• 제목/요약/키워드: PH type

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The α-Effect in Nucleophilic Substitution Reactions of Y-Substituted-Phenyl X-Substituted-Cinnamates with Butane-2,3-dione Monoximate

  • Kim, Min-Young;Son, Yu-Jin;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제34권10호
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    • pp.2877-2882
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    • 2013
  • Second-order rate constants ($k_{Ox^-}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl X-substituted-cinnamates (7a-7e) and Y-substituted-phenyl cinnamates (8a-8e) with butane-2,3-dione monoximate ($Ox^-$) in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Hammett plot for the reactions of 7a-7e consists of two intersecting straight lines while the Yukawa-Tsuno plot exhibits an excellent linearity with ${\rho}_X$=0.85 and r=0.58, indicating that the nonlinear Hammett plot is not due to a change in the rate-determining step but is caused by resonance stabilization of the ground state (GS) of the substrate possessing an electron-donating group (EDG). The Br${\o}$nsted-type plot for the reactions of Y-substituted-phenyl cinnamates (8a-8e) is linear with ${\beta}_{lg}$ = -0.64, which is typical of reactions reported previously to proceed through a concerted mechanism. The ${\alpha}$-nucleophile ($Ox^-$) is more reactive than the reference normal-nucleophile ($4-ClPhO^-$). The magnitude of the ${\alpha}$-effect (i.e., the $k_{Ox^-}/k_{4-ClPhO^-}$ ratio) is independent of the electronic nature of the substituent X in the nonleaving group but increases linearly as the substituent Y in the leaving group becomes a weaker electron-withdrawing group (EWG). It has been concluded that the difference in solvation energy between $Ox^-$ and $4-ClPhO^-$ (i.e., GS effect) is not solely responsible for the ${\alpha}$-effect but stabilization of transition state (TS) through a cyclic TS structure contributes also to the Y-dependent ${\alpha}$-effect trend (i.e., TS effect).

Biphasic augmentation of alpha-adrenergic contraction by plumbagin in rat systemic arteries

  • Kim, Hae Jin;Yoo, Hae Young;Zhang, Yin Hua;Kim, Woo Kyung;Kim, Sung Joon
    • The Korean Journal of Physiology and Pharmacology
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    • 제21권6호
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    • pp.687-694
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    • 2017
  • Plumbagin, a hydroxy 1,4-naphthoquinone compound from plant metabolites, exhibits anticancer, antibacterial, and antifungal activities via modulating various signaling molecules. However, its effects on vascular functions are rarely studied except in pulmonary and coronary arteries where NADPH oxidase (NOX) inhibition was suggested as a mechanism. Here we investigate the effects of plumbagin on the contractility of skeletal artery (deep femoral artery, DFA), mesenteric artery (MA) and renal artery (RA) in rats. Although plumbagin alone had no effect on the isometric tone of DFA, $1{\mu}M$ phenylephrine (PhE)-induced partial contraction was largely augmented by plumbagin (${\Delta}T_{Plum}$, 125% of 80 mM KCl-induced contraction at $1{\mu}M$). With relatively higher concentrations (>$5{\mu}M$), plumbagin induced a transient contraction followed by tonic relaxation of DFA. Similar biphasic augmentation of the PhE-induced contraction was observed in MA and RA. VAS2870 and GKT137831, specific NOX4 inhibitors, neither mimicked nor inhibited ${\Delta}T_{Plum}$ in DFA. Also, pretreatment with tiron or catalase did not affect ${\Delta}T_{Plum}$ of DFA. Under the inhibition of PhE-contraction with L-type $Ca^{2+}$ channel blocker (nifedipine, $1{\mu}M$), plumbagin still induced tonic contraction, suggesting $Ca^{2+}$-sensitization mechanism of smooth muscle. Although ${\Delta}T_{Plum}$ was consistently observed under pretreatment with Rho A-kinase inhibitor (Y27632, $1{\mu}M$), a PKC inhibitor (GF 109203X, $10{\mu}M$) largely suppressed ${\Delta}T_{Plum}$. Taken together, it is suggested that plumbagin facilitates the PKC activation in the presence of vasoactive agonists in skeletal arteries. The biphasic contractile effects on the systemic arteries should be considered in the pharmacological studies of plumbagin and 1,4-naphthoquinones.

Nucleophilic Substitution Reactions of Phenyl Y-Substituted-Phenyl Carbonates with Butane-2,3-dione Monoximate and 4-Chlorophenoxide: Origin of the α-Effect

  • Kim, Min-Young;Min, Se-Won;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제34권1호
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    • pp.49-53
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    • 2013
  • Second-order rate constants have been measured spectrophotometrically for the reactions of phenyl Y-substituted-phenyl carbonates 7a-g with butane-2,3-dione monoximate ($Ox^-$) in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The ${\alpha}$-nucleophile $Ox^-$ is 53-95 times more reactive than the corresponding normal-nucleophile 4-$ClPhO^-$ toward 7a-g, indicating that the ${\alpha}$-effect is operative. The magnitude of the ${\alpha}$-effect (e.g., the $k_{Ox^-}/k_{4-ClPhO^-}$ ratio) is independent of the electronic nature of the substituent Y. The cause of the ${\alpha}$-effect for the reactions of 7a-g has been suggested to be ground-state (GS) effect rather than transition-state (TS) stabilization through a six-membered cyclic TS, in which $Ox^-$ behaves a general acid/base catalyst. This idea is further supported by the result that $OH^-$ exhibits negative deviation from the linear Br${\o}$nsted-type plot composed of a series of aryloxides, while $Ox^-$ deviates positively from the linearity. Differential solvation of the GS of $Ox^-$ and 4-$ClPhO^-$ has been suggested to be responsible for the ${\alpha}$-effect exerted by $Ox^-$.

PECVD 이용한 비정질 실리콘형 마이크로 볼로미터 특성 (Properties of the Amorphous Silicon Microbolometer using PECVD)

  • 강태영;김경환
    • 반도체디스플레이기술학회지
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    • 제11권4호
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    • pp.19-23
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    • 2012
  • We report microbolometer characteristic with n-type and p-type amorphous silicon thin film. The n-type and p-type amorphous silicon thin films were made by PECVD. The electrical properties of n-type and p-type a-Si:H thin films were investigated as a function of doping gas flow rate. The doping gas used $B_2H_6/Ar$ (1:9) and $PH_3/Ar$ (1:9). In general, the conductivity of doping a-Si:H thin films increased as doping gas increase but the conductivity of a-Si:H thin films decreased as the doping gas increase because doping gas concentration increase led to dilution gas (Ar) increase as the same time. We fabricated an amorphous silicon microbolometer using surface micromachining technology. The fabricated microbolometer had a negative TCR of 2.3%. The p-type microbolometer had responsivity of $5{\times}10^4V/W$ and high detectivity of $3{\times}10^8cm(Hz)^{1/2}/W$. The p-type microbolometer had more detectivity than n-type for less noise value.

AN MMAP[3]/PH/1 QUEUE WITH NEGATIVE CUSTOMERS AND DISASTERS

  • Shin, Yang-Woo
    • 대한수학회보
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    • 제43권2호
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    • pp.277-292
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    • 2006
  • We consider a single-server queue with service time distribution of phase type where positive customers, negative customers and disasters arrive according to a Markovian arrival process with marked transitions (MMAP). We derive simple formulae for the stationary queue length distributions. The Laplace-Stieltjes transforms (LST's) of the sojourn time distributions under the combinations of removal policies and service disciplines are also obtained by using the absorption time distribution of a Markov chain.

PH 수명분포를 갖는 보증제품의 수리-교체 전략 (Repair-Replacement Strategies for Warranted Items with Phase-Type Lifetimes)

  • 김호균;;배창옥;김승철
    • 대한산업공학회지
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    • 제31권4호
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    • pp.341-348
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    • 2005
  • This paper is concerned with the question of servicing warranties for repairable items. During the warranty period, each time an item fails the manufacturer has the obligation to restore the item to operational condition either by repairing the item or by replacing it with a new item. In this paper, we consider repair-replacement strategies based on the condition of the failed item. For products with phase-type lifetime distributions where the phases represent the condition of the item, we develop algorithms to determine the expected cost of servicing a warranty and use it in making the repair-replacement decision. Illustrative numerical examples are presented. We also propose a dynamic strategy by taking the expected remaining warranty cost into consideration.

Dissolution Characteristics of ph-Dependent Antacid Granules Agglomerated in High Speed Agitation Type Speed Agitation Type Granulator

  • Choi, Woo-Sik;Lee, Jung-Sun
    • Archives of Pharmacal Research
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    • 제18권5호
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    • pp.314-319
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    • 1995
  • Antacid granules were prepared by agglomeration and powder method in high speed agitation type granulator. The copmositions of the test antacids were sodium bicarbonate nad magnesium carbonate nad a coating material was powder of polyvinylacetal diethyl-aminocacetate (AEA) and an additive material was talc powder. The dissolution characteristics of base from the antacid granules were investigated to evaluate neutralization capacity of hydrochloric profile of base and neutralization behavior, the following results were obtained : The prepared granules showed a pH-dependent dissolution pattern of a base. The dissolution profile of a base was varied with addition of talc powder as well as coating amount of AEA. The relationship between the ratio of dissolution retarded time for 20% and 10% AEA. The relationship between the ratio of dissolution retarded time for 20% AEA coated granules $\theta_{20}/\theta_{10}$ and the diameter reduction of the granules was explained by the rate process of neutralization of hydrochloric acid.

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ANALYSIS OF M/M/c RETRIAL QUEUE WITH THRESHOLDS, PH DISTRIBUTION OF RETRIAL TIMES AND UNRELIABLE SERVERS

  • CHAKRAVARTHY, SRINIVAS R.;OZKAR, SERIFE;SHRUTI, SHRUTI
    • Journal of applied mathematics & informatics
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    • 제39권1_2호
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    • pp.173-196
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    • 2021
  • This paper treats a retrial queue with phase type retrial times and a threshold type-policy, where each server is subject to breakdowns and repairs. Upon a server failure, the customer whose service gets interrupted will be handed over to another available server, if any; otherwise, the customer may opt to join the retrial orbit or depart from the system according to a Bernoulli trial. We analyze such a multi-server retrial queue using the recently introduced threshold-based retrial times for orbiting customers. Applying the matrix-analytic method, we carry out the steady-state analysis and report a few illustrative numerical examples.

플라즈마 도핑 후 급속열처리법을 이용한 n+/p 얕은 접합 형성

  • 도승우;서영호;이재성;이용현
    • 한국전기전자재료학회:학술대회논문집
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    • 한국전기전자재료학회 2009년도 추계학술대회 논문집
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    • pp.50-50
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    • 2009
  • In this paper, the plasma doping is performed on p-type wafers using $PH_3$ gas(10 %) diluted with He gas(90 %). The wafer is placed in the plasma generated with 200 W and a negative DC bias (1 kV) is applied to the substrate for 60 sec under no substrate heating. the flow rate of the diluted $PH_3$ gas and the process pressure are 100 sccm and 10 mTorr, respectively. In order to diffuse and activate the dopant, annealing process such as rapid thermal annealing (RTA) is performed. RTA process is performed either in $N_2$, $O_2$ or $O_2+N_2$ ambient at $900{\sim}950^{\circ}C$ for 10 sec. The sheet resistance is measured using four point probe. The shallow n+/p doping profiles are investigated using secondary ion mass spectromtry (SIMS). The analysis of crystalline defect is also done using transmission electron microscopy (TEM) and double crystal X-ray diffraction (DXRD).

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