• Title/Summary/Keyword: phosphate complexes

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A Study of Phosphate Adsorption on Kaolinite by $^{31}$P NMP Spectroscopy ($^{31}$P NMR을 이용한 카올리나이트에 흡착된 인산염의 연구)

  • 김영규
    • Journal of the Mineralogical Society of Korea
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    • v.13 no.4
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    • pp.186-195
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    • 2000
  • To study phosphate adsorption on kaolinite, $^{31}$ P MAS NMR(magic angle spinning nuclear magnetic resonance spectroscopy)has been used for kaolinite reacted in 0.1 M phosphate solutions at pH’s from 3 to 11. There are at least 3 different forms of phosphate on kaolinite. One is the phosphate physically adsorbed on kaolinite surface (outer-sphere complexes) or species left after vacuum-filtering. The second is the phosphate adsorbed by ligand exchange (inner-sphere complexes), and the third is Al-phosphate precipitates which are pH dependent. Most of the inner-spherer complexes and surface precipitates are mainly on hydroxided Al(aluminol) rather than hydroxided Si(silanol). These are pertinent with the results obtained from the phosphate adsorption experiments on silica gel and ${\gamma}$-Al$_2$O$_3$ as model compounds, respectively. The two peaks with more negative chemical shifts(more shielded) than the ortho-phosphate peak (positive chemical shift) are assigned to be the inner-sphere complexes and surface precipitates. The $^{31}$ P chemical shifts of the Al-phosphate precipitates are more negative than those of inner-sphere complexes at a given pH due to the larger number of P-O-Al linkages per tetrahedron. The chemical shifts of both the inner-sphere complexes and surface precipitates are more negative than those of inner-sphere complexes at a given pH due to the larger number of P-O-Al linkages per tetrahedron. The chemical shifts of both the inner-sphere complexes and surface precipitates become progressively less shielded with increasing pH. For the inner-sphere complexes, decreasing phosphate protonation combined with peak averaging by rapid proton exchange among phosphate tetrahedra with different numbers of protons is though to be the reason for the peak change. The decreasing shielding with increasing pH for surface precipitates is probably due to the decreasing average number of P-O-Al linkages per tetrahedron combined with decreasing protonation like inner-sphere complexes.

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Electrostatic Interaction Between Oligopeptides and Phosphate Residues by Determination of Absolute Raman Intensities

  • Kye-Taek Lim
    • Bulletin of the Korean Chemical Society
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    • v.12 no.3
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    • pp.286-289
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    • 1991
  • The changed isotropic absolute Raman intensities of the phosphate residue in the complexes of positive charge oligopeptides, lys-lys, arg-arg, lys-aromat-lys, negative charge diethyl phosphoric acid (DEP) and polyriboadenylic acid{poly(rA)} were reported and discussed. Our measurements showed that the absolute intensities of phosphate stretch vibration in complexes were different according to the reaction partners. Due to the partial electrical charge and molecular structure of oligopeptides for the complex formation lysine can interact more strongly than arginine when the reaction partners have short chain and no steric hindrance. Owing to these reasons the intensity of phosphate stretching vibration is very sensitive according to the circumstance of reaction. From our results we could suggest that we can discriminate any one of the the lysine and arginine in the complicated biological molecule during interaction between nucleotides and proteins. The activity of reaction of two basical oligopeptides is not quite similar for complex formation in aqueous solution. The activity of dipeptides depends upon the structure of molecule and environment for complex formation. Aromatic ring contributes to electrostatic interaction in complexes. The amount of the absolute intensity for pure stacking interaction is smaller than electrostatic interaction in macromolecular complexes.

Theoretical Studies for Strong Hydrogen Bonds in Trimethyl Phosphate-(HNO3)n Complexes, n=1-3

  • Kim, Yong-Ho;Kim, Hak-Won;Park, Kwang-Heon
    • Bulletin of the Korean Chemical Society
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    • v.23 no.12
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    • pp.1811-1815
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    • 2002
  • We have calculated energies and structures for the hydrogen bonded clusters between trimethyl phosphate and nitric acids. The hydrogen bond lengths between phosphoryl oxygen and the proton of nitric acid are short compared to normal hydrogen bonds, and the H-bond strengths are fairly strong. The hydrogen bond length becomes longer, and the strength becomes weaker, as more nitric acids are bound to the TMP. The average H-bond strengths for the $TMP-(HNO_3)_n$ complexes with n = 1, 2, and 3, are 9.6, 7.9 and 6.4kcal/mol at 300K respectively. Weak hydrogen bonds between nitrate oxygen and methyl proton might contribute to the stability of the clusters. Not only the BSSE but also the fragment relaxation energies should be considered to calculate hydrogen bond strengths for the complexes accurately.

Nucleophilic Addition of Phosphate to Coordinated (Arene)manganes Tricarbonyl Cations

  • Chung, Young-Keun;Bae, Hye-Kyung;Jung, Il-Nam
    • Bulletin of the Korean Chemical Society
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    • v.9 no.6
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    • pp.349-352
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    • 1988
  • [(Benzene)Mn$(CO)_3$]$^+$ reacts with NaP(O) (OR)$_2$ (R = Me, Et, Ph) to give the phosphonate compound 1. Compound 1 reacts with R'Li (R = Me, Ph, $^nBu, ^tBu$) to yield the isomerized compound 2 and the alkylated compound 3. [(Toluene)Mn$(CO)_3$]$^+$ reacts with NaP(O)$(OMe)_2$ to give the phosphonate complexes 1-A and 1-B. Treatment of 1-A with $^tBuLi$ in THF affords complexes 3-A and 3-B with the later major. With 1-B only the complex 3-C is formed. [(Anisole)Mn$(CO)_3$]$^+$ reacts with NaP(O)$(OMe)_2$ to give the phosphate complex 1-C, which on treatment with $^tBuLi$ and then $H_2O$ yields compound 3-D. After demetallation of compound 3-D, meta-tertbutyl-anisole is obtained in a reasonable yield.

Determination of Pd(II) and Pt(II) Metal Cyano Complexes Using Capillary Electrophoresis

  • Lee, Hue-Jin;Lee, Sang-Ho;Chung, Koo-Soon;Lee, Kwang-Woo
    • Bulletin of the Korean Chemical Society
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    • v.15 no.11
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    • pp.945-949
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    • 1994
  • Mixtures of cyano complexes of palladium(II) and platinum(II) were separated by capillary electrophoresis using a fused silica capillary as a separation column and 30 mM phosphate buffer (pH 7) containing 15 wt. % acetonitrile as a running buffer. By virtue of the high ionic mobilities of the negatively charged cyano complexes of Pd(II) and Pt(II), they were separated using a cathodic injection and anodic detection scheme. The metal complexes eluted through the capillary were detected by direct UV absorption at 214 nm. A linear relationship between peak area and concentration was obtained for both ions and the detection limit was lower than $10^{-14}$ mole. The proposed method was applied to real sample, e.g., anode slime obtained from an electrolytic copper refinary, as a method for the simultaneous determination of palladium and platinum.

Phosphate solubilization by phosphate solubilizing microorganisms: insight into the mechanisms

  • Buddhi Charana, Walpola;Kodithuwakku Kankanange Indika Upali, Arunakumara;Min Ho, Yoon
    • Korean Journal of Agricultural Science
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    • v.49 no.3
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    • pp.463-481
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    • 2022
  • Phosphorous (P) is considered to be one of the key essential elements demanded by crop plants. Approximately 70 - 90% of phosphatic fertilizers applied to crops are fixed in soil as Ca, Fe, and Al metal cations, which are insoluble and thus not readily available for plant uptake. Therefore, most soils are deficient in plant available P. This is usually rectified by applying phosphate fertilizers continuously, although this is not economically viable or environmentally acceptable. The present paper reviews the mechanisms involved with phosphate solubilization and mineralization by phosphate solubilizing microorganisms (PSMs) with the associated factors that determine the success. PSMs are effectively involved in mediating the bioavailability of soil P. Their contribution includes mineralization of organic P solubilization of inorganic P minerals, and storing sizable amounts of P in biomass through different mechanisms such as the production of organic and inorganic acids, H2S, siderophores, exopolysaccharides, and production of enzymes such as phosphatases, phytase, and phosphonatases/C-P lyases, which are capable of chelating the metal ions, forming complexes, and making plant available P. PSMs manifest a wide range of metabolic functions in different environments, resulting in significantly higher plant growth, enhanced soil properties, and increased biological activities. Therefore, development of bio-inoculants with efficient novel PSM strains and further investigations on exploring such strains from diverse ecological niches with multifunctional plant-growth-promoting traits are needed.

Electrochemical and Raman Spectroscopy Analysis for D- and L-Tryptophan-b-Cyclodextrin Inclusion Complexes

  • Jeong, Yu-Ra;Lee, So-Ra;Son, Pyeong-Soo;Choi, Seong-Ho
    • Journal of the Korean Applied Science and Technology
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    • v.32 no.3
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    • pp.451-460
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    • 2015
  • An enantioselective recognition of D- and L-tryptophan (Trp)-b-cyclodextrin (CD) inclusion complex was performed using electrochemical and FT-Raman spectroscopic analysis. From the electrochemical analysis, the selectivity coefficient ($K_{DL}$) of b-CD inclusion complexes was found higher than that of the D- and L-Trp in phosphate buffered saline (PBS, pH=7.0) solution. The percentage of enantioselectivity ($I_{%{ee}}$) for peak current of D-Trp-b-CD inclusion complexes was observed higher than that of L-Trp-b-CD inclusion complexes in PBS solution. From Raman spectroscopy, chemical shift difference (D, $cm^{-1}$) for the C=C stretch, ring vibration, and ring breathing of D-Try-b-CD inclusion complex were observed higher than that of L-Trp-b-CD inclusion complex. The electrochemical and Raman spectroscopic analyses were found very useful for chiral detection of racemic amino acid in the presence of b-CD.

A Study on the Flame Retardant Effect for Metal Complexes-Cellulose Hybrid Insulator (금속착물-셀룰로오스 복합 단열재의 난연 효과 연구)

  • Kim, Hong;Kang, Young-Goo
    • Journal of the Korean Society of Safety
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    • v.10 no.3
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    • pp.62-67
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    • 1995
  • The combustion characteristics of cellulose Insulation treated with several metal complexes such as Aluminium hydroxide, Cupric sulfate pentahydrate, Magnesium sulfate heptahydrate, Manganese chloride tetrahydrate and Tnisodium phosphate dodecahydrate are studied to evaluate the effectiveness as a potential flame retardant for cellulosic materials. In this study, we found that LOI values of cellulosic materials treated with the metal complexes are generally increased with the increase of their content. At high concentration, CS(24% ) and SP(24% ) show high LOI values, suggesting resistance to flame spread, The materials examined in this study were found to be relatively more resistance to smouldering and flaming combustion in comparision with untreated cellulosic material. The flammability behavior of the materials exhibits combustion process as follows : LOI$\rightarrow$smouldering region$\rightarrow$smouldering-flaming spread region$\rightarrow$flame spread region.

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Crystal Structures of Substrate and Inhibitor Complexes of Ribose 5-Phosphate Isomerase A from Vibrio vulnificus YJ016

  • Kim, Tae Gyun;Kwon, Taek Hun;Min, Kyoungin;Dong, Mi-Sook;Park, Young In;Ban, Changill
    • Molecules and Cells
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    • v.27 no.1
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    • pp.99-103
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    • 2009
  • Ribose-5-phosphate isomerase A (RpiA) plays an important role in interconverting between ribose-5-phosphate (R5P) and ribulose-5-phosphate in the pentose phosphate pathway and the Calvin cycle. We have determined the crystal structures of the open form RpiA from Vibrio vulnificus YJ106 (VvRpiA) in complex with the R5P and the closed form with arabinose-5-phosphate (A5P) in parallel with the apo VvRpiA at $2.0{\AA}$ resolution. VvRpiA is highly similar to Escherichia coli RpiA, and the VvRpiA-R5P complex strongly resembles the E. coli RpiA-A5P complex. Interestingly, unlike the E. coli RpiA-A5P complex, the position of A5P in the VvRpiA-A5P complex reveals a different position than the R5P binding mode. VvRpiA-A5P has a sugar ring inside the binding pocket and a phosphate group outside the binding pocket: By contrast, the sugar ring of A5P interacts with the Asp4, Lys7, Ser30, Asp118, and Lys121 residues; the phosphate group of A5P interacts with two water molecules, W51 and W82.