• 한국환경농학회지
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• 제12권2호
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• pp.169-175
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• 1993

유기인계 화합물중 독성이 매우 강한 O-ethyl S-methyl ethylphosphonothioate (1)의 화학적, 대사적 산화생성물들에 대한 $^{31}P-NMR$ 분석에서 주된 산화 생성물인 O-ethyl ethylphosphonic acid (2)의 chemical shift가 MCPBA 반응에서 40.15ppm, MMPP 반응에서 30.98ppm, microsomal oxidation system에서 29.31ppm, 그리고 집파리 생체실험에서 29.10ppm으로 반응조건에 따라 서로 상당히 상이하게 관찰되었다. 이 산화 생성물의 $^{31}P-NMR$ spectrum 상에서의 chemical shift에 대한 용매효과는 deutero-chloroform을 사용했을때 30.70ppm, 극성 용매인 deuterium oxide를 사용했을때 40.15ppm으로 관찰되었으며, pH에 대한 효과는 pH 3, 5.6, 14에서는 30ppm을 전후하여, pH 1의 강산성 조건하에서는 47.91ppm에서 나타났다. 이는 유기산 형태의 생성물 (2)가 ionized form이 형성될수있는 조건하에서는 산소원자의 비공유전자쌍들에 의하여 인원자가 차폐되어 chemical shift가 upfield쪽으로 이동을하고, 반면 비극성과 강산성 조건하에서는 Protonated form으로 존재하여 인(燐)원자에 대한 차폐효과가 줄어들기 때문에 downfield쪽으로 이동하는 것으로 관찰되었다.

• Bulletin of the Korean Chemical Society
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• 제30권6호
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• pp.1257-1261
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• 2009

We present the theoretical and experimental results of $^{31}P$ NMR and low energy CID MS/MS study of $Hg^{2+}$ binding to fenitrothion (FN). The calculated $^{31}P$ NMR chemical shifts order for FN with $Hg^{2+}$ complex is in good agreement with experimental $^{31}P$ NMR chemical shifts order. The experimental and theoretical $^{31}P$ NMR study of organophosphorus pesticide with $Hg^{2+}$ gives to important information for organophosphorus pesticide metal complexes. ESI-MS and low energy CID MS/MS experiments of $Hg^{2+}$-FN complexes combined with accurate mass measurements give insight into the metal localization and allow unambiguous identification of fragments and hydrolysis products.

• Bulletin of the Korean Chemical Society
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• 제29권11호
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• pp.2252-2258
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• 2008

• 한국자기공명학회논문지
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• 제19권3호
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• pp.112-118
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• 2015

Hsp31 protein is one of the members of DJ-1 superfamily proteins and has a dimeric structure of which molecular weight (MW) is 62 kDa. The mutation of DJ-1 is closely related to early onset of Parkinson's disease. Hsp31 displays $Zn^{+2}$-binding activity and was first reported to be a holding chaperone in E. coli. Its additional glyoxalase III active has recently been characterized. Moreover, an incubation at $60^{\circ}C$ induces Hsp31 protein to form a high MW oligomer (HMW) in vitro, which accomplishes an elevated holding chaperone activity. The NMR technique is elegant method to probe any local or global structural change of a protein in responses to environmental stresses (heat, pH, and metal). Although the presence of the backbone chemical shifts (bbCSs) is a prerequisite for detailed NMR analyses of the structural changes, general HSQC-based triple resonance experiments could not be used for 62 kDa Hsp31 protein. Here, we prepared the per-deuterated Hsp31 and performed the TROSY-based triple resonance experiments for the bbCSs assignment. Here, detailed processes of per-deuteration and the NMR experiments are described for other similar NMR approaches.

• 한국광물학회지
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• 제13권4호
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• pp.186-195
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• 2000

To study phosphate adsorption on kaolinite, $^{31}$ P MAS NMR(magic angle spinning nuclear magnetic resonance spectroscopy)has been used for kaolinite reacted in 0.1 M phosphate solutions at pH’s from 3 to 11. There are at least 3 different forms of phosphate on kaolinite. One is the phosphate physically adsorbed on kaolinite surface (outer-sphere complexes) or species left after vacuum-filtering. The second is the phosphate adsorbed by ligand exchange (inner-sphere complexes), and the third is Al-phosphate precipitates which are pH dependent. Most of the inner-spherer complexes and surface precipitates are mainly on hydroxided Al(aluminol) rather than hydroxided Si(silanol). These are pertinent with the results obtained from the phosphate adsorption experiments on silica gel and ${\gamma}$-Al$_2$O$_3$ as model compounds, respectively. The two peaks with more negative chemical shifts(more shielded) than the ortho-phosphate peak (positive chemical shift) are assigned to be the inner-sphere complexes and surface precipitates. The $^{31}$ P chemical shifts of the Al-phosphate precipitates are more negative than those of inner-sphere complexes at a given pH due to the larger number of P-O-Al linkages per tetrahedron. The chemical shifts of both the inner-sphere complexes and surface precipitates are more negative than those of inner-sphere complexes at a given pH due to the larger number of P-O-Al linkages per tetrahedron. The chemical shifts of both the inner-sphere complexes and surface precipitates become progressively less shielded with increasing pH. For the inner-sphere complexes, decreasing phosphate protonation combined with peak averaging by rapid proton exchange among phosphate tetrahedra with different numbers of protons is though to be the reason for the peak change. The decreasing shielding with increasing pH for surface precipitates is probably due to the decreasing average number of P-O-Al linkages per tetrahedron combined with decreasing protonation like inner-sphere complexes.

• 한국자기공명학회논문지
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• 제11권2호
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• pp.110-114
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• 2007

[ $^{31}P$ ] powder pattern spectra were measured to investigate the aspects of the interaction between the MLV (Multilamellar vesicle) and PMAP-23, a membrane of cathelicidin family and then CSAs(chemical shift anisotropy) were calculated to indentify the extent of perturbation of phospholipid mobility by the peptides. We found that acidic phospholipid interacts strongly with PMAP-23, and the analogues which modified to increase the amphipathic property showed that larger change of CSA. The analogue which introduced positive charge showed the same effects with amphipathic property.

• BMB Reports
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• 제34권5호
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• pp.446-451
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• 2001

The interaction of cytochrome c with binary phospholipid mixtures was investigated by solid-state $^2H$- and $^{31}P$-NMR. To examine the effect of the interaction on the glycerol backbones, the glycerol moieties of phosphatidylcholine (PC), and cardioliph (CL) were specifically deuterated. On the binding of cytochrome c to the binary mixed bilayers, no changes in the quadrupole splittings of each of the components were observed for the PC/PG, PE/CL and PE/PG liposomes. In contrast, the splittings of CL decreased on binging of protein to the PC/CL liposomes, although those of PC did not change at all. This showed that cytochrome c specifically interacts with CL in PC/CL bilayers, and penetrates into the lipid bilayer to some extent so as to perturb the dynamic structure of the glycerol backbone. This is distinctly different from the mode of interaction of cytochrome c with other binary mixed bilayers. In the $^{31}P$-NMR spectra, line broadening and a decrease of the chemical shift anisotropy were observed on the binding of cytochrome c for all binary mixed bilayers that were examined. These changes were more significant for the PC/CL bilayers. Furthermore, the line broadening is more significant for PC than for CL in PC/CL bilayers. Therefore, it can be concluded that with the polar head groups, not only CL but also PC are involved in the interaction with cytochrome c.

• 미생물학회지
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• 제28권2호
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• pp.134-144
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• 1990

In order to examine that what kind of system correlated with cadmium detoxification mechanism in Klebsiella aerogenes ATCC 10031, we tried to investigate the effect of phosphate upon the detoxification and also elucidate whether the cadmium phosphate and/or polymeric Cd-Pi complex is formed actually in cell or not. As the results, it was shown that growing pattern had long lag adaptive phase of 12 hr to 24 hr, at the concentrations of 0.02 mM and 0.08 mM cadmium, respectively. Cadmium was accumulated more highly in the fraction of cell wall and membrane than in those of cytoplasm. In case of phosphate starving cells added cadmium, inorganic polyphosphate system was primarily correlated with Cd-detoxification during the lag phase for the accommodation to cadmium, on the other hand, Cd:Sulfide complex system secondarily correlated it during the stationary phase. These results implied that polyphosphate system and Cd:sulfide complex system, these two systems were operated compensatively each other. Considering the results obsdrved with EM and examined tha changes of sulfide and polyphosphate amount, it was reflected that Cd:S complex was located at the cell surface. In the results of $in-vivo^{31}$P NMR spectra in the cells with cadmium pressure, several phosphate signals arose newly from the polyphosphate region with moving chemical shift of it. This phinomenon strongly implied the actual existence of Dd:Pi comples and /or Cd:poly-P complex in the cell and also the cellular compartmentalization of cadmium detoxifying mechanism.

• Investigative Magnetic Resonance Imaging
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• 제8권2호
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• pp.94-99
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• 2004

목적 : 인체의 심근 및 간조직의 생체내 $^{31}P$ MRS에서 NOE 효과에 의한 분광신호 세기의 증가를 평가하고자 하였으며 또한 동일 장기에서 대사물질에 따른 NOE 효과의 차이를 알아보고자 하였다. 대상 및 방법: 열명의 정상 성인군(남:여=8:2, 연령분포=24-32)을 대상으로 1.5T 자기공명영상/분광 장치에서 $^1H-^{31}P$ 이중 튜닝 표면 코일을 사용하여 생체내 $^{31}P$ MRS를 시행하였다. $^{31}P$ MRS 측정은 이차원 화학변위영상기법을 사용하였으며 동일한 파라미터에서 NOE 효과 없이 그리고 $^1H$ decoupling상태에서 NOE 효과에 의한 $^{31}P$ MRS 데이터를 획득하였다. $^{31}P$ MRS raw data의 postprocessing 후 얻어진 스펙트럼에서 주요 대사물질들의 신호증가를 비교하였다. 결과: 간조직의 $^{31}P$ HRS에서 NOE 효과에 의한 신호증가율은 $\alpha-ATP\;(7\%),\;\beta-ATP\;(9\%),\;\gamma-ATP\;(17\%),\;Pi\;(1\%),\;PDE\;(19\%),\;PME\;(31\%)$였다. 간조직의 경우 크리아틴 키나제가 없기 때문에 PCr 신호는 관찰되지 않았다. 심근의 $^{31}P$ MRS은 whole body 코일이 표면 코일보다 우수한 scout 영상을 제공하여 $^{31}P$ MRS의 localization에 유리하였다. $^{31}P$ 심근 다중 체적 스펙트럼에서 , 혈액의 DPG 신호는 심근으로부터 멀어질 수록 증가하는 양상을 나타내었고 NOE 효과에 의한 신호증가율은 $\alpha-ATP\;(12\%),\;\beta-ATP\;(19\%),\;\gamma-ATP\;(30\%),\;PCr\;(34\%),\;Pi\;(20\%),\;PDE\;(51\%),\;DPG\;(72\%)$ 였다. 결론: 간조직에 비해 심근의 경우 큰 신호증가를 보였고 이는 간조직 대사물질들의 $^{31}P$가 심근과는 다른 $^1H$ coupling을 나타냄을 의미한다고 해석할 수 있다.