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A Kinetic Study on Aminolysis of 2-Pyridyl X-Substituted Benzoates: Effect of Changing Leaving Group from 4-Nitrophenolate to 2-Pyridinolate on Reactivity and Mechanism

  • Lee, Jong-Pal;Bae, Ae-Ri;Im, Li-Ra;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.31 no.12
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    • pp.3588-3592
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    • 2010
  • Second-order rate constants ($k_N$) have been measured spectrophotometrically for nucleophilic substitution reactions of 2-pyridyl X-substituted benzoates 8a-e with a series of alicyclic secondary amines in $H_2O$ at $25.0{\pm}0.1^{\circ}C$. The $k_N$ values for the reactions of 8a-e are slightly smaller than the corresponding reactions of 4-nitrophenyl X-substituted benzoates 1a-e (e.g., $kN^{1a-e}/k_N^{8a-e}$ = 1.1 ~ 3.1), although 2-pyridinolate in 8a-e is ca. 4.5 $pK_a$ units more basic than 4-nitrophenolate in 1a-e. The Br$\o$nsted-type plot for the aminolysis of 8c (X = H) is linear with $\beta_{nuc}$ = 0.77 and $R^2$ = 0.991 (Figure 1), which is typical for reactions reported previously to proceed through a stepwise mechanism with breakdown of a zwitterionic tetrahedral intermediate $T^{\pm}$ being the rate-determining step (RDS), e.g., aminolysis of 4-nitrophenyl benzoate 1c. The Hammett plot for the reactions of 8a-e with piperidine consists of two intersecting straight lines (Figure 2), i.e., $\rho$ = 1.71 for substrates possessing an electron-donating group (EDG) while $\rho$ = 0.86 for those bearing an electron-withdrawing group (EWG). Traditionally, such a nonlinear Hammett plot has been interpreted as a change in RDS upon changing substituent X in the benzoyl moiety. However, it has been proposed that the nonlinear Hammett is not due to a change in RDS since the corresponding Yukawa-Tsuno plot exhibits excellent linear correlation with $\rho$ = 0.85 and r = 0.62 ($R^2$ = 0.995, Figure 3). Stabilization of substrates 8a-e in the ground state has been concluded to be responsible for the nonlinear Hammett plot.

Analysis of the Characteristics of National Assessment of Educational Achievement (NAEA) Items for Science Subject through the use of Option Response Rate Distribution Curve (답지 반응률 분포 곡선을 통한 국가수준 학업성취도 과학 평가 문항 특성 분석)

  • Kim, Hyun-Kyung;Lee, In-Ho;Lee, Bongwoo;Lee, Kiyoung;Sim, Jaeho
    • Journal of The Korean Association For Science Education
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    • v.35 no.1
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    • pp.121-130
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    • 2015
  • Identifying students' achievement level and reflecting it on educational policy making or instructional improvement by analyzing the results of nationwide standardized assessment is an integral part of accountability in education. On the basis of this premise, we analyzed the characteristics of National Assessment of Educational Achievement (NAEA) items for middle school science subject conducted from 2010 to 2013 by using the option response rate distribution curve, the fittest graph estimated from the response rate of correct/incorrect options by achievement score. Furthermore, we classified the type of option response rate curve in terms of correct and incorrect options. Results of the analysis of option response curve showed that five types of correct option response curve (S-shaped, J-shaped, straight-shaped, F-shaped, and step-shaped) and 4 types of incorrect option response curve (down-slope, flat, mound, and up-slope) were identified. The most common type of items was the combination of S-shaped correct option response curve and down-slope incorrect option response curve, which are considered as appropriate items to discriminate the students according to achievement level. Moreover, correct option response was found to be correlated with incorrect option response. Based on the results, we also discussed some implications on teaching-learning method and classroom assessment in science education.

Study on the effect of cable on the lateral behavior of S-shaped Pedestrian-CSB (S형 보도사장교의 케이블이 횡방향 거동에 미치는 영향 연구)

  • Ji, Seon-Geun;Yhim, Sung-Soon
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.20 no.5
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    • pp.577-584
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    • 2019
  • Recently, CSB(Cable-Stayed Bridge) have been attempted to be atypical forms for landscape elements in Korea. CSB with new geometry need to analyze their characteristics clearly to ensure structural safety. This study's bridge is the S-shaped curved pedestrian CSB that has a girder with S-shape plane curve and reverse triangular truss cross section, inclined independent pylon, modified Fan type main cable and vertical backstay cable. Curved CSB can have excessive lateral displacement and moment when the tension is adjusted, focusing only on longitudinal behavior, such as a straight CSB. In order to analyze the effect of the cable on the lateral behavior of bridges, the cable is divided into two groups according to the lateral displacement direction of the pylon due to tension. The influence of the combination ratio of GR1 and GR2 on the girder, bearing, pylon, and vertical anchor cable was analyzed. When the tension applied to the bridge is 1.0GR1 plus 1.0GR2, In the combination of 1.2GR1 plus 0.8GR2, the stress on the left and right upper member of the truss girder and the deviation of the both were minimized. In addition, the horizontal force of the bearing, the lateral displacement and moment of the pylon, and the tension of the vertical backstay cable also decreased. This study is expected to be used as basic data for determination of tension of CSB with similar geometry.

Proposal of a New Type of 4-Lane Soundproof Tunnel Girder and Structural Performance Evaluation (4차선급 신형식 방음터널 거더 제안 및 구조적 성능평가)

  • Goh, Won-Hui;Kim, Min-Jae;Ma, Chuan;Kang, Duck-Man;Zi, Goang-Suep
    • Journal of the Korea institute for structural maintenance and inspection
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    • v.25 no.5
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    • pp.24-31
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    • 2021
  • The soundproof tunnels have been generally designed with H-beam girders, and the high weight of H-beam may cause the excessive design of the substructure. To solve this problem, this paper proposes a new soundproof tunnel girder design composed of pipes and discontinuous plates. First, the structural behavior of the straight girder according to the design parameters was examined through finite element analysis. The arrangement and shape of the plates were determined as the design parameter, to obtain the optimal design of girder. After then, the structural behavior and buckling stability of the arched girder were subsequently evaluated. As a result of the parameter analysis, it was confirmed that the axial force acting on the girder increased and the moment decreased as the ratio of unsupported sections decreased or the number of supporting plates increased. The stress concentration on the pipe member was relieved by increasing the long axis length of the elliptical plate. Arched girder analysis showed that the structural efficiency increase as the long axis of elliptical plate increase. As a result of the buckling evaluation, the buckling threshold load of the three connected girders was about 3.7 times higher than the design load. Consequently, it was confirmed that the proposed soundproof tunnel structure design satisfies both light weight and structural safety.

A Study on the Design Improvement of Street Facilities in Jeollabuk-do Province (전라북도 가로시설물의 디자인 제고를 위한 연구)

  • Kim, Sang Hyun;Kim, Hong Bae
    • Journal of the Korean Institute of Rural Architecture
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    • v.25 no.2
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    • pp.1-8
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    • 2023
  • This study reveals the absence of standard design guidelines by region through investigation and analysis centered on public design cases by region in Jeollabuk-do and design elements that can reflect the integration, identity, and diversity of public design in each region by five regions. Through this, the following conclusions could be obtained. First, to improve the quality of street facilities in Jeollabuk-do, the design elements (design motif, color, pattern) applicable to the standard design were analyzed by dividing them into five regions. As a design motif, it was possible to extract patterns containing straight lines, sophistication, dignity, and smartness. In the Northeast region, it is comfortable with the motif of the mountain ridge reflecting geographical characteristics, and it can be extracted elements that contain warm and natural colors. In the southeastern region, patterns that reflect design elements were extracted by applying safe, lively, and peaceful colors with the design motif of curves that blend nature and agriculture. In the southwestern region, design pattern elements that highlight nature, history, and culture were extracted with various cultural assets and natural greenery as motifs. Lastly, in the Saemangeum region, the ocean flow and greenery could be used as a design motif to reflect a positive, clear, future-oriented image in the design spot zones by region. Second, based on the standard design elements (design motive, color, pattern) by region extracted for the standard design development of street facilities in each region in Jeollabuk-do, an integrated zone(Form, structure, material, color, functional element) to which regional design guidelines can be applied. Third, an integrated zone (form, structure, material, color, functional elements) was composed. In addition, design spot zones (patterns and colors in city and county units) that can contain the diversity and identity of each region were designated. By designating design spot zones (patterns and colors in city and county units) that can contain the diversity and identity of each region, standard design development plans (integrated pillars, jaywalking prevention fences, roundabouts (urban type, rural type), street trees) Eight standard designs, including protective covers, street planters, flat benches, light benches, visual media for user guidance, and parking zones for personal mobile devices) were presented.

PASTELS project - overall progress of the project on experimental and numerical activities on passive safety systems

  • Michael Montout;Christophe Herer;Joonas Telkka
    • Nuclear Engineering and Technology
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    • v.56 no.3
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    • pp.803-811
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    • 2024
  • Nuclear accidents such as Fukushima Daiichi have highlighted the potential of passive safety systems to replace or complement active safety systems as part of the overall prevention and/or mitigation strategies. In addition, passive systems are key features of Small Modular Reactors (SMRs), for which they are becoming almost unavoidable and are part of the basic design of many reactors available in today's nuclear market. Nevertheless, their potential to significantly increase the safety of nuclear power plants still needs to be strengthened, in particular the ability of computer codes to determine their performance and reliability in industrial applications and support the safety demonstration. The PASTELS project (September 2020-February 2024), funded by the European Commission "Euratom H2020" programme, is devoted to the study of passive systems relying on natural circulation. The project focuses on two types, namely the SAfety COndenser (SACO) for the evacuation of the core residual power and the Containment Wall Condenser (CWC) for the reduction of heat and pressure in the containment vessel in case of accident. A specific design for each of these systems is being investigated in the project. Firstly, a straight vertical pool type of SACO has been implemented on the Framatome's PKL loop at Erlangen. It represents a tube bundle type heat exchanger that transfers heat from the secondary circuit to the water pool in which it is immersed by condensing the vapour generated in the steam generator. Secondly, the project relies on the CWC installed on the PASI test loop at LUT University in Finland. This facility reproduces the thermal-hydraulic behaviour of a Passive Containment Cooling System (PCCS) mainly composed of a CWC, a heat exchanger in the containment vessel connected to a water tank at atmospheric pressure outside the vessel which represents the ultimate heat sink. Several activities are carried out within the framework of the project. Different tests are conducted on these integral test facilities to produce new and relevant experimental data allowing to better characterize the physical behaviours and the performances of these systems for various thermo-hydraulic conditions. These test programmes are simulated by different codes acting at different scales, mainly system and CFD codes. New "system/CFD" coupling approaches are also considered to evaluate their potential to benefit both from the accuracy of CFD in regions where local 3D effects are dominant and system codes whose computational speed, robustness and general level of physical validation are particularly appreciated in industrial studies. In parallel, the project includes the study of single and two-phase natural circulation loops through a bibliographical study and the simulations of the PERSEO and HERO-2 experimental facilities. After a synthetic presentation of the project and its objectives, this article provides the reader with findings related to the physical analysis of the test results obtained on the PKL and PASI installations as well an overall evaluation of the capability of the different numerical tools to simulate passive systems.

The Characteristics of Transitional Garden in The Early National Period in America - Focused on the analysis of Paca's Garden, Mount Vernon and Monticello - (미국 초기국가시대 전환기 정원의 특성 - 파커 정원, 마운트 버논, 몬티첼로 분석을 중심으로 -)

  • Paek, Nan-Young;Lee, Jong-Sung;Kim, Hyun
    • Journal of the Korean Institute of Traditional Landscape Architecture
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    • v.32 no.4
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    • pp.132-142
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    • 2014
  • This study is the first stage to identify distinctive characteristics of American Romantic Garden compared to English Romantic Garden. The purpose of the study is to identify characteristics of transitional garden in the early period of America by analyzing of Paca garden, Mount Vernon and Monticello when English Naturalistic Garden was firstly imported. The analysis studied historical background, people who designed garden, formal garden and characteristics of natural garden through reference. Also based on data through reference and field research, spatial configuration and garden factors of each site were analyzed. In spatial configuration, straight line and curve line, formal terrace and natural slope, visible axis and invisible axis, symetric and asymmetric, and perspective and oblique perspectives were used as analyzing factors. As a result of analysis, each garden showed different type from that of formal gardens from colony period, which is natural garden of asymmetric garden(English natural garden) coexisted. Paca garden which planned formal garden and natural garden in each space showed characteristics of each space, but in formal garden residential axis and garden axis does not coincide which shows it is out of formal garden type. Such phenomena and the fact that naturalistic garden coexist in the same garden shows that the formal garden type from early days in US is starting to change in different types. Mount Vernon garden, similar to Paca garden, was designed to have two different types of gardens in harmony rather than divide the space into different space and design it. It adapted serpent walkway but shows symmetric by central axis and considered formalistic plan through same materials. However through terrace in hills and spatial plan of oblique perspective, one could observe that naturalistic type was beginning to settle in US gardens. Through Monticello analysis, space was designed with major characteristics of naturalistic garden which is serpent walkway, ornamental farm, winding flower bed grove and bush and oblique perspective, and it completely duplicates characteristics of naturalistic garden which could not be found in gardens imported from UK.

A study on the accuracy of source position in HDR brachytherapy according to the curvature of Universal applicator transfer tube and applicator type (원격 후 장전치료기를 사용한 고선량률 근접치료시 기구의 형태와 선원 전달 도관의 곡률 변화에 따른 선원위치 정확성에 관한 고찰)

  • Shin, Hyeon Kyung;Lee, Sang Kyoo;Kim, Joo Ho;Cho, Jeong Hee
    • The Journal of Korean Society for Radiation Therapy
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    • v.27 no.2
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    • pp.123-129
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    • 2015
  • Purpose : The goal of this study was to verify and analyze the source position according to the curvature of the universal applicator and 4 different angle applicators when using RALS(Remote After Loading System). Materials and Methods : An interval of 1 cm and 15 second dwell times in each source position were applied for plan. To verify the accuracy of source position, we narrowed the distance between MultiSource container and GAFCHROMIC$^{(R)}$ EBT3 film by 5 cm, 10 cm, 20 cm so that the universal applicator transfer tube had some curvature. Also 4 applicators(Intrauterine tube: $0^{\circ}$, $15^{\circ}$, $30^{\circ}$, Ovoid tube: $65^{\circ}$) were used in the same condition. The differences between desired and actual source position were measured by using Image J. Results : In case of using 4 different angles of applicator with the straight universal applicator transfer tube, the average error was the lowest for $0^{\circ}$ applicator, greatest for $65^{\circ}$ applicator. However, All average errors were within ${\pm}2mm$ recommended in TG-56. When MultiSource container was moved 5 cm, 10 cm, 20 cm towards the EBT3 film, the average errors were beyond ${\pm}2mm$. The first dwell position was relatively located in accuracy, while the second and third dwells were displaced by an increasing magnitude with increasing curvature of the transfer tube. Furthermore, with increasing the angle of applicators, the error of all other dwell positioning was increased. Conclusion : The results of this study showed that both the curvature of universal applicator transfer tube and the angle of applicators affect the source dwell position. It is recommended that using straight universal applicator transfer tubes is followed in all cases, in order to avoid deviations in the delivered source dwell position. Also, It is advisable to verify the actual dwell position, using video camera quality control tool prior to all treatments.

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A Study of Esthetic Facial Profile Preference In Korean (한국인의 연조직측모 선호경향에 대한 연구)

  • Choi, Jun-Gyu;Lee, Ki-Soo
    • The korean journal of orthodontics
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    • v.32 no.5 s.94
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    • pp.327-342
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    • 2002
  • Soft tissue profile is a critical area of interest in the development of an orthodontic treatment and diagnosis. The purpose of this study was to determine the facial profile preference of diversified group and to investigate the relationship between most Preferred facial Profile and existing soft tissue reference lines. A survey instrument of constructed facial silhouettes was evaluated by 894 lay person. The silhouettes had varied nose, lips, chin and soft tissue subnasale point. Seven sets of facial type were computer-generated by an orthodontist to represent distinct facial types. The varied facial profiles were graded on the basis of most preferred to least preferred. Every facial profile were measured by soft tissue reference lines(Ricketts E-line, Burstone B-line) to observe the most preferred facial profile. The results as follows: 1. In reliability test, the childhood group showed lower value than other groups, which means that this group has no concern on facial profile preference. 2. It appears that sexual and age difference made no significant difference in selecting the profile 3. An agreement to least preferred facial profile was higher than an agreement to most preferred facial profile. 4. Coefficient of concordance (Kendall W) was higher in the twentieth group. It means that a profile preference of the twentieth is distinct. 5. A lip protrusion (to Ricketts E-line and Burstone B-line) of most preferred facial profile was similar to measurements of previous study that investigate skeletal and soft tissue of esthetic facial profile of young Korean. So these reference lines can be used valuably in clinics. 6. Profile of excessive lip protrusion or retrusion to E-line & B-line was least preferred. 7. Most preferred profile of all respondents group was straight profile. Profile that showing convex profile was not pre(erred and the least preferred profile was concave profile.

An Exploration of Discrepancies between Text and Content Knowledge of Pre-service Elementary Teachers through an Analysis of Questions and Answers Created in the Interactive Reading of a Teacher's Guide: Focusing on a 'Shadow and Mirror' Unit (상호작용적 독해 과정에서 생성된 질문과 답변의 분석을 통한 교사용 지도서와 초등예비교사의 내용지식 사이의 불일치 탐색 -'그림자와 거울' 단원을 중심으로)

  • Arla Go;Jiwon Lee
    • Journal of The Korean Association For Science Education
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    • v.43 no.3
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    • pp.253-263
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    • 2023
  • This study explored the discrepancy between the text of a teacher's guide about straight and reflective light and the content knowledge of pre-service elementary teachers. A total of 455 questions and 543 answers generated by 279 pre-service elementary teachers after reading a 'Shadow and Mirror' unit in the teacher's guide were analyzed. The questions were classified according to the types of concepts and discrepancies, and the answers were analyzed for accuracy. The results of analyzing the concepts of questions revealed that the pre-service elementary teachers were most curious about the shadow in the straight concept, the mirror image in the reflection concept, and the light source in other concepts. The questions with a low correct answer rate due to incorrect- or non-answers, such as those concerning the superposition principle of light by reflection, the principle of experimental tools, and images by lenses, were only partially or not included in the teacher's guide. When the questions were classified according to the type of discrepancy, the frequency of questions due to knowledge deficit was higher than that due to knowledge clash. This demonstrates that the concepts that teachers need to know must be supplemented with the contents of the teacher's guide. Discrepancies due to knowledge clashes are often caused by conflicts between what is experienced in everyday life and what is presented in textbooks. Therefore, it is necessary to reduce the discrepancy between the texts of the teacher's guide and the knowledge of pre-service elementary teachers by including the differences between the actual context of everyday life and the context of the textbook in the teacher's guide.