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Physical Properties of the Nonstoichiometric Perovskite $Dy_{1-x}Sr_xCoO_{3-y}$ System

  • 정수경;김민규;김규홍;여철현
    • Bulletin of the Korean Chemical Society
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    • v.17 no.9
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    • pp.794-798
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    • 1996
  • Solid solutions of the nonstoichiometric Dy1-xSrxCoO3-y system with the compositions of x=0.00, 0.25, 0.50, 0.75, and 1.00 have been synthesized by the solid state reaction at 1000 ℃ under atmospheric air pressure. The crystallographic structures of the solid solutions are analyzed by the powder X-ray diffraction patterns at room temperature. The analyses assign the compositions of x=0.00 and 0.25 to the orthorhombic system with space group of Pbnm/D2h16, the compositions of x=0.50 and 0.75 to the tetragonal system like a typical SrCoO2.86, and the composition of x=l.00 or SrCoO2.50 to the brownmillerite type system with space group of I**a. The reduced lattice volumes increase with x value due to the larger radius of Sr2+ ion than that of Dy3+ ion. The mole ratio of Co4+ ion to total Co ion with mixed valence state between Co3+ and Co4+ ions at B sites or τ value has been determined by an iodometric titration. All the samples except for the DyCoO3 compound show the mixed valnce state and thus the composition of x=0.50 has the maximum τ value in the system. The oxygen vacancies increasing with x value are randomly distributed over the crystal lattice except for the composition of x=l.00 which have the ordering of the oxygen vacancies. The nonstoichiometric chemical formulas of the Dy1-xSrxCo3+1-τCo4+τO3-(x-τ)/2 system are formulated from the x, τ, and y values. The electrical conductivity in the temperature range of 100 to 900 K increases with τ value linearly because of positive holes of the Co4+ ions in π* band as a conducting carrier. The activation energy of the x=0.50 as Ea=0.17 eV is minimum among other compouds. Broad and high order transition due to the overlap between σ* and π* bands broadened by the thermal activation is observed near 1000 K and shows a low temperature-semiconducting behavior. Magnetic properties following the Currie-Weiss law show the low to high spin transition in the cobaltate perovskite. Especially, the composition of x=0.75 presents weak ferromagnetic behavior due to the Co3+-O2--Co4+ indirect superexchange interaction.

The effect of the divalant Metal ions on the ATPase activity in Myofibrillar protein of the Muscle of Rabbit fed Vegetable Oils. (식물성 식용유로 사육한 토끼근육의 근원섬유 단백질의 ATPase 활성에 미치는 금속의 영향)

  • 남현근
    • Microbiology and Biotechnology Letters
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    • v.8 no.2
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    • pp.113-117
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    • 1980
  • The effects of divalant metal ions on the ATPase activity were studied by using my of ibrillar protein of rabbit (Chin-Chilla species) fed with vegetable oils. The results obtained were as follows : 1. The ATPase activity in myofibrillar protein of the is not significant to Rabbit exhibited a common biohapsic respnse, such as the ATPase activity is high at a lower ionic strength and low at a higher ionic strength. 2. The effect of EDTA on the ATPase activity of Myofibrillar protein extracted from Rabbit fed vegetable oils was tested by using various concentrations. The ATPase activity was inhibited from 0.2mM and over concentration of EDTA. 3. The ATPase activity in Myofibrillar protein was decreased remarkably in 0.2mM and over concentration for $Mg^{2+}$, and in 1.0mM and over concentration for $Ca^{2+}$. 4. in vitro, the digestibilities in A, B, C and D groups of Rabbit muscle treated with Papsin and Trypsin for 30 minutes at 36$^{\circ}C$ water bath were 71.66%, 73.87% ; 70.62%, 77.93% ; 67.93%, 76.52% ; and 86.79%, 90.22%, respectively.y.

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Removal of Chromium (VI) by Escherichia coli Cells Expressing Cytoplasmic or Surface-Displayed ChrB: a Comparative Study

  • Zhou, Xiaofeng;Li, Jianghui;Wang, Weilong;Yang, Fan;Fan, Bingqian;Zhang, Chenlu;Ren, Xiaojun;Liang, Feng;Cheng, Rong;Jiang, Fengying;Zhou, Huaibin;Yang, Juanjuan;Tan, Guoqiang;Lyu, Jianxin;Wang, Wu
    • Journal of Microbiology and Biotechnology
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    • v.30 no.7
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    • pp.996-1004
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    • 2020
  • Various genetically engineered microorganisms have been developed for the removal of heavy metal contaminants. Metal biosorption by whole-cell biosorbents can be enhanced by overproduction of metal-binding proteins/peptides in the cytoplasm or on the cell surface. However, few studies have compared the biosorption capacity of whole cells expressing intracellular or surface-displayed metal-adsorbing proteins. In this study, several constructs were prepared for expressing intracellular and surface-displayed Ochrobactrum tritici 5bvl1 ChrB in Escherichia coli BL21(DE3) cells. E. coli cells expressing surface-displayed ChrB removed more Cr(VI) from aqueous solutions than cells with cytoplasmic ChrB under the same conditions. However, intracellular ChrB was less susceptible to variation in extracellular conditions (pH and ionic strength), and more effectively removed Cr(VI) from industrial wastewater than the surface-displayed ChrB at low pH (<3). An adsorption-desorption experiment demonstrated that compared with intracellular accumulation, cell-surface adsorption is reversible, which allows easy desorption of the adsorbed metal ions and regeneration of the bioadsorbent. In addition, an intrinsic ChrB protein fluorescence assay suggested that pH and salinity may influence the Cr(VI) adsorption capacity of ChrB-expressing E. coli cells by modulating the ChrB protein conformation. Although the characteristics of ChrB may not be universal for all metal-binding proteins, our study provides new insights into different engineering strategies for whole-cell biosorbents for removing heavy metals from industrial effluents.

Simultaneous Determination of Five Porphyrins in Human Urine and Plasma Using High Performance Liquid Chromatography-Tandem Mass Spectrometry

  • Hur, Yeoun;Tae, Sookil;Koh, Yun-Joo;Hong, Sung-Hyun;Yoon, Young Ho;Jang, Haejong;Kim, Sooji;Kim, Kyeong Ho;Kang, Seung Woo;Lee, Youngshin;Han, Sang Beom
    • Mass Spectrometry Letters
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    • v.5 no.2
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    • pp.42-48
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    • 2014
  • A specific and sensitive liquid chromatography-electrospray ionization tandem mass spectrometry method (LC-ESI-MS/MS) was developed and validated for the simultaneous quantification of porphyrins (coproporphyrin, pentacarboxylporphyrin, hexacarboxylporphyrin, heptacarboxylporphyrin, and uroporphyrin) in human plasma and urine. Acidified plasma samples and urine samples were prepared by using liquid-liquid extraction using ethyl acetate and protein precipitation with acetonitrile, respectively. The separation was achieved onto a Synergi Fusion RP column ($150mm{\times}2.0mm$, $4{\mu}m$) with a gradient elution of mobile phase A (0.1% formic acid in 2 mmol/L ammonium acetate, v/v) and mobile phase B (20% methanol in acetonitrile, v/v) at a flow rate of $450{\mu}L$/min. Porphyrins and the internal standard (IS), coproporphyrin I-$^{15}N_4$, were detected by a tandem mass spectrometer equipped with an electrospray ion source operating in positive ion mode. Multiple reaction monitoring (MRM) transitions of the protonated precursor ions and the related product ions were optimized to increase selectivity and sensitivity. The proposed method was validated by assessing selectivity, linearity, limit of quantification (LOQ), precision, accuracy, recovery, and stability. The calibration curves were obtained in the range of 0.1-100 nmol/L and the LOQs were estimated as 0.1 nmol/L for all porphyrins. Results obtained from the validation study of porphyrins showed good accuracy, precision, recovery, and stability. Finally, the proposed method was successfully applied to clinical studies on the autism spectrum disorder (ASD) diagnosis of 203 Korean children.

Desmutagenicity of the Enzymatic Browning Reaction Products Which Obtained from Prunus salicina (yellow) Enzyme and Polyphenol Compounds (재래종 황색자두효소 갈변반응 생성물의 돌연변이 억제작용)

  • Ham, Seung-Shi
    • Applied Biological Chemistry
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    • v.30 no.1
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    • pp.71-76
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    • 1987
  • The mutagenicity and desmutagenicity on enzymatic browning reaction products which obtained from prunes salicina (yellow) enzyme and polyphenol compounds were carried out. In the rec-assay on Bacillus subtilis strains H17 and M45, the enzymatic browning reaction products of pyrogallol, hydroxyhydroquinone, 3,4-dihydroxytoluene and catechol of $10^{-2}M$ did not showed mutagenicity. In the effects of various metal ions on the rec-assay, the enzymatic browning reaction products of pyrogallol showed mutagenic activity by $Fe^{3+},\;Mn^{2+},\;Zn^{2+},\;Ni^{2+}$ and $Al^{3+}$. In the enzymatic browning reaction products of hydroxyhydroquinone, $Cu^{2+},\;Mn^{2+}$ and $Pb^{2+}$ were effected in mutagenic action and the enzymatic browning reaction products of catechol was effected in mutagenic action by $Mn^{2+}$. In the DNA-breaking action of enzymatic browning reaction products of pyrogallol, hydroxyhydroquinone, 3,4-dihyroxytoluene and catechol did not show, DNA-breaking action. In the effects of various metal ions on the DNA-breaking action of enzymatic browning reaction products, $Cu^{2+}$ showed DNA-breaking action. In the mutagenicity test on Sal. typhimurium strains TA98 and TA 100 with S-9 mix, 4 kinds of browned substances did sot shove muragenicity, all the browned substances showed strong desmutagenic activity in the presence of benzo $({\alpha})-pyrene$ with S-9 mix.

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Study on of Process Parameters for Adsorption of Reactive Orange 16 Dye by Activated Carbon (활성탄에 의한 Reactive Orange 16 염료 흡착에 대한 공정 파라미터 연구)

  • Lee, Jong Jib
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.21 no.7
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    • pp.667-674
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    • 2020
  • The adsorption of reactive orange 16 (RO 16) dye by activated carbon was investigated using the amount of adsorbent, pH, initial concentration, contact time and temperature as adsorption variables. The investigated process parameters were separation coefficient, rate constant, rate controlling step, activation energy, enthalpy, entropy, and free energy. The adsorption of RO 16 was the highest at pH 3 due to the electrostatic attraction between the cations (H+) on the surface of the activated carbon and the sulfonate ions and hydroxy ions possessed by RO 16. Isotherm data were fitted into Langmuir, Freundlich and Temkin isotherm models by applying the evaluated separation factor of Langmuir (RL=0.459~0.491) and Freundlich (1/n=0.398~0.441). Therefore, the adsorption operation of RO 16 by activated carbon was confirmed as an appropriate removal method. Temkin's adsorption energy indicated that this adsorption process was physical adsorption. The adsorption kinetics studies showed that the adsorption of RO 16 follows the pseudo-second-order kinetic model and that the rate controlling step in the adsorption process was the intraparticle diffusion step. The positive enthalpy change indicated an endothermic process. The negative Gibbs free energy change decreased in the order of -3.16 <-11.60 <-14.01 kJ/mol as the temperature increased. Therefore, it was shown that the spontaneity of the adsorption process of RO 16 increases with increasing temperature.

Structural analysis and thermal expansion property of Cu doped LSM for SOFCs (Cu가 도핑된 LSM의 구조분석과 열팽창특성 연구)

  • Noh, Tai-Min;Ryu, Ji-Seung;Kim, Jin-Seong;Jeong, Cheol-Weon;Lee, Hee-Soo
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.21 no.4
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    • pp.175-180
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    • 2011
  • The doping effect of Cu in the Sr-doped lanthan manganites (LSM) has been investigated in terms of structural analysis and thermal expansion coefficient (TEC). The $La_{0.8}Sr_{0.2}Mn_{1-x}Cu_xO_3$ ($0{\leq}x{\leq}0.3$) were prepared by solid state reaction method and their crystal structure and TEC were measured. A decrease in the lattice parameters and the TEC were observed with increase eu content, whereas they were decreased for x = 0.3. For $0{\leq}x{\leq}0.2$, the decrease of the lattice parameter and the TEC with increase Cu content were attributed to the reduction of ionic radius of Cu ions due to the presence of $Cu^{3+}$ ions. For x = 0.3, however, the increase was originated from the formation of oxygen vacancies due 10 the presence of $Cu^{2+}$ and $Mn^{4+}$.

Neuropeptides in Clinical Psychiatric Research : Endorphins and Cholecystokinins (정신질환에 있어서의 신경펩타이드 연구 - Endorphin과 cholecystokinin을 중심으로 -)

  • Kim, Young Hoon;Shim, Joo Chul
    • Korean Journal of Biological Psychiatry
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    • v.5 no.1
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    • pp.34-45
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    • 1998
  • We provide the reader with a brief introduction to the neurobiology of neuropeptides. Several comprehensive reviews of the distribution and neurochemical, neurophysiological, neuropharmacological and behavioral effects of the major neuropeptides have recently appeared. In reviews of the large number of neuropeptides in brain and their occurance in brain regions thought to be involved in the pathogenesis of major psychiatric disorders, investigators have sought to determine whether alternations in neuropeptide systems are associated with schizophrenia, mood disorders, anxiety disorders, alcoholism and neurodegenerative disease. There is no longer any doubt that neuropeptide-containing neurons are altered in several neuropsychiatric disorders. One of the factors that has hindered neuropeptide research to a considerable extent is the lack of pharmacological agents that specifically alter the synaptic availability of neuropeptides. With the exception of naloxone and naltrexone, the opiate-receptor antagonists, there are few available neuropeptide- receptor antagonists. Two independent classes of neuropeptide-receptor antagonists has been expected to be clinically useful. Naltrexone, a potent ${\mu}$-receptor antagonist, has been used successfully to reduce the need for alcohol consumption. And cholecycstokinin antagonists are now in development as a new class of anxiolytics, which would be expected to be free from tolerance and physical dependence and lack of sedation. In this review, we deal with these two kinds of neuropeptide system, the opioid system and cholesystokinins in the brain. The role of opioid systems in the reinforcement after alcohol consumtion and that of cholesystokinins in the pathogenesis of anxiety will be discussed briefly. As we know, the future for neuropeptides in psychiatry remains bright indeed.

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Synthesis, Sytructure, and Magnetic Properties of One-Dimensional Thiophoshates, $Al_2NiP_2S_6$ (A=Rb, Cs) (1차원 구조를 갖는 Thiophoshates, $Al_2NiP_2S_6$ (A=Rb, Cs)의 합성, 구조 및 자기적 성질)

  • Dong, Yong Kwan;Lee, Kun Soo;Yun, Ho Seop;Hur, Nam Hwi
    • Journal of the Korean Chemical Society
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    • v.45 no.3
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    • pp.242-246
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    • 2001
  • The quaternary thiophosphates, $A_2NiP_2S_6$ (A=Rb, Cs), have been synthesized with halide fluxes and structurally characterized by single-crystal X-ray diffraction technique. These compounds crystallize in the space group $C_{2h}^5-P2_1/n$ of the monoclinic system with two formula units in a cell of dimensions a=5.960(2), b=12.323(4), $c=7.491(3)\AA$, $\beta=97.05(3)^{\circ}$, and $V=546.0(3)\AA^3$ for Rb2NiP2S6 and a=5.957(4), b=12.696(7), $c=7.679(4)\AA$, $b=93.60(5)^{\circ}$, and $V=579.7(5)\AA^3$ for $Cs_2NiP_2S_6.$ These compounds are isostructural. The structure of $Cs_2NiP_2S_6$ is made up of one-dimensional $_\infty^1[NiP_2S_6^{2-}]$ chains along the a axis and these chains are isolated by $Cs^+$ ions. The Ni atom is octahedrally coordinated by six S atoms. These Ni$S_6$ octahedral units are linked by sharing three m-S atoms of the $[P_2S_6^{4-}]$ anions to form the infinite one-dimensional $_\infty^1[NiP_2S_6^{2-}]$ chain. For $Cs_2NiP_2S_6$, the magnetic susceptibility reveals an antiferromagnetic exchange interaction below 8K,which corresponds to the Neel temperature ($T_N$). Above $T_N$, this compound obeys Curie-Weiss law. The magnetic moment, C, and ${\theta}forCs_2NiP_2S_6$ are 2.77 B.M., 0.9593 K, and -19.02 K, respectively. The effective magnetic moment obtained from the magnetic data is agreed with the spin-only value of $Ni^{2+}d^8$(2.83 B.M.) system.

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Formation of Au Particles in Cu2-xICu2IIO3-δ (x ≈ 0.20; δ ≈ 0.10) Oxide Matrix by Sol-Gel Growth

  • Das, Bidhu Bhusan;Palanisamy, Kuppan;venugopal, Potu;Sandeep, Eesam;Kumar, Karrothu Varun
    • Journal of the Korean Chemical Society
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    • v.61 no.1
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    • pp.29-33
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    • 2017
  • Formation of Au particles in nonstoichiometric $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$) oxide from aniline + hydrochloric acid mixtures and chloroauric acid in the ratios 30 : 1; 60 : 1; 90 : 1 (S1-S3) by volume and 0.01 mol of copper acetate, $Cu(OCOCH_3)_2.H_2O$, in each case is performed by sol-gel growth. Powder x-ray diffraction (XRD) results show Au particles are dispersed in tetragonal nonstoichiometric dicopper (I) dicopper (II) oxides, $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$). Average crystallite sizes of Au particles determined using Scherrer equation are found to be in the approximate ranges ${\sim}85-140{\AA}$, ${\sim}85-150{\AA}$ and ${\sim}80-150{\AA}$ in S1-S3, respectively which indicate the formation of Au nano-micro size particles in $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$) oxides. Hysteresis behaviour at 300 K having low loop areas and magnetic susceptibility values ${\sim}5.835{\times}10^{-6}-9.889{\times}10^{-6}emu/gG$ in S1-S3 show weakly ferromagnetic nature of the samples. Broad and isotropic electron paramagnetic resonance (EPR) lineshapes of S1-S4 at 300, 77 and 8 K having $g_{iso}$-values ${\sim}2.053{\pm}0.008-2.304{\pm}0.008$ show rapid spin-lattice relaxation process in magnetic $Cu^{2+}$ ($3d^9$) sites as well as delocalized electrons in Au ($6s^1$) nano-micro size particles in the $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$) oxides. Broad and weak UV-Vis diffuse reflectance optical absorption band ~725 nm is assigned to $^2B_{1g}{\rightarrow}^2A_{1g}$ transitions, and the weak band ~470 nm is due to $^2B_{1g}{\rightarrow}^2E_g$ transitions from the ground state $^2B_{1g}$(${\mid}d_{x^2-y^2}$>) of $Cu^{2+}$ ($3d^9$) ions in octahedral coordination having tetragonal distortion.