• Applied Chemistry for Engineering
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• v.18 no.3
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• pp.218-226
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• 2007

The stereoselective synthesis of chiral terminal epoxides is of immense academic and industrial interest due to their utility as versatile starting materials as well as chiral intermediates. In this study, new dinuclear chiral Co (salen) complexes bearing gallium-, indium- and tallium-chloride have been synthesized and characterized. The mass and EXAFS spectra provided the direct evidence of formation of dinuclear complex. Their catalytic activity and selectivity have been demonstrated for the asymmetric ring opening of various terminal epoxides having ether or ester groups by hydrolytic kinetic resolution technology. The easily prepared dimeric complexes exhibited very high enantioselectivity for the asymmetric ring opening of epoxides with $H_2O$ nucleophile, providing enantiomerically enriched terminal epoxides (> 99% ee). The dimeric structured chiral salen showed remarkably enhanced reactivity and may be employed substantially lower loadings than its monomeric analogues. The system described in this work is very efficient for the synthesis of chiral epoxide and 1,2-diol intermediates

• Bulletin of the Korean Chemical Society
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• v.35 no.9
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• pp.2649-2654
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• 2014

Synthesis of north-5'-methylbicyclo[3.1.0]hexyl adenine and hypoxanthine nucleosides with an ethenyl group at C3' position was successfully achieved by a highly facile method. Methylbicyclo[3.1.0]hexanone (${\pm}$)-7 with three contiguous chiral centers and its epimer (${\pm}$)-6 was remarkably simply constructed only by four steps involving a carbenoid insertion reaction in the presence of rhodium (II) acetate dimer as a metal catalyst, giving a correct relative stereochemistry of the generated three chiral centers. Due to steric hindrance from the concave face of the bicyclo[3.1.0]hexanone system, a Grignard reaction of (${\pm}$)-7 with ethenylmagnesium bromide showed exclusive diastereoselectivity towards the b-face. The Grignard reaction chemoselectively proceeded without reacting with ester functionality. Coupling reaction of glycosyl donor (${\pm}$)-11 with 6-chloropurine nucleobase afforded only the desired $N^9$-alkylated nucleoside without the formation of $N^7$-regioisomer. By the conventional method, 6-chloro group was converted into 6-amino and 6-hydroxy groups to give the desired adenine and hypoxanthine bicyclo[3.1.0]hexyl carbanucleosides with 3'-ethenyl group, respectively.

• Tribology and Lubricants
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• v.31 no.5
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• pp.195-204
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• 2015

Several researches are focused on improving the value of fine chemicals based on biomass resources due to environmental and other concerns associated with the use of petroleum-based products. Therefore, the synthesis and application of estolides derived from plant-based waste oil materials and their application as lubricants and as processing oil for butyl rubber products have been studied. Four kinds of estolide were prepared with conversions of 71~92% over 24h using various vegetable oils, as determined by size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. FT-IR spectroscopy determines the esterification of estolides using 2-ethylhexyl alcohol. The estolides have iodine values of 35~90, α-ester/α-acid ratios of 0.45~0.55, and total acid number of 114~134 mg KOH g^–1. Four ball wear tests show that the wear scar diameters (WSDs) of estolides as base oil significantly decreased to 0.328~0.494 mm, compared to WSDs of 0.735 and 0.810 mm of WSD for 150N and Yubase 6, respectively, as general base oil. Thus, the estolides have better wear resistance and satisfying design objectives for the engineering of a variety of lubricant base oils.

• Environmental Analysis Health and Toxicology
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• v.15 no.3
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• pp.69-80
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• 2000

ADP-rubosylation may be involved in the process of macrophage activation. Nitric oxide (NO) has emerged as an important intracellular and interacellular regulatory molecule with function as diverse as vasodilation, neural communication or host defense. NO is derived from the oxidation of the terminal guanidino nitrogen atom of L-arginine by the NADPH -dependent enzyme, nitric oxide synthase (NOS) which is one of the three different isomers in mammalian tissues. Since NO can exert protective or regulatory functions in the cell at a low concentration while toxic effects at higher concentrations, its role may be tightly regulated in the cell. Therefore, this paper was focused on signal transduction pathway of NO synthesis, role of endogenous TGF-$\beta$ in NO production. effect of NO on superoxide formation. Costimulation of murine peritoneal macrophages with interferon-gamma (IFN-γ) and phorbol 12-myristate 13-acetate (PMA) increased both NO secretion and mRNA expression of inducible nitric oxide synthase (iNOS) when PMA abolished costimulation. Pretreatmnet of the cells with PMA abolished costimuation effects due to the depletion of protein kinase C (PKC) activities . The involvement of PKC in NO secretion could be further confirmed by PKC inhibitor, stauroprine, and phorbol ester derivative, phorbol 12,13-didecanoate. Addition of actinomycine D in IFN-γ plus PMA stimulated cells inhibited both NO secretion and mRNA expression of iNOS indication that PMA stabilizes mRNA of iNOS . Exogenous TGF-$\beta$ reduced NO secretion in IFN -γ stimulated murine macrophages. However addition of antisense oligodeoxynucleotide (ODN) to TGF-$\beta$ to this system recovered the ability of NO production and inhibited mRNA expression of TGF-$\beta$. ACAS interactive laser cytometry analysis showed that transportation of FITC -labeled antisense ODN complementary to TGF-$\beta$ mRNA could be observed within 5 min and reached maximal intensity in 30 min in the murine macrophage cells. NO released by activated macrophages inhibits superoxide formation in the same cells . This inhibition nay be related on NO-induced auto -adenosine diphosphate (ADP) -ribosylation . In addition, ADP-ribosylation may be involved in the process of macrophage activation .

• The Korean Journal of Pesticide Science
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• v.10 no.1
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• pp.1-6
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• 2006

A methodology for the syntheses of carboxanilides using solid support of 4-chloro-3-nitorbenzophenone oxime resin 5 was developed. Condensation of 4-chloro-3-nitorbenzophenone resin 6 with hydroxylamine hydrochloride salt gave oxime resin 5. The reaction of oxime resin 5 with dioxin and oxathiin derivatives 7a-d afforded the corresponding polymer-bound dioxin and oxathiin derivatives 9a-d. These polymer-bound resins 9a-d were treated respectively with aniline in the presence of acetic acid resulted in the corresponding dioxin carboxanilides 10a-d (yield, 5%-quantitative).

• Journal of Microbiology and Biotechnology
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• v.30 no.10
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• pp.1597-1606
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• 2020

Transcription factor engineering to regulate multiple genes has shown promise in the field of microalgae genetic engineering. Here, we report the first use of transcription factor engineering in Chlorella sp. HS2, thought to have potential for producing biofuels and bioproducts. We identified seven endogenous bZIP transcription factors in Chlorella sp. HS2 and named them HSbZIP1 through HSbZIP7. We overexpressed HSbZIP1, a C-type bZIP transcription factor, in Chlorella sp. HS2 with the goal of enhancing lipid production. Phenotype screening under heterotrophic conditions showed that all transformants exhibited increased fatty acid production. In particular, HSbZIP1 37 and 58 showed fatty acid methyl ester (FAME) yields of 859 and 1,052 mg/l, respectively, at day 10 of growth under heterotrophic conditions, and these yields were 74% and 113% higher, respectively, than that of WT. To elucidate the mechanism underlying the improved phenotypes, we identified candidate HSbZIP1-regulated genes via transcription factor binding site analysis. We then selected three genes involved in fatty acid synthesis and investigated mRNA expression levels of the genes by qRT-PCR. The result revealed that the possible HSbZIP1-regulated genes involved in fatty acid synthesis were upregulated in the HSbZIP1 transformants. Taken together, our results demonstrate that HSbZIP1 can be utilized to improve lipid production in Chlorella sp. HS2 under heterotrophic conditions.

• Journal of the Korean Chemical Society
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• v.25 no.4
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• pp.283-290
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• 1981

The reaction rates for the transesterification reaction were measured on the excess sucrose with the five fatty acid methyl ester systems such as methyl laurate, methyl myristate, methyl palmitate, methyl stearate and methyl oleate at temperature range of $50^{\circ}C$ to $90^{\circ}C$ in N,N-dimethylformamide solvent and potassium carbonate as a catalyst. Their activation parameters as well as rate constants were calculated from these measurements. And these reactions were found to be pseudo-first order and depended mainly on the structural changes in fatty acid residue of methyl esters. Also their reactions were found to be of enthalpy-controlled, which were disfavored in the order of methyl laurate, methyl myristate, methyl palmitate, methyl oleate and methyl stearate. Correspondingly their activation energies were 9.3, 9.9, 10.3, 10.9 and 11.1 kcal/mole, respectively.

• Journal of the Korean Chemical Society
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• v.34 no.2
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• pp.203-210
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• 1990

As a possible biocompatible and biodegrable polymer skeleton for drug delivery system, block copolymers of L-lactic acid and L-glutamic acid with different composition were synthesized and characterized. Poly (L-lactide) was prepared by polymerization of L-lactide with zine oxide at $130^{\circ}C$ for 72 hrs. 3-Amino-l-propanol was introduced to poly (L-lactide) by an ester linkage in order to initiate polymerization. Polymerization of $\gamma-benzyl-L-glutamate-N-carboxyanhydride(\gamma-BLG-NCA)$ utiliizing the amino group of modified poly (L-lactide) as an initiator gave rise to the block copoly $(L-lactide-\gamma-benzyl-L-glutamate).$ The NMR study of resulting block copolymers showed that the composition of L-lactic acid and $\gamma-benzyl-L-glutamate$ in block copolymers was depended on the weight ratio of poly (L-lactide) and $\gamma-BLG-NCA.$ The thermal properties of the resulting block copolymers were determined by the differential scanning calorimetry and by the thermogravimetry.

• Korean Journal of Agricultural Science
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• v.40 no.4
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• pp.367-375
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• 2013

The enzymatic interesterification was performed to produce structured lipids (SLs) with palm mid fraction (PMF) and stearic ethyl ester (STEE) for 1, 3, 6, 9, 12 and 15 hr at $80^{\circ}C$. The reaction was catalyzed by Lipozyme TLIM (immobilized lipase from Thermomyces lanuginosus, amount of 20% by weight of total substrates) in a shaking water bath set at 180 rpm. The optimum condition for synthesis of asymmetric SLs were: substrate molar ratio 1:0.5 (PMF:STEE, by weight), reaction time 6 hr, enzyme 20% (wt%, water activity=0.085) of total substrate and reaction temperature $80^{\circ}C$. After reaction at optimized condition, triacylglycerols (symmetrical and asymmetrical TAGs) from reactants were isolated. POP/PPO (1,3-palmitoyl-2-oleoyl glycerol or 1,2-palmitoyl-3-oleoyl glycerol), POS/PSO (palmitoyl-oleoyl-stearoyl glycerol or palmitoyl-stearoyl-oleoyl glycerol), SOS/SSO (1,3-stearoyl-2-oleoyl glycerol or 1,2-stearoyl-3-oleoyl glycerol) were obtained by solvent fractionation. Finally, refined SLs contained stearic acid of 16.91%. Solid fat index and thermogram of the refined SLs were obtained using differential scanning calorimetry. The degree of asymmetric triacylglycerol in the refined SLs was analyzed by Ag-HPLC equipped with evaporated light scattering detector (ELSD). The refined SLs consisted of symmetric TAG of 41.15 area% and asymmetric TAG of 58.85 area%.

• BMB Reports
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• v.38 no.4
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• pp.391-398
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• 2005

3-hydrogenwadaphnin (3-HK) is a new daphnane-type diterpene ester isolated from Dendrostellera lessertii with strong anti-tumoral activity in animal models and in cultures. Here, prolonged effects of this new agent on proliferation and viability of several different cancerous cell lines were evaluated. Using [$^3H$]thymidine incorporation, it was found that the drug inhibited cell proliferation and induced G1/S cell cycle arrest in leukemic cells 24 h after a single dose treatment. The cell viability of Jurkat cells was also decreased by almost 10%, 31% and 40% after a single dose treatment (7.5 nM) at 24, 48 and 72 h, respectively. The drug-treated cells were stained with acridine orange/ethidium bromide to document the chromatin condensation and DNA fragmentation. These observations were further confirmed by detection of DNA laddering pattern in the agarose gel electrophoresis of the extracted DNA from the treated cells. Treatment of K562 cells with the drug at 7.5, 15 and 30 nM caused apoptosis in 25%, 45% and 65% of the cells, respectively. Exogenous addition of $25-50\;{\mu}M$ guanosine and/or deoxyguanosine to the cell culture of the drug-treated cells restored DNA synthesis, released cell arrest at G1/S checkpoint and decreased the apoptotic cell death caused by the drug. These observations were not made using adenosine. However, the drug effects on K562 cells were potentiated by hypoxanthine. Based on these observations, perturbation of GTP metabolism is considered as one of the main reasons for apoptotic cell death by 3-HK.