• Title/Summary/Keyword: Axial coordination

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Syntheses and Characterization of Cr(III)-Hydrogensalicylato and -Hydroxonitrophenolato Tetraaza Macrocyclic Complexes

  • Byun, Jong-Chul;Yoon, Chang-Hoon;Mun, Dae-Hun;Kim, Ki-Ju;Park, Yu-Chul
    • Bulletin of the Korean Chemical Society
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    • v.27 no.5
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    • pp.687-693
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    • 2006
  • Chromium(III) complexes, cis-[Cr([14]-decane)$(HOC _6H _4COO) _2$]$ClO _4$ I and cis-[Cr([14]-decane)(OH) $(OC _6H _4NO _2)$]$ClO _4{\cdot}H _2O$ II ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) are synthesized and structurally characterized by a combination of elemental analysis, conductivity, IR and VIS spectroscopy, and X-ray crystallography. The complexes crystallizes in the monoclinic space groups, $C2 _1$/a in I and $P2 _1$/n in II. Analysis of the crystal structure of complex I reveals that central chromium(III) ion has a distorted octahedral coordination environment and two hydrogensalicylato ligands are unidentate to the chromium(III) ion via the carboxyl groups in the cis-position. For monomeric complex I the hydrogensalicylato coordination geometry is as follows: Cr-O(average) = 1.984(3) $\AA$;Cr-N range = 2.105(3)-2.141(4) $\AA$;C(24)-O(4) = 1.286(5) $\AA$;N(2)-Cr-N(4) (equatorial position) = 96.97(15)${^{\circ}}$; N(1)-Cr-N(3) (axial position) = 168.27(15)${^{\circ}}$; O(1)-Cr-O(4) = 85.70(13)${^{\circ}}$. The crystal structure of II has indicated that chromium(III) ion is six-coordinated by four secondary amines of the macrocycle, hydroxide anion and nitrophenolate anion.

CT Simulation후 DRR film를 이용한 치료중심점을 재확인하기 위한 Conventional simulation의 유용성에 대한 분석

  • Park, Gwang-Ho;Im, Yeong-Seok;Kim, Jeong-Man
    • The Journal of Korean Society for Radiation Therapy
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    • v.11 no.1
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    • pp.100-105
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    • 1999
  • Purpose : When the value of X,Y,Z coordination of the isocenter are reallocated from an arbitrary point using DRR (Digitally Reconstructed Radiographs) image in CT Simulation, conventional simulation is normally performed to verify the accuracy of this reallocation of the isocenter through the fluroscopy. The purpose of our experiment is to determine whether repeated test of the verification is necessary or not, and to analyze errors of reallocation with respect to the body region and the beam projection, if necessary, Material and Method : For 200 simulation patient, an arbitrary point is marked on each body and axial scaning is performed using CT, and treatment planing is done by drawing tumor and target volume on each slice. Using the planing data and the reallocated point of the isocenter, DRR image can be obtained and the final isocenter are marked on the patient's skin. In order to verify this reallocation of X,Y.Z coordination from CT simulation, We measure and evaluate the errors of these value on the fluoroscopy monitor and systematize them by classifying according to each body region (Brain, Neck and SCL, Lung, Esophagus, abdomen, Breast and Pelvis) and each beam projection {AP(PA), Supine, Prone and conformal : etc. } Conclusion : Isocenters are shifted by 3-5 mm in the case of Neck & SCL, Breast. at Abdomen, while noticeable differences are not found in other regions. Also, there are not correlations between the errors and the body regions or beam projections. However, our experiment intends to decide whether the procedure of verification is necessary on the vase of time and economy. It is regretful that we could not fully analyze the geometrical errors of DRR image and visual errors from the divergence. In conclusion, according to how much doctor consider tumor margin in drawing tumor and target volume, the meaning of analysis on the reallocation of isocenter should be reinterpreted, (which depends on the experience and capability of doctors)

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Cr(III)-Tetraaza Macrocyclic Complexes Containing Auxiliary Ligands (Part IV); Synthesis and Characterization of Cr(III)-Acetylacetonato, -Malonato and -Oxalato Macrocyclic Complexes

  • Byun, Jong-Chul;Han, Chung-Hun
    • Bulletin of the Korean Chemical Society
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    • v.26 no.9
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    • pp.1395-1402
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    • 2005
  • The reaction of cis-[Cr([14]-decane)$(OH)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = acetylacetonate (acac), oxalate (ox) or malonate (mal)} leads to a new cis-[Cr([14]-decane)(acac)]$(ClO_4)_2{\cdot}(1/2)H_2O\;(1),\;cis-[Cr([14]-decane)(ox)]ClO_4{\cdot}(1/2)H_2O\;(2)\;or\;cis-[Cr([14]-decane)(mal)]ClO_4{\cdot}(1/4)H_2O\;(3)$. These complexes have been characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. Analysis of the crystal structure of cis-[Cr([14]-decane)(acac)]$(ClO_4)_2{\cdot}(1/2)H_2O$ reveals that central chromium(III) has a distorted octahedral coordination environment and two acetylacetonate-oxygen atoms are bonded to the chromium(III) ion in the cis positions. The angle $N_{axial}-Cr-N_{axial}$ deviates by $11^{\circ}$ from the ideal value of $180^{\circ}$ for a perfect octahedron. The bond angle O-Cr-O between the chromium(III) ion and the two acetylacetonate-oxygen atoms is close to $90^{\circ}$. The bond lengths of Cr-O between the chromium and the acetylacetonate-oxygen atoms are 1.950(3) and 1.954(2) $\AA$. They are shorter than those between chromium and nitrogen atoms of the macrocycle. The IR spectra of 1, 2 and 3 display bands at 1560 {ν (C=O)}, 1710 {${\nu}_{as}$(OCO)} and 1660 $cm^{-1}$ {${\nu}_{as}$(OCO)} attributed to the acac, ox and mal auxiliary ligands stretching vibrations, respectively.

Synthesis and Characterization of Zinc(II) Tetraaza Macrocyclic Complexes with Aquo and Nitrate Ligands

  • Lim, In-Taek;Kim, Chong-Hyeak;Choi, Yoon-Mi;Park, Jong-Hoon;Choi, Ki-Young
    • Journal of the Korean Chemical Society
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    • v.62 no.1
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    • pp.14-18
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    • 2018
  • The complexes $[Zn(L)(H_2O)_2]{\cdot}2NO_2$ (1) and $[Zn(L)(NO_3)_2]$ (2) (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo $[14,4,0^{1.18},0^{7.12}]$docosane) have been synthesized and structurally characterized. The compound 1 crystallizes in the monoclinic system $P2_1/c$ with a = 8.74650(10), b = 18.6880(3), c = $7.96680(10){\AA}$, ${\beta}=109.1920(10)^{\circ}$, $V=1229.84(3){\AA}^3$, Z = 2. The compound 2 crystallizes in the monoclinic system P1 with a = 8.1292(5), b = 8.9244(5), c = $9.1398(5){\AA}$, ${\alpha}=68.035(2)$, ${\beta}=70.109(2)$, ${\gamma}=75.649(3)^{\circ}$, $V=572.70(6){\AA}^3$, Z = 1. The crystal structures of the compounds 1 and 2 show a distorted octahedral coordination geometry around the zinc(II) ion, with four secondary amines and two oxygen atoms of the two water and two nitrate ligands at the axial position. The TGA behaviors of the complexes are significantly affected by the nature of the tetraaza macrocycle and the axial ligands.

Cr(III)-Tetraaza Macrocyclic Complexes Containing Auxiliary Ligands (Part III); Synthesis and Characterization of Cr(III)-Isothiocyanato, -Azido and -Chloroacetato Macrocyclic Complexes

  • Byun, Jong-Chul;Han, Chung-Hun;Park, Yu-Chul
    • Bulletin of the Korean Chemical Society
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    • v.26 no.7
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    • pp.1044-1050
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    • 2005
  • The reaction of cis-[Cr([14]-decane)($OH_2)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = isothiocyanate ($NCS^-$), azide ($N3^-$) or chloroacetate(caa)} leads to a new cis-[Cr([14]-decane)($NCS)_2]ClO_4{\cdot}H_2O$ (1), cis-[Cr([14]-decane)($N_3)_2]ClO_4$ (2) or cis-[Cr([14]-decane)($caa)_2]ClO_4$ (3). These complexes have been characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. Analysis of the crystal structure of cis-[Cr([14]-decane)($NCS)_2]ClO_4{\cdot}H_2O$ reveals that central chromium(III) has a distorted octahedral coordination environment and two $NCS^-$anions are bonded to the chromium(III) ion via the Ndonor atom in the cis positions. The angle $N_{axial}-Cr-N_{axial}$ deviates by 13$^{\circ}$ from the ideal value of 180$^{\circ}$ for a perfect octahedron. The bond angle N-Cr-N between the Cr(III) ion and the two nitrogen atoms of the isothiocyanate ligands is close to 90$^{\circ}$. The bond lengths of Cr-N between the chromium and $NCS^-$groups are 1.964(5) and 2.000(5) $\AA$. They are shorter than those between chromium and nitrogen atoms of the macrocycle. The IR spectra of 1, 2 and 3 display bands at 2073, 1344 and 1684 $cm^{-1}$ attributed to the $NCS^-$, ${N_3}^-$ and caa groups stretching vibrations, respectively.

Numerical Evaluation of Dynamic Behavior of Retaining Structure in a Deep Excavation (수치해석을 통한 대심도 흙막이 시설물의 동적 거동 평가)

  • Yang, Eui-Kyu;Yu, Sang-Hwa;Kim, Jong-Kwan;Kim, Dong-Chan;Kim, Seok-Jung;Han, Jin-Tae
    • Journal of the Korean Geotechnical Society
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    • v.37 no.12
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    • pp.89-105
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    • 2021
  • In this paper, feasibility study was carried out to evaluate necessity of seismic design of earth retaining structures in a deep excavation. Dynamic behavior of retaining system was analyzed using FLAC, a finite difference analysis program. It was shown that maximum bending moments of retaining walls and axial forces of supports were increased up to 98% and 87% during earthquake, respectively, compared to final excavation step, which indicates that dynamic earth pressure has a large effect on a retaining system. The stability of retaining system designed according to current design specifications was evaluated using structural forces obtained by numerical analysis, and effect of earthquake loading on structural design was analyzed.

Evaluation of the Effect of Waveform Micropiles on Reinforcement of Foundation Structures Through Field Load Tests (현장 재하시험을 통한 파형 마이크로파일의 기초보강 효과 분석)

  • Baek, Sung-Ha;Han, Jin-Tae;Kim, Seok-Jung;Kim, Joonyoung
    • Journal of the Korean Geotechnical Society
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    • v.39 no.3
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    • pp.29-40
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    • 2023
  • In this study, we investigated the reinforcing effects of waveform micropiles in a stratigraphic setting comprising buried soil, weathered soil, and weathered rock. We conducted a series of field load tests and determined that waveform micropiles exhibited sufficient bearing capacity through frictional resistance in the soil layer and demonstrated favorable constructability in conditions with deep bedrock layers. Moreover, the vertical stiffness of waveform micropiles was approximately 2.2 times higher than that of conventional micropiles when subjected to the same design load. Pile group load tests comprising conventional and waveform micropiles showed that micropiles with higher stiffness carried a greater proportion of the load. Although there was no significant difference in the bearing capacity between conventional and waveform micropiles under the same design load, waveform micropiles with higher stiffness showed a load-carrying capacity 1.7 to 3.2 times greater than that of conventional micropiles. These findings suggest that waveform micropiles can be effectively used for foundation reinforcement and reduce the risk of foundation failure when increased loads due to modifications such as expansion remodeling are expected.

Cr(III)-Tetraaza Macrocyclic Complexes Containing Auxiliary Ligands (Part II); Synthesis and Characterization of Cr(III)-Citrato Macrocyclic Complex

  • Byun, Jong-Chul;Park, Yu-Chul;Youn, Jeung-Su;Han, Chung-Hun;Lee, Nam-Ho
    • Bulletin of the Korean Chemical Society
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    • v.26 no.4
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    • pp.634-640
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    • 2005
  • The reaction of cis-[Cr([14]-decane)(OH$_2)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = citrate(cit)} leads to a new dimeric complex cis-[{Cr([14]-decane)($\mu$-cit)}$_2](ClO_4)_2$. This binuclear complex has been structurally characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. Analysis of the crystal structure of cis-[{Cr([14]-decane)($\mu$-cit)})($_2]^+$ reveals that each chromium has a distorted octahedral coordination environment and citrato ligands are monodentate to the two chromium atoms via the carboxyl groups. For dimeric complex the bridging geometry is as follows: Cr$\ldots$Cr = 7.361 $\AA$; Cr-O(average) = 1.958 (8) $\AA$; Cr-N range = 2.108 (9)-2.147(9) $\AA$; N(1)-Cr-N(3) (equatorial position) = 98.0(4)$^{\circ}$; N(2)-Cr-N(4) (axial position) = 166.4(4)$^{\circ}$; O(1)-Cr-N(2) = 98.1(4)$^{\circ}$; O(3)-Cr-N(4) = 96.6(3)$^{\circ}$; O(1)-Cr-O(3) = 90.4$^{\circ}$. The FAB mass spectrum of the dimeric complex displays peak due to the molecular ions cis-[{Cr([14]-decane)($\mu$-cit)})($_2]^+$ at m/z 1053.

Self-Assembly of Three-Dimensional Copper(II) Macrocyclic Complex with 2,5-Pyridinedicarboxylate Linked by Hydrogen Bond (수소 결합에 의한 삼차원의 Copper(II) 거대고리 착물과 2,5-Pyridinedicarboxylate와의 자기조립)

  • Ki-Young Choi;Haiil Ryu;Yong-Son Kim
    • Journal of the Korean Chemical Society
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    • v.47 no.2
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    • pp.104-108
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    • 2003
  • The reaction of $[Cu(L)]Cl_2{\cdot}H_2O(L=3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0^{1.18},0^{7.12}]docosane)$ with 2,5-pyridinedicarboxylate(pdc) led to the formation of $[Cu(L)(H_2O)](pdc){\cdot}6H_2O(1)$. The structure was characterized by X-ray crystallography and spectroscopic method. The coordination geometry around the copper atom is a distorted square-pyramid with four secondary amines of the macrocycle occupying the basal sites and a water molecule at the axial position. Intermolecular hydrogen bonds in 1 form a three-dimensional molecular network.

Synthesis and Characterization of Dinuclear Ni(II) Complexes with Tetraazadiphenol Macrocycle Bearing Cyclohexanes

  • Kim, Ki-Ju;Jung, Duk-Sang;Kim, Duk-Soo;Choi, Chi-Kyu;Park, Ki-Min;Byun, Jong-Chul
    • Bulletin of the Korean Chemical Society
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    • v.27 no.11
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    • pp.1747-1751
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    • 2006
  • The dinuclear tetraazadiphenol macrocyclic nickel(II) complexes [$Ni_2$([20]-DCHDC)]$Cl_2$ (I), [$Ni_2$([20]-DCHDC)]$(ClO_4)_2{\cdot}2CH_3CN $ (II(b)) and [$Ni_2$([20]-DCHDC)$(NCS)_2$] (III) {$H_2$[20]-DCHDC = 14,29-dimethyl-3,10,18,25-tetraazapentacyclo-[25,3,1,$0^{4,9}$,$1^{12,16}$,$0^{19,24}$]ditriacontane-2,10,12,14,16(32),17,27(31), 28,30-decane-31,32-diol} have been synthesized by self-assembly and characterized by elemental analyses, conductances, FT-IR and FAB-MS spectra, and single crystal X-ray diffraction. The crystal structure of II(b) is determined. It crystallizes in the monoclinic space group P2(1)/c. The coordination geometries around Ni(II) ions in I and II(b) are identical and square planes. In complex III each Ni(II) ion is coordinated to $N_2O_2$ plane from the macrocycle and N atoms of NCS- ions occupying the axial positions, forming a square pyramidal geometry. The nonbonded Ni…Ni intermetallic separation in the complex II(b) is 2.8078(10) $\AA$. The FAB mass spectra of I, II and III display major fragments at m/z 635.1, 699.4 and 662.4 corresponding to [$Ni_2$([20]-DCHDC)(Cl + 2H)]$^+$, [$Ni_2$([20]-DCHDC)$(ClO_4\;+\;2H)]^+$ and [$Ni_2$([20]-DCHDC)(NCS) + 6H]$^+$, respectively.