• Title/Summary/Keyword: Phosphate esters

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An Eurpium(III) Hydrolytic Catalyst Favoring Anionic Phosphate Esters over Phosphate Triester'

  • Yun, Chang Won;O, Sun Jin;Jeon, Yeong Jin;Choe, Yeong Seo;Son, Yun Gyeong;HwangBo, Seok;Gu, Ja Gang;Park, Jun Won
    • Bulletin of the Korean Chemical Society
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    • v.22 no.2
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    • pp.199-204
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    • 2001
  • A Cryptate (221) having a short alcohol pendant (2) was metallated with europium(Ⅲ) in anhydrous condition, and its hydrolytic activity for phosphate esters at neutral pH was examined. While the activity for the phosphate diester and monoester is comparable to that of the parent metal complex [1Eu]3+, its hydrolytic activity towards a phosphate triester is significantly suppressed. Potentiometric titration and luminescence spectroscopic studies for the equilibrium behavior of the complex in solution suggest that a dimer formation through the metal hydroxides as well as the pendant alcohol is likely to happen. The low hydrolytic activity for the triester seems to be associated with the dimer formation.

Synthesis and Characterization of Non-halogen Type Phosphorus-Based Flame Retardants (비할로겐형 phosphate계 난연제의 합성 및 특성결정)

  • Han, Young Gyun;Min, Seong Kee;Park, Chan Young
    • Elastomers and Composites
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    • v.49 no.4
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    • pp.313-322
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    • 2014
  • Among many types of flame retardants, the most available halogen-containing flame retardants were put under environmental restrictions in their use, so non-halogen type phosphorus-based flame retardants have come into the spotlight. When added to resins, flame retardants commonly bring about thermal degradation and decrease in mechanical properties of resins. Studies of new flame retardants were carried out in an attempt to minimize degradation of physical properties and require enough flame retardancy. In this study, three types of non-halogen phosphorus-based flame retardants were synthesized with diaryl alkyl phosphate esters, aromatic phosphate esters and phosphonium nitron flame retardants, which were then identified for the synthesis and thermal properties by gas chromatography (GC), IR and thermal gravimetric analysis (TGA).

High Temperature Lubrication with Phosphate Esters

  • Hanyaloglu, Bengi
    • Tribology and Lubricants
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    • v.11 no.5
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    • pp.177-183
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    • 1995
  • Recent work with phosphate esters has shown that a lubricious polymeric film can formed from the vapor phase on interacting during and sliding. This lubrication technique has led to methods to reduce friction and wear to very low values at high temperatures up to 700$^{\circ}$C. Preliminary with synthetic tri aryl phosphates are very promising. The vaporized lubricant forms a polymeric film on the sliding and rolling surfaces reducing the coefficient of friction below 0.05. In-situ formation of the polymeric films shows that the polymer that is formed on the surface exists in different states depending on surface temperature.

Infinite Dilution Activity Coefficients by Gab Chromatography for Variously Polarized Solute-Solvent Systems (극성이 상이한 용질-용매계에서 무한희석 활동도 계수의 가스크로마토그래피에 의한 측정)

  • Kim, Chol-Woo;Kim, Hee-Duk;Park, Jun-Ok;Nam, Se-Jong
    • Applied Chemistry for Engineering
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    • v.4 no.3
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    • pp.474-481
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    • 1993
  • The infinite dilution activity coefficients(${\gamma}{\infty}$) of nonpolar and polar solutes have been determined in different solvents at temperature between 60 and $100^{\circ}C$ by using gas chromatography. The $ln{\gamma}{\infty}$ values of nonpolar solutes(alkanes, cyclohexane, benzene, toluene and $CCl_4$) were linearly increased as 1/T in the nonpolar solvent (n-octadecane) and the polar solvent(n-hexadecyl alcohol) systems and the $ln{\gamma}{\infty}$ values at the constant temperature were increased with the number of carbon atoms of solute molecule. For the polar solutes(alcohols, esters and ketones) and the weak polar solvent(di-2-ethyl adiphate and di-2-ethylhexyl sebacate) systems, the relations of $ln{\gamma}{\infty}$ vs. 1/T were found to be curved with increased slope, and the $ln{\gamma}{\infty}$ values at constant temperature were linearly diminished as increasing the number of carbon atoms of solute molecule. For the polar solutes(alcohols, esters and ketones) and the strong polar solvents(triphenyl phosphate and tricresyl phosphate)systems, the relations of $ln{\gamma}{\infty}$ vs. 1/T were found to be curved with increased slope but $ln{\gamma}{\infty}$ values at constant temperature were linearly increased as increasing the number of carbon atoms of solute molecule.

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Hydrolysis of p-Nitrophenyl Acetate and p-Nitrophenyldiphenyl Phosphate in Micellar Solution by N-Chloro Compounds : Involvement of Counter Ions in Micellar Catalysis

  • 박병덕;이윤식
    • Bulletin of the Korean Chemical Society
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    • v.16 no.10
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    • pp.938-945
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    • 1995
  • Hydrolysis of p-nitrophenyl acetate (PNPA) and p-nitrophenyldiphenyl phosphate (PNPDPP) by N-chloro compounds in micellar solution were studied. N,N'-dichloroisocyanuric acid sodium salt (DCI) in cetyltrimethylammonium chloride (CTACl) micellar solution gave pseudo first-order kinetics. But, DCI in cetyltrimethylammonium bromide (CTABr) micellar solution showed typical series first-order kinetics - fast hydrolysis of the esters and concomitant slow decay of the hydrolyzed product, p-nitrophenolate. The hydrolysis rate was decreased as the hydrophobicity of N-chloro compounds was increased, which is the opposite trend to the usual bimolecular micellar reaction. This curious behavior of the N-chloro compounds in the catalytic hydrolysis of PNPA and PNPDPP in a cationic micellar system can be best explained by participation of counter ions of the surfactants during hydrolysis.

Crystal Structure and Molecular Stereochemistry of Novel Polymeric Cu2(DMP)44(DMSO) as a Platform for Phosphate Diester Binding

  • Rafizadeh, Massoud;Tayebee, Reza;Amani, Vahid;Nasseh, Mohammad
    • Bulletin of the Korean Chemical Society
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    • v.26 no.4
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    • pp.594-598
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    • 2005
  • Treatment of a solution of $CuCl_2$ in dimethyl phosphate (DMP) with DMSO under nitrogen atmosphere afforded to a light blue fluorescence powder. Slow evaporation of $H_2O$-DMSO solution of this powder resulted in blue-sky crystals of a new polymeric Cu(II) complex, with a unit cell composed of $Cu_2(DMP)_4$(DMSO), (1). The crystal and molecular structure of the complex acquired crystallographically. Compound (1) crystallizes in the monoclinic space group $P2_1$/n with a = 12.8920(11) $\AA$, b = 13.1966(11) $\AA$, c = 14.7926(13) $\AA$, $\alpha$ = 90$^{\circ}$, $\beta$ = 98.943(2)$^{\circ}$, $\gamma$ = 90$^{\circ}$, V= 2486.1(4) ${\AA}^3$, and Z = 4. A square pyramidal environment for the metal center was established by coordination of oxygen atoms of four bridging DMP ligands in the basal positions and binding a tri-centered oxygen atom of DMSO in the apical disposition of Cu(II). The sixth position was also affected by a weak interaction with the sulfur atom of another DMSO. The phosphorous atom in the bridging DMP was arranged in a deformed tetrahedron with (gg) conformation for methyl esters with $C_{2v}$ symmetry.

Seasonal Changes in Concentrations of Proteins and Lipids in Growing Goat Oocytes

  • Sangha, G.K.;Bhatia, H.;Khera, K.S.
    • Asian-Australasian Journal of Animal Sciences
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    • v.20 no.1
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    • pp.36-40
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    • 2007
  • Proteins and lipids not only provide a source of energy to the cell, but also play vital roles in modifying the physical properties and function of the biological membranes. In the present study, we investigated the biochemical constituents, viz. proteins and lipids, in growing oocytes of goat antral follicles during summer and winter seasons. Goat genitalia in phosphate buffered saline (pH 7.4) were brought to the laboratory within one hour of slaughter under aseptic conditions at $37^{\circ}C$. Oocytes were aspirated from normal small (<3 mm in diameter) and large (>3 mm) follicles and pooled for biochemical estimations. A significant increase in the amount of protein and lipid was observed with the growth of the oocyte. The amount of protein varied non-significantly with the season, while the amount of lipid varied significantly. The amounts of phospholipid, cholesterol, free fatty acid, and triglyceride increased with the growth of the oocyte, but no significant effect of season in these constituents was observed. Lysolecithin, sphingomyelin, and sterols were the polar lipids identified in both oocytes prepared from small follicles (small oocytes) as well as large follicles (large oocytes). In addition, the small oocytes also contained phosphatidyl serine, while large oocytes contained phosphatidyl glycerol phosphate and phosphatidyl inositol. Among non-polar lipids, triglycerides and long chain alcohols appear only in small oocytes and not in large oocytes. Monoglycerides, 1,2-diglycerides, 1,3-diglycerides and o-dialkyl glycerol ethers, fatty acids, fatty acid methyl esters, and wax esters were identified in both small and large oocytes. Information on biochemical composition of growing oocytes is relevant to oocyte and embryo competence, culture and cryopreservation.

Structure function relationships amongst the purple acid phosphatase family of binuclear metal-containing enzymes

  • Hamilton, Susan
    • Proceedings of the Korean Society for Bioinformatics Conference
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    • 2003.10a
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    • pp.5-5
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    • 2003
  • The purple acid phosphatases comprise a family of binuclear metal-containing enzymes. The metal centre contains one ferric ion and one divalent metal ion. Spectroscopic studies of the monomeric, ${\sim}$36 kDa mammalian purple acid phosphatases reveal the presence of an Fe(III)Fe(II) centre in which the metals are weakly antiferromagnetically coupled, whereas the dimeric, ${\sim}$110 000 kDa plant enzymes contain either Fe(III)Zn(II) or Fe(III)Mn(II). The three dimensional structures of the red kidney bean and pig enzymes show very similar arrangements of the metal ligands but some significant differences beyond the immediate vicinity of the metals. In addition to the catalytic domain, the plant enzyme contains a second domain of unknown function. A search of sequence databases was undertaken using a sequence pattern which includes the conserved metal-binding residues in the plant and animal enzymes. The search revealed the presence in plants of a 'mammalian-type' low molecular weight purple acid phosphatase, a high molecular weight form in some fungi, and a homologue in some bacteria. The catalytic mechanism of the enzyme has been investigated with a view to understanding the marked difference in specificity between the Fe-Mn sweet potato enzyme, which exhibits highly efficient catalysis towards both activated and unactivated phosphate esters, and other PAPs, which hydrolyse only activated esters. Comparison of the active site structures of the enzymes reveal some interesting differences between them which may account for the difference. The implications fur understanding the physiological functions of the enzymes will be discussed.

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