• Title/Summary/Keyword: Michael Addition

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Kinetics and Mechanism of Alkalie Hydrolysis of Cinnamonitrile (II) (Cinnamonitrile의 알카리 가수분해(加水分解) 반응(反應)메카니즘 (II))

  • Sung, Nack Do;Chung, Woo Jin;Kwon, Ki Sung;Park, Byung Kwan
    • Korean Journal of Agricultural Science
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    • v.10 no.2
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    • pp.354-364
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    • 1983
  • Confonmation of (Z)-cinnamonitrile have been studied by molecular orbital theoretically using extended Huckel theory(EHT) and CNDO/2 molecular orbital calculation methods. The results indicate that the stability of conformation is(Z)-gauch>(Z)-planar. The rate constants for alkalie hydrolysis of cinnamonitrile at pH 7.0-14.0 range have been determined by ultra-violet spectrophotometry in 50% methanol at $25^{\circ}C$ and the following rate equation which can be applied over wide pH range was obtained; $${\therefore}k=({\frac{1.41{\times}10^{-14}+1.21{\times}10^7/[H_3O^+]}{2.65{\times}10^{-7}+1.64/[H_3O^+]})+9.14{\times}10^9/[H_3O^+]$$ The rate equation reveals that, at pH 7.0-10.0, the reaction is initiated by the addition of water molecule to unsaturated cabon-carhon double bond of cinnamonitrile and ${\alpha}C-{\beta}C$ bond scission follow subsequently in neutral and alkalie media. At pH 12.0-14.0, in strong alkalie solution, that so-called Michael type nucleophilic addition that the over-all rate constants is only dependent upon the concentration of hydroxide ion occurs competitively and are very complicated. Hence, the reaction mechanism of alkalie hydrolysis of cinnamonitrile which did not carefully before can be fully explained.

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Effects of Candida norvegensis Live Cells on In vitro Oat Straw Rumen Fermentation

  • Ruiz, Oscar;Castillo, Yamicela;Arzola, Claudio;Burrola, Eduviges;Salinas, Jaime;Corral, Agustin;Hume, Michael E.;Murillo, Manuel;Itza, Mateo
    • Asian-Australasian Journal of Animal Sciences
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    • v.29 no.2
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    • pp.211-218
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    • 2016
  • This study evaluated the effect of Candida norvegensis (C. norvegensis) viable yeast culture on in vitro ruminal fermentation of oat straw. Ruminal fluid was mixed with buffer solution (1:2) and anaerobically incubated with or without yeast at $39^{\circ}C$ for 0, 4, 8, 16, and 24 h. A fully randomized design was used. There was a decrease in lactic acid (quadratic, p = 0.01), pH, (quadratic, p = 0.02), and yeasts counts (linear, p<0.01) across fermentation times. However, in vitro dry matter disappearance (IVDMD) and ammonia-N increased across fermentation times (quadratic; p<0.01 and p<0.02, respectively). Addition of yeast cells caused a decrease in pH values compared over all fermentation times (p<0.01), and lactic acid decreased at 12 h (p = 0.05). Meanwhile, yeast counts increased (p = 0.01) at 12 h. C. norvegensis increased ammonia-N at 4, 8, 12, and 24 h (p<0.01), and IVDMD of oat straw increased at 8, 12, and 24 h (p<0.01) of fermentation. Yeast cells increased acetate (p<0.01), propionate (p<0.03), and butyrate (p<0.03) at 8 h, while valeriate and isovaleriate increased at 8, 12, and 24 h (p<0.01). The yeast did not affect cellulolytic bacteria (p = 0.05), but cellulolytic fungi increased at 4 and 8 h (p<0.01), whereas production of methane decreased (p<0.01) at 8 h. It is concluded that addition of C. norvegensis to in vitro oat straw fermentation increased ruminal fermentation parameters as well as microbial growth with reduction of methane production. Additionally, yeast inoculum also improved IVDMD.

Proinflammatory Cytokine and Nitric Oxide Production by Human Macrophages Stimulated with Trichomonas vaginalis

  • Han, Ik-Hwan;Goo, Sung-Young;Park, Soon-Jung;Hwang, Se-Jin;Kim, Yong-Seok;Yang, Michael Sungwoo;Ahn, Myoung-Hee;Ryu, Jae-Sook
    • Parasites, Hosts and Diseases
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    • v.47 no.3
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    • pp.205-212
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    • 2009
  • Trichomonas vaginalis commonly causes vaginitis and perhaps cervicitis in women and urethritis in men and women. Macrophages are important immune cells in response to T. vaginalis infection. In this study, we investigated whether human macrophages could be involved in inflammation induced by T. vaginalis. Human monocyte-derived macrophages (HMDM) were co-cultured with T. vaginalis. Live, opsonized-live trichomonads, and T. vaginalis Iysates increased proinflammatory cytokines, such as TNF-${\alpha}$, IL-$1{\beta}$, and IL-6 by HMDM. The involvement of nuclear factor (NF)-${\kappa}B$ signaling pathway in cytokine production induced by T. vaginalis was confirmed by phosphorylation and nuclear translocation of p65 NF-${\kappa}B$. In addition, stimulation with live T. vaginalis induced marked augmentation of nitric oxide (NO) production and expression of inducible NO synthase (iNOS) levels in HMDM. However, trichomonad-induced NF-${\kappa}B$ activation and TNF-${\alpha}$ production in macrophages were significantly inhibited by inhibition of iNOS levels with L-NMMA (NO synthase inhibitor). Moreover, pretreatment with NF-${\kappa}B$ inhibitors (PDTC or Bay11-7082) caused human macrophages to produce less TNF-${\alpha}$. These results suggest that T. vaginalis stimulates human macrophages to produce proinflammatory cytokines, such as IL-1, IL-6, and TNF-${\alpha}$, and NO. In particular, we showed that T. vaginalis induced TNF-${\alpha}$ production in macrophages through NO-dependent activation of NF-${\kappa}B$, which might be closely involved in inflammation caused by T. vaginalis.

Optimization of Contaminated Land Investigation based on Different Fitness-for-Purpose Criteria (조사목적별 기준에 부합하는 오염부지 조사방법의 최적화 방안에 관한 연구)

  • Jong-Chun Lee;Michael H. Ramsey
    • Economic and Environmental Geology
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    • v.36 no.3
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    • pp.191-200
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    • 2003
  • Investigations on the contaminated lands due to heavy metals from mining activities or hydrocarbons from oil spillage for example, should be planned based on specific fitness-for-purpose criteria(FFP criteria). A FFP criterion is site specific or varies with situation, based on which not only the data quality but also the decision quality can be determined. The limiting factors on the qualities can be, for example, the total budget for the investigation, regulatory guidance or expert's subjective fitness-for-purpose criterion. This paper deals with planning of investigation methods that can satisfy each suggested FFP criterion based on economic factors and the data quality. To this aim, a probabilistic loss function was applied to derive the cost effective investigation method that balances the measurement uncertainty, which estimates the degree of the data quality, with the decision quality. In addition, investigation planning methods when the objectives of investigations do not lie in the classification of the land but simply in producing the estimation of the mean concentration of the contaminant at the site(e.g. for the use in risk assessment), were also suggested. Furthermore, the efficient allocation of resources between sampling and analysis was also devised. These methods were applied to the two contaminated sites in the UK to test the validity of each method.

Analysis of a Large-scale Protein Structural Interactome: Ageing Protein structures and the most important protein domain

  • Bolser, Dan;Dafas, Panos;Harrington, Richard;Schroeder, Michael;Park, Jong
    • Proceedings of the Korean Society for Bioinformatics Conference
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    • 2003.10a
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    • pp.26-51
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    • 2003
  • Large scale protein interaction maps provide a new, global perspective with which to analyse protein function. PSIMAP, the Protein Structural Interactome Map, is a database of all the structurally observed interactions between superfamilies of protein domains with known three-dimensional structure in thePDB. PSIMAP incorporates both functional and evolutionary information into a single network. It makes it possible to age protein domains in terms of taxonomic diversity, interaction and function. One consequence of it is to predict the most important protein domain structure in evolution. We present a global analysis of PSIMAP using several distinct network measures relating to centrality, interactivity, fault-tolerance, and taxonomic diversity. We found the following results: ${\bullet}$ Centrality: we show that the center and barycenter of PSIMAP do not coincide, and that the superfamilies forming the barycenter relate to very general functions, while those constituting the center relate to enzymatic activity. ${\bullet}$ Interactivity: we identify the P-loop and immunoglobulin superfamilies as the most highly interactive. We successfully use connectivity and cluster index, which characterise the connectivity of a superfamily's neighbourhood, to discover superfamilies of complex I and II. This is particularly significant as the structure of complex I is not yet solved. ${\bullet}$ Taxonomic diversity: we found that highly interactive superfamilies are in general taxonomically very diverse and are thus amongst the oldest. This led to the prediction of the oldest and most important protein domain in evolution of lift. ${\bullet}$ Fault-tolerance: we found that the network is very robust as for the majority of superfamilies removal from the network will not break up the network. Overall, we can single out the P-loop containing nucleotide triphosphate hydrolases superfamily as it is the most highly connected and has the highest taxonomic diversity. In addition, this superfamily has the highest interaction rank, is the barycenter of the network (it has the shortest average path to every other superfamily in the network), and is an articulation vertex, whose removal will disconnect the network. More generally, we conclude that the graph-theoretic and taxonomic analysis of PSIMAP is an important step towards the understanding of protein function and could be an important tool for tracing the evolution of life at the molecular level.

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TERRAPOWER, LLC TRAVELING WAVE REACTOR DEVELOPMENT PROGRAM OVERVIEW

  • Hejzlar, Pavel;Petroski, Robert;Cheatham, Jesse;Touran, Nick;Cohen, Michael;Truong, Bao;Latta, Ryan;Werner, Mark;Burke, Tom;Tandy, Jay;Garrett, Mike;Johnson, Brian;Ellis, Tyler;Mcwhirter, Jon;Odedra, Ash;Schweiger, Pat;Adkisson, Doug;Gilleland, John
    • Nuclear Engineering and Technology
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    • v.45 no.6
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    • pp.731-744
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    • 2013
  • Energy security is a topic of high importance to many countries throughout the world. Countries with access to vast energy supplies enjoy all of the economic and political benefits that come with controlling a highly sought after commodity. Given the desire to diversify away from fossil fuels due to rising environmental and economic concerns, there are limited technology options available for baseload electricity generation. Further complicating this issue is the desire for energy sources to be sustainable and globally scalable in addition to being economic and environmentally benign. Nuclear energy in its current form meets many but not all of these attributes. In order to address these limitations, TerraPower, LLC has developed the Traveling Wave Reactor (TWR) which is a near-term deployable and truly sustainable energy solution that is globally scalable for the indefinite future. The fast neutron spectrum allows up to a ~30-fold gain in fuel utilization efficiency when compared to conventional light water reactors utilizing enriched fuel. When compared to other fast reactors, TWRs represent the lowest cost alternative to enjoy the energy security benefits of an advanced nuclear fuel cycle without the associated proliferation concerns of chemical reprocessing. On a country level, this represents a significant savings in the energy generation infrastructure for several reasons 1) no reprocessing plants need to be built, 2) a reduced number of enrichment plants need to be built, 3) reduced waste production results in a lower repository capacity requirement and reduced waste transportation costs and 4) less uranium ore needs to be mined or purchased since natural or depleted uranium can be used directly as fuel. With advanced technological development and added cost, TWRs are also capable of reusing both their own used fuel and used fuel from LWRs, thereby eliminating the need for enrichment in the longer term and reducing the overall societal waste burden. This paper describes the origins and current status of the TWR development program at TerraPower, LLC. Some of the areas covered include the key TWR design challenges and brief descriptions of TWR-Prototype (TWR-P) reactor. Selected information on the TWR-P core designs are also provided in the areas of neutronic, thermal hydraulic and fuel performance. The TWR-P plant design is also described in such areas as; system design descriptions, mechanical design, and safety performance.

Prognostic Factor Analysis of Overall Survival in Gastric Cancer from Two Phase III Studies of Second-line Ramucirumab (REGARD and RAINBOW) Using Pooled Patient Data

  • Fuchs, Charles S.;Muro, Kei;Tomasek, Jiri;Van Cutsem, Eric;Cho, Jae Yong;Oh, Sang-Cheul;Safran, Howard;Bodoky, Gyorgy;Chau, Ian;Shimada, Yasuhiro;Al-Batran, Salah-Eddin;Passalacqua, Rodolfo;Ohtsu, Atsushi;Emig, Michael;Ferry, David;Chandrawansa, Kumari;Hsu, Yanzhi;Sashegyi, Andreas;Liepa, Astra M.;Wilke, Hansjochen
    • Journal of Gastric Cancer
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    • v.17 no.2
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    • pp.132-144
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    • 2017
  • Purpose: To identify baseline prognostic factors for survival in patients with disease progression, during or after chemotherapy for the treatment of advanced gastric or gastroesophageal junction (GEJ) cancer. Materials and Methods: We pooled data from patients randomized between 2009 and 2012 in 2 phase III, global double-blind studies of ramucirumab for the treatment of advanced gastric or GEJ adenocarcinoma following disease progression on first-line platinum- and/or fluoropyrimidine-containing therapy (REGARD and RAINBOW). Forty-one key baseline clinical and laboratory factors common in both studies were examined. Model building started with covariate screening using univariate Cox models (significance level=0.05). A stepwise multivariable Cox model identified the final prognostic factors (entry+exit significance level=0.01). Cox models were stratified by treatment and geographic region. The process was repeated to identify baseline prognostic quality of life (QoL) parameters. Results: Of 1,020 randomized patients, 953 (93%) patients without any missing covariates were included in the analysis. We identified 12 independent prognostic factors of poor survival: 1) peritoneal metastases; 2) Eastern Cooperative Oncology Group (ECOG) performance score 1; 3) the presence of a primary tumor; 4) time to progression since prior therapy <6 months; 5) poor/unknown tumor differentiation; abnormally low blood levels of 6) albumin, 7) sodium, and/or 8) lymphocytes; and abnormally high blood levels of 9) neutrophils, 10) aspartate aminotransferase (AST), 11) alkaline phosphatase (ALP), and/or 12) lactate dehydrogenase (LDH). Factors were used to devise a 4-tier prognostic index (median overall survival [OS] by risk [months]: high=3.4, moderate=6.4, medium=9.9, and low=14.5; Harrell's C-index=0.66; 95% confidence interval [CI], 0.64-0.68). Addition of QoL to the model identified patient-reported appetite loss as an independent prognostic factor. Conclusions: The identified prognostic factors and the reported prognostic index may help clinical decision-making, patient stratification, and planning of future clinical studies.

On the Decomposition of Dimethyl-2, 2-dichlorovinylphosphate (Dimethyl-2, 2-dichlorovinylphosphate의 분해반응에 관한 연구)

  • Sung, Nack-Do;Park, Seung-Heui
    • Applied Biological Chemistry
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    • v.26 no.2
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    • pp.125-131
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    • 1983
  • Formal net charges, bond populations, atomic orbital coefficients, energy components and conformation of dimethyl-2,2-dichlorovinylphosphate have been studied theoretically by using the CNDO/2 molecular orbital calculation method in attempt to describe the reactivity and the stability of the molecule. From the analysis of rate equation, molecular orbital calculations and identification of the hydrolysis products, 2,2-dichloroacetaldehyde and dimethylphosphoric acid, a mechanism of the hydrolysis of dimethyl-2,2-dichlorovinylphosphate(DDVP) has been proposed. The hydrolysis of DDVP proceeds through the mechanism of nucleophilic addition, typical Micheal reaction in basic media. Therefore, it appears probable that the attack by strong nucleophile, hydroxide ion occurs at the increased positive charge $C_2({\alpha})$ atom of a staggered conformation due to the inductive effect (-)I>(+)R of 2,2-dichlorovinyl, electron-attracting group. And then, the hydrolytic scission involves the $C_2({\alpha})-O_3$, ${\pi}-anti-bonding\;orbital({\pi}^*)$ in the subsequent reaction in aqueous solution.

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"Poor Theatre, Poor Art" - Jerzy Grotowsky's Play and Arte Povera ('가난한 연극, 가난한 미술' - 그로토프스키 연극이론과 아르테 포베라)

  • Kang, Young-Joo
    • The Journal of Art Theory & Practice
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    • no.5
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    • pp.109-133
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    • 2007
  • What a concept of theatricality in modern art became more controversial is through a review "art and object-hood" on Michael Fried's minimal art, as having been already known broadly. As he had been concerned, the art following the minimalism is accepting as the very important elements such as the introduction of temporality, the stage in the exhibition space, and the audience's positive participation, enough to be no exaggeration to say that it was involved in almost all the theatricality. Particularly even in the installation art and the environment art, which have substantially positioned since the 1970s, the space is staged, and the audience's participation is greatly highlighted due to the temporal character and the site-specific in works. In such way, the theatricality in art work is today regarded as one of the most important elements. In this context, it is thought to have significance to examine theatricality, which is shown in the works of Arte Povera artists, who had been active energetically between 1967-1971. That is because the name of this group itself is what was borrowed from "Poor Theatre" in Jerzy Grotowski, who is a play director and theorist coming from Poland, and because of having many common points in the aspect of content and form. It reveals that the art called Arte Povera is sharing many critical minds in the face of commanding the field called a play and other media. Grotowski's theatre theory is very close to the theory and substance in Arte Povera in a sense that liberates a play, which was locked in literature, above all, renews the relationship between stage and seat and between actor and audience, and pursues a human being's change in consciousness through this. That is because Arte Povera also emphasizes the communication with the audience through appealing to a human being's perception and through the direct and living method, not the objective art concept of centering on the work. In addition, the poor play or poor art all has tendency that denies a system, which relies upon economic and cultural system, and seeks for what is anti-cultural, elemental, and fundamental. It is very similar even in a sense that focuses on the exploration process itself rather than the result, excludes the transcendental concept, and attaches importance to empiricism. However, Arte Povera accepts contradictoriness and complexity, and suggests eclecticism and tolerance, thereby being basically the nomadic art and the art difficult to be captured constitutively. On the other hand, there is difference in a sense that the poor play is characterized by purity, asceticism, seriousness, and solemnity. If so, which significance does this theatricality, which was introduced to art, ultimately have? As all the arts desire to be revealed with invisible things beyond the visual thing, theatricality comes to play a very important role at this time. If all the artists and audiences today came to acquire actual or virtual freedom much more, that can be said to be a point attributable to that art relied upon diverse conditions in a play.

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Environmental Regulation, Firm Heterogeneity and Innovation (환경규제, 기업 이질성, 그리고 기업의 혁신 활동에 대한 행태적 접근)

  • Park, Minje;Jin, Byungchae
    • Journal of Technology Innovation
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    • v.30 no.1
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    • pp.21-56
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    • 2022
  • Since Michael Porter (1991) has proposed that environmental regulation can help a firm increase its competitiveness by encouraging it to engage in more innovative activities to meet the environmental regulation, a number of researchers have empirically investigated the "Porter Hypothesis." However, the empirical results still remain mixed. Combining the perspectives of the behavioral theory of the firm and firm heterogeneity, we argue that the levels of regulation stringency and time-pressure would differentially influence a firm's innovative behavior depending on the firm's aspiration level, performance feedback and technological capabilities. Using the U.S. Corporate Average Fuel Efficiency (CAFE) regulation context, we empirically demonstrate that lagging firms that do not meet the new regulation standard announced by the government tend to search for more distant knowledge and that the impact of the patents they file for decreases as the regulation becomes more stringent. In addition, we also find that as time-pressure increases, lagging firms stand to apply for more patents than do leading firms whereas the overall impact of the patents decreases. These results help us advance our understanding of the nuanced causal relationship between regulation and innovation and provide practical implications for policymakers.