• Title/Summary/Keyword: Near-rings

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Thermodynamic and Kinetic Study on the Protonation of Free Base Tetraphenylporpyrin Derivatives in Solution

  • 유종완;유병수;정갑상;최호섭;유수창
    • Bulletin of the Korean Chemical Society
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    • v.19 no.4
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    • pp.439-444
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    • 1998
  • The protonation of tetraphenylporphyrin (TPP) in acidic organic solutions was analyzed by acid titrimetric and temperature-dependent absorption measurements. Competition between the protonation of free base TPP $(TPPH_2)$ and the solvation of proton by near solvent molecules determines the equilibrium of the diprotonated TPP $(TPPH_4^{2+})$ formation. The diprotonated TPP exists as an ion pair complex with the acid counterions, which are found to affect the degree of red shift of the Soret band. The rotation of the phenyl rings also plays an important role in the diprotonation, as suggested by the decrease in the degree of diprotonation for the fluorophenyl TPP derivatives whose phenyl ring rotation is significantly hindered relative to normal TPP. The difference of fluorescence lifetime between $TPPH_2 \;({\pi}_{FL}=19.6\;ns)\; and\; TPPH_4^{2+} \;({\pi}_{FL}=2.1 \;ns)$ was used advantageously to measure the rate of protonation in the excited state. The protonation of TPPH2 are found to occur much slower than the diffusion of protons from bulk solution to the porphyrin ring. The monoprotonated TPP is suggested to be the transient species for the diprotonation process.

Thick Accretion Disk and Its Super Eddington Luminosity around a Spinning Black Hole

  • Jang, Uicheol;Kim, Hongsu;Yi, Yu
    • Journal of Astronomy and Space Sciences
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    • v.38 no.1
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    • pp.39-44
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    • 2021
  • In the general accretion disk model theory, the accretion disk surrounding an astronomical object comprises fluid rings obeying Keplerian motion. However, we should consider relativistic and rotational effects as we close in toward the center of accretion disk surrounding spinning compact massive objects such as a black hole or a neutron star. In this study, we explore the geometry of the inner portion of the accretion disk in the context of Mukhopadhyay's pseudo-Newtonian potential approximation for the full general relativity theory. We found that the shape of the accretion disk "puffs up" or becomes thicker and the luminosity of the disk could exceed the Eddington luminosity near the surface of the compact spinning black hole.

Ring Formation of Furan on Epitaxial Graphene (단결정 그라핀 위에서의 퓨란의 고리모양 형성)

  • Kim, Ki-Jeong;Yang, Se-Na;Park, Young-Chan;Lee, Han-Koo;Kim, Bong-Soo;Lee, Han-Gil
    • Journal of the Korean Vacuum Society
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    • v.20 no.4
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    • pp.252-257
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    • 2011
  • The ring formation and electronic properties of furan adsorbed on graphene layers grown on 6H-SiC (0001) has been investigated using atomic force microscopy (AFM), near edge X-ray absorption fine structure (NEXAFS) spectra for the C K-edge, and core level photoemission spectroscopy (CLPES). Moreover, we observed that furan molecules adsorbed on graphene could be used for chemical functionalization via the lone pair electrons of the oxygen group, allowing chemical doping. We also found that furan spontaneously form rings with one of three different bonding configurations and the electronic properties of the ring formed by furan on graphene can be described using by AFM, NEXAFS and CLPES, respectively.

A Single Cell Multimedia Fate Model for Endocrine Disrupting Chemicals

  • Park, Kyunghee;Junheon Youn;Daeil Kang;Lee, Choong;Lee, Dongsoo;Jaeryoung Oh;Sunghwan Jeon;Jingyun Na
    • Proceedings of the Korea Society of Environmental Toocicology Conference
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    • 2003.05a
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    • pp.149-149
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    • 2003
  • To understand environmental paths of the transport and accumulation of endocrine disrupting chemicals (EDCs), a single cell multimedia fate model has been constructed and evaluated. The EDCs of concern were PAHs, Organochlorine Pesticides (OCPs), PCBs, Alkyl phenols, and phthalates. An evaluation model was designed for the multimedia distribution, including air, water, soil, sediment and vegetation. This model was verified using reported values and via monitoring data. Based on collected data, the distribution trends of EDCs with respect to environmental media were analyzed. Those results have applied to the model for the prediction of the spatial and temporal distribution of EDCs in Seoul. Especially, phenol compound, phthalates, PAHs, PCBs and organochlorine pesticides were estimated and the model was verified. This model was successfully conducted to environmental media, such as air (vapor and suspended particles), soils (forest soil, bare soil, and cement-concrete covered soil), water (dissolved and suspended solids), sediment, trees (deciduous and coniferous). The discrepancies between the model prediction and the measured data are approximately within or near a factor of 10 for the PAHs of three rings through that of six rings, implying that multimedia distribution of the PAHs could be predicted with a factor of 10. Concerning about the air equilibrium may be assumed, a fugacity at steady state is similar in all environmental media. Considering the uncertainties of this model, the use of equilibrium models may be sufficient for assessing chemical fates. In this study, a suggestion was made that modeling and estimation of chemicals in environmental multimedia be rigorously evaluated using the measured flux data. In addition, these data should be obtained, for example, from the precise and standardized inventory of the target chemicals. The model (EDC Seoul) will be refined in an on-going research effort and will be used to support decision-making concerning the management of EDCs.

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Chemistry and Crystallographic Studies of Metal Ion Exchanged Zeolite X. Ⅰ. The Crystal Structure of Fully Dehydrated and Fully $K^+$-Exchanged Zeolite X, $K_{92}$-X

  • 장세복;김양
    • Bulletin of the Korean Chemical Society
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    • v.16 no.6
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    • pp.539-542
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    • 1995
  • The crystal structure of K92-X (K92Al92Si100O384), a=25.128(1) Å, dehydrated at 360 ℃ and 2X 10-6 Torr, has been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd&bar{3} at 21(1) ℃. The structure was refined to the final error indices R1=0.044 and Rw=0.039 with 242 reflections for which I<3σ(I). In this structure, ninety-two K+ ions are located at the five different crystallographic sites. Sixteen K+ ions are located at the centers of the double six rings (site I; K(1)-O(3)=2.65(2) Å and O(3)-K(1)-O(3)=92.0(6)°). About twelve K+ ions lie at site I' in the sodalite cavity opposite double six rings (D6R's) and these K+ ions are recessed ca. 1.62 Å into the sodalite cavity from their O(3) plane (K(2)-O(3)=2.74(2) Å, O(3)-K(2)-O(3)=88.5(8)°). About thirty-two K+ ions are located at the site II in the supercage and these K+ ions are recessed ca. 1.20 Å into the supercage from their O(2) plane (K(3)-O(2)=2.64(2) Å, and O(2)-K(3)-O(2)=101(1)°). About twenty-two K+ ions lie at the site III in the supercage opposite 4-ring ladder and the remaining ten K+ ions lie at the site III' near the 4-ring ladder in the supercage (K(4)-O(4)=2.88(3) Å, O(4)-K(4)-O(4)=79.8(9)°, K(5)-O(4)=2.8(2) Å, and O(4)-K(5)-O(4)=68(5)°).

Study on the Mobility of Cd Ion Using Extraction by Solutions in Stem Wood of Pinus densiflora L. (용매추출(溶媒抽出)에 의한 소나무(Pinus densiflora L.) 수간부(樹幹部)에서의 Cd 이동성(移動性)에 관(關한) 연구(硏究))

  • Shin, Kyungwon;Cho, Namhoon;Kim, Jeong-Gyu
    • Journal of Korean Society of Forest Science
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    • v.89 no.1
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    • pp.77-84
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    • 2000
  • In order to understand the chemical binding forms of Cd in terms of its binding strength in wood, the radial distribution of it through dendroanalysis and its different chemical fractions in trunk wood of mature red pine(Pinus densiflora L.) trees grown in a relatively unpolluted area, in Kangwon-Province, were examined. Total Cd concentration in stem wood was determined by dry digestion and $H_2O$ and 0.01 M solutions of citric acid, malic acid, $CaCl_2$, $MgCl_2$, $Na_2EDTA$ were used as extracting solutions for Cd. Extracting efficiencies of applied solutions were expressed as % of Cd concentration extracted by $Na_2EDTA$ which extracted all Cd instead of Cd total concentration. Total concentration of Cd decreased from the innermost rings near pith towards the the outermost rings near cambium. Especially through the transition zone this tendency was observed clearly. $H_2O$ was the least effective extractant of Cd, then extracting efficiency increased in the order $MgCl_2$ < $CaCl_2$ $Na_2EDTA$ (extracted all Cd). According to the radial position, extracting efficiency of Cd was ranging from 7 to 30% by $H_2O$ and even from 60 to 95% by citric acid. The Cd extracting efficiencies of $H_2O$ and organic acids increased continuously from the stem center to outermost annual rings, whereas salts showed somewhat different tendency, suddenly decreasing near the outermost ring. The results are discussed with regard to the different chemical binding forms of Cd and the mobility of Cd in wood and comparable with ones in previous studies on Pinus sylvestris and Quercus patraea. According to the results, usefulness of radial distribution pattern of Cd in pine tree trunks for retrosective biomonitoring is questioned.

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Synthesis and Crystal Structure of Ag4Br4 Nanoclusters in the Sodalite Cavities of Fully K+-Exchanged Zeolite A (LTA)

  • Lim, Woo-Taik;Choi, Sik-Young;Kim, Bok-Jo;Kim, Chang-Min;Lee, In-Su;Kim, Seok-Han;Heo, Nam-Ho
    • Bulletin of the Korean Chemical Society
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    • v.26 no.7
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    • pp.1090-1096
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    • 2005
  • $Ag_4Br_4$ nanoclusters have been synthesized in about 75% of the sodalite cavities of fully $K^+$-exchanged zeolite A (LTA). An additional KBr molecule is retained in each large cavity as part of a near square-planar $K_4Br^{3+}$ cation. A single crystal of $Ag_{12}$-A, prepared by the dynamic ion-exchange of $Na_{12}$-A with aqueous 0.05 M $AgNO_3$ and washed with $CH_3OH$, was placed in a stream of flowing 0.05 M KBr in $CH_3OH$ for two days. The crystal structure of the product ($K_9(K_4Br)Si_{12}Al_{12}O_{48}{\cdot}0.75Ag_4Br_4$, a = 12.186(1) $\AA$) was determined at 294 K by single-crystal X-ray diffraction in the space group Pm m. It was refined with all measured reflections to the final error index $R_1$ = 0.080 for the 99 reflections for which $F_o\;{\gt}\;4_{\sigma}\;(F_o)$. The thirteen $K^+$ ions per unit cell are found at three crystallographically distinct positions: eight $K^+$ ions in the large cavity fill the six-ring site, three $K^+$ ions fill the eight-rings, and two $K^+$ ions are opposite four-rings in the large cavity. One bromide ion per unit cell lies opposite a four-ring in the large cavity, held there by two eight-ring and two six-ring $K^+$ ions ($K_4Br^{3+}$). Three $Ag^+$ and three $Br^-$ions per unit cell are found on 3-fold axes in the sodalite unit, indicating the formation of nano-sized $Ag_4Br_4$ clusters (interpenetrating tetrahedra; symmetry $T_d$; diameter ca. 7.9 $\AA$) in 75% of the sodalite units. Each cluster (Ag-Br = 2.93(3) $\AA$) is held in place by the coordination of its four $Ag^+$ ions to the zeolite framework (each $Ag^+$ cation is 2.52(3) $\AA$ from three six-ring oxygens) and by the coordination of its four $Br^-$ ions to $K^+$ ions through six-rings (Br-K = 3.00(4) $\AA$).

Two Crystal Structures of Dehydrated $Ag^{+}$- and $Ca^{2+}$-Exchanged Zeolite $A,\;Ag_{12-2x}Ca_x-A\;(x=2\;and\;3)$ Treated with Cesium Vapor (탈수한 $Ag^{+}$ 이온과 $Ca^{2+}$ 이온으로 치환한 제올라이트 $A,\;Ag_{12-2x}Ca_x-A\;(x=2\;and\;3)$를 Cs 증기로 처리한 결정구조)

  • Song, Seung Hwan;Kim, Yang
    • Journal of the Korean Chemical Society
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    • v.38 no.9
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    • pp.621-627
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    • 1994
  • Two crystal structures of dehydrated, $Ag^{+}$ and $Ca^{2+}$-exchanged zeolite A treated at $250^{\circ}C$ with 0.15 torr of Cs vapor have been determined by single-crystal X-ray diffraction technique in the cubic space group $Pm{\bar\3m$ at $21(1)^{\circ}C$ (a = 12.344(2) $\AA$ and 12.304(2) $\AA$). Their structures were refined to the final error indices, R (weighted), of 0.091 with 180 reflections, and 0.093 with 179 reflections, respectively, for which I > $3\sigma(I).$ In each structure, Cs species are found at four different crystallographic sites: 3 $Cs^{+}$ ions per unit cell are located at 8-ring centers, ca. 6.81∼7.14 $Cs^{+}$ ions are found on opposite 6-rings on threefold axes in the large cavity, ca. 1.93∼2.03 $Cs^{+}$ ions are found on threefold axes in the sodalite unit, and 0.53∼0.66 $Cs^{+}$ ions lie on opposite 4-rings. Also, ca. 4.12∼4.27 Ag atoms are located near the center of the large cavity. In these structures, excess cesium atoms in a unit cell are associated with other $Cs^{+}$ ions on a single threefold axis to form the linear cationic cluster $(Cs_4)^{3+}$. By blocking 8-rings, the $Cs^{+}$ ions may have prevented silver atoms from migrating out of the structure. The Ag atoms are likely to have formed hexasilver clusters at the centers of the large cavities. Each hexasilver cluster is stabilized by coordination to 14 $Cs^{+}$ ions.

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Crystal Structures of $Cd_6-A$ Dehydrated at $750^{\circ}C$ and Dehydrated $Cd_6-A$ Reacted with Cs Vapor ($750^{\circ}C$ 에서 탈수한 $Cd_6-A$의 결정구조와 이 결정을 세슘 증기로 반응시킨 결정구조)

  • Se Bok Jang;Yang Kim
    • Journal of the Korean Chemical Society
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    • v.37 no.2
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    • pp.191-198
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    • 1993
  • The crystal structures of $Cd_{6-}A$ evacuated at $2{\times}10^{-6}$ torr and $750^{\circ}C$ (a = 12.204(1) $\AA$) and dehydrated $Cd_{6-}A$ reacted with 0.1 torr of Cs vapor at $250^{\circ}C$ for 12 hours (a = 12.279(1) $\AA$) have been determined by single crystal X-ray diffraction techniques in the cubic space group Pm3m at $21(1)^{\circ}C.$ Their structures were refined to final error indices, $R_1=$ 0.081 and $R_2=$ 0.091 with 151 reflections and $R_1=$ 0.095 and $R_2=$ 0.089 with 82 reflections, respectively, for which I > $3\sigma(I).$ In vacuum dehydrated $Cd_{6-}A$, six $Cd^{2+}$ ions occupy threefold-axis positions near 6-ring, recessed 0.460(3) $\AA$ into the sodalite cavity from the (111) plane at O(3) : Cd-O(3) = 2.18(2) $\AA$ and O(3)-Cd-O(3) = $115.7(4)^{\circ}.$ Upon treating it with 0.1 torr of Cs vapor at $250^{\circ}C$, all 6 $Cd^{2+}$ ions in dehydrated $Cd_{6-}A$ are reduced by Cs vapor and Cs species are found at 4 crystallographic sites : 3.0 $Cs^+$ ions lie at the centers of the 8-rings at sites of $D_{4h}$ symmetry; ca. 9.0 Cs+ ions lie on the threefold axes of unit cell, ca. 7 in the large cavity and ca. 2 in the sodalite cavity; ca. 0.5 $Cs^+$ ion is found near a 4-ring. In this structure, ca. 12.5 Cs species are found per unit cell, more than the twelve $Cs^+$ ions needed to balance the anionic charge of zeolite framework, indicating that sorption of Cs0 has occurred. The occupancies observed are simply explained by two unit cell arrangements, $Cs_{12}-A$ and $Cs_{13}-A$. About 50% of unit cells may have two $Cs^+$ ions in sodalite unit near opposite 6-rings, six in the large cavity near 6-ring and one in the large cavity near a 4-ring. The remaining 50% of unit cells may have two Cs species in the sodalite unit which are closely associated with two out of 8 $Cs^+$ ions in the large cavity to form linear $(Cs_4)^{3+}$ clusters. These clusters lie on threefold axes and extend through the centers of sodalite units. In all unit cells, three $Cs^+$ ions fill equipoints of symmetry $D_{4h}$ at the centers of 8-rings.

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Anatomical Characteristics of Paulownia tomentosa Root Wood

  • Qi, Yue;Jang, Jaehyuk;Hidayat, Wahyu;Lee, Aehee;Park, Sehwi;Lee, Seunghwan;Kim, Namhun
    • Journal of the Korean Wood Science and Technology
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    • v.44 no.2
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    • pp.157-165
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    • 2016
  • This study investigated several anatomical characteristics of Paulownia tomentosa roots. The root wood was separated into three parts from stem base (top, middle, and base) at different positions below ground. Qualitative anatomical data suggested that the growth rings in earlywood and latewood were structurally different. Furthermore, the root wood vessels were found having 2 to 3 radial multiples and they were appeared in the form of clusters. In addition, some sheath cells and septate axial parenchyma were observed. Regarding the quantitative anatomical characteristics, vessel and ray numbers per $mm^2$, as well as ray width and height differed significantly among the top, middle, and base rood wood parts. However, there were no significant differences in vessel diameters, cell wall thickness, and width and length of wood fibers among those parts. The crystallinity of the root top part was slightly higher than that of the middle and base parts. Furthermore, the vessel numbers, ray numbers, and ray width and height in the near pith (NP) area were higher compared to those in the near bark (NB) area. However, the fiber width and fiber length at NP were lower than those at NB. Overall, this study demonstrated some significant differences in the anatomical characteristics of the top, middle, and base parts of root wood from Paulownia tomentosa.