• Title/Summary/Keyword: $NH_4-N$

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Anomalous Behavior of the Ethyl Group in the Aminolysis of S-Phenyl Acetate with Benzylamine in Acetonitrile

  • Lee, Ik-Choon;Lee, Hai-Whang;Lee, Byung-Choon;Choi, Jin-Heui
    • Bulletin of the Korean Chemical Society
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    • v.23 no.2
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    • pp.201-204
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    • 2002
  • The rates of the aminolysis of S-phenyl substituted-acetate series $(RC(=O)SC_6H_4Z$, with R=Me, Et, i-Pr, t-Bu and Bn) with benzylamines $(XC_6H_4CH_2NH_2)$ are not correlated simply with the Taft's polar $({\sigma}^{\ast})$ and/or steric effect constants $(E_s)$ of the substituents due to abnormally enhanced rate of the substrate with R=Et. Furthermore, the cross-interaction constant, ${\rho}x_z$ , is the largest with R=Et. These anomalous behaviors can only be explained by invoking the vicinal bond $({\sigma})$-antibond $({\sigma}^{\ast})$ charge transfer interaction between C-$C{\alpha}$ and C-S bonds. In the tetrahedral zwitterionic intermediate, $T^{\pm}$ , formed with R=Et the vicinal ${\sigma}_{c-c}-{\sigma}^{\ast}_{c-s}$ delocalization is the strongest with an optimum antiperiplanar arrangement and a narrow energy gap, ${\Delta}{\varepsilon}={\varepsilon}_{{\sigma}^{\ast}}-{\varepsilon}_{\sigma}$. Due to this charge transfer interaction, the stability of the intermediate increases (with the concomitant increase in the equilibrium constant K (= $k_a/k_{-a}$)) and also the leaving ability of the thiophenolate leaving group increases (and hence $k_b$ increases) so that the overall rate, $k_n\;=\;Kk_b$, is strongly enhanced. Theoretical support is provided by the natural bond orbital (NBO) analyses at the B3LYP/6-31+$G^{\ast}$ level. The anomaly exhibited by R=Et attests to the stepwise reaction mechanism in which the leaving group departure is rate limiting.

Multi-functional Finish of Polypropylene Nonwoven by Photo-induced Graft Polymerization (II) - Grafting of Styrene and Its Ammonia Adsorption Behavior - (광그라프팅에 의한 폴리프로필렌 부직포의 복합기능화 가공(II) -스티렌의 그라프트 반응 및 암모니아 흡착거동 -)

  • 김상률;최창남
    • Polymer(Korea)
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    • v.25 no.5
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    • pp.642-648
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    • 2001
  • An attempt was made to synthesize an ammonia adsorbent by the photo-induced grafting of styrene (St) onto polypropylene (PP) nonwoven using benzoin ethyl ether (BEE) as a photosensitizer with urea and trimethylol propane triacrylate in methanol medium. As styrene concentration was increased, the graft yield was increased. It was also found that the graft yield increased with reaction time. The polypropylene grafted with styrene (PP-g-St) was sulfonated by chlorosulfonic acid in dichloroethane and complexed with several metal ion, such as $cO^{+2}$, $nI^{+2}$, $cU^{+2}$, $Zn^{+2}$. The amount of ammonia gas adsorbed by these sample was dependent on the degree of sulfonation, adsorption time, and ammonia gas pressure. The adsorption capacity of ammonia gas by the sulfonated PP-g-St(SPP-g-St) nonwoven with 4. 25 mmol $H^+$/g was 6.61 mmol/g. Metal ion complexed SPP-g-St nonwovens had higher adsorption capacity than SPP-g-St nonwoven and the $Co^{+2}$ complexed SPP-g-St showed 9.90 mmol $NH_3$/g, which was much higher than that of active carbon or silica gel.

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The Effect of Solvent and Carrier Gas on the Deposition Rate aid the Properties of Pyrosol Deposited $SnO_2$ : F Transparent Conducting Films (용매와 반송가스가 초음파 분무 열분해에 의한 불소 도핑 이산화 주석 투명전도막의 성장속도와 특성에 미치는 영향)

  • Yoon, Kyung-Hoon;Song, Jin-Soo;Kang, Gi-Hwan
    • Proceedings of the KIEE Conference
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    • 1991.07a
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    • pp.174-177
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    • 1991
  • Fluorine-doped $SnO_2\;(SnO_2:F)$ films were prepared in ordinary atmosphere on borosilicate glass substrates using pyrosol deposition method starting from the solutions composed of $SnCl_4-5H_2O-NH_4F-CH_3OH-H_2O-HCl$ in an attempt to develop transparent conductors for use in amorphous silicon (a-Si) solar cello. The deposition rate of films increased with the increase in the content of $H_2O$, whereas it decreased with increasing the content of $CH_3OH$. When air was used as the carrier gas, the lowest electrical resistivity was obtained from a solution having $CH_3OH/H_2O$ mol ratio of about $2{\sim}3$ in the solution. The use of $N_2$ of the same flow rate as the carrier gab resulted always in the high resistive films, but the resistivity of the films decreased continuously with the increase in the content of $H_2O$. The surface morphology and preferred orientation of films were also affected by the solvent composition and the content of HCl in the solution. The room-temperature resistance of the films were fairly stable after heat-treatments up to $600^{\circ}C$.

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Chemical Modification of 5-Lipoxygenase from the Korean Red Potato

  • Kim, Kyoung-Ja
    • BMB Reports
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    • v.33 no.2
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    • pp.172-178
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    • 2000
  • The lipoxygenase was purified 35 fold to homogeneity from the Korean red potato by an ammonium sulfate precipitation and DEAE-cellulose column chromatography. The simple purification method is useful for the preparation of pure lipoxygenase. The molecular weight of the enzyme was estimated to be 38,000 by SDS-polyacrylamide gel electrophoreses and Sepharose 6B column chromatography. The purified enzyme with 2 M $(NH_4)_2SO_4$ in a potassium phosphate buffer, pH 7.0, was very stable for 5 months at $-20^{\circ}C$. Because the purified lipoxygenase is very stable, it could be useful for the screening of a lipoxygenase inhibitor. The optimal pH and temperature for lipoxygenase purified from the red potato were found to be pH 9.0. and $30^{\circ}C$, respectively. The Km and Vmax values for linoleic acid of the lipoxygenase purified from the red potato were $48\;{\mu}M$ and $0.03\;{\mu}M$ per minute per milligram of protein, respectively. The enzyme was insensitive to the metal chelating agents tested (2 mM KCN, 1 and 10mM EDTA, and 1 mM $NaN_3$), but was inhibited by several divalent cations, such as $Cu^{++}$, $Co^{++}$ and $Ni^{++}$. The essential amino acids that were involved in the catalytic mechanism of the 5-lipoxygenase from the Korean red potato were determined by chemical modification studies. The catalytic activity of lipoxygenase from the red potato was seriously reduced after treatment with a diethylpyrocarbonate (DEPC) modifying histidine residue and Woodward's reagent (WRK) modifying aspartic/glutamic acid. The inactivation reaction of DEPC (WRK) processed in the form of pseudo-first-order kinetics. The double-logarithmic plot of the observed pseudo-first-order rate constant against the modifier concentration yielded a reaction order 2, indicating that two histidine residues (carboxylic acids) were essential for the lipoxygenase activity from the red potato. The linoleic acid protected the enzyme against inactivation by DEPC(WRK), revealing that histidine and carboxylic amino acids residues were present at the substrate binding site of the enzyme molecules.

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Short-term effects of elevated CO2 on periphyton community in an artificially constructed channel

  • Park, Hye-Jin;Kwon, Dae-Ryul;Kim, Baik-Ho;Hwang, Soon-Jin
    • Journal of Ecology and Environment
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    • v.40 no.1
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    • pp.12-19
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    • 2016
  • Background: Direct impact of inorganic carbon (i.e., carbon dioxide ($CO_2$)) on the periphyton community is important to understand how and to what extent atmospheric conditions can affect the structure and dynamics of these communities in lotic systems. We investigated the influence of elevated $CO_2$ concentration on the periphyton community in the artificially constructed channels during the winter period. The channels made of acrylic paneling were continuously supplied with surface water discharged from a small reservoir, which was supported with ground water, at a flow rate of 5 L/min, and water temperature ranging $4-5^{\circ}C$. The effects of elevated $CO_2$ concentrations (790 ppm) were evaluated in comparison with the control (395 ppm $CO_2$) by analyzing pH, water carbon content and nutrients in water, periphyton composition and biomass, chlorophyll-a, ash-free dry-matter at 2-day intervals for 10 days. Results: After the addition of $CO_2$, significant decreases of pH, $NH_3-N$, and $PO_4-P$ (p < 0.05) and increases of chlorophyll-a, ash-free dry-matter, and the cell density of periphyton (p < 0.01) were observed, whereas the species composition of periphyton and water carbon content did not change. Conclusions: These results suggest that elevated $CO_2$ in flowing water system with low temperature could facilitate the growth of periphyton resulting in biomass increase, which could further influence water quality and the consumers throughout the food web.

Dietary Supplementation of Fat Increased Milk Fat Percentage without Affecting Ruminal Characteristics in Holstein Cows in a Warm Tropical Environment

  • Wang, A.S.;Jan, D.F.;Chen, K.J.;Yang, D.W.;Fan, Y.K.
    • Asian-Australasian Journal of Animal Sciences
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    • v.17 no.2
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    • pp.213-220
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    • 2004
  • The purpose of this experiment was to investigate the effect of the diets supplemented with lard or prilled fat ($Carolac^{(R)}$) on lactation performance, plasma constituents and ruminal characteristics of Holstein cows under a warm climate. In trial 1, 18 Holstein cows, 14 primiparas at 43 DIM and 4 multiparas at 55 DIM, were randomly assigned into six $3{\times3}$ Latin squares, in which three dietary treatments were isoproteinous but varying in energy contents and three 21 d periods. The treatments were basal diet (Control), basal diet supplemented with 2.5% lard (LD), and basal diet supplemented with 2.5% commercial Prilled fat (PF). In trial 2, three rumen canulated pregnant nonlactating Holstein cows with 550 kg average body weight were allotted into a $3{\times}3$ Latin square design with diets same as in trial 1 were fed to the cows at the level of 1.5% body weight on dry matter (DM) basis. The results indicated that the DM intake did not differ among the treatments. Milk yield and 4% FCM yield were greater (p<0.05) in PF than in Control. LD and PF resulted in greater milk fat percentage. Protein, lactose and solid contents in milk were not different among the three dietary treatments. The concentration of nonesterified fatty acids (NEFA) in plasma was significantly greater in LD and PF than that in Control. However, the concentrations of triglycerides, urea nitrogen, and cholesterol in plasma were not significantly different among the three treatments. Although the ruminal molar percentage of isobutyrate in LD and PF was greater, no significant difference was observed in ruminal pH, NH3-N concentration and VFA production among the three treatments. Diet supplemented with fat can improve milk yield and milk fat percentage without resulting in disadvantages of ruminal characteristics in cows at early lactation and under warm climate.

Kinetics and Mechanism of the Anilinolysis of Ethylene Phosphorochloridate in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.12
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    • pp.4185-4190
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    • 2011
  • The nucleophilic substitution reactions of ethylene phosphorochloridate (1c) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $5.0^{\circ}C$. The anilinolysis rate of 1c involving a cyclic five-membered ring is four thousand times faster than its acyclic counterpart (1a: diethyl chlorophosphate) because of great positive value of the entropy of activation of 1c (${\Delta}S^{\neq}=+30\;cal\;mol^{-1}K^{-1}$ compared to negative value of 1a (${\Delta}S^{\neq}=-45\;cal\;mol^{-1}K^{-1}$) over considerably unfavorable enthalpy of activation of 1c (${\Delta}H^{\neq}=27.7\;kcal\;mol^{-1}$) compared to 1a (${\Delta}H^{\neq}=8.3\;kcal\;mol^{-1}$). Great enthalpy and positive entropy of activation are ascribed to sterically congested transition state (TS) and solvent structure breaking in the TS. The free energy correlations exhibit biphasic concave upwards for substituent X variations in the X-anilines with a break point at X = 3-Me. The deuterium kinetic isotope effects are secondary inverse ($k_H/k_D$ < 1) with the strongly basic anilines and primary normal ($k_H/k_D$ > 1) with the weakly basic anilines and rationalized by the TS variation from a dominant backside attack to a dominant frontside attack, respectively. A concerted $S_N2$ mechanism is proposed and the primary normal deuterium kinetic isotope effects are substantiated by a hydrogen bonded, four-center-type TS.

Effect of Carbon dioxide in Fuel on the Performance of PEM Fuel Cell (연료중의 이산화탄소 불순물에 의한 연료전지 성능변화 연구)

  • Seo, Jung-Geun;Kwon, Jung-Taek;Kim, Jun-Bom
    • 한국신재생에너지학회:학술대회논문집
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    • 2007.11a
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    • pp.184-187
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    • 2007
  • Hydrogen could be produced from any substance containing hydrogen atoms, such as water, hydrocarbon (HC) fuels, acids or bases. Hydrocarbon fuels couold be converted to hydrogen-rich gas through reforming process for hydrogen production. Even though fuel cell have high efficiency with pure hydrogen from gas tank, it is more beneficial to generate hydrogen from city gas (mainly methane) in residential application such as domestic or office environments. Thus hydrogen is generated by reforming process using hydrocarbon. Unfortunately, the reforming process for hydrogen production is accompanied with unavoidable impurities. Impurities such as CO, $CO_2$, $H_2S$, $NH_3$, and $CH_4$ in hydrogen could cause negative effects on fuel cell performance. Those effects are kinetic losses due to poisoning of electrode catalysts, ohmic losses due to proton conductivity reduction including membrane and catalyst ionomer layers, and mass transport losses due to degrading catalyst layer structure and hydrophobic property. Hydrogen produced from reformer eventually contains around 73% of $H_2$, 20% or less of $CO_2$, 5.8% of less of $N_2$, or 2% less of $CH_4$, and 10ppm or less of CO. Most impurities are removed using pressure swing adsorption (PSA) process to get high purity hydrogen. However, high purity hydrogen production requires high operation cost of reforming process. The effect of carbon dioxide on fuel cell performance was investigated in this experiment. The performance of PEM fuel cell was investigated using current vs. potential experiment, long run (10 hr) test, and electrochemical impedance measurement when the concentrations of carbon dioxide were 10%, 20% and 30%. Also, the concentration of impurity supplied to the fuel cell was verified by gas chromatography (GC).

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Effects of Branched-chain Amino Acids on In vitro Ruminal Fermentation of Wheat Straw

  • Zhang, Hui Ling;Chen, Yong;Xu, Xiao Li;Yang, Yu Xia
    • Asian-Australasian Journal of Animal Sciences
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    • v.26 no.4
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    • pp.523-528
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    • 2013
  • This study investigates the effects of three branched-chain amino acids (BCAA; valine, leucine, and isoleucine) on the in vitro ruminal fermentation of wheat straw using batch cultures of mixed ruminal microorganisms. BCAA were added to the buffered ruminal fluid at a concentration of 0, 2, 4, 7, or 10 mmol/L. After 72 h of anaerobic incubation, pH, volatile fatty acids (VFA), and ammonia nitrogen ($NH_3$-N) in the ruminal fluid were determined. Dry matter (DM) and neutral detergent fiber (NDF) degradability were calculated after determining the DM and NDF in the original material and in the residue after incubation. The addition of valine, leucine, or isoleucine increased the total VFA yields ($p{\leq}0.001$). However, the total VFA yields did not increase with the increase of BCAA supplement level. Total branched-chain VFA yields linearly increased as the supplemental amount of BCAA increased (p<0.001). The molar proportions of acetate and propionate decreased, whereas that of butyrate increased with the addition of valine and isoleucine (p<0.05). Moreover, the proportions of propionate and butyrate decreased (p<0.01) with the addition of leucine. Meanwhile, the molar proportions of isobutyrate were increased and linearly decreased (p<0.001) by valine and leucine, respectively. The addition of leucine or isoleucine resulted in a linear (p<0.001) increase in the molar proportions of isovalerate. The degradability of NDF achieved the maximum when valine or isoleucine was added at 2 mmol/L. The results suggest that low concentrations of BCAA (2 mmol/L) allow more efficient regulation of ruminal fermentation in vitro, as indicated by higher VFA yield and NDF degradability. Therefore, the optimum initial dose of BCAA for in vitro ruminal fermentation is 2 mmol/L.

Effects of Temperature, Irradiance, and Nutrient Type on the Fragment Growth of Green Tide Alga Cladophora vadorum (녹조 대발생종 금발대마디말(Cladophora vadorum)의 절편 생장에 온도, 조도 및 영양염 종류가 미치는 영향)

  • Na, Yeon Ju;Jeon, Da Vine;Lee, Jung Rok;Kim, Young Sik;Choi, Han Gil;Nam, Ki Wan
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.49 no.5
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    • pp.657-664
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    • 2016
  • The green macroalga Cladophora vadorum bloomed along the coast at Sangrok Beach, Buan, South Korea, in September 2015. To elucidate the cause of bloom, the effects of environmental factors on the vegetative growth of adult fragments were examined. Growth experiments were carried out under different combinations of temperatures and irradiances, and with a single factor of nutrients (nitrogen, phosphorus). The maximal growth of C. vadorum was reported under the combination of 25°C and 100 μmol photons m−2s−1. The species grew under a wide range of N and P concentrations. The growth of C. vadorum peaked at 50 μM PO43−, 80 μM NH4+, and 100 μM NO3. Adult fragments formed holdfasts and new branches within 3 days in culture and became adults, showing polarized growth patterns, in 2 weeks. This is the first report showing the development of numerous bladelets from a segment in Cladophora species. The present results indicate that Cladophora blooms appear under growth conditions that are favorable in terms of temperatures, irradiance, and nutrients via fragment growth patterns producing rapid holdfasts and many bladelets.