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Chiral [Iminophosphoranyl]ferrocenes: Synthesis, Coordination Chemistry, and Catalytic Application

  • Co, Thanh Thien;Shim, Sang-Chul;Cho, Chan-Sik;Kim, Dong-Uk;Kim, Tae-Jeong
    • Bulletin of the Korean Chemical Society
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    • v.26 no.9
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    • pp.1359-1365
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    • 2005
  • A series of new chiral [iminophosphoranyl]ferrocenes, {${\eta}^5-C_5H_4-(PPh_2=N-2,6-R_2-C_6H_3)$}Fe{${\eta}^5-C_5H_3-1-PPh^2-2-CH(Me)NMe_2$} (1: R = Me, $^iPr$), {${\eta}^5{-C_5H_4-(PPh_2=N-2,6-R_2}^1-C_6H_3)$}Fe{${\eta}^5-C_5H_3-1-(PPh_2=N-2,6-R_2-C_6H_3)-2-CH(Me)R_2$} (2: $R^1\;=\;Me,\;^iPr;\;R^2\;=\;NMe_2$, OMe), and $({\eta}^5-C_5H_5)Fe${${\eta}^5-C_5H_4-1-PR_2-2-CH(Me)N=PPh_3$} (3:R = Ph, $C_6H_{11}$) have been prepared from the reaction of [1,1'-diphenylphosphino-2-(N,N-dimethylamino) ethyl]ferrocene with arylazides (1 & 2) and the reaction of phosphine dichlorides ($R_3PCl_{2}$) with [1,1'-diphenylphosphino-2-aminoethyl]ferrocene (3), respectively. They form palladium complexes of the type $[Pd(C_3H_5)(L)]BF_4$ (4-6: L = 1-3), where the ligand (L) adopts an ${\eta}^2-N,N\;(2)\;or\;{\eta}^2$-P,N (3) as expected. In the case of 1, a potential terdentate, an ${\eta}^2$-P,N mode is realized with the exclusion of the –=NAr group from the coordination sphere. Complexes 4-6 were employed as catalysts for allylic alkylation of 1,3-diphenylallyl acetate leading to an almost stoichiometric product yield with modest enantiomeric excess (up to 74% ee). Rh(I)-complexes incorporating 1-3 were also prepared in situ for allylic alkylation of cinnamyl acetate as a probe for both regio- and enantioselectivities of the reaction. The reaction exhibited high regiocontrol in favor of a linear achiral isomer regardless of the ligand employed.

Optimum Conditions of Enzymatic Reactions for Production of Isomaltooligosaccharides from Rice Flour (쌀가루로부터 이소말토올리고당 제조를 위한 효소반응 최적 조건)

  • Park, Ji-in;Shin, Jiyoung;Yang, Ji-young
    • Journal of Food Hygiene and Safety
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    • v.35 no.1
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    • pp.83-92
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    • 2020
  • This study investigated the optimal conditions of enzymatic reaction for production of isomaltooligosaccharides (IMO) using rice flour. To manufacture IMO, commercial enzymes (Termamyl 2X, Maltogenase L, Promozyme D2, Fungamyl 800L and Transglucosidase L) were used. The sugar composition and amount of IMO were examined by HPLC with charged aerosol detector (HPLC-CAD) in each manufacturing process. Liquefaction reaction was performed according to different Termamyl 2X concentrations (0.025%, 0.05%, 0.075%, 0.1%) and reaction times (1 h, 2 h). As a result, the reducing sugar content was the highest at 138.26 g/L when 0.075% Termamyl 2X was added for 2 hours. In order to optimize simultaneous saccharification and transglucosylation, experiments on enzyme selection, enzyme concentration and enzyme reaction time were conducted. Reaction with 0.0015% Maltogenase L, 0.05-0.1% Promozyme D2 and 0.1% Tansglucosidase L was effective in decreasing glucose content and increasing content of IMO with a high degree of polymerization. A change in sugar content was observed every 6 hours to determine the optimal reaction time, and the highest IMO was produced after 36 hours of reaction (75.36 g/L). The IMO prepared under optimal conditions showed isomaltose, 35.11 g/L; panose, 11.97 g/L; isomaltotriose, 19.95 g/L; isomaltotetraose, 7.46 g/L; isomaltopentaose, 1.05 g/L at 18 brix and the ratio of IMO in the total sugar was 56.37%.

Effect of pH on UV Photodegradation of N-Nitrosamines in Water (수용액상 니트로스아민의 UV 광분해에서 pH 영향)

  • Shim, Jae-Goo;Aqeel, Afzal;Choi, Bo-Mi;Lee, Jung-Hyun;Kwak, No-Sang;Lim, Ho-Jin
    • Journal of Korean Society on Water Environment
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    • v.32 no.4
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    • pp.357-366
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    • 2016
  • N-nitrosamines are a class of carcinogenic chemicals that can pose significant hazards to the human life. Ultraviolet (UV) light irradiation is considered as one of the effective methods to reduce N-nitrosamines in the aqueous phase. This study aimed to investigate the pH influence on UV photodegradation of N-nitrosamines (i.e., N-nitrosodibutylamine (NDBA) and N-nitrosopyrrolidine (NPYR)) closely related to water treatment. Photodegradation rate constants of NDBA and NPYR remained between 3.26×10-2 L/W-min to 5.08×10-3 L/W-min and 1.14×10-2 L/W-min to 2.80×10-3 L/W-min at pH2-10, respectively. This study also focused on the formation of oxidized products (i.e., primarily NO2- and NO3-). Under slightly acidic and neutral conditions, NO2- formation was more prevalent than NO3- formation, while under strong acidic conditions, NO3- was more prevalent. There was no significant change in total organic carbon (TOC) and total nitrogen (TN), suggesting negligible loss of N-nitrosamines and degradation products from the system. NDBA was easily photodegraded than NPYR. This study also demonstrated that a lower pH is a favorable condition for photolytic degradation of N-nitrosamines in water.

Acute Toxicity of Ammonia on Juvenile banded Catfish(Pseudobagurus fulvidraco) (동자개 치어의 암모니아 급성 독성)

  • SOHN, Sang-Gyu;LEE, Joo-Yong;LEE, Young-Sik;KIM, Kwang-Seog;KIM, Bong-Rae;LEE, Jeong-Ho;CHOI, Hye-Sung
    • Journal of Fisheries and Marine Sciences Education
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    • v.27 no.5
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    • pp.1229-1235
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    • 2015
  • Juvenile banded catfish(Pseudobagurus fulvidraco, mean length $10.7{\pm}0.42cm$ and mean weight $15.0{\pm}0.23g$) were exposed to varies TAN(total ammonia) concentrations at pH levels of $6.12{\pm}0.51$, $7.00{\pm}0.26$ and $8.04{\pm}0.07$ for 96hrs to check the level of acute toxicity on biofloc technology aquaculture system(BFT). The result showed that cumulative mortalities for juvenile banded catfish at TAN levels 48.95, 55.96, 66.47, and 78.88 mg/L at pH $6.12{\pm}0.51$ were 0, 30, 30, and 50%, respectively. At pH $7.00{\pm}0.26$, its mortalities to TAN 5.20, 11.68, 15.31, and 18.31 mg/L were 0, 10, 20, and 70%, respectively and at pH $8.04{\pm}0.07$, the mortalities to TAN 0.96, 1.49, 2.13, and 3.62 mg/L were 10, 20, 40, and 100%, respectively. Its $96h-LC_{50}$ (median lethal concentration, $LC_{50}$) at pH $6.12{\pm}0.51$, $7.00{\pm}0.26$, and $8.04{\pm}0.07$ were 78.12, 15.87, and 2.21 mg/L for TAN, and 0.05, 0.10, and 0.14 mg/L for $NH_3$, respectively, and the acute toxicity for ammonia to juvenile banded catfish increased exponentially with increase of pH.

Improved Coexpression and Multiassembly Properties of Recombinant Human Ferritin Subunits in Escherichia coli

  • Lee, Jung-Lim;Levin, Robert E.;Kim, Hae-Yeong
    • Journal of Microbiology and Biotechnology
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    • v.18 no.5
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    • pp.926-932
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    • 2008
  • Human heavy chain (H-) and light chain (L-) ferritins were amplified from a human cDNA library. Each ferritin gene was inserted downstream of the T7 promoter of bacterial expression vectors, and two types of coexpression vectors were constructed. The expression levels of recombinant ferritins ranged about 26-36% of whole-cell protein. H-ferritin exhibited a lower expression ratio compared with L-ferritin, by a coexpression system. However, the coexpression of HL-ferritins was significantly increased above the expression ratio of H-ferritin by cultivation without IPTG induction overnight. Purified recombinant H-, L-, HL-, and LH-ferritins were shown to be homo- and heteropolymeric high molecular complexes and it was indicated that their assembled subunits would be able to work functionally in the cell. Thus, these results indicate an improvement in the expression strategy of H-ferritin for heteropolymeric production and studies of ferritin assembly in Escherichia coli.

Isolation and Identification of Lactic Acid Bacteria with Probiotic Activities from Kimchi and Their Fermentation Properties in Milk (전통 김치로부터 Probiotic 유산균의 분리 및 우유 발효 특성)

  • Lim, Young-Soon;Kim, JiYoun;Kang, HyeonCheol
    • Journal of Dairy Science and Biotechnology
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    • v.37 no.2
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    • pp.115-128
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    • 2019
  • Lactic acid bacteria obtained from traditional Kimchi were selected on the basis of their caseinolytic activity and lactose usability and examined for availability as a starter in probiotic activity. Thirty-two strains were selected as lactic acid producing bacteria in BCP agar, and two strains (KC23 and KF26) with more than 90% resistance for both acid and bile salts were selected. The two strains were identified as L. plantarum (KC23) and L. paracasei (KF26) by API 50 CHL system and 16S rRNA sequence analysis. L. plantarum (KC23) was finally selected based on its biochemical characteristics for lactose and raffinose usability. Free tyrosine content increased rapidly in 10% skimmed milk medium, from $24.1{\mu}g/mL$ after 8 h to $43.9{\mu}g/mL$ after 16 h. Additionally, the caseinolytic clear zone of 12 mm of L. plantarum (KC23) was greater than the 9 mm zone of commercial L. acidophilus CSLA. The bacterium exhibited mesophilic growth and yielded $8.9{\times}10^8CFU/mL$ when incubated at $37^{\circ}C$ for 12 h at pH 4.25. Moreover, L. plantarum KC23 exhibited antibacterial activity as it formed a clear zone of 8-13 mm for the 5 pathogens. Adherent activity was 2.23 fold higher than that of LGG. The acidity of 10% skimmed milk fermented for 12 h was 0.74%.

Changes in Free Sugars, Organic Acids and Fatty Acid Composition of Kanjang Prepared with Different Cooking Conditions of Whole Black Bean (원료콩의 증자조건을 달리한 검정콩 간장의 유리당, 유기산 및 지방산의 변화)

  • 권선화;최재훈;고영란;손미예;박석규
    • Food Science and Preservation
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    • v.10 no.3
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    • pp.333-338
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    • 2003
  • pH values in all samples were in the range of 5.04 to 5.32. pH of kanjang prepared with normal pressure(NPK) was higher than that of kanjang prepared with high pressure(HPK) and kanjang prepared with steam(SPK). Titratable acidity(TA) in all samples were found to be 4.26~7.72 mL. TA in HPK(5.99~6.96 mL) was lower than that in SPK(4.26~5.61 mL) and NPK(7.32 mL). Reducing sugar(RS) contents in all samples were in the range of 25.18 to 194.81 mg%. RS contents of HPK and SPK were a similar pattern and were higher than that of NPK. Major free sugars(FS) were glucose, fructose and xylose. In total FS, SPK was higher than that of NPK and HPK. Major organic acids(OA) were succinic acid, oxalic acid, tartaric acid, malic acid and citric acid. In total OA contents, SPK(40.38~76.96 mg%) was higher than that of NPK(55.85 mg%)and HPK(27.78~34.21mg%). OA contents in HPK and SPK were decreased slightly according to the heating time of whole black bean. The highest percentage of fatty acid (FA) in all samples was palmitic acid(33.28~43.51 % as area % of GC chromatogram), followed in a decreasing order by stearic acid(14.15~19.16%) and myristic acid(5.93~19.14%). The composition ratios of three FA to total FA ranged from 55.97 to 72.85&. In all samples, there was myristic acid that was not contained in raw soybean.

The immune enhancing effects and characteristics of Bifidobacterium longum and Bifidobacterium breve for the probiotic use in humans and animals

  • Park, Ho-Eun;Um, Hyun-Bum;Lee, Wan-Kyu
    • Journal of Biomedical and Translational Research
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    • v.19 no.4
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    • pp.65-72
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    • 2018
  • The purpose of this study was to investigate probiotic characteristics and immune enhancing effects of Bifidobacterium (B.) longum KBB1-26 and BIF-4, B. breve KBB5-22 isolated from human intestine for probiotic use in humans and animals. We measured acid, bile and heat tolerance, antimicrobial activity against pathogenic bacteria, Escherichia (E.) coli, Salmonella (S.) Enteritidis, Staphylococcus (S.) aureus, and Listeria (L.) monocytogenes. Immune enhancing effects of B. longum and B. breve were investigated by measuring nitric oxide (NO), nuclear factor ($NF-{\kappa}b$), $interleukin-1{\beta}$ ($IL-1{\beta}$), interleukin-6 (IL-6), interleukin-12 (IL-12) and tumor necrosis $factor-{\alpha}$ ($TNF-{\alpha}$) in RAW 264.7 cells or RAW BLUE cells. B. longum KBB1-26 was survived at pH 2.0. B. longum KBB1-26 and BIF-4, B. breve KBB5-22 also showed tolerance to 0.3% of oxgall bile salt. B. longum KBB1-26 was able to survive at $70^{\circ}C$ and $80^{\circ}C$ for 20 min. KBB1-26 showed the antimicrobial inhibition zone to pathogenic bacteria such as E. coli (12 mm), S. Enteritidis (14 mm), S. aureus (14 mm) and L. monocytogenes (41 mm). The production of NO ($4.5{\pm}0.00{\mu}M/mL$) and $IL-1{\beta}$ ($39.7{\pm}0.55pg/mL$) of KBB1-26 significantly higher than BIF-4 and KBB5-22, respectively. In addition, KBB1-26 and KBB5-22 induce the production of high level of $TNF-{\alpha}$ and IL-6 in macrophages. Collectively, B. longum KBB1-26 have acid, bile, heat tolerance, antimicrobial activity and immune enhancing effects. These results suggest that KBB1-26 can be used as probiotics for humans and animals.

Studies on the Adsorption of Linear Alkylbenzene Sulfonate from Waste Water by Fibrous Aminated Acrylic ion-Exchanger (아민화 아크릴계 이온교환섬유의 폐수 중 Linear Alkylbenzene Sulfonate 흡착에 관한 연구)

  • 황택성;박진원;김원종
    • Polymer(Korea)
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    • v.26 no.4
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    • pp.516-522
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    • 2002
  • The ion exchange characteristic of quaternary ammonium as functional group containing aminated acrylic fibrous ion exchanger were studied for the adsorption of linear alkylbenzene sulfonate (LAS) in a continuous ion exchange process. The adsorption capacities of aminated acrylic for LAS as the adsorption temperature were increased with increasing adsorption temperature and were equilibrated at $40^{\circ}C$. The maximum adsorption capacities as column packing ratio (L/D) were obtained at L/D>2. The adsorption capacity for LAS was increased with increasing pH and the maximum adsorption capacity as pH was obtained at pH 7. The effects of temperature and pH were similar to those of flow rate and concentration of LAS tin the breakthrough curves, the breakthrough time and slope of breakthrough corves decreased with increasing flow rate and concentration of LAS in adsorption process.