• Title/Summary/Keyword: $Zn^{2+}$ complex

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Synthesis of New N2O Tridentate Ligands and Their Stability Constants of Transition Metal Complexes (새로운 N2O계 세 자리 리간드의 합성과 전이금속 착물 안정도상수)

  • Kim, Sun-Deuk;Park, Young-Sik
    • Journal of the Korean Chemical Society
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    • v.47 no.6
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    • pp.569-577
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    • 2003
  • Ligands, Br-PEMP, Cl-PEMP and $CH_3O-PEMP$ having Br, Cl and $CH_3O$ substituents at 5-position of the $N_2O$ tridentate ligand, 2-[(2-pyridine-2-ethylamio)-methyl]-phenol (H-PEMP) containing pyridine and phenol were synthesized. Another ligand, Naph-PEMP having pyridine and 2-hydroxy-1-naphthalene was also synthesized. The ligands were characterized using elemental analysis, UV-visible, IR, $^1H\;NMR\;and\;^{13}C$ NMR spectroscopy and mass analysis. The potentiometric titration study in aqueous solution revealed that the proton dissociation of the ligands occurred in three steps and the order of overall proton dissociation constants (log${\beta}$) was $CH_3O-PEMP$ > Naph-PEMP > H-PEMP > Cl-PEMP > Br-PEMP. The order of stability constants (logML and log$ML_2$) of their transition metal complexes was Co(II) < Ni(II) < Cu(II) > Zn(II). The order in their stability constants values of each transition metal complex agreed well with that in overall proton dissociation constant value of the ligands.

Evaluation of Organic Matter and Trace Metal Contamination in Surface Sediments around the Geum River Estuary using Sediment Quality Guidelines (퇴적물 오염기준을 이용한 금강 하구역 표층 퇴적물내 유기물 및 미량금속 오염 평가)

  • Hwang, Dong-Woon;Lee, In-Seok;Choi, Minkyu;Kim, Sook-Yang;Choi, Hee-Gu
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.46 no.6
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    • pp.930-940
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    • 2013
  • We evaluated contamination with organic matter and trace metals by analyzing grain size, ignition loss (IL), chemical oxygen demand (COD), acid volatile sulfide (AVS), and trace metals (Al, Fe, Cu, Pb, Zn, Cd, Ni, Cr, Mn, Hg, and As) in surface sediments at 28 stations around the Geum River estuary in July 2008. The surface sediments in the estuary were mainly composed of coarse sediment (sand and muddy sand), with mean grain size (Mz) ranging between $2-4{\O}$. The high concentrations of IL, COD, and trace metals were mainly found at stations in front of the Gusan outer port and industrial complex, and near the Seocheon coast with relatively fine sediments. In addition, the concentrations of IL and all trace metals, except Pb and As, showed good positive correlations with Mz, indicating that the concentrations of organic matter and trace metals were mainly dependent on sediment grain size. The concentrations of COD, AVS, and trace metals in most sediments did not exceed the sediment quality guideline (SQGs). Although the sediments in the study region are not polluted with organic matter and trace metals, there are many point sources of pollutants, such as Gusan port and industrial complex, Janghang refinery, and a thermoelectric power plant around the Geum River estuary. Thus, the management of coastal environments through periodic monitoring of organic matter and trace metals is required in the future.

Stability Constants of Nitrogen-Oxygen Donor Macrocyclic Ligand-Metal Ion Complexes in Aqueous Solutions (질소-산소 주개 거대고리 화합물-금속착물의 수용액에서의 안정도상수)

  • Jeong Kim;Chang-Ju Yoon;Hyu-Bum Park;Si-Joong Kim
    • Journal of the Korean Chemical Society
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    • v.35 no.2
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    • pp.119-127
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    • 1991
  • The protonation and the metal ion complexation of 15 to 18 membered diaza crown ether such as 1,12-diaza-3, 4 : 9, 10-dibenzo-5, 8-dioxacyclopentadecane(NtnOenH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-hydroxy-5,9-dioxacyclohexadecane(NtnOtnH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-15-hydroxy-5,9-dioxacyclohexadecane(Ntn(OH)OtnH$_4$), 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacycloheptadecane (NenOdienH$_4$) and 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane(NtnOdienH$_4$) were studlied by potentiometry and NMR spectroscopy. The protonation constants were used to predict basicity of crown ethers. The sequence of the basicity was NenOdienH$_4$ < Ntn(OH)OtnH$_4$ < NtnOenH$_4$ < NtnOtnH$_4$ < NtnOdienH$_4$. Changes on the basicity were explained in terms of the effects of substituents and the degree of twistness of the macrocyclic ring. The sequence of the complex stabilities were Co(II) < Ni(II) < Cu(II) < Zn(II) for the transition metal complexes and Cd(II) < pb(II) < Hg(II) for the post-transition metal complexes. These changes on the stabilities were dependent on the basicity of the ligand and cavity size of the ring. For the heavy post-transiton metal complexes and Zn(Ⅱ) complex, the former factor was predominent and for the other transition metal complexes, the latter was affected on the stabilities. $^1$H and $^{13}$C-NMR studies for heavy post-transition metal complexes indicated that the nitrogen atom has greater affinity on metal ions than oxygen atom and the planarity of the rings was losed by the complexation with metal ions.

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Magnetite and Scheelite-Bearing Skarns in Ulsan Mine, Korea (울산 광산의 철-텅그스텐 스카른화작용)

  • Choi, Seon-Gyu;Imai, Naoya
    • Economic and Environmental Geology
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    • v.26 no.1
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    • pp.41-54
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    • 1993
  • The Ulsan Fe-W deposit, which can be classified as a calcareous skarn deposit, is represented by ore pipe consisting principally of magnetite and lesser amounts of scheelite with minor sulphides, sulphosaits, arsenides, sulpharsenides, etc. At Ulsan mine, metasomatic processes of skarn growth may be divided broadly into two stages based on the paragenetic sequence of calc-silicate minerals and their chemical composition; early and late skarn stages. Early stage has started with the formation of highly calcic assemblages of wollastonite, diopsidic clinopyroxene and nearly pure grossular, which are followed by the formation of clinopyroxenes with salite to ferrosalite composition and grandite garnets with intermediate composition. Based on these calc-silicate assemblages, the temperatures of early skarn formations have been in the ranges of $550^{\circ}$ to $450^{\circ}$. The calc-silicate assemblages formed during the earlier half period of late skarn stage show the enrichment of notable iron and slight manganese, and the depletion of magnesium; clinopyroxenes are hedenbergitic, and grandite garnets are andraditic. The formation temperatures during this skarn stage are inferred to have been in the range of $430^{\circ}$ to $470^{\circ}C$ at low $X_{CO_2}$ by data from fluid inclusions of late andraditic garnets. The later half period of late skarn stage is characterized by the hydrous alteration of pre-existing minerals and the formation of hydrous silicates. The main iron-tungsten mineralization representing prominent deposition of magnetite immediately followed by minor scheelite impregnation has taken place at the middle of early skarn stage, while complex polymetallic mineralization has proceeded during and after the late skarn stage. Various metals and semimetals of Fe, Ni, Co, Cu, Zn, As, Mo, Ag, In, Sn, Sb, Te, Pb and Bi have been in various states such as native metal, sulphides, arsenides, sulphosaits, sulpharsenides and tellurides.

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Pyritization of heavy metals in Lake Shihwa sediments, Korea

  • Shim, Moo-Joon;Kim, Eun-Soo;Kim, Kyung-Tae;Lee, Kwang-Woo
    • Journal of the korean society of oceanography
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    • v.35 no.2
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    • pp.89-97
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    • 2000
  • The pyritization of heavy metals in Lake Shihwa sediments was investigated to determine sedimentary Pyrite-heavy metal associations influenced by various metal fractions, organic carbon, and total reduced sulfur. Parameters indicating the degree of heavy metal pyritization (DTMP) and degree of pyritization (DOP) were used to study the incorporation of heavy metals into the pyrite phase. The DOP levels ranged from 3.28-39.45%, showing wide differences among sampling stations. The levels were greater near the water gate and the center of the lake than near the industrial complex. The spatial pattern of the DOP levels was similar to the S/C ratio and also to the salinity. Based on the measured relationships between DOP and DTMP, heavy metals can be divided into three groups. In the first group was As, which showed a high affinity for pyrite. In the second group were Ni, Co and Cu, which showed a gradual increase in DTMP with increasing DOP. In the final group were Pb, Zn, Mn and Cr, which all showed a low DTMP with constant values with respect to DOP.

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Macrobenthic Community Structure Along the Environmental Gradients of Ulsan Bay, Korea (울산만의 저서환경 구배에 따른 저서동물군집 구조)

  • Yoon, Sang-Pil;Jung, Rae-Hong;Kim, Youn-Jung;Kim, Seong-Gil;Choi, Min-Kyu;Lee, Won-Chan;Oh, Hyun-Taik;Hong, Sok-Jin
    • The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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    • v.14 no.2
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    • pp.102-117
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    • 2009
  • This study was carried out to investigate the extent to which benthic environment of Ulsan Bay was disturbed by organic materials and trace metals from the megacity and industrial complex. Field survey for benthic environment and macroinvertebrate community was seasonally conducted from February to November 2006 at nine stations covering the inside and outside of the bay. TOC was on average 1.7% while four (As, Cu, Pb, Zn) out of seven trace metals measured exceeded the Effects Range Low (ERL) in most of the stations. Total number of species sampled was 199 and mean density was 4,578 ind./$m^2$, both of which were greatly dominated by the polychaetes. Dominant species were Aphelochaeta monilaris (22.6%), Ruditapes philippinarum (17.1%), Magelona japonica (12.2%), Lumbrineris longifolia (9.9%) and their distribution was ruled by the difference in the benthic environmental condition of each station. From the multivariate analyses, four stational groups were identified: northern part of the bay, middle and lower part of the bay, the intersection of Taewha River and Gosa stream and outside of the bay. As a result, the community heterogeneity of inner bay was much more greater than that of outer bay. SIMPER analysis showed that four groups were represented by R. philippinarum-Capitella capitata, A. monilaris-Balanoglossus carnosus, Sinocorophium sinensis-Cyathura higoensis and M. japonica-Ampharete arctica, respectively. Spatio-temporal changes of macroinvertebrate communities in Ulsan Bay were closely related to those of depth, mean grain size and organic content, and Zn was also a meaningful factor in that context.

Synthesis of Pentadentate Nitrogen-Oxygen(N2O3) Ligands with Substituting Groups and Determination of Stability Constants of Their Transition Metal(II) Complexes (치환기를 가진 다섯 자리 질소-산소 (N2O3)계 리간드의 합성 및 전이금속(II) 이온과의 착물 안정도상수 결정)

  • Kim, Seon-Deuk;Lee, Hye-Won;Jin, Gyoung-Rok
    • Journal of Environmental Science International
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    • v.18 no.7
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    • pp.735-746
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    • 2009
  • Hydrochloric acid salt of a new $N_2O_3$ pentadentate ligand, N,N'-Bis(2-Hydroxybenzyl)-1,3-diamino-2-propanol(H-BHDP 2HCl) was synthesized. Br-BHDP 2HCl, CI-BHDP 2HCl, $CH_3-BHDP$ 2HCl and $CH_3O$-BHDP 2HCl having Br, Cl, $CH_3$ and $CH_3O$ substituents at 5-position of the phenol group of H-BHDP 2HCl were also synthesized. The potentiometry study in aqueous solution revealed that the proton dissociations of the synthesized ligands occurred in four steps and their order of the calculated overall proton dissociation constants($log{\beta}_p$) was Br-BHDP < Cl-BHDP < H-BHDP < $CH_3O-BHDP$ < $CH_3-BHDP$. The order showed a similar trend to that of Hammett substituent constants(${\delta}_p$). The order of the stability constants($logK_{ML}$) was Co(II) < Ni(II) < Cu(II) < Zn(II) < Cd(II) < Pb(II). The order in their stability constants ($logK_{ML}$) of each transition metal complex agreed with that of the overall proton dissociation constants ($log{\beta}_p$).

Monitoring of Particulate Matter and Analysis of Black Carbon and Some Particle Containing Toxic Trace in the City of Yaoundé, Cameroon

  • Tchuente, Siaka Y.F.;Saidou, Saidou;Yakum, N.Y.;Kenmoe, N.X.;Abdourahimi, Abdourahimi
    • Asian Journal of Atmospheric Environment
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    • v.7 no.2
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    • pp.120-128
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    • 2013
  • The concentration and composition of particulate matter (PM) in the atmosphere can directly reflect the environmental pollution. The atmospheric pollution in some Cameroonian cities is increasing with the industrial development and urbanization. Air pollution is inherently complex, containing PM of varied size and composition. This PM exists as a dynamic cloud interacting with sunlight and is modified by the meteorology. The reflectometer and the EDXRF spectrometry are applied to determine the concentration of some specific elements at four sites in the city of Yaound$\acute{e}$. The particular aim of the present work is to put in place data base on air pollution in urban area and elaborate regulations on the emissions issued to industrial and vehicle activities. This study provides an overview of the concentration of black carbon and some specific elements in the air, which have impacts on human health. The measurement was done by distinguishing the size of particle. So that, the particle with aerodynamic diameter between $2.5-10{\mu}m$ (so-called coarse particle) and aerodynamic diameter < $2.5{\mu}m$ (so-called fine particle) were considered to obtain more information about levels of the inhalable fraction of the location. The results obtained in four locations of the city of Yaound$\acute{e}$ show that the black carbon concentration is very considerable, the element sulfur is a major pollutant and the concentration of fine particle is very greater. The results obtained of fine and coarse filters range from $5-17{\mu}g/m^3$ and $10-18{\mu}g/m^3$ for the black carbon. S, Cu, Zn, Pb, Cd, As, Se and Hg are the specific findings of this work. The pollutants with a greater concentration are S, Pb, and Zn. These later seem to be non-uniformly, non-regular in some location and high compared to other countries. This work allows us to make a potential relation between pollutants and emission sources. In this framework, some suggestions have been proposed to reduce emissions for an improvement of the air quality in the environment and thus, the one of the city of Yaound$\acute{e}$.

Gadolinium Complexes of Bifunctional Diethylenetriaminepentaacetic Acid (DTPA)-bis(amides) as Copper Responsive Smart Magnetic Resonance Imaging Contrast Agents (MRI CAs)

  • Nam, Ki Soo;Park, Ji-Ae;Jung, Ki-Hye;Chang, Yongmin;Kim, Tae-Jeong
    • Bulletin of the Korean Chemical Society
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    • v.34 no.10
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    • pp.2900-2904
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    • 2013
  • We present the synthesis and characterization of DTPA-bis(histidylamide) (1a), DTPA-bis(aspartamide) (1b), and their gadolinium complexes of the type $[Gd(L)(H_2O)]$ (2a:L = 1a; 2b:L = 1b). Thermodynamic stabilities and $R_1$ relaxivities of 2a-b compare well with Omniscan$^{(R)}$, a well-known commercial, extracellular (ECF) MRI CA which adopts the DTPA-bis(amide) framework for the chelate: $R_1$ = 5.5 and 5.1 $mM^{-1}$ for 2a and 2b, respectively. Addition of the Cu(II) ion to a solution containing 2b triggers relaxivity enhancement to raise $R_1$ as high as 15.3 $mM^{-1}$, which corresponds to a 300% enhancement. Such an increase levels off at the concentration beyond two equiv. of Cu(II), suggesting the formation of a trimetallic ($Gd/Cu_2$) complex in situ. Such a relaxivity increase is almost negligible with Zn(II) and other endogenous ions such as Na(I), K(I), Mg(II), and Ca(II). In vivo MR images and the signal-to-noise ratio (SNR) obtained with an aqueous mixture of 2b and Cu(II) ion in an 1:2 ratio demonstrate the potentiality of 2 as a copper responsive MRI CA.

Syntheses of New Nitrogen-Oxygen Multidentate Ligands and Their Stability Constants of Transition Metal(Ⅱ) Ions (새로운 질소-산소계 여러 자리 리간드의 합성 및 전이금속(Ⅱ)이온 착물의 안정도상수)

  • Kim, Sun Deuk;Jang, Ki Ho;Kim, Jun Kwang
    • Journal of the Korean Chemical Society
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    • v.42 no.5
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    • pp.539-548
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    • 1998
  • Multidentate N,O-containing ligands, such as N,N'-bis(2-hydroxybenzyl)-ethylenediamine(BHED), N,N'-bis(2-hydroxybenzyl)-propylenediamine(BHPD), N,N'-bis(2-hydroxybenzyl)-diethylenetriamine(BHDT), N,N'-bis(2-hydroxybenzyl)-triethylenetriamine(BHTT) and N,N'-bis(2-hydroxybenzyl)-tetraethylenepentaamine (BHTP) were synthesized by reduction of the imine group of Bis(salicylidene)-ethylendiamine(BSED), Bis (salicylidene)-propylenediamine(BSPD), Bis(salicylidene)-diethylentriamine(BSDT), Bis(salicylidene)-triethylenetetraamine(BSTT) and Bis(salicylidene)-tetraethylenepentaamine(BSTP). Proton dissociation constants of the ligands and stability constants of transition metal(Ⅱ) ion complexes with BHED, BHPD, BHDT, BHTT, and BHTP were determined by potentiometic titration. The sequence of stability constants $(logK_{ML})$ of complex increases as BHED Zn(Ⅱ) which follows the Irving-Williams series.

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