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Substituent Effects and Correlations of Electrochemical Behaviors with Molecular Orbital Calculation of Thioxantone DerivativesⅠ

  • 곽경도;서무룡;하광수;백우현
    • Bulletin of the Korean Chemical Society
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    • v.19 no.5
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    • pp.527-530
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    • 1998
  • This paper presents the electrochemistry and molecular orbital (MO) picture of a series of conformationally-restricted thioxantone derivatives. A series of $C_2-substituted$ thioxanthones were examined to probe the electronic influence of the substituent on the electrooxidation and electroreduction sites (i.e., on the electron densities at the 10-and 9-positions), respectively. In the presence of "electrophoric" groups such as C=O and S, characteristic electrochemical reduction and oxidation responses are observed. The electrochemical reaction was diffusion-controlled, because the $I_p/{\upsilon}^{1/2}$ ratio was constant for the anodic and cathodic wave of thioxantone derivatives. These substituent effects are presented in terms of correlations of oxidation (or reduction) potentials with the highest occupied molecular orbital (HOMO), or lowest unoccupied molecular orbital (LUMO) energies, respectively. There is good correlation between energies of the HOMO vs. $E_{pa}^{(+)}$ and energies of the LUMO vs. $E_{pc}^{(-)}$. Frontier Molecular Orbital (FMO) is changed by the functional group of thioxanthones. FMO energy level was offered us the information about the electron transfer direction, and the coefficient of FMO was offered the information about the electron transfer position. Sulfur atom has an important effect on oxidation potential, $E_{pa}^{(+)}$ and the carbonyl carbon has an important effect on reduction potential, $E_{pc}^{(-)}$. Therefore we were appreciated that the contribution of sulfur atom for the $E_{pa}^{(+)}$ and HOMO energies is larger than the contribution of carbonyl group for the $E_{pc}^{(-)}$ and LUMO energies.

Association Between $\beta_2$ Adrenoceptor Polymorphisms and Atopy/serum IgE in Asthmatic Patients ($\beta_2$ 교감신경 수용체 다형성이 아토피 및 혈청 IgE에 미치는 영향)

  • Lee, Sin-Hyung;Shim, Jae-Jeong;Kang, Yong-Koo;Jeong, Hye-Cheol;Kim, Kyung-Kyu;Kwon, Young-Hwan;Kim, Je-Hyeong;Lee, Sung-Yong;Lee, So-Ra;Lee, Sang-Youb;Cho, Jae-Youn;In, Kwang-Ho;Yoo, Sa-Hwa;Kang, Kyung-Ho
    • Tuberculosis and Respiratory Diseases
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    • v.46 no.6
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    • pp.826-835
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    • 1999
  • Background : The $\beta_2$ adrenergic receptor ($\beta_2$ AR) polymorphisms occurring at amino acid position 16 (Arg to Gly), 27 (Gln to Glu), 34 (Val to Met), and 164 (Thr to Ile) are known to be functionally relevant and also disease-modifying in subjects with asthma. However the contribution of these polymorphisms to the development of the asthmatic phenotype or other markers for allergic disease remains to be established. Methods : 109 patients with bronchial asthma and 42 healthy person were included. Serum total IgE, allergen specific IgE, and skin prick test were performed to all of the subjects. $\beta_2$ AR polymorphisms were checked by mutated allele specific amplification (MASA) method. Results : The results were as follows. The frequencies of $\beta_2$ AR polymorphisms in asthmatic patients and healthy person were not statistically different(p>0.05). There was no association between $\beta_2$ AR polymorphisms of amino acid position 16, 27, 34 and the existence of atopy among asthmatic patients(p>0.05). Between asthmatic patients with or without elevated IgE level and $\beta_2$ AR polymorphisms of amino acid position 16, 27, 34, there was no statistically significant association(p>0.05). Conclusion : There was no difference in frequency of the $\beta_2$ AR polymorphism between asthmatic patients and healthy person. In the bronchial asthma, association of $\beta_2$ AR polymorphism and atopy/serum total IgE was not found.

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Effects of pitch accent and prosodic boundary on English vowel production by native versus nonnative (Korean) speakers. (영어의 강세와 운율경계가 모음 발화에 미치는 영향에 관한 음향 연구;원어민과 한국인을 대상으로)

  • Hur, Yu-Na;Kim, Sa-Hyang;Cho, Tae-Hong
    • Proceedings of the KSPS conference
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    • 2007.05a
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    • pp.240-242
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    • 2007
  • The goal of this paper is to investigate effects of three prosodic factors, such as phrasal accent (accented vs. unaccented), prosodic boundary (IP-initial vs. IP-medial) and coda voicing (e.g., bed vs. bet), on acoustic realization of English vowels (/i, $_I/$, $/{\varepsilon}$, ${\ae}/$) as produced by native (Canadian) and nonnative (Korean) speakers. The speech corpus included 16 minimal pairs (e.g., bet-bat, bet-bed) embedded in a sentence. Results show that phonological contrast between vowels are maximized when they were accented, though the contrast maximization pattern was not the same between the English and Korean speakers. However, domain-initial position do not affect the phonetic manifestation of vowels. Results also show that phonological contrast due to coda voicing is maximized only when the vowels are accented. These results propose that the phonetic realization of vowels is affected by phrasal accent only, and not by the location within prosodic position.

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DFT/B3LYP Study of the Substituent Effects on the Reaction Enthalpies of the Antioxidant Mechanisms of Magnolol Derivatives in the Gas-Phase and Water

  • Najafi, Meysam;Najafi, Mohammad;Najafi, Houshang
    • Bulletin of the Korean Chemical Society
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    • v.33 no.11
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    • pp.3607-3617
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    • 2012
  • In this paper, the study of various ortho- and meta-substituted Magnolol derivatives is presented. The reaction enthalpies related to three antioxidant action mechanisms HAT, SET-PT and SPLET for substituted Magnolols have been calculated using DFT/B3LYP method in gas-phase and water. Calculated results show that electron-withdrawing substituents increase the bond dissociation enthalpy (BDE), ionization potential (IP) and oxidation/reduction enthalpy (O/RE), while electron-donating ones cause a rise in the proton dissociation enthalpy (PDE) and proton affinity (PA). In ortho- position, substituents show larger effect on reaction enthalpies than in meta-position. In comparison to gas-phase, water attenuates the substituent effect on all reaction enthalpies. In gas-phase, BDEs are lower than PAs and IPs, i.e. HAT represents the thermodynamically preferred pathway. On the other hand, SPLET mechanism represents the thermodynamically favored process in water. Results show that calculated enthalpies can be successfully correlated with Hammett constants (${\sigma}_m$) of the substituted Magnolols. Furthermore, calculated IP and PA values for substituted Magnolols show linear dependence on the energy of the highest occupied molecular orbital ($E_{HOMO}$).

Effect of Substituted Trifluoromethyl Groups on Thermal and Mechanical Properties of Fluorine-containing Epoxy Resin

  • Heo, Gun-Young;Park, Soo-Jin
    • Macromolecular Research
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    • v.17 no.11
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    • pp.870-873
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    • 2009
  • In this study, 2-diglycidylether of benzotrifluoride (2-DGEBTF) and 4-diglycidylether of benzotrifluoride (4-DGEBTF) epoxy resins, which contained fluorine groups in the main chain, were synthesized. The resins were characterized by FTIR, $^1H$ NMR, $^{13}C$ NMR and $^{19}F$ NMR spectroscopy. The 2-DGEBTF and 4-DGEBTF epoxy resins were cured with triethylene tetramine (TETA), and the effect of the fluorine group on the synthesized epoxy resin on the cure behavior, thermal, and mechanical properties was investigated. The 2-DGEBTF/TETA system was more reactive than the 4-DGEBTF/TETA system, whereas the thermal stability factor i.e., the decomposition activation energy ($E_d$), of 4-DGEBTF/TETA was higher than that of 2-DGEBTF/TETA. These results can be explained by the decrease in cross-linking density and decomposition of the short side chains, resulting in the $CF_3$ group at the para position. However, the $K_{IC}$ value of 4-DGEBTF/TETA was higher than that of 2-DGEBTF/TETA. This was attributed to the increase in flexibility in the epoxy backbone, resulting in a difference in steric hindrance and polarlizability.

A development of accuracy diagnostic system 2-dimensional circular interpolation of machining centers (Machining Center의 2차원 원호보간정밀도 진단 System의 개발)

  • Kim, Jeong-Soon;Namgung, Suk;Tsutusmi, Masacmi
    • Journal of the Korean Society for Precision Engineering
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    • v.10 no.2
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    • pp.54-65
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    • 1993
  • The paper describes and alternative method based on a new idea to measure the circular movement of machining centers. ISO has employed three testing methods for the acceptance tests of machine tools; the first is a rotating one-dimensional probe method, the second is a two-dimensional probe and a master circular ring, and the third is a kinematic ball bar. The last two methods were proposed and introduced by W. Knapp and J. B. Bryan, respectively. The newly developed method is superior to above two methods; the rotating angle can be detected and the rotating radius is variable. Circular movement errors of machining centers were investigated by the analysis of data measured by R- .THETA. method. Followint observations are obtained 1) The errors which depend on positions, i.e., periodical errors by the pitch of ball screws, errors by compensation of backlash and errors by perpendicularity of X and Y-axis, were analyzed. 2) The errors which depend on NC control system, i.e., errors by the unbalance of position-loop-gaians, errors by velocity-loop-gains and errors by feed speeds, were quantiatively analyzed. 3) The method of extracting error information, which uses moving technique of averaging angle and fourier's analysis data mesured by the R- .THETA. method, was proposed.

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The Optimal Location Environment of the Bronze Age Settlement in Yongdu Stream and its Surrounding Area in Asan through the Ridge Environment's Perspective (능선환경으로 본 아산 용두천 유역 및 주변 지역에 있어서 청동기시대 취락의 최적 입지환경)

  • Park, Ji Hoon;Lee, Ae Jin
    • Journal of The Geomorphological Association of Korea
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    • v.27 no.4
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    • pp.89-112
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    • 2020
  • The purpose of this study is as follows: First, we restore the optimal topographical environment of the Bronze Age settlements in the Yongdu Stream and its surrounding area in Asan City. Second, we reveal the relative importance of the topographical factors that the Bronze Age people considered when selecting their dwelling locations. We compared and analyzed topographical factors (ridge scale, ridge direction, slope direction of the ridge, micro-landform of the ridge, position of the ridge) from the ridge's environmental perspective of 123 Bronze Age dwellings (hereinafter referred to as dwellings) found in the survey area for that purpose. The results are as follows: First, from a macro perspective, the optimal topographical environment for the location of the Bronze Age settlement is the second ridge that have the E-W direction. And from a micro perspective, it is the southeast direction slope of the Crest slope at the summit. Second, it appears that the Bronze Age people have taken important consideration in determining the location of their dwelling in the following order: ① position (eg. summit), ② micro-landform (eg. Crest slope, Upper slope), ③ slope direction (eg. southward, South, Southeast), ④ scale (eg. sub-ridge, secondary, tertiary), ⑤ direction (eg. E-W, NNE-SSE).

A Study on the influence of job transfer in E&T programs characteristics & organizational situational characteristics of the medium and small-sized hospitals (중소병원의 교육훈련 프로그램 특성 및 조직상황적 특성이 직무전이에 미치는 영향에 관한 연구)

  • Kim, Young-Hyuk
    • Korea Journal of Hospital Management
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    • v.16 no.4
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    • pp.131-160
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    • 2011
  • The purpose of this study was 1) to understand the job transfer in education & training(E&T) programs & organizational situational characteristics, and 2) to analyze the effects of the E&T programs & organizational situational characteristic groups on each of the levels of job transfer. There is intimate relationship between E&T programs characteristics & organizational situational characteristics and job transfer, so we can't think of them separately. With this point of view the most frequently discussed problem is how to apply the theory in actual job, but in reality it's true that the improvement of job transfer can't reach the expectations of the E&T programs. In literature view study, the concepts of job transfer in E&T, the general theory on E&T, and the actual condition and points at issue of the existing E&T practices in the medium and small-sized hospitals were defined. As the results from empirical analysis, we could find followings: First, in evaluation of the job transfer, demographic characteristics (seniority, occupational category, position) variables have a significant different. Second, in degree of the job transfer, E&T programs characteristics(contents of E&T, design of E&T, conditions of E&T, teaching ability of lecturer, methods of E&T) variables have a different influence upon each of the evaluation levels of E&T. Third, support of CEO variables have a different influence on the job transfer according to contents, design, conditions of the E&T programs. Fourth, support of co-works variables have a different influence on the job transfer according to design, conditions, method of the E&T programs. Fifty, support of organizational atmosphere variables have a different influence on the job transfer according to contents, design, conditions of the E&T programs.

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A survey of infant sleep positions associated with sudden infant death syndrome (영아 돌연사 증후군과 연관하여 아기를 재우는 방법에 대한 인식 연구)

  • Lee, Dong Jun;Jang, So Ick;Shim, Eun Jung;Cho, Do Jun;Kim, Dug Ha;Min, Ki Sik;Yoo, Ki Yang
    • Clinical and Experimental Pediatrics
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    • v.49 no.6
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    • pp.602-609
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    • 2006
  • Purpose : As the prone position is thought to be an important factor in sudden infant death syndrome(SIDS), this study was conducted to contribute to reducing SIDS by analyzing sleeping positions of infants. Methods : A face-to-face questionnaire was carried out with a total of 170 parents with a baby aged less than 6 months. Results : A total of 170 infants included 95 males(55.9 percent) and 75 females(44.1 percent); their average age was 2.8 months. 45.3 percent slept in a supine position; 34.7 percent in a side or supine position; 7.1 percent in a side position; 4.7 percent in a prone position; 4.1 percent in a non-specific position. Among those in a side position, 59.7 percent were in a supine position in the morning; 19.5 percent were in the side position; 13.4 percent were in a non-specific position; and 4.1 percent were in a prone position. To the question why they slept in a specific position, 34.9 percent answered their baby slept comfortably, and particularly, 42.9 percent in the prone position group answered so. In the supine position group, 21.6 percent answered they had no reason. Both in the prone position and side position groups, 21 percent each answered they were worried about the shape of their baby's head. In the side position group, 22 percent answered that they had a fear of choking due to vomiting. In all sleeping position groups, 8.2 percent and 7.4 percent answered it was because they had a fear of suffocation and they wanted to avoid SIDS, respectively. Conclusion : Many of the parents preferred unstable positions, e.g. the side position and the prone position, which could cause SIDS. Their decision on their baby's sleeping position was not based on exact medical knowledge, but on convenience in taking care of their baby. As it was found that only 6 percent of the subjects were advised from their pediatrist about their baby's sleeping position, moreover, it is necessary to carry out more studies and activities for preventing SIDS caused by improper sleeping positions and educating patents about recommended sleeping positions for their baby.

Changes in Blood pH, $Pco_2$ and $Po_2$ During Passive Tilt (체위 변화시의 혈액 pH, $Pco_2$$Po_2$의 변화)

  • Jun, Sang-Yun;Chae, E-Up
    • The Korean Journal of Physiology
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    • v.12 no.1_2
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    • pp.35-40
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    • 1978
  • To evaluate orthostatic brain hypoxia from the passive tilt, anesthetized dogs were tilted from supine to $90^{\circ}C$ upright and $90^{\circ}C$ head down position. Blood pH, $Pco_2$ and $Po_2$ changes during tilt were measured on 8 dogs. Respiratory rate was decreased in upright position and increased in head down position comparing to that in rte horizontal position. pH in arterial blood was increased in upright position and decreased in venous blood comparing to that in the horizontal position. No significant changes were found in the head down position. $Pco_2$ of arterial and venous blood was decreased both in upright and head down. position A significant decrease was found in the head down position. $Po_2$ in arterial blood was increased both in the upright and head down position. However, it was decreased in the venous blood. The cause of increased $Po_2$ in arterial blood seemed to do due to hyperventilation and the cause of decreased $Po_2$ in venous blood was thought to be due to increased $O_2$ consumption of animals during the tilt.

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