃ (M = Li, Na, K), the stronger basicity of Cs₂CO₃ and the lower ionic potential of cesium ion can raise the effective concentration of the αACC intermediate, and thus the conversion of the αACC intermediate into the cesium salt of the TA can be achieved with high yield.     

单片机应用系统综合实验装置的设计

单片机原理与应用作为电子技术类学科中的必修课程具有很强实践性,要求学生掌握实际应用能力,为此研制了基于单片机系统通信为基础的实验板,依据单片机应用系统特点,可完成SPI、I^2C、UART串行通信以及并行总线方式通信。实验板有利于学生更好地了解和掌握单片机应用系统设计的方法,有利于学生进行自主设计和内容拓展。做到培养学生的学习能力、提高学生的学习兴趣、发挥学生的创造性。     

Nano palladium supported on high‐surface‐area metal–organic framework MIL‐101: an efficient catalyst for Sonogashira coupling of aryl and heteroaryl bromides with alkynes

Palladium nanoparticle‐incorporated metal–organic framework MIL‐101 (Pd/MIL‐101) was successfully synthesized and characterized using X‐ray diffraction, nitrogen physisorption, X‐ray photoelectron, UV–visible and infrared spectroscopies, and transmission electron microscopy. The characterization techniques confirmed high porosity and high surface area of MIL‐101 and high stability of nano‐size palladium particles. Pd/MIL‐101 nanocomposite was investigated for the Sonogashira cross‐coupling reaction of aryl and heteroaryl bromides with various alkynes under copper‐free conditions. The reusability of the catalyst was tested for up to four cycles without any significant loss in catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Achieving Rich and Active Alkaline Hydrogen Evolution Heterostructures via Interface Engineering on 2D 1T‐MoS2 Quantum Sheets

Large‐scale production of hydrogen from water‐alkali electrolyzers is impeded by the sluggish kinetics of hydrogen evolution reaction (HER) electrocatalysts. The hybridization of an acid‐active HER catalyst with a cocatalyst at the nanoscale helps boost HER kinetics in alkaline media. Here, it is demonstrated that 1T–MoS₂ nanosheet edges (instead of basal planes) decorated by metal hydroxides form highly active ${\text{edge}}_{{\text{1T‐MoS}}_{\text{2}}}$/ ${\text{edge}}_{\text{Ni}{(\text{OH})}_{\text{2}}}$ heterostructures, which significantly enhance HER performance in alkaline media. Featured with rich ${\text{edge}}_{{\text{1T‐MoS}}_{\text{2}}}$/ ${\text{edge}}_{\text{Ni}{(\text{OH})}_{\text{2}}}$ sites, the fabricated 1T–MoS₂ QS/Ni(OH)₂ hybrid (quantum sized 1T–MoS₂ sheets decorated with Ni(OH)₂ via interface engineering) only requires overpotentials of 57 and 112 mV to drive HER current densities of 10 and 100 mA cm^?2, respectively, and has a low Tafel slope of 30 mV dec^?1 in 1 m KOH. So far, this is the best performance for MoS₂‐based electrocatalysts and the 1T–MoS₂ QS/Ni(OH)₂ hybrid is among the best‐performing non‐Pt alkaline HER electrocatalysts known. The HER process is durable for 100 h at current densities up to 500 mA cm^?2. This work not only provides an active, cost‐effective, and robust alkaline HER electrocatalyst, but also demonstrates a design strategy for preparing high‐performance catalysts based on edge‐rich 2D quantum sheets for other catalytic reactions.     

Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis

Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β^2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis.