• Bulletin of the Korean Chemical Society
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• 제8권2호
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• pp.69-72
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• 1987

The structures of dehydrated $Ag_9Cs_3$-A treated with hydrogen gas at three different temperatures have been determined by single-crystal X-ray diffraction techniques. Their structures were solved and refined in the cubic space group Pm3m at 23(1) $^{\circ}C$. All crystals were ion exchanged in flowing streams of aqueous $AgNO_3$/$CsNO_3$ with a mole ratio 1:3.0 to achieve the desired crystal composition. The structures treated with hydrogen at $23^{\circ}C(a=12.288(1)\;{\AA})\;and\;310^{\circ}C(a=12.291(2)\;{\AA})$ refined to the final error indices R1 = 0.091 and R2 = 0.079, and 0.065 and 0.073, respectively, using the 216 and 227 reflections, respectively, for which I >3${\sigma}$(I). In both of these structures, eight $Ag^+$ ions are found nearly at 6-ring centers, and three $Cs^+$ ions lie at the centers of the 8-rings at sites of $D_{4h}$ symmetry. One $Ag^{\circ}atom$, presumably formed from the reduction of a $Ag^+$ ion by an oxide ion of a residual water molecule or of the zeolite framework during the dehydration process, is retained within the zeolite, perhaps in a cluster. In these two structures hydrogen gas could not enter the zeolite to reduce the $Ag^+$ ions because the large $Cs^+$ ions blocked all the 8-windows. However, hydrogen could slowly diffuse into the zeolite and was able to reach and to reduce about half of the $Ag^+$ ions in the structure only at high temperature ($470^{\circ}C$). The silver atoms produced migrated out of the zeolite framework, and the protons generated led to substantial crystal damage.

• Bulletin of the Korean Chemical Society
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• 제13권4호
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• pp.363-367
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• 1992

The crystal structure of (1,3,6,9,11,14-hexaazatricycol[12.2.1.$1^{6,9}$]octadecane)copper(Ⅱ) perchlorate, Cu($C_{12}H_{26}N_6$)$(ClO_4)_2$, has been determined by the X-ray diffraction methods. The crystal data are as follows: Mr=516.9, triclinic, ${\alpha}=8.572\;(2)$, b=8.499 (3), c=15.204 (3) ${\AA}$, ${\alpha}=80.42\;(5),\;{\beta}=73.57\;(3),\;{\gamma}=69.82\;(4)^{\circ},\;V=994.2\;{\AA}^3,\;D_C=1.726\;gcm^{-3}$, space group $P{\tilde{1}},\;Z=2,\;{\mu}=21.27\;cm^{-1}&, F(000)=534 and T=297 K. The structure was solved by direct methods and refined by full-matrix least-squares methods to and R value of 0.081 for 1608 observed reflections measured with graphite-mono-chromated Mo Ka radiation on a diffractometer. There are two independent complexes in the unit cell. The two copper ions lie at the special positions (1/2, 0, 0) and (0, 1/2, 1/2)and each complex possesses crystallographic center of symmetry. Each Cu ion is coordinated to four nitrogen donors if the hexaazamacrotricyclic ligand and weakly interacts with two oxygen atoms of the perchlorate ions to form a tetragonally distorted octahedral coordination geometry. The Cu_N (sec), Cu_N(tert) and Cu_O coordination distances are 1.985 (14), 2.055 (14) and 2.757 (13) ${\AA}$ for the complex A and 1.996 (10), 2.040 (11) and 2.660 (13) ${\AA}$ for the complex B, respectively. The macrocycles in the two independent cations assume a similar conformation with the average r.m.s. deviation of 0.073 ${\AA}$. Two 1,3-diazacyclopentane ring moieties of the hexaazamacrotricyclic ligand are placed oppositely and almost perpendicularly to the square coordination plane of the ruffled 14-membered macrocycle. The secondary N atoms are hydrogen-bonded to the perchlorate O atoms with distances of 3.017 (23) and 3.025 (19) ${\AA}$ for the complexes A and B, respectively.

• 한국자기학회지
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• 제9권3호
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• pp.143-148
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• 1999

Spin-Peierls(SP) 전이를 하는 CuGeO3에서 Cu 이온과 Ge 이온을 자성 이온인 Fe 이온으로 일부 치환시킨 Cu1-xGe1-yFex+yO3계를 제조하여 전이온도 전후에서 자기적 특성과 결정학적 특성의 변화를 밝히기 위하여 자기감수율과 Mossbauer 스펙트럼을 측정 분석하였다. 결정구조는 모든 시료가 직방정계(orthorhombic)였고 격자 상수는 Fe의 치환량이 증가할수록 a축과 c축만 약간 감소하였다. 온도를 내리면서 측정한 자기감수율의 값이 12.5K 근처에서 급격히 감소하는 SP 전이를 나타냈는데 이 온도는 Fe의 치환량이 많아질수록 약간씩 낮아졌다. Mossbauer 스펙트럼은 Fe3+ 이온에 의한 두 개의 Zeeman sextet와 한 개의 이중선이 중첩되어 나타났는데 특히 SP 전이 온도(Tsp)에서 Mossbauer변수들이 불연속이었다. 즉, Tsp이하에서 두 번째 Zeeman선의 자기장이 크게 증가했고 이중선의 사중극자 분열값(QS)과 이성질체 이동값(IS)도 증가했는데, 이를 Tsp에서 이중체 형성에 따른 이온들의 위치 이동 계산 결과와 비교하여 초교한 상호작용, 대칭성 및 공유 결합성 등의 변화와 관련시켜 해석하였다.

• 한국광물학회지
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• 제26권1호
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• pp.35-44
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• 2013

유사 올리빈 구조를 가지는 탄소코팅 합성 $Li^+Fe^{2+}(PO_4)^{3-}$ 분말시료에 대한 상온-고압실험을 대칭 다이아몬드 앤빌기기를 이용하여 35.0 GPa까지 시행하였다. $LiFePO_4$의 압축 데이터를 이용하여 계산된 체적탄성률은 $130.1{\pm}10.3$ GPa이다. 18 GPa 이상의 압력에서 d = 3.386 ${\AA}$ 위치에 새로운 피크가 관찰되고 35 GPa에서는 d = 2.854 ${\AA}$에 또 다른 피크가 관찰되고 있으나 주 결정구조는 사방정계인 것으로 판단된다. 압력에 대한 단위 포 부피의 압축은 M1($Li^+O_6$)의 수축이 두드러지고 M2($Fe^{2+}O_6$)와 사면체($PO_4$)의 수축은 상대적으로 작은 것으로 나타났다.

• 한국결정학회지
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• 제11권1호
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• pp.22-27
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• 2000

The structure of cis-(malonato)[(4R,5R)-4,5-bis(aminomethyl)-2-isopropyl-1,3-dioxolane]platinum(II) with a potent anticancer activity has been determined by the X-ray crystallographic method. Crystal data are as follows: Pt(C/sub 11/H/sub 20/N₂O/sub 6/), M/sub 4/=471.38, monoclinic, P2₁, a=7.112(1), b=33.615(3), c=7.135(1)Å, β=116.80(1)°, V=1522.6(3)Å, and Z=4. The two independent molecules with very similar structures are approximately related by pseudo two-fold screw axis symmetry, which makes the monolinic cell look like the orthorhombic cell with one molecule in the asymmetric unit and space group C222₁. The crystal packing mode is similar to that of the analogue with the dimethyl substituents instead of the isopropyl group. The Pt atom is coordinate to two O and two N atoms in a square planar structure. The six-membered chelate ring in the leaving ligand assumes a conformation intermediate between the half chair and the boat forms. The seven-membered ring in the carrier ligand assumes a twist-chair conformation and the oxolane ring assumes an envelope conformation. Crystal packing consists of the extensive hydrogen-bonding network in the two-dimensional molecular layers and weak van der Waals interactions between these layers.

• 한국결정학회지
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• 제13권1호
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• pp.21-24
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• 2002

Cholesterol crotonate(CH₃CH = CHCOOC/sub 27/H/sub 45/)의 분자 및 결정 구조를 X-선 회절법으로 연구하였다. 결정은 P2₁, a = 13.446(4) , b = 11.802(3) , c = 18.782(5) , β = 103.99(2)°, Z = 4이다. 회절 반점들의 세기는 흑연 단색화 장치가 있는 Enraf-Nonius CAD-4 diffractometei로 얻었으며 (2θ/sub max/ = 25°, Mo-Kα X선(λ= 0.7107 )을 사용하였다. 분자 구조는 직접법으로 풀었으며, 최소자승법으로 정밀화하였고, 최종신뢰도 R값은 1604개의 회절 반점에 대하여 0.092이었다. 화합물의 결정 구조는 cholesterol ethylcarbonate, propylcarbonate, crotylcarbonate등의 결정 구조와 isostructure로, 분자들은 monolayer를 이루면서 쌓여 있으며, monolayer 중심부에서는 A 분자의 cholesteryl ring system들끼리, B 분자의 cholesterol ring system과 분자 B의 C(17)-side chain들이 서로 촘촘히 쌓여있다. 층(layer)들 사이에는 crotonate tail들과 분자 A의 C(17)-side chain들이 느슨하게 모여있다. 결정은 cholesteric phase를 갖는 liquid crystalline state을 보여주고 있다.

• 한국광물학회지
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• 제4권2호
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• pp.99-107
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• 1991

Three fully dehydrated fully Rb+-exchanged zeolite A single crystals have been prepared by the reduction of all Na+ ions in dehydrated Na12-A by rubidium vapor at various experimental conditions (220 $\leq$ T $\leq$ 33$0^{\circ}C$, 2 $\leq$ t $\leq$24 hours, and 0.1 $\leq$ PRb $\leq$ 1.1 Torr). Their structures were determined by single-crystal X-ray diffraction methods in the space group {{{{ RHO }}m3m (a=12.245(3) A) at 22(1)$^{\circ}C$. In these structures 12.6(2) to 13.5(2) Rb species are found per unit cell, more than the 12 Rb+ ions needed to balance the anionic charge of the zeolite framework, indication that the sorption of Rb0 has occurred. In each structure, three Rb+ ions per unit cell are located at the centers of 8-rings. Beyond that, the fractional occupancies observed are simply explained by two unit cell arrangments. In one, two Rb+ ions are in the sodalite unit near opposite 6-rings, six are in the large cavity near 6-ring, and one is in the large cavity near a 4-ring. In the other, three Rb species in the sodalite cavity (forming a triangle 3.7 A on an edge) each bond (3.4 A) through a 6-ring to an Rb species in the large cavity to give an (Rb6)4+ cluster of symmetry 3m (C3V). Five additional Rb+ ions fill the remaining large-cavity 6-ring sites.

• Bulletin of the Korean Chemical Society
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• 제5권3호
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• pp.117-121
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• 1984

The structure of $CS_{7.3}Ag_{4.7}Si_{12}Al_{12}O_{48}$, vacuum dehydrated zeolite A with all Na+ ions replaced by $Cs^+$ and $Ag^+$ as indicated, has been determined by single-crystal x-ray diffraction techniques in the cubic space group, Pm3m (a = 12.282 (1) ${\AA}$). The structure was refined to the final error indices $R_1$$R_2$ (weighted) = 0.099 using 347 independent reflections for whind intlch $I_0\;>\;3{\sigma}(I_0)$. Although deydration occurred at $360^{\circ}C$, no silver atoms or clusters have been observed. The 8-ring sites are occupied only by $Cs^+$ ion, and the 4-ring sites only by a single $Ag^+$ ion. The 6-ring sites contain $Ag^+$ and $Cs^+$ ions with $Ag^+$ nearly in 6-ring planes and $Cs^+$ well off them, one on the sodalite unit side. With regard to the 6-rings, the structure can be represented as a superposition of two types of unit cells: about 70 % have $4Ag^+$ and $4Cs^+$ ions, and the remaining 30 % have $3Ag^+$ and $5Cs^+$. In all unit cells, $3Cs^+$ ions lie at the centers of the 8-rings at sites of D4h symmetry; these ions are approximately 0.3 ${\AA}$ further from their nearest framework-oxygen neighbors than the sum of the appropriate ionic radii would indicate. To minimize electrostatic repulsions, the $Cs^+$ ions at Cs(1) are not likely to occupy adjacent 6-rings in the large cavity; they are likely to be tetrahedrally arranged when there are 4.

• Bulletin of the Korean Chemical Society
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• 제7권3호
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• pp.190-193
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• 1986

The structure of partially $Ag^+$-exchanged zeolite 4A, $Ag_{7.6}Na_{4.4}-A$, vacuum dehydrated at $370^{\circ}C$, has been determined by single-crystal x-ray diffraction techniques in the cubic space group, Pm3m (a = 12.311(1)${\AA}$) at $24(1)^{\circ}}C$. The structure was refined to the final error indices $R_1$ = $R_2$ (weighted) = 0.064 using 266 independent reflections for which $I_0$>$3{\sigma}(I_0)$. Three $Na^+$ ions occupy the 3 8-ring sites, and the remaining ions, 1.4 $Na^+$ and 6.6 $Ag^+$, fill the 8 6-ring sites; each $Ag^+$ ion is nearly in the [111] plane of its 3 O(3) ligands, and each $Na^+$ ion is 0.9${\AA}$ from its corresponding plane, on the large-cavity side. One reduced silver atom per unit cell was found inside the sodalite unit. It was presumably formed from the reduction of a $Ag^+$ ion by an oxide ion of a residual water molecule or of the zeolite framework. It may be present as a hexasilver cluster in 1/6 of the sodalite units, or, most attractively among several alternatives, as an isolated Ag atom coordinated to 4 Ag ions in each sodalite unit to give $(Ag_5)^{4+}$, symmetry 4mm.

• Radiation Oncology Journal
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• 제9권1호
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• pp.131-141
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• 1991

국내에서 처음으로 사용되는 CLINAC 1800에서 발생된 15MV X-선의 특성을 구하기 위하여 3 Dimensional water Phantom Dosimetry system)를 이용하여 방사선 치료에 근간이 되는 심부선량 백분율(POD), 최대 조직 비율(TMR), 편평도(beam profile), 대칭도, Wedge인자 등을 측정하였고 선량계산을 위하여 출력 인자들을 구하였다. 1. 선축상 최대치 지점(Dmax)은 SSD 100cm일때 조사면이 $10\times10cm^2$에서 $3.0\pm0.1$ cm이였고 $4\times4cm^2,\;35\times35cm^2$에서 각각 $3.1\pm0.1\;cm,2.2\pm0.1$ cm으로 조사면이 넓어지면서 측정치가 표면에 가까워지는 결과를 보였다. 2. 조직표면 선량(Surface Dose)는 SSD 100cm일때 조사면이 $10\times10cm^2$에서 $15.5\%$이였고 $4\times4cm^2,\;35\times35cm^2$에서 각각 $9.8\%\;,51.2\%$로 조사면이 넓어지면서 표면 선량은 증가하는 결과를 보였다. 3. 심부선량 백분율(PDO)은 SSD 100cm에서 측정하였고 조사면이 $10\times10cm^2$이고 10cm depth에서 $76.8\%$이였고 $80\%,\;50\%$ 선량의 깊이는 각각 $9.1\pm0.1\;cm,19.9\pm0.2\;cm$으로 측정되었다. 4. 최대조직비율(TMR)은 심부선량 백분율(PDD)로부터 계산하였고 측정값과의 차이는 $10\times10cm^2$ 조사면에서 평균 $1\;%$ 이내의 오차를 보였다. 5. 대칭도(symmetry)와 편평도(flatness)는 조사면 $10\times10cm^2$일때 각각 $0.73\%,\;2.72\%$이였다. 6. 출력인자(output factor)는 $10\times10cm^2$ 기준 조사면에서 흡수선량을 1로 하였을때 $4\times4cm^2,\;35\times35cm^2$ 조사면에서는 각각 0.927, 1.087로 측정되었는데 조사면이 증가할수록 흡수량이 증가하는 결과를 보였다. 7. Wedge factor는 $15^{\circ}\;30^{\circ}\;45^{\circ}\;60^{\circ}$를 10cm깊이에서 측정하였는데 0.825, 0.099, 0.560, 0.457로 각각 측정되었고 아크릴 0.4 mm Tray의 투과율은 0.976이였다. 8. 15 MV X-선에 의한 납벽층의 반가층 두께는 13 mm였고 Cerrobend의 반가층은 15.5 mm으로 측정되었다.