• 제목/요약/키워드: acyclic

검색결과 245건 처리시간 0.019초

Kinetics and Mechanism of the Anilinolysis of 1,2-Phenylene Phosphorochloridate in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
    • /
    • 제32권9호
    • /
    • pp.3355-3360
    • /
    • 2011
  • The nucleophilic substitution reactions of 1,2-phenylene phosphorochloridate (1) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $-15.0^{\circ}C$. The studied substrate of 1,2-phenylene phosphorochloridate is cyclic five-membered ring of phosphorus ester, and the anilinolysis rate of 1 is much faster than its acyclic analogue (4: ethyl phenyl chlorophosphate) because of extremely small magnitude of the entropy of activation of 1 compared to 4. The Hammett and Bronsted plots exhibit biphasic concave upwards for substituent X variations in the nucleophiles with a break point at X = 3-Me. The values of deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) change from secondary inverse ($k_H/k_D$ < 1) with the strongly basic anilines to primary normal ($k_H/k_D$ > 1) with the weakly basic anilines. The secondary inverse with the strongly basic anilines and primary normal DKIEs with the weakly basic anilines are rationalized by the transition state (TS) variation from a predominant backside attack to a predominant frontside attack, in which the reaction mechanism is a concerted $S_N2$ pathway. The primary normal DKIEs are substantiated by a hydrogen bonded, four-center-type TS.

Kinetics and Mechanism of the Pyridinolysis of Ethylene Phosphorochloridate in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
    • /
    • 제32권12호
    • /
    • pp.4347-4351
    • /
    • 2011
  • The nucleophilic substitution reactions of ethylene phosphorochloridate (2) with X-pyridines are investigated kinetically in acetonitrile at $-20.0^{\circ}C$. The free energy correlations for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Ph. Unusual positive ${\rho}_X$ (= +2.49) and negative ${\beta}_X$ (= -0.41) values are obtained with the weakly basic pyridines, and rationalized by the isokinetic relationship with isokinetic temperature at $t_{ISOKINETIC}=6.6^{\circ}C$. The pyridinolysis rate of 2 with a cyclic five-membered ring is forty thousand times faster than its acyclic counterpart (3: diethyl chlorophosphate) because of great positive value of the entropy of activation of 2 (${\Delta}S^{\neq}$ = +49.2 eu) compared to negative value of 3 (${\Delta}S^{\neq}$ = -44.1 eu) over considerably unfavorable enthalpy of activation of 2 (${\Delta}H^{\neq}=28.4\;kcal\;mol^{-1}$) compared to 3 (${\Delta}H^{\neq}=6.3\;kcal\;mol^{-1}$). Great enthalpy and positive entropy of activation are ascribed to sterically congested transition state (TS) and solvent structure breaking in the TS. A concerted mechanism involving a change of nucleophilic attacking direction from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines is proposed.

제한된 글자 디자인에 의한 한글 조합형 글꼴의 자동생성 (Automatic generation of Hangul Johap typeface using small character set)

  • 강상수;조환규
    • 한국정보과학회 언어공학연구회:학술대회논문집(한글 및 한국어 정보처리)
    • /
    • 한국정보과학회언어공학연구회 1994년도 제6회 한글 및 한국어정보처리 학술대회
    • /
    • pp.217-222
    • /
    • 1994
  • 한글 글꼴을 새롭게 만들려면 지금까지는 기본 글자인 자소를 디자인하든지 아니면 완성된 글자 전체를 디자인해야 했다. 조합형의 글자디자인의 경우, 전체 글자가 아니라 부분적인 한글 전자사전은 많은 양의 데이타를 저장할 수 있어야 하며, 빠른 검색 속도를 제공해야 한다. 기존의 트라이는 공통접두사만을 압축하기 때문에 사전의 크기가 방대하다는 단점이 있다. 본 논문에서는 DAWG(Directed Acyclic Word Graph)를 이용하여 공통접미사까지 압축하였고, 검색과 기억장소의 효율을 위하여, 링크드리스트 구조의 DAWG를 유형별 배열 구조로 바꾸었다. 전국의 각 학교 이름들을 대상으로 실험한 결과, 본 논문에서 제안한 DAWG를 이용한 배열 구조의 사전은 트라이와 비교하여 볼 때, 검색 연산의 성능은 동일하게 유지하면서 기억 장소의 효율과 압축율에서 효과적이었다. 또한, 트라이보다 주기억장치와 보조기억장치와의 블록 입출력횟수를 줄임으로써 전체 검색 시간을 낮출 수 있었다.소를 디자인하기 때문에 전체 글자의 모양이 좋지 않다는 단점이 있었고 완성형의 경우 완성된 글자 전체를 모두 디자인해야하는 단점이 있었다. 본 논문에서는 한글 글꼴 개발의 한 방법으로 제한된 글자의 디자인에 의한 전체 글꼴 생성에 관한 한 방법을 제시한다. 이 방법은 표준으로 설정된 몇 글자를 디자인하면 그 글자를 분석하여 자소들을 위한 글꼴 화일이 만들어지고 자소 글꼴 화일로부터 다른 모든 글자를 만들어 낸다.

  • PDF

On the edge independence number of a random (N,N)-tree

  • J. H. Cho;Woo, Moo-Ha
    • 대한수학회보
    • /
    • 제33권1호
    • /
    • pp.119-126
    • /
    • 1996
  • In this paper we study the asymptotic behavior of the edge independence number of a random (n,n)-tree. The tools we use include the matrix-tree theorem, the probabilistic method and Hall's theorem. We begin with some definitions. An (n,n)_tree T is a connected, acyclic, bipartite graph with n light and n dark vertices (see [Pa92]). A subset M of edges of a graph is called independent(or matching) if no two edges of M are adfacent. A subset S of vertices of a graph is called independent if no two vertices of S are adjacent. The edge independence number of a graph T is the number $\beta_1(T)$ of edges in any largest independent subset of edges of T. Let $\Gamma(n,n)$ denote the set of all (n,n)-tree with n light vertices labeled 1, $\ldots$, n and n dark vertices labeled 1, $\ldots$, n. We give $\Gamma(n,n)$ the uniform probability distribution. Our aim in this paper is to find bounds on $\beta_1$(T) for a random (n,n)-tree T is $\Gamma(n,n)$.

  • PDF

Application of Ultrasonography to Investigate Postpartum Anestrus in Water Buffaloes

  • Rahman, Md Saidur;Shohag, Abu Said;Kamal, Md. Mostafa;Parveen, Nasreen;Shamsuddin, Mohammed
    • Reproductive and Developmental Biology
    • /
    • 제36권2호
    • /
    • pp.103-108
    • /
    • 2012
  • Anestrus is one of the most important production limiting disorders in dairy buffaloes and its underlying causes have been a current topic of studies. The objectives of this study were to explore the causes of anestrus in buffaloes with the application of ultrasonography. Two examinations were performed by transrectal ultrasonography at 12 days apart in buffalo cows that were not seen in oestrus at 60 or more days postpartum. As high as 54.5% buffaloes had silent ovulation and 45.5% suffered from the true anestrus with ovarian dysfunction. The duration of anestrus after calving was 60~90, 91~120, 121~180 and 181~365 days in 27%, 32%, 18% and 23% buffalo cows, respectively. Treatment with prostaglandin of cyclic buffalo cows with a corpus luteum (72.7%) resulted in higher estrous rate as compared with close observation of estrus (23.1%) by the farmer (p=0.021). Acyclic buffalo cows without any corpus luteum on ovaries were successfully treated with gonadotropin releasing hormone (70%), resulting in higher estrous detection rate than those treated with a vitamin-mineral mixture (20%) (p=0.035). In conclusion, poor heat detection due to silent ovulation is the most important cause of apparent anoestrus in buffaloes; however the percentage of the true anestrous is also quite high in postpartum buffaloes.

블록체인 기법의 확장가능성을 위한 병행 수행 제어 기법에 대한 연구 (A Study on Concurrency Control Scheme for Scalability of Blockchain)

  • 강용혁;박원형
    • 융합보안논문지
    • /
    • 제20권3호
    • /
    • pp.71-78
    • /
    • 2020
  • 비트코인에 기반한 블록체인 기술은 익명성이 있는 스마트 계약, 저렴한 송금, 온라인 거래 등을 가능하게 하는 하부구조를 제시하고 있다. 하지만, 비트코인을 구현하는 블록체인 기술은 처리량과 지연시간 간의 트레이드오프 관계에 있는 확장가능성 제한을 갖고 있다. 이러한 문제를 해결하기 위한 비잔틴 고장 감내 기반 블록체인 기술이 제안되었다. 이 기법은 리더를 선출하고 리더에 의해 기존 블록 내에 작업증명을 포함하지 않는 많은 마이크로 블록을 구성하여 지연시간 증가 없이 처리량을 향상시켰다. 하지만 이 기법은 리더를 선출하는 부분에서 기존 기법보다 보안성이 떨어질 수 있다. 본 논문에서는 마이크로 블록기술과 병행수행 기법을 통해 블록체인 기술의 확장가능성을 위한 기법을 제안한다. 하나의 마이크로 블록 내에는 여러 개의 거래에 대한 정보가 있다.

Kinetics and Mechanism of the Pyridinolysis of 1,2-Phenylene Phosphorochloridate in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
    • /
    • 제33권1호
    • /
    • pp.270-274
    • /
    • 2012
  • The nucleophilic substitution reactions of 1,2-phenylene phosphorochloridate (1c) with X-pyridines are investigated kinetically in acetonitrile at $-25.0^{\circ}C$. The free energy correlations for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Ph. The pyridinolysis rate of 1c with a cyclic five-membered ring is $2.70{\times}10^5$ times faster than its acyclic counterpart (1a: phenyl ethyl chlorophosphate) because of great positive value of the entropy of activation of 1c (${\Delta}S^{\neq}$ = +26 eu) compared to negative value of 1a (${\Delta}S^{\neq}$= -24 eu) over considerably unfavorable enthalpy of activation of 1c (${\Delta}H^{\neq}=20.5kcal\;mol^{-1}$) compared to 1a (${\Delta}H^{\neq}=12.7kcal\;mol^{-1}$). Great enthalpy and positive entropy of activation are ascribed to sterically congested transition state (TS) and solvent structure breaking in the TS. A concerted mechanism involving a change of nucleophilic attacking direction from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines is proposed on the basis of greater selectivity parameters (${\rho}_X$ = -1.99 and ${\beta}_X$ = 0.41) with the strongly basic pyridines compared to those (${\rho}_X$ = -0.42 and ${\beta}_X$ = 0.07) with the weakly basic pyridines.

Transaction Mining for Fraud Detection in ERP Systems

  • Khan, Roheena;Corney, Malcolm;Clark, Andrew;Mohay, George
    • Industrial Engineering and Management Systems
    • /
    • 제9권2호
    • /
    • pp.141-156
    • /
    • 2010
  • Despite all attempts to prevent fraud, it continues to be a major threat to industry and government. Traditionally, organizations have focused on fraud prevention rather than detection, to combat fraud. In this paper we present a role mining inspired approach to represent user behaviour in Enterprise Resource Planning (ERP) systems, primarily aimed at detecting opportunities to commit fraud or potentially suspicious activities. We have adapted an approach which uses set theory to create transaction profiles based on analysis of user activity records. Based on these transaction profiles, we propose a set of (1) anomaly types to detect potentially suspicious user behaviour, and (2) scenarios to identify inadequate segregation of duties in an ERP environment. In addition, we present two algorithms to construct a directed acyclic graph to represent relationships between transaction profiles. Experiments were conducted using a real dataset obtained from a teaching environment and a demonstration dataset, both using SAP R/3, presently the predominant ERP system. The results of this empirical research demonstrate the effectiveness of the proposed approach.

Chelators for 68Ga radiopharmaceuticals

  • Seelam, Sudhakara Reddy;Lee, Yun-Sang;Jeong, Jae Min
    • 대한방사성의약품학회지
    • /
    • 제2권1호
    • /
    • pp.22-36
    • /
    • 2016
  • $^{68}Ga$ is a promising radionuclide for positron emission tomography (PET). It is a generator-produced ($^{68}Ge/^{68}Ga$-generator) radionuclide with a half-life of 68 min. The employment of $^{68}Ga$ for basic research and clinical applications is growing exponentially. Bifunctional chelators (BFCs) that can be efficiently radiolabeled with $^{68}Ga$ to yield complexes with good in vivo stability are needed. Given the practical advantages of $^{68}Ga$ in PET applications, gallium complexes are gaining increasing attention in biomedical imaging. However, new $^{68}Ga$-labeled radiopharmaceuticals that can replace $^{18}F$-labeled agents like [$^{18}F$]fluorodeoxyglucose (FDG) are needed. The majority of $^{68}Ga$-labeled derivatives currently in use consist of peptide agents, but the development of other agents, such as amino acid or nitroimidazole derivatives and glycosylated human serum albumin, is being actively pursued in many laboratories. Thus, the availability of new $^{68}Ga$-labeled radiopharmaceuticals with high impact is expected in the near future. Here, we present an overview of the different new classes of chelators for application in molecular imaging using $^{68}Ga$ PET.

The Crystal and Molecular Structure of Thiamphenicol

  • Shin, Whan-chul;Kim, Sang-soo
    • Bulletin of the Korean Chemical Society
    • /
    • 제4권2호
    • /
    • pp.79-83
    • /
    • 1983
  • The structure of thiamphenicol, one of the congeners of chloramphenicol which is a well-known antibiotic, has been determined by single crystal x-ray diffraction techniques. The crystal structure was determined using diffractometer data obtained by the $2{\theta}:{\omega}$ scan technique with $MoK{\alpha}$ radiation from a crystal having space group symmetry $P2_{1}2_{1}2_{1}$, and unit cell parameters a = 5.779, b = 15.292 and c = 17.322 ${\AA}$ . The structure was solved by direct methods and refined by least squares to an R = 0.070 for the 2116 reflections. The overall V-shaped conformation of thiamphenicol revealed in this study is consistent with those from the crystallographic studies and the proposed models from the theoretical and nmr studies of chloramphenicol. However there is no intramolecular hydrogen bond and the propanediol moiety is fully extended in the thiamphenicol molecule, while the crystal structures of chloramphenicol show the existence of the hydrogen bond between the two hydroxyl groups of the propanediol moiety forming an acyclic ring. All of the thiamphenicol molecules in the crystal are linked by a threedimensional hydrogen bonding network.