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Synthesis of Binuclear Bismacrocyclic Iron(II) Complex by the Aerobic Oxidation of Iron(II) Complex of 1,4,8,11-Tetraazacyclotetradecane

  • Myunghyun Paik Suh;Gee-Yeon Kong;Il-Soon Kim
    • Bulletin of the Korean Chemical Society
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    • v.14 no.4
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    • pp.439-444
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    • 1993
  • The aerobic oxidation of the Fe(II) complex of 1,4,8,11-tetraazacyclotetradecane, [Fe(cyclam)$(CH_3CN)_2](ClO_4)_2$, in MeCN in the presence of a few drops of $HClO_4$ leads to low spin Fe(III) species [Fe(cyclam)$(CH_3CN)_2](ClO_4)_3$. The Fe(III) cyclam complex is further oxidized in the air in the presence of a trace of water to produce the deep green binuclear bismacrocyclic Fe(II) complex $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$. The Fe(II) ions of the complex are six-coordinated and the bismacrocyclic ligand is extensively unsaturated. $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$ crystallizes in the monoclinic space group $P2_1/n$ with a= 13.099 (1) ${\AA}$, b= 10.930 (1) ${\AA}$, c= 17.859 (1) ${\AA}$, ${\beta}$= 95.315 $(7)^{\circ}$, and Z= 2. The structure was solved by heavy atom methods and refined anisotropically to R values of R= 0.0633 and $R_w$= 0.0702 for 1819 observed reflections with F > $4{\sigma}$ (F) measured with Mo K${\alpha}$ radiation on a CAD-4 diffractometer. The two macrocyclic units are coupled through the bridgehead carbons of ${\beta}$-diimitie moieties by a double bond. The double bonds in each macrocycle unit are localized. The average bond distances of $Fe(II)-N_{imine}$, $Fe(II)-N_{amine}$, and $Fe(II)-N_{MeCN}$ are 1.890 (5), 2.001 (5), and 1.925 (6) ${\AA}$, respectively. The complex is diamagnetic, containing two low spin Fe(II) ions in the molecule. The complex shows extremely intense charge transfer band in the near infrared at 868 nm with ${\varepsilon}$= 25,000 $M^{-1}cm^{-1}$. The complex shows a one-electron oxidation wave at +0.83 volts and two one-electron reduction waves at -0.43 and-0.72 volts vs. Ag/AgCl reference electrode. The complex reacts with carbon monoxide in $MeNO_2$ to form carbonyl adducts, whose $v_{CO}$ value (2010 $cm^{-1}$) indicates the ${\pi}$-accepting property of the present bismacrocyclic ligand.

The Geology and Variations of Soil Properties on the Slow-moving Landslide in Yangbuk-myun, Gyungju-si, Gyeongsangbuk-do (경상북도 경주시 양북면 땅밀림지의 지질 및 토양물리성의 변화)

  • Park, Jae-Hyeon;Park, Seonggyun
    • Journal of Korean Society of Forest Science
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    • v.108 no.2
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    • pp.216-223
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    • 2019
  • This study was conducted to measure the changes in the geological and soil properties following slow-moving landslide events in Yangbuk-myun and Gyungju-si, Gyeongsangbuk-do, South Korea. The geological characteristics of the study site comprised black shale in the Gyeongsang nodal group formed in the Cretaceous period and quartz feldspar carcinoma in the east side with conglomerate in the Yeonil group formed in the Quaternary period. The study site exhibited the geologic characteristics of a slow-moving landslide with severely weathered rocks. The maximum collapsing depth of the slow-moving landslide was 12.0 m with colluvial deposits. The strike and joint aspects in the slope areas of the slow-moving landslides were $N46^{\circ}E$ in lower slope and $N62^{\circ}E$ in upper slope, respectively. Soil hardness of ${\leq}20cm$ deep was not measured because of the completely disturbed soil resulting from soil creeping. Soil from 25 to 90 cm deep was 1.4-4.7 times softer in the slow-moving landslide areas than in the undisturbed or natural forests. Soil bulk density was $1.24-1.29g/cm^3$ in land creep areas. Soil bulk in both areas was 1.6 times denser than that in the natural forest. The soil pore space was 51.5-53.3% in the land creep areas. The values are 1.3-1.4 times lower than those within the natural forest. Black shale areas showed the lowest coefficient of permeability (8.75 E-06 cm/s) and mesopore ratio (pF 2.7: 9.8%) compared with those resulting from other study areas.

Evaluation of Mechanical Interactions Between Bentonite Buffer and Jointed Rock Using the Quasi-Static Resonant Column Test (유사정적 공진주 시험을 이용한 벤토나이트 완충재와 절리 암반의 역학적 상호작용 특성 평가)

  • Kim, Ji-Won;Kang, Seok-Jun;Kim, Jin-Seop;Cho, Gye-Chun
    • Tunnel and Underground Space
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    • v.31 no.6
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    • pp.561-577
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    • 2021
  • The compacted bentonite buffer in a geological repository for high-level radioactive waste disposal is saturated due to groundwater inflow. Saturation of the bentonite buffer results in bentonite swelling and bentonite penetration into the rock discontinuities present around the disposal hole. The penetrated bentonite is exposed to groundwater flow and can be eroded out of the repository, resulting in bentonite mass loss which can affect the physical integrity of the engineered barrier system. Hence, the evaluation of buffer-rock interactions and coupled behavior due to groundwater inflow and bentonite penetration is necessary to ensure long-term disposal safety. In this study, the effects of the bentonite penetration and swelling on the physical properties of jointed rock mass were evaluated using the quasi-static resonant column test. Jointed rock specimens with bentonite penetration were manufactured using Gyeongju bentonite and hollow cylindrical granite rock discs obtained from the KAERI underground research tunnel. The effects of vertical stress and saturation were assessed using the P-wave and S-wave velocities for intact rock, jointed rock and jointed rock with bentonite penetration specimens. The joint normal and joint shear stiffnesses of each joint condition were inferred from the wave velocity results assuming an equivalent continuum. The joint normal and joint shear stiffnesses obtained from this study can be used as input factors for future numerical analysis on the performance evaluation of geological waste disposal considering rock discontinuities.

Intrawound Vancomycin Powder Application for Preventing Surgical Site Infection Following Cranioplasty

  • Seong Bin Youn;Gyojun Hwang;Hyun-Gon Kim;Jae Seong Kang;Hyung Cheol Kim;Sung Han Oh;Mi-Kyung Kim;Bong Sub Chung;Jong Kook Rhim;Seung Hun Sheen
    • Journal of Korean Neurosurgical Society
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    • v.66 no.5
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    • pp.536-542
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    • 2023
  • Objective : Surgical site infection is the most detrimental complication following cranioplasty. In other surgical fields, intrawound vancomycin powder application has been introduced to prevent surgical site infection and is widely used based on results in multiple studies. This study evaluated the effect of intrawound vancomycin powder in cranioplasty compared with the conventional method without topical antibiotics. Methods : This retrospective study included 580 patients with skull defects who underwent cranioplasty between August 1, 1998 and December 31, 2021. The conventional method was used in 475 (81.9%; conventional group) and vancomycin powder (1 g) was applied on the dura mater and bone flap in 105 patients (18.1%; vancomycin powder group). Surgical site infection was defined as infection of the incision, organ, or space that occurred after cranioplasty. Surgical site infection within 1-year surveillance period was compared between the conventional and vancomycin powder groups with logistic regression analysis. Penalized likelihood estimation method was used in logistic regression to deal with zero events. All local and systemic adverse events associated with topical vancomycin application were also evaluated. Results : Surgical site infection occurred in 31 patients (5.3%) and all were observed in the conventional group. The median time between cranioplasty and detection of surgical site infection was 13 days (range, 4-333). Staphylococci were the most common organisms and identified in 25 (80.6%) of 31 cases with surgical site infections. The surgical site infection rate in the vancomycin powder group (0/105, 0.0%) was significantly lower than that in the conventional group (31/475, 6.5%; crude odds ratio [OR], 0.067; 95% confidence interval [CI], 0.006-0.762; adjusted OR, 0.068; 95% CI, 0.006-0.731; p=0.026). No adverse events associated with intrawound vancomycin powder were observed during the follow-up. Conclusion : Intrawound vancomycin powder effectively prevented surgical site infections following cranioplasty without local or systemic adverse events. Our results suggest that intrawound vancomycin powder is an effective and safe strategy for patients undergoing cranioplasty.

A Nuclide Transport Model in the Fractured Rock Medium Using a Continuous Time Markov Process (연속시간 마코프 프로세스를 이용한 균열암반매질에서의 핵종이동 모델)

  • Lee, Y.M.;Kang, C.H.;Hahn, P.S.;Park, H.H.;Lee, K.J.
    • Nuclear Engineering and Technology
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    • v.25 no.4
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    • pp.529-538
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    • 1993
  • A stochastic way using continuous time Markov process is presented to model the one-dimensional nuclide transport in fractured rock matrix as an extended study for previous work [1]. A nuclide migration model by the continuous time Markov process for single planar fractured rock matrix, which is considered as a transient system where a process by which the nuclide is diffused into the rock matrix from the fracture may be no more time homogeneous, is compared with a conventional deterministic analytical solution. The primary desired quantities from a stochastic model are the expected values and variance of the state variables as a function of time. The time-dependent probability distributions of nuclides are presented for each discretized compartment of the medium given intensities of transition. Since this model is discrete in medium space, parameters which affect nuclide transport could be easily incorporated for such heterogeneous media as the fractured rock matrix and the layered porous media. Even though the model developed in this study was shown to be sensitive to the number of discretized compartment showing numerical dispersion as the number of compartments are decreased, with small compensating of dispersion coefficient, the model agrees well to analytical solution.

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Awareness and Demand Analysis of Participants in Physical Activity Therapy Program of Social-welfare Type Cultural Regeneration Spaces in Urban-rural Region - The Case of Kimcheon - (도농지역 사회복지형 문화재생 공간의 신체활동 치유 프로그램 참여자의 인식 및 수요분석 - 김천시를 대상으로 -)

  • Park, Sang-Kyun;Tomita, Sigeru;Oh, Yoon-Ji;Kim, Dae-Sik;Lee, Wang-Lok
    • Journal of Korean Society of Rural Planning
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    • v.28 no.1
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    • pp.81-87
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    • 2022
  • This study analyzed the awareness and demand of participants in a physical activity therapy program(PATP) of a social welfare-type cultural regeneration space in urban and rural areas. As a result of analyzing the demographic characteristics, the female(68.4%) were more than the male, and 30-39 years old(53.3%) were the most generation in the PATP participants. As a result of frequency analysis by all subjects, gender and age, 78.4% of the respondents had never participated in PATP before. The most duration of the PATP was 30 to 60 minutes(24.6%). 73.5% of the respondents answered that it was not feeling difficult at all to the intensity of PATP, and 94.8% of the respondents were satisfied with the intensity of PATP. The most respondents preferred to participate again with if the new PATP starts(97.2%) and to join the new PATP with his or her family members(85.7%). In addition, the participants under the age of 39(24.3%) perceived that the effect of improving physical fitness by PATP was higher than over 40 years of age(11.9%). As a result of logistic regression analysis, it was found that only the age had a significant effect(p<.01) on intensity of PATP. It means that the perceived intensity of PATP was different between the older and young generation. However, the PATP was not designed to meet the participants age and fitness levels, and even the general exercise prescription guidelines based on professional scientific data such as exercise frequency, exercise intensity, exercise time, exercise type, and characteristics of the participants in the spaces. In conclusion, to encourage and promote the participants motivation and health-related fitness level in the spaces for the future. The various type of PATP that include a few different intensities for all genders and age groups, and a customized program based on systematic and scientific exercise prescription guidelines.

Purification and Characterization of Mitochondrial Mg2+-Independent Sphingomyelinase from Rat Brain

  • Jong Min Choi;Yongwei Piao;Kyong Hoon Ahn;Seok Kyun Kim;Jong Hoon Won;Jae Hong Lee;Ji Min Jang;In Chul Shin;Zhicheng Fu;Sung Yun Jung;Eui Man Jeong;Dae Kyong Kim
    • Molecules and Cells
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    • v.46 no.9
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    • pp.545-557
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    • 2023
  • Sphingomyelinase (SMase) catalyzes ceramide production from sphingomyelin. Ceramides are critical in cellular responses such as apoptosis. They enhance mitochondrial outer membrane permeabilization (MOMP) through self-assembly in the mitochondrial outer membrane to form channels that release cytochrome c from intermembrane space (IMS) into the cytosol, triggering caspase-9 activation. However, the SMase involved in MOMP is yet to be identified. Here, we identified a mitochondrial Mg2+-independent SMase (mt-iSMase) from rat brain, which was purified 6,130-fold using a Percoll gradient, pulled down with biotinylated sphingomyelin, and subjected to Mono Q anion exchange. A single peak of mt-iSMase activity was eluted at a molecular mass of approximately 65 kDa using Superose 6 gel filtration. The purified enzyme showed optimal activity at pH of 6.5 and was inhibited by dithiothreitol and Mg2+, Mn2+, Ni2+, Cu2+, Zn2+, Fe2+, and Fe3+ ions. It was also inhibited by GW4869, which is a non-competitive inhibitor of Mg2+-dependent neutral SMase 2 (encoded by SMPD3), that protects against cytochrome c release-mediated cell death. Subfractionation experiments showed that mt-iSMase localizes in the IMS of the mitochondria, implying that mt-iSMase may play a critical role in generating ceramides for MOMP, cytochrome c release, and apoptosis. These data suggest that the purified enzyme in this study is a novel SMase.

Neutrophil to Lymphocyte Ratio and Serum Biomarkers : A Potential Tool for Prediction of Clinically Relevant Cerebral Vasospasm after Aneurysmal Subarachnoid Hemorrhage

  • Osman Kula;Burak Gunay;Merve Yaren Kayabas;Yener Akturk;Ezgi Kula;Banu Tutunculer;Necdet Sut;Serdar Solak
    • Journal of Korean Neurosurgical Society
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    • v.66 no.6
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    • pp.681-689
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    • 2023
  • Objective : Subarachnoid hemorrhage (SAH) is a condition characterized by bleeding in the subarachnoid space, often resulting from the rupture of a cerebral aneurysm. Delayed cerebral ischemia caused by vasospasm is a significant cause of mortality and morbidity in SAH patients, and inflammatory markers such as systemic inflammatory response index (SIRI), systemic inflammatory index (SII), neutrophil-to-lymphocyte ratio (NLR), and derived NLR (dNLR) have shown potential in predicting clinical vasospasm and outcomes in SAH patients. This article aims to investigate the relationship between inflammatory markers and cerebral vasospasm after aneurysmatic SAH (aSAH) and evaluate the predictive value of various indices, including SIRI, SII, NLR, and dNLR, in predicting clinical vasospasm. Methods : A retrospective analysis was performed on a cohort of 96 patients who met the inclusion criteria out of a total of 139 patients admitted Trakya University Hospital with a confirmed diagnosis of aSAH between January 2013 and December 2021. Diagnostic procedures, neurological examinations, and laboratory tests were performed to assess the patients' condition. The Student's t-test compared age variables, while the chi-square test compared categorical variables between the non-vasospasm (NVS) and vasospasm (VS) groups. Receiver operating characteristic (ROC) curve analyses were used to evaluate the diagnostic accuracy of laboratory parameters, calculating the area under the ROC curve, cut-off values, sensitivity, and specificity. A significance level of p<0.05 was considered statistically significant. Results : The study included 96 patients divided into two groups : NVS and VS. Various laboratory parameters, such as NLR, SII, and dNLR, were measured daily for 15 days, and statistically significant differences were found in NLR on 7 days, with specific cut-off values identified for each day. SII showed a significant difference on day 9, while dNLR had significant differences on days 2, 4, and 9. Graphs depicting the values of these markers for each day are provided. Conclusion : Neuroinflammatory biomarkers, when used alongside radiology and scoring scales, can aid in predicting prognosis, determining severity and treatment decisions for aSAH, and further studies with larger patient groups are needed to gain more insights.

Comparison between village characteristics and habitat quality to application OECM in Nakdong-Jeongmaek (낙동정맥 내 OECM 적용 가능 지역 발굴을 위한 마을 특성과 서식지 질 비교)

  • Oh, Ju-Hyeong;Kim, Su-Jin;Kim, Tae-Su;Jang, Gab-Su;Jeon, Seong-Woo
    • Journal of the Korean Society of Environmental Restoration Technology
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    • v.26 no.6
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    • pp.51-65
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    • 2023
  • The Jeongmaeks are Korea's unique forest space recognition system that diverged from the Baekdudaegan. The Jeongmaeks are easily exposed to pressure because it is adjacent to the living area. Among them, Nakdong-Jeongmaek has high biodiversity, but damage is accelerating. According to the Convention on Biological Diversity (CBD) in 2022, the target is to expand the area of terrestrial and marine protected areas to 30% of national territory by 2030. As of September 2023, the area of terrestrial protected areas in South Korea is only 16.97% of the country's territory. This is due in part to the high proportion of private forests in the region, which makes it difficult to establish protected areas. Therefore, there is a need to establish Other Effective Area-based Conservation Measure (OECMs), which pursue complex and effective conservation that considers multiple values, as an alternative to protected areas. This study aims to identify areas suitable for OECM and to provide opinions on the establishment of appropriate management plans for each value using SOM and InVEST Habitat Quality model. This study evaluated the habitat quality of 206 villages located within 1km of the Nakdong-Jeongmaek and compared the characteristics of villages classified by SOM. As a result, the habitat quality was 0.867 for Tourism village (ClusterIV), 0.838 for Conservation village (ClusterVI), 0.835 for Mixed village (ClusterI), 0.796 for Production (ClusterV), 0.731 for Rural village (ClusterIII) and 0.625 for Urban village (ClusterII). When the distribution was identified through statistical analysis, the Kruskal-Wallis test showed that the distributions were not identical, with a p-value of 1.53e-08. Dunn's test showed a difference between Tourism, Conservation and Rural, Urban village. However, Mixed village was overestimated due to the lack of villages and the small area included in the study area. Moreover, Conservation village was somewhat under-evaluated in the analysis due to the use of a single weight for protected areas. It is necessary to perform additional reinforcement of the value evaluation of Jeongmaeks by conducting Forest Resource Survey and the National Natural Environment Survey. Therefore, we believe that sufficient validity for the establishment of OECMs in the Nakdong-Jeongmaek can be provided by addressing these limitations and conducting additional research.

Utilization of air bubble device to improve removal Ulva linza and cleaning effects from Pyropia nets (김 양식망의 파래류 제거 및 세척 효과 증대를 위한 공기방울처리장치의 활용)

  • Hak-Jeung Lee;Young Hee Kim;Ji Yeon Nam;Chan Song Kim;Jin suk Heo
    • Korean Journal of Environmental Biology
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    • v.41 no.4
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    • pp.706-711
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    • 2023
  • At Pyropia farms, organic acid treatments have enhanced productivity and quality by removing pest algae (such as Ulva spp. and diatoms) and reducing the occurrence of diseases. Ulva spp. attaches to the Pyropia nets competing for inorganic nutrients & space and diminishing productivity. Additionally, the presence of attached contaminants (such as diatoms and middy particles) on the Pyropia nets negatively affects the quality of Pyropia. This study investigated the effects of removing Ulva linza and washing the Pyropia yezoensis nets using an activating treatment agent (organic acid and highly saline solution) with an air bubble device. The results of measuring the dead cell ratios after treatment under different conditions showed that the dead cell ratio of U. linza did not significantly increase when the air bubble device combined the activating treatment agent with the activating treatment agent alone. When washing the P. yezoensis nets, the air bubble device was about 19-37% more effective than the activating treatment agent alone. The findings of this study suggest that the air bubble device enhances the efficacy of the activating treatment agent, resulting in the effective cleaning of the Pyropia nets.