• Title/Summary/Keyword: donor-state

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Photosystem I and II Reaction Centers in a New Type Oxygenic Photosynthesis of Acaryochloris marina Based on Chlorophyll d: Studies of Delayed Fluorescence and Triplet State ESR

  • Itoh, Shigeru;Fukushima, Yoshimasa;Itoh, Kunihiro;Maeda, Masanori;Mino, Hiroyuki;Kumazaki, Shigeichi
    • Journal of Photoscience
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    • v.9 no.2
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    • pp.70-73
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    • 2002
  • A cyanobacteria-like organism Aaryochloris marina performs oxygenic photosynthesis with near far-red light by the use of chlorophyll d. Reaction center chlorophyll (Chl) of Photosystem (PS) II of A. marina was studied by analysis of millisecond-delayed fluorescence. Delayed fluorescence is emitted by Chi d indicating efficient energy transfer between antenna Chi d molecules and the unknown primary electron donor of PS II. P740 a reaction center Chl of PS I of A. marina is shown to give a dimer type cation, and triplet state with a D value of 245xlO$\^$-4/ cm$\^$-l/ in contrast to the 280-290 xlO$\^$-4/cm$\^$-l/ values of P700 suggesting triplet spins interacting at a 5% larger distance in P740 than in P700.

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Ab Initio Study of Mechanism of Forming Spiro-Heterocyclic Ring Compound Involving Si and Ge from Dichlorosilylene Germylidene (Cl2Si-Ge:) and Acetone

  • Liu, Dongting;Ji, Hua;Lu, Xiuhui
    • Bulletin of the Korean Chemical Society
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    • v.33 no.12
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    • pp.4079-4083
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    • 2012
  • The mechanism of the cycloaddition reaction between singlet state dichlorosilylene germylidene ($Cl_2Si=Ge:$) and acetone has been investigated with B3LYP/6-$31G^*$ and B3LYP/6-$31G^{**}$ method, from the potential energy profile, we predict that the reaction has one dominant reaction pathway. The presented rule of the reaction is that the two reactants firstly form a Si-heterocyclic four-membered ring germylene through the [2+2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge atom in the Si-heterocyclic four-membered ring germylene and the ${\pi}$ orbital of acetone forming a ${\pi}{\rightarrow}p$ donor-acceptor bond, the Si-heterocyclic four-membered ring germylene further combines with acetone to form an intermediate. Because the Ge atom in the intermediate hybridizes to an $sp^3$ hybrid orbital after the transition state, then, the intermediate isomerizes to spiro-heterocyclic ring compound involving Si and Ge (P4) via a transition state.

Ultrafast Excited State Intramolecular Proton Transfer Dynamics of 1-Hydroxyanthraquinone in Solution

  • Ryu, Jaehyun;Kim, Hyun Woo;Kim, Myung Soo;Joo, Taiha
    • Bulletin of the Korean Chemical Society
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    • v.34 no.2
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    • pp.465-469
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    • 2013
  • Proton transfer reaction is one of the most fundamental processes in chemistry and life science. Excited state intramolecular proton transfer (ESIPT) has been studied as a model system of the proton transfer, since it can be conveniently initiated by light. We report ESIPT reaction dynamic of 1-hydroxy-anthraquione (1-HAQ) in solution by highly time-resolved fluorescence. ESIPT time of 1-HAQ is determined to be $45{\pm}10$ fs directly from decay of the reactant fluorescence and rise of the product fluorescence. High time resolution allows observation of the coherent vibrational wave packet motion in the excited state of the reaction product tautomer. The coherently excited vibrational mode involves large displacement of the atoms, which shortens the distance between the proton donor and the acceptor. With the theoretical analysis, we propose that the ESIPT of 1-HAQ proceeds barrierlessly with assistance of the skeletal vibration, which in turn becomes excited coherently by the ESIPT reaction.

Relation Between Defect State and Negative Ultra-Violet Photoresponse from n-ZnO/p-Si Heterojunction Diode

  • Jo, Seong-Guk;Nam, Chang-U;Kim, Eun-Gyu
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.08a
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    • pp.191.2-191.2
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    • 2013
  • The negative photoconductivity was frequently observed in some semiconductors. It was known that the origin of the negative photoresponse from ZnO is molecular chemisorption or the charging effect of nanoparticles in bulk matrix. However, the origin of the negative photoresponse of thin film was not still clear. One of possible explanation is due to the deep level trap scheme, which describes the origin of the negative photoresponse via defect state under illumination of light. However, the defect states below Fermi level have high capture rate by Coulomb effect, so that these states are usually filled by electrons if the defect states have donor-like character. Therefore the condition which the defect states located in below Fermi level should be partially filled by electrons make more difficult to understand of mechanism of the negative photoresponse. In this study, n-ZnO/p-Si heterojunction diodes were fabricated by UHV RF magnetron sputter. Then, some diodes show the negative photoresponse under ultra-violet light illumination. The defect state of the ZnO was analyzed by photoluminescence and deep level transient spectroscopy. To interpret the negative photoconductivity, band diagram was simulated by using SCAPS program.

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Dissolution and Duodenal Permeation Characteristics of Lovastatin from Bile Salt Solid Dispersions (담즙산염과의 고체분산체로부터 로바스타틴의 용출 및 십이지장 점막 투과 특성)

  • Chun, In-Koo
    • Journal of Pharmaceutical Investigation
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    • v.39 no.2
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    • pp.97-106
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    • 2009
  • Although lovastatin (LS) is widely used in the treatment of hypercholesterolemia, its bioavailability is known to be around 5%. This study was aimed to increase the solubility and dissolution-permeation rates of LS using solid dispersions (SDs) with bile salts. The solubilities of LS in water, aqueous bile salt solutions and non-aqueous vehicles were determined, and effects of bile salts on the cellulose or duodenal permeation of LS from SDs were evaluated using a horizontal permeation system. SDs were prepared at various ratios of LS to carriers, such as sodium deoxycholate (SDC), sodium glycocholate (SGC) and/or 2-hydroxypropyl-$\beta$-cyclodextrin (HPCD). The addition of bile salts (25 mM) in water increased markedly the solubility of LS by the micellar solubilization. Some non-aqueous vehicles were effective in solubilizing LS. From differential scanning calorimetric studies, it was found that the crystallinity of LS in SDs disappeared, indicating a formation of amorphous state. The SDs showed markedly enhanced dissolution compared with those of their physical mixtures (PMs) and drug alone. In the dissolution-permeation studies using a cellulose membrane, the donor and receptor solutions were maintained as a sink condition using pH 7.0 phosphate buffer containing 0.05% sodium lauryl sulfate (SLS). The flux of LS alone was nearly same as that of LS-SDC-HPCD (1:3:6) PM. However, the flux of LS-SDC-HPCD (1:3:6) SD slightly increased compared with drug alone and PM, suggesting that entrapment of LS in micelles does not significantly hinder the permeation across cellulose membrane. In the dissolution-duodenal permeation studies using a LS-HPCD-SDC (1:3:6) SD, the addition of various bile salts in donor solutions (25 mM) enhanced the permeation of LS markedly, and the fluxes were found to be $0.69{\pm}0.41$, $0.87{\pm}0.51$, $0.84{\pm}0.46$, $0.47{\pm}0.17$ and $0.68{\pm}0.32{\mu}g/cm^2/hr$ for sodium cholate (SC), SDC, SGC, sodium taurodeoxycholate (STDC) and sodium taurocholate (STC), respectively. The stepwise increase of donor SGC concentration increased the flux dose-dependently. From the relationship of donor SGC concentration and flux, the concentration of SGC initiating the permeation across the duodenal mucosa was calculated to be 11.1 mM, which is nearly same as the critical micelle concentration (CMC, 11.6 mM) of SGC. However, with no addition of bile salts and below CMC, the permeation was very limited and irratic, indicating that LS itself is very poor permeable. Higher protions of bile salt in SD such as LS-SDC or LS-SGC (1 : 49 and 1 : 69) showed highly promoted fluxes. In conclusion, SD systems with bile salts, which may form their micelles in intestinal fluids, might be a promising means for providing enhanced dissolution and intestinal permeation of practically insoluble and non-absorbable LS.

Relationship between Transferable Embryos and Major Metabolite Concentrations in Holstein Donor Cows

  • Son, Jun-Kyu;Jung, Yeon-Sub;Cho, Sang-Rae;Baek, Kwang-Soo;Yoon, Ho-Beak;Lim, Hyun-Joo;Kwon, Eung-Gi;Kim, Sang-Bum;Choe, Changyong
    • Journal of Embryo Transfer
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    • v.27 no.4
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    • pp.229-235
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    • 2012
  • This research was investigated the relationship, in high-producing Holstein donor cows, between the number of the transferable embryos and the blood serum concentrations of Blood Urea Nitrogen (BUN), glucose and cholesterol, which affect the nutritional state of cows. CIDRs were inserted into the vaginas of twenty two heads of Holstein cows, regardless of estrous cycle. Superovulation was induced using folliclar stimulating hormone (FSH). For artificial insemination, donor cows were injected with $PGF_{2{\alpha}}$ and estrus was checked about 48 hours after the injection. Then they were treated with 4 straws of semen 3 times, with 12-hour intervals. Embryos were collected by a non-surgical method 7 days after the first artificial insemination. The total numbers of ova collected from 3 experimental groups whose blood BUN concentrations were <10 mg/dl, 11~18 mg/dl and ${\geq}19$ mg/dl were 8.9, 12.5 and 19.0, respectively; whereas the numbers of transferable embryos were 5.8 + 1.9, 7.9 + 2.8 and 5.2 + 1.4, respectively. When glucose concentration was <60 mg/dl, the total number of collected ova was 9.9, which was smaller than when the concentration was 60~70 mg/dl or ${\geq}70$ mg/dl. When glucose concentration was 60~70 mg/dl, the number of transferable embryos was 7.1 + 2.4, which was slightly larger than the numbers 6.4 + 2.1 and 6.1 + 1.7 that were obtained when the concentrations were <60 mg/dl and ${\geq}70$ mg/dl, respectively ; however, the differences were not significant (p>0.05). When cholesterol concentrations were <150 mg/dl, 150~200 mg/dl and ${\geq}200$ mg/dl, the total numbers of collected ova were 11.2, 11.3 and 8.6, respectively. Whereas the numbers of transferable embryos were 7.1 + 2.1, 7.3 + 1.9 and 5.6 + 1.3, respectively ; however, the differences were again not significant (p>0.05). The result of this research showed no significant difference in ovum recovery rate and the number of transferable embryos according to major metabolite concentrations in high-producing Holstein donor cows. However, it is considered that the failure of maintaining proper nutritional status would cause the fall in in vivo embryo productivity.

Inhibition of Graft Versus Host Disease Using CD4+CD25+ T Cells Induced with Interleukin-2 in Mismatched Allogeneic Murine Hematopoietic Stem Cell Transplantation (주조직적합항원이 불일치하는 마우스 동종 조혈모세포이식에서 IL-2로 유도된 CD4+CD25+ T세포를 이용한 이식편대숙주병의 억제)

  • Hyun, Jae Ho;Jeong, Dae Chul;Chung, Nak Gyun;Park, Soo Jeong;Min, Woo Sung;Kim, Tai Gyu;Choi, Byung Ock;Kim, Won Il;Han, Chi Wha;Kim, Hack Ki
    • IMMUNE NETWORK
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    • v.3 no.4
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    • pp.287-294
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    • 2003
  • Background: In kidney transplantation, donor specific transfusion may induce tolerance as a result of some immune regulatory cells against the graft. In organ transplantation, the immune state arises from a relationship between the immunocompromised graft and the immunocompetent host. However, a reverse immunological situation exists between the graft and the host in hematopoietic stem cell transplantation (HSCT). In addition, early IL-2 injections after an allogeneic murine HSCT have been shown to prevent lethal graft versus host disease (GVHD) due to CD4+ cells. We investigated the induction of the regulatory CD4+CD25+ cells after a transfusion of irradiated recipient cells with IL-2 into a donor. Methods: The splenocytes (SP) were obtained from 6 week-old BALB/c mice ($H-2^d$) and irradiated as a single cell suspension. The donor mice (C3H/He, $H-2^k$) received $5{\times}10^6$ irradiated SP, and 5,000 IU IL-2 injected intraperitoneally on the day prior to HSCT. The CD4+CD25+ cell populations in SP treated C3H/He were analyzed. In order to determine the in vivo effect of CD4+CD25+ cells, the lethally irradiated BALB/c were transplanted with $1{\times}10^7$ donor BM and $5{\times}10^6$ CD4+CD25+ cells. The other recipient mice received either $1{\times}10^7$ donor BM with $5{\times}10^6$ CD4+ CD25- cells or the untreated SP. The survival and GVHD was assessed daily by a clinical scoring system. Results: In the MLR assay, BALB/c SP was used as a stimulator with C3H/He SP, as a responder, with or without treatment. The inhibition of proliferation was $30.0{\pm}13%$ compared to the control. In addition, the MLR with either the CD4+CD25+ or CD4+CD25- cells, which were isolated by MidiMacs, from the C3H/He SP treated with the recipient SP and IL-2 was evaluated. The donor SP treated with the recipient cells and IL-2 contained more CD4+CD25+ cells ($5.4{\pm}1.5%$) than the untreated mice SP ($1.4{\pm}0.3%$)(P<0.01). There was a profound inhibition in the CD4+CD25+ cells ($61.1{\pm}6.1%$), but a marked proliferation in the CD4+CD25- cells ($129.8{\pm}65.2%$). Mice in the CD4+CD25+ group showed low GVHD scores and a slow progression from the post-HSCT day 4 to day 9, but those in the control and CD4+CD25- groups had a high score and rapid progression (P<0.001). The probability of survival was 83.3% in the CD4+CD25+ group until post-HSC day 35 and all mice in the control and CD4+CD25- groups died on post-HSCT day 8 or 9 (P=0.0105). Conclusion: Donor graft engineering with irradiated recipient SP and IL-2 (recipient specific transfusion) can induce abundant regulatory CD4+CD25+ cells to prevent GVHD.

The Rate Maxima and Hammett Correlation for the Nucleophilic Substitution (친핵성 치환반응에서 최대속도현상과 Hammett상관관계)

  • 성대동;임귀택
    • The Korean Journal of Food And Nutrition
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    • v.8 no.3
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    • pp.172-183
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    • 1995
  • The nucleophilic substitution reactions of p-substituted benzyl bromide with l-substituted N,N-dimethylanilines in methanol and acetonitrile binary solvent mixture which is known to an isodielectric solvent system kinetically and the results are as follows. The positive charge is developed on the reaction center of the substrate and it means that the bond cleavage is preceded more than bond formation in the transition state on the analogy of Hammett px values. The bond form3tlon is not progressed in the case of electron donating substituent of substrate. However, the bond formation is much developed in the case of electron withdrawing substituent of substrate on the analogy of Hammett py values. The nucleophilic attacking ability is shown a highest at 80% (V/V) methanol content and the bond formation is well progressed at the same methanol composition on the result of a cross interaction coefficient, pxy. The result of transition state structure that is applicated to the potential energy surface model is in accord with the result that Is applicated to the reaction susceptibilities. The reaction Is subject to the polarity-polarizability term more than the hydrogen bond donor acidity term by application to the solvatochromic parameter eouation.

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A FRET Assay for Celiac Disease

  • Lee, Sae A;Cho, Chul Min;Jang, Il Ho;Kang, Jung Sook
    • Biomedical Science Letters
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    • v.22 no.4
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    • pp.160-166
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    • 2016
  • To provide a basis for a homogeneous fluorescence resonance energy transfer (FRET) immunoassay for celiac disease, we carried out a FRET experiment using guinea pig tissue transglutaminase (tTG) and antibodies to tTG (anti-tTG) purified from rat serum. Fluorescein was utilized as the probe, and a nonfluorescent dye, QSY 7 served as the quencher. We labeled anti-tTG and tTG with fluorescein isothiocyanate and QSY 7 succinimidyl ester, respectively. Fluorescein-labeled anti-tTG was the donor, and QSY 7-labeled tTG was the acceptor of the FRET experiment. When we titrated fluorescein-labeled anti-tTG with QSY 7-labeled tTG, we observed a large decrease in the steady-state fluorescence intensity, which was due to strong FRET from fluorescein-labeled anti-tTG to QSY 7-labeled tTG. Using time-resolved fluorescence spectroscopy, we could also observe a decrease in the fluorescence lifetime, which confirms the steady-state data. We expect that these results might be useful in the development of a novel fluorescence immunoassay for an easy screening and follow-up of celiac patients.

Influence of NiO additive on electrical properties of ZnO-based ceramic varistors (ZnO세라믹 바리스터에 NiO첨가가 전기적 특성에 미치는 영향)

  • 남춘우
    • Electrical & Electronic Materials
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    • v.9 no.6
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    • pp.542-550
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    • 1996
  • ZnO-based ceramic varistors containing NiO range 0.5 mol% to 4.0 mol% were fabricated by standard ceramic techniques. The influence of NiO on the microstructure and electrical behavior of ZnO varistor was investigated. As the content of NiO additive increases, average grain size decreased from 16.5.mu.m to 13.2.mu.m, and the amount of NiO existing in the grain interior and grain boundary region was approximately equal. NiO acted as an acceptor which decreases donor concentration due to the increase of Zn vacancy in the grain, and as a driver which migrates Zn interstitial in the depletion region toward the interface of grain boundary, which resulted in the decrease of interface state density. As a result, increasing the content of NiO additive, barrier height, nonlinear exponent, and varistor voltage decreased, and leakage current increased. Wholly, the physical and electrical properties of the ZnO varistor can be said to be affected by the NiO additive.

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