• Title/Summary/Keyword: Ni(II)

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Cyanide-bridged Trinuclear and Ethylenediamine-bridged One-dimensional Cobalt(III)-Manganese(II) Complexes: Synthesis, Crystal Structures and Magnetic Properties

  • Zhang, Daopeng;Zhang, Lifang;Zhao, Zengdian;Ni, Zhonghai
    • Bulletin of the Korean Chemical Society
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    • v.32 no.8
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    • pp.2544-2548
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    • 2011
  • Two pyridinecarboxamide cobalt dicyanide building blocks and Mn(III) compounds have been employed to assemble cyanide-bridged heterometallic complexes, resulting in three trinuclear cyanide-bridged $Co^{III}-Mn^{II}$ complexes: $\{[Mn(MeOH)_4][Co(bpb)(CN)_2]_2\}{\cdot}2MeOH{\cdot}2H_2O$ (1), $\{[Mn(MeOH)_4][Co(bpmb)(CN)_2]_2\}{\cdot}2MeOH{\cdot}2H_2O$ (2) and $\{[Mn(DMF)_2(en)_2][Co(bpb)(CN)_2]_2\}{\cdot}2DMF{\cdot}H_2O$ (3) ($bpb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)benzenate, $bpmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate, en = ethylenediamine). Single crystal X-ray diffraction analysis shows their similar sandwich-like structures, in which the two cyanide-containing building blocks act as monodentate ligands through one of their two cyanide groups to coordinate the Mn(II) center. For complex 3, it was further linked into one-dimensional structure by ethylenediamine acting as bridges. Investigation of the magnetic properties of complex 3 reveals weak antiferromagnetic coupling between the neighboring Mn(II) centers through the bridging ethylenediamine molecule. A best-fit to the magnetic susceptibilities of complex 3 gave the magnetic coupling constant J = -0.073(2) $cm^{-1}$.

Separation of Optical Isomers of DNS-Amino Acids in High-Performance Liquid Chromatography (고성능 액체크로마토 그래피에 의한 Dansyl-아미노산 광학이성질체의 분리)

  • Sun Haing Lee;Tae Sub O;Kyung Sug Park
    • Journal of the Korean Chemical Society
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    • v.30 no.2
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    • pp.216-223
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    • 1986
  • Separation of optical isomers of DNS derivatized amino acids by a reversed-phase high-performance liquid chromatography has been studied by adding a complex of an optically active amino acid (L-arginine) with the metal ion (Cu(II), Zn(II), Cd(II), Ni(II)) to the mobile phase. The separations are affected by the concentrations of acetonitrile, chelate and buffer. They are also affected by the pH and the kinds of metal and buffer. A separation mechanism, which is based on steric effect of the ligand exchange reaction for the formation of ternary complexes by the D,L-DNS-amino acids and the chiral additive associated with the stationary phase, is proposed to interpret the elution behaviors of D, L-dansyl-amino acids.

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Catalytic Activity of Metal-phthalocyanine Bonded on Polymer for Decomposition of Hydrogen Peroxide (고분자에 결합된 금속-프탈로시아닌의 과산화수소수 분해반응에 대한 촉매활성)

  • KimKong Soo 김공수;Yong Chul Chun;Young Woo Lee;Sang Ho Lee
    • Journal of the Korean Chemical Society
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    • v.33 no.6
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    • pp.662-668
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    • 1989
  • The decomposition reaction of hydrogen peroxide was carried out by using metal-4,4',4",4"'-tetraaminophthalocyanine [Mt-$PcNH_2$, Mt = Fe(III), Co(II)] supported on poly (styrene-co-methacrylic acid), in heterogeneous aqueous system. These catalysts showed a catalse-like activity and Fe(III)-$PcNH_2$ supported on the copolymer was particularly effective for the decomposition of hydrogen peroxide. It was found that the rate of decomposition increased smoothly in the higher pH region and catalytic reaction was interfered by adding $CN^-,\;CNS^-,\;{C_2O_4}^{-2},\;I^-$ ions. The kinetics of the catalytic reaction was also investigated and the reaction proceeds according to the Michaelis-Menten type mechanism.

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Studies on Solvent Sublation of Trace Heavy Metals by Continuous Flow System as Ternary Complexes of 1,10-Phenanthroline and Thiocyanate Ion

  • Kim, Young-Sang;Choi, Yoon-Seok;Lee, Won
    • Bulletin of the Korean Chemical Society
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    • v.24 no.12
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    • pp.1775-1780
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    • 2003
  • A continuous flow system has been developed to determine trace Cu(II), Mn(II), Ni(II) and Zn(II) in a large volume of water samples by a solvent sublation technique. The mixed solution of 1,10-phenanthroline(phen) and thiocyanate ion was used as ligands for the formation of their ternary complexes. The continuous system was constructed in this laboratory with a peristaltic pump, a mini shaker, three mixing bottles and a flotation cell by connecting each part with a polyethylene tube. The flotation conditions such as the flow rate of sample solution and the injection rates of ligand, buffer and surfactant solutions have been investigated to obtain the best sublation efficiencies. Each solution flowed into the flotation cell through each polyethylene tube by the peristaltic pumps. The ternary complexes were floated and extracted into MIBK in a flotation cell of 2 L by bubbling a nitrogen gas. The absorbances of extracted analytes in MIBK were directly measured by graphite furnace-AAS. The concentrations of 1,10-phenanthroline and thiocyanate ion were $2.6\;{\times}\;10^{-3}$ M and $2.3\;{\times}\;10^{-2}$ M in the mixed solution, respectively. The pH of sample solution was adjusted to 5.0 with a buffer solution and 1%(m/v) sodium lauryl sulphate solution was added as a surfactant to support the effective flotation of the complexes. The $N_2$ gas was bubbled at 30 mL/min for 90 minutes for 20 L of sample. Reproducible results of less than 10% RSD and recoveries of 80-120% could be obtained in real samples.

Mossbauer Spectroscopic Study of La2-2xSr2xCu1-xFexO4-y(0≤x≤0.5) Solid-solution

  • Park, Jung-Chul;Byeon, Song-Ho;Kim, Don;Lee, Choong-Sub
    • Bulletin of the Korean Chemical Society
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    • v.25 no.1
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    • pp.97-100
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    • 2004
  • Tetragonal $K_2NiF_4$-type $La_{2-2x}Sr_{2x}Cu_{1-x}Fe_xO_{4-y}$ solid-solution have been synthesized by citrate based sol-gel method. The valence state of iron was determined by Mossbauer spectroscopy and subsequent iodometric titration clearly showed that the copper ions in this solid-solution are in the mixed valence state Cu(II/III). When x ${\geq}$ 0.3, Fe(III) is competing with the mixture of Cu(II) and Cu(III) and $La_{2-2x}Sr_{2x}Cu_{1-x}Fe_xO_{4-y}$ exhibits a metallic character. No evidence for Cu(II)-O-Fe(IV) ${\leftrightarrow}$ Cu(III)-O-Fe(III) valence degeneracy was observed. In contrast, a small amount of Fe(IV) is observed with increasing x (x = 0.4 and 0.5), revealing a semiconducting behavior. These results suggest that the electronic interaction of Cu(III)-O-Fe(III) contributes greatly to the metallic character, while the electronic interaction of Cu(II)-O-Fe(IV) deteriorates the metallic character of $La_{2-2x}Sr_{2x}Cu_{1-x}Fe_xO_{4-y}$.

An Intravenous Replenishment of Salivary Components and Dry Forage Intake in Freely Drinking Large-type Goats

  • Sunagawa, K.;Hashimoto, T.;Izuno, M.;Hashizume, N.;Okano, M.;Nagamine, I.;Hirata, T.
    • Asian-Australasian Journal of Animal Sciences
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    • v.21 no.4
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    • pp.538-546
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    • 2008
  • Large-type goats eating dry forage secreted large volumes of saliva which resulted in the loss of $NaHCO_3$ from the blood and decreased plasma volume (hypovolemia). This research investigated whether or not the loss of $NaHCO_3$ from the blood and hypovolemia brought about by dry forage feeding actually depresses feed intake in large-type goats under free drinking conditions. The present experiment consisted of three treatments (NI, ASI, MI). All treatments in this experiment were carried out under free drinking conditions. In the NI control (NI), a solution was not infused. In the ASI treatment, i.v. infusion of artificial saliva was initiated 2 h before feeding and was continued for a total of 3 h concluding 1 h after the commencement of the feeding perod. In the MI treatment, mannitol solution was infused to replenish only water lost from the blood in the form of saliva. The hematocrit and plasma total protein concentrations during feeding in the NI control were observed to be higher than pre-feeding levels. This indicated that dry forage feeding-induced hypovolemia was caused by the accelerated secretion of saliva during the initial stages of feeding in freely drinking large-type goats. Increases in hematocrit and plasma total protein concentrations due to dry forage feeding were significantly suppressed by the ASI treatment. While hematocrit during feeding in the MI treatment was significantly lower than the NI control, plasma total protein concentrations were not different. From these results, it is clear that the MI treatment was less effective than the ASI treatment in mitigating the decreases in plasma volume brought about by dry forage feeding. This indicates that plasma volume increased during dry forage feeding in the ASI treatment which inhibited production of angiotensin II in the blood. The ASI treatment lessened the levels of suppression on dry forage feeding, but the MI treatment had no effect on it under free drinking conditions. The results indicate that despite the free drinking conditions, increases in saliva secretion during the initial stages of dry forage feeding in large-type goats caused $NaHCO_3$ to be lost from the blood into the rumen which in turn caused a decrease in circulating plasma volume and resulted in activation of the renin-angiotensin system and thus feeding was suppressed.

Inhibitory Actions of Quercetin and Rutin on $Fe^{2+}-induced$ Lipid Peroxidation ($Fe^{2+}$에 의한 지질 과산화에 있어서 Quercetin과 Rutin의 억제 작용)

  • Chung, Jin-Hee;Lee, Chung-Soo;Shin, Yong-Kyoo;Lee, Kwang-Soo
    • The Korean Journal of Pharmacology
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    • v.27 no.1
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    • pp.69-80
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    • 1991
  • Inhibitory effects of quercetin and rutin on lipid peroxidation of microsomes caused by iron(II) were investigated with respect to the scavenging action for oxygen radicals produced during oxidation of iron and the chelating action for iron. Lipid peroxidation by $Fe^{2+}$ alone was markedly inhibited by quercetin or rutin in a dose dependent fashion. Lipid peroxidation by ascorbate or NADPH in the presence of $Fe^{2+}$ was almost completely inhibited by both quercetin and rutin. The peroxidative action of $Fe^{2+}$ was inhibited by SOD and DABCO and slightly inhibited by catalase, DMSO and mannitol. Quercetin and rutin inhibited oxidation of $Fe^{2+}$ which is responsible for DETAPAC and they showed a significant initial chelating effect. Quercetin and rutin effectively inhibited lipid peroxidation by $H_{2}O_{2}$ and decomposed $H_{2}O_{2}$. Both $OH{\cdot}$ production in the presence of $Fe^{2+}$ and $^1O_2$ production by U.V. irradiation were inhibited by quercetin and rutin. Lipid peroxidations by $Cd^{2+},\;Cu^{2+},\;Ni^{2+},\;Pb^{2+}$ and $Zn^{2+}$ were almost completely inhibited by quercetin. Quercetin and rutin significantly prevented the loss of sulfhydryl groups by $Fe^{2+}$. These results suggest that inhibitory effects of quercetin and rutin on the peroxidative action of $Fe^{2+}$ in the presence or absence of ascorbate and NADPH may be attributable to their scavenging action on reactive oxygen species and chelating action on iron.

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Neutron fluence measurement at HANARO using fluence monitor method (Fluence Monitor를 이용한 HANARO 노심 내 중성자 플루언스 측정)

  • Lee, Seung-Kyu;Jo, Kwang-Ho;Choo, Kee-Nam;Park, Jin-Suk;Kim, Yong-Kyun
    • Journal of Radiation Protection and Research
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    • v.36 no.4
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    • pp.200-208
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    • 2011
  • The neutron fluence measurement and evaluation technology is very important for material irradiation test. The most essential technology in this study is the neutron irradiation evaluation method using a fluence monitor. The fluence monitors were fabricated with metal wires of the purity ${\geq}$ 99.9%, whose dimensions were 0.1mm diameter, about 3 mm length, and around 150-200 ${\mu}g$ mass range. Three wire samples (Fe, Ni, Ti) were prepared for one irradiation aluminum capsule. Five capsules were irradiated in the OR5 hole of the HANARO reactor at 30 MW power for about 25 days. After irradiation tests, radiation activities were measured with the high purity germanium (HPGe) detector. The reaction rates were calculated by using the measured radiation activity data, and then neutron fluence were obtained from the reaction rates and the weighted neutron cross section with calculated neutron spectrum at the fluence monitor position.

Comparison of Blood Metal Concentration in Ohjeok-san(Wuji-san) Treated Rats - Dose-Response Relationship and Mechanism - (오적산을 투여한 흰쥐의 혈액중 금속농도 비교에 관한 연구 - 용량-반응관계와 기전을 중심으로 -)

  • 이정렬;이선동
    • The Journal of Korean Medicine
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    • v.23 no.1
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    • pp.67-82
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    • 2002
  • Objectives: In recent years, extensive focus has been laid on adulteration of herbal medicine with heavy metals. This may be mainly due to soil contamination by environmental pollution. The objective of this study is to identify the contents of various heavy metals in the blood from Ohjeok-san (Wuji-san) Decoction (OD) treated-rats. Methods: For this study, 13 kinds of metals including essential and heavy metals, i.e. A1, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se and Zn were analyzed by a slight modification of EP A methods and the following results are obtained. Results: 1. There was no significant difference between the OD-treated groups and control group in liver, kidney, bone, brain and weight, especially no significant difference at the 5th and 10th days in weight and the amount of food intake. 2. The amount of each metal analyzed in the blood were as follows; A1: 2.3~3.07 mg/l, As: 2.90~3.66 mg/l, Cd: 0~0.001 mg/l, Co: 0~0.01 mg/l, Cr: 0.40~043 mg/l, Cu: 0.93~1.88 mg/l, Fe: 414.35~464.46 mg/l, Hg: 0.01 mg/l, Mn: 0.10~0.17 mg/l, Ni: 0.01 mg/l, Pb: 0.03~012 mg/l, Se: 0.73 mg/l, Zn: 3.41~4.13 mg/l by groups, respectively. In control and experimental group, Experimental I and other experimental II, III, IV, and V groups, there were no significant differences. 3. The amount of non-toxic metals (A1, Co, Cu, Fe, Mn, Se, Zn) were $64.1{\pm}7.71{\;}mg/l$ in the control group and 60.70~67.58 mg/l in the experimental groups I, II, III, IV and V. The amount of Toxic metals (As, Cd, Cr, Ag, Pb) were $0.68{\pm}0.21{\;}mg/l$ in the control group and 0.57 ~ 0.66mg/l in the experimental groups. The total amount of metals were 32.35 mg/l in the control group and 30.48~34.12 mg/l in the test groups I, II, III, IV and V, respectively. Conclusions: There was no significant difference of metal concentration in the blood from the OD-treated-rats compared to those of the control group even if higher dosage (1~8 times the dosage for a person) of OD was administered. This may be mainly due to a decoction treatment which contains only supernatants filtered from the herb-mass after boiling. This indicates the legal limitation for metal concentration in herbal medicine must be applied according to different treatment methods of herbal medicine.

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Study on Solid Phase Extraction and Spectrophotometric Determination of Nickel in Waters and Biological Samples

  • Hu, Qiu-Fen;Yang, Guan-Gyu;Huang, Zhang-Jie;Yin, Jia-Yuan
    • Bulletin of the Korean Chemical Society
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    • v.25 no.4
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    • pp.545-548
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    • 2004
  • A sensitive, selective and rapid method for the determination of nickel based on the rapid reaction of nickel(II) with QADMAA and the solid phase extraction of the Ni(II)-QADMAA chelate with $C_{18}$ membrane disks has been developed. In the presence of pH 6.0 buffer solution and sodium dodecyl sulfonate (SDS) medium, QADMAA reacts with nickel to form a violet complex of a molar ratio of 1 : 2 (nickel to QADMAA). This chelate was enriched by solid phase extraction with $C_{18}$ membrane disks. An enrichment factor of 50 was obtained by elution of the chelates form the disks with the minimal amount of isopentyl alcohol. The molar absorptivity of the chelate was $1.32{\times}10^5L\;mol^{-1}cm^{- 1}$ at 590 nm in the measured solution. Beer's law was obeyed in the range of 0.01-0.6 ${\mu}$g/mL. This method was applied to the determination of nickel in water and biological samples with good results.