• Journal of the Korean Chemical Society
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• v.30 no.1
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• pp.9-18
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• 1986

MNDO and STO-3G calculations were performed to determine relative stabilities of rotamers for ${\alpha}$-substituted acetones, $CH_2XCOCH_3$, X = F, Cl, OH, SH, and $NH_2$. It was found that rotamers corresponding to gauche forms are preferred for all the ${\alpha}$-substituents except for X = F and NH$_2$, for which the cis forms were the preferred ones. The stability of gauche form was dictated by the stabilizing two-orbital-two-electron interaction ${\sigma}_{cx}$-${\pi}_{co}^*$, operating uniquely in the gauche form due to the substantial vicinal overlap and energy gap narrowing between ${\sigma}_{cx}$ and ${\pi}_{co}^*$ orbitals. The energy gap narrowing was caused by the lowering of ${\pi}_{co}^*$ level due to the hyperconjugative ${\sigma}_{cx}^*$-${\pi}_{co}^*$ interactions; the red shift in the n-${\pi}^*$ transition was another effect of the relatively large ${\sigma}_{cx}^*$-${\pi}_{co}^*$ splitting. Various ${\sigma}-{\pi}$ interactions in the gauche form were found to be stronger in the third-row hetero atom system, X = Cl and SH. Interactions between nonbonding orbital on N, $n_N$ and vicinal C-C ${\sigma}$ bond were shown to be stronger in the trans than in the cis orientation.

• Korean Journal of Pharmacognosy
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• v.27 no.3
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• pp.238-245
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• 1996

The activity guided fractionation of $CH_2Cl_2$ soluble part of Platycarya strobilacea leaves(Juglandaceae) has led to the isolation of eight active principles, identified as 5-hydroxy-2-methoxy-1,4-naphthoquinone(1), ursolic acid(2), gallic acid(3), 4,8-dihydroxynaphthalene $1-O-{\beta}-_D-glucoside(4)$, eriodictyol(5), quercetin $3-O-(2'-O-galloyl)-{\beta}-_D-glucoside(6)$. quercetin $3-O-(2'-O-galloyl)-{\beta}-_D-galactoside(7)$ and quercetin $3-O-{\alpha}-_L-rhamnoside(8)$ by the means of chemical and spectral evidence, respectively.

• Asian-Australasian Journal of Animal Sciences
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• v.22 no.6
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• pp.819-826
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• 2009

An in vitro study was conducted to investigate the effect of malate or fumarate on fermentation characteristics, and production of conjugated linoleic acid (CLA) and methane ($CH_4$) by rumen microbes when incubated with linolenic acid (${\alpha}-C_{18:3}$). Sixty milligrams of ${\alpha}-C_{18:3}$ alone (LNA), or ${\alpha}-C_{18:3}$ with 24 mM malic acid (M-LNA) or ${\alpha}-C_{18:3}$ with 24 mM fumaric acid (F-LNA) were added to the 150 ml culture solution consisting of 75 ml strained rumen fluid and 75ml McDougall's artificial saliva. Culture solution for incubation was also made without malate, fumarate and ${\alpha}-C_{18:3}$ (Control). Two grams of feed consisting of 70% concentrate and 30% ground alfalfa (DM basis) were also added to the culture solution of each treatment. In vitro incubation was made anaerobically in a shaking incubator up to 12 h at $39^{\circ}C$. Supplementation of malate (M-LNA) or fumarate (F-LNA) increased pH at 6 h (p<0.01) and 12 h (p<0.001) incubation times compared to control and linolenic acid (LNA) treatments. Both malate and fumarate did not influence the ammonia-N concentration. Concentration of total VFA in culture solution was higher for M-LNA and F-LNA supplementation than for control and LNA treatments from 6 h (p<0.040) to 12 h (p<0.027) incubation times, but was not different between malate and fumarate for all incubation times. Molar proportion of $C_3$ was increased by F-LNA and M-LNA supplementation from 6 h (p<0.0001) to 12 h (p<0.004) incubation times compared to control and LNA treatments. No differences in $C_{3}$ proportion, however, were observed between M-LNA and F-LNA treatments. Accumulated total gas production for 12h incubation was increased (p<0.0002) by M-LNA or F-LNA compared to control or LNA treatment. Accumulated $CH_4$ production for 12 h incubation, however, was greatly reduced (p<0.0002) by supplementing malate or fumarate compared to the control, and its production from M-LNA or F-LNA treatment was smaller than that from LNA treatment. Methane production from LNA, M-LNA or F-LNA treatment was steadily lower (p<0.01 - p<0.001) from 3 h incubation time than that from the control, and was also lower for M-LNA or F-LNA treatment at incubation times of 6 h (p<0.01) and 9 h (p<0.001) than for LNA treatment. Methane production from LNA, however, was reduced (p<0.01 - p<0.001) from 3 h to 9 h incubation times compared to the control. Both malate and fumarate increased concentration of trans11-$C_{18:1}$ from 3 h to 12 h incubation (p<0.01), cis9,trans11-CLA up to 6 h incubation (p<0.01 - p<0.01), trans10,cis12-CLA at 3 h (p<0.05) and 12 h (p<0.01), and total CLA for all incubation times (p<0.05) compared to corresponding values for the ${\alpha}-C_{18:3}$ supplemented treatment (LNA). In conclusion, malate and fumarate rechanneled the metabolic $H_2 pathway to production of propionate and CLA, and depressed the process of biohydrogenation and methane generation. Linolenic acid alone would also be one of the optimistic alternatives to suppress the $CH_4$ generation.

• Journal of Life Science
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• v.23 no.1
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• pp.69-78
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• 2013

Vitis amurensis Rupreche, a sort of grape, grows naturally in Asian countries. It is known for important biological effects such as antioxidation, anti-inflammation, neuroprotection, and angiogenesis inhibition. Although its root is used as a traditional folk medicine in Korea, the root's biological activities are poorly studied. In the present study, the effects of V. amurensis root methanol extract (VARM) and its solvent fractions on adipocyte differentiation and adipogenesis in 3T3-L1 preadipocytes were investigated. The VARM significantly suppressed adipocyte differentiation, lipid accumulation, and the triglyceride (TG) content of 3T3-L1 preadipocytes in a dose-dependent manner, without cytotoxicity. To identify active molecules, the VARM was fractionated with a series of organic solvents including dichloromethane ($CH_2Cl_2$), ethyl acetate (EtOAc), and n-butanol (n-BuOH). All the fractions also showed inhibition of lipid accumulation in the 3T3-L1 preadipocytes. The $CH_2Cl_2$ fraction showed the most powerful anti-obesity effect through the modulation of cytidine-cytidine-adenosine-adenosinethymidine (CCAAT)/enhancer binding protein ${\alpha}$ ($C/EBP{\alpha}$), $C/EBP{\beta}$, peroxisome proliferator-activated receptor ${\gamma}$ ($PPAR{\gamma}$) gene and protein expression. Oleanolic acid was one of the main active compounds involved in the anti-obesity activity of the V. amurensis root. These results provide important new insight into the potential potent anti-adipogenic effect of the V. amurensis root and illustrate that one of the main compounds involved in this effect is oleanolic acid.

• Bulletin of the Korean Chemical Society
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• v.10 no.2
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• pp.177-184
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• 1989

The structure of cholesteryl isobutyrate, $(CH_3)_2CHCOOC_{27}H_{45}$, was determined by single crystal X-ray diffraction methods. Cholesteryl isobutyrate crystallized monoclinic space group $P2_1$, with a = 15.115 (8)${\AA}$, b = 9.636 (5)${\AA}$, c = 20.224 (9)${\AA}$, ${\beta}$ = 93.15 (5)$^{\circ}$, z = 4, $D_c = 1.03 g/cm^3 $and Dm= 1.04 g/$cm^3$. The intensity data were measured for the 3417 reflections, within $sin{\theta}/{\lambda} = 0.59{\AA}^{-1}$, using an automatic four-circle diffractometer and graphite monochromated Mo-$K_{\alpha}$ radiation. The structure was solved by fragment search Patterson methods and direct methods and refined by full-matrix least-squares methods. The final R factor was 0.129 for 2984 observed reflections. The two symmetry-independent molecules (A) and (B) are almost fully extended. The molecules are in antiparallel array forming monolayers with thickness $d_{100}$ = 15.2${\AA}$, and molecular long axes are nearly parallel to the [$\bar{1}$01] directions. The two distinct molecules form separate stacks with almost the same orientations, but with differing degrees of steroid overlap. Thers is a close packing of cholesteryl groups within the monolayers. The packing type is similar to those of cholesteryl hexanoate and cholesteryl oleate.

• Journal of Microbiology and Biotechnology
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• v.24 no.7
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• pp.969-978
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• 2014

The aprE2 gene with its prosequence from Bacillus subtilis CH3-5 was overexpressed in Escherichia coli BL21(DE3) by using plasmid pET26b(+). After IPTG induction, active and mature AprE2 was produced when cells were grown at $20^{\circ}C$, whereas inactive and insoluble enzyme was produced in a large amount when cells were grown at $37^{\circ}C$. The insoluble fraction was resuspended with 6 M guanidine-HCl and dialyzed against 2 M Tris-HCl (pH 7.0) or 0.5 M sodium acetate (pH 7.0) buffer. Then active AprE2 was regenerated and purified by a Ni-NTA column. Purified AprE2 from the soluble fraction had a specific activity of $1,069.4{\pm}42.4U/mg$ protein, higher than that from the renatured insoluble fraction. However, more active AprE2 was obtained by renaturation of the insoluble fraction. AprE2 was most stable at pH 7 and $40^{\circ}C$, respectively. The fibrinolytic activity of AprE2 was inhibited by PMSF, but not by EDTA and metal ions. AprE2 degraded $A{\alpha}$ and $B{\beta}$ chains of fibrinogen quickly, but not the ${\gamma}$-chain. AprE2 exhibited the highest specificity for N-succinyl-Ala-Ala-Pro-Phe-pNA. The $K_m$ and $k_{cat}/K_m$ of AprE2 was 0.56 mM and $3.10{\times}10^4S^{-1}M^{-1}$, respectively.

• Bulletin of the Korean Chemical Society
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• v.21 no.9
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• pp.882-890
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• 2000

Ab initio calculations are carried out on protonation equilibria of 5-memberedheteroaromatic aldehydes (5MHAs;heteroatom Y = NH, O, PH,and S and substituentZ = NH2, OCH3, SCH3, CH3, H, Cl, CHO, CN,NO2) at the $MP2}6-31G*$ level. Naturalbond orbital (NBO) analyses show that the optimal localized natural Lewis structures of the protonated aldehydes,(P), are ortho (C3) protonated (for Y = O, PH and S) and N-pro-tonated (for Y = NH) forms in contrast to the standard structural Lewis formula for aldehydes, (R). The delo-calizability of ${\pilone}-pairon$ the heteroatom $(n{\pi}(Y))$ is in the order Y = NH > O > S > PH. The transmission efficiency of (Z) substituent effects to the carbonyl moiety run parallel to the delocalizability of $n{\pi}(Y)$ for R,but is dominantly influenced by the cationic charge on $C{\alpha}(C{\alpha}+)$ for P, which is in the reverse order of thede-localizability of $n{\pi}(Y).$ The Hammett ${\rho}values$ for variation of Z in the protonation are determined by the dif-ference in the transmission efficiencies between Pand R stateat simple interpretation of their magnitude is not warranted. However,the magnitude of the gas-phase ${\rho}z+$ values decreases as the level ofcomputation is raised from RHF/3-21G* to RHF/6-31G* and to $MP2}6-31G*$ but increases again at the MP4SDQ/6-31G* level. Further decrease occurs when solvent effect (water) is accounted for by the SCRF method. Comparison of the SCRF ${\rho}z+values$ with those determined in the aqueous acid solution for Y = S and CHCH shows inadequacy of accounting for the solvent effects on the ${\rho}values$ by a continuum model. It is noteworthy that semiempirical calculations, especially theAM1 method, give even lower magnitude of the gas-phase ${\rho}values.

• Journal of the Korean Society of Food Science and Nutrition
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• v.41 no.9
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• pp.1242-1247
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• 2012

Acer barbinerve Maxim belongs to the Aceraceae tree family and is often consumed as an Oriental medicine. In this study, we investigated whether or not ethanol extract from the bark of A. barbinerve Max. (EBA) inhibits lipopolysaccharide (LPS)-induced inflammatory responses in Raw264.7 macrophages. EBA was fractionated using n-hexane, $CH_2Cl_2$, ethyl acetate (EtOAc), and water. Raw264.7 cells were treated with 20 ${\mu}g/mL$ of EBA and the EBA fractions. EBA inhibited LPS-induced nitric oxide (NO) production. Among the three fractions, EtOAc fraction of EBA (EFEBA) was the most effective in inhibiting LPS-induced NO production without significant cytotoxicity in Raw264.7 cells. EFEBA futher reduced LPS-induced expression of inducible NO synthase (iNOS) proteins and its corresponding mRNA. Additionally, EFEBA decreased the mRNA levels of interleukin (IL)-6, IL-$1{\beta}$, and tumor necrosis factor-${\alpha}$ in LPS-treated Raw264.7 cells. Lastly, EFEBA inhibited LPS-induced degradation of the inhibitor of kappaBalpha ($I{\kappa}B{\alpha}$) as well as phosphorylation of p65 nuclear factor-${\kappa}B$ (NF-${\kappa}B$). These results indicate that EFEBA exhibits strong anti-inflammatory effects and can be developed as a potential anti-inflammatory agent.

• Journal of Korea Foresty Energy
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• v.17 no.1
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• pp.56-70
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• 1998

This study was carried out to investigate the structural characteristics of kraft lignin and the wood degrading characteristics, the productivity of ligninolytic enzymes and the enzymatic degradation of kraft lignin by white-rot fungi. To purify kraft lignin, precipitation of kraft pulping black liquors of pitch pine meal was done by titration with lN $H_{2}SO_{4}$ reaching to pH 2, and isolation of the precipitates done by centrifugation. The isolated precipitates from pitch pine were redissloved in lN NaOH, reprecipitated by titration with lN $H_{2}SO_{4}$, washed with deionized water, and kept ofr analysis after freeze drying. Fractionation of the precipitates in solution by successive extraction with $CH_{2}Cl_{2}$ and MeOH, and the fractionates were named SwKL, SwKL I, SwKL II, and SwKL III for pitch pine kraft lignin. The more molecular weights of kraft lignin increased, the less phenolic hydroxyl groups and the more aliphatic hydroxyl groups. Because as the molecular weights increased, the ratio of etherified guaiayl/syringyl(G/S ratio) and the percentage were increased. The spectra obtained by 13C NMR and FTIR assigned by comparing the chemical shifts of various signals with shifts of signals from autherized ones reported. The optimal growth temperature and pH of white-rot fungi in medium were $28^{\circ}C$ and 4.5-5.0, respectively. Especially, in temperature and pH range, and mycelial growth, the best white-rot fungus selected was Phanerochaete chrysosporium for biodegradation. For the degradation pathways, the ligninolytic fungus jcultivated with stationary culture using medium of 1% kraft lignin as a substrate for 3 weeks at $28^{\circ}C$. The weight loss of pitch pine kraft lignin was 15.8%. The degraded products extracted successively methoanol, 90% dioxane and diethyl ether. The ether solubles were analyzed by HPLC. Kraft lignin degradation was initiated in $\beta$-O-4 bonds of lignin by the laccase from Phanerochaete chrysosporium and the degraded compounds were produced from the cleavage of $C\alpha$-$C\beta$ linkages at the side chains by oxidation process. After $C\alpha$-$C\beta$ cleavage, $C\alpha$-Carbon was oxidized and changed into aldehyde and acidic compounds such as syringic acid, syringic aldehyde and vanilline. And the other compound as quinonemethide, coumarin, was analyzed. The structural characteristics of kraft lignin were composed of guaiacyl group substituted functional OHs, methoxyl, and carbonyl at C-3, -4, and -5 and these groups were combinated with $\alpha$ aryl ether, $\beta$ aryl ether and biphenyl. Kraft lignin degradation pathways by Phanerochaete chrysosporium were initially accomplished cleavage of $C\alpha$-$C\beta$ linkages and $C\alpha$ oxidation at the propyl side chains and finally cleavage of aromatic ring and oxidation of OHs.

• Bulletin of the Korean Chemical Society
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• v.26 no.7
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• pp.1065-1070
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• 2005

$[Mn_{12}O_{12}(O_2CPh-4-SMe)_{16}(H_2O)_4]{\cdot}7CH_2Cl_2$ (1), a new single-molecule magnet complex has been successfully synthesized by substitution of acetate ligand of Mn12ac with 4-(methylthio)benzoic acid. Complex 1 crystallizes into triclinic P$\overline{1}$ with a = 18.321(3) $\AA$, b = 19.011(3) $\AA$, c = 27.230(4) $\AA$, $\alpha$ = 86.973(3)$^{\circ}$, $\beta$ = 76.919(3)$^{\circ}$, $\gamma$ = 87.613(3)$^{\circ}$, and Z = 2. In complex 1, one Mn(III) ion has an abnormal Jahn-Teller elongation axis oriented at an oxide ion. Complex 1 has two out-of-phase ac susceptibility peaks in the 2-4 K and 4-7 K regions. Effective anisotropy energy barrier and pre-exponential factor are $U_{eff}$ = 45.95 K, 1/$\tau$0 = 8.6 ${\times}\;10^9s^{-1}\;for\;{\chi}_M$'' peaks in the lower temperature region and $U_{eff}$ = 59.45 K, 1/$\tau_0$ = 2.2 ${\times}\;10^8\;s^{-1}$ for $\chi_M$'' peaks in the higher temperature region. The parameters of S = 10, g = 1.87, D = -0.40 $cm^{-1}$, and E = 0.00034 $cm^{-1}$ were obtained from the M/N${\mu}_B$ vs. H/T plot of complex 1.