• Bulletin of the Korean Chemical Society
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• v.20 no.4
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• pp.422-426
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• 1999

The Grignard reactions of bis(chloromethyl)dimethylsilane (1) with trimethylchlorosilane (2) in THF give both the intermolecular C-Si coupling and intramolecular C-C coupling products. At beginning stage, 1 reacts with Mg to give the mono-Grignard reagent ClCH2Me2SiCH2MgCl (1) which undergoes the C-Si coupling reaction to give MC2Si(CH2SiMe3)2 3, or C-C coupling to a mixture of formula Me3SiCH2(SiMe2CH2CH2)nR1 (n = 1, 2, 3, ..; 4a, R1I = H: 4b, R1 = SiMe3). In the reaction, two reaction pathways are involved: a) Ⅰ reacts with 2 to give Me3SiCH2SiMe2CH2Cl 6 which further reacts with Mg to afford a Me2SiCH2Mel-SiCH2MgCl (Ⅱ) or b) I cyclizes intramolecularly to a silacyclopropane intermediate A, which undergoes a ring-opening polymerization by the nucleophilic attack of the intermediates I or Ⅱ, followed by the termination reaction with H2O and 2, to give 4a and 4b, respectively. As the mole ratio of 2/1 increased from 2 to 16 folds, the formation of product 3 increased from 16% to 47% while the formation of polymeric products 4 was reduced from 60% to 40%. The intermolecular C-Si coupling reaction of the pathway a becomes more favorable than the intramolecular C-C coupling reaction of the pathways b at the higher mole ratio of 2/1.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1897-1901
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• 2011

This report shows the rates of solvolyses for phenyl methanesulfonyl chloride ($C_6H_5CH_2SO_2Cl$, I) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, 2,2,2-trifluroethanol (TFE) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) are reported. Three representative solvents, studies were made at several temperatures and activation parameters were determined. The thirty kinds of solvents gave a reasonably precise extended Grunwald-Winstein plot, coefficient (R) of 0.954. The sensitivity values (l = 0.61 and m = 0.34, l/m = 1.8) of phenyl methanesulfonyl chloride (I) were smaller than those obtained for benzenesulfonyl chloride ($C_6H_5SO_2Cl$, II; l = 1.01 and m = 0.61) and 2-propanesulfonyl chloride ($(CH_3)_2CHSO_2Cl$, III; l = 1.28 and m = 0.64). As with the two previously studied solvolyses, an $S_N2$ pathway with somewhat ionization reaction is proposed for the solvolyses of I. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were determined and they are also in line with values expected for a bimolecular reaction mechanism. The kinetic solvent isotope effect of 2.34 in $CH_3OH/CH_3OD$ is in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

• Advances in nano research
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• v.5 no.3
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• pp.203-214
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• 2017

In this study we present the reaction mechanism of $Cu_2ZnSnSe_4$ (CZTSe) nanoparticles synthesized by microwave-assisted chemical synthesis. We performed reactions every 10 minutes in order to identify different phases during quaternary CZTSe formation. The powder samples were analyzed by x-ray diffraction (XRD), Raman spectroscopy, energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The results showed that in the first minutes copper phases are predominant, then copper and tin secondary phases react to form ternary phase. The quaternary phase is formed at 50 minutes while ternary and secondary phases are consumed. At 60 minutes pure quaternary CZTSe phase is present. After 60 minutes the quaternary phase decomposes in the previous ternary and secondary phases, which indicates that 60 minutes is ideal reaction time. The EDS analysis of pure quaternary nanocrystals (CZTSe) showed stoichiometric relations similar to the reported research in the literature, which falls in the range of Cu/(Zn+Sn): 0.8-1.0, Zn/Sn: 1.0-1.20. In conclusion, the evolution pathway of CZTSe synthesized by this novel method is similar to other synthesis methods reported before. Nanoparticles synthesized in this study present desirable properties in order to use them in solar cell and photoelectrochemical cell applications.

• Journal of Environmental Science International
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• v.14 no.8
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• pp.749-760
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• 2005

This study examines the local ozone photochemistry in the urban air. The photochemical formation and destruction of ozone was modeled using a photochemical box model. For the model prediction of ozone budget, measurements were carried out from an urban monitoring station in Seoul ($37.6^{\circ}N,\;127^{\circ}E$), Korea for intensive sampling time period (Jun. $1\~15$, 2003). Photochemical process is likely to play significant role in higher ozone concentrations during the sampling period. The results of model simulation indicated that photochemical ozone production pathway was the reaction of NO with $HO_2$ while ozone destruction was mainly controlled by a photochemical destruction pathway, a reaction of $H_2O$ with $O(^1D).$ The contribution of NMHCs to formation and destruction of ozone in the urban was significant. This was entirely different from remote marine environment. The rates of net photochemical ozone production ranged from 0.1 to 1.3 ppbv $h^{-1}$ during the study period.

• Bulletin of the Korean Chemical Society
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• v.31 no.10
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• pp.2877-2883
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• 2010

The folding kinetics of $WT^*$ ubiquitin variant with valine to alanine mutation at sequence position 26 (HubWA) was studied by stopped-flow fluorescence spectroscopy. While unfolding kinetics showed a single exponential phase, refolding reaction showed three exponential phases. The semi-logarithmic plot of urea concentration vs. rate constant for the first phase showed v-shape pattern while the second phase showed v-shape with roll-over effect at low urea concentration. The rate constant and the amplitude of the third phase were constant throughout the urea concentrations, suggesting that this phase represents parallel process due to the configurational isomerization. Interestingly, the first and second phases appeared to be coupled since the amplitude of the second phase increased at the expense of the amplitude of the first phase in increasing urea concentrations. This observation together with the roll-over effect in the second folding phase indicates the presence of intermediate state during the folding reaction of HubWA. Quantitative analysis of Hub-WA folding kinetics indicated that this intermediate state is on the folding pathway. Folding kinetics measurement of a mutant HubWA with hydrophobic core residue mutation, Val to Ala at residue position 17, suggested that the intermediate state has significant amount of native interactions, supporting the interpretation that the intermediate is on the folding pathway. It is considered that HubWA is a useful model protein to study the contribution of residues to protein folding process using folding kinetics measurements in conjunction with protein engineering.

• Journal of Ginseng Research
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• v.43 no.2
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• pp.282-290
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• 2019

Background: Ginsenoside Rg3 (G-Rg3) is the major bioactive ingredient of Panax ginseng and has many pharmacological effects, including antiadipogenic, antiviral, and anticancer effects. However, the effect of G-Rg3 on mast cell-mediated allergic inflammation has not been investigated. Method: The antiallergic effects of G-Rg3 on allergic inflammation were evaluated using the human and rat mast cell lines HMC-1 and RBL-2H3. Antiallergic effects of G-Rg3 were detected by measuring cyclic adenosine monophosphate (cAMP), detecting calcium influx, and using real-time reverse transcription polymerase chain reaction, enzyme-linked immunosorbent assay, Western blotting, and in vivo experiments. Results: G-Rg3 decreased histamine release from activated mast cells by enhancing cAMP levels and calcium influx. Proinflammatory cytokine production was suppressed by G-Rg3 treatment via regulation of the mitogen-activated protein kinases/nuclear factor-kappa B and receptor-interacting protein kinase 2 (RIP2)/caspase-1 signaling pathway in mast cells. Moreover, G-Rg3 protected mice against the IgE-mediated passive cutaneous anaphylaxis reaction and compound 48/80-induced anaphylactic shock. Conclusion: G-Rg3 may serve as an alternative therapeutic agent for improving allergic inflammatory disorders.

• Proceedings of the Korean Society of Life Science Conference
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• 2001.11a
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• pp.3-8
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• 2001

Isopentenyl diphosphate (IPP) is the common, five-carbon building block in the biosynthesis of all carotenoids, IPP in Escherichia coli is synthesized through the non-mevalonate pathway. The first reaction of IPP biosynthesis in E. coli is the formation of 1-deoxy-D-xylulose-5-phosphate (DXP), catalyzed by DXP synthase and encoded by dxs. The second reaction in the pathway is the reduction of DXP to 2-C-methyl-D-erythritol-4-phosphate, catalyzed by DXP reductoisomerase and encoded by dxr. To determine if one or more of the reactions in the non-mevalonate pathway controlled flux to IPP, dxs and dxr were placed on several expression vectors under the control of three different promoters and transformed into three E. coli strains (DH5(, XL1-Blue, and JM101) that had been engineered to produce lycopene. Lycopene production was improved significantly in strains transformed with the dxs expression vectors. When the dxs gene was expressed from the arabinose-inducible araBAD promoter (PBAD) on a medium-copy plasmid, lycopene production was 2-fold higher than when dxs was expressed from the IPTG-inducible trc and lac promoters (Ptrc and Plac, respectively) on medium-copy and high-copy plasmids, Given the low final densities of cells expressing dxs from IPTG-inducible promoters, the low lycopene production was probably due to the metabolic burden of plasmid maintenance and an excessive drain of central metabolic intermediates. At arabinose concentrations between 0 and 1.33 mM, cells expressing both dxs and dxr from PBAD on a medium-copy plasmid produced 1.4 - 2.0 times more lycopene than cells expressing dxs only. However, at higher arabinose concentrations lycopene production in cells expressing both dxs and dxr was lower than in cells expressing dxs only. A comparison of the three E. coli strains transformed with the arabinose-inducible dxs on a medium-copy plamid revealed that lycopene production was highest in XL1-Blue.

• Bulletin of the Korean Chemical Society
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• v.33 no.12
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• pp.4079-4083
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• 2012

The mechanism of the cycloaddition reaction between singlet state dichlorosilylene germylidene ($Cl_2Si=Ge:$) and acetone has been investigated with B3LYP/6-$31G^*$ and B3LYP/6-$31G^{**}$ method, from the potential energy profile, we predict that the reaction has one dominant reaction pathway. The presented rule of the reaction is that the two reactants firstly form a Si-heterocyclic four-membered ring germylene through the [2+2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge atom in the Si-heterocyclic four-membered ring germylene and the ${\pi}$ orbital of acetone forming a ${\pi}{\rightarrow}p$ donor-acceptor bond, the Si-heterocyclic four-membered ring germylene further combines with acetone to form an intermediate. Because the Ge atom in the intermediate hybridizes to an $sp^3$ hybrid orbital after the transition state, then, the intermediate isomerizes to spiro-heterocyclic ring compound involving Si and Ge (P4) via a transition state.

• Bulletin of the Korean Chemical Society
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• v.12 no.4
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• pp.429-433
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• 1991

The photoinduced electron transfer reactions of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) in various polar solvents were studied by measuring time-resolved fluorescence. The temperature dependence on the fluorescence decay rate in acetonitrile, methanol, ethanol and buthanol was carried out to obtain the activation energy and Arrehnius factor for the photoinduced electron transfer reaction. It was found that as the dielectric constant of the solvent increases, the activation energy and the reaction rate increase. This implys that the Arrehnius factor is important in controlling the photoinduced electron transfer reaction rate. In water, TMPD exists in three forms (cationic, protonated and neutral forms) due to the high dielectric constant and strong proton donating power of water. The photoinduced electron transfer reaction was found to be very fast (< 50 ps) and also the long liverd component in the fluorescence decay profile attributable to the photoexcited protonated form of TMPD was observed. Probably, the reaction pathway and the reaction coordinate seem to be different depending on the solvents studied here.

• Proceedings of the Korean Society of Crop Science Conference
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• 2017.06a
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• pp.167-167
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• 2017

Our previous study for developing seeds of Iksan 526 (I.526), an inbred line of resveratrol-producing transgenic rice line, showed that, in 20 days after heading (DAH) seeds, resveratrol was almost saturated and accumulation of piceid was highest though the expression of Arachis hypogaea resveratrol synthase 3 (AhRS3, GenBank DQ124938) was highest in 31 DAH seeds. In this study, it was investigated how the overexpression of AhRS3 affects phenylpropanoid pathway genes. p-Coumaroyl-CoA is derived from phenylpropanoid pathway and used as a substrate of AhRS3 reaction for resveratrol production. In 6, 13, 20, 31 and 41 (45 for Dongjin) DAH seeds of I526 and Dongjin, a wild type of I.526, respectively, the expression pattern of phenylpropanoid pathway genes, including phenylalanine ammonia-lyase (PAL: LOC_Os02g41630.2, LOC_Os04g43760.1), cinnamate 4-hydroxylase (C4H: LOC_Os05g25640.1), 4-coumarate-CoA ligase (4CL: LOC_Os02g08100.1), cinnamoyl-CoA reductase (CCR: LOC_ Os09g25150.1, LOC_Os08g34280.1), hydroxycinnamoyl-CoA shikimate/quinate hydroxycinnamoyl transferase (HCT: LOC_Os04g42250.2, LOC_Os02g39850.1) and cinnamyl alcohol dehydrogenase (CAD: LOC_Os02g09490.1), was examined using real time (RT)-PCR. Compared to developing seeds of Dongjin, RT-PCR results showed that the expression pattern of phenylpropanoid pathway genes was modified in developing seeds of I.526. In most genes, except for CAD, of I.526 developing seeds, the gene expression was highest in 20 DAH corresponding to biosynthesis of resveratrol and piceid, i.e. the expression of phenylpropanoid pathway genes was gradually increased by 20 DAH and decreased as seeds develop. Especially, in Dongjin, the highest expression of PALs and 4CL was in 6 DAH and their expression was gradually decreased as seeds develop. These genes expression data also exhibited that, in developing seeds of I.526, phenylpropanoid pathway genes were slightly or significantly (in some genes) upregulated compared to Dongjin. Therefore, the overexpression of AhRS3 changed the expression pattern of phenylpropanoid pathway genes in I.526 developing seeds and this modification for gene expression is closely related to biosynthesis of resveratrol and piceid.