• Title/Summary/Keyword: Steric Effect

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Effect of Ethanolamine Species on Paper Aging by Metals (에탄올아민이 금속에 의한 종이의 노화 방지에 미치는 영향)

  • Yoon, Byung-Ho;Kim, Yong-Sik;Choi, Kyoung-Hwa
    • Journal of Korea Technical Association of The Pulp and Paper Industry
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    • v.40 no.3
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    • pp.36-41
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    • 2008
  • It is known that ethanolamines play a critical role for deacidification of paper sized by alum-rosin. However, amines also are effective as a chelating agent of metal. The present work was focused on whether amines could scavenge metals and prevent from the aging of paper. Metals such as alum, copper(II) and iron(III) was added to paper, and the paper treated with amines was aged in a thermo-hygrostat for 3-6 days. In the case of paper added to alum, the amines efficiency against paper aging was good in the oder of triethanolamine, diethanolamine and monoethanolamine attributable to the intensity of basicity and steric effect. Even in the case of paper treated with copper(II) chloride, iron(III) chloride, and copper(II) chloride, the significant preservation efficiency was shown by ethanolamine during accelerated aging. This outcome pinpoints the fact that ethanolamine can prevent paper aging not only from acid by neutralizing acid contained in paper but also from metals by producing of complexes with metals. These consequences above convince that ethanolamine makes it possible for mass deacidification for paper which contains acid and metals. Future studies should be conducted concerning whether, in reality, the treatment of its gas mode, in a single or multiple applications, has significant effect on lessening paper aging.

Effect of Phenolic Antioxidants System on Yellowing of Amorphous Poly-α-olefin (페놀계 산화방지제에 의한 비결정성 올레핀 수지의 황변 거동)

  • Kim, Si-Yong;Kim, Ho-Gyum;Park, Sang-Cheol;Min, Kyung-Eun
    • Polymer(Korea)
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    • v.37 no.2
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    • pp.156-161
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    • 2013
  • Phenolic antioxidants are effective stabilizers that provide excellent long-term heat stability by preventing thermo-oxidative degradation during processing and service life. However, under a selected set of circumstances, certain types of phenolics have been susceptible to discoloration due to prolonged storage in an environment containing oxides of nitrogen. It is investigated that the effect of addition of secondary antioxidant and chemical structure of primary antioxidant on discoloration of amorphous poly-${\alpha}$-olefin (APAO), which is especially prone to be decomposed in high processing temperature. From the result, it is concluded that a higher level of steric hindrance of phenolic antioxidant provided by long alkyl chain allows a more enhanced synergic effect with secondary antioxidant.

Dephosphorylation of Diphenyl-4-Nitrophenyl Phosphinate(DPNPIN) onto 2-Alkylbenzimidazolide Anion in TTABr Micellar Solution (TTABr 미셀 용액속에서 2-알킬벤즈이미다졸 음이온에 의해 추진되는 디페닐-4-니트로페닐 포스페네이트(DPNPIN)의 탈인산화반응)

  • Kim, Jeung-Bea
    • Journal of Environmental Science International
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    • v.24 no.8
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    • pp.981-992
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    • 2015
  • This study is mainly focused on micellar effect of tetradecyltrimethyl ammonium bromide(TTABr) solution including alkylbenzimidazole(R-BI) on dephosphorylation of diphenyl-4-nitrophenylphosphinate(DPNPIN) in carbonate buffer(pH 10.7). Dephosphorylation of DPNPIN is accelerated by $BI^{\Theta}$ ion in $10^2$ M Carbonate buffer(pH 10.7) of $4{\times}10^{-4}$ M TTABr solution up to 80 times as compared with the reaction in Carbonate buffer by no benzimidazole(BI) solution of TTABr. The value of pseudo first order rate constant($k_{\psi}$) of the reaction in TTABr solution reached a maximum rate constant increasing micelle concentration. The reaction mediated by $R-BI^{\Theta}$ in micellar solutions are obviously slower than those by $BI^{\Theta}$, and the reaction rate were decreased with increase of lengths of alkyl groups. It seems due to steric effect of alkyl groups of $R-BI^{\Theta}$ in Stern layer of micellar solution. The surfactant reagent, TTABr, strongly catalyzes the reaction of DPNPIN with R-BI and its anion($R-BI^{\Theta}$) in Carbonate buffer(pH 10.7). For example, $4{\times}10^{-4}$ M TTABr in $1{\times}10^{-4}$ M BI solution increase the rate constant($k_{\psi}=99.7{\times}10^{-4}1/sec$) of the dephosphorylation by a factor ca. 28, when compared with reaction($k_{\psi}=3.5{\times}10^{-4}1/sec$) in BI solution(without TTABr). And no TTABr solution, in BI solution increase the rate constant($k_{\psi}=3.5{\times}10^{-4}1/sec$) of the dephosphorylation by a factor ca. 39, when compared with reaction ($k_{\psi}=1.0{\times}10^{-5}1/sec$) in water solution(without BI).

Conformational Analysis of Sulfonylureas (술포닐 우레아 유도체들의 형태분석)

  • Kang, Kee-Long;Lee, Sung-Hee;Chung, Uoo-Tae
    • YAKHAK HOEJI
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    • v.36 no.6
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    • pp.518-528
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    • 1992
  • To determine the optimal conformation of sulfonylureas, the correlation between conformation and hypoglycemic activity of the two sulfonylureas of tolbutamide and chlorpropamide as hypoglycemic agent was studied using an empirical potential function (ECEPP/2) and the hydration shell model in the unhydrated and hydrated states. The conformational energy was minimized from several starting conformations with possible torsion angles in each molecule. The conformational entropy change of each conformation was computed using a harmonic approximation. To understand the hydration effect on the conformation of the molecules in aqueous solution, the contribution of water-accessible volume of each group or atom in the lowest-free-energy conformation was calculated and compared each other. From comparison of the computed lowest-free-energy conformations of two sulfonylureas, it could be suggested that the hydration of sulfonylurea moiety is related to increase the hypoglycemic activity. From the calculation results, it was known that the conformational entropy is the major contribution to stabilize the low-free-energy conformations of two sulfonylureas in unhydrated state. Whereas, in hydrated state, the hydration free energy largely contributes to the total free energies of low-free-energy conformations of tolbutamide and conformational entropy contributes to stabilize the low-free-energy conformations of chlorpropamide. The torsion angles from phenyl ring to urea moiety of the low-free-energy conformations of the two sulfonylureas were shown the nearly regular trend. On the basis of these results, the conformation exhibiting the optimal hypoglycemic activity of sulfonylureas and the binding direction to pancreatic receptor site A could be predicted. Also, according to the side chain lengthening of urea moiety, tolbutamide showed various conformational change. Therefore, steric effect may be important factor in the interaction between sulfonylureas and the putative pancreatic receptor.

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Origin of Decreasing the Dielectric Constant and the Effect of Ionic Polarization (유전상수가 낮아지는 원인과 이온 분극의 효과)

  • Oh, Teresa
    • Journal of the Korean Vacuum Society
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    • v.18 no.6
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    • pp.453-458
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    • 2009
  • SiOC film was deposited by the chemical vapor deposition using BTMSM and oxygen mixed precursor. The characteristic of SiOC film varied with increasing of the gas flow rate ratios. The dielectric constant was obtained by C-V measurement using the structure of metal/SiOC film/Si. The space effect due to the steric hindrance between alkyl group at terminal bond of Si-$CH_3$ made the pores, and increased the thickness. However, the SiOC film due to the lowering of the polarization decreased the thickness and then decreased the dielectric constant. After annealing process, the dielectric constant decreased because of the evaporation of the OH or $H_2O$ sites. The thickness was related to the lowering of the dielectric constant by the reduction of the polarization and the thickness decreased with the decrease of the dielectric constant. The refractive index was in inverse proportion to thickness. The trends of the thickness and refractive index did not change after annealing.

Influence of 3-(N-methyl-N-X(Sub.)Phenylaminooxoacetyl) Group on the Herbicidal Activity of Imazapyr Derivatives (Imazapyr 유도체의 제초활성에 미치는 3-(N-methyl-N(X)-치환-Phenylaminooxoacetyl) Group의 영향)

  • Sung, N.D.;Ryu, T.S.;Chang, H.S.;Kim, D.W.
    • Applied Biological Chemistry
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    • v.37 no.6
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    • pp.516-521
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    • 1994
  • New seventeen imazapyr derivatives, 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-3-(N-methyl-N-X(sub.)-phenylaminooxoacetyl)pyridine, 6 were synthesized and their pre-emergence herbicidal activity$(pI_{50})$ in vivo against Corn (Zea mays L.) and Pigweed (Amaranthus viridis L.) were studied by the pot test under paddly conditions. Quantitative structure activity relationships (QSARs) were analyzed using the physicochemical parameters of substituent(X) on the phenyl ring of 3-(N-methyl-N-X(sub.)-phenylaminooxoacetyl) group and regression analysis. The herbicidal activities were related to the steric effect of X-substituent. The effect was rationalized by paraholic function of MR and $L_1$, where the optimal values were MR=5.56 (Zea mays L.) and $L_1=3.34\;{{\AA}}$ (Amaranthus viridis L.). Among them, 2,5-difluoro substituted compound, 6i showed good herbicidal activity against Pigweed with excellent tolerance to Corn.

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The Farnesyl Protein Transferase Inhibition Activity of Chalcone Derivatives (Chalcone 유도체의 Farnesyl Protein Transferase 저해활성)

  • Yu, Seong-Jae;Myung, Pyung-Keun;Kwon, Byung-Mok;Lee, Seung-Ho;Sung, Nack-Do
    • Applied Biological Chemistry
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    • v.42 no.3
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    • pp.252-255
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    • 1999
  • Inhibition activities$(pI_{50})$ of chalcone derivatives as substrate with farnesyl protein transferase(FPTase) were determined in vitro. The structure activity relationships(SAR) between the activity and physicochemical parameters of X & Y-substituents on the phenyl groups were analyzed by Free-Wilson and Hansch method. X-substituents on the benzoyl group have the more important role to inhibition activity than Y-substituents on the styryl group. Among them, none substituent, 8 showed the highest FPTase inhibition activity$(pI_{50}=4.30)$. Particularly, the SAR equation could be formulated, showing a parabolic relationship between the activity and hydrophobicity(logP) where the optimal value$({\Sigma}logP)_{opt}$ was 3.915. And also the activity depends on the steric effect(Es > 0) with X-substituent and the resonance effect(R < 0) with electron donating Y-substituents. Based on the results of SAR analyses, the interactions between substrates and receptor, FPTase, could be assumed.

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Substituents Effect on Aziridine Chemistry: N-Inversion Energy, Reactivity and Regioselectivity of Nucleophilic Ring-opening

  • Park, Gyoo-Soon;Kim, Seok-Chan;Kang, Han-Young
    • Bulletin of the Korean Chemical Society
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    • v.26 no.9
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    • pp.1339-1343
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    • 2005
  • The N-inversion energies and nucleophilic ring-opening reactions of N-substituted aziridine compounds are investigated using B3LYP/6-31+$G^*$ methods, where substituents (R) on the nitrogen atom has been H (1), Me (2), Ph (3), Bn (4), CHMePh (5), $CO_2Me$ (6), COPh (7) and $SO_2Ph$ (8). The N-inversion energy with X group are decreased as the following order: R = CHMePh (17.06 kcal/mol) $\gt$ Me (16.97) $\gt$ Bn (16.70) $\gt$ H (16.64) $\gt$ $SO_2Ph$ (12.18) $\gt$ Ph (8.91) $\gt$ COPh (5.75) $\gt$ $CO_2Me$ (5.48). For reactivity of the ring opening toward cyanide ion, the aziridine 6 (R=$CO_2Me$) is shown to be the most reactive one. During the ring opening of aziridine 6 by CN$^{\ominus}$, the torsional OCNC angle becomes near to $180^{\circ}$, where the geometry allows for the effective incorporation of electrons of the nitrogen atom to the C=O bond. It would be a possible driving force for nucleophilic ring opening reaction as well as decreasing the N-inversion energy barrier. Regarding to the regioselectivity, the orientation of nucleophile in ring opening reaction appears to be different in the case of 9 and 10. The results are discussed in terms of steric/electronic effect of the $C_2$-substituents.

Development and Evaluation of Protected Fat in Wheat Straw Based Total Mixed Ration

  • Sirohi, S.K.;Malik, Raman;Walli, T.K.
    • Asian-Australasian Journal of Animal Sciences
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    • v.14 no.10
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    • pp.1405-1408
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    • 2001
  • Ca salt of soybean oil (PSO) and that of mustard oil plus mahua oil (PMOMO) (50:50) were prepared using double decomposition method, and further tested for their fatty acid composition and degree of saponification. Furthermore, the different levels of protected fat of PSO and PMOMO were evaluated in wheat straw based total mixed ration (TMR) in vitro. Results indicated that capric, lauric, myristic, palmitic, steric, oleic, linoleic, leinolenic acids were traces, traces, traces, 10.00, 2.00, 25.00, 58.50, 5.0% in PSO while the corresponding values in PMOMO were 1.08, 0.28, 0.45, 16.9, 12.95, 44.38, 17.46 and 6.50%, respectively. The degree of saponification of both protected fat supplements was more than 80%. Six treatment combinations were tested I.e., blank without feed and fat supplement (T1); control diet with out fat supplement (T2); control diet plus bypass fat supplement (PSO) so that diet contain 5% fat (T3); control diet plus bypass fat supplement (PSO) so that diet contain 7.5% fat (T4); two more diets viz. T5 and T6 were formulated using bypass fat supplement from PMOMO containing 5 and 7.5% fat respectively. TMR was prepared using 50% concentrate mixture and 50% wheat straw. Result indicated that TVFA, $NH_3-N$,TCA-N, total-N and total gas production were increased in treatment diets at 7.5% level of supplementation, however, fermentation pattern remain similar at 5.0% level of supplementation with respect to control diet. Nevertheless, IVDMD and IVOMD values remained unchanged, rather non-significant at both fat levels and with the both fat sources. On the basis of results it was concluded that Ca-salt of Soybean oil or Mustard plus Mahua oil did not show any negative effect either on digestibility or on microbial protein synthesis in rumen, hence the dietary fat upto 7.5% level in total mixed ration based on wheat straw, could be safely used without any adverse effect on rumen fermentation.

Synthesis of Poly(MMA-co-PEGMA) Electrolytes by Grafting-onto Method and Effect of Composition on Ionic Conductivities (Grafting-onto법에 의한 poly(MMA-co-PEGMA) 전해질의 합성과 이온전도도에 대한 조성의 영향)

  • Lee, Ju-Hyung;Ryu, Sang-Woog
    • Journal of the Korean Electrochemical Society
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    • v.16 no.4
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    • pp.198-203
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    • 2013
  • Copolymer consisted of MMA and tBMA was synthesized by radical polymerization and poly(MMA-co-MA) was prepared by selective hydrolysis of tert-butyl group. The obtained polymer was coupled with epoxy functionalized PEO of various molecular weight to synthesize poly(MMA-co-PEGMA) with different side chain length. The AC-impedance measurement shows $1.88{\times}10^{-6}Scm^{-1}$ of room temperature ionic conductivity from 48mol% of MMA while $5.11{\times}10^{-8}Scm^{-1}$ was observed in 82mol% sample. In addition, there was an effect of PEGMA molecular weight on ionic conductivity possibly due to the steric hindrance in grafting-onto coupling reaction. Finally, the polymer electrolytes shows electrochemical stability up to 6V at room temperature.