• 제목/요약/키워드: ESR Spectroscopy

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Comparative Evaluation of Mn(II) Framework Substitution in MnAPSO-34 and Mn-impregnated SAPO-34 Molecular Sieves Studied by Electron Spin Resonance and Electron Spin Echo Modulation Spectroscopy

  • Gernho Back;Kim, Yanghee;Cho, Young-Soo;Lee, Yong-Ill;Lee, Chul-Wee
    • 한국자기공명학회논문지
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    • 제6권1호
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    • pp.20-37
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    • 2002
  • MnAPSO-34 and Mn-impregnated SAPO-34(Mn-SAPO-34) sample were prepared with various manganese contents and studied by electron spin resonance(ESR) and electron spin echo modulation(ESEM). Electron spin echo modulation analysis of 0.07mo1 % Mn(relative to p) in MnAPSO-34 with adsorbed D$_{2}$O shows two deuteriums at 0.26 nm and two at 0.36 nm from Mn. This suggests that two waters hydrate an MnO$_{4}$ configuration with a D-O bond orientation for the waters as expect for a negatively charged site at low manganese content (0.1 mol%), the ESR spectra of MnAPSO-34 and MnH-SAPO-34 exhibit the same parameters(g 2.01 and A 89 G), but the spectra obtained from MnAPSO-34 samples are better resolved. The decomposition temperature of as-synthesized MnAPSO-34 were in the range of 200-600 $^{\circ}C$ of the morpholine which is 12 $^{\circ}C$ higher than that in as-synthesized MnH-SAPO-34. Infrared spectra showed that the position of a band at 3450 $cm^{-1}$ / shifted about 15 $cm^{-1}$ / toward higher energy in MnAPSO-34 versus MnH-SAPO-34. The modulation depth of the two-pulse ESE of MnAPSO-34 with adsorbed D$_{2}$O is deeper than that of MnH-SAPO-34 with adsorbed D$_{2}$O. Three-pulse ESEM of MnAPSO-34 and MnH-SAPO-34 with adsorbed deuterium oxide shows that the local environments of manganese in the hydrated samples are different, suggesting that Mn(II) is framework substituted in MnAPSO-34 since it obviously occupies an extraframework position in MnH-SAPO-34.

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Radical Scavenging Potential of Hydrophilic Phlorotannins of Hizikia fusiformis

  • Siriwardhana, Nalin;Lee, Ki-Wan;Jeon, You-Jin
    • ALGAE
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    • 제20권1호
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    • pp.69-75
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    • 2005
  • Hizikia fusiformis is well known edible brown seaweed both in Korea and Japan. It has been intensively studied due to its pronounced health benefits. In this study, the radical scavenging (antioxidative) activities of its hydrophilic phlorotannin constituents were studied. An aqueous extract/original extract (OE) of H. fusiformis was initially prepared with heat, enzymes and pH control treatments. Then the original extract was further fractionated (with methylene chloride and methanol) and crude hydrophilic phlorotannin extract (CHPE) was prepared. The radical scavenging activities of both OE and CHPE were determined by using electron spin resonance (ESR) spectrophotometric assays such as 1,1-diphenyl-2-picrylhydrazyl (DPPH), hydroxyl and alkyl radical assays. The CHPE reported significantly (p < 0.05) higher total phenolic (phlorotannins) content (1.23 mg ${\cdot}ml^{-1}$) than that of the OE (0.21 mg ${\cdot}ml^{-1}$). Both OE and CHPE have reported good radical scavenging activities and those activities were dose-dependent. The CHPE have demonstrated significantly higher radical scavenging activities than that of the OE. In comparison, the DPPH radical (6 $\times$ 10$^{-5}$ M) scavenging activities of all the CHPE concentrations (0.25, 0.5 and 1 mg ${\cdot}ml^{-1}$) tested were significantly higher (37.3, 78.2 and 91.6%, respectively) than that of the OE counterparts (11.4, 34.6 and 61.7%, respectively). Alkyl radical scavenging percentages of CHPE at 0.0625, 0.125, 0.25 and 0.5 mg${\cdot}ml^{-1}$ were significantly higher (34.3, 69.2, 80.4 and 88.7%, respectively) than that of the OE (16.6, 41.4, 62.3 and 77.4%, respectively). The percentages of hydroxyl radical scavenging activities of CHPE at the concentrations of 0.25, 0.5 and 1 mg ${\cdot}ml^{-1}$ were 32.5, 59.4 and 84.2 % respectively. Moreover, the hydroxyl radical scavenging activity of OE was quite lower than that of the CHPE. Therefore, these results suggest that the hydrophilic phlorotannins of H. fusiformis are potential radical scavengers thus, a great source of antioxidative nutraceuticles.

Comparative Evaluation of Mn Substitution in a Framework Site in MnAPSO-34 and Mn-impregnated SAPO-34 Molecular Sieves Studied by Electron Spin Resonance and Electron Spin-Echo Modulation Spectroscopy

  • Gernho Back;Cho, Young-Soo
    • 한국자기공명학회:학술대회논문집
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    • 한국자기공명학회 2002년도 International Symposium on Magnetic Resonance
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    • pp.80-80
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    • 2002
  • MnPSO-34 and Mn-impregnated SAPO-34 (Mn-SAPO-34) sample were prepared with various manganese contents and studied by electron spin resonance (ESR) and electron spin-echo modulation (ESEM). Electron spin-echo modulation analysis of 0.07mol % Mn(relative to p) in MnAPSO-34 with adsorbed D$_2$O shows two deuteriums at 0.25 nm and two at 0.36 nm from Mn. This suggests that two waters hydrate an MnO4 configuration with a D-O bond orientation for the waters as expect for a negatively charged site at low manganese content (0.07 mol%), the ESR spectra of MnAPSO-34 and MnH-SAPO-34 exhibit the same parameters (g 2.02 and A 87 G), but the spectra obtained from MnAPSO-34 samples are better resolved. TGA of as-synthesized MnAPSO-34 shows that the decomposition temperature in the range 200-$600^{\circ}C$ of the morpholine is 12$^{\circ}C$ higher than that in as-synthesized MnH-SAPO-34. Infrared spectra shows that the position of a band at about 15 cm-1 toward higher energy in MnAPSO-34 versus MnH-SAPO-34. The modulation depth of the two-pulse ESE of MnAPSO-34 with absorbed D$_2$O is deeper than that of MnH-SAPO-34 with absorbed D$_2$O. Three-pulse ESEM of MnAPSO-34 and MnH-SAPO-34 with absorbed deuterium oxide shows that the local environments of manganese in the hydrated samples are different, suggesting that Mn(II) is framework substituted in MnAPSO-34 since it obviously occupies an extra-framework position in MnH-SAPO-34

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Dioxygen Binding to Dirhodium(Ⅱ, Ⅱ), (Ⅱ, Ⅲ), and (Ⅲ, Ⅲ) Complexes. Spectroscopic Characterization of $[Rh_{2}(ap)_{4}(O_{2})]^{+},\;Rh_{2}(ap)_{4}(O_{2}),\;and\;[Rh_{2}(ap)_{4}(O_{2})]^-$, where ap=2-anilinopyridinate Ion

  • Lee, Jae-Duck;Yao, Chao-Liang;Capdevielle, Francoise J.;Han, Bao-Cheng;Bear, John L.;Kadish, Karl M.
    • Bulletin of the Korean Chemical Society
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    • 제14권2호
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    • pp.195-200
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    • 1993
  • The neutral, reduced, and oxidized 2,2-trans isomers of $Rh_2(ap)_4$ (ap=2-anilinopyridinate) were investigated with respect to dioxygen binding in $CH_2Cl_2$ containing 0.1 M tetrabutyl-ammonium perchlorate. $Rh_2(ap)_4$ binds dioxygen in nonaqueous media and forms a $Rh^{II}Rh^{III}$ superoxide complex, $Rh_2(ap)_4(O_2)$. This neutral species was isolated and is characterized by UV-visible and IR spectroscopy, mass spectrometry and cyclic voltammetry. It can be reduced by one electron at $E_{1/2}$ = -0.45 V vs. SCE in $CH_2Cl_2$ and gives ${[Rh_2(ap)_4(O_2)]}^-$ as demonstrated by the ESR spectrum of a frozen solution taken after controlled potential reduction. The superoxide ion in ${[Rh_2(ap)_4(O_2)]}^-$ is axially bound to one of the two rhodium ions, both of which are in a +2 oxidation state. $Rh_2(ap)_4(O_2)$ can also be stepwise oxidized in two one-electron transfer steps at $E_{1/2}$ = 0.21 V and 0.85 V vs. SCE in $CH_2Cl_2$ and gives ${[Rh_2(ap)_4(O_2)]}^+$ followed by ${[Rh_2(ap)_4(O_2)]}^{2+}$. ESR spectra demonstrate that the singly oxidized complex is best described as ${[Rh^{II}Rh^{III}(ap)_4(O_2)]}^+$ where the odd electron is delocalized on both of the two rhodium ions and the axial ligand is molecular oxygen.

Alaternin and Emodin with Hydroxyl Radical inhibitory and/or Scavenging Activities and Hepatoprotective Activity on Tacrine-Induced Cytotoxicity in HepG2 Cells

  • Jung, Hyun-Ah;Chung, Hae-Young;Takaka, Yokezawa;Kim, Youn-Chul;Hyun, Sook-Kyung;Choi, Jae-Sue
    • Archives of Pharmacal Research
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    • 제27권9호
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    • pp.947-953
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    • 2004
  • The antioxidative and hepatoprotective potentials of two anthraquinones, alaternin (2-hydroxy-emodin) and emodin, to scavenge and/or inhibit hydroxyl radicals generated by the Fenton reaction and to protect tacrine-induced cytotoxicity in human liver derived HepG2 cells were evaluated, respectively. The inhibitory activity on hydroxyl radical generated in a cell-free chemical system (FeSO$_4$/$H_2O$$_2$) was investigated by a fluorescence spectrophotometer using a highly fluorescent probe, 2$^1$,7$^1$-dichlorofluorescein. The hydroxyl radical scavenging activity was determined by electron spin resonance spectroscopy using 5,5-dimethy-1-pyrroline-N-oxide as hydroxyl radicals trapping agents. Tacrine-induced HepG2 cell toxicity was determined by a 3-[4,5-dimethylthiazole-2yl]-2,5-diphenyltertrazolium bromide assay. Although the scavenging activity of alaternin on hydroxyl radical was similar to that of emodin in dose-dependent pat-terns, the inhibitory activity exhibited by the former on hydroxyl radical generation was stron-ger than that of the latter, with $IC_{50}$/ values of 3.05$\pm$0.26 $\mu$M and 13.29$\pm$3.20 $\mu$M, respectively. In addition, the two anthraquinones, alaternin and emodin showed their hepatoprotective activ-ities on tacrine-induced cytotoxicity, and the EC$_{50}$ values were 4.02 11M and 2.37 $\mu$M, respec-tively. Silymarin, an antihepatotoxic agent used as a positive control exhibited the EC$_{50}$ value of 2.00 $\mu$M. These results demonstrated that both alaternin and emodin had the simultaneous antioxidant and hepatoprotective activities.ies.

Dexamethasone Release from Glutaraldehyde Cross-Linked Chitosan Microspheres: In Vitro/In Vivo Studies and Non-Clinical Parameters Response in Rat Arthritic Model

  • Dhanaraju, Magharla Dasaratha;Elizabeth, Sheela;Poovi, Ganesan
    • Journal of Pharmaceutical Investigation
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    • 제41권5호
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    • pp.279-288
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    • 2011
  • The Dexamethasone (DEX) loaded chitosan microspheres were prepared by thermal denaturation and chemical cross-linking method using a dierent concentration of glutaraldehyde as chemical cross-linking agent. The prepared microspheres were evaluated for the percentage of Drug Loading (DL), Encapsulation Efficiency (EE) and surface morphology by Scanning Electron Microscopy (SEM). DL and EE were found to be maximum range of 10.0 to 10.79 % and 58.19 to 64.73 % respectively. The SEM Photographs of the resultant microspheres exhibited fairly smooth surfaces and predominantly spherical in appearance. In addition, Fourier Transform Infrared Spectroscopy (FTIR) and Differential Scanning Calorimetry (DSC) shown that there was no interaction between the drug and polymer. In vitro and in vivo release studies revealed that the release of dexamethasone was sustained and extended up to 63 days and effectively controlled by the extent of cross-linking agent. Non-clinical parameters such as paw volume, hematological parameters like Erythrocyte Sedimentation Rate (ESR), Paced Cell Volume (PCV), Total Leucocytes Count (TLC), Hemoglobin (Hb), Differential Cell Count (DCC) were investigated in Fruend's Complete Adjuvant (FCA) induced arthritic rats. Radiology and histopathological studies were also performed in order to evaluate the therapeutic efficacy of the DEX-loaded microspheres in extenuating the rat arthritic model.

PECVD 증착조건 변화에 따른 a-C;H 박막의 구조 변화

  • 조영옥;노옥환;윤원주;이정근;최영철;이영희;최용각;유수창
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2000년도 제18회 학술발표회 논문개요집
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    • pp.93-93
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    • 2000
  • 수소화된 비정질 탄소(a-C:H)는 그 증착 조건에 따라서 여러 가지 다른 구조와 특성을 갖게 되며, 특히 DLC(diamond-like carbon) 및 CNT(Carbon nanotube)는 FED (field emission display) 개발 면에서 중요하게 연구되고 있다. 우리는 a-C:H 박막을 PECVD (plasma-enhanced chemical vapor deposition) 방법으로 증착하고 CH4 가스를 사용하였고 기판 온도는 상온-32$0^{\circ}C$ 사이에서 변화되었다. 기판은 Corning 1737 glass, quartz, Si, Ni 등을 사용하였다. 증착 압력과 R.F. power는 각각 0.1-1 Torr 와 12-60w 사이에서 변화되었다. ESR 측정은 X-band(주파수 약 9 GHz)에서 그리고 상온에서 행해졌다. 상온에서의 스핀밀도는 약한-표준피치(weak-pitch standard) 스펙트럼과 비교하여 얻을 수 있었다. 그리고 a-C:H 박막의 구조는 He-Ne laser(파장 632.8 nm)를 이용하는 micro-Raman spectroscopy로 분석하였다. 증착조건에 따른 스핀밀도의 변화 및 Raman 스펙트럼에서의 D-peak, G-peak의 위치 및 반치록, I(D)/I(G) 등을 조사하였다. 증착된 a-C:H 박막은 R.F.power가 증가할수록 대체로 스핀밀도가 증가하였으며, Raman 스펙트럼에서의 I(D)/I(G) 비율은 대체로 감소하였다. 증착된 박막들은 polymer-like Carbon으로 추정되었으며, 스핀밀도가 증가할수록 대체적으로 흑연 구조 영역이 증가됨을 알 수 있었다. 또한 glass나 Si 기판에 비해 Ni 기판위에서 polymer-like Carbon 구조는 향상되는 경향을 보였다.

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전자빔 조사된 황마섬유의 화학적 및 열적 특성분석 (Chemical and Thermal Characterizations of Electron Beam Irradiated Jute Fibers)

  • 지상규;조동환;이병철
    • 접착 및 계면
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    • 제11권4호
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    • pp.162-167
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    • 2010
  • 본 연구에서는 셀룰로스계 섬유인 황마(jute)의 화학적 특성 및 열적 특성에 미치는 전자빔조사의 영향을 원소분석, ESR분석, ATR-FTIR 분광분석, 열중량분석 그리고 열기계분석을 통하여 탐구하였다. 전자빔 조사는 전자빔터널 내에서 콘베이어 카트를 이용한 연속식 방법에 의해 2~100 kGy까지 다양한 세기의 전자빔이 황마섬유다발에 일정하게 행하였다. 전자빔 처리는 황마섬유의 화학조성을 다소 변화시켰으며, 전자빔세기가 커질수록 황마섬유에 형성된 라디칼이 증가하는 것으로 확인되었다. 그러나 전자빔 조사는 황마섬유표면의 화학관능기를 크게 변화시키지 않는 것으로 판단되었다. 또한 전자빔 조사는 황마섬유의 열안정성과 열수축/팽창 거동에 영향을 주었으며, 그 거동은 전자빔세기에 의존하였다.

RF 마그네트론 코스퍼터링을 이용한 Si3N4 매트릭스 내부의 실리콘 양자점 제조연구 (Fabrication of Silicon Quantum Dots in Si3N4 Matrix Using RF Magnetron Co-Sputtering)

  • 하린;김신호;이현주;박영빈;이정철;배종성;김양도
    • 한국재료학회지
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    • 제20권11호
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    • pp.606-610
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    • 2010
  • Films consisting of a silicon quantum dot superlattice were fabricated by alternating deposition of silicon rich silicon nitride and $Si_3N_4$ layers using an rf magnetron co-sputtering system. In order to use the silicon quantum dot super lattice structure for third generation multi junction solar cell applications, it is important to control the dot size. Moreover, silicon quantum dots have to be in a regularly spaced array in the dielectric matrix material for in order to allow for effective carrier transport. In this study, therefore, we fabricated silicon quantum dot superlattice films under various conditions and investigated crystallization behavior of the silicon quantum dot super lattice structure. Fourier transform infrared spectroscopy (FTIR) spectra showed an increased intensity of the $840\;cm^{-1}$ peak with increasing annealing temperature due to the increase in the number of Si-N bonds. A more conspicuous characteristic of this process is the increased intensity of the $1100\;cm^{-1}$ peak. This peak was attributed to annealing induced reordering in the films that led to increased Si-$N_4$ bonding. X-ray photoelectron spectroscopy (XPS) analysis showed that peak position was shifted to higher bonding energy as silicon 2p bonding energy changed. This transition is related to the formation of silicon quantum dots. Transmission electron microscopy (TEM) and electron spin resonance (ESR) analysis also confirmed the formation of silicon quantum dots. This study revealed that post annealing at $1100^{\circ}C$ for at least one hour is necessary to precipitate the silicon quantum dots in the $SiN_x$ matrix.

Tumor-like Presentation of Tubercular Brain Abscess: Case Report

  • Karki, Dan B.;Gurung, Ghanashyam;Sharma, Mohan R.;Shrestha, Ram K.;Sayami, Gita;Sedain, Gopal;Shrestha, Amina;Ghimire, Ram K.
    • Investigative Magnetic Resonance Imaging
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    • 제19권4호
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    • pp.231-236
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    • 2015
  • A 17-year-old girl presented with complaints of headache and decreasing vision of one month's duration, without any history of fever, weight loss, or any evidence of an immuno-compromised state. Her neurological examination was normal, except for papilledema. Laboratory investigations were within normal limits, except for a slightly increased Erythrocyte Sedimentation Rate (ESR). Non-contrast computerized tomography of her head revealed complex mass in left frontal lobe with a concentric, slightly hyperdense, thickened wall, and moderate perilesional edema with mass effect. Differential diagnoses considered in this case were pilocytic astrocytoma, metastasis and abscess. Magnetic resonance imaging (MRI) obtained in 3.0 Tesla (3.0T) scanner revealed a lobulated outline cystic mass in the left frontal lobe with two concentric layers of T2 hypointense wall, with T2 hyperintensity between the concentric ring. Moderate perilesional edema and mass effect were seen. Post gadolinium study showed a markedly enhancing irregular wall with some enhancing nodular solid component. No restricted diffusion was seen in this mass in diffusion weighted imaging (DWI). Magnetic resonance spectroscopy (MRS) showed increased lactate and lipid peaks in the central part of this mass, although some areas at the wall and perilesional T2 hyperintensity showed an increased choline peak without significant decrease in N-acetylaspartate (NAA) level. Arterial spin labelling (ASL) and dynamic susceptibility contrast (DSC) enhanced perfusion study showed decrease in relative cerebral blood volume at this region. These features in MRI were suggestive of brain abscess. The patient underwent craniotomy with excision of a grayish nodular lesion. Abundant acid fast bacilli (AFB) in acid fast staining, and epithelioid cell granulomas, caseation necrosis and Langhans giant cells in histopathology, were conclusive of tubercular abscess. Tubercular brain abscess is a rare manifestation that simulates malignancy and cause diagnostic dilemma. MRI along with MRS and magnetic resonance perfusion studies, are powerful tools to differentiate lesions in such equivocal cases.