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Synthesis and Spectroscopic Characterization of Manganese(II), Iron(III) and Cobalt(III) Complexes of Macrocyclic Ligand. Potential of Cobalt(III) Complex in Biological Activity

  • El-Tabl, Abdou S.;Shakdofa, Mohamad M.E.;El-Seidy, Ahmed M.A.
    • Journal of the Korean Chemical Society
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    • v.55 no.6
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    • pp.919-925
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    • 2011
  • A new series of manganese(II), iron(III) and cobalt(III) complexes of 14-membered macrocyclic ligand, (3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane-1,8-diamine) have been prepared and characterized by elemental analyses, IR, UV-VIS, $^1H$- and $^{13}C$- NMR spectra, magnetic susceptibilities, conductivities, and ESR measurements. Molar conductance measurements in DMF solution indicate that the complexes are electrolytes. The ESR spectrum for cobalt(III) complex in $CD_3OD+10%D_2O$ after exposure to $^{60}Co-{\gamma}$-rays at 77 K using a 0.2217 M rad $h^{-1}$ vicrad source showed $g_{\perp}$ > $g_{\parallel}$ > $g_e$, indicating that, the unpaired electron site is mainly present in the $d_z2$ orbital with covalent bond character. In this case, the ligand hyperfine tensors are nearly collinear with ${\gamma}$-tensors, so there is no major tendency to bend. Therefore, little extra delocalization via the ring lobe of the $dz^2$ orbital occurs. However, the ESR spectrum in solid state after exposure to $^{60}Co-{\gamma}$-rays at 77 K showed $g_{\parallel}$ > $g_{\perp}$ > $g_e$, indicating that, the unpaired electron site is mainly present in the $d_x2_{-y}2$ ground state as the resulting spectrum contains a large number of randomly oriented molecules provided that, the principle directions of g and A tensors. Manganese (II) complex 2, $[H_{12}LMn]Cl_4.2H_2O$, showed six isotropic lines characteristic to an unpaired electron interacting with a nucleus of spin 5/2, however, iron(III) complex 3, $[H_{12}LFe]Cl_5.H_2O$, showed spectrum of a high spin $^{57}Fe$ (I=1/2), $d^5$ configuration. The geometry of these complexes was supported by elemental analyses, IR, electronic and ESR spectral studies. Complex 1 showed exploitation in reducing the amount of electron adducts formed in DNA during irradiation with low radiation products.

Synthesis of Binuclear Bismacrocyclic Iron(II) Complex by the Aerobic Oxidation of Iron(II) Complex of 1,4,8,11-Tetraazacyclotetradecane

  • Myunghyun Paik Suh;Gee-Yeon Kong;Il-Soon Kim
    • Bulletin of the Korean Chemical Society
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    • v.14 no.4
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    • pp.439-444
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    • 1993
  • The aerobic oxidation of the Fe(II) complex of 1,4,8,11-tetraazacyclotetradecane, [Fe(cyclam)$(CH_3CN)_2](ClO_4)_2$, in MeCN in the presence of a few drops of $HClO_4$ leads to low spin Fe(III) species [Fe(cyclam)$(CH_3CN)_2](ClO_4)_3$. The Fe(III) cyclam complex is further oxidized in the air in the presence of a trace of water to produce the deep green binuclear bismacrocyclic Fe(II) complex $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$. The Fe(II) ions of the complex are six-coordinated and the bismacrocyclic ligand is extensively unsaturated. $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$ crystallizes in the monoclinic space group $P2_1/n$ with a= 13.099 (1) ${\AA}$, b= 10.930 (1) ${\AA}$, c= 17.859 (1) ${\AA}$, ${\beta}$= 95.315 $(7)^{\circ}$, and Z= 2. The structure was solved by heavy atom methods and refined anisotropically to R values of R= 0.0633 and $R_w$= 0.0702 for 1819 observed reflections with F > $4{\sigma}$ (F) measured with Mo K${\alpha}$ radiation on a CAD-4 diffractometer. The two macrocyclic units are coupled through the bridgehead carbons of ${\beta}$-diimitie moieties by a double bond. The double bonds in each macrocycle unit are localized. The average bond distances of $Fe(II)-N_{imine}$, $Fe(II)-N_{amine}$, and $Fe(II)-N_{MeCN}$ are 1.890 (5), 2.001 (5), and 1.925 (6) ${\AA}$, respectively. The complex is diamagnetic, containing two low spin Fe(II) ions in the molecule. The complex shows extremely intense charge transfer band in the near infrared at 868 nm with ${\varepsilon}$= 25,000 $M^{-1}cm^{-1}$. The complex shows a one-electron oxidation wave at +0.83 volts and two one-electron reduction waves at -0.43 and-0.72 volts vs. Ag/AgCl reference electrode. The complex reacts with carbon monoxide in $MeNO_2$ to form carbonyl adducts, whose $v_{CO}$ value (2010 $cm^{-1}$) indicates the ${\pi}$-accepting property of the present bismacrocyclic ligand.

Habitat Characteristics and Spawning Ecology of Hippocampus haema (Pisces: Syngnathidae) Inhabiting the Soando (Island) (소안도에 서식하는 해마(Hippocampus haema) (Pisces: Syngnathidae)의 서식지 특성 및 산란생태)

  • Hyun-Geun Cho;Jung-Kwan Ahn;Hyeong-Su Kim
    • Korean Journal of Environment and Ecology
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    • v.36 no.6
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    • pp.615-626
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    • 2022
  • This study investigated the habitat characteristics and spawning ecology of Hippocampus haema (Syngnathidae) in Soando Island, Korea, from May 2015 to December 2016. The survey site where seahorses inhabit was mainly formed by seagrass of Zostera marina populations. Total density and biomass (Mean±SE) of Z. marina were the highest at 136±14.4 shoots/m2 and 489.8g DW/m2, respectively, in spring (May), while the total density was lowest at 93±7.0shoots/m2in autumn (October), and biomass was the lowest and at 122.3g DW/m2 in winter (February). During the study period, 293 individuals were identified through a diving and kick net survey, and the total length of H. haema ranged from 10.1 to 87.0mm. Male individuals nurturing fertilized eggs or larvae appeared beginning in May and were collected until October in both 2015 and 2016. Juvenile individuals were captured beginning in July 2015 and June 2016. As a result of a comprehensive analysis of the spawning season characteristics, it was estimated that the spawning season of H. haema was from April to October. The number of fertilized egg or larvae inside the male brood pouch were 38.3±14.8 (20-76), and the number of fecundity identified from female were 47.2±8.6 (31-59). The male-to-female ratio of H. haema was 1:1.7, indicating the dominance of males.

The Relationships between Plasma Insulin-like Growth Factor (IGF)-1 and IGF-Binding Proteins (IGFBPs) to Growth Pattern, and Characteristics of Plasma IGFBPs in Steers

  • Lee, H.G.;Hidari, H.;Kang, S.K.;Hong, Z.S.;Xu, C.X.;Kim, S.H.;Seo, K.S.;Yoon, D.H.;Choi, Y.J.
    • Asian-Australasian Journal of Animal Sciences
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    • v.18 no.11
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    • pp.1575-1581
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    • 2005
  • This study was conducted to determine the characteristics of IGFBPs in plasma of steers, and to profile the relationship between growth and plasma IGF-1 and IGFBPs with aging in Holstein steers. Four blots of IGFBP at molecular weights of 38-43, 34, 29-32 and 24 kDa bands were detected by western ligand blot assay using $^{125}I-IGF-1$. On the basis of immunoblotting with anti-bovine IGFBP-2 and -3 antiserums, we observed the band for IGFBP-2 at approximately 34 kDa, and the IGFBP-3 band was detected at 38-43 kDa and 34 kDa in adult steers and calves. The IGFBP-3 antiserum used on the blots exhibited significant cross-reactivity with 34 kDa IGFBP-2. Furthermore, the 38-43 kDa IGFBP-3 bands were reduced to a 36 kDa band after deglycosylation, whereas the 34 kDa IGFBP-2 was intact. The plasma IGF-1, IGFBP-3 and other IGFBPs showed stability throughout a whole day. The change in live weight was found to be positively correlated to the plasma IGF-1 concentration (r = 0.6801, n = 64, p<0.05) and plasma IGFBP-3 (r = 0.6321, n = 64, p<0.05), while inversely correlated to plasma IGFBP-2 (r = -0.2919, n = 64, p<0.05). Furthermore, plasma IGF-1 was positively correlated to plasma IGFBP-3 (r = 0.6191, p<0.001), but was not correlated to plasma IGFBP-2. The portion of IGFBP-2 for total IGFBPs in calves was higher than in adult steers (p<0.05) and was decreased with growth, whereas that of IGFBP-3 was increased with increased live weight (p<0.05). The ratio IGFBP-3 for IGFBP-2 (BP-3/BP-2) was increased with growing of liveweight. Therefore, the changes in plasma IGF-1 level with increased liveweight may be related to the changes in plasma IGFBP-3 level and IGFBP-2 may give an important role in anabolic action of IGF-1 with the growth of body during calfhood in Holstein steers.

A Study of Optimal SOAmin for Motor and Language Tasks in Event-related fMRI using Stochastic Design (통계학적 자극설계를 이용한 Event-related fMRl에서 운동과 언어과제의 최적 SOAmin에 대한 연구)

  • 문찬홍;유재욱;나동규;이은정;변홍식
    • Investigative Magnetic Resonance Imaging
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    • v.6 no.1
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    • pp.28-34
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    • 2002
  • Purpose : The minimum stimulus onset asynchronoy(SOAmin) is one of important experimental parameters for an event-related fMRI experiment designed with the stochastic stimulus. In this study, the most efficient SOAmin is explored for the stronger activation in motor and language tasks with the stimulus designed stochastically. Materials and methods : The event-related fMRI during motor and language tasks were obtained in four normal right-handed subjects. EPI-BOLD sequence is used at 1.5Tesla MR system for the acquisition of event-related fMRI. For each task the subjects are responded for the stimulus' with 2, 3, 4, and 6 seconds SOAmin. The obtained images are processed with SPM99, and the p value is set as 0.05 for the significant activation detection. The Z value and the number of activated pixels are compared for each task. Results : For the motor task, the primary and supplementary motor areas are activated, and for the language task the consistent activated signals are detected in the Broca's. The activated signal is to be stronger for the shorter SOAmin for both motor and language tasks. At primary motor area, the activated signals is the strongest for 3 seconds SOAmin and for the supplementary motor area the result with 2 seconds SOAmin shows the strongest activation. And the result of language task shows the strongest activation at the 2 seconds SOAmin. Conclusion : In the event-related fMRI of motor and language tasks with the stochastically designed stimulus, the 2 or 3 seconds SOAmin is efficient for more activated and clustered activation.

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Estimation of C Storage and Annual $CO_2$ Uptake by Street Trees in Gyeonggi-do (경기도 도시가로수의 탄소저장량과 연간 이산화탄소 흡수량 산정)

  • Park, Eun-Jin;Kang, Kyu-Yi
    • Korean Journal of Environment and Ecology
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    • v.24 no.5
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    • pp.591-600
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    • 2010
  • We estimated and compared C storages and annual $CO_2$ uptakes by 9 dominant tree species planted along the streets. DBH and age by tree species were measured in the sites selected considering the planting status and distributions of tree species, and biomass, C storage, growth rate, and annual $CO_2$ uptake were estimated for each species. As a result, L. tulipifera, M. glyptostroboides, P. occidentalis were classified into fast-growing group, P. serrulata, G. biloba, Z. serrata, S. japonica, A. palmatum showed intermediate growth rates, and P. densiflora was slow-growing. Average C storage per tree was 205kgC/tree and ranged from 518kgC/tree(L. tulipifera) to 41kgC/tree(P. densiflora). Average annual $CO_2$ uptake by urban street trees over their lifespan ranged from $7.6kgCO_2$/tree/y to $99.1kgCO_2$/tree/y and L. tulipifera was the greatest, followed by glyptostroboides and P. occidentalis, and P. densiflora was the lowest. Total annual $CO_2$ uptake by all street trees in Gyeonggi-do, estimated based on the annual $CO_2$ uptake by each species, was as small as approximately 0.67% of that by forest in Gyeonggi-do. However, urban trees are still important because forest area continues to decrease and urbanization occurs annually in Gyeonggi-do, and should be managed considering their multi-functional aspects, including mitigation of heat island effect and building energy saving(indirect $CO_2$ uptake).

Enhanced Light Harvesting by Fast Charge Collection Using the ITO Nanowire Arrays in Solid State Dye-sensitized Solar Cells

  • Han, Gill Sang;Yu, Jin Sun;Jung, Hyun Suk
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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    • pp.463-463
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    • 2014
  • Dye-sensitized solar cells (DSSCs) have generated a strong interest in the development of solid-state devices owing to their low cost and simple preparation procedures. Effort has been devoted to the study of electrolytes that allow light-to-electrical power conversion for DSSC applications. Several attempts have been made to substitute the liquid electrolyte in the original solar cells by using (2,2',7,7'-tetrakis (N,N-di-p-methoxyphenylamine)-9-9'-spirobi-fluorene (spiro-OMeTAD) that act as hole conductor [1]. Although efficiencies above 3% have been reached by several groups, here the major challenging is limited photoelectrode thickness ($2{\mu}m$), which is very low due to electron diffusion length (Ln) for spiro-OMeTAD ($4.4{\mu}m$) [2]. In principle, the $TiO_2$ layer can be thicker than had been thought previously. This has important implications for the design of high-efficiency solid-state DSSCs. In the present study, we have fabricated 3-D Transparent Conducting Oxide (TCO) by growing tin-doped indium oxide (ITO) nanowire (NWs) arrays via a vapor transport method [3] and mesoporous $TiO_2$ nanoparticle (NP)-based photoelectrodes were prepared using doctor blade method. Finally optimized light-harvesting solid-state DSSCs is made using 3-D TCO where electron life time is controlled the recombination rate through fast charge collection and also ITO NWs length can be controlled in the range of over $2{\mu}m$ and has been characterized using field emission scanning electron microscopy (FE-SEM). Structural analyses by high-resolution transmission electron microscopy (HRTEM) and X-Ray diffraction (XRD) results reveal that the ITO NWs formed single crystal oriented [100] direction. Also to compare the charge collection properties of conventional NPs based solid-state DSSCs with ITO NWs based solid-state DSSCs, we have studied intensity modulated photovoltage spectroscopy (IMVS), intensity modulated photocurrent spectroscopy (IMPS) and transient open circuit voltages. As a result, above $4{\mu}m$ thick ITO NWs based photoelectrodes with Z907 dye shown the best performing device, exhibiting a short-circuit current density of 7.21 mA cm-2 under simulated solar emission of 100 mW cm-2 associated with an overall power conversion efficiency of 2.80 %. Finally, we achieved the efficiency of 7.5% by applying a CH3NH3PbI3 perovskite sensitizer.

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THE INFLUENCE OF IRM TEMPORARY RESTORATIONS ON MARGINAL MICROLEAKAGE OF DENTIN ADHESIVES (IRM 임시수복이 상아질 접착제의 변연 미세누출에 미치는 영향)

  • Cho, Young-Gon;Kim, Hyun-Kyung;Lee, Young-Gon
    • Restorative Dentistry and Endodontics
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    • v.28 no.1
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    • pp.1-10
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    • 2003
  • This study investigated the influence of IRM on marginal microleakage of 5th generation adhesives. Class V cavities with gingival margins in dentin were prepared on both buccal and lingual surfaces of 60 extract-ed human molar teeth. Prepared teeth were randomly divided into six groups. Group 1 and 4 received no temporary restoration with IRM. Group 2 and 5 were covered with IRM mixed at P/L ratio(10g/1g). Group 3 and 6 were covered with IRM mixed at P/L ratio(10g/2g). The temporary restorations were removed mechanically with an ultrasonic scaler after one-week storage in distilled water. The cavities were restored using one of two adhesives and composites ; Single Bond/Filtek Z 250(Croup 1, 2 and 3), UniFil Bond/UniFil F(Group 4, 5 and 6). Following one day storage in distilled water, the restored teeth were thermocycled for 500 cycles(between $5^{\circ}C{\;}and{\;}55^{\circ}C$) and immersed in 2 % methylene blue for dye penetration testing. The results were analysed using Kruskal-Wallis Test, Mann-Whitney and Wilcoxon signed ranked test at a significance level of 0.05. The results of this study were as follows 1. Ranking of mean microleakage scores at the enamel margins was Group 10.05) 4. At the dentin margins, the microleakage of the group not pretreated with IRM was lower than that of the group pretreated with IRM. And the microleakage of UniFil Bond was lower than that of Single Bond. 5. Compared with microleakages between the enamel and dentin margins of each groups, Group 1, 2, 3, 4, 5 and 6 at dentin margin were higher microleakage than those at enamel margin. There were significant difference between enamel and dentin microleakage of Group 2 and 3(p<0.05).

Theoretical Exploration of a Process-centered Assessment Model for STEAM Competency Based on Learning Progressions (학습발달과정에 근거한 과정중심 STEAM 역량 평가 모델에 대한 이론적 탐색)

  • Ryu, Suna;Kwak, Youngsun;Yang, Sung Ho
    • Journal of Science Education
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    • v.42 no.2
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    • pp.132-147
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    • 2018
  • The goal of this research is to suggest a theoretical process-centered assessment model based on Learning Progressions of key competencies in the context of STEAM instructions. The "Process-Products Combined Module-type (P2CM) STEAM Assessment Model (P2CM STEAM Assessment Model, hereafter) can be used both as an instructional model and as an assesment model, applicable for various STEAM topics and instructional types. consists of 3 axes. The first X axis stands for 4C competencies that should be emphasized through STEAM instruction. The second Y axis stands for the types and the hierarchy of STEAM instructions. The third Z axis stands for the assessment standards based on LP. We also exemplified an assessment module combined creativity competency with creativity-based instruction based on . Based on the research results, we suggested elaboration of assessment models based on Korean LP research outcomes, development and supply of formative assessment models through field-based in-depth research, modification of formative assessment models with the participation of teacher communities and in-service teachers, and the necessity of further research on assessment models for tracking LP.

THE COMPARISON OF POLYMERIZATION OF COMPOSITE RESIN INFLUENCED BY CURING DEPTH AND SHADE (광중합 복합레진의 색상과 깊이에 따른 중합도의 비교)

  • Choi, Kung-Ho;Lee, Ju-Hyun;Park, Ho-Won
    • Journal of the korean academy of Pediatric Dentistry
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    • v.31 no.2
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    • pp.280-289
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    • 2004
  • Adequate polymerization is a crucial factor in obtaining optimal physical properties and clinical performance of resin composite restorative materials. The purpose of this study was to determine the effectiveness of shade and depth on dental composite resin polymerized with plasma arc curing unit employing FTIR and microhardness. From this experiment, the following results were obtained : 1. The light transmission and microhardness by mode 6 in plasma arc curing were similar to by 20 secs in halogen light curing. 2. The experimental groups of A1, A2, A3, A3.5 were not signifcant difference to light transmission and microhardness on surface and 2mm depth, but were significant difference on 3mm and 4mm depth. Especially light transmission and microhardness were small in darker shade and deeper thickness. 3. Compared with depth cure, uncured monomer amount increased at more than 2mm depth. 4. The light transmission by FTIR and polymerization by microhardness were significant corelation.

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