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Selective Dimerization and Cyclotrimerization of Phenylacetylene with Rhodium and Iridium Complexes

  • Chin, Chong-Shik;Won, Gyong-Shik;Song, Joong-Ho
    • Bulletin of the Korean Chemical Society
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    • v.15 no.11
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    • pp.961-966
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    • 1994
  • Oligomerization of phenylacetylene is catalyzed by $Rh(ClO_4)(CO)(PPh_3)_2$ (Rh-1), $[Rh(CO)(PPh_3)_3]ClO_4$ (Rh-2), $[Rh(COD)L_2]ClO_4 (L_2=(PPh_3)_2$, Rh-3; $(PPh_3)(PhCN)$, Rh-4; $(PhCN)_2$, Rh-5), $[Rh(C_3H_5)(Cl)(CO)(SbPh_3)_2]ClO_4$ (Rh-6), $[Ir(COD)L_2]ClO_4 (L_2=(PPh_3)_2$, $Ir-1; (PPh_3)(PhCN)$, $Ir-2; (PhCN)_2$, Ir-3; (AsPh_3)(PhCN)$, $Ir-4; Ph_2PCH_2CH_2PPh_2$, Ir-5; COD, Ir-6 and 2,2'-dipyridyl, Ir-7), $Ir(ClO_4)(CO)(PPh_3)_2$, $Ir-8, [Ir(PhCN)(CO)(PPh_3)_2]ClO_4$, Ir-9 to produce dimerization products, 1,3-diphenylbut-1-yn-3-ene, 1, (E)-1,4-diphenylbut-1-yn-3-ene, 2 and (Z)-1,4-diphenylbut-1-yn-3-ene, 3, and cyclotrimerization products, 1,3,5-triphenylbenzene, 4 and 1,2,4-triphenylbenzene, 5. Product distribution of the oligomers varies depending on various factors such as the nature of catalysts, reaction temperature, counter anions and excess ligand present in the reaction mixtures. Increasing reaction temperature in general increases the yield of the cyclotrimerization products. Exclusive production of dimer 1 and trimer 4 can be obtained with Ir-1 at 0 $^{\circ}$C and with Ir-2 in the presence of excess PhCN (or $CH_3CN$) at 50 $^{\circ}$C, respectively. Dimer 2 (up to 81%) and trimer 5 (up to 98%) are selectively produced with Rh-1 at 50 and 100 $^{\circ}$C respectively. Production of 3 is selectively increased up to 85% by using $PF_6$- salt of $[Ir(COD)(PPh_3)_2]$+ at 25 $^{\circ}$C. Addition of $CH_3I$ to Rh-1 produces $CH_3PPh_3^+I-$ and increases the rate of oligomerization(disappearance of phenylacetylene). Among the metal compounds investigated in this study, Ir-1 catalyzes most rapidly the oligomerization where the catalytically active species seems to contain lr(PPh3)2 moiety. The stoichiometric reaction of phenylacetylene wth Ir-9 at 25 $^{\circ}$C quantitatively produces hydridophenyl-ethynyl iridium(III) complex, $[lr(H)(C{\equiv}CPh)(PhCN)(CO)(PPh_3)_2]ClO_4$ (Ir-11), which seems to be an intermediate for the oligomerization.

Studies on the Citric Acid Fermentation with Fungi (Part III) Citric Acid Fermentation with Selected Strains (사상균에 의한 구연산발효에 관한 연구 (제III보) 선정균에 의한 구연산발효)

  • 성낙계;김명찬;심기환;정덕화
    • Microbiology and Biotechnology Letters
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    • v.8 no.3
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    • pp.181-191
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    • 1980
  • For the purpose of studies on the citric acid production, some experiments were carried out with isolated strains. The results obtained were as follows. 1) The optimal culture media of the strain M-80 in surface culture contained 140g of sucrose, 3.0g of (N $H_4$)$_2$S $O_4$, 1.5g of K $H_2$P $O_4$, 0.2g of MgS $O_4$.7$H_2O$, 3.0mg of F $e^{++}$, 1.0mg of Z $n^{++}$, 0.5N HCI to a pH of 5.0 and distilled water to 1.0 liter; and that of the strain M-315 in surface culture contained 140g of sucrose, 2.0g of N $H_4$N $O_3$, 1.0g of K $H_2$P $O_4$, 0.25g of MgS $O_4$. 7$H_2O$, 2.0mg of F $e^{++}$, 2.0mg of Z $n^{++}$, 0.05mg of C $u^{++}$, 0.5N HCI to a pH of 4.5 and distilled water to 1.0 liter. While that of the strain M-315 in submerged culture contained 140g of sucrose, 2.5g of N $H_4$N $O_3$, 1.5g of K $H_2$P $O_4$, 0.3g of MgS $O_4$. 7$H_2O$, 3.0mg of F $e^{++}$, 0.1mg of C $u^{++}$, 0.5N HCI to a pH of 4.5 and distilled water to 1.0 liter. The optimal temperature and size of inoculum were mostly 28-3$0^{\circ}C$, 10$^{7}$ -10$^{8}$ spores/50ml, respectively. 2) Through the course of citric acid production, the growth of strains had nearly been completed, pH value was rapidly decreased below 2.0 and the content of sugar was also reduced, while the accumulation of citric acid in media was remarkably begun in about 3-4 days. The yields of citric acid generally reached the maximum level in 8-10 days in surface or submerged fermentation process. 3) Methanol was effective citric acid production when they were added to fermentation media. In the case of surface culture, by addition of 2% (strain M-80), 3% (strain M-315), the yields of citric acid was increased 6.5%, 20.6%, respectively and 5.0% yield was increased by addition of 3% methanol in submerged culture media of the strain M-315. 4) Chromatography analysis of culture broth after fermentation under optimal culture conditions detected that the majority of acid in media was citric acid. 72.1mg/ml, 98.1mg/ml, of citric acid were determined in surface culture media by strains of M-80, M-315, and 59.8 mg/ml of citric acid was contained in the submerged culture media by the strain M-315. strain M-315.

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[ $2{\beta}$ ], $3{\alpha}$, 23-trihydroxyrus-12-ene-28-oic Acid Induces the Apoptosis of Human Hepatoma HepG2 Cells ($2{\beta}$, $3{\alpha}$, 23-trihydroxyrus-12-ene-28-oic acid처리에 의한 인간 간암세포주 HepG2의 apoptosis 유도)

  • Yoo, Ki-Hyun;Lee, Jong-Min;HwangBo, Jeon;Song, Myoung-Chong;Yang, Hye-Joung;Baek, Nam-In;Kim, Soung-Hoon;Kim, Dae-Keun;Kwon, Byoung-Mok;Park, Mi-Hyun;Chung, In-Sik
    • Applied Biological Chemistry
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    • v.49 no.4
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    • pp.270-275
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    • 2006
  • [ $2{\beta},\;3{\alpha}$ ], 23-trihydroxyrus-12-ene-28-oic acid was isolated from Trapa pseudoincisa S. et Z. It has a common structure of pentacyclic triterpenes and belongs to the amyrin ursolic acid group. The cytotoxic effect of this compound was investigated in human hepatoma cell line HepG2. $2{\beta},\;3{\alpha}$, 23-trihydroxyrus-12-ene-28-oic acid showed dose-dependent cytotoxicity in HepG2 cells. Confocal microscopy data showed that green fluorescence was increased in $2{\beta},\;3{\alpha}$, 23-trihydroxyrus-12-ene-28-oic acid treated-HepG2 cells in a time-dependent manner. $2{\beta},\;3{\alpha}$, 23-trihydroxyrus-12-ene-28-oic acid also increased the sub-G1 cell population of HepG2 cells as well as ladder-like DNA fragmentation. Taken together, our results indicate that $2{\beta},\;3{\alpha}$, 23-trihydroxyrus-12-ene-28-oic acid induced apoptosis in HepG2 cells.

THE EFFECT OF IRRADIATION MODES ON POLYMERIZATION AND MICROLEAKAGE OF COMPOSITE RESIN (광조사 방식이 복합레진의 중합과 누출에 미치는 영향)

  • Park, Jong-Jin;Park, Jeong-Won;Park, Sung-Ho;Park, Ju-Myong;Kwon, Tae-Kyung;Kim, Sung-Kyo
    • Restorative Dentistry and Endodontics
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    • v.27 no.2
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    • pp.158-174
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    • 2002
  • The aim of this study was to investigate the effect of light irradiation modes on polymerization shrinkage, degree of cure and microleakage of a composite resin. VIP$^{TM}$ (Bisco Dental Products, Schaumburg, IL, USA) and Optilux 501$^{TM}$ (Demetron/Kerr, Danbury, CT, USA) were used for curing Filtek$^{TM}$ Z-250 (3M Dental Products, St. Paul., MN, USA) composite resin using following irradiation modes: VIP$^{TM}$ (Bisco) 200mW/$\textrm{cm}^2$ (V2), 400mW/$\textrm{cm}^2$ (V4), 600mW/$\textrm{cm}^2$ (V6), Pulse-delay (200 mW/$\textrm{cm}^2$ 3 seconds, 5 minutes wait, 600mW/$\textrm{cm}^2$ 30seconds, VPD) and Optilux 501$^{TM}$ (Demetron/Kerr) C-mode (OC), R-mode (OR). Linear polymerization shrinkage of the composite specimens were measured using Linometer (R&B, Daejeon, Korea) for 90 seconds for V2, V4, V6, OC, OR groups and for up to 363 seconds for VPD group (n=10, each). Degree of conversion was measured using FTIR spectrometer (IFS 120 HR, Bruker Karlsruhe, Germany) at the bottom surface of 2 mm thick composite specimens V2, Y4, V6, OC groups were measured separately at five irradiation times (5, 10, 20, 40, 60 seconds) and OR, VPD groups were measured in the above mentioned irradiation modes (n=5 each). Microhardness was measured using Digital microhardness tester (FM7, Future-Tech Co., Tokyo, Japan) at the top and bottom surfaces of 2mm thick composite specimens after exposure to the same irradiation modes as the test of degree of conversion(n=3, each). For the microleakage test, class V cavities were prepared on the distal surface of the ninety extracted human third molars. The cavities were restored with one of the following irradiation modes : V2/60 seconds, V4/40 seconds, V6/30 seconds, VPD , OC and OR. Microleakage was assessed by dye penetration along enamel and dentin margins of cavities. Mean polymerization shrinkage, mean degree of conversion and mean microhardness values for all groups at each time were analyzed using one-way ANOVA and Duncan's multiple range test, and using chi-square test far microleakage values. The results were as follows : . Polymerization shrinkage was increased with higher light intensity in groups using VIP$^{TM}$ (Bisco) : the highest with 600mW/$\textrm{cm}^2$, followed by Pulse-delay, 400mW/$\textrm{cm}^2$ and 200mW/$\textrm{cm}^2$ groups, The degree of polymerization shrinkage was higher with Continuous mode than with Ramp mode in groups using Optilux 501$^{TM}$ (Demetron/Kerr). . Degree of conversion and microhardness values were higher with higher light intensity. The final degree of conversion was in the range of 44.7 to 54.98% and the final microhardness value in the range of 34.10 to 56.30. . Microleakage was greater in dentin margin than in enamel margin. Higher light intensity showed more microleakage in dentin margin in groups using VIP$^{TM}$ (Bisco). The microleakage was the lowest with Continuous mode in enamel margin and with Ramp mode in dentin margin when Optilux 501$^{TM}$ (Demetron/Kerr) was used.

Protective Effects of Samul-tang on Oxidative Stress induced Death of H9c2 Cardioblast Cells (배양심근세포의 산화적 손상에 대한 사물탕의 방어효과)

  • Cho Kwon-Il;Jung Seung-Won;Jang Jae-Ho;Lee Dae-Yong;Park Sae-Wook;Lee In;Sin Sun-Ho;Moon Byung-Soon
    • The Journal of Korean Medicine
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    • v.26 no.1 s.61
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    • pp.174-186
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    • 2005
  • Objectives : The water extract of Samul-tang (SMT) has traditionally been used for treatment of ischemic heart and brain damage in oriental medicine. However, little is known about the mechanism by which the water extract of SMT rescues cells from these damages. Methods: This study was designed to investigate the protective mechanisms of SMT on oxidative stress-induced toxicity in H9c2 cardiomyoblast cells. Treatment with $H_2O_2$ markedly induced death of H9c2 cardiomyoblast cells in a dose-dependent manner. Results: The characteristics of H20z-induced death of H9c2 showed apparent apoptotic features such as DNA fragmentation and morphological change. However, SMT significantly reduced both H202-induced cell death and morphological change. The decrease of Bc-2 expression by High were inhibited by SMT. In addition, the increase of Bax expression was also inhibited by SMT. The cotreatment of SMT and $H_2O_2$ in H9c2 cells also induced the phosphorylation of ERK in a time-dependent manner. Moreover, PD98059, a specific inhibitor of ERK1/2 attenuated the protective effects of SMT on $H_2O_2-induced$ toxicity in H9c2 cardiomyoblast cells. These results suggest that both ERK1/2 signaling pathways play important roles in the protective effects of SMT on $H_2O_2-induced$ apoptotic death of H9c2 cells. Also, the expression profile of proteins in $H_2O_2$ cardiomyoblast cells were screened by using two-dimensional (2-D) gel electrophoresis. Among 300 spots resolved in 2-D gels, the comparison of control versus apoptosis cells revealed that signal intensity of 17 spots increased and 11 spots decreased. Conclusions: Taken together, this study suggests that the protectiw effects of the water extract of SMT against oxidative damages may be mediated by the modulation of Bc1-2 and Bax expression via the regulation of the ERK signaling pathway.

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Electronic Structure and Properties of High-Tc Superconductor Y-Ba-Cu-O. 1. Oxygen-deficiency in the $YBa_2Cu_3O_x $Superconductor ($6{\leq}{\times}{\leq}7$)

  • U-Hyon Paek;U-Sung Choi;Kee-Hag Lee;Chang-Hong Kim
    • Bulletin of the Korean Chemical Society
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    • v.10 no.6
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    • pp.504-509
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    • 1989
  • The effect of oxygen-deficiency on the charge distributions and orbital energies for small copper oxide clusters representing the superconducting materials $YBa_2Cu_3O_x (6{\leq}x{\leq}7)$ were investigated by the extended Huckel molecular orbital (EHMO) method with the tight-binding model. Our calculations show +3 oxidation state of Cu(1) in the $CuO_3$ chain and +2 or +1 of Cu(2) in the $CuO_2$ layers for $YBa_2Cu_3O_7$ with the nominal charge of $Cu_3$ = +7 (or +5), while for $YBa_2Cu_3O_6$ +1 oxidation state of Cu(1) and +3 (or +2) of Cu(2) in the $CuO_2$ layers with the nominal charge of $Cu_3$ = +7 (or +5). For $Cu_3O_{12}$ cluster representing $YBa_2Cu_3O_7$ with the nominal charge of $Cu_3$ = +7 the Cu(2) $d_{{x^2}-{y^2}}$ orbitals in the $CuO_2$ layers is a typical Jahn-Teller $d^9$ system with the partial hole and the Cu(1) $d_{{_z2}-{_y2}}$ orbital in the $CuO_3$ chain contains hole occupancy. For $Cu_3O_{10}$ cluster representing $YBa_2Cu_3O_6$ with the nominal charge of Cu = +5 the orbital character of the highest partially occupied MO (HPOMO) and the lowest completely unoccupied MO (LCUMO) of $Cu_3O_{12}$ representing $YBa_2Cu_3O_7$ with the nominal charge of $Cu_3$ = +7 is reversed, and the character of Cu(1) $d{{x^2}-{y^2}}$ orbital of LCUMO of the $Cu_3O_{12} $cluster is vanished. It is suggested that the local crystal field environment of Cu(1) by the oxygens in the Cu(1) chain may play a vital role in conductivity and superconductivity, either alone or through cooperative electronic coupling with the Cu(2) layers in $YBa_2Cu_3O_7.$.

Investigation of Furfural Yields of Liquid Hydrolyzate during Dilute Acid Pretreatment Process on Quercus Mongolica using Response Surface Methodology (신갈나무 약산 전처리 공정 중 반응표면분석법을 이용한 액상 가수분해물의 furfural 수율 탐색)

  • Ryu, Ga-Hee;Jeong, Han-Seob;Jang, Soo-Kyeong;Hong, Chang-Young;Choi, Joon Weon;Choi, In-Gyu
    • Journal of the Korean Wood Science and Technology
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    • v.44 no.1
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    • pp.85-95
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    • 2016
  • In this study, furfural, which is one of the value-added chemicals, was produced from the hydrolyzate of Quercus mongolica using dilute acid pretreatment, and the optimal pretreatment condition was determined by Response Surface Methodology (RSM) to obtain high yield of furfural. Based on Central Composite Design, the pretreatment experiment was designed with parameters such as reaction temperature ($X_1$), acid concentration ($X_2$), and reaction time ($X_3$) as independent variables, while dependent variable was furfural concentration (Y), and furfural yield (Z) was shown as percentage of Y per a dry weight basis. According to results of RSM, it was confirmed that reaction temperature ($X_1$) was the most influence factor and reaction temperature ($X_1$)-acid concentration ($X_2$) was the most significant interaction factor on furfural yield. Also, the optimal condition for the highest furfural yield was predicted at reaction temperature of $184^{\circ}C$, acid concentration of 1.17%, and reaction time of 5 min by RSM, and expected maximum yield of furfural was 6.37%. Experimentally, the maximum yield of furfural produced at above optimal condition was 6.21%, and it was considerably similar with the predicted value, and therefore the model for furfural production from the hydrolyzate of Quercus mongolica during dilute acid pretreatment could be built using RSM.

Evaluation of Natural Antimicrobial Formulas against Yeasts in Functional Bevereges (기능성 음료 중 효모 제어를 위한 천연항균제 혼합조성 물 평가)

  • Yeon, Ji-Hye;Jo, Seo-Hee;Lee, Hee-Seok;Ha, Sang-Do;Park, Chul-Soo;Woo, Moon-Jea;Lee, Sang-Hun;Kim, Jin-Soo;Lee, Chon
    • Journal of Food Hygiene and Safety
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    • v.24 no.3
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    • pp.189-193
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    • 2009
  • The purpose of this study was to investigate the antimicrobial activities of natural antimicrobials (10 formulas, $F1{\sim}F10$) against yeasts in functional beverages. The growth rates of yeasts were different with the ten different natural antimicrobial formulas tested. Yeasts grew for 14 days and the antimicrobial effect was observed between 14 and 18 days. Levels of S. cerevisiae, Z. bailii, and P. membranaefaciens were reduced to the limit of detection (ND) < 10 CFU/mL) after 28 days. Resistance against the antimicrobial effect was greatest for P. membranaefaciens, which grew to a level of $0.12{\sim}1.48\;\log_{10}\;CFU$/mL after 14 days and was reduced to a level of $1.61{\sim}3.55\;\log_{10}\;CFU$/mL after 28 days. The resistance of C. albicans was also high with a growth level of $0.13{\sim}1.28\;\log_{10}\;CFU$/mL after 14 days and reduction to $1.51{\sim}5.30\;\log_{10}\;CFU$/mL after 28 days. The antimicrobial effect of F10 was strongest for P. membranaefaciens. Every treatment reduced the microbial levels to $2.68{\sim}5.62\;\log_{10}\;CFU$/mL after 6 months. F2, F4, F5, F6, and F10 reduced the C. albicans level to ND after 28 days while F1, F3, F8, and F9 reduced yeasts to the ND level after 6 months. The antimicrobial activities observed here will be useful for development of natural antimicrobials.

Chemical Composition and Antitumor Apoptogenic Activity of Methylene Chloride Extracts from the Leaves of Zanthoxylum schinifolium (Zanthoxylum schinifolium잎의 methylene chloride 추출물의 화학적 조성 및 암세포에 대한 세포자살 유도활성과 그 작용기전)

  • Kim Jun-Seok;Jun Do-Youn;Woo Mi-Hee;Rhee In-Koo;Kim Young-Ho
    • Journal of Life Science
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    • v.16 no.3 s.76
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    • pp.546-554
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    • 2006
  • To understand antitumor activity of Zanthoxylum schinfolium, which has been used as an aromatic and medicinal plant in Korea, the cytotoxic effect of various organic solvent extracts of its leaves on human tumor cells were investigated. Among these extracts such as methanol extract (SL-13), methylene chloride extract (SL-14), ethyl acetate extract (SL-15), n-butanol extract (SL-16), and residual fraction (SL-17), SL-14 appeared to contain the most cytotoxic activity against leukemia and breast cancer cells tested. The methylene chloride extra.1 (SL-14) possessed an apoptogenic activity causing apoptotic DNA fragmentation of human acute leukemia Jurkat T cells via mitochondrial cytochrome c release into cytoplasm, subsequent activation of caspase-9 and caspase-3, and cleavage of PARP, which could be negatively regulated by antiapoptotic protein Bcl-xL. The GC-MS analysis of SL-14 revealed that the twenty-two ingredients of SL-14 were 9,19-cyclolanost-24-en-3-ol (15.1%), 2-a-methyl-17, b-hop-21-ene (15.1%), 15-methyl-2,3-dihydro-1H benzazepin (11.95%), phytol (10.38%), lupeol (9.92%), 12-methylbenzofuran (8.23%), hexadecanoic acid (5.96%), cis,cis,cis-9,12,15-octadecatrienoic acid-methyl-ester (5.49%), 9,12,15-octadecatrienoic acid-methylester (3.59%), 15-methyl-4-(1-methylethylidene)-2-(4-nitrophenyl) (3.36%), hexadecanoic acid methyl ester (1.93%), vitamine E (1.88%), beta-amyrin (0.96%), and auraptene (0.89%). These results demonstrate that the cytotoxicity of the methylene chloride extract of the leaves of Z. schinifolium toward Jurkat T cells is mainly attributable to apoptosis mediated by mitochondria-dependent caspase cascade regulated by Bcl-xL, and provide an insight into the mechanism underlying antitumor activity of the edible plant Z. schinifolium.

Development and Expression of Porcine Embryos by Direct Injection of Sperm Treated with Exogenous DNA (외래유전자 도입정자를 이용한 돼지 체외성숙 난포란의 Intracytoplasmic Sperm Injection (ICSI) 후 후기 배로의 발달율과 외래유전자의 발현에 관한 연구)

  • 정기화;조성근
    • Journal of Embryo Transfer
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    • v.17 no.1
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    • pp.45-53
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    • 2002
  • The main goal of this study was to produce transgenic porcine embryos by direct injection of sperm-mediated exogenous DNA. Spermatozoa (6$\times$10$^{6}$ sperms of final concentration) were mixed with pcDNA LAC Z (20 ng/$\mu$l) and subjected into electroporation (300~750 volts, 25 $\mu$F, 0.4 cm electrode). After sperm injection, the oocytes were activated electrically (1.7 KV/cm, 30$\mu$sec, single pulse) in 0.3 M mannitol solution or not. The sperm injected eggs were cultured in NCSU 23 medium (0.4% BSA) at 39$^{\circ}C$, 5% $CO_2$ in air fur 144 h. The rates of cleavage and development into blastocyst stage in activation group were significantly higher than those of non-activation group (79.6% and 24.1% vs. 46.3% and 14.4%, respectively, p<0.05). Control oocytes and shame injection were developed to blastocysts low (2.5%). Sixty five (27.1%) out of 240 embryos observed in activation and non-activation groups were showed positive by X-gal staining. However, all embryos in both groups were expressed partial or mosaic pattern. These results suggested that electrical stimulation far oocytes activation after sperm injection enhances the incidence of both fertilization and development fellowing sperm injection in the pig. Our study also suggested that sperm-mediated transfer of exogenous DNA by ICSI would be used as a valuable tool for the production of transgenic porcine embryos.