The “element effect” in nucleophilic aromatic substitution reactions (SNAr) is characterized by the leaving group order, F > NO2 > Cl ≈ Br > I, in activated aryl halides. Multiple causes for this result have been proposed. Experimental evidence shows that the element effect order in the reaction of piperidine with 2,4-dinitrophenyl halides in methanol is governed by the differences in enthalpies of activation. Computational studies of the reaction of piperidine and dimethylamine with the same aryl halides using the polarizable continuum model (PCM) for solvation indicate that polar, polarizability, solvation, and negative hyperconjugative effects are all of some importance in producing the element effect in methanol. In addition, a reversal of polarity of the C–X bond from reactant to transition state in the case of ArCl and ArBr compared to ArF also contributes to their difference in reactivity. The polarity reversal, and hyperconjugative influences have received little or no attention in the past. Nor has differential solvation of the different transition states been strongly emphasized. An anionic nucleophile, thiolate, gives very early transition states and negative activation enthalpies with activated aryl halides. The element effect is not established for these reactions. We suggest that the leaving group order in the gas phase will be dependent on the exact combination of nucleophile, leaving group, and substrate framework. The geometry of the SNAr transition state permits useful, qualitative conceptual distinctions to be made between this reaction and other modes of nucleophilic attack.
The purpose of this research was to determine the efficacy of iron oxide nanoparticles (Fe3O4-NPs) using microalgal products as a plant growth stimulant and antifungal agent. The work was conducted with the phyco-synthesis and characterization of Fe3O4-NPs using 0.1 M ferric/ferrous chloride solution (2:1 ratio; 65 °C) with aqueous extract of the green microalga Chlorella K01. Protein, carbohydrate and polyphenol contents of Chlorella K01 extract were measured. The synthesized microalgal Fe3O4-NPs made a significant contribution to the germination and vigor index of rice, maize, mustard, green grams, and watermelons. Fe3O4-NPs also exhibited antifungal activity against Fusarium oxysporum, Fusarium tricinctum, Fusarium maniliforme, Rhizoctonia solani, and Phythium sp. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) scanning electron microscopy (SEM), transmission electron microscopy (TEM), particle size analysers (PSA), and zeta potential (ZP) measurements were used to characterize these green fabricated magnetite NPs. FTIR analysis showed that the synergy of microalgal proteins, carbohydrtates and polyphenols is responsible for the biofabrication of iron nanoparticles. A spheroid dispersion of biosynthesized Fe3O4-NPs with an average diameter of 76.5 nm was produced in the synthetic process.
Blending hydrogen into the existing natural gas pipeline network is regarded as a potential mode in the future. However, the influence of hydrogen on the economic and environmental performance of natural gas pipeline networks remained unclear. This paper established a mathematical programming model to get the optimal operation plan of the pipeline system under different hydrogen blending ratios, and the operation costs and carbon emissions of the hydrogen mixed system are analyzed accordingly. The studied case demonstrated that: (1) The optimization model has significant potential in reducing the economic cost and carbon emission of the system with an average decrease of 11.48%. (2) For every 1% of hydrogen added, the annual operating cost varies from minus $0.73 million to positive $1.67 million, and carbon emission varies from minus 0.38 kiloton to $0.76 kiloton. The proposed optimization model can provide theoretical guidance for the further application of this transportation mode.
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