• 제목/요약/키워드: chemical interaction

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Theoretical Mechanism Studies on the Enantioselectivity of aza-MBH-type Reaction of Nitroalkene to N-tosylimine Catalyzed by Thiourea-tertiary Amine

  • Lu, Nan;Wang, Huatian;Wang, Yangping
    • Bulletin of the Korean Chemical Society
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    • 제34권12호
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    • pp.3591-3596
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    • 2013
  • The enantioselective aza-Morita Baylis Hillman reaction of nitroalkene and N-tosylimine catalyzed by thiourea-tertiary amine has been investigated using density functional theory. Enantioselectivity is dominated by the cooperative effect of non-covalent and weak covalent interactions imposed by different units of catalyst. As Lewis base, the tertiary amine unit activates nitroalkene via weak covalent bond. The weak covalent interaction orients the reaction in a major path with smaller variations of this bond. The aromatic ring unit activates N-tosylimine via ${\pi}-{\pi}$ stacking. The non-covalent interaction selects the major path with smaller changes of the efficient packing areas. Thiourea unit donates more compact H-bonded network for species of the major path. The calculated ee value in xylene solution phase (97.6%) is much higher than that in N,N-Dimethylformamide (27.2%). Our conclusion is also supported by NBO analysis.

Modeling Techniques for Geoenvironmental Engineering Problems

  • Singh, D.N.;Rao, B. Hanumantha
    • 한국지반공학회:학술대회논문집
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    • 한국지반공학회 2007년 가을학술발표회
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    • pp.542-557
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    • 2007
  • Contamination of subsurface results in degradation of geomaterials (i.e., soils and rock mass), in the long run. This is mainly due to the presence of chemical and/or radiological materials in undesirable concentrations and at elevated temperatures. However, as contaminant-geomaterial interaction is an extremely slow and complex process, which primarily depends on their physical, chemical and mineralogical properties, it is quite difficult to study this interaction under laboratory or in situ conditions. In such a situation, accelerated physical modeling, using a geotechnical centrifuge, and finite element/difference based numerical modeling techniques are found to be quite useful. This paper presents details of various modeling techniques developed by the researchers at the Indian Institute of Technology Bombay, Mumbai, India, for studying heat migration, flow and interaction (fate) of reactive and non-reactive contaminants in the geoenvironment, under saturated and unsaturated conditions. In addition, paper presents details of the technique that can be employed for determining susceptibility of a material to undergo physico-chemico-mineralogical alterations due to its interaction with contaminants.

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Reversible Excited-State Proton Transfer: Effect of the Switching of Interaction Potential by Reaction

  • Lee, Jin-uk;Uhm, Je-sik;Lee, Woo-Jin;Lee, Sang-youb;Sung, Jae-young
    • Bulletin of the Korean Chemical Society
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    • 제27권2호
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    • pp.197-202
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    • 2006
  • In the reaction A + B $^\rightarrow_\leftarrow$ C, where A and B are ionic reactants having opposite charges, a B molecule approaching an A will experience a switching of the interaction potential when the A molecule is captured by one of the other B molecules in the medium. In the reversible case, the former B molecule still has a chance to react with the A, so that one needs to take into account the switched interaction between the reactant B and the product C as well as that between the reactants to treat the kinetics accurately. It is shown that this kind of interaction potential switching affects the relaxation kinetics in an intriguing way as observed in a recent experiment on an excited-state proton transfer reaction.

The Gauge Invariant Formulation for the Interaction of the Quantized Radiation Field with Matter

  • 이덕환
    • Bulletin of the Korean Chemical Society
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    • 제20권6호
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    • pp.720-726
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    • 1999
  • It has been proved by the semi-classical gauge invariant formulation (GIF) that the correct interaction operator for coupling the field-free material states with the radiation field must be the position form regardless of the gauge chosen for expressing the electromagnetic potentials, in accordance with the well-established principle of gauge invariance. The semi-classical GIF is now extended to the quantized radiation field interacting with matter by defining the energy operator for the quantized radiation field in the presence of matter. It will be shown in this paper that the use of the energy operator guarantees the position form of the interaction operator even in the Coulomb gauge, contrary to the conventional approach in which the dark material Hamiltonian is used to get the interaction operator of the momentum form. The multipolar Hamiltonian is examined in the context of the quantum mechanical gauge transformation.

Chiral Recognition Models of Enantiomeric Separation on Cyclodextrin Chiral Staionary Phases

  • 이선행;김병학;이영철
    • Bulletin of the Korean Chemical Society
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    • 제16권4호
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    • pp.305-309
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    • 1995
  • The enantiomeric separation of several amino acid derivatives by reversed-phase liquid chromatography using two (R)-and (S)-naphthylethylcarbamate-β-cyclodextrin(NEC-β-CD) bonded stationary phases was studied to illustrate the chiral recognition model of the enantiomeric separation. The retention and enantioselectivity of the chiral separations with (R)-and (S)-NEC-β-CD bonded phases were compared with similar separations with the native β-CD stationary phases. Especially, the enantioselectivity and elution orders between the derivatized amino acid enantiomers are carefully examined. These results can be illustrated by the chiral recognition models involving inclusion complexation, π-π interaction, and/or hydrophobic interaction. Inclusion complexation and hydrophobic interaction of the naphthyl group of the NEC moiety seem to be major chiral recognition components in the enantiomeric separation of 2,4-dinitrophenyl amino acids and dabsyl amino acids on (R)-and (S)-NEC-β-CD columns. For dansyl amino acids, only the inclusion complexation is the dominant factor. Three different chiral recognition models containing π-π interaction, inclusion complexation and hydrogen bonding were proposed for the separation of the 3,5-dinitrobenzoyl amino acid enantiomers, depending on the size and shape of amino acids.

Impacts of C60-Ionic Liquids (ILs) Interactions and IL Alkyl Chain Length on C60 Dispersion Behavior: Insights at the Molecular Level

  • Wang, Zhuang;Tang, Lili;Wang, Degao
    • Bulletin of the Korean Chemical Society
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    • 제35권9호
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    • pp.2679-2683
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    • 2014
  • Mechanisms underlying the impacts of interactions between carbon nanoparticles (CNPs) and ionic liquids (ILs) on the physicochemical behavior of CNPs need to be more full worked out. This manuscript describes a theoretical investigation at multiple levels on the interactions of fullerene $C_{60}$ with 21 imidazolium-based ILs of varying alkyl side chain lengths and anionic types and their impacts on $C_{60}$ dispersion behavior. Results show that ${\pi}$-cation interaction contributed to mechanism of the $C_{60}$-IL interaction more than ${\pi}$-anion interaction. The calculated interaction energy ($E_{INT}$) indicates that $C_{60}$ can form stable complex with each IL molecule. Moreover, the direction of charge transfer occurred from IL to $C_{60}$ during the $C_{60}$-IL interaction. Quantitative models were developed to evaluate the self-diffusion coefficient of $C_{60}$ ($D_{fullerene}$) in bulk ILs. Three interpretative molecular descriptors (heat of formation, $E_{INT}$, and charge) that describe the $C_{60}$-IL interactions and the alkyl side chain length were found to be determinants affecting $D_{fullerene}$.

The Interaction of HIV-1 Inhibitor 3,3',3",3‴-Ethylenetetrakis-4-Hydroxycoumarin with Bovine Serum Albumin at Different pH

  • Dong, Sheying;Yu, Zhuqing;Li, Zhiqin;Huang, Tinglin
    • Bulletin of the Korean Chemical Society
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    • 제32권6호
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    • pp.2063-2069
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    • 2011
  • We studied the interaction of 3,3',3'',3'''-ethylenetetrakis-4-hydroxycoumarin (EHC) with bovine serum albumin (BSA) in acetate buffer and phosphate buffer with different pH values by UV-vis absorption spectrometry and fluorescence spectrometry respectively. It was found that the pH values of the buffer solutions had an effect on the interaction process. In acetate buffer of pH 4.70, the carbonyl groups in EHC bound to the amino groups in BSA by means of hydrogen bond and van der Waals force, which made the extent of peptide chain in BSA changed. By contrast, in phosphate buffer of pH 7.40, hydrophobic force played a major role in the interaction between EHC and BSA, while the hydrogen bond and van der Waals force were also involved in the interaction. The results of spectrometry indicated that BSA could enhance the fluorescence intensity of EHC by forming a 1:1 EHC-BSA fluorescent complex through static mechanism at pH 4.70 and 7.40 respectively. Furthermore, EHC bound on site 1 in BSA.

Charge-Transfer Complexing Properties of 1-Methyl Nicotinamide and Adenine in Relation to the Intramolecular Interaction in Nicotinamide Adenine Dinucleotide (NAD$^+$)

  • Park, Joon-woo;Paik, Young-Hee
    • Bulletin of the Korean Chemical Society
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    • 제6권1호
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    • pp.23-29
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    • 1985
  • The charge-transfer complexing properties of 1-methyl nicotinamide (MNA), an acceptor, and adenine, a donor, were investigated in water and SDS micellar solutions in relation to the intramolecular interaction in nicotinamide adenine dinucleotide ($NAD^+$). The spectral and thermodynamic parameters of MNA-indole and methyl viologen-adenine complex formations were determined, and the data were utilized to evaluate the charge-transfer abilities of MNA and adenine. The electron affinity of nicotinamide was estimated to be 0.28 eV from charge-transfer energy $of{\sim}300$ nm for MNA-indole. The large enhancement of MNA-indole complexation in SDS solutions by entropy effect was attributed to hydrophobic nature of indole. The complex between adenine and methyl viologen showed an absorption band peaked near 360 nm. The ionization potential of adenine was evaluated to be 8.28 eV from this. The much smaller enhancement of charge-transfer interaction involving adenine than that of indole in SDS solutions was attributed to weaker hydrophobic nature of the donor. The charge-transfer energy of 4.41 eV (280 nm) was estimated for nicotinamide-adenine complex. The spectral behaviors of $NAD^+$ were accounted to the presence of intramolecular interaction in $NAD^+$, which is only slightly enhanced in SDS solutions. The replacement of nicotinamide-adenine interaction in $NAD^+$ by intermolecular nicotinamide-indole interaction in enzyme bound $NAD^+$, and guiding role of adenine moiety in $NAD^+$ were discussed.

유기화제로 3-aminopropyltriethoxysilane 을 이용하여 라텍스법으로 제조된 SBR/organoclay 컴파운드의 혼련 온도에 따른 팽윤도 및 기계적 물성 (Swelling Ratio and Mechanical Properties of SBR/organoclay Nanocomposites according to the Mixing Temperature; using 3-Aminopropyltriethoxysilane as a Modifier and the Latex Method for Manufacturing)

  • 김욱수;박득주;강윤희;하기룡;김원호
    • Elastomers and Composites
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    • 제45권2호
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    • pp.112-121
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    • 2010
  • 본 연구에서는 filler-rubber interaction을 향상시키기 위하여 clay의 유기화제로 3-aminopropyltriethoxysilane(APTES)을 사용하여 styrene butadiene rubber(SBR)/organoclay nanocomposite를 라텍스법으로 제조하였다. 컴파운딩시 혼련 온도에 따라 bis(triethoxysilylpropyl)tetrasulfide(TESPT)를 첨가하여 APTES에 의해 생성된 hydroxyl group과 TESPT의 ethoxy group 사이에 실란화 반응 정도에 따른 filler-rubber interaction 향상 정도를 연구하기 위하여 X-선 회절법을 이용한 silicates의 층간구조분석, 모폴로지(morphology), 적외선분광법, 팽윤도 및 기계적물성을 평가하였다. XRD분석과 TEM이미지로 관찰한 결과 silicates 층간에 APTES가 삽입된 구조를 형성하였고 고무기질 내에 organoclay의 분산이 잘 이루어졌다는 것을 알 수 있었다. 또한, 적외선 분광법을 이용하여 APTES-MMT를 분석한 결과 APTES에 의해 silicates 표면에 다량의 hydroxyl 그룹이 형성되어 TESPT의 ethoxy group과 실란화 반응이 가능하였다. SBR/APTES-MMT 컴파운드에 TESPT를 첨가시 SBR/APTESMMT 컴파운드보다 300% 모듈러스가 약 1.3 배 정도 증가하였다. 이는 APTES의 hydroxyl group과 TESPT의 ethoxy group 사이에 실란화 반응이 이루어져 filler-rubber interaction이 향상된 결과였으며, 컴파운딩시 혼련온도 증가에 따른 모듈러스 향상 효과는 미미하였다. 결과적으로 SBR/APTES-MMT 컴파운드의 경우 고무 기질 내에 silicates의 분산 정도와 가교도 증가에 따라 모듈러스가 증가하였으며, SBR/APTES-MMT 컴파운드에 TESPT를 첨가시 filler-rubber interaction이 향상되어 모듈러스가 더욱 증가하였다.

H2-공기와 CO-공기 예혼합화염 사이의 후류상호작용에 있어서 CO2 첨가 효과 (Effects of CO2 Addition in Downstream Interaction between 2-Air and CO-Air Premixed Flames)

  • 길상인;박정
    • 한국연소학회지
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    • 제18권4호
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    • pp.29-36
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    • 2013
  • Numerical study was conducted to clarify effects of added $CO_2$ for the downstream interaction between $H_2$-air and CO-air premixed flames in counterflow configuration. The reaction mechanism adopted was Davis model which had been known to be well in agreement with reliable experimental data. The results showed that both lean and rich flammable limits were reduced. The most discernible difference between the two with and without having $CO_2$ addition into $H_2$-air and CO-air premixtures was two flammable islands for the former and one island for the latter at high strain flame conditions. Even a small amount of $H_2$, in which $H_2$-air premixed flame cannot be sustained by itself, participates in CO oxidation, thereby altering the CO-oxidation reaction path from the main reaction route $CO+O_2{\rightarrow}CO_2+O$ with a very long chemical time in CO-air flame to the (H, O, OH)-related reaction routes including $CO+OH{\rightarrow}CO_2+H$ with relatively short chemical times. This intrinsic nature alters flame stability maps appreciably. The results also showed that chemical effects of added $CO_2$ suppressed flame stabilization. Particularly this phenomenon was appreciable at flame conditions which lean and rich extinction boundary was merged. The detailed discussion of chemical effects of added $CO_2$ was addressed to the present downstream interaction.