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Isomerization and Dissociation of the Acrylonitrile Radical Cation: A Theoretical Study

  • Jung, Sun-Hwa;Lee, Gee-Hyung;Choe, Joong-Chul
    • Bulletin of the Korean Chemical Society
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    • v.32 no.11
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    • pp.3873-3879
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    • 2011
  • The potential energy surface (PES) for the isomerizations and dissociations of the acrylonitrile radical cation was determined from the CBS-QB3 and CBS-APNO calculations. The Rice-Ramsperger-Kassel-Marcus model calculations were performed based on the PES in order to predict the competitions among the dissociation channels. The mechanisms for the loss of $H^{\bullet}$, $H_2$, $CN^{\bullet}$, HCN, and HNC were proposed. The $C_3H_2N^+$ ion formed by loss of $H^{\bullet}$ was predicted as a mixture of $CH{\equiv}C-C=NH^+$, $CH{\equiv}C-N{\equiv}CH^+$, and $CH_2=C-C{\equiv}N^+$. Furthermore $CH{\equiv}C-C{\equiv}N^{+{\bullet}}$ was formed mainly by a consecutive 1,2-H shift and 1,2-H2 elimination.

Physical Properties of Thin Films Generated by Two Kinds of Different Function (2가지 서로 다른 기능에 의해 생성된 박막의 물리적인 특성의 기원)

  • Oh, Teresa
    • Proceedings of the IEEK Conference
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    • 2008.06a
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    • pp.487-488
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    • 2008
  • SiOC films containing alkyl groups have a low dielectric constant because of the interaction between the C-H hydrogen bonds and the oxygen of high electro-negative atom. The Si-$CH_3$ in a void is broken by the $O_2$, therefore the strength of CH bond in Si-O-O-$CH_3$ bond increases. The Si-O-O-$CH_3$ bond is broken by nucleophilic attack due to Si atom, again. The elongation of C-H bond causes the red shift, and the compression of C-H bond causes the blue shift. Among these chemical shifts, the blue shift from $1000\;cm^{-1}$ to $1250\;cm^{-1}$ was related with the formation of pores. If the oxygen is deficient condition, the methylradicals of the electron-rich substitution group terminate easily the Si-O-Si cross-link, and the pore is originated from the cross-link breakdown due to much methyl radicals of Si-$CH_3$. The dielectric constant of the films decreases due to pore generation.

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Factors Affecting and Techniques to Quantify $CH_4\;and\;N_2O$ Emissions from Stored Liquid Manure

  • Park, K.H.;Wagner-Riddle, Claudia
    • Journal of Animal Environmental Science
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    • v.13 no.1
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    • pp.1-12
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    • 2007
  • Stored animal manure is considered as a significant agricultural source of methane $(CH_4)$ and nitrous oxide $(N_2O)$ which have 23 and 297 times higher global warming effect when compared to carbon dioxide $(CO_2)$. Uncertainties caused by lack of understanding physical and biochemical environment in stored animal manure and by errors of emission measurement methods, even though many researches measuring $CH_4\;and\;N_2O$ emissions from stored manure have been conducted for a few decades. In this paper, general information of $CH_4\;and\;N_2O$ generation and emissions from stored animal manure and the measurement methods for quantifying $CH_4\;and\;N_2O$ emissions are discussed.

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The Development of a Short Reaction Mechanism for Premixed CH4/CHF3/Air Flames (CH4/CHF3/Air 예혼합 화염의 축소 반응 메카니즘 개발)

  • Lee, Ki Yong
    • Journal of the Korean Society of Combustion
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    • v.19 no.1
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    • pp.39-44
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    • 2014
  • A short reaction mechanism for premixed $CH_4/CHF_3/Air$ flames was developed with a reduction method of the combined application of simulation error minimization (SEM) which included connectivity method and principal component analysis. It consisted of 43 species and 403 elementary reactions at the condition of less than 5% of maximum error. The calculation time operated with a short mechanism was over 5 times faster than one with a detailed reaction mechanism. Good agreement was found between the flame speeds calculated by the short reaction mechanism and those by the detailed reaction mechanism for the entire range of $CHF_3/CH_4$ mole ratios and equivalence ratios. In addition excellent agreements were determined for the profiles of temperature, species concentration, and the production rates of the various species. So the short reaction mechanism was able to accurately predict the flame structure for premixed $CH_4/CHF_3/Air$ flames.

Syntheses and Theoretical Study of Palladium(II) Complexes with Aminophosphines as 7-Membered Chelate Rings

  • 김봉곤;양기열;정맹준;이배욱;도명기
    • Bulletin of the Korean Chemical Society
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    • v.18 no.11
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    • pp.1162-1166
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    • 1997
  • Nature of palladium(Ⅱ) complexes with 7-membered chelates was studied by experimental and theoretical methods on a Pd(L)Cl2 system, where L is Ph2PNHCH2CH2NHPPh2(L1), Ph2PNHC6H4NHPPh2(L2). The palladium(Ⅱ) complexes were prepared and characterized by elemental analysis, IR, UV, 1H, and 31P NMR spectroscopy. Ab initio calculations with geometry optimizations were also performed for related model systems, Pd(L)Cl2; L=R2PNH(CH2)2NHPR2(L3), R2PNHC6H4NHPR2(L4), R2P(CH2)4PR2(L5), R2PCH2(C6H4)CH2PR2(L6); R=H, CH3.

A Study on the Costumes of Ch'oyong Dance(I) - focus on the structure and change- (처용무복포의 연구(I) -구조적 특징과 변천을 중심으로-)

  • 박진아;조우현
    • Journal of the Korean Society of Clothing and Textiles
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    • v.21 no.1
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    • pp.129-143
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    • 1997
  • This study is about'The Costumes of Ch'oyong dance. (namely Ch'oyong-mu-bok; 처용무복)': emphasis on its structure and change. 1 studied Akhakguebum (the book of music and dance; 낙학궤범), Eui-Gue-Do (a collection of a series of paintings showing the whole processes of the royal courtesies and ceremonies; 의궤도) and some genre painting (풍증화). 'The costumes of Ch'oyong-Dance'were composed of robe(의), pants-skirt(대) , outer-skirt (상) , scarf-string(천의·길경) , shirt(한삼) , hat with mask (사교·가면) , belt(대) and shoes (혜) . According to the position, the colours of robe(의) and pants-skirt(군) were different. What is called, it is'the Colour of Five-Position (오방색) .'The Costumes of choyong-Dance' can be divided three factors by its symbolic means; i. e. shamanism, buddhism and bureaucratism. The pants-skirt(군), outer-skirts(상), scarf · string(천의·길경) and mask are considered as shamanic factor. However, the scarf(천의) , string(길경) and patterns(만화)which are decorated with many lotus patterns enclosed with vine are considered as buddhistic factor. And the hat (사모) , robe(의) , outer-skirt(상) , belt(대) and shoes(잔) are considered as bureaucratic factor. Ch'oyong is endowed with some power by these factors, and its symbolic means became stronger and enlarged by 'the Colour of five-position'. As time goes, the forms and details of robe had been changed noticeable; sleeve-width, neck-line and patterns. The shamanic, buddhistic and bureaucratic factors are reduced. These changes were derived from the changes of Ch'oyong·Dance. On the ground of the shape of mask and round-neckline robe(단영) , someone has an opinion that Ch'oyong is an aribian. However, according to this study, Ch'oyonh is Korean traditional thing; round-neckline robe already existed and settled in Silla dynasty and Ch'oyong-mask symbolized shamanic power.

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Water-repellency and Bonding Characteristics of the Cement Hydrate-Organic Acid Compound (시멘트 수화물-유기산의 결합특성과 그 Compound의 발수성)

  • Rho, Jae-Seong;Cho, Heon-Young;Hong, Seong-Soo;Choi, Jeong-Bong
    • Applied Chemistry for Engineering
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    • v.3 no.4
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    • pp.639-648
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    • 1992
  • For recycling cement hydrate(CH) as waterproofers for mortar and concrete or a filler for rubber & plastics, the cement hydrates were treated with stearic acid(SA). And the bonding characteristics and the water repellency of the CH-SA compounds were investigated by using FT-IR, TGA, SEM, XRD, and contact angle measuring apparatus. Water tightness of the remitars used CH-SA compounds was also tested. The results are summarized as follows : 1) If the cement hydrates are treated with over 2.0% of stearic acid, the CH-SA compounds show very strong water repellency. 2) The stearic acids are solidified on the surfaces of cement hydrate in calcium stearate and aluminium stearate. 3) If CH-SA compounds which is cement hydrate treated with 5~10% of stearic acid are used 3%~6% in remitar, water absorption ratio and water permeatility ratio of remitar are decreased in below 30% of those of the ordinary remitar.

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Spatial Patterns of Methane Oxidation and Methanotrophic Diversity in Landfill Cover Soils of Southern China

  • Chi, Zi-Fang;Lu, Wen-Jing;Wang, Hong-Tao
    • Journal of Microbiology and Biotechnology
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    • v.25 no.4
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    • pp.423-430
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    • 2015
  • Aerobic CH4 oxidation is an important CH4 sink in landfills. To investigate the distribution and community diversity of methanotrophs and link with soil characteristics and operational parameters (e.g., concentrations of O2, CH4), cover soil samples were collected at different locations and depths from the Mengzi semi-aerobic landfill (SAL) in Yunnan Province of southern China. Specific PCR followed by denaturing gradient gel electrophoresis and realtime PCR were used to examine methanotrophs in the landfill cover soils. The results showed that different locations did harbor distinct methanotroph communities. Methanotrophs were more abundant in areas near the venting pipes because of the higher O2 concentrations. The depth of 20-25 cm, where the ratio of the CH4 to O2 was within the range from 1.3 to 8.6, was more conducive to the growth of CH4-oxidizing bacteria. Type II methanotrophs dominated in all samples compared with Type I methanotrophs, as evidenced by the high ratio of Type II to Type I methanotrophic copy numbers (from 1.76 to 11.60). The total copy numbers of methanotrophs detected were similar to other ecosystems, although the CH4 concentration was much higher in SAL cover soil. Methylobacter and Methylocystis were the most abundant Type I and Type II methanotrophs genera, respectively, in the Mengzi SAL. The results suggested that SALs could provide a special environment with both high concentrations of CH4 and O2 for methanotrophs, especially around the vertical venting pipes.

The Relaxation Effects of Cynomorii herba in Isolated Corpus Cavernosum Tissues (발기부전 처방에 사용되는 쇄양(鎖陽)이 음경해면체 이완에 미치는 영향)

  • Shin, Seon-mi;Park, Sun-young
    • The Journal of Internal Korean Medicine
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    • v.37 no.4
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    • pp.591-600
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    • 2016
  • Objective: This study aimed to examine the relaxation effects and underlying mechanisms of Cynomorii herba (CH) extract in isolated rabbit corpus cavernous tissues.Methods: We experimented with CH extract (0.01-3.0 mg/mL). Nω-nitro-L-arginine (L-NNA) was experimented before the CH extract to contracted strips induced by phenylephrine (PE, 1 μM)and compared with nonexperimented. In addition, we experimented with calcium chloride (Ca2+, 1 mM) after pretreatment of the CH extract in Ca2+-free Krebs-Ringer solution to contracted strips induced by PE. The cell viability and nitric oxide (NO) concentration of human umbilical vein endothelial cells (HUVECs) were measured by an methylthiazol-2-yl-2, 5-diphenyl tetrazoliumbromide (MTT) assay and Griess reagent system. The ratio of smooth muscles to collagen fibers, in addition to eNOS- and PDE-5-positive reactions, was examined by histochemical and immunohistochemical staining.Results: The CH extract significantly induced the relaxation of the cavernous strips, and the pretreatment with L-NNA inhibited CH extract-induced relaxation. The L-NNA pretreatment reduced the increased contraction induced by the addition of Ca2+in Ca2+-free solution. Furthermore, the NO concentration of the HUVECs increased. When the CH extract was applied to the corpus cavernosum of the penis (CCP) of Sprague Dawley rats, the ratio of smooth muscles to collagen fibers by PE and the formation of eNOS around the helicine artery increased. However, the CH extract treatment decreased PDE-5 positive reactions.Conclusions: These results show that the relaxation effects induced by the CH extract are associated with the suppression of the influx of extracellular Ca2+ via the production of NO and eNOS and inhibition of PDE-5.

Distribution and Differentiation of the Choline Acetyltransferase-immunoreactive Nerve Cells in the Basal Nucleus of Meynert of the Rat Forebrains During the Postnatal Development (흰쥐 출생후 발생에 따른 전뇌 기저부 Meynert기저핵에서 Choline Acetyltranseferase 면역반응 신경세포의 분포 및 분화)

  • Lee, Nam-Seob;Chung, Young-Wha
    • Applied Microscopy
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    • v.29 no.4
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    • pp.479-491
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    • 1999
  • This study was performed to investigate the distribution and differentiation of choline acetyltransferase (ChAT)-immunoreactive cells in the basal nucleus of Meynert of the postnatal and adult rat forebrains, utilizing techniques of immunocytochemistry. According to the cell shape and the ratio of long axis vs short axis of cell soma, the ChAT-immunoreactive nerve cells in the basal nucleus of Meynert of the adult rat were classified into six types. In the adult rat, the frequency distributions (FD) of round, oval, elongated, fusiform, triangular and polygonal cells were 9.4%, 35.5%, 32.1%, 5.9%, 9.1% and 8.0%, respectively. The FD of oval and round nerve cells on the postnatal day (PND) 14 were observed to be 18.7% and 51.5%, respectively. Those were shown to be progressively decreased during developmental process to the adult. Also, those of elongated and triangular nerve cells on the PND 21 were observed to be 30.4% and 10.1%, respectively. Those were shown to be same phenomenon a,1 those in the round and oval cells. Meanwhile, those of the triangular and polygonal nerve cells were progressively increased from the early postnatal stage to the adult. The total mean volumes of ChAT-immunoreactive cell somata in the PND 7 rat were the lowest $(1,083{\mu}m^3)$ and those in the PND 21 rat were shown to be the highest $(5,045{\mu}m^3)$. But in the adult, those were decreased to $(2,731{\mu}m^3)$. Those in the PND 21 rat were shown to be about 84.7% larger than those in the adult. On the electron micrography, the cell organelles such as ribosomes, polysomes, rough endoplasmic reticula (RER) and mitochondria were well developed in the PND 21 rat forebrains, but Golgi complexes were shown to be proliferating phase. Especially, ribosomes, polysomes and RER were immunoreactive in the tissues treated with 0.05% triton X-100. According to the observations in the present study, it is considered that the ChAT-immunoreactive nerve cells in the basal nucleus of Meynert of the rat forebrains are differentiated throughout the following processes of changes during the postnatal development: 1) increase of cell soma volumes with the differentiation of tell organelles and neurites, 2) increase in the FD of differentiated tell types and 3) cell schrinkage without cell loss. The ribosomes, polysomes and RER are considered to be closely related to the intracellular localization and biosynthesis of the ChAT but not Colgi complex.

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