• 제목/요약/키워드: State transition

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Kinetic Study on Aminolysis of Y-Substituted-Phenyl Picolinates: Effect of H-Bonding Interaction on Reactivity and Transition-State Structure

  • Kim, Min-Young;Kang, Tae-Ah;Yoon, Jung Hwan;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제35권8호
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    • pp.2410-2414
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    • 2014
  • A kinetic study is reported on nucleophilic substitution reactions of Y-substituted-phenyl picolinates (7a-7h) with a series of cyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. Comparison of the kinetic results with those reported previously for the corresponding reactions of Y-substituted-phenyl benzoates (1a-1f) reveals that 7a-7h are significantly more reactive than 1a-1f. The Br${\o}$nsted-type plot for the aminolysis of 4-nitrophenyl picolinate (7a) is linear with ${\beta}_{nuc}=0.78$, which is typical for reactions proceeding through a stepwise mechanism with expulsion of the leaving group being the rate-determining step. The Br${\o}$nsted-type plots for the piperidinolysis of 7a-7h and 1a-1f are also linear with ${\beta}_{lg}=-1.04$ and -1.39, respectively, indicating that the more reactive 7a-7h are less selective than the less reactive 1a-1f to the leaving-group basicity. One might suggest that the enhanced reactivity of 7a-7h is due to the inductive effect exerted by the electronegative N atom in the picolinyl moiety, while the decreased selectivity of the more reactive substrates is in accord with the reactivity-selectivity principle. However, the nature of intermediate (e.g., a stabilized cyclic intermediate through the intramolecular H-bonding interaction for the reactions of 7a-7h, which is structurally not possible for the reactions of 1a-1f) is also responsible for the enhanced reactivity with a decreased selectivity.

Asymmetrical Volume Loss in Hippocampal Subfield During the Early Stages of Alzheimer Disease: A Cross Sectional Study

  • Kannappan, Balaji
    • 통합자연과학논문집
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    • 제11권3호
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    • pp.139-147
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    • 2018
  • Hippocampal atrophy is a well-established imaging biomarker of Alzheimer disease (AD). However, hippocampus is a non-homogenous structure with cytoarchitecturally and functionally distinct sub-regions or subfield, with each region performing distinct functions. Certain regions of the subfield have shown selective vulnerability to AD. Here, we are interested in studying the effects of normal aging and mild cognitive impairment on these sub-regional volumes. With a reliable automated segmentation technique, we segmented these subregions of the hippocampus in 101 cognitively normal (CN), 135 early mild cognitive impairment (EMCI), 67 late mild cognitive impairment (LMCI) and 48 AD subjects. Thereby, dividing the hippocampus into hippocampal tail (tail), subiculum (SUB), cornu ammonis 1 (CA1), hippocampal fissure (fissure), presubiculum (PSUB), parasubiculum (ParaSUB), molecular layer (ML), granule cells/molecular layer/dentate gyrus (GCMLDG), cornu ammonis 3(CA3), cornu ammonis 4(CA4), fimbria and hippocampal-amygdala transition area (HATA). In this cross sectional study of 351 ADNI subjects, no differences in terms of age, gender, and years of education were observed among the groups. Though, the groups had statistically significant differences (p < 0.05 after the multiple comparison correction) in the Mini-Mental State Examination (MMSE) scores. There was asymmetrical volume loss in the early stages of AD with the left hemisphere showing volume loss in regions that were unaffected in the right hemisphere. Bilateral parasubiculum, right cornu ammonis 1, 3 and 4, right fimbria and right HATA regions did not show any volume loss till the late MCI stages. Our findings suggest that the hippocampal subfield regions are selectively vulnerable to AD and also that these vulnerabilities are asymmetrical especially during the early stages of AD.

Ethnic Differences in the Adjustment to Poverty and Disability among Unmarried Elderly Americans : An Analysis of Multi-State Transitions in Living Arrangements from 1984-1990

  • 박경숙;프랜시스골드샤이더;로저애버리
    • 한국인구학
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    • 제22권1호
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    • pp.123-151
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    • 1999
  • 미국사회에서 노인의 거주지 적응양식은 인종간에 차이가 크다. 일반적으로 소수인종노인은 백인 노인에 비하여 자녀와 함께 사는 경향이 강하다. 이에 대하여 문화적 입장에서는 소수인종은 백인에 비하여 가족부양규범이 강하다고 주장한다. 다른 한편 경제적 입장에서는 소수인종은 그들의 생애를 지배하는 빈곤 때문에 규모의 경제를 통하여 가계비용을 줄이기 위하여 확대가족을 유지할 수밖에 없다고 주장한다. 본 연구는 노인이 질병과 빈곤에 적응하는 방식에 있어 인종간 차이를 검토함으로써 기존의 경제학적 논의와 문화적 논의의 적합성을 검정하는데 목적을 두고 있다. 이를 위하여 노인의 거주지 적응에 대한 문화적 영향과 관련하여 두가지 가설을 검정하고 있다. 첫째, 소수인종 노인은 백인노인에 비하여 빈곤과 질병상황에서 가족으로부터 더 오랜기간 보호를 받는지를 검토한다. 둘째, 소수인종 노인은 백인노인에 비하여 건강이 악화될 때 더욱 신속하게 가족으로부터 보호를 받을 수 있는지를 검토한다. 분석을 위해서 1984년에서 1990년기간 동안 실시된 "고령화에 대한 종단적 조사(Longitudinal Survey on Aging)"를 이용하여 마르코비안 다중생명표 모형과 사건분석을 수행하였다. 본 연구결과에 따르면 소수인종 노인은 가족부양규범의 문화적 이점을 그다지 크게 다지고 있지 않다. 인종간 사망력과 시설입소의 차이를 통제할 때, 소수인종 노인은 백인노인에 비하여 보다 흔하게 자녀동거에서 단독거주형태로 혹은 그 반대방향으로 거주지 변화를 경험하고 있다. 백인 노인은 소수인종에 비하여 질병상태와 관련하여 자녀와 동거하는 경향이 더 강하다. 사망력과 시설입소의 인종간 차이를 통제할 때 소수인종노인이 백인노인보다 쉽게 자녀동거에서 단독거주로 이행하는데 이는 소수인종에서 가족부양체계가 불안정함을 의미한다. 또한 빈곤시에 소수인종 노인은 백인노인에 비하여 쉽게 자녀와 떨어져 살게 된다. 이러한 결과는 소수인종 노인에 대한 가족의 지원은 그 가족의 경제적 제약속에서 매우 안정적이지 못함을 시사한다. 못함을 시사한다.

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DGEBA-MDA-SN-Hydroxyl계 복합재료의 제조 -DGEBA-MDA-SN-HQ계의 경화반응 속도론 및 메카니즘- (DGEBA-MDA-SN-Hydroxyl Group System and Composites -Cure Kinetics and Mechanism in DGEBA/MDA/SN/HQ System-)

  • 심미자;김상욱
    • 공업화학
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    • 제5권3호
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    • pp.517-523
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    • 1994
  • DGEBA(diglycidyl ether of bisphenol A)/MDA(4,4'-methylene dianiline)/SN(succinonitrile)/HQ(hydroquinone)계의 경화반응 속도론 및 메카니즘을 연구하였다. SN과 HQ는 반응성 첨가제와 촉매로 도입하였다. 경화반응 속도론은 DSC 분석에 의해 Kissinger equation과 fractional-life법을 이용하여 연구하였다. DGEBA/MDA/SN 계의 활성화에너지와 반응차수는 SN의 함량에 관계없이 거의 일정하였고, 촉매로써 HQ가 첨가됨으로 인해 활성화 에너지와 반응시작온도가 낮아졌다. 이들 계의 반응 메카니즘을 고찰하기위하여 SN의 함량에 따라 FT-IR을 측정하였다. 그리고, SN:HQ의 혼합비는 4:1이었다. Diamine으로 경화되는 에폭시 수지의 경화반응 메카니즘은 primary amine-epoxy 반응, secondary amine-epoxy 반응, epoxy-hydroxyl 반응이 일어나는 것으로 알려져 있다. DGEBA/MDA/SN/HQ 계에서는 HQ의 hydroxyl 기가 epoxy 및 amine과 결합하여 전이상태를 형성하여 epoxide ring을 빠르게 개환시켜줌으로써 amine-epoxy반응이 쉽게 일어남을 알았다.

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0.96(Na0.5K0.5)NbO3-0.04(Ba(1-x)Srx)TiO3 무연 세라믹스의 유전 및 압전 특성 (Dielectric and piezoelectric properties of 0.96(Na0.5K0.5)NbO3-0.04(Ba(1-x)Srx)TiO3 lead-free ceramics)

  • 김미로;윤석진;최지원
    • 센서학회지
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    • 제19권2호
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    • pp.155-159
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    • 2010
  • 0.96$(Na_{0.5}K_{0.5})NbO_3$-0.04$(Ba_{(1-x)}Sr_x)TiO_3$ lead free piezoelectric ceramics were synthesized to enhance the piezoelectric properties of (Na,K)$NbO_3$. The systhesis and sintering method were the conventional solid state reaction method and general sintering method in air atmosphere. The polymorphic phase transition(PPT) was observed at all composition(0 $\leq$ x $\leq$ 0.05) when $(Ba_{(1-x)}Sr_x)TiO_3$ were added in the $(Na_{0.5}K_{0.5})NbO_3$. As Sr concentration was increased, grain size, dielectric loss(tan$\delta$) and mechanical quality factor($Q_m$) were decreased and piezoelectric constant($d_{33}$) and electromechanical coupling factor($k_p$) were increased within a limited value. The optimized piezoelectric and properties, $d_{33}$, $k_p$, $Q_m$, and tand, of 0.96$(Na_{0.5}K_{0.5})NbO_3$-0.04$(Ba_{(1-x)}Sr_x)TiO_3$ were 139 pC/N, 0.31 %, 95, 0.04 at the composition of x=0.04.

한국미션건축에 있어서 장로교 소속 개척선교사들의 건축활동에 관한 사적 고찰 (A Historical Study on the Activities of the Presbyterian Pioneer Missionaries in Korea Protestant Mission Architecture)

  • 정창원
    • 건축역사연구
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    • 제13권3호
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    • pp.69-83
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    • 2004
  • The objective of this study is to clarify the early state of modern architecture, specifically mission architecture, with the introduction of the Christianity, and for the goal it deals with the architectural activities of pioneer missionaries. Especially it is a piece in a series of those researches after on Graham Lee, and it is focused on the other representative missionary, R. M. Wilson, A. M. Sharrocks, and C. A. Clark. Although coming in the capacity of a medical doctor or an educator, they should play all kinds of roles, such as carpenters, educators, and officers. For this mission, even they didn't have a professional knowledge for construction, they should carried on to establish mission compounds, only with their experience and informations. In this process they needed to be assisted by Korean carpenters, surely. The architectures born by them-selves are designed with a unique eclectic style compounded with those of Korean traditional and occidental. That is to say, the pioneer missionaries made a profound influence to create a new tradition of modern architecture in Korea, which is called as Korean-occidental eclectic style in the period of transition. Moreover, some pioneer missionary, such as Sharrocks, took a part in education of architectural skills. The educated carpenters seemed to be called from outside, and the unique styles could get spread away. On this point this paper has the meaning to clarify historically the continuous development of the Korean architecture through the survey on their activities, on the contrary of the existed recognition that Korean modern architecture has been evaluated to be imported from outside; therefore having a crevice with the its own architectural tradition.

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Ubiquitous 통신을 위한 Acoustic 모뎀의 동기부 성능을 개선하는 새로운 M진 상태천이 주파수 쉬프트 키잉 변조 기법 (New M-ary Differential-Frequency Shift Keying Modulation Enhancing Acoustic Modem's Synchronization For Ubiquitous Communication)

  • 김은기;김영주;이인성
    • 대한전자공학회논문지TC
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    • 제43권1호
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    • pp.25-32
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    • 2006
  • 주파수 쉬프트 키잉(FSK, Frequency Shift Keying) 기법을 이용하는 acoustic 모뎀[2]에서 복조기 심벌 동기 성능을 개선하는 새로운 M진 상태천이 주파수 쉬프트 키잉 변조기법을 제안하다 기존의 방식은 동일한 심벌을 연속하여 전송할 경우 복조기 동기부 성능이 저하되는 문제점이 있다. 제안하는 방식은 전송되는 매 심벌마다 항상 다른 주파수로 천이하면서 변조되므로, 복조기 동기부에서 심벌 동기 획득 성능을 획기적으로 향상시킬 수 있고, 또한 간단한 변복조 구조 및 프레임 구조를 갖는다. 한편 M진 FSK의 심벌 동기 획득 기법인 modulation-derived synchronization(MDS)을 개선하고 성능을 분석한다. 마지막으로 제안하는 기법을 주파수 효율 측면에서 고찰하여 acoustic 모뎀에 적합함을 증명한다.

Addition effects of nanoscale NiO on microstructure and superconducting properties of MgB2

  • Ranot, Mahipal;Jang, S.H.;Oh, Y.S.;Shinde, K.P.;Kang, S.H.;Chung, K.C.
    • 한국초전도ㆍ저온공학회논문지
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    • 제18권1호
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    • pp.37-40
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    • 2016
  • We have investigated the addition effect of NiO magnetic nanoparticles on crystal structure, microstructure as well as superconducting properties of $MgB_2$. NiO-added $MgB_2$ samples were prepared by the solid-state reaction method. The superconducting transition temperature ($T_c$) of 37.91 K was obtained for pure $MgB_2$, and $T_c$ was found to decrease systematically on increasing the addition level of NiO. X-ray diffraction (XRD) analysis revealed that no substitution of Ni for Mg in the lattice of $MgB_2$ was occurred. The microstructural analysis shows that the pure $MgB_2$ sample consists of plate shape $MgB_2$ grains, and the grains get refined to smaller size with the addition of NiO nanoparticles. At 5 K, high values of critical current density ($J_c$) were obtained for small amount NiO-added $MgB_2$ samples as compared to pure sample. The enhancement in $J_c$ could be attributed to the refinement of $MgB_2$ grains which leads to high density of grain boundaries in NiO-added $MgB_2$ samples.

Repeat Colonoscopy Every 10 Years or Single Colonoscopy for Colorectal Neoplasm Screening in Average-risk Chinese: A Cost-effectiveness Analysis

  • Wang, Zhen-Hua;Gao, Qin-Yan;Fang, Jing-Yuan
    • Asian Pacific Journal of Cancer Prevention
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    • 제13권5호
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    • pp.1761-1766
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    • 2012
  • Background: The appropriate interval between negative colonoscopy screenings is uncertain, but the numbers of advanced neoplasms 10 years after a negative result are generally low. We aimed to evaluate the cost-effectiveness of colorectal neoplasm screening and management based on repeat screening colonoscopy every 10 years or single colonoscopy, compared with no screening in the general population. Methods and materials: A state-transition Markov model simulated 100,000 individuals aged 50-80 years accepting repeat screening colonoscopy every 10 years or single colonoscopy, offered to every subject. Colorectal adenomas found during colonoscopy were removed by polypectomy, and the subjects were followed with surveillance every three years. For subjects with a normal result, colonoscopy was resumed within ten years in the repeat screening strategy. In single screening strategy, screening process was terminated. Direct costs such as screening tests, cancer treatment and costs of complications were included. Indirect costs were excluded from the model. The incremental cost-effectiveness ratio was used to evaluate the cost-effectiveness of the different screening strategies. Results: Assuming a first-time compliance rate of 90%, repeat screening colonoscopy and single colonoscopy can reduce the incidence of colorectal cancer by 65.8% and 67.2% respectively. The incremental cost-effectiveness ratio for single colonoscopy (49 Renminbi Yuan [RMB]) was much lower than that for repeat screening colonoscopy (474 RMB). Single colonoscopy was a more cost-effective strategy, which was not sensitive to the compliance rate of colonoscopy and the cost of advanced colorectal cancer. Conclusion: Single colonoscopy is suggested to be the more cost-effective strategy for screening and management of colorectal neoplasms and may be recommended in China clinical practice.

황의 친핵성 치환반응 (제17보) 2-염화안트라센 술포닐의 가용매 분해반응 (Nucleophilic Displacement at Sulfur Center (XVII). Solvolysis of 2-Anthracenesulfonyl Chloride)

  • 김형태;여수동;이익춘
    • 대한화학회지
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    • 제27권3호
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    • pp.167-177
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    • 1983
  • 물-메탄올, 물-에탄올, 물-아세톤 및 물-아세토니트릴의 2-성분 혼합용매 속에서 2-염화안트라센 술포닐의 가용매 분해반응을 전기전도도법을 써서 속도론적으로 고찰하였다. 물의 몰분률이 같은 혼합용매속에서는 쌍극자성 반양성자 용매에서 보다 양성자성 용매에서 속도가 컸으며, 물-메탄올 혼합용매에서는 실험 농도의 전체 범위에 걸쳐 물-에탄올에서 보다 항상 속도가 컸으나 아세톤과 아세토니트링의 경우에는 몰분율 0.9에서 속도의 크기가 뒤바뀌었다. 용매의 이온화 능력에 대한 반응의 감도를 나타내는 m와 전이상태에서의 물의 관여차수 n값은 모두 쌍극자성 반양성자용매에서 컸다. 이들 값과, 속도상수에서 결정한 활성화 파라미터로부터 2-염화안트라센 술포닐의 가용매분해반응은$ S_N2$ 메카니즘으로 진행된다는 것을 알았다.

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