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MO Theoretical Studies on the Benzylic and Resonance Shunt Effects

  • Ikchoon Lee;Jeong Ki Cho;Chang Kon Kim
    • Bulletin of the Korean Chemical Society
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    • v.12 no.2
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    • pp.182-188
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    • 1991
  • The reactions of aniline with benzyl and phenacyl compounds are studied by the AM1 method. Two types of modeling were adopted: Cation-neutral, in which a proton is attached to the leaving group F and anion-neutral model, in which aniline was replaced by phenoxide with Cl as the leaving group. The cation-neutral model represented the reactvery well, reproducing the various solution-phase experimental results. In the benzyl system, the ${\pi}$-electrons of the two rings (X-ring in the nucleophile and Y-ring in the substrate) interact conjugatively in the transition state (TS) resulting in a bond contraction of the $C_{\alpha}-C_{Y1}$ bond (benzylic effect), whereas in the phenacyl system the ${\pi}$ electrons of the X-ring delocalizes more efficiently into the carbonyl group than into the Y-ring (resonance shunt effect) with a bond contraction of the $C_{\alpha}-C_{\beta}$ bond. The bond contraction in the benzylic effect was substantially greater than that in the resonance shunt effect. The TS was rather loose for benzyl while it was tighter for phenacyl system. Various bond length changes with substituents in the TS were, however, found to be irregular.

Classification Model and Crime Occurrence City Forecasting Based on Random Forest Algorithm

  • KANG, Sea-Am;CHOI, Jeong-Hyun;KANG, Min-soo
    • Korean Journal of Artificial Intelligence
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    • v.10 no.1
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    • pp.21-25
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    • 2022
  • Korea has relatively less crime than other countries. However, the crime rate is steadily increasing. Many people think the crime rate is decreasing, but the crime arrest rate has increased. The goal is to check the relationship between CCTV and the crime rate as a way to lower the crime rate, and to identify the correlation between areas without CCTV and areas without CCTV. If you see a crime that can happen at any time, I think you should use a random forest algorithm. We also plan to use machine learning random forest algorithms to reduce the risk of overfitting, reduce the required training time, and verify high-level accuracy. The goal is to identify the relationship between CCTV and crime occurrence by creating a crime prevention algorithm using machine learning random forest techniques. Assuming that no crime occurs without CCTV, it compares the crime rate between the areas where the most crimes occur and the areas where there are no crimes, and predicts areas where there are many crimes. The impact of CCTV on crime prevention and arrest can be interpreted as a comprehensive effect in part, and the purpose isto identify areas and frequency of frequent crimes by comparing the time and time without CCTV.

Epistemic Reflexivity and its Applications to Southeast Asian Studies

  • KIM, Yekyoum
    • SUVANNABHUMI
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    • v.13 no.1
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    • pp.7-33
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    • 2021
  • With a view to contributing to the epistemological and methodological debates in Southeast Asian Studies, the aim of this paper is to examine critically the epistemic concepts and approaches in the social sciences and then to seek an epistemic reflexivity and its potential methodological applications to Southeast Asian Studies. Although the field of social sciences has attempted to search for a means of tackling the ontological and epistemological dilemmas in its major paradigms, Southeast Asian Studies still demands a more 'actor-centered' epistemic account of reflexive interaction between actors and social structures. Bearing in mind the need for a more 'actor-centered' epistemic approach, this paper continues to discuss the 'epistemic reflexivity' in the social sciences and its potential applications to Southeast Asian Studies. In this paper, I will consider 'epistemic reflexivity' as an alternative methodological orientation. It emerges as interlinked with the ontological standpoint of what is called 'reflexive approaches' and its application to the detailed 'reflexive methodology' which I am proposing in this paper. In doing so, this paper discusses the autobiographical experiences of the author arising from his ethnographic field research in North Sulawesi, Indonesia and their implication for a reflexive methodology in Southeast Asian Studies. In conclusion, the paper argues that we need a 'more actor-centered' epistemic framework to compensate for the epistemological and methodological dilemmas in the social sciences and the alternative framework will equip Southeast Asian Studies with a reflexive methodology relevant to the life-dynamics of the social world in the process of developing its inquiries, methodological technics, analysis, and validation.

A Study About Radionuclides Migration Behavior in Terms of Solubility at Gyeongju Low- and Intermediate-Level Radioactive Waste (LILW) Repository

  • Park, Sang June;Byon, Jihyang;Lee, Jun-Yeop;Ahn, Seokyoung
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.19 no.1
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    • pp.113-121
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    • 2021
  • A safety assessment of radioactive waste repositories is a mandatory requirement process because there are possible radiological hazards owing to radionuclide migration from radioactive waste to the biosphere. For a reliable safety assessment, it is important to establish a parameter database that reflects the site-specific characteristics of the disposal facility and repository site. From this perspective, solubility, a major geochemical parameter, has been chosen as an important parameter for modeling the migration behavior of radionuclides. The solubilities were derived for Am, Ni, Tc, and U, which were major radionuclides in this study, and on-site groundwater data reflecting the operational conditions of the Gyeongju low and intermediate level radioactive waste (LILW) repository were applied to reflect the site-specific characteristics. The radiation dose was derived by applying the solubility and radionuclide inventory data to the RESRAD-OFFSITE code, and sensitivity analysis of the dose according to the solubility variation was performed. As a result, owing to the low amount of radionuclide inventory, the dose variation was insignificant. The derived solubility can be used as the main input data for the safety assessment of the Gyeongju LILW repository in the future.

Nootkatol prevents ultraviolet radiation-induced photoaging via ORAI1 and TRPV1 inhibition in melanocytes and keratinocytes

  • Woo, Joo Han;Nam, Da Yeong;Kim, Hyun Jong;Hong, Phan Thi Lam;Kim, Woo Kyung;Nam, Joo Hyun
    • The Korean Journal of Physiology and Pharmacology
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    • v.25 no.1
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    • pp.87-94
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    • 2021
  • Skin photoaging occurs due to chronic exposure to solar ultraviolet radiation (UV), the main factor contributing to extrinsic skin aging. Clinical signs of photoaging include the formation of deep, coarse skin wrinkles and hyperpigmentation. Although melanogenesis and skin wrinkling occur in different skin cells and have different underlying mechanisms, their initiation involves intracellular calcium signaling via calcium ion channels. The ORAI1 channel initiates melanogenesis in melanocytes, and the TRPV1 channel initiates MMP-1 production in keratinocytes in response to UV stimulation. We aimed to develop a drug that may simultaneously inhibit ORAI1 and TRPV1 activity to help prevent photoaging. We synthesized nootkatol, a chemical derivative of valencene. TRPV1 and ORAI1 activities were measured using the whole-cell patch-clamp technique. Intracellular calcium concentration [Ca2+]i was measured using calcium-sensitive fluorescent dye (Fura-2 AM). UV-induced melanin formation and MMP-1 production were quantified in B16F10 melanoma cells and HaCaT cells, respectively. Our results indicate that nootkatol (90 μM) reduced TRPV1 current by 94% ± 2% at -60 mV and ORAI1 current by 97% ± 1% at -120 mV. Intracellular calcium signaling was significantly inhibited by nootkatol in response to ORAI1 activation in human primary melanocytes (51.6% ± 0.98% at 100 μM). Additionally, UV-induced melanin synthesis was reduced by 76.38% ± 5.90% in B16F10 melanoma cells, and UV-induced MMP-1 production was reduced by 59.33% ± 1.49% in HaCaT cells. In conclusion, nootkatol inhibits both TRPV1 and ORAI1 to prevent photoaging, and targeting ion channels may be a promising strategy for preventing photoaging.

Synthesis and Characterization of Thiophene-Based Copolymers Containing Urethane and Alkyl Functional Side Chains for Hybrid Bulk Heterojunction Photovoltaic Cell Applications

  • Im, Min-Joung;Kim, Chul-Hyun;Song, Myung-Kwan;Park, Jin-Su;Lee, Jae-Wook;Gal, Yeong-Soon;Lee, Jun-Hee;Jin, Sung-Ho
    • Bulletin of the Korean Chemical Society
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    • v.32 no.2
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    • pp.559-565
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    • 2011
  • The following noble series of statistical copolymers, poly[(2-(3-thienyl)ethanol n-butoxycarbonylmethylurethane)-co-3-hexylthiophene] (PURET-co-P3HT), were synthesized by the chemical dehydrogenation method using anhydrous $FeCl_3$. The structure and electro-optical properties of these copolymers were characterized using $^1H$-NMR, UV-visible spectroscopy, elemental analysis, GPC, DSC, TGA, photoluminescence (PL), and cyclic voltammetry (CV). The statistical copolymers, PURET-co-P3HT (1:0, 2:1, 1:1, 1:2, 1:3), were soluble in common organic solvents and easily spin coated onto indium-tin oxide (ITO) coated glass substrates. Hybrid bulk heterojunction photovoltaic cells with an ITO/G-PEDOT/PURET-co-P3HT:PCBM:Ag nanowires/$TiO_x$/Al configuration were fabricated, and the photovoltaic cells using PURET-co-P3HT (1:2) showed the best photovoltaic performance compared with those using PURET-co-P3HT (1:0, 2:1, 1:1, 1:3). The optimal hybrid bulk heterojunction photovoltaic cell exhibits a power conversion efficiency (PCE) of 1.58% ($V_{oc}$ = 0.82 V, $J_{sc}$ = 5.58, FF = 0.35) with PURET-co-P3HT (1:2) measured by using an AM 1.5 G irradiation (100 mW/$cm^2$) on an Oriel Xenon solar simulator (Oriel 300 W).

Effects of Composition and Concentration of Media on the Acclimation of the Shoots of Scrophularia buergeriana Miquel Produced in Bioreactor (생물반응기 생산 현삼 신초의 순화에 미치는 배지의 영향)

  • Hahn, Suk-Hoon;Chae, Young-Am
    • Korean Journal of Medicinal Crop Science
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    • v.9 no.1
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    • pp.62-67
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    • 2001
  • This study was carried out to investigate the optimum composition and concentration of medium for the acclimation of the shoots derived from bioreactor culture of Scrophularia buergeriana. Rooting and growth of the shoots cultured in bioreactor for 4 weeks were better on liquid full strength MS medium while one-tenth of MS medium was good for rooting and growth of the shoots cultured in bioreactor for 6 weeks. Leaf expansion was more effective in the shoots cultured for 6 weeks on solid MS medium than in those cultured for 4 weeks. No leaf expanded in liquid medium. Vitrification rate was higher in full strength solid MS medium than in half strength MS medium. It is concluded that acclimation of the shoots is more effective on the half strength solid MS medium containing 1.2% agar.

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A Study of Eight Cases According to Hyeongsang Diagnosis Applying Sa-am Acupuncture Therapy (8증례를 통한 사암침법(舍巖鍼法)의 형상의학적(形象醫學的) 운용에 관한 고찰)

  • Choi, Jun-Young;Nam, Sang-Soo;Kim, Yong-Suk;Lee, Jae-Dong
    • Journal of Acupuncture Research
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    • v.29 no.1
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    • pp.139-150
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    • 2012
  • Objectives : The puropse of this study was to report the availability of Hyeongsang diagnosis compensating for visceral pattern identification in applying Sa-am acupuncture therapy. Methods : Eight cases was presented to substantiate the above. Results : According to the characteristic diagnostic method of Hyeongsang medicine by feature such as face, ears, eyes, nose and mouth shape, There are 8 pattern differentiations, including essence family, Qi family, spirit family, blood family, fish type, bird type, beast(running) type and crust(crustacea) type which are correlated with essence deficiency, heat harassing the heart spirit, Qi stagnation, blood stasis, kidney essence deficiency, intense heart fire, liver blood deficiency and lung Qi deficiency in the established visceral pattern identification, respectively. Eight patients was diagnosed by the above Hyeongsang 8 pattern differentiations, of whom Sinjeonggyeok(kidney reinforcing prescription) was applied to a patient with fish type and essence family to nourish kidney essence, and Giul prescription(Qi stagnation prescription) was given to a patient with Qi family for regulating Qi, and Sanghwa priscription(ministerial fire prescription) was delivered to a patient with Spirit family to clear the heart fire and tranquilize, and Sojangjeonggyeok(small intestine reinforcing prescription) was used for a patient with blood family to nourish blood and remove blood stasis, and Sinjeonggyeok(kidney reinforcing prescription), Simhangyeok(heart heat clearing prescription), Ganjeonggyeok(liver reinforcing prescription) and Pyejeonggyeok(lung reinforcing prescription) were utilized for fish type, bird type, beast(running) type and crust(crustacea) type respectively to reinforce the relevant visceral function. Conclusions : It was suggested that characteristic diagnostic method of Hyeongsang medicine should be helpful for enhancing the accuracy of the established visceral pattern identification, applying Sa-am acupuncture therapy more appropriately.

Low-dose radiation activates Nrf1/2 through reactive species and the Ca2+/ERK1/2 signaling pathway in human skin fibroblast cells

  • Lee, Eun Kyeong;Kim, Jin-Ah;Park, Seong Joon;Kim, Jeung Ki;Heo, Kyu;Yang, Kwang Mo;Son, Tae Gen
    • BMB Reports
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    • v.46 no.5
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    • pp.258-263
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    • 2013
  • In the current study, we explored the effect of LDR on the activation of Nrfs transcription factor involved in cellular redox events. Experiments were carried out utilizing 0.05 and 0.5 Gy X-ray irradiated normal human skin fibroblast HS27 cells. The results showed LDR induced Nrf1 and Nrf2 activation and expression of antioxidant genes HO-1, Mn-SOD, and NQO1. In particular, 0.05 Gy-irradiation increased only Nrf1 activation, but 0.5 Gy induced both Nrf1 and Nrf2 activation. LDR-mediated Nrf1/2 activation was accompanied by reactive species (RS) generation and $Ca^{2+}$ flux. This effect was abolished in the presence of N-acetyl-cysteine and BAPTA- AM. Furthermore, Nrf1/2 activation by LDR was suppressed by PD98059, an inhibitor of ERK1/2. In conclusion, LDR induces Nrf1 and Nrf2 activation and expression of Nrf-regulated antioxidant defense genes through RS and $Ca^{2+}$/ERK1/2 pathways, suggesting new insights into the molecular mechanism underlying the beneficial role of LDR in HS27 cells.

Metamorphic Evolution of Metabasites and Country Gneiss in Baekdong Area and Its Tectonic Implication (백동지역의 변성염기성암과 주변 편마암의 변성진화과정과 그 지구조적 의미)

  • 오창환;최선규;송석환
    • The Journal of the Petrological Society of Korea
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    • v.11 no.3_4
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    • pp.103-120
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    • 2002
  • In the Baekdong-Hongseong area, the southwestern part of the Gyeonggi Massif in Korea, ultramafic rocks occur as lenses within Precambrian granitic gneiss. At Baekdong area, ultramafic lens contains metabasite boudin which had undergone at least three stages of metamorphisms. The mineral assemblage on the first stage, Garnet+Sodic Augite+Hornblende+Plagioclase+Titanite, is recognized from the inclusions in garnet. The second stage is represented by the assemblage in matrix, Garnet+ Augite+Hornblende+Plagioclase, while the third stage is identified by the Hornblende+Plagjoclase $\pm$ Garnet assemblage in the symplectite formed around garnet. The P-T conditions of the first and the third stages are $690-780^{\circ}C$, 11.8-15.9 kb and $490-610^{\circ}C$, 4.0-6.3 kb, respectively. These data indicate that metabasite in Baekdong area had experienced a retrouade P-T path from the eclogite(EG) - high-pressure granulite (HG)-amphibolite (AM) transitional facies to the AM through HG-AM transitional facies. The core and rim of garnet in country granitic gneiss give $605-815^{\circ}C$, 10.7-16.0 kb and $575-680^{\circ}C$, 5.4-7.0 kb, respectively, indicating that the retrograde P-T path of granitic gneiss is similar to that of metabasite. Trace element data reveals that the tectonic setting of metabasite is island uc. The general geology, the metamorphic evolution, the mineral chemistry and the tectonic setting of Baekdong area indicate that the Baekdong-Hongseong area in Korea is a possible extension of the Sulu collision Belt in China. On the other hand, the Sm-Nd whole rock-garnet isochron ages of metabasites are 268.7-297.9 Ma which are older than the ages of UHP metamorphism (208-245 Ma) in the Dabie-Sulu Collision Belt. The older metamorphic ages suggest that collision between Sino-Korea and Yangtz plates may have occurred earlier in Korean Peninsula than China.