• Title/Summary/Keyword: proton reaction

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Studies on the Reactions of Urea with Paraformaldehyde (Urea와 Paraformaldehyde 반응산물(反應産物)의 화학적(化學的) 특성(特性) 연구)

  • Choi, Du-Hoi;Norwood, Verrill M.
    • Korean Journal of Soil Science and Fertilizer
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    • v.24 no.1
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    • pp.41-49
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    • 1991
  • The reaction of molten urea with paraformaldehyde in sealed tubes has been examined, and the concentrations of the products obtained from this reaction have been contrasted to previous results from the identical reaction carried out in open beakers. In these studies, high performance liquid chromatography(HPLC) and nuclear magnetic resonance(NMR) spectroscopy were used to analyze the products formed in the reactions. These products were biuret, triuret, dimethylenetriurea, methylenediurea, and biuretmethyleneurea. The results from the HPLC analyses showed that the concentrations of dimethylenetriurea and methylenediurea in the reaction products increased as the amount of the paraformaldehyde starting material increased. However, the amount of biuret formed in the products decreased as the paraformaldehyde concentration was increased in the urea melt. The results from the NMR analyses showed that the $NH_2$ resonance frequencies for urea, methylenediurea, and dimethylenetriurea all occurred at approximately 5.6 ppm, while the $NH_2$ frequencies for biuret and triuret occurred at approximately 6.9ppm. In the case of biuret and triuret, NH protons absorb between 8.5 and 9.5 ppm, whereas the NH protons in methylenediurea and dimethylenetriurea absorb in the 6.5-6.6ppm region. The melt reaction seems to hold promise as a different technique for ureaform preparation in general.

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The Effect of S130A Mutant of pharaonis Halorhodopsin on Ability of Chloride Binding and Photocycle

  • Sato, Maki;Kikukawa, Takashi;Araiso, Tsunehisa;Okita, Hirotaka;Shimono, Kazumi;Kamo, Naoki;Demura, Makoto;Nitta, Katsutoshi
    • Journal of Photoscience
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    • v.9 no.2
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    • pp.308-310
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    • 2002
  • Bacteriorhodopsin (bR) and halorhodopsin (hR), which exist in the membrane of Halobacterium salinarum, are light-driven ion pumps. In spite of high similarity of primary and tertiary structures between bR and hR, these membrane proteins transport different ions, proton and chloride, in the opposite direction. From alignment of the amino acid sequences, Thr-89 of bR is homologous to Ser-l15 of hR from Halobacterium salinarum (shR). X-ray structure of shR has revealed that OH group of this residue directly interacts with CI$\^$-/ Thus, Ser-lI5 of shR is expected to play an important role in CI$\^$-/ binding and transport. In this study, we expressed wild type hR from Natronobacterium pharaonis (PhR) and Sl30A, which corresponds to Ser-l15 of shR, in E. coli in order to clarify binding affinity of chloride ion and photocycle reactions. From the titration with CI$\^$-/, affinity of Sl30A became quite lower than that of WT (WT 6 mM, Sl30A 89 mM). Furthermore, from the flash photolysis with pulse laser of λ$\_$max/ at 532 nm, the reaction rate of SI30A from 0 intermediate to hR ground state was found to become apparently slower than that of WT. The singular value decomposition (SVD) and global fitting analyses of the photocycles were performed to identify all photointermediates and determine the reaction rates.

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Study of Characteristic of Covalent Cross-linked SPEEK/Silane 4wt%/Cs-substituted MoPA/Ceria hybrid Membrane for Water Electrolysis (Ceria 첨가에 따른 수전해용 공유가교 CL-SPEEK/Silane 4wt%/Cs-MoPA/Ceria 복합막의 특성 연구)

  • Oh, Seunghee;Park, Daeyong;Hwang, Sungha;Yoon, Daejin;Oh, Yunsun;Moon, Sangbong;Chung, Janghoon
    • Journal of Hydrogen and New Energy
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    • v.25 no.6
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    • pp.561-569
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    • 2014
  • Ceria ($CeO_2$) was used to increase the durability of the membrane in the polymer electrolyte membrane water electrolysis (PEMWE) circumstance. The sulfonated polyether ether ketone (SPEEK) as polymer matrix was prepared in the sulfonation reaction of polyether ether ketone (PEEK) to improve electrochemical characteristics. After sulfonation reaction, the organic-inorganic blended composite membranes were prepared by means of sol-gel casting method with loading the highly dispersed $CeO_2$ and Cs-substituted molybdophosphoric acid (Cs-MoPA) with cross-linking agent (tetrapropyl orthosilicate). Consequently, the composite membrane CL-SPEEK/Silane 4wt%/Cs-MoPA/Ceria(1%) showed the improved characteristics such as 82% of water content, 0.11136 S/cm of proton conductivity at $80^{\circ}C$, 55.50 MPa of tensile strength and 4.37% of breeding out of MoPA.

Biosynthesis of L-Azetidine-2-Carboxylic Acid In Actinoplanes ferrugineus

  • Lee, Kang-Man
    • Proceedings of the Korean Society for Applied Microbiology Conference
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    • 1986.12a
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    • pp.505.2-506
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    • 1986
  • L-Azetidine-2-carboxylic acid (A-2-C), a four-membered cyclic imino acid has been identified in certain plants, and the microorganism Actinoplanes ferrugineus. The imino acid A-2-C has a physiological significance as an antgaonist of proline during peptide synthesis. The biosynthetic mechanism for the formation of A-2-C has not been studied in any detail. By using various amino acids such as methionine and S-adenosyl-L-methionine labeled with deuterium or carbon-14, the details of the biosynthetic pathway and a possible mechanism for the formation of L-A-2-C in .4. ferrugineus have been unravelled, Both in vivo and in vitro experimental results suggest the biosynthesis of L-A-2-C is mediated by a confactor containing a carbonyl group, probably pyridoxal Phosphate. S-Adenosyl-L-methionine, which seems to be the direct biosynthetic substrate, has undergone a f-displacement by an ${\alpha}$-amino group of the amino acid portion of the substrate S-adenosyl-L-methionine potentially via a vinylglycine intermediate. The overall stereochemical events at the ${\beta}$-carbon of the substrate have been shown to inversion of configuration. The overall stereochemical events at the -position of the sub- strate have also been shown to occur with inversion of configuration. The ${\beta}$, ${\gamma}$-elimination reaction of the substrate seems to follow a cisoidal-type mechanism and the addition portion of the reaction a transoidal-type mechanism . The assignment of the proton NMR of A-2-C has been deduced by apply- ing NOE difference experiments, Gd(III) line-broadening experiments and 2D-NOESY experiments of regio-and stereospecificially deuterated A-2-C's.

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Thermal Stability of Photo-produced H3O+ in the Photolyzed Water-ice Film

  • Moon, Eui-Seong;Kang, Heon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.08a
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    • pp.192-192
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    • 2011
  • Hyperthermal ion scattering experiments were conducted with low kinetic energy (<35 eV) cesium ion beams to analyze the UV-photolyzed water-ice films. Neutral molecules (X) on the surface were detected as cesium-molecule ion clusters ($CsX^+$) which were formed through a Reactive Ion Scattering (RIS) process. Ionic species on the surface were desorbed from the surface via a low energy sputtering (LES) process, and were analyzed [1]. Using these methods, the thermal stability of hydronium ion ($H_3O^+$) that was produced by UV light was examined. As the thermal stability of $H_3O^+$ is related with the reaction, $H_3O^+$ + OH + $e^-$ (or $OH^-$) ${\rightarrow}$ $2H_2O$, which is similar or same with the reverse reaction of the auto-ionization of water, the result from this work would be helpful to understand the auto-ionization of $H_2O$ in water-ice that has not been well-understood yet. However, as $H_3O^+$ was not detected through a LES method, the titration experiment of $H_3O^+$ with methylamine ($CH_3NH_2$, MA), MA + $H_3O^+\;{\rightarrow}\;MAH^+$ + $H_2O$, was conducted. In this case, the presence of $MAH^+$ indicates that of $H_3O^+$ in the ice. Thus the pristine ice was photolyzed with UV light for a few minutes and this photolyzed ice was remained at the certain temperature for minutes without UV light. Then MA was adsorbed on that surface so that the population of $H_3O^+$ was found. From the calibration experiments, the relation of $MAH^+$ and $H_3O^+$ was found, so that the thermal stability of $H_3O^+$ can be investigated [2].

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Selective Reduction with Lithium Borohydride. Reaction of Lithium Borohydride with Selected Organic Compounds Containing Representative Functional Groups (수소화붕소리튬에 의한 선택환원. 수소화붕소리튬과 대표적 유기화합물과의 반응)

  • Nung Min Yoon;Jin Soon Cha
    • Journal of the Korean Chemical Society
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    • v.21 no.2
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    • pp.108-120
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    • 1977
  • The approximate rates and stoichiometries of the reaction of lithium borohydride, with fifty two selected organic compounds containing representative functional groups under the standard condition (tetrahydrofuran, $0^{\circ}$), were studied.Among the active hydrogen compounds,primary alcohols and compounds containing an acidic proton liberated hydrogen relatively fast, but secondary and tertiary alcohols very sluggishly. All the carbonyl compounds examined were reduced rapidly within one hour. Especially, among the ${\alpha}{\beta}$-unsaturated carbonyl compounds tested, the aldehydes consumed one hydride cleanly, however the cyclic ketones consumed more than one hydride even at $-20^{\circ}$. Carboxylic acids were reduced very slowly, showing about 60% reduction in 6 days at $25^{\circ}$, however acyl chlorides reduced immediately within 30 minutes. On the other hand, the reductions of cyclic anhydrides proceeded moderately to the hydroxy acid stage, however the further reductions were very slow. Aromatic and aliphatic esters, with exception of the relatively moderate reduction of acetate, were reduced very slowly, however lactones were reduced at a moderate rate. Epoxides reacted slowly, but amides and nitriles as well as the nitro compounds were all inert to this reagent. And cyclohexanone oxime and phenyl isocyanate were reduced very sluggishly. Last of all, all sulfur compounds studied were inert to this hydride.

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Effect of Annealing Temperature on the Durability of PEMFC Polymer Membrane (PEMFC 고분자막의 어닐링 온도가 내구성에 미치는 영향)

  • Lee, Mihwa;Oh, Sohyeong;Park, Yujun;Yoo, Donggeun;Park, Kwonpil
    • Korean Chemical Engineering Research
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    • v.60 no.1
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    • pp.7-11
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    • 2022
  • In the membrane forming process of a proton exchange membrane fuel cell (PEMFC), drying and annealing heat treatment processes are required for performance and durability. In this study, the optimal annealing temperature for improving the durability of the polymer membrane was studied. It was annealed in the temperature range of 125~175 ℃, and thermal stability and hydrogen permeability were measured as basic data of durability at each annealing temperature. The electrochemical durability was analyzed by Fenton reaction and open circuit voltage (OCV) holding. The annealing temperature of 165 ℃ was the optimal temperature in terms of thermal stability and hydrogen permeability. In the Fenton reaction, the fluorine emission rate of the membrane annealed at 165 ℃ was the lowest, and the lifespan of the membrane annealed at 165 ℃ was the longest in the OCV holding experiment, confirming that 165 ℃ was the optimal temperature for the durability of the polymer membrane.

Research Trend in Electrocatalysts for Anion Exchange Membrane Water Electrolysis (음이온교환막 수전해 촉매기술 동향)

  • Kim, Jiyoung;Lee, Kiyoung
    • Journal of the Korean Electrochemical Society
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    • v.25 no.2
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    • pp.69-80
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    • 2022
  • The anion exchange membrane (AEM) water electrolysis for high purity hydrogen production is attracting attention as a next-generation green hydrogen production technology by using inexpensive non-noble metal-based catalysts instead of conventional precious metal catalysts used in proton exchange membrane (PEM) water electrolysis systems. However, since AEM water electrolysis technology is in the early stages of development, it is necessary to develop research on AEM, ionomers, electrode supports and catalysts, which are key elements of AEM water electrolysis. Among them, current research in the field of catalysts is being studied to apply a previously developed half-cell catalyst for alkali to the AEM system, and the applied catalyst has disadvantages of low activity and durability. Therefore, this review presented a catalyst synthesis technique that promoted oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) using a non-noble metal-based catalyst in an alkaline medium.

Development of Chemical Separation Process for Thallium-201 Radioisotope with Lead Standard Material (납 표준물질을 이용한 방사성동위원소 Thallium-201의 화학적 분리공정 개발)

  • JunYoung Lee;TaeHyun Kim;JeongHoon Park
    • Journal of Radiation Industry
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    • v.17 no.4
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    • pp.543-549
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    • 2023
  • Thallium-201 (201Tl) is a medical radioisotope which emits gamma rays when it decays and used in myocardial perfusion scans in single-photon emission tomography due to its similar properties to potassium. Currently, the Korea Institute of Radiological & Medical Sciences is the only institution producing 201Tl in Korea, and optimization of 201Tl production research is necessary to meet supply compared to domestic demand. To this end, technical analysis of plating target production and chemical separation methods essential for 201Tl production research is conducted. It deals with the process of generating and separating 201Tl radioisotope and target production, It can be generated through a nuclear reaction such as natHg(p,xn)201Tl, 201Hg(p,n)201Tl, natPb(p,xn)201Bi → 201Pb → 201Tl, 205Tl(p,5n)201Pb → 201Tl, and considering impure nuclide generated simultaneously with the use of proton beam energy of 35 MeV or less, it is intended to be produced using the 203Tl(p,3n)201Pb→201Tl nuclear reaction. In particular, the chemical separation of Tl is a very important element, and the chemical separation methods that can separate it is broadly divided into four types, including solid phase extraction, liquid-liquid, electrochemical, and ion exchange membrane separation. Some chemical separations require additional separation steps, such as methods using selective adsorption. Therefore, this technical report describes four chemical separation methods and seeks to separate high-purity 201Tl using a method without additional separation steps

Kinetic and Mechanism of the Addition of Benzylamines to α-Phenyl-β-thiophenylacrylonitriles in Acetonitrile

  • Hwang, Jae-young;Yang, Ki-yull;Koo, In-Sun;Sung, Dae-Dong;Lee, Ik-choon
    • Bulletin of the Korean Chemical Society
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    • v.27 no.5
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    • pp.733-738
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    • 2006
  • Nucleophilic addition reactions of p-substitutedbenzylamines $(XC _6H_4CH _2NH _2)$ to $\alpha$-phenyl-$\beta$-thiophenyl-acrylonitriles ($YC _4SH _2CH=C(CN)C_6H_4$Y') have been studied in acetonitrile at 25.0, 30.0, and 35.0 ${^{\circ}C}$. The reactions take place in single step in which the $C_\beta$ -N bond formation and proton transfer to $C_\alpha$ of $\alpha$-phenyl-$\beta$-thiophenylacrylonitriles occur concurrently with four-membered cyclic transition structure. These mechanistic conclusions are drawn based on (i) the large negative $\rho$x and large positive $\rho$Y' values and also large magnitude of $\rho$X, (ii) the negative sign and large magnitude of the cross-interaction constants ($\rho$XY), (iii) the normal kinetic isotope effects ($k_H/k_D$ > 1.0), and (iv) relatively low $\Delta H ^\neq$ and large negative $\Delta S ^\neq$ values.