• Bulletin of the Korean Chemical Society
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• 제27권5호
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• pp.679-686
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• 2006

The positions of $PbI _2$ molecule synthesized into the molecular-dimensioned cavities of $\mid K_6 (Pb _4I_2)(PbI_2) _{0.67}-(H_2O)_2\mid [Si _{12}Al _{12}O _{48}]$-LTA have been determined. A single crystal of $\mid Pb _6\mid [Si _{12}Al _{12}O _{48}]$-LTA, prepared by the dynamic ion-exchange of $\mid Na _{12}\mid [Si _{12}Al _{12}O _{48}]$-LTA with aqueous 0.05 M $Pb _(NO _3)_2$ and washed with deionized water, was placed in a stream of flowing aqueous 0.05 M KI at 294 K for three days. The resulting crystal structure of the product $( \mid K_6 (Pb _4I_2)(PbI_2) _{0.67}(H_2O)_2\mid [Si _{12}Al _{12}O _{48}]$-LTA, a = 12.353(1) $\AA$) was determined at 294 K by single-crystal X-ray diffraction in the space group Pm3 m. It was refined with all measured reflections to the final error index $R_1$ = 0.062 for 623 reflections which $F_o$ > 4$\sigma$($F_o$). 4.67 $Pb ^{2+}$ and six $K^+$ ions per unit cell are found at three crystallographically distinct positions: 3.67 $Pb ^{2+}$ and three $K^+$ ions on the 3-fold axes opposite six-rings in the large cavity, three $K^+$ ions off the plane of the eight-rings, and the remaining one $Pb ^{2+}$ ion lies opposite four-ring in the large cavity. 0.67 $Pb ^{2+}$ ions and 1.34 $I^-$ ions per unit cell are found in the sodalite units, indicating the formation of a $PbI _2$ molecule in 67% of the sodalite units. Each $PbI _2$ (Pb-I = 3.392(7) $\AA$) is held in place by the coordination of its one $Pb ^{2+}$ ion to the zeolite framework (a $Pb ^{2+}$ cation is 0.74 $\AA$ from a six-ring oxygens) and by the coordination of its two $I^-$ ions to $K^+$ ions through six-rings (I-K = 3.63(4) $\AA$). Two additional $I^-$ ions per unit cell are found opposite a four-ring in the large cavity and form $Pb _2K_2I^{5+}$ and $Pb _2K_2I^{3+}$ moieties, respectively, and two water molecules per unit cell are also found on the 3-fold axes in the large cavity.

• Bulletin of the Korean Chemical Society
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• 제26권7호
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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) $\AA$).

• Bulletin of the Korean Chemical Society
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• 제14권2호
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• pp.258-262
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• 1993

Two single crystals of fully dehydrated $Rb^+$ -exchanged zeolite A have been prepared by the reduction of all $Ca^{2+}$ ions in dehydrated $Ca_6$-A by rubidium vapor. Their structures were determined by single crystal X-ray diffraction methods in the cubic space group Pm3m (a=12.160(2) $^{\AA}$ and 12.166(2) $^{\AA}$) at 22(1)$^{\circ}$C. In these structures, 12.4(2) to 13.3(2) Rb species are found per unit cell, more than 12 Rb$^+$ ions needed to balance the anionic charge of the zeolite framework, indicating that the sorption $Rb^0$ has occurred. In each structure, three $Rb^+$ ions per unit cell are located at the centers of the 8-rings. Six to eight $Rb^+$ ions are found opposite the 6-rings on threefold axes, and three $Rb^+$ ions are found in a sodalite unit. About 0.5 $Rb^+$ ion lies opposite a 4-ring. The structural analysis indicates the presence of a triangular rubidium cluster in the sodalite cavities. The triangular rubidium clusters may be stabilized by the coordination to two and/or three rubidium ions in the large cavity. Therefore, this cluster may be viewed as $(Rb_5)^{4+}$ and/or $(Rb_6)^{4+}$.

• Bulletin of the Korean Chemical Society
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• 제28권2호
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• pp.251-256
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• 2007

The crystal structure of fully dehydrated partially Cs+-exchanged zeolite X, [Cs52Na40Si100Al92O384], a = 24.9765(10) A, has been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at 21 °C. The crystal was prepared by flow method for 5 days using exchange solution in which mole ratio of CsOH and CsNO3 was 1 : 1 with total concentration of 0.05 M. The crystal was then dehydrated at 400 °C and 2 × 10-6 Torr for 2 days. The structure was refined to the final error indices, R1 = 0.051 and wR2 (based on F2) = 0.094 with 247 reflections for which Fo > 4σ (Fo). In this structure, about fifty-two Cs+ ions per unit cell are located at six different crystallographic sites with special selectivity; about one Cs+ ion is located at site I, at the centers of double oxygen-rings (D6Rs), two Cs+ ions are located at site I', and six Cs+ ions are found at site II'. This is contrary to common view that Cs+ ions cannot pass sodalite cavities nor D6Rs because six-ring entrances are too small. Ring-opening by the formation of ?OH groups and ring-flexing make Cs+ ions at sites I, I', and II' enter six-oxygen rings. The defects of zeolite frameworks also give enough mobility to Cs+ ions to enter sodalite cavities and D6Rs. Another six Cs+ ions are found at site II, thirty-six are located at site III, and one is located at site III' in the supercage, respectively. Forty Na+ ions per unit cell are located at two different crystallographic sites; about fourteen are located at site I, the centers of D6Rs and twenty-six are also located at site II in the supercage. Cs+ ions and Na+ ions at site II are recessed ca. 0.34(1) A and 1.91(1) A into the supercage, respectively. In this work, the highest exchange level of Cs+ ions per unit cell was achieved in zeolite X by conventional aqueous solution methods and it was also shown that Cs+ ion could pass through the sixoxygen rings.

• Bulletin of the Korean Chemical Society
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• 제16권10호
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• pp.923-929
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• 1995

Four crystal structures of M3-A (M3Na9-xHx-A, M=Rb or K and x=1 or 0), Rb3Na8H-A(a=12.228(1) Å and R1=0.046), Rb3Na9-A (a=12.258(3) Å and R1=0.058), K3Na8H-A (a=12.257(3) Å and R1=0.048) and K3Na9-A (a=12.257(3) Å and R1=0.052), have been determined by single crystal x-ray diffraction technique in the cubic space group Pm3^m at 21 ℃. In all structures, each unit cell contained three M+ ions all located at one crystallographically distinct position on 8-rings. Rb+ ions are 3.12 and 3.21 Å away respectively from O(1) and O(2) oxygens, about 0.40 Å away from the centers of the 8-rings, and K+ ions are 2.87 and 2.81 Å apart from the corresponding oxygens. These distances are the shortest ones among those previously found for the corresoponding ones. Eight 6-rings per unit cell are occupied by eight Na+ ions, each with a distance of 2.31 Å to three O(3) oxygens. The twelfth cation per unit cell is found as Na+ opposite 4-ring in the large cavities of M3Na9-A and assumed to be H+ for M3Na8H-A. With these noble non-framework cationic arrangements, larger M+ ions preferably on all larger 8-rings and the compact Na+ ions on all 6-rings, the bond angles in the 8-rings of M3-A, 145.1 and 161.0 respectively for (Si,Al)-O(1)-(Si,Al) and (Si,Al)-O(2)-(Si,Al), turned out to be remarkably stable and smaller, by more than 12 to 17°, than the corresponding angles found in the crystal structures of zeolites A with high concentration of M+ ions. It is to achieve these remarkably relaxed 8-rings, the main windows for the passage of gas molecules, with simultaneously maximized cavity volumes that M3-A have been selected as one of the efficient zeolite A systems for gas encapsulation.

• 대한안전경영과학회지
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• 제13권2호
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• pp.91-96
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• 2011

The purpose of this study was to minimize of entrance surface dose (ESD) at the eye using high kVp technique in the computed radiography. We used REX-650R (Listem, Korea) general X-ray unit, and external detector with ESD dosimeter of Piranha 657 (RTI Electronics, Sweden). We used head of the whole body phantom. The total 64 images of X-ray anterior-posterior of skull were acquired using the film/screen (F/S) method and the digital of computed radiography method. The three radiology professor of more 10 years of clinical career evaluated a X-rays images in the same space by 5-point scale. The external detector was performed measurement of ESD of three times by same condition on the eye of the head phantom. The good image quality in the F/S method (90 kVp, 2.5 mAs) showed at the minimized ESD of 0.310 ${\pm}$ 0.001 mGy. the good image quality in the computed radiography method (90 kVp, 2.0 mAs) showed at the minimized ESD of 0.180 ${\pm}$ 0.002 mGy (P = 0.002). Finally the radiation dose could reduced about 50% in the computed radiography method more than the F/S method. In addition the eye entrance surface dose using high kVp technique with the computed radiography was reduced 92% more than conventional technique (F/S method).

• 한국결정학회지
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• 제2권2호
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• pp.13-21
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• 1991

50% terephthaloyl chloride(TPA)와 50%(1-phenylethyl) hydroquinone(PEHQ)으로부터 합성된 열 액정폴리에스터 poly(1-phenylethyl-p-phenylene-terephthalate)의 chalk conformation 및 packing 상태를 X-선 회절법을 이용하여 해석하였다. 단위세포상수는 a=12.77 A, b=10.17 A(unlque axis), c=12.58 A (fiber axis), β=90.1°, 그리고 공간군은 P2l 이고 단사정계이며 Z:4 이었다. 미세구조는 주쇄상의 Phenyl-COO 그리고 COO-Phenyl 평면간의 그리고 주축과 측쇄간의 torsion angle 들을 중심으로 37개의 회절반점에 대해 Linked Atom Least Square(LALS) 방법을 이용하여 해석하였으며, 1-phenylethyl 치환체는 ortho-와 met a위치에 각각 확률적으로 0.5의 가중치를 부여함에 의해 구조적으로 모델링 되었다. 주쇄상의 Phenyl-COO그리고 Phenyl-COO평면간의 torsion angle은 각각 -6.1°와 65.6°로 주어졌으며 결국 주축상의 Phenol 평면들은 서로 59.5°로 엇갈려 주축을 형성하고 있음을 알 수 있었다. (단 ester, COO-, 기는 평면으로 가정되었다.)

• Bulletin of the Korean Chemical Society
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• 제27권4호
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• pp.568-572
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• 2006

To study the effect of sequence on DNA structure, the two decamer crystal structures one alternating,d(GTACGCGTAC), and the other non-alternating, d(GGCCGCGGCC), were solved. Crystals of both decamers belong to the hexagonal space group $P6_122$, with one strand in the asymmetric unit. The unit cell constants of the alternating decamer are a = b = 39.26 $\AA$, c = 77.70 $\AA$. The structure was refined with 1,828 reflections from 8.0 to 2.0 Aresolution to an R value of 21.3% with all DNA atoms and 63 water molecules. The isomorphous non-alternating decamer had unit cell dimensions of a = b = 39.05 $\AA$, c = 82.15 $\AA$. The structure was refined with 2,423 reflections from 8.0 to 2.0 $\AA$ resolution to a final R value of 22.2% for all DNA atoms and 65 water molecules. Although the average helical parameters of the decamers are typical of A-DNAs, there are some minor differences between them. The helical twist, rise, x-displacement, inclination and roll alternate in the alternating decamer, but do not in the non-alternating decamer. The backbone conformations in both structures show some differences; the residue G(7) of the alternating decamer is trans for $\alpha$ and $\gamma$ while the trans conformations are observed at the residue G(8) of the non-alternating decamer.

• Bulletin of the Korean Chemical Society
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• 제22권2호
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• pp.164-170
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• 2001

The crystal structures of fully dehydrated Ni2+- and Tl+ -exchanged zeolite X (Ni17Tl58-X, and Ni12Tl68-X; X=Si100Al92O384) have been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at $21(1)^{\circ}C$ (a=24.380(4) $\AA$, 24.660(4) $\AA$, respectively). Their structures have been refined to the final error indices R1=0.037 and R2=0.043 with 485 reflections, and R1=0.039 and R2=0.040 with 306 reflections, respectively, for which I >36(I). In Ni17Tl58-X, 17 Ni2+ ions per unit cell were found at only two sites: 15 at site I at the center of the hexagonal prism (Ni-O=2.203(9) $\AA)$ and the remaining 2 at site II near single six-oxygen rings in the supercage (Ni-O=2.16(3) $\AA).$ Fifty-eight Tl+ ions were found at five crystallographic sites: 28 at site II (Tl-O=2.626(8) $\AA)$, 2 at site I' in the sodalite cavity near the hexagonal prism (Tl-O=2.85(1) $\AA)$, another 2 at site II' in the sodalite cavity (Tl-O=2.77(1) $\AA).$ The remaining 26 were found at two nonequivalent Ⅲ' sites with occupancies of 23 and 3. In Ni12Tl68-X, 12 Ni2+ ions per unit cell were found at two sites: 10 at site I (Ni-O=2.37(2) $\AA)$ and the remaining 2 at site II (Ni-O=2.13(2) $\AA).$ Sixty-eight Tl+ ions were found at five crystallographic sites: 28 at site II (Tl-O=2.63(1) $\AA)$, 12 at site I' (Tl-O=2.62(1) $\AA)$, 2 at site II' (Tl-O=3.01(2) $\AA)$, and the remaining 26 at two III' sites with occupancies of 23 and 3. It appears that Ni 2+ ions prefer to occupy site I and II, in that order. The large Tl+ ions occupy the remaining sites, I', II, II' and two different III' sites. In both crystals, only the Ni2+ ions at site II were reduced and migrated to the external surface of zeolite X when these crystals were treated with hydrogen gas.

• 대한화학회지
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• 제36권1호
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• pp.51-56
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• 1992

페로브스카이트구조를 갖는 $Pb(Zr_{1-y}Ti_y)O_3$ (PZT)계의 $Pb^{2+}$ 위치에 $Nd^{3+}$ 이온을 치환시키면서 그 결정구조와 결합특성을 X-선 회절분석법 및 적외선 분광광도법으로 알아보았으며, 이런 구조변화가 (Pb1-xNdx)(Zr1-yTiy)O3 (PNZT)계의 전기적 및 광학적 특성에 미치는 영향에 대하여 조사하였다. $Pb^{2+}$ 이온이 $Nd^{3+}$ 이온으로 치환될수록 정방성이 감소하며, 8${\sim}$12 mol% 치환되었을 때 입방정계의 구조이다. 결정내의 결합강도는 입방정게의 구조일 때 가장 강하고 높은 투광도를 나타냈으며, PNZT계 화합물이 투광도를 나타내는 것은 전자의 전하-이동 전이에 의한 것으로 생각된다.