• Title/Summary/Keyword: $OH^-$

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Change of Seed Dormancy and Viability of Chinese Milk Vetch (Astragalus sinicus L.) in Rice Field (토양속에서 자운영 종자의 휴면성 및 종자활력 변화)

  • Kim, Sang-Yeol;Hwang, Woon-Ha;Lee, Jong-Hee;Oh, Seong-Hwan;Cho, Jun-Hyeon;Han, Sang-Ik;Jeong, Kuk-Hyun;Park, Sung-Tae;Choi, Kyung-Jin;Kim, Jeong-Il;Lee, Ji-Yoon;Song, You-Cheon;Yeo, Un-Sang;Kang, Hang-Won
    • KOREAN JOURNAL OF CROP SCIENCE
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    • v.55 no.1
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    • pp.76-82
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    • 2010
  • Experiments were conducted to investigate seed persistence of Chinese milk vetch(CMV) in naturally reseeded rice field in 2007~2009. The seed and pods with seeds were buried in rice field at 0, 5 and 10 cm depths and retrieved from the field at one to three month intervals from July to the following year March and determined change of seed dormancy and viability. In the second experiment, persistence of the CMV seeds in the naturally reseeded rice field at different tillage methods and soil depths were also investigated after rice harvest in autumn. Burial depths and durations affected recovery rate, dormancy and viability of CMV seed. The viability loss was faster and greater in the seed than the pod with seeds and on the soil surface than the 5 or 10 cm burial depths. The recovery rate of CMV seed was decreased starting from one month as seed burial and it was significantly decreased to 52~65% for the seed in September. However, unlike the seed burial, the nearly 100% CMV seeds were recovered for burial as pod with seeds even after four months burial in both 0 and 5 cm depths. However, the recovery rate was sharply declined to below 30% at October in 2007 in both seed and pods with seeds and in the 2008/2009 experiment. the 15~47% of CMV seeds still remained even after October. The CMV had high seed dormancy of 95%, showing only 4~5% germination at the beginning in June but the seed germination increased to 25 to 35% in seed and 55 to 61% in pod with seeds in September due to breakage of hard seed dormancy. The viability loss was faster in the seed than in the pod with seeds regardless of depths of placement in the soil base on decayed seeds. Also the seed placed on the soil surface lost viability faster than the 5~10 burial depths. On the other hand, field observation in the naturally reseeded CMV rice field showed that as many as 917~2,185 CMV seeds $m^2$ were from the 0~15 cm soil depth in the rotary tillage and 250~10,105 CMV seeds in minimum tillage treatmints. The recovered seed germinated 25~33%, 23~43% but still had high percentage of hard seed having 64~72% and 51~77% even after rice harvest in autumn. These results indicate that freshly harvested CMV seeds had high level of primary dormancy and the dormancy was gradually broken in soil with time during rice cultivation periods and appreciable number of CMV seeds remained even 4 month after burial in soil. CMV plant regenerated naturally from the remained seed bank at rice harvest time in autumn. The CMV seedling still emerged even after 2 years of continuous destructive killing of emerged CMV plant by rotary tillage in naturally reseeded CMV plant in rice field, indicating that CMV seeds do persistent as least two years in soil.

Origin of Organic Matter and Geochemical Variation of Upper Quaternary Sediments from the Ulleung Basin (울릉분지 상부 제4기 퇴적물의 유기물 기원 및 지화학적 분포)

  • Kim, Ji-Hoon;Park, Myong-Ho;Ryu, Byong-Jae;Lee, Young-Joo;Oh, Jae-Ho;Cheong, Tae-Jin;Chang, Ho-Wan
    • Economic and Environmental Geology
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    • v.40 no.5
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    • pp.605-622
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    • 2007
  • Elemental, Rock-Eval pyrolysis and isotopic analysis of the core sediments from the northwestern and eastern Ulleung Basin of the East were carried out to identify their geochemical characteristics, spatial and vertical variation and origin of organic matter in Upper Quaternary sediments from the northwestern and eastern Ulleung Basin of the East Sea. TOC, m and TS did not show spatial variation between the sampling locations whereas they showed systematic vertical variation associated with MIS stages related to the sea-level change of the East Sea. It is suggested that these past changes of sea-level influenced the sedimentary depositional environments and/or diagenesis which resulted the patterns observed in this study. Based on the results of TOC/N, TS/TOC, ${\delta}^{13}C_{org}\;and\;{\delta}^{15}N_{org}$ analysis, organic matters in the study area appears to be predominantly originated from the marine algae rather than land plant and deposited under normal marine oxic condition during MIS I and MIS III period, and under euxinic/anoxic condition during MIS II period. TOC/N, ${\delta}^{13}C_{org}\;and\;{\delta}^{15}N_{org}$ have a relatively constant value irrespective of MIS stages, implying that the organic matter source does not change by the sea-level fluctuations. However, the results of Rock-Eval pyrolysis indicates that the organic matter is in immature stage and originated from land-plant (Type III), locating in the immature stage land plant (Type III). Similar differences were reported from other areas such as the Atlantic Ocean, Iberia Abyssal Plain, Mediterranean Sea, suggesting that Rock-Eval method does not exactly reflect the characteristic of immature organic matters. Accordingly, the application of Rock-Eval pyrolysis for delineating the source of immature organic matters should be approached with caution and all other geochemical proxies should be considered altogether at the same time.

Community Distribution on Mountain Forest Vegetation of the Gyebangsan Area in the Odaesan National Park, Korea (오대산 국립공원 계방산 일대 삼림식생의 군락분포에 관한 연구)

  • Kim, Chang-Hwan;Oh, Jang-Geun;Kang, Eun-Ok;Yun, Chil-Sun;Lim, Jin-Keun
    • Korean Journal of Ecology and Environment
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    • v.47 no.3
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    • pp.135-145
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    • 2014
  • The mountain forest vegetation of Gyebangsan (1,577 m) in Odaesan National Park is classified into deciduous broad-leaved forest, mountain valley forest, coniferous forest, subalpine coniferous forest, subalpine deciduous forest, plantation forest, and other vegetation which includes Actinidia argute community and agricultural land. As for the number of communities distributed in the each forest vegetation which were categorized by the physiognomy classification, deciduous broad-leaved forest had 33 communities, mountain valley forest 41 communities, coniferous forest 8 communities, subalpine coniferous forest 4 communities, subalpine deciduous forest 2 communities, plantation forest 6 communities and other vegetation 4 communities. Regarding the distribution rate of communities in the vegetation, in the deciduous broad-leaved forest. Quercus mongolica community accounted for 80.226% with $30,909,942.967m^2$, followed by Quercus variabilis community of 2.771% with $1,067,479.335m^2$. 55.463% of deciduous broad-leaved forest in the Gyebangsan had Quercus mongolica as a dominant or second dominant species. In the mountain valley forest, Fraxinus rhynchophylla - Juglans mandshurica community accounted for 10.955%. And there were ten mixed communities having Fraxinus rhynchophylla and upper layer at a similar level of coverage, taking up 32.776%. In the coniferous forest, Pinus densiflora and the community living with Pinus densiflora accounted for 100%, showing that the coniferous forest has the community with Pinus densiflora as a dominant species at upper layer. For other vegetation, subalpine coniferous forest had a total of four communities including Abies holophylla - Quercus mongolica community, and accounted for 4.980% of vegetation area of Odaesan National Park. Two communities including Betula ermani - Cornus controversa community were found in the subalpine deciduous forest, taking up 0.006% of total vegetation area of Odaesan National Park. Regarding plantation forest, Larix leptolepis was planted the most with 51.652%, followed by Betula platyphylla var. japonica with 38.975%, and Pinus koraiensis with 7.969%. These three species combined accounted for 98.565%. In conclusion, the forest vegetation found in the Gyebangsan of Odaesan National Park has Quercus mongolica as a dominant species at the top layer. A lot of other communities related with this species are expected to be quickly replaced due to vegetation succession and climatic causes. Therefore, Quercus mongolica is expected to become the main species in the deciduous broad-leaved forest, Fraxinus rhynchophylla, Juglans mandshurica and Fraxinus mandshurica in the mountain valley forest. Around the border line between deciduous broad-leaved forest and mountain valley forest, highly humid valley area is expected to be quickly taken up by Cornus controversa and Fraxinus mandshurica, and the slope area by Quercus mongolica. However, in the subalpine coniferous forest, the distribution rate of deciduous broad-leaved trees is expected to increase due to climate warming.

Oxidative Inactivation of Peroxiredoxin Isoforms by H2O2 in Pulmonary Epithelial, Macrophage, and other Cell Lines with their Subsequent Regeneration (폐포상피세포, 대식세포를 비롯한 각종 세포주에서 H2O2에 의한 Peroxiredoxin 동위효소들의 산화에 따른 불활성화와 재생)

  • Oh, Yoon Jung;Kim, Young Sun;Choi, Young In;Shin, Seung Soo;Park, Joo Hun;Choi, Young Hwa;Park, Kwang Joo;Park, Rae Woong;Hwang, Sung Chul
    • Tuberculosis and Respiratory Diseases
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    • v.58 no.1
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    • pp.31-42
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    • 2005
  • Background : Peroxiredoxins (Prxs) are a relatively newly recognized, novel family of peroxidases that reduce $H_2O_2$ and alkylhydroperoxide into water and alcohol, respectively. There are 6 known isoforms of Prxs present in human cells. Normally, Prxs exist in a head-to-tail homodimeric state in a reduced form. However, in the presence of excess $H_2O_2$, it can be oxidized on its catalytically active cysteine site into inactive oxidized forms. This study surveyed the types of the Prx isoforms present in the pulmonary epithelial, macrophage, endothelial, and other cell lines and observed their response to oxidative stress. Methods : This study examined the effect of exogenous, excess $H_2O_2$ on the Prxs of established cell lines originating from the pulmonary epithelium, macrophages, and other cell lines, which are known to be exposed to high oxygen partial pressures or are believed to be subject to frequent oxidative stress, using non-reducing SDS polyacrylamide electrophoresis (PAGE) and 2 dimensional electrophoresis. Result : The addition of excess $H_2O_2$ to the culture media of the various cell-lines caused the immediate inactivation of Prxs, as evidenced by their inability to form dimers by a disulfide cross linkage. This was detected as a subsequent shift to its monomeric forms on the non-reducing SDS PAGE. These findings were further confirmed by 2 dimensional electrophoresis and immunoblot analysis by a shift toward a more acidic isoelectric point (pI). However, the subsequent reappearance of the dimeric Prxs with a comparable, corresponding decrease in the monomeric bands was noted on the non-reducing SDS PAGE as early as 30 minutes after the $H_2O_2$ treatment suggesting regeneration after oxidation. The regenerated dimers can again be converted to the inactivated form by a repeated $H_2O_2$ treatment, indicating that the protein is still catalytically active. The recovery of Prxs to the original dimeric state was not inhibited by a pre-treatment with cycloheximide, nor by a pretreatment with inhibitors of protein synthesis, which suggests that the reappearance of dimers occurs via a regeneration process rather than via the de novo synthesis of the active protein. Conclusion : The cells, in general, appeared to be equipped with an established system for regenerating inactivated Prxs, and this system may function as a molecular "on-off switch" in various oxidative signal transduction processes. The same mechanisms might applicable other proteins associated with signal transduction where the active catalytic site cysteines exist.

The Central Venous Catheter-related Infection of Chlorhexidine-silver Sulfadiazine Coated Catheters in Medical ICU (내과계 중환자실 환자에서 Chlorhexidine-silver Sulfadiazine Coated Catheter의 중심정맥관 감염에 대한 연구)

  • Jung, Young Ju;Koh, Younsuck;Lim, Chae-Man;Lee, Jae Seung;Yu, Mi Hyun;Oh, Yeon Mok;Shim, Tae Sun;Lee, Sang Do;Kim, Woo Sung;Kim, Dong Soon;Kim, Won Dong;Hong, Sang-Bum
    • Tuberculosis and Respiratory Diseases
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    • v.59 no.4
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    • pp.389-396
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    • 2005
  • Background : Central venous catheters(CVCs) area major source of nosocomial infection. Chlorhexidine-silver sulfadiazine coated catheters (CHSS) were developed to reduce the rate of CVC infection. However, the clinical effectiveness of CHSS in comparison wth non-coated catheter (NCC) remains to be evaluated. Methods : From January 2004 to December 2004 in medical intensive care unit (ICU) of Asan Medical Center, CVCs were inserted in 446 cases. We retrospectively analyzed characteristics of patients and catheterization,the catheter-related infection rate and colonization, microbiologic findings, and insertion sites (subclavian, jugular, femoral) according to the type of inserted CVCs (NCC: 187 cases, CHSS: 259 cases). Catheter related infection is defined as catheter related bacteremia and catheter related non-bacteremic sepsis. Results : 1) The mean age of the patients in each group was $62{\pm}16$ years, $63{\pm}15$ years (p=0.42), and sex ratio 94:50, 141:69 (p=0.9) in NCC and CHSS. Duration of ICU admission ($29{\pm}37$, $26{\pm}44$ p=0.42), duration of mechanical ventilation ($17{\pm}22$, $15{\pm}19$ p=0.17), and APACHE III score at the time of CVC insertion ($81{\pm}34$, $82{\pm}37$ p=0.61) were not different between both groups. 2) Mean duration of catheterization was 118 in NCC and 119 in CHSS (p=0.98). Number of catheter-days was 2176 days in NCC and 3035 days in CHSS. Catheter-related infection occurred in 9 (4.8%) cases receiving NCC and 4 cases (1.5%) receiving CHSS. Catheterrelated infection incidence per 1000 catheter-days was 4.1 and 1.3, respectively (p=0.04). CHSS was associated with a significant reduction of infection in jugular catheters regarding to insertion sites (p=0.01). 3) Microorganisms causing infection were Staphylococcus aureus (n=3), Candida (n=3), coagulase-negative Staphylococci (n=2), and Klebsiella (n=1) in NCC, and Candida species (n=2), coagulase-negative Staphylococci (n=2), Proteus (n=1) in CHSS. Conclusion : CHSS has significantly reduced the episodes of infection compared to NCC in jugular catheterization in medical ICU.

The Etiologies and Initial Antimicrobial Therapy Outcomes in One Tertiary Hospital ICU-admitted Patient with Severe Community-acquired Pneumonia (국내 한 3차 병원 중환자실에 입원한 중증지역획득폐렴 환자의 원인 미생물과 경험적 항균제 치료 성적의 고찰)

  • Lee, Jae Seung;Chung, Joo Won;Koh, Yunsuck;Lim, Chae-Man;Jung, Young Joo;Oh, Youn Mok;Shim, Tae Sun;Lee, Sang Do;Kim, Woo Sung;Kim, Dong-Soon;Kim, Won Dong;Hong, Sang-Bum
    • Tuberculosis and Respiratory Diseases
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    • v.59 no.5
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    • pp.522-529
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    • 2005
  • Background : Several national societies have published guidelines for empirical antimicrobial therapy in patients with severe community-acquired pneumonia (SCAP). This study investigated the etiologies of SCAP in the Asan Medical Center and assessed the relationship between the initial empirical antimicrobial regimen and 30 day mortality rate. Method : retrospective analysis was performed on patients with SCAP admitted to the ICU between March 2002 and February 2004 in the Asan Medical Center. The basic demographic data, bacteriologic study results and initial antimicrobial regimen were examined for all patients. The clinical outcomes including the ICU length of stay, the ICU mortality rate, and 30 days mortality rates were assessed by the initial antimicrobial regimen. Results : One hundred sixteen consecutive patients were admitted to the ICU (mean age 66.5 years, 81.9 % male, 30 days mortality 28.4 %). The microbiologic diagnosis was established in 58 patients (50 %). The most common pathogens were S. pneumoniae (n=12), P. aeruginosae (n=9), K. pneumonia (n=9) and S. aureus (n=8). The initial empirical antimicrobial regimens were classified as: ${\beta}$-lactam plus macrolide; ${\beta}$-lactam plus fluoroquinolone; anti-Pseudomonal ${\beta}$-lactam plus fluoroquinolone; Aminoglycoside combination regimen; ${\beta}$-lactam plus clindamycin; and ${\beta}$-lactam alone. There were no statistical significant differences in the 30-day mortality rate according to the initial antimicrobial regimen (p = 0.682). Multivariate analysis revealed that acute renal failure, acute respiratory distress syndrome and K. pneumonae were independent risk factors related to the 30 day mortality rate. Conclusion : S. pneumoniae, P. aeruginosae, K. pneumonia and S. aureus were the most common causative pathogens in patients with SCAP and K. pneumoniae was an independent risk factor for 30 day mortality. The initial antimicrobial regimen was not associated with the 30-day mortality.

Postoperative Radiotherapy in the Rectal Cancers Patterns of Care Study for the Years of $1998\~1999$ (직장암의 방사선치료에 대한 Patterns of Care Study: $1998{\sim}1999$년도 수술 후 방사선치료 환자들의 특성 및 치료내용에 대한 분석결과)

  • Kim, Jong-Hoon;Oh, Do-Hoon;Kang, Ki-Moon;Kim, Woo-Cheol;Kim, Won-Dong;Kim, Jung, Soo;Kim, June-Sang;Kim, Jin-Hee;Kil, Hak-Jae;Suh, Chang-Ok;Sohn, Seung-Chang;Ahn, Yong-Chan;Yang, Dae-Sik
    • Radiation Oncology Journal
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    • v.23 no.1
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    • pp.22-31
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    • 2005
  • Purpose : To conduct a nationwide survey on the principals in radiotherapy for rectal cancer, and produce a database of Korean Patterns of Care Study. Materials and Methods : We developed web-based Patterns of Care Study system and a national survey was conducted using random sampling based on power allocation methods. Eligible patients were who had postoperative radiotherapy for rectal cancer without gross residual tumor after surgical resection and without previous history of other cancer and radiotherapy to pelvis. Data of patients were Inputted to the web based PCS system by each investigators in 19 institutions. Results : Informations on 309 patients with rectal cancer who received radiotherapy between 1998 and 1999 were collected. Male to female ratio was 59 : 41, and the most common location of tumor was lower rectum ($46\%$). Preoperative CEA was checked in $79\%$ of cases and its value was higher than 6 ng/ml in $32\%$. Pathologic stage were I in $1.5\%$, II in $32\%$, III in $53\%$, and IV in $1.6\%$. Low anterior resection was the most common type of surgery and complete resection was peformed in $95\%$ of cases. Distal resection margin was less than 2 cm in $30\%$, and number of lymph node dissected was less than 12 in $31\%$. Chemotherapy was peformed in $91\%$ and most common regimen was 5-FU and leucovorine ($59\%$). The most common type of field arrangement used for the initial pelvic field was the four field box (Posterior-Right-Left) technique ($65.0\%$), and there was no AP-PA parallel opposing field used. Patient position was prone in $81.2\%$, and the boost field was used in $61.8\%$. To displace bowel outward, pressure modulating devices or bladder filling was used in $40.1\%$. Radiation dose was prescribed to isocenter in $45.3\%$ and to isodose line in 123 cases ($39.8\%$). Percent delivered dose over $90\%$ was achieved in $92.9\%$. Conclusion : We could find the Patterns of Care for the radiotherapy in Korean rectal cancer patients was similar to that of US national survey. The type of surgery and the regimen of chemotherapy were variable according to institutions and the variations of radiation dose and field arrangement were within acceptable range.

Feeding Preference of Foraging Ants on Insect Cadavers Killed by Entomopathogenic Nematode and Symbiotic Bacteria in Golf Courses (골프장에서 곤충병원성 선충과 공생세균 처리에 대한 개미의 섭식 선호성)

  • Lee Dong Woon;Lyu Dong Pyeo;Choo Ho Yul;Kim Hyeong Hwan;Kweon Tae Woong;Oh Byung Seog
    • Korean journal of applied entomology
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    • v.44 no.1 s.138
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    • pp.21-30
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    • 2005
  • Feeding behavior of foraging ants including visiting numbers, species, and preference on insect cadavers killed by entomopathogenic nematodes <(Heterorhabditis sp. KCTC 0991BP (He) and Steinernema carpocapsae KCTC 0981BP (Sc)> and their symbiotic bacteria was investigated in Dongrae Benest Golf Club, Anyang Benest Golf Club, Gapyung Benest Golf Club and Ulsan Golf Club. The number of ants, kinds and numbers of cadavers taken away by ants were different depending on killing method, golf club and site within the golf courses (fairway and rough). The feeding preference of ants was the lowest on cadavers killed by He. At Dongrae Benest Golf Club Lasius japonicu ($75{\pm}5\%$) and Monomorium floricola ($10\%$) took away cadavers only at the rough. The visiting rate of ants was $85{\pm}6\%$ at the rough, but none at the fairway by 16 hours. The taken rate of cadavers by ants was the lowest on He-killed cadavers representing $16.7\%$ compared with $40.0\%$ on Sc-killed cadavers, $53.3\%$ on fenitrithion-killed cadavers, and $56.7\%$ on natural dead cadavers by 12 hours. At the rough of hole 6 in Anyang Benest Golf Club, Tetramorium tsushimae ($33{\pm}12\%$), Pheidole fervida ($17{\pm}15\%$), Camponatus japonicus ($10\%$), Formica japonica ($7{\pm}6\%$), Paratrechina flavipes ($3{\pm}6\%$), and Crematogaster matsumurai ($3{\pm}6\%$) took away cadavers, but $23{\pm}15\%$ of cadavers were not visited by ants. Ants took away $40\%$ of Sc-killed cadavers, $16.7\%$ of frozen-killed cadavers, and $3.4\%$ of He-killed cadavers. The number of visiting ants was low at the hole 9 of Cherry course in Gapyung Benest Golf Club and only Tetramorium tsuhimae and Paratrechina flavipes were found from one site. The density of entomopathogenic nematodes did not influence ant visiting on cadavers, but burying affected ant visiting. Although ants took away unburied cadavers, buried cadavers were taken away at the hole 6 of Dongrae Benest Golf Club by 16 hours. Ant visiting had the same tendency on symbiotic bacterium-treated biscuit as nematode-killed cadavers. The visiting was less on biscuit inoculated by Photorhabdus sp., a symbiotic bacterium of He than on biscuit inoculated by Xenorhabdus nematophila, a symbiotic bacterium of Sc.

Effects of Size and Environmental Condition on Burrowing of Artificial Seedling of Ark Shell, Scapharca broughtonii (Schrenck) (피조개, Scapharca broughtonii (Schrenck) 인공치패의 크기 및 환경조건이 잠입에 미치는 영향)

  • Kim, Byeong-Hak;Shin, Yun-Kyung;Choi, Nack-Joong;Oh, Bong-Se;Sohn, Sang-Gyu;Jung, Choon-Goo;Son, Tai-Sun;Kang, Kyoung-Ho
    • The Korean Journal of Malacology
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    • v.23 no.1
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    • pp.1-8
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    • 2007
  • The influence of individual size, sediment, gain size, water temperature, salinity and air exposure on burrowing rate was investigated in order to obtain the basic biological data on applying shellfish farm for a sustainable production of ark shell, Scapharca broughtonii (Schrenk). The burrowing rate on individual size 300 minutes after starting the experiment was the highest in the shell length $16.3\;{\pm}\;1.2\;mm$, 97.7%. The highest burrowing rates were 97.0% in $12.8\;{\pm}\;0.8\;mm$, 96.7% in $9.2\;{\pm}\;1.0\;mm$, and 96.3% in $5.9\;{\pm}\;0.7\;mm$. The clams over 6 mm of shell length had burrowing ability and the burrowing rate was not related to the shell size. The burrowing rate depending on the kind of grain at the bottom after 300 minutes was the highest, 98.3%, in the mixture of sand and silt with a ratio of 75:25. The rates were 98% in silt (100%), 97.3% in mixture sand and silt with a ratio of 50:50, 97.3% in sand and silt ratio of 25:75, and 86.3% in sand (100%) in this specific order. On grain size of the soil in the seafloor, the burrowing rates after 300 minutes was at its highest in the group of sand in pore size 1 mm with 85.0%, and the $12\;{\mu}m$ to 1 mm in the grain size was fitted to burrowing of artificial seed. In the case of water temperature, the burrowing rates were at its highest after 300 minutes. In $30^{\circ}C$ group, the rate was 96.7% and in $25^{\circ}C$ and $20^{\circ}C$, 90.0%. The rates decreased as the water temperature decreased below $15^{\circ}C$. The burrowing rates on salinity were the highest in 30 psu with 93.3% and at 15 psu and below, there was no noticeable change in the burrowing rate. On air exposure, the burrowing rates after 300 minutes were the highest in 1 hour with 93.3%, and remarkably decreased as air exposure time is longer after 12 hours of air exposure.

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$Hg^{2+}$-promoted Aquation and Chelation of cis-[Co(en)$_2$(L)Cl]$^{2+}$ (L = Amines) Complexes ($Hg^{2+}$에 의한 cis-[Co(en)$_2$(L)Cl]$^{2+}$ (L = 아민류) 착물의 아쿠아화 및 킬레이트화 반응)

  • Chang Eon Oh;Doo Cheon Yoon;Bok Jo Kim;Myung Ki Doh
    • Journal of the Korean Chemical Society
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    • v.36 no.4
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    • pp.565-578
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    • 1992
  • It has been suggested that Hg$^{2+}$-promoted reaction of a series of cis-[Co(en)$_2$(L)Cl]$^{2+}$ (en = 1,2-diaminoethane) with L = NH$_3$, NH$_2$CH$_3$, glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, and NH$_2$CH$_2$CN proceeds by dissociative interchange(I$_d$) mechanism from kinetic data, circular dichroism spectra, analyses of products, and the values of m(Grunwald-Winstein plot) using Y (solvent ionizing power) in aqueous solution and in mixed aqueous-organic solvent. It has been found that chloride replacement by water (aquation) for the series with L = NH$_3$ and NH$_2$CH$_3$ and chelation of ligand L to Co(Ⅲ) for the series with L = glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, and NH$_2$CH$_2$CN occurs, respectively. The rate constants on Hg$^{2+}$-induced reaction of the series except cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ were increased with increasing the contents of ethanol in mixed water-ethanol solvents. In mixed water-30${\%}$ organic solvents, the rate constants of the series except cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ have also been measured in the order 30${\%}$ 2-propanol-water > 30${\%}$ ethanol-water > water. However, the rate constants of cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ were reversed. The rate constants of the series with L= NH$_3$ and NH$_2$CH$_3$ were related to ligand field parameter (${\Delta}$), but those of the series with L = glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, NH$_2$CH$_2$CN were not. The reaction between the series and Hg2+ in aqueous media containing NO$_3^-$ has been investigated. The results for the reaction do not alter the mechanism, but the rate only was altered.

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