Synthesis and chemical properties of polyethyleneimines crosslinked by penta-2,4-dienylideneammonium unit

The reaction of N-(2,4-dinitrophenyl)pyridinium anion ( salt(A) ; A = Cl⁻, FeCl₄⁻, and (CN)₂N⁻) with linear polyethyleneimine (LPEI; M_n = 20 380) and branched polyethyleneimines (BPEI1; M_n = 600, BPEI2; M_n = 10 000) at various molar feed ratios without using a catalyst resulted in pyridinium ring opening to yield ionic LPEI and BPEIs that were crosslinked by conjugated penta-2,4-dienylideneammonium (PDA) units, LPEI-PDA , BPEI1-PDA , and BPEI2-PDA , respectively. A model compound was synthesized by the reaction of salt(Cl) with diethylamine. The solubilities of BPEI1-PDA and BPEI2-PDA depended on the feed ratios between salt(Cl) and BPEI1 or BPEI2. Dipping LPEI-PDA into water and methanol yielded hydro- and organogels, respectively. UV–vis and reflection measurements revealed an expanded π-conjugation length between the polymer chains due to the through-space orbital interaction of the electrons on the two nitrogen atoms at the crosslinked positions in LPEI-PDA , BPEI1-PDA , and BPEI2-PDA . Cyclic voltammetry analysis suggested that the polymers underwent electrochemical oxidation. Measurement using a superconducting quantum interference device (SQUID) indicated that LPEI-PDA having FeCl₄⁻ anions was paramagnetic. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48712.     

Effect of Ultrasonic Irradiation on the Probability of Primary Nucleation of L-Arginine Hydrochloride

Most of the amino acids that are utilized as medical raw materials and food additives show polymorphism. To improve the functionality of amino acid crystals, an effective method of polymorph control is required in the crystallization process. Here, primary nucleation of L-arginine hydrochloride by ultrasonication was investigated. L-Arginine hydrochloride exhibits polymorphism, and it crystallizes into three distinct crystal forms. A cooling crystallization experiment was performed, and nucleation of each polymorph upon ultrasonication was observed. In addition, the nucleation was analyzed using the nucleation probability theory. The results indicate that ultrasonic irradiation would significantly induce the nucleation of a particular polymorph.     

Optimal operation of cogeneration system coordinated by aggregator for providing the demand and supply regulation capacity

Recent growth of renewable energy generations with natural variability, such as photovoltaic generation and wind turbine generation, would make the demand and supply control in a whole power system more difficult, and therefore, alternatives for demand and supply regulation resources would be required. The authors focus on cogeneration system (CGS) as one of regulation resources. In order to procure adequate volume of regulation capability, an aggregator coordinates a number of CGSs efficiently and flexibly considering the wide variety of electricity/thermal demands of CGS owners. This paper proposes a novel optimal operation strategy of CGS coordinated by the aggregator considering the energy balance and operation cost of individual CGS owner. This paper also demonstrates the availability of CGSs for regulation capability by numerical case studies in which the actual consumption profile is employed.     

Planar‐Chiral Cyclopentadienyl‐Ruthenium‐Catalyzed Regio‐ and Enantioselective Asymmetric Allylic Alkylation of Silyl Enolates under Unusually Mild Conditions

We report the asymmetric allylic alkylation of allylic chlorides with silyl enolates as a carbon nucleophile using a planar‐chiral cyclopentadienyl‐ruthenium (Cp′Ru) catalyst. The reaction proceeds under unusually mild conditions to give the desired branched products with complete regioselectivity and high enantioselectivity, and reactive functional groups, such as aldehyde, can be tolerated. In this reaction system, Cp′Ru plays an important role in activating both silyl enolate and allylic chloride.

     

Chemical Synthesis of a Synthetic Analogue of the Sialic Acid‐Binding Lectin Siglec‐7

As a basis for the development of an artificial carbohydrate‐binding lectin, we chemically synthesized a domain of siglec‐7, a well‐characterized sialic‐acid‐binding lectin. The full polypeptide (127 amino acids) was constructed by sequential native chemical ligation (NCL) of five peptide segments. Because of poor cysteine availability for NCL, cysteine residues were introduced at suitable ligation sites; these cysteine residues were alkylated in order to mimic native glutamine or asparagine residues, or converted to an alanine residue by desulfurization after NCL. After folding the full‐length polypeptide, the sialic‐acid‐binding activity of the synthetic siglec‐7 was clearly demonstrated by STD NMR and ELISA experiments. We succeeded in the synthesis of siglec‐7 by installing three extra cysteine residues with side‐chain modifications and found that these modifications did not affect the binding activity.     

Effects of isocyanuric acid on the monochlorodimedone chlorinating rates with free chlorine and ammonia chloramine in water

Changes in monochlorodimedone (MCD) chlorinating rates with free chlorine (mixture of HOCl and OCl-) and ammonia monochloramine (NH2Cl) in water at pH 7 by the addition of isocyanuric acid (H3Cy) were determined at room temperature. Decreases in MCD absorbance at 290nm in equimolar (0.04mM) reactions of MCD and free available chlorine solutions containing H3Cy (0.01-1.60 mM) were recorded in a stopped-flow spectrophotometer. The rates indicate second-order reactions. Since the rate with free chlorine was high (> 7.6 x 10(6) M(-1) s(-1)), the amounts of free chlorine in the solutions could be distinguished from that of chlorinated cyanurates. The chlorinating rates with chlorinated cyanurates decreased with an increase in H3Cy concentrations. Plotting the rates against the molar ratio of chlorine to H3Cy showed a linear correlation and the rates with chlorinated cyanurates (H2ClCy) was estimated at 0.5 x 10(5) M(-1) s(-1). In contrast, the rates with the NH2Cl solution containing H3Cy increased with an increase in H3Cy concentrations, increasing from 1.2 x 10 to 2.7 x 10 M(-1) s(-1) by the addition of 1.55 mM H3Cy. The DPD color development rates (OD512/t1/2/M) with free available chlorine (0.015mM) declined from 1.3 x 10(5) to 0.9 x 10(5)M(-1) by the addition of 0.61 mM H3Cy.     

Lightning occurrence data observed with lightning location systems of electric power companies in Japan: 2009–2013

Nine electric power companies in Japan have been collecting lightning data with lightning location systems. Five years of the lightning data (2009–2013) are summarized and analyzed in this paper. The recent annual number of lightning flashes of which the current is more than 10 kA in Japan is around 1 million. The variations of lightning occurrence characteristics by areas, seasons, and so on, are clarified. Meteorological conditions that may affect lightning occurrence are also discussed. Furthermore, we show that there is a clear correlation between the number of lightning strikes and the outage rate of transmission lines. © 2016 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc.