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Aminolyses of Y-substituted Phenyl 2-Furoates and Cinnamates: Effect of Nonleaving Group Substituent on Reactivity and Mechanism

  • Um, Ik-Hwan;Akhtar, Kalsoom;Park, Youn-Min;Khan, Sher Bahadar
    • Bulletin of the Korean Chemical Society
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    • v.28 no.8
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    • pp.1353-1357
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    • 2007
  • Second-order rate constants (kN) have been determined spectrophotometrically for reactions of Y-substituted phenyl 2-furoates (1a-h) with piperidine and morpholine in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1 oC. The Brønsted-type plot exhibits a downward curvature for the reactions with strongly basic piperidine but is linear for the reactions with weakly basic morpholine. The slope of the curved Brønsted-type plot changes from -1.25 to ?0.28 as the pKa of the conjugate acid of the leaving aryloxides decreases. The pKa at the center of the Brønsted curvature, defined as pKa°, was determined to be 6.4. The aminolysis of 1a-h has been concluded to proceed through a stepwise mechanism on the basis of the curved Brønsted-type plot. The reactions of Ysubstituted phenyl cinnamates (2a-g) with piperidine resulted in a curved Brønsted-type plot with a pKa° values of 6.4. However, the curved Brønsted-type plot has been suggested to be not due to a change in the RDS but due to a normal Hammond effect of a concerted mechanism, since the Brønsted-type plot for the corresponding reactions with morpholine results in also a curved Brønsted-type plot with a pKa° values of 6.1. The furoates with a basic leaving group (i.e., 1b-g) are less reactive than the corresponding cinnamates (i.e., 2b-g). The k2/ k-1 ratios for the reactions of 1b-h are much smaller than unity, which has been suggested to be responsible for their low reactivity.

Effect of Kainic Acid on the Phosphorylation of Mitogen Activated Protein Kinases in Rat Hippocampus

  • Won, Je-Seong;Lee, Jin-Koo;Choi, Seong-Soo;Song, Dong-Keun;Huh, Sung-Oh;Kim, Yung-Hi;Suh, Hong-Won
    • The Korean Journal of Physiology and Pharmacology
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    • v.5 no.6
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    • pp.451-456
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    • 2001
  • In rat hippocampus, kainic acid (KA; 10 mg/kg; i.p.) increased the phosphorylated forms of ERK1/2 (p-ERK1/2) and Jun kinase1 (p-JNK1), but not p-JNK2 and p38 (p-p38). The preadministration with cycloheximide (CHX; 5 mg/kg; i.p.) inhibited KA-induced increase of p-JNK1, but not p-ERK1/2. Surprisingly, the phosphorylated upstream MAP kinase kinases (p-MKKs) were not correlated with their downstream MAP kinases. The basal p-MKK1/2 levels were completely abolished by KA, which were reversed by CHX. In addition, p-MKK4 and p-MKK3/6 levels were enhanced by CHX alone, but were attenuated by KA. Thus, our results showed that KA increased the p-ERK and p-JNK levels in rat hippocampus, which were not parallel with their classical upstreamal kinases.

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KEY SCIENCE OBSERVATIONS OF AGNs WITH THE KaVA ARRAY

  • KINO, MOTOKI;NIINUMA, KOTARO;ZHAO, GUANG-YAO;SOHN, BONG WON
    • Publications of The Korean Astronomical Society
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    • v.30 no.2
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    • pp.633-636
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    • 2015
  • KaVA (KVN and VERA Array) is a new combined VLBI array composed of KVN (Korean VLBI Network) and VERA (VLBI Exploration of Radio Astrometry). Here, we report the following two issues. (1) We review the initial results of imaging observations of M87 at 23 GHz following Niinuma et al. (2014). The KaVA images reveal extended outflows including complex substructures such as knots and limb-brightening, in agreement with previous VLBI observations. KaVA achieves a high dynamic range of ~1000, more than three times better than that achieved by VERA alone. (2) Based on subsequent observations and discussions led by the KaVA AGN SubWorking Group, we set monitoring observations of Sgr $A^{\ast}$ and M87 as our Key Science Project (hereafter KSP) because of the closeness and largeness of their central super-massive black holes. The main science goals of the KSP are (i) testing the magnetically-driven-jet paradigm by mapping velocity fields of the M87 jet, and (ii) obtaining tight constraints on physical properties of the radio emitting region in Sgr $A^{\ast}$. Towards KSP, we show the first preliminary images of M87 at 23 GHz and Sgr $A^{\ast}$ at 43 GHz with the bandwidth of 256 MHz.

The Accessible Study on the Hypothesis About Seeing if Jeo(Kimchi) of ${\ulcorner}Chea\;Mihn\;Yho\;Sul{\lrcorner}$ is Back-Jae's Kimchi ("제민요술(齋民要術)"의 저(菹)가 백제의 김치 인가에 관한 가설의 접근적 연구 (I))

  • Kim, Sang-Bo
    • Journal of the Korean Society of Food Culture
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    • v.13 no.2
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    • pp.135-139
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    • 1998
  • Ka Sa Hyeob, who wrote ${\ulcorner}Chea\;Mihn\;Yho\;Sul{\lrcorner}$, lived in the times of Book-Wi (A.D. 386-535) and his birthplace was San-Dong Peninsula. If the Back-Jae dynasty governed San-Dong Peninsula during A.D. 285-500, Jeo(Kimchi) of ${\ulcorner}Chea\;Mihn\;Yho\;Sul{\lrcorner}$ should be investigated as Back-Jae's Kimchi, because it accorded with Ka Sa Hyeob's time of existence.

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The Study of Prosodic Features in Korean Topic Constructions (한국어 화제구문의 운율적 고찰)

  • Hwang, Son-Moon
    • Speech Sciences
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    • v.9 no.2
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    • pp.59-68
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    • 2002
  • This paper analyzes the prosodic features distinctively associated with Korean topic constructions (marked by nun or its variant un) and subject constructions (marked by ka or its variant i) as a way of explicating the role that prosody plays in differentially constituting their discourse messages. Using both spoken data elicited in controlled settings and spontaneous conversational data, an attempt is made to identify differentiating prosodic features and intonation contours associated with distinct meanings and functions of nun- and ka-constructions evoked in a variety of discourse contexts.

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Novel Synthesis of Sulfated Chitosan Derivatives and its Anti-HIV-1 Activity (황산화 키토산 유도체의 합성과 항에이즈활성)

  • Han Sang-Mun
    • Journal of environmental and Sanitary engineering
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    • v.21 no.1 s.59
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    • pp.21-34
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    • 2006
  • To investigate anti-HIV-1 activity of water soluble chitosans, sulfated chitosan derivatives were prepared in mild condition. Various sulfated chitosan derivatives (N-3,6-O-S-chitosan, N-desulfated 3,6-O-S-chitosan, 3,6-O-S-chitin, and 3,6-O-sulfated-N-(o-carboxybenzoyl) chitosan) were synthesized with sulfurtrioxidepyridene complex in pyridine solvent. Characterization of the sulfated chitosan derivatives was carried out by $^{13}C$ NMR and IR spectroscopies. To observe ionic reaction properties, pKas of the sulfated chitosan derivatives and chitosan of low molecular weight were estimated by potentiometric titration. The sulfated chitosan derivatives had high water solubility, pKas (pKa : 7.7) of N-3,6-O-S-chitosan and N-desulfated 3,6-O-S-chitosan were increased than pKa of water insoluble chitosan (pKa : 6.2), These results suggest the participation of electrostatic interaction of amino and sulfate groups on the sulfated chitosans. Anti-HIV-1 drugs, such as AZT, ddC, and ddI for anti-HIV activity had higher selective index compared with SCB-chitosan but N-3,6-O-S-chitosan has shown higher selective index compared with ddC and ddI as HIV drugs.. These results suggest that sulfated chitosan derivatives were expected as an anti-HIV drug with differential driving force mechanism against some nucleoside analogs drug in the future.

Effects of Cutter Runout on End Milling Forces I-Up Eng Milling- (엔드밀링 절삭력에 미치는 공구형상오차 I- 상향 엔드밀링 -)

  • Lee, Yeong-Mun;Yang, Seung-Han;Song, Tae-Seong;Gwon, O-Jin;Baek, Seung-Gi
    • Journal of the Korean Society for Precision Engineering
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    • v.19 no.8
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    • pp.63-70
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    • 2002
  • In end milling process, the undeformed chip section area and cutting forces vary periodically with phase change of the tool. However the real undeformed chip section area deviates from the geometrically ideal one owing to cutter runout and tool shape error. In this study, a method of estimating the real undeformed chip section area which reflects cutter runout and tool shape error was presented in up end milling process using measured cutting forces. The average specific cutting resistance, Ka is defined as the main cutting force component divided by the modified chip section area. Ka value becomes smaller as the helix angle increases from $30^circC \;to\;40\circC$. But it becomes larger as the helix angle increases from $40^\circ$to 50 . On one hand, the Ka value shows a tendency to decrease with increase of the modified chip section area and this tendency becomes distinct with smaller helix angle.

Observational Studies of Masers in Star-forming Regions with KVN and KaVA

  • Kim, Kee-Tae;Hirota, Tomoya
    • The Bulletin of The Korean Astronomical Society
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    • v.39 no.2
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    • pp.113.2-113.2
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    • 2014
  • Methanol masers are divided into two classes, I and II. Class II methanol masers trace the disk-outflow systems of massive young stellar objects (YSOs), while class I methanol masers appear to trace the interaction regions of outflows with the ambient molecular gas. Class II masers have been extensively studied by single dishes, connected arrays, and VLBIs. Meanwhile, class I masers have been much less studied. They have not been detected by any VLBI facility. Thus they have been believed to have more extended structures than class II masers. We made fringe surveys of 44GHz class I methanol maser emission towards more than 150 massive YSOs with flux densities >10 Jy using the Korean VLBI Network (KVN), and detected fringes in ~10% of the sources. We performed follow-up imaging observations of the detected maser sources with KVN and KVN+VERA (KaVA). The observations aim to investigate the distribution and kinematics of 44GHz methanol maser features in each source at milli-arcsecond resolutions, and to understand what they trace. In this talk we will present the fringe survey and imaging results and our plans for further studies. Additionally, we will also introduce the preliminary results of single-dish polarization observations of water and class I methanol masers.

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