• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2299-2303
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• 2014

Two diastereoisomers of cyclo(Pro-Tyr) have been synthesized simultaneously. The crystal structures and conformations of both cyclo($\small{L}$-Pro-$\small{L}$-Tyr) and a racemic mixture of cyclo($\small{D}$-Pro-$\small{L}$-Tyr) and cyclo($\small{L}$-Pro-$\small{D}$-Tyr), abbreviated as rac-cyclo($\small{D}$-Pro-$\small{L}$-Tyr/$\small{L}$-Pro-$\small{D}$-Tyr), have been determined by a single-crystal X-ray diffraction study at low temperature. The crystals of rac-cyclo($\small{D}$-Pro-$\small{L}$-Tyr/$\small{L}$-Pro-$\small{D}$-Tyr) belong to orthorhombic space group $Pna2_1$ with a = 10.755 (1), b = 12.699 (1), c = 9.600 (1) ${\AA}$ and Z = 4. The tyrosine side chain is folded towards the diketopiperazine (DKP) ring. The DKP ring adopts a twist boat conformation with pseudo symmetry $C_{2v}$. The pyrrolidine ring has an envelope conformation with the N5, C4, C7 and C8 atoms in a plane. The crystal of rac-cyclo($\small{D}$-Pro-$\small{L}$-Tyr/$\small{L}$-Pro-$\small{D}$-Tyr) is stabilized by hydrogen bonds between amide N2-H2 and carbonyl oxygen O2 in the neighbor. The hydroxyl group of tyrosine residue is also hydrogen bonded to the oxygen of the carbonyl group of the DKP ring in the next molecule. The spectroscopic properties of both isomers are also described.

• Bulletin of the Korean Chemical Society
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• v.10 no.3
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• pp.234-238
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• 1989

The crystal structure of partially $Ag^+$-exchanged zeolite A, $Ag_{3.2}Na_{8.8}$-A, vacuum dehydrated at $360^{\circ}C$ and then exposed to 0.1 torr of cesium vapor for 12 hours at $250^{\circ}C$ has been determined by single-crystal X-ray diffraction techniques in the cubic space group Pm3m (a = 12.262(2)${\AA})\;at\;21(1)^{\circ}C$. The structure was refined to the final error indexes $R_1=0.068\;and\;R_2=0.072$ by using 338 reflections for which $I_o\;>\;3{\sigma}(I_o)$ and the composition of unit cell is $Ag_{3.2}Cs_{8.8}-A.\;3\;Cs^+$ ions lie on the centers of the 8-rings at sites of D4h symmetry. Two crystallographycally different 6-ring $Cs^+$ ions were found: 1.5 $Cs^+$ ions at Cs(2) are located inside of sodalite cavity and 4.3 $Cs^+$ ions at Cs(3) are located in the large cavity. The fractional occupancies observed at Cs(2) and Cs(3) indicate that the existence of at least three types of unit cells with regard to the 6-ring $Cs^+$ ions. For example, 50% of unit cells may have two $Cs^+$ ions at Cs(2) and 4 $Cs^+$ ions at Cs(3). 30% of unit cells may have one Cs+ ion at Cs(2) and 5 $Cs^+$ ions at Cs(3). The remaining 20% would have one $Cs^+$ ion at Cs(2) and 4 $Cs^+$ ions at Cs(3). On threefold axes of the unit cell two non-equivalent Ag atom positions are found in the large cavity, each containing 0.64 and 1.92 Ag atoms, respectively. A crystallographic analysis may be interpreted to indicate that 0.64 $(Ag_5)^+$ clusters are present in each large cavity. This cluster may be viewed as a tetrasilver molecule $(Ag_4)^0$(bond length, 2.84${\AA}$) stabilized by the coordination of one $Ag^+$ ion.

• Korean Journal of Materials Research
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• v.22 no.3
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• pp.145-149
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• 2012

Red phosphors of $Gd_{1-x}Al_3(BO_3)_4:{Eu_x}^{3+}$ were synthesized by using the solid-state reaction method. The phase structure and morphology of the phosphors were measured using X-ray diffraction (XRD) and field emission-scanning electron microscopy (FE-SEM), respectively. The optical properties of $GdAl_3(BO_3)_4:Eu^{3+}$ phosphors with concentrations of $Eu^{3+}$ ions of 0, 0.05, 0.10, 0.15, and 0.20 mol were investigated at room temperature. The crystals were hexagonal with a rhombohedral lattice. The excitation spectra of all the phosphors, irrespective of the $Eu^{3+}$ concentrations, were composed of a broad band centered at 265 nm and a narrow band having peak at 274 nm. As for the emission spectra, the peak wavelength was 613 nm under a 274 nm ultraviolet excitation. The intensity ratio of the red emission transition ($^5D_0{\rightarrow}^7F_2$) to orange ($^5D_0{\rightarrow}^7F_1$) shows that the $Eu^{3+}$ ions occupy sites of no inversion symmetry in the host. In conclusion, the optimum doping concentration of $Eu^{3+}$ ions for preparing $GdAl_3(BO_3)_4:Eu^{3+}$ phosphors was found to be 0.15 mol.

• Korean Journal of Materials Research
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• v.21 no.11
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• pp.611-616
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• 2011

Red-orange phosphors $Gd_{1-x}PO_4:{Eu_x}^{3+}$ (x = 0, 0.05, 0.10, 0.15, 0.20) were synthesized with changing the concentration of $Eu^{3+}$ ions using a solid-state reaction method. The crystal structures, surface morphology, and optical properties of the ceramic phosphors were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) spectrophotometry. The XRD results were in accordance with JCPDS (32-0386), and the crystal structures of all the red-orange phosphors were found to be a monoclinic system. The SEM results showed that the size of grains increases and then decreases as the concentration of $Eu^{3+}$ ionincreases. As for the PL properties, all of the ceramic phosphors, irrespective of $Eu^{3+}$ ion concentration, had orange and red emissions peaks at 594 nm and 613 nm, respectively. The maximum excitation and emission spectra were observed at 0.10 mol of $Eu^{3+}$ ion concentration, just like the grain size. An orange color stronger than the red means that $^5D_0{\rightarrow}^7F_1$ (magnetic dipole transition) is dominant over the $^5D_0{\rightarrow}^7F_2$ (electric dipole transition), and $Eu^{3+}$ is located at the center of the inversion symmetry. These properties contrasted with those of a red phosphor $Y_{1-x}PO_4:{Eu_x}^{3+}$, which has a tetragonal system. Therefore, we confirm that the crystal structure of the host material has a major effect on the resulting color.

• Bulletin of the Korean Chemical Society
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• v.14 no.6
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• pp.713-717
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• 1993

The crystal structure of the potassium salt of penicillin V has been studied by the X-ray crystallographic methods. Crystal data are as follows; potassium 3,3-dimethyl-7-oxo-6-phenoxyacetoamido-4-thia-1- azabicyclo[3.2.0]-heptane-2${\alpha}$-carboxylate, $K^+{\cdot}C_{16}H_{18}N_2O_5S^-$, $M_r$= 388.5, triclinic, Pl, a= 9.371 (1), b= 12.497 (2), c= 15.313 (2) ${\AA},\;{\alpha}= 93.74\;(2),\;{\beta}=99.32\;(1),\;{\gamma}=90.17\;(1)^{\circ},\;V=1765.7\;(2)\;{\AA}^3$, Z=4, $D_m=1.461\;gcm^{-1},\;{\lambda}(Cu\;K{\alpha})=1.5418\;{\AA},\;{\mu}=40.1\;cm^{-1}$, F(000)=808, T=296 K. The structure was solved by the heavy atom and difference Fourier methods with intensity data measured on an automated four-circle diffractometer. The structure was refined by the full-matrix least-squares method to a final R= 0.081 for 3563 observed $[I_0{\geq}2{\sigam}(I_0)]$ reflections. The four independent molecules assume different overall conformations with systematically different orientations of the phenyl groups although the penam moieties have the same closed conformations. There are intramolecular hydrogen bonds between the exocyclic amide nitrogen and phenoxy oxygen atoms. The penam moiety is conformationally very restricted although the carboxyl and exocyclic amide groups apparently have certain rotational degrees of freedom but the phenyl group is flexible about the ether bond despite the presence of the intramolecular N-H${\cdots}$O hydrogen bond. There are complicated pseudo symmetric relationships in the crystal lattice. The penam moieties are related by pseudo 20.5 screw axes and the phenyl groups by pseudo centers of symmetry. The potassium ions, related by both pseudo symmetries, form an infinite zigzag planar chain parallel to the b axis. Each potassium ion is coordinated to seven oxygen atoms in a severely distorted pentagonal bipyramid configuration, forming the infinite hydrophilic channels which in turn form the molecular stacks. Between these stacks, there are only lipophilic interactions involving the phenyl groups.

• Advances in materials Research
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• v.5 no.2
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• pp.93-105
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• 2016

KNN-based ceramics modified with small amounts of $Bi_4Zr_3O_{12}$ (BiZ) has been synthesized using high-throughput experimentation (HTE). The results from X-ray diffraction show that for samples with base composition $(K_{0.5}Na_{0.5})NbO_3$ (KNN), the phase present changes from orthorhombic to pseudo-cubic with more than 0.2 mol% BiZ addition; for samples with base composition $(K_{0.48}Na_{0.48}Li_{0.04})(Nb_{0.9}Ta_{0.1})O_3$ (KNNLT), the phase present changes from a mixture of orthorhombic and tetragonal symmetry to pseudo-cubic with more than 0.4 mol % while for samples with base composition $(K_{0.48}Na_{0.48}Li_{0.04})(Nb_{0.86}Ta_{0.1}Sb_{0.04})O_3$ (KNNLST), the phase present is tetragonal with <0.3 mol% BiZ addition and transforms to pseudo-cubic with more dopant addition. The microstructures of the samples show that addition of BiZ decreases the average grain size and increases the volume of pores at the grain boundaries. The values of dielectric constant for KNN and KNNLT compositions increase slightly with BiZ addition while that for KNNLST decreases gradually with BiZ addition. The dielectric loss values are between 0.02 and 0.04 for KNNLT and KNNLST compositions while they are ~ 0.05 for KNN samples. The resistivity values increases with BiZ addition and values in the range of $10^{10}{\Omega}cm$ and $10^{12}{\Omega}cm$ are obtained. The piezoelectric charge coefficient ($d{^*}_{33}$) is highest for KNNLST samples and decreases gradually from ~400 pm/V to ~100 pm/V with BiZ addition.

• Bulletin of the Korean Chemical Society
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• v.14 no.2
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• pp.200-206
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• 1993

Structures of two polymorphs of ${\alpha},{\alpha}$-trehalose octaacetate monohydrate, $C_{28}H_{38}O_{19}\;{\cdot}\;H_2O$, have been studied by X-ray diffraction method. ${\alpha},{\alpha}$-trehalose (${\alpha}$-D-glucopyranosyl ${\alpha}$-D-glucopyranoside) is a nonreducing disaccharide. The polymorph I belongs to the monoclinic $P2_1$, and has unit cell parameters of a=10.725(l), b=15.110(4), c=11.199(5) ${\AA}$, ${\beta}=108.16(2)^{\circ}$ and Z=2. The polymorph II is orthorhombic $P2_12_12_1$, with a=13.684(4), b=15.802(4), c=17.990(9) ${\AA}$ and Z=4. The final R and R$_w$ values for monoclinic polymorph I are 0.043 and 0.048 and for orthorhombic polymorph II are 0.116 and 0.118, respectively. Those R values of polymorph II are high because the large thermal motions of acetyl groups and the poor quality of the crystal. The molecular conformations in the two polymorphs are similar. Both D-glucopyranosyl rings have chair $^4C_1$ conformations and atoms of glycosidic chain ${\alpha}(1{\rightarrow}1)$ linkage are coplanar. The primary acetate groups of the pyranose residues assume both gauche-trans conformations. The molecules of two polymorphs have pseudo-C$_2$ symmetry at glycosidic O(1) atom. The bond lengths and angles are normal compared with those in other acetylated sugar compounds. The molecules in the monoclinic crystal are held by the hydrogen bonds with the water molecules and by van der Waals forces.

• Progress in Superconductivity
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• v.8 no.2
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• pp.175-180
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• 2007

High temperature superconductor $YBa_2Cu_3O_{7-x}$ (YBCO) films have been grown by in-situ electron beam evaporation on artificial metal tapes such as ion-beam assisted deposition (IBAD) and rolling assisted biaxially textured substrates (RABiTS). Deposition rate of the YBCO films is $10{\sim}100{\AA}/sec$. X-ray diffraction shows that the films are grown epitaxially but have inter-diffusion phases, like as $BaZrO_3\;or\;BaCeO_3$, at their interfaces between YBCO and yttrium-stabilized zirconia (YSZ) or $CeO_2$, respectively. Secondary ion mass spectroscopy depth profile of the films confirms diffused region between YBCO and the buffer layers, indicating that the growth temperature ($850{\sim}900^{\circ}C$) is high enough to cause diffusion of Zr and Ba. The films on both the substrates show four-fold symmetry of in-plane alignment but their width in the -scan is around $12{\sim}15^{\circ}$. Transmission electron microscopy shows an interesting interface layer of epitaxial CuO between YBCO and YSZ, of which growth origin may be related to liquid flukes of Ba-Cu-O. Resistivity vs temperature curves of the films on both substrates were measured. Resistivity at room temperature is between 300 and 500 cm, the extrapolated value of resistivity at 0 K is nearly zero, and superconducting transition temperature is $85{\sim}90K$. However, critical current density of the films is very low, ${\sim}10^3A/cm^2$. Cracking of the grains and high-growth-temperature induced reaction between YBCO and buffer layers are possible reasons for this low critical current density.

• Bulletin of the Korean Chemical Society
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• v.27 no.11
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• pp.1809-1814
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• 2006

The L-Valinate anion coordinating zinc complex, [$Zn(val)_2(H-2O)$], was isolated and structurally characterized by single crystal X-ray crystallography. The crystal possess orthorhombic symmetry with a space group $P2_12_12_1$, Z = 4, and a = 7.4279(2)$\AA$, b = 9.4342(2)$\AA$, c =20.5862(7)$\AA$ respectively. The compound features a penta-coordinate zinc ion in which the two valine anion molecules are directly coordinating the central zinc metal ion via their N (amine) and O (carboxylate) atoms, and an additional coordination to zinc is made by water molecule (solvent) to form a distorted square pyramidal structure. In addition, further synthesis of the valine capped ZnS:Mn nanocrystal from the reaction of [$Zn(val)_2(H-2O)$] precursor with $Na_2S$ and 1.95 weight % of $Mn^{2+}$ dopant is described. Obtained valine capped nanocrystal was water dispersible and was optically characterized by UV-vis and solution PL spectroscopy. The solution PL spectrum for the valine capped ZnS:Mn nanocrystal showed an excitation peak at 280 nm and a very narrow emission peak at 558 nm respectively. The measured and calculated PL efficiency of the nanocrystal in water was 15.8%. The obtained powders were characterized by XRD, HR-TEM, and EDXS analyses. The particle size of the nanocrystal was also measured via a TEM image. The measured average particle size was 3.3 nm.

• Bulletin of the Korean Chemical Society
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• v.8 no.2
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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.