• Title/Summary/Keyword: H-킬레이트

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The Mechanism to Oxidative Polymerization of N-Methyl-p-Aminophenol and Thermal Characteristics of the Polymer Formed (N-Methyl-p-Aminophenol의 酸化重合機構 및 生成重合體의 熱特性)

  • Choi Kyu Suck
    • Journal of the Korean Chemical Society
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    • v.16 no.5
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    • pp.314-319
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    • 1972
  • N-Methyl-p-aminophenol was polymerized by oxidative couplng in the aqueous iron chelate solution in the presence of oxygen, and black precipitate of oligo-(N-methyl-p-aminophenol) was formed quantitatively. In this oxidative polymerization reaction, methyl group attached to N in the monomer was partly eliminated, and it was clarified by the infrared spectra from the fact that the absorption of ${\delta}\;asym\;CH_3\;1460\;cm^{-1}$ and ${\delta}\;sym\;CH_3\;1380\;cm^{-1}$ in acetone insoluble fraction was much weaker than that in acetone soluble fraction. From Thermo-gravimetric analysis, oligo-(N-methyl-p-aminophenol) showed about 40% weight loss at $600^{\circ}C$ and it was less heat-resistant than oligo (p-aminophenol) that methyl group was not contained. In pyrolysis of oligo-(N-methyl-p-aminophenol) in He atmosphere, monomer N-methyl-p-aminophenol and water were formed, and in the pyrolytic gases, $H_2,\;CO,\;CO_2$ were detected by gas chromatography. From the above facts, to the structural change on oligo-(N-methyl-p-aminophenol) when it was heat-treated, it was considered that original linear structure was partly degraded, and the most of the oligomer was to go in with melt polycondensation to form polymer, and heat-resistant cyclic structure was formed at a time.

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Determination and preconcentration of Cu(II) using microcrystalline p-Dichlorobenzene loaded with salicylaldoxime (Salicylaldoxime이 내포된 p-Dichlorobenzene 미세결정을 이용한 Cu(II)의 예비농축 및 정량)

  • Lee, Ha-Na;Choi, Hee-Seon
    • Analytical Science and Technology
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    • v.23 no.3
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    • pp.240-246
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    • 2010
  • A technique for the determination of trace Cu(II) in various real samples by FAAS after the column preconcentration onto p-dichlorobenzene-SA adsorbent, which is microcrystalline p-dichlorobenzene loaded with salicylaldoxime (SA) has been developed. Several experimental conditions such as pH of the sample solution, the amount of chelating agent salicylaldoxime, the amount of adsorbent p-dichlorobenzene-SA, and flow rate of sample solution were optimized. The interfering effects of various concomitant ions were investigated. $CN^-$ interfered more seriously than any other ions. However, the interference by $1\;{\mu}g\;mL^{-1}\;CN^-$ could be overcome completely by controlling the concentration of Ni(II) to $20\;{\mu}g\;mL^{-1}$. The linear range, correlation coefficient ($R^2$) and detection limit obtained by this technique were $3.0\sim100\;ng\;mL^{-1}$, 0.9901, and $3.1\;ng\;mL^{-1}$, respectively. For validating this technique, the aqueous samples (wastewater, reservoir water and stream water) and the food samples (orange juice, fresh egg and skim milk) were used. Recovery yields of 93~104% were obtained. These measured mean values were not differents from ICP-MS data at 95% confidence level. The good results were obtained from the experiments using the rice flour certified reference material (CRM) sample. Based on the experimental results, it was found that this technique could be applied to the preconcentration and determination of Cu(II) for various real samples.

Changes and Availability of Inorganic Phosphate during the Composting (Pig Manure) (퇴비화 과정 중 인산의 가용화와 무기태 인산의 변화)

  • Lee, Yu-Ri;Lee, Jong-Eun;Chang, Ki-Woon
    • Journal of the Korea Organic Resources Recycling Association
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    • v.11 no.1
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    • pp.127-128
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    • 2003
  • 본 연구는 퇴비화 과정 중 난용성 인산의 가용화와 무기태 인산의 변화를 알아보기 위하여 수행하였다. 비료와 퇴비중의 인산형태는 다른 성분들보다 토양에 흡착 또는 고정되거나 불용화 되는 양이 많아 작물의 흡수량이 적다. 시비된 인산의 흡수율은 낮고, 그 대부분은 난용화되기 때문에 토양에 축적되거나 세탈과 용탈에 의해 수질을 오염화시키는 주원인이 되고 있다. 퇴비화 과정중의 인산형태별 함량변화를 분석조사하여 작물에 시비되는 인산비료와 퇴비의 시용량을 적절하게 조절하여 인산의 과잉 시비량을 저감시키기 위한 연구이다. 돈분을 원료로 한 퇴비화 과정에서 단계별로 퇴비시료를 채취하여 총인산(T-P), 유효인산(Avail. -P)과 무기태인산분획별(Ca-P, Al-P, Fe-P)로 분석한 결과는 다음과 같다. 퇴적더미의 초기부피는 570L였으며, 약 2개월간의 퇴비화를 통해서 시료채취와 미생물등의 분해작용으로 최종부피는 430L정도로 감소하였다. 이는 초기의 부피보다 25% 감소하였다. 퇴적더미의 분해로 인한 용적밀도의 변화를 고려하면, 총인산 함량은 초기 약 17,500mg/kg에서 최종시료는 22,500mg/kg로 증가되었다. 또한 퇴비화가 진행됨에 따라 인산의 가용태가 증가하는 결과를 보였으며, 초기의 유효인산이 4,500mg/kg에서 최종시료에서는 8,900mg/kg으로 증가되었다. 그리고 무기태 인산분획별 인산의 형태별 변화를 조사한 결과, 퇴비화 과정 중 Ca-P의 경우 pH와의 중요한 상관관계를 갖고 있었다. 유기물분해를 통해 유리된 인산과 Ca은 난용태로 전환되는데, 초기의 약 10일 동안 Ca-P의 감소원인은 pH의 감소로 인한 Ca이 유리되는 정도가 낮기 때문인 것으로 해석된다. 초기 Ca-P형태의 인산함량은 11,900mg/kg으로 Fe-P와 Al-P보다 많았다. 또한 퇴비화가 안정화되어 부숙된 최종시료의 무기태 인산분획물 중 Ca-P는 18,000mg/kg로 증가하였으며, Ca-P>Al-P>Fe-P의 순 이었다. 그러나 Al-P와 Fe-P 형태의 무기태인산은 초기의 함량비율보다 다소 감소한 결과를 보였다. 결론적으로, 퇴비화과정 중 단계별 인산함량의 형태전환을 분석한 결과 총인산의 함량은 퇴비화가 안정화될수록 부피감소로 인한 인산함량이 증가하는 경향을 보였지만, 유기물질의 분해로 인한 원료내 인산의 형태가 불용태와 난용태에서 가용태 인산으로 전환되는 것을 도출하였다. 또한 무기태 인산분획물에서는 Ca-P 인산형태가 퇴비화가 진행될수록 증가한다는 결과를 얻었으며, Fe-P와 Al-P는 분해된 유기물의 킬레이트작용으로 감소되었다고 판단되며, 그 존재형태가 경쟁적임을 알 수 있었다. 따라서 화학비료와 퇴비의 시용이 병행될 경우에는 퇴비의 가용태 인산함량뿐만 아니라 무기태 인산의 함량을 분석한 후 인산질비료의 시비량을 조절해야할 것으로 판단된다.

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Metal-Dinitrosyl Complexes(III) : Synthesis and Structural Study of Homo-, Hetero-dinuclear Molybdenum and Tungsten Complexes, $[Cl(phen)(NO)_2M({\mu}-pyz)M'(NO)_2(phen)Cl][ClO_4]_2 $(phen = 1,10-phenanthroline, pyz = pyrazine) (금속-디니트로실 착물 (제 3 보) : 몰리브덴과 텅스텐의 호모 및 헤테로 이핵 착물, $[Cl(phen)(NO)_2M({\mu}-pyz)M'(NO)_2(phen)Cl][ClO_4]_2 (phen=1,10-phenanthroline,\;pyz=pyrazine)$의 합성 및 구조에 대한 연구)

  • Sang-Oh Oh;Seong-Jong Mo
    • Journal of the Korean Chemical Society
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    • v.37 no.7
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    • pp.655-661
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    • 1993
  • The neutral monomeric compounds $[Mo(NO)_2Cl_2(phen)]$ and $[W(NO)_2Cl_2(phen)]$ (phen= 1,10-phenanthroline) have been prepared by reactions of polymeric compounds $[{Mo(NO)_2Cl_2}n],\;[{W(NO)_2Cl_2}n]$ with chelate ligands. Additions of one equivalent of silver(I) perchlorate to these cis-dinitrosyl compounds in acetone solution produce $[Mo(NO)_2(phen)(S)Cl][ClO_4]\;and\;[W(NO)_2(phen)(S)Cl][ClO_4]$ (S = acetone). The homo- and hetero-dinuclear complexes, $[Cl(phen)(NO)_2M(pyz)M'(NO)_2(phen)Cl][ClO_4]_2$ (M = Mo, W) and $[Cl(phen)(NO)_2M(pyz)M'(NO)_2(phen)Cl][C1O_4]_2$ (M = Mo, M' = W) have been prepared by these monocationic complexes with pyrazine ligand respectively. These complexes characterized by elemental analysis, $1^H-\;and\;^{13}C-NMR$, infrared, and UV-visible spectroscopy are reported. The spectral data indicate that homo- and hetero-dinuclear complexes were symmetrical structures of $C_{2v}$.

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Antioxidant Activity of Leaf, Stem and Root Extracts from Orostachys japonicus and Their Heat and pH Stabilities (와송(Orostachys japonicus) 잎, 줄기 및 뿌리 추출물의 항산화활성과 열 및 pH 안정성)

  • Lee, So-Jeong;Song, Eu-Jin;Lee, So-Young;Kim, Kotch-Bong-Woo-Ri;Kim, Seo-Jin;Yoon, So-Young;Lee, Chung-Jo;Ahn, Dong-Hyun
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.38 no.11
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    • pp.1571-1579
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    • 2009
  • Antioxidant activities of ethanol and water extracts from Orostachys japonicus leaf, stem, and root were determined by rancimat method, DPPH radical scavenging effect, chelating effect, and reducing power analysis. The highest total phenolic compound (TPC) as 14.6 mg/g of dry sample and the strongest antioxidant activity in rancimat method (value of AI 1.98), DPPH radical scavenging effect (96% in 4 mg/mL), and reducing power (1.50 in 4 mg/mL) were observed in ethanol extracts from Orostachys japonicus leaf. Heat and pH stabilities on antioxidant activity of Orostachys japonicus leaf extract were studied through TPC and DPPH radical scavenging effect. As a result, the extracts from Orostachys japonicus leaf showed high stability. These results suggest that extracts from Orostachys japonicus leaf can be potentially used as proper natural antioxidant in the food industry.

Radiolabeling of NOTA and DOTA with Positron Emitting $^{68}$Ga and Investigation of In Vitro Properties (양전자 방출핵종 $^{68}$Ga을 이용한 NOTA와 DOTA의 표지 및 시험관내 특성 연구)

  • Jeong, Jae-Min;Kim, Young-Ju;Lee, Yun-Sang;Lee, Dong-Soo;Chung, June-Key;Lee, Myung-Chul
    • Nuclear Medicine and Molecular Imaging
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    • v.43 no.4
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    • pp.330-336
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    • 2009
  • Purpose: We established radiolabeling conditions of NOTA and DOTA with a generator-produced PET radionuclide $^{68}$Ga and studied in vitro characteristics such as stability, serum protein binding, octanol/water distribution, and interference with other metal ions. Materials and Methods: Various concentrations of NOTA 3HCl and DOTA 4HCl were labeled with 1 mL $^{68}$GaCl$_3$ (0.18$\sim$5.75 mCi in 0.1 M HCl in various pH. NOTA 3HCl (0.373 mM) was labeled with $^{68}$GaCl$_3$(0.183$\sim$0.232 mCi/0.1 M HCl 1.0 mL) in the presence of CuCl$_2$, FeCl$_2$, InCl$_3$, FeCl$_3$, GaCl$_3$, MgCl$_2$ or CaCl$_2$ (0$\sim$6.07 mM) at room temperature. The labeling efficiencies of $^{68}$Ga-NOTA and $^{68}$Ga-DOTA were checked by ITLC-SG using acetone or saline as mobile phase. Stabilities, protein bindings, and octanol distribution coefficients of the labeled compounds also were investigated. Results: $^{68}$Ga-NOTA and $^{68}$Ga-DOTA were labeled optimally at pH 6.5 and pH 3.5, respectively, and the chelates were stable for 4 hr either in the reaction mixture at room temperature or in the human serum at 37$^{\circ}C$. NOTA was labeled at room temperature while DOTA required heating for labeling. $^{68}$Ga-NOTA labeling efficiency was reduced by CuCl$_2$, FeCl$_2$, InCl$_2$, FeCl$_3$ or CaCl$_3$, however, was not influenced by MgCl$_2$ or CaCl$_2$. The protein binding was low (2.04$\sim$3.32%). Log P value of $^{68}$Ga-NOTA was -3.07 indicating high hydrophilicity. Conclusion: We found that NOTA is a better bifunctional chelating agent than DOTA for $^{68}$Ga labeling. Although, $^{68}$Ga-NOTA labeling is interfered by various metal ions, it shows high stability and low serum protein binding.

Assessment Techniques of Heavy Metal Bioavailability in Soil - A critical Review (토양 중 중금속 생물유효도 평가방법 - 총설)

  • Kim, Kwon-Rae;Owens, Gary;Naidu, Ravi;Kim, Kye-Hoon
    • Korean Journal of Soil Science and Fertilizer
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    • v.40 no.4
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    • pp.311-325
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    • 2007
  • The concept of metal bioavailability, rather than total metal in soils, is increasingly becoming important for a thorough understanding of risk assessment and remediation. This is because bioavailable metals generally represented by the labile or soluble metal components existing as either free ions or soluble complexed ions are likely to be accessible to receptor organismsrather than heavy metals tightly bound on soil surface. Consequently, many researchers have investigated the bioavailability of metals in both soil and solution phases together with the key soil properties influencing bioavailability. In order to study bioavailability changes various techniques have been developed including chemical based extraction (weak salt solution extraction, chelate extraction, etc.) and speciation of metals using devices such as ion selective electrode (ISE) and diffusive gradient in the thin film (DGT). Changes in soil metal bioavailability typically occur through adsorption/desorption reactions of metal ions exchanged between soil solution and soil binding sites in response to changes in environment factors such as soil pH, organic matter (OM), dissolved organic carbon (DOC), low-molecular weight organic acids (LMWOAs), and index cations. Increasesin soil pH result in decreases in metal bioavailability through adsorption of metal ions on deprotonated binding sites. Organic matter may also decrease metal bioavailability by providing more negatively charged binding sites, and metal bioavailability can also be decreases as concentrations of DOC and LMWOAs increase as these both form strong chelate complexeswith metal ions in soil solution. The interaction of metal ions with these soil properties also varies depending on the soil and metal type.

Protective Effect of Isoflavone, Genistein from Soybean on Singlet Oxygen Induced Photohemolysis of Human Erythrocytes ($^1O_2$으로 유도된 사람 적혈구의 광용혈에 있어서 대두의 아이소플라본인 제니스테인의 보호작용)

  • Park, Soo-Nam
    • Korean Journal of Food Science and Technology
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    • v.35 no.3
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    • pp.510-518
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    • 2003
  • Protective effects of natural components including genistein (4',5,7-trihydroxyisoflavone) from Glycine max MERRILL on the rose-bengal sensitized photohemolysis of human erythrocytes were investigated. Genistein $(10{\sim}100\;{\mu}m)$ suppressed photohemolysis in a concentration-dependent manner, and was more effective than the lipid peroxidation chain blocker, ${\alpha}$-tocopherol (Vit. E). Glycoside of genistein, genistin, the water-soluble antioxidant, L-ascorbate, and the iron chelator, myo-inositol hexaphosphoric acid dodecasodium salt (sodium phytate) did not exhibit protective effect against photohemolysis. L-Ascorbate and sodium phytate stimulated photohemolysis at high concentration $(500\;{\mu}m)$. ${\alpha}$-Carotene 3,3'-diol (lutein), a singlet oxygen $(^1O_2)$ quencher, exhibited pronounced protective effect, an indication that $^1O_2$ is important in photohemolysis sensitized by rose-bengal. Reactive oxygen scavenging activities $(OSC_{50})$ of natural antioxidants including genistein on reactive oxygen species (ROS) generated in $Fe^{3+}-EDTA/H_2O_2$ system using the luminol-dependent chemiluminescence assay were in the order of sodium phytate > L-ascorbate > ${\alpha}$-tocopherol > genistein > genistin. $OSC_{50}$ value of genistein, genistin, ${\alpha}$-tocopherol, L-ascorbate, and sodium phytate were 41.0, 109.0, 9.0, 5.2, and $0.56{\mu}m$ respectively. The order of free radical (1,1-diphenyl-2-picrylhydrazyl, DPPH) scavenging activity $(FSC_{50})$ was L-ascorbate > ${\alpha}$-tocopherol > genistein > genistin. These results indicate that genistein can function as an antioxidant in biological systems, particularly skin exposed to solar UV radiation by scavenging $^1O_2$ and other ROS, and to protect cellular membranes against ROS.

Quality characteristics and antioxidant activity of drink prepared with black garlic and Oenanthe javanica DC (흑마늘과 미나리를 이용하여 제조한 음료의 품질 및 항산화 특성)

  • Jeong, Tae-Seong;Kim, Jin-Hak;An, Sin-Ae;Won, Yong-Duk;Lee, Shin-Ho
    • Food Science and Preservation
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    • v.21 no.2
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    • pp.193-198
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    • 2014
  • The quality and antioxidative characteristics of drinks prepared with different mixing ratios of black garlic and Oenanthe javanica DC., BD-1 (black garlic only), BD-2 (black garlic:Oenanthe javanica DC.=2:1), BD-3 (black garlic:Oenanthe javanica DC.=1:1), and BD-4 (black garlic:Oenanthe javanica DC.=1:2), were studied. The pH increased with the increasing concentration of Oenanthe javanica DC. extract in all the tested drinks, but the sugar contents decreased. The total polyphenol contents of the drinks were 28.48 ${\mu}g/mL$ (BD-1), 41.91 ${\mu}g/mL$ (BD-2), 42.36 ${\mu}g/mL$ (BD-3), and 46.96 ${\mu}g/mL$ (BD-4). The SOD-like activity was highest for BD-4 (18.60%), followed by BD-3 (15.53%), BD-2 (12.53%), and BD-1 (10.27%). The thiobarbituric acid reactive substances (TBARS) was highest for BD-4 (52.51%), followed by BD-3 (45.70%), BD-2 (39.44%), and BD-1 (28.72%). The ferrous ion chelating activity increased with the increasing concentration of Oenanthe javanica DC extract, and BD-4 showed the best activities among all the tested drinks. The water-soluble vitamin content (vitamins B1, B2, B6, and C) of BD-4 (1197.77 ${\mu}g/mL$) was higher than those of the other drinks (BD-1, 213.02 ${\mu}g/mL$; BD-2, 477.87 ${\mu}g/mL$; BD-3, 914.72 ${\mu}g/mL$), and the vitamin C (806.21 ${\mu}g/mL$) content of the water-soluble vitamins at BD-4 was higher than those of vitamins B1 (68.04 ${\mu}g/mL$), B2 (312.51 ${\mu}g/mL$), and B6 (11.01 ${\mu}g/mL$). BD-4 showed the best score in the sensory evaluations, such as in the evaluation of the color, flavor, taste, and overall acceptability.

Spectroscopic Studies on U(VI) Complex with 2,6-Dihydroxybenzoic acid as a Model Ligand of Humic Acid (분광학을 이용한 흄산의 모델 리간드인 2,6-Dihydroxybenzoic acid와 우라늄(VI)의 착물형성 반응에 관한 연구)

  • Cha, Wan-Sik;Cho, Hye-Ryun;Jung, Euo-Chang
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.9 no.4
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    • pp.207-217
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    • 2011
  • In this study the complex formation reactions between uranium(VI) and 2,6-dihydroxybenzoate (DHB) as a model ligand of humic acid were investigated by using UV-Vis spectrophotometry and time-resolved laser-induced fluorescence spectroscopy (TRLFS). The analysis of the spectrophotometric data, i.e., absorbance changes at the characteristic charge-transfer bands of the U(VI)-DHB complex, indicates that both 1:1 and 1:2 (U(VI):DHB) complexes occur as a result of dual equilibria and their distribution varies in a pH-dependent manner. The stepwise stability constants determined (log $K_1$ and log $K_2$) are $12.4{\pm}0.1$ and $11.4{\pm}0.1$. Further, the TRLFS study shows that DHB plays a role as a fluorescence quencher of U(VI) species. The presence of both a dynamic and static quenching process was identified for all U(VI) species examined, i.e., ${UO_2}^{2+}$, $(UO_2)_2{(OH)_2}^{2+}$, and $(UO_2)_3{(OH)_5}^+$. The fluorescence intensity and lifetimes of each species were measured from the time-resolved spectra at various ligand concentrations, and then analyzed based on Stern-Volmer equations. The static quenching constants (log $K_s$) obtained are $4.2{\pm}0.1$, $4.3{\pm}0.1$, and $4.34{\pm}0.08$ for ${UO_2}^{2+}$, $(UO_2)_2{(OH)_2}^{2+}$, and $(UO_2)_3{(OH)_5}^+$, respectively. The results of Stern-Volmer analysis suggest that both mono- and bi-dentate U(VI)-DHB complexes serve as groundstate complexes inducing static quenching.