Controlled synthesis of ZnO nanoparticles from a Zn(II) coordination polymer: Structural characterization,optical properties and photocatalytic activity

A zinc coordination polymer derived from pyridine-2,6-dicarboxylate (PDC), {[Zn₂(PDC)₂]}_n, was successfully prepared via conventional, sonication and microwave-irradiation methods. The composition and characteristics of the obtained coordination polymers (CPs) were investigated by elemental analysis, TGA/DTA, X-ray diffraction and spectroscopic techniques. The so obtained CPs were heat-treated in the air at 600 °C for 2 h to produce ZnO of nanosized particles (NPs). It is of interest to note that the synthesis approach of the precursor greatly affects both the nanoparticle size and the structure of the resulting ZnO NPs. Moreover, the smallest particle size was associated with the sample derived from the ultrasonically prepared precursor. TEM analysis revealed that all samples have sphere-like morphologies. Structural analysis of the prepared ZnO samples was conducted and compared using Rietveld analysis of their PXRD patterns. Optical band gap calculations based on analysis of the UV–vis spectra of ZnO samples using Tauc's power law were achieved. The highest band gap of 3.63 eV was observed for ZnO sample obtained from the ultrasonically prepared precursor. Furthermore, the photocatalytic activity of ZnO NPs for the removal of Eosin Y color was monitored. The highest removal efficiency was recorded for ZnO originated from the ultrasonically synthesized precursor. Enhancement of removal efficiency that reached 98% was attained in only a period of 8 min. Its recycling test showed that it can be reused without structural changes over four cycling experiments.     

Zinc(II)-poly(urea-formaldehyde) supported on magnetic nanoparticles: A hybrid nanocatalyst for green synthesis of spiropyrans,spiroxanthenes, and spiropyrimidines

Immobilization of metal ions onto inorganic supports has very interesting biological, industrial, and catalysis applications. In this study, CoFe₂O₄@SiO₂@PUF@Zn(OAc)₂ nanostructure was successfully fabricated by immobilization of zinc acetate on the surface of poly(urea-formaldehyde) supported on magnetic CoFe₂O₄@SiO₂ nanoparticles through a layer-by-layer assembly. The structure of hybrid nanoparticles was characterized by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, energy-dispersive X-ray spectroscopy, inductively coupled plasma atomic emission spectroscopy, vibrating sample magnetometry, Brunauer–Emmett–Teller surface area analysis, scanning electron microscopy, and transmission electron microscopy. Zinc-poly(urea-formaldehyde) supported on magnetic nanoparticles (MNPs@SiO₂@PUF@Zn) was successfully used for the synthesis of spirooxindolopyran and spirooxindoloxanthene derivatives in aqueous medium as an environmentally benign condition. High yields, short reaction times, green solvent, reusability without significant reduction in catalytic activity, and simple separation of the catalyst using an external magnet along with environmental compatibility are some benefits of this procedure.     

Nb(iPrNPMe2)3Fe–PMe3: A potential high reactivity heterobimetallic catalyst for acetylene cycloadditions

Alkynes cycloaddition reactions are powerful tools for constructing cyclic molecules with optimal atom efficiency, but these reactions cannot proceed at ambient temperature without transition-metal catalysts. In this work, a heterobimetallic complex featuring an Nb–Fe triple bond, Nb(ⁱPrNPMe₂)₃Fe–PMe₃, has been evaluated as the potential catalyst for acetylene cycloaddition, using density functional theory. The calculated results show that the singlet-state (i.e. ground-state) Nb(ⁱPrNPMe₂)₃Fe–PMe₃ can be applied to benzene synthesis, but is not suitable for cyclobutadiene. Benzene can be obtained easily at room temperature and is the unique product on the singlet potential surface. The irradiation of infrared-red light can drive the excitation of singlet Nb(ⁱPrNPMe₂)₃Fe–PMe₃ to its triplet state. Both benzene and cyclobutadiene can be formed on the triplet reaction potential surface due to their low energy barriers. Therefore, Nb(ⁱPrNPMe₂)₃Fe–PMe₃ is a potential high reactivity heterobimetallic catalyst for the cyclotrimerization of alkynes. In the reaction process, the catalytic active site of Nb(ⁱPrNPMe₂)₃Fe–PMe₃ moves from niobium to iron.     

Optimization of extraction and quantification technique for phenolics content of garlic (Allium sativum): An application for comparative phytochemical evaluation based on cultivar origin

A range of conventional, i.e. maceration, percolation, ultrasonic assisted, Soxhlet and Soxtec extraction (STE), to advanced extraction techniques of accelerated solvent extraction (ASE) was utilized for the first time in order to optimize the extract yield and recovery of phenolics—gallic acid (GA), rutin (RT) and quercetin (QT)—quantified via ultra-high performance liquid chromatography with diode array detector (UHPLC–DAD). The effect of solvents (n-hexane, dichloromethane and methanol) and temperature (60, 80 and 100°C) upon extraction yield, phenolic content and antioxidant activity (DPPH, ABTS and DPPH) was studied, and the method was validated in commercial food samples from Saudi Arabia, China and India. A high extract yield with percentage recovery was observed for STE (1221.10 mg/5 g; 24.42%) and ASE techniques (91.50 mg/1 g; 9.15%) in methanol at 100°C. UHPLC–DAD showed retention times (min) of 0.67, 1.93 and 1.90 for GA, RT and QT, respectively in the shortest runtime of 3 min. The yield for phenolics was higher for STE/ASE (ppm): 15.27/15.29 (GA), 85.24/37.56 (RT) and 52.20/33.40 (QT), respectively. In terms of antioxidant activities, low IC₅₀ values (μg/ml) of 1.09/1.18 (DPPH), 2.11/5.32 (ABTS) and 4.35/7.88 (phenazine methosulfate–nicotinamide adenine dinucleotide) were observed for STE and ASE, respectively. Multivariate analysis for STE showed a significant (P = 0.000) correlation for extraction type vs. extract yield and phenolics content; however, there was no significance for antioxidant activities vs. extraction type. ASE showed a positive correlation for solvent vs. extraction yield, phenolics and antioxidant activity; however, there was no correlation for extraction yield and DPPH activity. Principal component analysis for STE showed a major variability (52.02%) for extraction yield and phenolics in PC1 followed by PC2 (38.30%) for antioxidant activities. For ASE, PC1 (48.68%) showed a positive correlation for solvent vs. extraction yield and phenolics while PC2 (33.12%) showed a positive correlation for temperature and antioxidant activities. STE and ASE were the optimized extraction techniques for the garlic food sample while a significant effect of solvent and temperature was observed upon extraction yield, phenolics and antioxidant activity.     

How to measure long-range proton-carbon coupling constants from 1H-selective HSQMBC experiments

Heteronuclear long-range scalar coupling constants (ⁿJ_CH) are a valuable tool for solving problems in organic chemistry and are especially suited for stereochemical and configurational analyses of small molecules and natural products. This tutorial will focus on the step-by-step implementation of several 2D ¹H frequency selective HSQMBC experiments for the easy and accurate measurement of either the magnitude or both the magnitude and the sign of long-range ⁿJ_CH couplings. The performance of these experiments will be showcased with several scenarios in a range of different experimental conditions.     

What is the form of muscimol from fly agaric mushroom (Amanita muscaria) in water? An insight from NMR experiment supported by molecular modeling

The biologically active alkaloid muscimol is present in fly agaric mushroom (Amanita muscaria), and its structure and action is related to human neurotransmitter _γ-aminobutyric acid (GABA). The current study reports on determination of muscimol form present in water solution using multinuclear ¹H and ¹³C nuclear magnetic resonance (NMR) experiments supported by density functional theory molecular modeling. The structures of three forms of free muscimol molecule both in the gas phase and in the presence of water solvent, modeled by polarized continuous model, and nuclear magnetic isotropic shieldings, the corresponding chemical shifts, and indirect spin–spin coupling constants were calculated. Several J-couplings observed in proton and carbon NMR spectra, not available before, are reported. The obtained experimental spectra, supported by theoretical calculations, favor the zwitterion form of muscimol in water. This structure differs from NH isomer, previously determined in dimethyl sulfoxide (DMSO) solution. In addition, positions of signals C3 and C5 are reversed in both solvents.     

Zn–Co Sulfide Microflowers Anchored on Three-Dimensional Graphene: A High-Capacitance and Long-Cycle-Life Electrode for Asymmetric Supercapacitors

Zinc–cobalt double-metal sulfides (ZCS) as Faradic electrode materials with high energy density have great potential for supercapacitors, but their poor transfer efficiency for electrons and ions hinders their electrochemical response. Herein, ZnCo₂(CO₃)_1.5(OH)₃@ZCS microflower hybrid arrays consisting of thin nanolayer petals were anchored on three-dimensional graphene (ZnCo₂(CO₃)_1.5(OH)₃@ZCS/3DG) by a simple hydrothermal method and additional ion-exchange process. A ZnCo₂(CO₃)_1.5(OH)₃@ZCS/3DG electrode delivered high capacitance (2228 F g⁻¹ at 1 A g⁻¹) and long cycling life (85.7 % retention after 17 000 cycles), which are ascribed to the multicomponent structural design. The 3DG conductive substrate improves the electron-transfer dynamics of the electrode material. Meanwhile, the microflowers consisting of thin nanolayer petals could not only provide many active sites for ions to improve the capacitance, but also alleviate the volume expansion to ensure the structural stability. Furthermore, an all-solid-state asymmetric supercapacitor based on a ZnCo₂(CO₃)_1.5(OH)₃@ZCS/3DG electrode achieved a high energy density of 27 W h kg⁻¹ at 528.3 W kg⁻¹ and exhibits exceptional cyclic stability for 23 000 cycles. Its ability to light a blue LED for 9 min verified the feasibility of its application for energy storage devices.     

Unlocking the Drug Potential of the Bryostatin Family: Recent Advances in Product Synthesis and Biomedical Applications

Bryostatins are a class of naturally occurring macrocyclic lactones with a unique fast developing portfolio of clinical applications, including treatment of AIDS, Alzheimer's disease, and cancer. This comprehensive account summarizes the recent progress (2014–present) in the development of bryostatins, including their total synthesis and biomedical applications. An emphasis is placed on the discussion of bryostatin 1 , the most-studied analogue to date. This review highlights the synthetic and biological challenges of bryostatins and provides an outlook on their future development.     

Flow Technology for the Genesis and Use of (Highly) Reactive Organometallic Reagents

In the field of organic synthesis, the advent of flow chemistry and flow microreactor technology represented a tremendous novelty in the way of thinking and performing chemical reactions, opening the doors to poorly explored or even impossible transformations using batch methods. In this Concept article, we would like to highlight the impact of flow chemistry for exploiting highly reactive organometallic reagents, and how, alongside the well-known advantages concerning safety, scalability, and productivity, flow chemistry makes possible processes that are impossible to control by using the traditional batch approach.     

Gold-Catalyzed Cross-Coupling Reactions: An Overview of Design Strategies,Mechanistic Studies,and Applications

Transition-metal-catalyzed cross-coupling reactions are central to many organic synthesis methodologies. Traditionally, Pd, Ni, Cu, and Fe catalysts are used to promote these reactions. Recently, many studies have showed that both homogeneous and heterogeneous Au catalysts can be used for activating selective cross-coupling reactions. Here, an overview of the past studies, current trends, and future directions in the field of gold-catalyzed coupling reactions is presented. Design strategies to accomplish selective homocoupling and cross-coupling reactions under both homogeneous and heterogeneous conditions, computational and experimental mechanistic studies, and their applications in diverse fields are critically reviewed. Specific topics covered are: oxidant-assisted and oxidant-free reactions; strain-assisted reactions; dual Au and photoredox catalysis; bimetallic synergistic reactions; mechanisms of reductive elimination processes; enzyme-mimicking Au chemistry; cluster and surface reactions; and plasmonic catalysis. In the relevant sections, theoretical and computational studies of Au^I/Au^III chemistry are discussed and the predictions from the calculations are compared with the experimental observations to derive useful design strategies.