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Synthesis and Characterization of New Polyaza Non-macrocyclic and Macrocyclic Nickel(II) Complexes Containing One 1,3-Diazacyclohexane Ring

  • Lee, Yun-Taek;Jang, Bo Woo;Kang, Shin-Geol
    • Bulletin of the Korean Chemical Society
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    • v.34 no.7
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    • pp.2125-2130
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    • 2013
  • A new nickel(II) complex $[NiL^1]^{2+}$ ($L^1$ = 1-(2-aminoethyl)-3-(N-{2-aminoethyl}aminomethyl-1,3-diazacyclohexane) containing one 1,3-diazacyclohexane ring has been prepared selectively by the metal-template condensation of formaldehyde with N-(2-aminoethyl)-1,3-propanediamine and ethylenediamine at room temperature. The complex reacts with nitroethane and formaldehyde to yield the pentaaza macrocyclic complex $[NiL^2]^{2+}$ ($L^2$ = 8-methyl-8-nitro-1,3,6,10,13-pentaazabicyclo[13.3.1]heptadecane) bearing one C-$NO_2$ pendant arm. The reduction of $[NiL^2]^{2+}$ by using Zn/HCl produces $[NiL^3(H_2O)]^{2+}$ ($L^3$ = 8-amino-8-methyl-1,3,6,10,13-pentaazabicyclo[13.3.1]heptadecane) bearing one coordinated C-$NH_2$ pendant arm that is readily protonated in acid solutions. The hexaaza macrocyclic complex $[NiL^4]^{2+}$ ($L^4$ = 8-phenylmethyl-8-nitro-1,3,6,8,10,13-hexaazabicyclo[13.3.1]heptadecane) bearing one N-$CH_2C_6H_5$ pendant arm has also been prepared by the reaction of $[NiL^1]^{2+}$ with benzylamine and formaldehyde. The nickel(II) complexes of $L^1$, $L^2$, and $L^4$ have square-planar coordination geometry in the solid states and in nitromethane. However, they exist as equilibrium mixtures of the square-planar $[NiL]^{2+}$ (L = $L^1$, $L^2$, or $L^4$) and octahedral $[NiL(S)_2]^{2+}$ species in various coordinating solvents (S); the proportion of the octahedral species $[NiL(S)_2]^{2+}$ is strongly influenced by the ligand structure and the nature of the solvent. Synthesis, spectra, and chemical properties of the nickel(II) complexes of $L^1-L^4$ are described.

Evaluation of circulating PD-1 and PD-L1 as diagnostic biomarkers in dogs with tumors

  • Song, Doo-Won;Ro, Woong-Bin;Park, Hee-Myung
    • Journal of Veterinary Science
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    • v.22 no.5
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    • pp.75.1-75.10
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    • 2021
  • Background: Programmed cell death protein-1 (PD-1) and programmed cell death ligand-1 (PD-L1) have important roles in tumor evasion of the immune system. Objectives: This study aimed to assess the diagnostic utility of circulating PD-1 and PD-L1 levels in healthy dogs and dogs with tumors. Methods: Circulating PD-1 and PD-L1 levels in the serum of 71 dogs with tumors were compared with those of 52 healthy dogs by performing enzyme-linked immunosorbent assay (ELISA). Results: The ELISA results revealed higher circulating PD-1 and PD-L1 levels in dogs with tumors (2.9 [2.2-3.7] ng/mL; median [IQR] and 2.4 [1.4-4.4] ng/mL, respectively) than in healthy dogs (2.4 [1.9-3.0] ng/mL; p = 0.012 and 1.4 [0.9-2.1] ng/mL; p < 0.001, respectively). Especially, there was a significant difference in circulating PD-1 levels between healthy dogs and dogs with malignant epithelial tumors (2.4 [1.9-3.0] ng/mL and 3.1 [2.6-4.4] ng/mL, respectively; p < 0.01). In addition, there was a significant difference in circulating PD-L1 levels between healthy dogs and dogs with lymphomas (1.4 [0.9-2.1] ng/mL and 2.7 [1.6-5.8] ng/mL, respectively; p < 0.001). Conclusion: This study indicates that circulating PD-1 and PD-L1 have potential as tumor diagnostic biomarkers in dogs with tumors.

In vitro micropropagation of radish (Raphanus sativus L.) using callus induction and plant regeneration (캘러스 유기와 식물체 재분화를 이용한 무의 기내 대량증식)

  • You Kyoung Kim;Sug Youn Mo;Su Bin Choi;Han Yong Park
    • Journal of Plant Biotechnology
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    • v.50
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    • pp.155-162
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    • 2023
  • Radish (Raphanus sativus L.), a root vegetable grown worldwide, is consumed in several ways. In the cross between parental lines to produce F1 seeds of radish, the problem of low purity may arise because of pollen contamination. Therefore, we aimed to establish conditions for callus induction and regeneration so that in vitro cultured plants could be used for the propagation of stock seeds. The most effective hormone combination containing various concentrations of 2,4-D, TDZ, and kinetin was selected for callus induction using radish hypocotyl, and the induced calli were transferred to two types of hormone media to investigate the optimal conditions for shoot regeneration of the callus. The combination of 1 mg/L 2,4-D + 0.05 mg/L kin was the most effective for callus induction of RA2 and RA10, 1 mg/L 2,4-D + 0.1 mg/L kin + 0.025 mg/L TDZ of RA4, and 1 mg/L 2,4-D + 0.2 mg/L kin of RA30. Shoot regeneration of the RA4 callus occurred in both shoot regeneration media, but the frequency was much higher in the 5H+1B medium (1 mg/L NAA + 0.1 mg/L 2,4-D + 1 mg/L IPA + 0.02 mg/L GA3 + 2 mg/L zeatin + 1 mg/L BA). For the in vitro micropropagation of radish, the conditions selected in this study can assist in the propagation and maintenance of stock seeds to produce F1 seeds.

Template Synthesis and Characterization of Four- and Five-Coordinate Copper(II) Complexes with Hexaaza Macrotricyclic Ligands 1,3,6,9,11,14-Hexaazatricyclo $[12.2.1.1^{6,9}]octadecane(L_1)$ and 1,3,6,10,12,15-Hexaazatricyclo $[13.3.1.1^{6,10}]eicosane(L_1)$

  • Myunghyun Paik Suh;Shin-Geol Kang;Teak-Mo Chung
    • Bulletin of the Korean Chemical Society
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    • v.11 no.3
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    • pp.206-208
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    • 1990
  • Cu(II) hexaazamacrotricyclic complexes $[Cu(L)](ClO_4)_2$ and $[(Cu(L)Cl]ClO_4$, where L = 1,3,6,9,11,14-hexaazatricyclo$[12.2.1.1^{6,9}]octadecane(L_1)$ or 1,3,6,10,12,15-hexaazatricyclo$[13.3.1.1^{6,10}]eicosane(L_2)$, have been prepared by the simple template condensation reactions of triamines, diethylenetriamine for $L_1$, and N-(2-aminoethyl)-1,3-propanediamine for $L_2$, with formaldehyde in the presence of $Cu(OAc)_2\;or\;CuCl_2$. The Cu(II) complexes of $L_1$ contain two 1,3-diazacyclopentane ring moieties and those of $L_2$ contain two 1,3-diazacyclohexane ring moieties that are fused to the 14-membered macrocyclic framework. Spectra indicate that complexes $[Cu(L)](ClO_4)_2\;and\;[Cu(L)Cl]ClO_4$ have square-planar and square-pyramidal chromophores, respectively. square-planar $[Cu(L)](ClO_4)_2$ are remarkably stable against ligand dissociation in acidic aqueous solutions. Square-pyramidal $[Cu(L)Cl]ClO_4$ complexes dissociate their axial Cl-ligands easily in aqueous solutions to form $[Cu(L)H_2O]^{2+}$ species. Infrared and UV/vis absorption spectra of the Cu(II) complexes reveal that Cu-N interactions and the ligand field strengths are significantly weaker in the complexes of $L_2$ than in the complexes of $L_1$.

Studies on Antioxidative Effect and Lactic Acid Bacteria Growth of Persimmon Leaf Extracts (감잎 추출물의 유산균 생육 및 항산화 효과에 관한 연구)

  • Woo Jun-Young;Paek Nam-Soo;Kim Young-Man
    • The Korean Journal of Food And Nutrition
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    • v.18 no.1
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    • pp.28-38
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    • 2005
  • This study was investigated the growth effect of persimmon leaf extracts on various Lactic acid bacteria, the effect as freeze-dry cryoprotectan, by the changes of vitamin C content, electron donating ability, total cell count and SOD-like activity. The total cell count of L. acidophilus MG501, L. brevis MG19, L. bulgaricus MG515, L. lactis MG530 and L. casei MG311 in the absence of persimmon leaf extracts(10%) at 37℃ after 48hr were 3.2×10/sup 9/cfu/mL, 2.9×10/sup 9/cfu/mL, 1.1×10/sup 9/cfu/mL, 1.6×10/sup 9/cfu/mL and 3×10/sup 9/cfu/mL, respectively, and pH and total acidity of those were 3.82∼3.88, and 1.697∼1.842. On the other hand, the total cell count of L. acidophilus MG501, L. brevis MG19, L. bulgaricus MG515, L. lactis MG530 and L. casei MG311 in the presence of persimmon leaf extracts at 37℃ after 48hr were 4.4×10/sup 9/cfu/mL, 4.3×10/sup 9/cfu/mL, 2×10/sup 9/cfu/mL, 3.3×10/sup 9/cfu/mL, and 3.4×10/sup 9/cfu/mL, respectively, and pH and total acidity of those were 3.74∼3.82 and 1.528∼1.805. The total cell counter of lactic acid bacteria in the presence of persimmon leaf extracts(10%) at 37℃ after 48hr higher than those in the absence of persimmon leaf extracts. In freeze-dry chryoprotectan, the survival rate of L. acidphilus MG501 decreased about 30%. In case of L. brevis MG19 and L. bulgaricus MG515, the survival rate decreased about 10%. However, the survival rate of L. lactis MG530 increased about 10% and L. casei MG311 showed the almost same effect. The changes of vitamin C content were the highest in L. lactis MG530(190.26mg/mL) and the lowest in L. acidophilus MG501(56.05 mg/mL). The electron donating ability indicated to L. acidophilus MG501, L. brevis MG19, L. bulgaricus MG515, L. lactis MG530 and L. casei MG311 added by 10% persimmon leaf extracts, respectively. when 10% persimmon leaf extracts were added L. brevis MG19, the electron donating ability is the highest of all lactic acid bacteria. The SOD-like activity of L. acidophilus MG501, L. brevis MG19, L. bulgaricus MG515, L. lactis MG530 and L. casei MG311 showed lower than that of control.

Characterization of L-Galactono-1, 4-lactone Oxidase Purified from Saccharomyces cerevisiae (Saccharomyces cerevisiae에서 분리한 L-Galactono-1, 4-lactone Oxidase의 특성)

  • 이승복;강사욱
    • Korean Journal of Microbiology
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    • v.26 no.1
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    • pp.52-59
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    • 1988
  • A partially purified preparation of L-galactonolactone oxidase which catalyzes the last step of L-ascorbic acid biosynthesis was obtained from Saccharomyces cerevisiae ATCc 26787. The purification procedures included Triton X-100 treatment, protamine sulfate precipitation, ammonium sulfate precipitation, DEAE-Sepharose CL-6B ion exchange chromatography, Sephadex G-150 gel filtration chromatography, and Phenyl-Sepharose CL-4B hydrophobic interaction chromatography. The optimum temperature for the enzyme activity was about $34^{\circ}C$ and the optimum pH was 6.8-7.0. The substrate specificity was confined to L-aldonolactones, L-galactono-1,4-lactone and L-gulono-1,4-lactone. An apparent Km value of 0.294mM with L-galactono-1,4-lactone as a substrate was found. By comparing the substrate specificities of this enzyme with those of isofunctional enzymes of higher plants and animals, it becomes evident that the enzyme of S. cerevisiae ATCC 26787 is rather similar to the L-gulonolactone oxidase of animals than the galactonolactone dehydrogenase of higher plants.

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An experimental study to develop operation technique of solid waste landfill for utilization of biomass (바이오매스 활용형 폐기물 매립지공법 개발을 위한 실험적 연구)

  • Kim, Hye-Jin;Park, Jin-Kyu;Jeong, Min-Kyo;Lee, Nam-hoon
    • Journal of the Korea Organic Resources Recycling Association
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    • v.15 no.1
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    • pp.171-177
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    • 2007
  • In order to investigate the effect of the methanogenic bacteria in bacteria in leachate on the degradability of landfill waste, this study has created 4 cylinder-shape PVC lysimeters (Diameter: 30cm, Height: 200cm, Volume: 140L) and for the biological treatment and recirculation of the leachate, two anaerobic batch reactors (Diameter: 20cm, Height: 30cm) were created. To simulate a conventional landfill, no recycling was done in L1. In L2, 1,068ml of leachate (twice of rainfall amount) was recycled. In L3 and L4, the leachate was anaerobically digested in a dark room (with $35{\pm}1^{\circ}C$) for a week and them recycled by 1,064ml and 2,128ml, respectively, with recycled water only. In terms of cumulative $CH_4$ production, however, L3 and L4 were much higher (three times) than L1 and L2. Between L3 and L4, the latter was 1.23 times higher than the former in terms of cumulative CH4 production. In other words, the more the methanogenic bacteria-activated leachate is recycled, the more active the degradation due to active methane fermentation by the recyled methanogenic bacteria. And methane recovery is different according to the amount of recycled the methanogenic bacteria in leachate.

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Response of broilers to supplementation of branched-chain amino acids blends with different valine contents in the starter period under summer conditions

  • Kop-Bozbay, Canan;Akdag, Ahmet;Atan, Helin;Ocak, Nuh
    • Animal Bioscience
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    • v.34 no.2
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    • pp.295-305
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    • 2021
  • Objective: The objectives of this study were to compare the effects of normal and low protein content (PC) of starter diet supplemented or not with blends of branched-chain amino acids (BCAAs) on growth performance of broilers under summer conditions and to investigate whether these effects altered some quality traits and the characteristics of gastrointestinal tract. Methods: A total of 768 mixed-sex broiler chicks (Ross 308, one-d-old) with an average initial body weight (BW) of 47.6±1.03 g were allocated into six treatments with four replications in 2×3 factorial arrangement. Factors were: PC, normal (N, 22% to d 15); and low (L, 20% to d 15); and added BCAA blends, L-leucine, L-isoleucine, and L-valine at zero (0L:0I:0V); 1.0, 0.25, and 0.25 (4L:1I:1V); or 1.0, 0.25, 0.75 (4L:1I:3V) g/kg of diet. Hence, six dietary treatments were named as N0L:0I:0V, N4L:1I:1V, N4L:1I:3V, L0L:0I:0V, L4L:1I:1V, and L4L:1I:3V. Average indoor temperature and humidity were 32.8℃±1.7℃ and 61.1%±4.12%, respectively. Results: BW, feed conversion ratio (FCR) and carcass weight were not affected by PC, BCCA and their interaction (p>0.05). The L diets decreased the water holding capacity of the breast (p = 0.002) and thigh (p = 0.050) meats and dressing percentage (p = 0.005) compared to the N diets. The 4L:1I:1V diet decreased breast yield compared to the 0L:0I:0V diets (p = 0.041). The effect of PC on feed intake, mortality and gastrointestinal trait weight were depended on the L:I:V ratios under summer conditions due to interactions between factors (p<0.05). The FI and mortality of L4L:1I:1V broilers were lower than those of N4L:1I:1V birds (p<0.05). Conclusion: It was concluded that the blends of BCAAs used failed to improve performance and to promote breast yields, because diets with normal or with reduced protein supplemented or not with BCAAs up to d 15 produced a similar BW and FCR in broilers raised in hot-climate conditions.

Morphological Characterization of 'Ailsa Craig' Tomato Callus and Effect on Plant Regeneration (`Ailsa Craig` 토마토 캘러스의 형태학적 특성과 식물체 재분화에 미치는 영향)

  • Seong, Eun-Soo;Wang, Myeong-Hyeon
    • Applied Biological Chemistry
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    • v.50 no.4
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    • pp.253-256
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    • 2007
  • In an attempt to optimize the in vitro-regeneration conditions necessary for the genetic manipulation of tomato species, we examined 'Ailsa Graig' cultivar of Lycopersicon for regeneration ability. The basal medium used for callus formation and shoot regeneration was MS (MS + vitamin) supplemented with six combinations of zeatin 2 mg/l, zeatin 2 mg/l + IAA 0.1 mg/l, zeatin 2 mg/l + IAA 0.5 mg/l, zeatin 4 mg/l, zeatin 4 mg/l + IAA 0.1 mg/l and zeatin 4 mg/l + IAA 0.5 mg/l. When all conditions tested were considered, however, only zeatin 2 mg/l was shown to be the best in shoot regeneration. The morphological characterization from in vitro-cultured callus of Lycopersicon esculentum L. var. 'Ailsa Craig' was investigated with scanning electron microscope (SEM). The surfaces of in vitro-cultured callus had well-defined epidermal cell in condition of zeatin 2 mg/l, but those of different treatments were twisted. These results suggested that shape of callus was involved in efficiency of shoot regeneration in tomato 'Ailsa Craig'.

Elution Profiles of Volatile Compounds and Free Amino Acids during Alcohol Soaking of Garlic(Allum sativum L.) (마늘의 alcohol 침지 중 휘발성 향기성분과 침출유리아미노산 함량)

  • Lee, Young-Guen
    • Journal of Life Science
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    • v.17 no.2 s.82
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    • pp.286-292
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    • 2007
  • Free amino acids and volatile compounds of fresh garlic and its liqueur were investigated to search elution profile of those components as basic data for development of garlic liqueur. The garlic was soaked in 20% alcohol solution and then sampled every week for 5 weeks. The major free amino acids were L-aspartic acid, L-glutamic acid, L-arginine, L-alanine, L-proline, L-asparagine and L-serine. Neutral amino acids such as L-threonine, L-proline, L-valine and L-leucine, and aromatic amino acids such as tyrosine and phenylalanine were eluted over 80% of those content in fresh garlic after 3 weeks of soaking, but acidic, basic and sulfur containing amino acids were below 80% even after 5 weeks. Sulfide compounds such as diallyl trisulfide, diallyl disulfide, methyl allyl disulfide, 2-vinyl-4H-1,3-dithi in, 3-vinyl-3,4-dihydro-1,2-dithiin, 3,5-diethyl-1,24-trithiolane, isobutyl isothiocyanate and diallyl sulfide were identified as major volatile compounds of fresh garlic by using GC/MS. Among volatile compounds of fresh garlic, allyl alcohol, diallyl disulfide, 3,5-diethyl-1,2,4-trithiolane, diallyl trisulfide and 3,4-dimethoxy furan were eluted to liqueur, but those compounds except 3,5-diethyl-1,2,4-trithiolane were lowered in liqueur during soaking. Furfural, 5-methylfurfural, 5-hydroxymethylfurfural, dimethyl pyrazine, furfuryl alcohol, 3-hydroxy-2-bytanone and 2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyr-an-4-one were generated newly and their content increased in liqueur during soaking.