• Title/Summary/Keyword: p-atom

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Transition Metal Complexes Derived From 2-hydroxy-4-(p-tolyldiazenyl)benzylidene)-2-(p-tolylamino)acetohydrazide Synthesis, Structural Characterization, and Biological Activities

  • Alhakimi, Ahmed N.;Shakdofa, Mohamad M.E.;Saeed, S. El-Sayed;Shakdofa, Adel M.E.;Al-Fakeh, Maged S.;Abdu, Ashwaq M.;Alhagri, Ibrahim A.
    • Journal of the Korean Chemical Society
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    • v.65 no.2
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    • pp.93-105
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    • 2021
  • Mononuclear Cu(II), Ni(II), Co(II), Mn(II), Zn(II), Fe(III), Ru(III), and UO2(II) complexes of 2-hydroxy-4-(p-tolyldiazenyl)benzylidene)-2-(p-tolylamino)acetohydrazide (H2L) were prepared by direct method. The ligand and its complexes were isolated in solid state and characterized by analytical techniques such as elemental and thermal analyses, molar conductance, magnetic susceptibility measurements and spectroscopic techniques such as UV-Visible, IR, 1H-NMR and 13C-NMR. The spectral data indicated that the ligand acted as neutral/monobasic bidentate or monobasic/dibasic tridentate ligand bonded to the metal ions through the oxygen atom of ketonic or enolic carbonyl group, azomethine nitrogen atom and deprotonated/protonated phenolic oxygen atom forming either tetragonally distorted octahedral or octahedral. Antimicrobial activities of the ligand and its complexes were evaluated against Escherichia coli, Bacillus subtilis and Aspergillus niger by well diffusion method. The results of antifungal activity showed that the Fe(III) complex (10) exhibited higher antifungal against Aspergillus niger than the other complexes. However, the results of antibacterial activity revealed that Cu(II) complex (4) is the most active against Escherichia coli while the Cu(II) complex (5) and Fe(III) complex (10) exhibited higher antibacterial effect on Bacillus subtilis than the other complexes.

Studies on the Semicarbazone Formation of Mono substituted Benzaldehydes (일치환 Bezaldehyde 의 Semicarbazone 생성 반응에 관한 연구)

  • Kim, Yong-In;Kim, Chang-Mean
    • Journal of the Korean Applied Science and Technology
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    • v.7 no.1
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    • pp.93-105
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    • 1990
  • Semicarbazone formation of nine monosubstituted benzaldehydes was studied kinetically in 20% methanol buffer solution at 15, 25, 35, and $45^{circ}C$. The rate of p-nitrobenzaldehyde semicarbazone formation is 2.7 times as fast as that of benzaldehyde, while p-hvdroxybenzaldehyde is 3.6 times as slow as that of benzaldehyde. Activation energies for p-chlorobenzaldehyde, benzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldshyde, p-hydroxybenzaldehyde, and p-dimethylaminobenzaldehyde semicarbazone formation are calculated as 5.80, 6.19, 6.57, 7.06, 8.03, and 6.46 kcal/mol respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ions but neutral molecules involving hydrogen bonding between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst, and concerted attack of the necleophilic reagent, free base on carbonyl compound. Also, the effect of solvent composition is small in 20% and 50% methanol (and ethanol) aqueous solutions. The ${\rho}-{\sigma}$ plots for the rates of semicarbazone formation at pH 7.1 show a linear ${\rho}-{\sigma}$ relationship (${\rho}=0.14l$, in contrast to that at pH 2.75 and pH 5.4 corresponding to ${\rho}-{\sigma}$ correlations reparted by Jencks. The rate of semicarbazone formation at pH 5.4 show a relationship which is convex upward, resulting in a break in the curve but at pH 2.75, slight difference from a linear relationship. As a result of studying citric acid catalysis, second-order rate constants increase linearly with citric acid concentration and show a 2 times increase as the catalyst concentration is varied from 0.025 to 0.1 mol/1 at pH 2,9, but slight increase at pH 5.3. The rate-determining step is addition below pH 5 but is dehydration between pH 5 and 7. Conclusively, the rate-determining step of the reaction changes from dehydration to addition in respect to hydrogen ion activity near pH 5. The ortho: para rate ratio of the hydroxybenzaldehydes for semicarbazone formation is about 17 at $15^{\circ}C$. It is concluded that the results constitute strong evidence in favor of greater stabilization of p- than o-hydroxybenzaldehyde by substituent which donate electrons by resonance and is due to hydrogen bonding between the carbon-bound hydrogen of the-CHO group and the oxygen atom of the substituent.

The Reaction between Organothioenamine Phosphonate and Styrene Oxide (유기 티오엔아민 포스포네이트와 산화스티렌과의 반응)

  • Keun Jae Kim;Chi Sun Han
    • Journal of the Korean Chemical Society
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    • v.20 no.4
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    • pp.295-298
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    • 1976
  • The fact that a reaction between organothioenamine phosphonate and styrene oxide produces a derivative of cyclopropane has been proved by structural identification. This suggests that an anionic oxygen atom from the ring opening of the styrene oxide by nucleophilic attack of thioenamine phosphonate links to the phosphorous atom to from a betaine as an intermediate which is followed by cleavage of the weak P-C bond. The dextrorotatory optical activity of the product showed that the reaction was under the control of steric stability of the benzyl carbon in styrene which leads to the product through a sterically stable pathway.

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The trans $\rightarrow$ cis Photoisomerization and Fluorescence of trans 1,2-Bispyrazylethylene: pH, Salt and Heavy Atom Effects

  • Shim, Sang-Chul;Bong, Pill-Hoon
    • Bulletin of the Korean Chemical Society
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    • v.7 no.1
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    • pp.53-55
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    • 1986
  • The $trans{\rightarrow}cis$ photoisomerization and fluorescence of trans-1,2-bispyrazylethylene were investigated in various conditions. The quantum yields of the $trans{\rightarrow}cis$ photoisomerization and the fluorescence intensity of trans-1,2-bispyrazylethylene decrease on going from neutral to acidic or basic solutions. The quantum yields of photoisomerization, however, are little affected by changing the concentration of salt while the fluorescence intensity increases as the concentration of salt increases. pH and salt effects on the energy levels of $^1(n,\;{\pi}^*)\;and\;^1({\pi},\; {\pi}^*)$ states lead to opposing changes in photoisomerization and fluorescence quantum yields. The heavy atom effect on the fluorescence of 1,2-bispyrazylethylene was also investigated.

Synthesis and Characterization of Polystyrene-b-Poly(acrylic acid) Block Ionomer via Atom Transfer Radical Polymerization (원자 이동 라디칼 중합을 이용한 Polystyrene-b-Poly(acrylic acid) 블록 이오노머의 합성 및 분석)

  • 박계리;안성국;조창기
    • Polymer(Korea)
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    • v.27 no.1
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    • pp.17-25
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    • 2003
  • Using atom transfer radical polymerization (ATRP), polystyrene macroinitiators and polystyrene-b-poly(t-butyl acrylate) (PS-b-P(tBA) block copolymers were synthesized by CuBr/PMDETA catalyst system in solution. After hydrolysis, polystyrene-b-poly(acrylic acid), amphiphilic block copolymers, were formed. Subsequent neutralization of polyacid block led to the block ionomers. The molecular weight of the synthesized PS-b-P(tBA) block copolymers was easily-controlled to 5000-10000 and their distributions were less than 1.2. The chemical structures of the synthesized block copolymers were characterized by $^1$H-NMR and FT-IR. In the DSC thermograms, $T_g$ appeared in the vicinity of 100 $^{\circ}C$ because of higher styrene content. In addition, the phase separation of the block ionomers was observed by TEM.

Synthesis of New pH-Sensitive Amphiphilic Block Copolymers and Study for the Micellization Using a Fluorescence Probe

  • Kim, Kyung-Min;Choi, Song-Yee;Jeon, Hee-Jeong;Lee, Jae-Yeol;Choo, Dong-Joon;Kim, Jung-Ahn;Kang, Yong-Soo;Yoo, Hyun-Oh
    • Macromolecular Research
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    • v.16 no.2
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    • pp.169-177
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    • 2008
  • This paper reports a facile synthesis of new water-soluble poly(ethylene oxide) (PEO)-based amphiphilic block copolymers showing pH sensitive phase transition behaviors. The copolymers were prepared by atom transfer radical polymerization (ATRP) of methacrylamide type of monomers carrying a sulfonamide group using a PEO-based macroinitiator and a Cu(I)Br/$Me_6TREN$ catalytic system in aqueous media. The resulting polymers were characterized by a combination of $^1H$-NMR, size exclusion chromatography, and UV/Visible spectrophotometeric analysis. The micellization of the block copolymers as a drug-loading mechanism in aqueous media using fluorescein salt was examined as a function of pH. The stable micelle formation and its loading efficacy suggest that the block copolymers can be used as precursors for drug-nanocontainers.

The Effects of the Structural Characteristics on Properties of Their Bridging OH Groups for $AlPO_4-5$ Molecular Sieve : MNDO Calculations ($AlPO_4-5$ 분자체에서 가교 OH 그룹의 성질에 대한 구조 특성 효과 : MNDO 계산)

  • Son, Man-Shick;Lee, Chong-Kwang;Paek, U-Hyon
    • Journal of the Korean Chemical Society
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    • v.37 no.9
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    • pp.787-792
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    • 1993
  • Semiempirical MNDO calculations are employed to study relation properties on bridging OH group with Al-O(P-O) bond length and Al-O-P bond angle of structural characteristics using birdging $(OH)_3AlOP(OH)_3$ and $(OH)_3AlOHP(OH)_3^+$ model culster. We know that the O-H bond dissociation energy of bridging OH group is increased with increasing Al-O(P-O) bond length and decreasing Al-O-P bond angle. The bridging OH group is formed into enlarged Al-O(P-O) bond length and shortened Al-O-P bond angle in bridging oxygen atom by a hydrogen migration. The negative net charge of bridging oxygen atom is increased with longer Al-O-P bond angle, while the positive net charge is decreased with longer Al-O-P bond angle.

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Two Possible Space Groups of Ttis(tekaethylammonium) [bis(trimetaphosphate $\kappa^3O, O^', O^{"}$)] Vanadate(3-),$[V(P_3O_9)_2](NC_8H_{20})3$ (Tris(tetraethylammnnium) [bis(trimetaphosphate $\kappa^3O, O^', O^{"}$)] Vamdate(3-),$[V(P_3O_9)_2](NC_8H_{20})_3$,의 두가지 가능한 공간군)

  • 서일환;이진호
    • Korean Journal of Crystallography
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    • v.5 no.1
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    • pp.1-6
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    • 1994
  • Two possible space groups of the comfound, VP6N3018C24H:60, are: P 1, a=14.022(1), b=12.644(2), c= 12.640(1)A, a=8038(1), B=102.12(1), r=102.16(1), V=2124.1A3, Z=2, μ=0.47cm-1, d=1.46g/cm3, R=0.083 for 3350 independent reflections with Fo>4o IFI, and C2/c, a=19.32(2), b=16.32(2), c=14.02(1)A, B=105.98(5), β=105.98(5), V=4248.2A3, Z=4 R=0.083 for 1590 independent reflections with Fo>4c IFoI . In the space group P T, there are two monlecules in a unit cell. Vanadium atoms in the two monlecules occupy the two different special positions such that the complete monlecules are accomplished by the two independent center of symmetry. Therefore two different half molecules of bis(trimetaphosphate)vanadate and three molecules of tetraethylammonium are the asymmetric unit in a unit cell. In the space group C2/c, however, the vanadium atom is located at a special position with centrosymmetry, and a two-fold symmetry axis passes through C2/c, N2 and C25 atoms. Therefore the asymmrtic unit in a unit cell consists of a half molecule of bis(trimetaphosphate)vanadate and one and a half molecules of tetraethylammonium. All the molecular conformations in both space groups are very similar: six oxygen atoms coordinated to a vanadium atom in the bi s(trimetaphosphate)vanadate molecule form an octahedron and the four carbon atoms bonded to a nitrogen atom in the tetraethylammonium molecule are disordered so that the eight carbon atoms around nitrogen atom exhibit an irregular dodecahedral form.

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Nitrogen-15 Determination in Tissues of Laying Hens Fed on Different Levels of $^{15}N-Chlorocholine$ Chloride ($^{15}N-CCC$) Diets

  • Nurhayati, Nurhayati;Thinggaard, Grete;Chakeredza, S.;Reineking, A.;Langel, R.;ter Meulen, U.
    • Asian-Australasian Journal of Animal Sciences
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    • v.20 no.3
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    • pp.412-417
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    • 2007
  • An experiment was conducted to determine the distribution of nitrogen-15 in tissues of laying hens receiving different levels of $^{15}N$-CCC in diets. Twenty brown laying hens were divided into four groups and randomly assigned into one of four dietary treatment groups consisting of 0, 5, 50 and 100 ppm $^{15}N$-CCC inclusion. The hens were individually fed with the $^{15}N$-CCC diets in battery cages for 11 days and then all hens restored to feeding on the control diet for 7 days. After eleven days, eight hens were slaughtered, and the others were slaughtered seven days after $^{15}N$-CCC diets withdrawal. Samples of blood, liver, heart and meat were collected and their $^{15}N$ contents were determined. The ${\delta}^{15}N$ excess (${\delta}^{15}N$-ex) and atom percentage excess in $^{15}N$ were calculated. The ${\delta}^{15}N$-ex and atom percentage excess $^{15}N$ increased significantly (p<0.05) with increasing levels of $^{15}N$-CCC in diets in all tissues after feeding $^{15}N$-CCC diets for eleven days. The highest concentration of ${\delta}^{15}N$-ex and atom percentage excess $^{15}N$ were detected in blood, followed in order by liver, heart and thigh meat. The concentrations reduced significantly (p<0.05) after $^{15}N$-CCC diets were withdrawn. Comparison between treatment groups showed that ${\delta}^{15}N$-ex and atom percentage excess $^{15}N$ were still higher in hens that had been fed diets with higher levels of $^{15}N$-CCC. This study showed that nitrogen-15 was distributed in blood, liver, heart and meat of laying hens.