• Title/Summary/Keyword: Reaction Oxygen

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Effects of Head Acupuncture Versus Upper and Lower Limbs Acupuncture on Signal Activation of Blood Oxygen Level Dependent(BOLD) fMRI on the Brain and Somatosensory Cortex (두침과 상하지 침자극이 뇌와 뇌의 체성감각피질에 미치는 영향에 대한 fMRI Study)

  • Park, Jung-Mi;Gwak, Ja-Young;Cho, Seung-Yeon;Park, Seong-Uk;Jung, Woo-Sang;Moon, Sang-Kwan;Ko, Chang-Nam;Cho, Ki-Ho;Kim, Young-Suk;Bae, Hyung-Sup;Jang, Geon-Ho;Bang, Jae-Seung
    • Journal of Acupuncture Research
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    • v.25 no.5
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    • pp.151-165
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    • 2008
  • Objectives : To evaluate the effects of Head Acupuncture versus Upper and Lower Limbs Acupuncture on signal activation of Blood Oxygen Level Dependent(BOLD) fMRI on the Brain and Somatosensory Cortex. Subjects and Methods : 10 healthy normal right-handed female volunteer were recruited. The average age of the 10 subjects was 30 years old. The BOLD functional MRI(fMRI) signal characteristics were determined during tactile stimulation was conducted by rubbing 4 acu-points in the right upper and lower limbs($LI_1$, $LI_{10}$, $LV_3$, $ST_{36}$). After stimulation of Head Acupuncture in Sishencong($HN_1$), $GB_{18}$, $GB_9$, $TH_{20}$ of Left versus Upper and Lower Limbs Acupuncture($LI_1$, $LI_{10}$, $LV_3$, $ST_{36}$ of Right) and took off needles. Then the BOLD fMRI signal characteristics were determined at the same manner. Results : 1. When touched with cotton buds(sensory stimulation), left Parietal Lobe, Post-central Gyrus, primary somatosensory cortex(BA 1, 2, 3), and primary motor cortex(BA 4) were mainly activated. When $ST_{36}$ was stimulated, Frontal Lobe, Parietal Lobe, Cerebellum, and Posterior Lobe as well as Inter-Hemispheric displaying a variety of regions. 2. In signal activation before and after Head Acupuncture reaction, it showed signal activation after removing the acupuncture needle and right Somatosensory Association Cortex, Postcentral Gyrus, and Parietal Lobe were more activated. 3. In reactions of before and after Upper and Lower Limb Acupuncture, it also showed signal activation after removing the acupuncture needle and bilateral Occipital Lobe, Lingual Gyrus, visual association cortex, and Cerebellum were activated. 4. After acupuncture stimulation, In Upper and Lower Limb Acupuncture Group, left frontal Lobe, Precentral Gyrus and Bilateral parietal lobe, Postcentral Gyrus and Primary Somatosensory Cortex(BA 2) were activated. In Head Acupuncture Group, which has most similar activation regions, but especially right Pre-Post central Gyrus, Primary Somatosensory Cortex(BA 3), Primary Motor Cortex, frontal Lobe and Parietal Lobe were activated. Conclusions : When sensory stimulation was done with cotton buds on four acup-points($LI_1$, $LI_{10}4, $LV_3$, $ST_{36}$), while bilaterally activated, contralateral sense was more dominant. It showed consistency with cerebral cortex function. When $ST_{36}$ was stimulated Frontal Lobe, Parietal Lobe, Cerebellum, Posterior Lobe as well as Inter-Hemispheric were stimulated. In Head Acupuncture, it showed more contralateral activation after acupuncture. In Upper and Lower Limb Acupuncture, it showed typically contralateral activation and deactivation of limbic system after acupuncture stimulation. Therefore, there were different fMRI BOLD signal activation reaction before and after Head Acupuncture vs Upper and Lower Limb Acupuncture which might be thought to be caused by acu-points' sensitivity and different sensory receptor to response acupuncture stimulation.

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Relationship between Stratum Corneum Carbonylated Protein (SCCP) and Skin Biophysical Parameters (Stratum Corneum Carbonylated Protein (SCCP)의 피부 생물학적 파라미터와의 관계)

  • Lee, Yongjik;Nam, Gaewon
    • Journal of the Society of Cosmetic Scientists of Korea
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    • v.45 no.2
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    • pp.131-138
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    • 2019
  • Carbonylated proteins (CPs) are synthesized by the chemical reaction of basic amino acid residues in proteins with aldehyde compounds yielded by lipid peroxidation. CPs are excited by a range of light from UVA to blue light, and resulted in the generation of superoxide anion radicals ($^{\cdot}O_2{^-}$) by photosensitizing reaction. Then, they CPs induce new protein carbonylation in stratum corneum through ROS generation. Furthermore, the superoxide anion radicals produce CPs in the stratum corneum (SC) through lipid peroxidation and finally affects skin conditions including color and moisture functions. The purpose of this study was to investigate the relationship between the production of stratum corneum carbonylated protein (SCCP) and the skin elasticity. 46 healthy female Koream at the ages of 30 ~ 50 years old were participated in this study for 8 weeks. The skin test was experiment conducted into two groups; placebo group (N = 23) used cream that did not contain active ingredients, and the other group (N = 23) used cream containing the elasticity improving ingredients. Test areas were the crow 's feet and the cheek. Various non-invasive methods were carried out to measure biophysical parameters on human skin indicating that dermis density and skin wrinkle were measured by using DUB scanner and Primos premium, respectively. Skin elasticity were measured using dermal torque meter (DTM310) and balistometer (BLS780). SCCP was assessed in a simple and non-invasive method using skin surface biopsy on the cheek of the subject. The amount of SCCP was determined using image analysis. All measurements were taken at 0, 4 and 8 8week. Results revealed that the amount of CP in SC was reduced when the skin wrinkle and skin elasticity related parameters were improved. This indicates that the correlation between the elasticity improvement and the amount of CP can be used as a anti-aging indicator and applicable to the skin clinical test for the measurement of skin aging in the future.

Salty-taste Activation of Human Brain Disclosed by Gustatory fMRI Study (뇌기능 자기공명영상 장치를 이용한 짠맛 자극에 따른 인간 뇌의 반응에 대한 기초 연구)

  • Kim S.H.;Choi K.S.;Lee H.Y.;Shin W.J.;Eun C.K.;Mun C.W.
    • Investigative Magnetic Resonance Imaging
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    • v.9 no.1
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    • pp.30-35
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    • 2005
  • Purpose : The purpose of this study is to observe the blood oxygen level dependent (BOLD) contrast changes due to the reaction of human brain at a gustatory sense in response to a salty-taste stimulation. Materials and Methods : Twelve healthy, non-smoking, right-handed male subjects (mean age: 25.6, range: 23-28 years) participated in this salty-taste stimulus functional magnetic resonance (fMRI) study. MRI scans were performed with 1.57 GE Signa, using a multi-slice GE-EPI sequence according to a blood-oxy-gen-level dependent (BOLD) experiment paradigm. Scan parameters included matrix size $128\times128$, FOV 250 mm, TR 5000 msec, TE 60 msec, TH/GAP 5/2 mm. Sequential data acquisitions were carried out for 42 measurements with a repetition time of 5 sec for each taste-stimulus experiments. Analysis of fMRI data was carried out using SPM99 implemented in Matlab. NaCl solution $(3\%)$ was used as a salty stimulus. The task paradigm consisted of alternating rest-stimulus cycles (30-second rest, 15-second stimulus) for 210 seconds. During the stimulus period, NaCl-solution was presented to the subject's mouth through plastic tubes as a bolus of delivered every 5 sec using -processor controlled auto-syringe pump. Results : Insula, frontal opercular taste cortex, amygdala and orbitofrontal cortex (OFC) were activated by a salty-taste stimulation $(NaCl,\;3\%)$ in the fMRI experiments. And dosolateral prefrontal cortex (DLPFC) was also significantly responded to salty-taste stimuli. Activation areas of the right side hemisphere were more superior to the left side hemisphere. Conclusion : The results of this study well correspond to the fact that both insula, amygdala, OFC, DLPFC areas are established as taste cortical areas by neuronal recordings in primates. Authors found that laboratory-developed auto-syringe pump is suitable for gustatory fMRI study. Further research in this field will accelerate to inquire into the mechanism of higher order gustatory process.

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Reactive Oxygen Species Mediates Lysophosphatidic Acid-induced Migration of SKOV-3 Ovarian Cancer Cells (SKOV-3 난소암 세포주에서 lysophosphatidic acid 유도 세포의 이동에 있어 활성산소의 역할)

  • Kim, Eun Kyoung;Lee, Hye Sun;Ha, Hong Koo;Yun, Sung Ji;Ha, Jung Min;Kim, Young Whan;Jin, In Hye;Shin, Hwa Kyoung;Bae, Sun Sik
    • Journal of Life Science
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    • v.22 no.12
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    • pp.1621-1627
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    • 2012
  • Cell motility plays an essential role in many physiological responses, such as development, immune reaction, and angiogenesis. In the present study, we showed that lysophosphatidic acid (LPA) modulates cancer cell migration by regulation of generation of reactive oxygen species (ROS). Stimulation of SKOV-3 ovarian cancer cells with LPA strongly promoted migration. but this migration was completely blocked by pharmacological inhibition of phosphatidylinositol 3-kinase (PI3K)/Akt signaling pathway. Inhibition of the ERK pathway had no effect on migration. Stimulation of SKOV-3 ovarian cancer cells with LPA significantly induced the generation of ROS in a time-dependent manner. LPA-induced generation of ROS was significantly blocked by pharmacological inhibition of PI3K or Akt, but inhibition of the ERK signaling pathway had little effect. LPA-induced generation of ROS was blocked by pretreatment of SKOV-3 ovarian cancer cells with an NADPH oxidase inhibitor, whereas inhibition of xanthine oxidase, cyclooxygenase, or mitochondrial respiratory chain complex I had no effect. Scavenging of ROS by N-acetylcysteine completely blocked LPA-induced migration of SKOV-3 ovarian cancer cells. Inhibition of NADPH oxidase blocked LPA-induced migration whereas inhibition of xanthine oxidase, cyclooxygenase, or mitochondrial respiratory chain complex I did not affect LPA-induced migration of SKOV-3 ovarian cancer cells. Given these results, we suggest that LPA induces ROS generation through the PI3K/Akt/NADPH oxidase signaling axis, thereby regulating cancer cell migration.

Equilibrium Fractionation of Clumped Isotopes in H2O Molecule: Insights from Quantum Chemical Calculations (양자화학 계산을 이용한 H2O 분자의 Clumped 동위원소 분배특성 분석)

  • Sehyeong Roh;Sung Keun Lee
    • Korean Journal of Mineralogy and Petrology
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    • v.36 no.4
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    • pp.355-363
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    • 2023
  • In this study, we explore the nature of clumped isotopes of H2O molecule using quantum chemical calculations. Particularly, we estimated the relative clumping strength between diverse isotopologues, consisting of oxygen (16O, 17O, and 18O) and hydrogen (hydrogen, deuterium, and tritium) isotopes and quantify the effect of temperature on the extent of isotope clumping. The optimized equilibrium bond lengths and the bond angles of the molecules are 0.9631-0.9633 Å and 104.59-104.62°, respectively, and show a negligible variation among the isotopologues. The calculated frequencies of the modes of H2O molecules decrease as isotope mass number increases, and show a more prominent change with varying hydrogen isotopes over those with oxygen isotopes. The equilibrium constants of isotope substitution reactions involving these isotopologues reveal a greater effect of hydrogen mass number than oxygen mass number. The calculated equilibrium constants of clumping reaction for four heavy isotopologues showed a strong correlation; particularly, the relative clumping strength of three isotopologues was 1.86 times (HT18O), 1.16 times (HT17O), and 0.703 times (HD17O) relative to HD18O, respectively. The relative clumping strength decreases with increasing temperature, and therefore, has potential for a novel paleo-temperature proxy. The current calculation results highlight the first theoretical study to establish the nature of clumped isotope fractions in H2O including 17O and tritium. The current results help to account for diverse geochemical processes in earth's surface environments. Future efforts include the calculations of isotope fractionations among various phases of H2O isotopologues with a full consideration of the effect of anharmonicity in molecular vibration.

MnO2 co-catalyst effect on Photoelectrochemical Properties of GaN Photoelectrode (MnO2 조촉매가 코팅된 GaN 광전극의 광전기화학적 특성)

  • Kim, Haseong;Bae, Hyojung;Kang, Sung-Ju;Ha, Jun-Seok
    • Journal of the Microelectronics and Packaging Society
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    • v.23 no.4
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    • pp.113-117
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    • 2016
  • Recently, hydrogen is regarded as important energy in the future, because it is clean and renewable. The photoelectrochemical (PEC) system, which produce hydrogen using water splitting by solar energy, is one of the most promising energy systems because it has abundant energy sources and good theoretical efficiency. GaN has recently been regarded as suitable photoelectrode that could be used to split water to generate hydrogen without extra bias because its band edge position include water redox potential ($V_{redox}=1.23$ vs. SHE). GaN also shows considerable corrosion resistance in aqueous solutions and it is possible to control its properties, such as structure, band gap, and catalyst characteristics, in order to improve solar energy conversion efficiency. But, even if the band edge position of GaN make PEC reaction facilitate without bias, the overpotential of oxygen evolution reaction could reduce the efficiency of system. One of the ways to decrease overpotential is introduction of co-catalyst on photoelectrode. In this paper, we will investigate the effect of manganese dioxide ($MnO_2$) as a co-catalyst. $MnO_2$ particles were dispersed on GaN photoelectrode by spincoater and analyzed properties of the PEC system using potentiostat (PARSTAT4000). After coating $MnO_2$, the flat-band potential ($V_{fb}$) and the onset voltage ($V_{onset}$) were moved negatively by 0.195 V and 0.116 V, respectively. The photocurrent density increased on $MnO_2$ coated sample and time dependence was also improved. These results showed $MnO_2$ has an effect as a co-catalyst and it would enhance the efficiency of overall PEC system.

Effect of Nicotinic Acid on Sperm Characteristic and Oocyte Development after In Vitro Fertilization using Cryopreserved Boar Semen

  • Kim, Yu-Jin;Lee, Sang-Hee;Lee, Yeon-Ju;Oh, Hae-In;Cheong, Hee-Tae;Yang, Boo-Keun;Lee, Seunghyung;Park, Choon-Keun
    • Journal of Embryo Transfer
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    • v.30 no.1
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    • pp.7-15
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    • 2015
  • The objective of this study was to investigate the efficiency of nicotinic acid on sperm cryosurvival and fertilization ability in frozen-thawed boar semen. Boar semen was collected by glove-hand method and was frozen using freezing solution treated to 0, 5, 10 and 20 mM of nicotinic acid. The frozen sperm for sperm characteristic analysis was thawed such as viability, acrosome reaction, and mitochondrial integrity. The frozen-thawed sperm was estimated by SYBR14/PI double staining for viability, FITC-PNA/PI double staining for acrosome reaction and Rhodamine123/PI double staining for mitochondrial integrity using a flow cytometry. The embryo was estimated in vitro development and DCFDA staining for reactive oxygen species assessment. As results, frozen-thawed sperm viability was significantly higher in 5 and 10 mM ($61.1{\pm}1.5%$,$64.7{\pm}2.0%$) of nicotinic acid than other groups (0 mM, $52.1{\pm}2.3%$; 20 mM, $47.8{\pm}5.1%$, P<0.05). The live sperm with acrosome reaction was significantly higher in 5 and 10 mM of nicotinic acid ($26.1{\pm}1.8%$, $24.9{\pm}1.5%$) than other groups (0 mM, $35.3{\pm}0.8%$; 20 mM, $36.5{\pm}1.9%$, P<0.05). The live sperm with mitochondrial integrity was significantly higher in 5 and 10 mM ($84.2{\pm}3.6%$, $88.4{\pm}2.3%$) of nicotinic acid than other groups (0 mM, $77.3{\pm}4.4%$; 20 mM, $73.3{\pm}3.6%$, P<0.05). Blastocyst rate of in vitro development was significantly higher in 10 mM ($17.0{\pm}1.3%$) of nicotinic acid than other groups (0 mM, $9.4{\pm}0.5%$; 5mM, $12.6{\pm}0.8%$; 20 mM, $5.0{\pm}1.0%$, P<0.05). Moreover, total cell number was higher in 5 and 10 mM ($53.6{\pm}2.9%$, $57.9{\pm}2.8%$) of nicotinic acid than other groups (0 mM, $41.0{\pm}1.4%$; 20 mM, $23.2{\pm}2.8%$, P<0.05). Hydrogen peroxide in embryos was lower in 5 mM nicotinic acid ($0.7{\pm}0.1%$) than other groups (0 mM, $1.0{\pm}0.1%$; 10mM, $0.9{\pm}0.0%$; 20 mM, $1.4{\pm}1.0%$, P<0.05). In conclusion, nicotinic acid-treated semen improves cryosurvival and quality of spermatozoa. Also, the fertilized oocytes with nicotinic acid improve quality of embryo and blastocyst formation.

Field Studios of In-situ Aerobic Cometabolism of Chlorinated Aliphatic Hydrocarbons

  • Semprini, Lewts
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2004.04a
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    • pp.3-4
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    • 2004
  • Results will be presented from two field studies that evaluated the in-situ treatment of chlorinated aliphatic hydrocarbons (CAHs) using aerobic cometabolism. In the first study, a cometabolic air sparging (CAS) demonstration was conducted at McClellan Air Force Base (AFB), California, to treat chlorinated aliphatic hydrocarbons (CAHs) in groundwater using propane as the cometabolic substrate. A propane-biostimulated zone was sparged with a propane/air mixture and a control zone was sparged with air alone. Propane-utilizers were effectively stimulated in the saturated zone with repeated intermediate sparging of propane and air. Propane delivery, however, was not uniform, with propane mainly observed in down-gradient observation wells. Trichloroethene (TCE), cis-1, 2-dichloroethene (c-DCE), and dissolved oxygen (DO) concentration levels decreased in proportion with propane usage, with c-DCE decreasing more rapidly than TCE. The more rapid removal of c-DCE indicated biotransformation and not just physical removal by stripping. Propane utilization rates and rates of CAH removal slowed after three to four months of repeated propane additions, which coincided with tile depletion of nitrogen (as nitrate). Ammonia was then added to the propane/air mixture as a nitrogen source. After a six-month period between propane additions, rapid propane-utilization was observed. Nitrate was present due to groundwater flow into the treatment zone and/or by the oxidation of tile previously injected ammonia. In the propane-stimulated zone, c-DCE concentrations decreased below tile detection limit (1 $\mu$g/L), and TCE concentrations ranged from less than 5 $\mu$g/L to 30 $\mu$g/L, representing removals of 90 to 97%. In the air sparged control zone, TCE was removed at only two monitoring locations nearest the sparge-well, to concentrations of 15 $\mu$g/L and 60 $\mu$g/L. The responses indicate that stripping as well as biological treatment were responsible for the removal of contaminants in the biostimulated zone, with biostimulation enhancing removals to lower contaminant levels. As part of that study bacterial population shifts that occurred in the groundwater during CAS and air sparging control were evaluated by length heterogeneity polymerase chain reaction (LH-PCR) fragment analysis. The results showed that an organism(5) that had a fragment size of 385 base pairs (385 bp) was positively correlated with propane removal rates. The 385 bp fragment consisted of up to 83% of the total fragments in the analysis when propane removal rates peaked. A 16S rRNA clone library made from the bacteria sampled in propane sparged groundwater included clones of a TM7 division bacterium that had a 385bp LH-PCR fragment; no other bacterial species with this fragment size were detected. Both propane removal rates and the 385bp LH-PCR fragment decreased as nitrate levels in the groundwater decreased. In the second study the potential for bioaugmentation of a butane culture was evaluated in a series of field tests conducted at the Moffett Field Air Station in California. A butane-utilizing mixed culture that was effective in transforming 1, 1-dichloroethene (1, 1-DCE), 1, 1, 1-trichloroethane (1, 1, 1-TCA), and 1, 1-dichloroethane (1, 1-DCA) was added to the saturated zone at the test site. This mixture of contaminants was evaluated since they are often present as together as the result of 1, 1, 1-TCA contamination and the abiotic and biotic transformation of 1, 1, 1-TCA to 1, 1-DCE and 1, 1-DCA. Model simulations were performed prior to the initiation of the field study. The simulations were performed with a transport code that included processes for in-situ cometabolism, including microbial growth and decay, substrate and oxygen utilization, and the cometabolism of dual contaminants (1, 1-DCE and 1, 1, 1-TCA). Based on the results of detailed kinetic studies with the culture, cometabolic transformation kinetics were incorporated that butane mixed-inhibition on 1, 1-DCE and 1, 1, 1-TCA transformation, and competitive inhibition of 1, 1-DCE and 1, 1, 1-TCA on butane utilization. A transformation capacity term was also included in the model formation that results in cell loss due to contaminant transformation. Parameters for the model simulations were determined independently in kinetic studies with the butane-utilizing culture and through batch microcosm tests with groundwater and aquifer solids from the field test zone with the butane-utilizing culture added. In microcosm tests, the model simulated well the repetitive utilization of butane and cometabolism of 1.1, 1-TCA and 1, 1-DCE, as well as the transformation of 1, 1-DCE as it was repeatedly transformed at increased aqueous concentrations. Model simulations were then performed under the transport conditions of the field test to explore the effects of the bioaugmentation dose and the response of the system to tile biostimulation with alternating pulses of dissolved butane and oxygen in the presence of 1, 1-DCE (50 $\mu$g/L) and 1, 1, 1-TCA (250 $\mu$g/L). A uniform aquifer bioaugmentation dose of 0.5 mg/L of cells resulted in complete utilization of the butane 2-meters downgradient of the injection well within 200-hrs of bioaugmentation and butane addition. 1, 1-DCE was much more rapidly transformed than 1, 1, 1-TCA, and efficient 1, 1, 1-TCA removal occurred only after 1, 1-DCE and butane were decreased in concentration. The simulations demonstrated the strong inhibition of both 1, 1-DCE and butane on 1, 1, 1-TCA transformation, and the more rapid 1, 1-DCE transformation kinetics. Results of tile field demonstration indicated that bioaugmentation was successfully implemented; however it was difficult to maintain effective treatment for long periods of time (50 days or more). The demonstration showed that the bioaugmented experimental leg effectively transformed 1, 1-DCE and 1, 1-DCA, and was somewhat effective in transforming 1, 1, 1-TCA. The indigenous experimental leg treated in the same way as the bioaugmented leg was much less effective in treating the contaminant mixture. The best operating performance was achieved in the bioaugmented leg with about over 90%, 80%, 60 % removal for 1, 1-DCE, 1, 1-DCA, and 1, 1, 1-TCA, respectively. Molecular methods were used to track and enumerate the bioaugmented culture in the test zone. Real Time PCR analysis was used to on enumerate the bioaugmented culture. The results show higher numbers of the bioaugmented microorganisms were present in the treatment zone groundwater when the contaminants were being effective transformed. A decrease in these numbers was associated with a reduction in treatment performance. The results of the field tests indicated that although bioaugmentation can be successfully implemented, competition for the growth substrate (butane) by the indigenous microorganisms likely lead to the decrease in long-term performance.

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Removal of Nitrogen Oxides Using Hydrocarbon Selective Catalytic Reduction Coupled with Plasma (플라즈마가 결합된 탄화수소 선택적 촉매환원 공정에서 질소산화물(NOx)의 저감)

  • Ihm, Tae Heon;Jo, Jin Oh;Hyun, Young Jin;Mok, Young Sun
    • Applied Chemistry for Engineering
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    • v.27 no.1
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    • pp.92-100
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    • 2016
  • Low-temperature conversion of nitrogen oxides using plasma-assisted hydrocarbon selective catalytic reduction of (HC-SCR) was investigated. Plasma was created in the catalyst-packed bed so that it could directly interact with the catalyst. The effect of the reaction temperature, the shape of catalyst, the concentration of n-heptane as a reducing agent, the oxygen content, the water vapor content and the energy density on $NO_x$ removal was examined. $NO_x$ conversion efficiencies achieved with the plasma-catalytic hybrid process at a temperature of $250^{\circ}C$ and an specific energy input (SIE) of $42J\;L^{-1}$ were 83% and 69% for one-dimensional Ag catalyst ($Ag\;(nanowire)/{\gamma}-Al_2O_3$) and spherical Ag catalyst ($Ag\;(sphere)/{\gamma}-Al_2O_3$), respectively, whereas that obtained with the catalyst-alone was considerably lower (about 30%) even with $Ag\;(nanowire)/{\gamma}-Al_2O_3$ under the same condition. The enhanced catalytic activity towards $NO_x$ conversion in the presence of plasma can be explained by the formation of more reactive $NO_2$ species and partially oxidized hydrocarbon intermediates from the oxidation of NO and n-heptane under plasma discharge. Increasing the SIE tended to improve $NO_x$ conversion efficiency, and so did the increase in the n-heptane concentration; however, a further increase in the n-heptane concentration beyond $C_1/NO_x$ ratio of 5 did not improve the $NO_x$ conversion efficiency any more. The increase in the humidity affected negatively the $NO_x$ conversion efficiency, resulting in lowering the $NO_x$ conversion efficiency at the higher water vapor content, because water molecules competed with $NO_x$ species for the same active site. The $NO_x$ conversion efficiency increased with increasing the oxygen content from 3 to 15%, in particular at low SIE values, because the formation of $NO_2$ and partially oxidized hydrocarbon intermediates was facilitated.

Macrocyclic Complexes of Actinide and Lanthanide Metals (Ⅰ). Formation and Properties of Cation Complexes with Macrocyclic Ligands (악틴 및 란탄족금속의 거대고리 착물 (제 1 보). 거대고리 리간드의 금속착물의 형성과 성질)

  • Jeong, O Jin;Choe, Chil Nam;Yun, Seok Jin;Son, Yeon Su
    • Journal of the Korean Chemical Society
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    • v.34 no.2
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    • pp.143-158
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    • 1990
  • Metal complexes were prepared by reacting uranium (Ⅵ), thorium (Ⅳ) and rare earth metal (Ⅲ) ions including Nd (Ⅲ), Sm (Ⅲ) and Ho (Ⅲ) with macrocyclic ligands including five crown ethers, nine crownands and one cryptand ligands, and subjected to NMR studies in order to examine coordination sites of the ligands and compositions of the complexes formed. Among the marcocyclic ligands, crown ethers and crownand ligands have shown down-field shifts of the methylene protons of the lcigands by forming stable complexes with all the metal ions and the differences of chemical shifts were decreased as increasing of the cavity-size of crown ethers for the same metal ions and decreasing of the atomic number of the rare earth metals for the same ligands. It has been found that crownand 22 gave a stable complex with uranium(Ⅵ) ion by the coordination through both oxygen and nitrogen atoms of the ligand whereas no complex was formed with the rare earth metal(Ⅲ) ions, which on the other hand were found to form stable complexes with cryptand 221. The rest of the crowand ligands have also been found to form stable complexes with uranium(Ⅵ) ion by coordinating through all the oxygen and nitrogen atoms of the ligands whereas no complexes were formed with the rare earth metal(Ⅲ) ions. It has also been shown by 1H-NMR study that uranium(Ⅵ), thorium(Ⅳ) and rare earth metal(Ⅲ) ions formed 1:1 complexes with the macrocyclic ligands except for thorium(Ⅳ) complex of 12C4 in which the mole ratio of metal to ligand is 1:2. More stable metal complexes show larger changes in chemical shifts of the coordinated ligand protons. Finally, the rare earth metal(Ⅲ) complexes of 18C6 have shown ligand exchange reaction with the solvent molecules in acetylacetone solution, which was not observed for the uranium (Ⅵ) complexes.

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