• Bulletin of the Korean Chemical Society
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• 제25권4호
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• pp.529-532
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• 2004

Cesium-133 NMR spectra of a single crystal of tetragonal $Cs^+ (15-crown-5)_2I^-$ were obtained as a function of crystal orientation in an applied magnetic field of 9.40T and analyzed to provide the magnitudes and orientations of the $^{133}Cs$ chemical shift and quadrupolar tensors for two magnetically nonequivalent and symmetry related sites. Chemical shift tensor components and parameters of quadrupolar interactions are obtained as ${\delta}_{11}=46(1),\;{\delta}_{22}=60(1),\;{\delta}_{33}=-30(1)$ ppm, quadrupole coupling constant QCC = 581(1) kHz, and asymmetry parameter ${\eta}$ = 0.481(1), respectively. The nonaxially symmetric NMR parameters imply that the local environment of the cesium nuclei is nonaxially symmetric. The DANTE experiment burned holes in the $^{133}Cs$ NMR line of the title compound. The hole burning of the single crystal and powder $^{133}Cs$ NMR lines showed that the NMR lines are not homogeneously broadened.

• Bulletin of the Korean Chemical Society
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• 제25권2호
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• pp.298-300
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• 2004

An alternative molecular porphyrin-phthalocyanine aggregate was prepared and characterized with UV-visible and X-ray absorption spectroscopies. UV-visible experiments evidence 1-dimensional porphyrin-phthalo-cyanine array formed by mixing $SnTPPCl_2 ({\lambda}_{max}=429,\;{\varepsilon}=2.4{\times10^ 5 /M{\cdot}cm)\;and\;NiPc(OBu)_8({\lambda}_{max}=744 nm,\;{\varepsilon}= 2.0{\times}10^ 5 /M{\cdot}cm)$ in solution. In the UV-visible spectrum of the porphyrin-phthalocyanine array, $(SnPNiPc)_n$, a new Q-band appeared at 844 nm with decrease of the Q-band peak of $NiPc(OBu)_8$ at 744 nm. The red-shift of Q-band evidences an alternative porphyrin-phthalocyanine array formed in solution through metal-halide interaction rather than ${\pi}-{\pi}$ facial interaction, in which nickel of $NiPc(OBu)_8$ coordinates with chloride of $SnTPPCl_2$ through self assembly. Ni K-edge XANES (X-ray absorption near edge structure) spectra also support the axial ligation of nickel to chloride. The square planar structure of $NiPc(OBu)_8$ turns to an octahedral structure in (SnPNiPcSnP) by axial ligation. A higher energy-shift (0.2 eV) of the preedge peak of (SnPNiPcSnP) indicaties partial oxidation of nickel by charge transfer from NiPc$(OBu)_8$ to SnTPPCl$_2$.

• Journal of Pharmaceutical Investigation
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• 제23권3호
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• pp.155-163
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• 1993

Inclusion complexation of 1,7,21,27-tetraaza[7.1.7.1]paracyclophane (CPM 55) with 2,7-dihydroxynaphthalene (2,7-DHN) or 1,3-dihydroxynaphthalene (1,3-DHN) in pD 1.17 $DCl-D_2O$ solution was investigated by $^1H$ nuclear magnetic resonance spectroscopy (NMR) using 4,4'-dimethylaminodiphenylmethane (ACM 11) as an acyclic analog of CPM 55. In CPM 55-naphthalene derivative complex, alkyl protons located in the cavity of CPM 55 were shown to be subjected to anisotropic shielding and protons of naphthalene moiety shifted remarkably to upfield. However, in ACM 11-naphthalene derivative systems, chemical shifts for protons of both DHN compounds were not significant. The remarkable chemical shift changes suggested that the naphthalene moiety of 2,7-DHN or 1,3-DHN was included in the hydrophobic cavity of CPM 55 in aqueous solution. From the continuous variation plots of induced chemical shifts of 2,7-DHN, it was found that 2,7-DHN was included in the cavity of CPM 55 at 1:1 molar stoichiometry. Both computer simulation of a inclusion complex and strong upfield chemical shift changes of 2,7-DHN protons supported the conformation of pseudoaxial inclusion as the presumed geometry of the host-guest complex.

• 대한화학회지
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• 제18권3호
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• pp.215-220
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• 1974

저자들은 tetrahedrane생성의 전구체인 t-butenedial bistosylhydrazone의 입체적인 구조를 연구할 목적으로 이의 유사한 구조인 ${\alpha},{\beta}$위치에 이중결합을 가지고 있는 몇 가지 phenylhydrazone을 합성하고 이들의 형태 및 배위를 nmr spectra의 해석으로부터 구명했다. 벤젠용매와 aliphatic solvent(CC14, DMSO)에서의 chemical shift의 차이로 부터 이들 물질이 syn-configuration을 가지고 있음을 알았으며 spin-spin coupling constant 로부터 이들 물질의 형태를 고찰하였다.

• 대한화학회지
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• 제40권10호
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• pp.656-662
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• 1996

저온상압법에 의해 Si/Al의 비가 100정도되는 ZSM-5를 합성하였으며 시간 경과에 따른 결정화과정을 $^{27}Al$ 및 $^{29}Si$ MAS NMR spectea 및 FT-IR로 고찰하였다. 저온상압 하에서 합성한 결과 초기 반응물질 및 성분비에 따라 화학적 이동은 기종의 연구와는 다른 경향을 보였으나 반응이 진행됨에 따라 최종 생성물의 화학적 이동은 전형적이 ZSM-5 영역에서 나타나고 있음을 확인하였다. 그리고 국부결함은 소성에 의해 제거되었으며 최종생성물의 XRD 및 SEM의 결과에서도 합성된 물질이 ZSM-5임을 확인하였다.

• Bulletin of the Korean Chemical Society
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• 제26권1호
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• pp.63-71
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• 2005

Equilibrium geometries, electronic structures, and energies of borocarbon clusters (binary compounds of carbon and boron), an unexplored class of molecules with highly unusual characteristics and potential for further development, have been investigated by means of B3LYP/6-311+G$^*$ density functional theory computations. A large number of B$_7$C${_1}^{1-}$, B$_6C_2$, and B$_5C_{3}\,^{1+}$ clusters with planar and non-planar monocyclic and polycyclic rings, as well as cage structures, have been systematically studied. Unexpectedly, planar forms are predicted not only to be the most stable structures, but also, in many cases, to have unprecedented planar heptacoordinate boron (p-heptaB) and planar heptacoordinate carbon (p-heptaC) arrangements. All these pheptaB and p-heptaC have 6π electrons and are aromatic according to the nucleus independent chemical shift (NICS). This novel bonding pattern is analyzed in terms of natural bond orbital (NBO) analysis. For virtually all possible B$_7$C${_1}^{1-}$, B$_6C_2$, and B$_5C_{3}\,^{1+}$ combinations, the p-heptaB arrangements are the more stable than other type structures.

• Journal of Microbiology and Biotechnology
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• 제25권1호
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• pp.11-17
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• 2015

In an attempt to shift the optimal pH of the xylanase B (XynB) from Aspergillus niger towards alkalinity, target mutation sites were selected by alignment between Aspergillus niger xylanase B and other xylanases that have alkalophilic pH optima that highlight charged residues in the eight-residues-longer loop in the alkalophilic xylanase. Multiple engineered XynB mutants were created by site-directed mutagenesis with substitutions Q164K and Q164K+D117N. The variant XynB-117 had the highest optimum pH (at 5.5), which corresponded to a basic 0.5 pH unit shift when compared with the wild-type enzyme. However, the optimal pH of the XynB-164 mutation was not changed, similar to the wild type. These results suggest that the residues at positions 164 and 117 in the eight-residues-longer loop and the cleft's edge are important in determining the pH optima of XynB from Aspergillus niger.

• Korean Chemical Engineering Research
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• 제48권6호
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• pp.737-740
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• 2010

높은 누설 전류와 문턱 전압의 이동은 비정질 실리콘(a-Si:H) 트랜지스터(TFT)의 단점이다. 이러한 특성은 게이트 절연체와 활성층 박막의 막 특성, 표면 거칠기와 공정 조건에 따라 영향을 받는다. 본 연구의 목적은 누설 전류와 문턱 전압의 특성을 개선하는데 목적이 있다. 게이트 절연체의 공정 조건에 대해서는 질소를 증가한 증착 공정 조건을 적용하였고, 활성층의 공정 조건에 대해서는 산소를 증가한 공정 조건을 적용하여 전자 포획을 감소시키고 박막의 밀도를 증가시켰다. $I_{off}$는 $65^{\circ}C$ 조건하에서 1.01 pA에서 0.18pA로, ${\Delta}V_{th}$는 -1.89 V에서 -1.22V로 개선되었다.

• 대한화학회지
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• 제21권2호
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• pp.94-101
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• 1977

2,4-치환 또는 2,4,6-치환아니솔유도체들의 핵자기공명스펙트라를 조사하여 벤젠고리 수소의 화학적 이동 값을 검토하였다. 그 결과 2-치환기에 인접된 고리 수소의 화학적이동 값이 그 치환기의 안가려막기효과(Deshielding effect)에 의하여서 영향을 받고 있으며 그 정도가 치환기이 Van der Waals 반경에 비례하여 증가함을 관찰하였다. 이들 관찰결과를 종합 고찰하여서 2-치환기가 인접된 고리 수소의 반응성에 입체적인 방해효과를 미치고 있는 한가지 근거로서 해석하고자 하였다. 핵자기 공명스펙트라에서 얻은 자료를 제시 하였으며, 그 결과를 이 관점에서 논의하였다.

• Bulletin of the Korean Chemical Society
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• 제32권11호
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• pp.4011-4015
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• 2011

We explored the interpretation of the well-accepted correlation between the apparent peak maximum position shift and extent of molecular interactions, like hydrogen bonding and dipole-dipole interactions, based on the overlapped multiple band model. The simulation of two overlapped Lorentzian bands was carried out to interpret how the maximum position of a composite peak relates to the relative contributions of two species representing the different levels of molecular interactions, i.e., free (or very weekly bound) vs. strongly bound. To demonstrate the validity of our interpretation of the origin of the peak position shift, the temperaturedependent IR spectra of ethylene glycol were also analyzed. It was found through the analysis of simulated and experimental spectra that the apparent peak shift in certain case can be safely interpreted as the measure of the strength of hydrogen bonding. The result of this study gives a new insight to interpret molecular interactions probed by vibrational spectroscopy.