• Bulletin of the Korean Chemical Society
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• 제35권4호
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• pp.1121-1127
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• 2014

The design, synthesis, and structural characterization of two new palladium complexes based on Schiff base ligands is reported; $[Pd(L1)_2]$ (1) and $[Pd(L2)_2]$ (2), [HL1 = 2-((E)-(2,6-diethylphenylimino)methyl)-4,6-dibromophenol, L2 = (E)-N-benzylidene-2,6-diethylbenzenamine], which are obtained by functionalizing Schiff base ligands with or without electron-withdrawing groups. Both compounds are mononuclear structures. Comparisons are made to the compounds 1 and 2 to analyze and understand the effect of electron-withdrawing groups. Antibacterial activity studies indicate the electron-withdrawing groups on Schiff base ligands enhance antibacterial activity. Catalytic activity, however, is reduced due to the enhanced steric-hindrance of the electron-withdrawing groups. Electronic absorption and emission properties of HL1, L2, 1 and 2 are also reported.

• Elastomers and Composites
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• 제47권2호
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• pp.148-155
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• 2012

EPDM, IIR, and BIIR composites were thermally aged and the crosslink density changes were investigated. Crosslink densities of the EPDM composite increased with increasing the aging time and temperature, whereas those of IIR and BIIR composites for long-term aging at high temperatures tended to decrease. Activation energies for the crosslink density changes of the EPDM composite were higher than those of the BIIR one. The experimental results were explained with the number of allylic hydrogens, activation of the zinc complex, the steric hindrance effect, and oxidation of rubber chain.

• Bulletin of the Korean Chemical Society
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• 제30권3호
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• pp.589-594
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• 2009

We have performed DFT B3LYP/6-31G(d,p) calculations to investigate the complexation behaviors of the ethyl ester derivative of p-tert-butylcalix[6]arene (1) toward a variety of alkylammonium ions. We have studied the binding sites of these host-guest complexes focusing on the p-tert-butylcalix[6]arene pocket (endo) of 1. The smaller alkylammonium cations have the better complexation efficiency than the bulkier alkylammonium ions with the p-tert-butylcalix[6]aryl ester. The hydrogen-bonding of N-H$\ldots$O is one of the important factors for the complexation behavior of the p-tert-butylcalix[6]aryl ester, in addition to the NH-aromatic π, CH-aromatic π and electrostatic interactions, and the steric hindrance of alkylammonium cation. The hydrogen-bonded distances and angles of N-H$\ldots$O are reported for the complexes of the p-tert-butylcalix[6]aryl ester with various alkylammonium ions.

• Journal of Hydrogen and New Energy
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• 제9권3호
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• pp.119-125
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• 1998

The modified statistical-mechanical theory for dense fluid mixtures of rigid spheres has been applied to rigid sphere fluids in the nonoverlapping pore model. The resulting expressions for the partition coefficient and diffusivity illustrate the influence of steric hindrance on the thermodynamic and transport properties in such systems. The open membrane model without the size-exclusion and shielding effects shows considerable overestimation of the diffusion flux when the effective mean pore radii of the order of $20{\AA}$ or less are involved. Theoretical predictions investigated here were also compared with experimental data for hydrogen gases in inorganic porous membranes and it was observed a qualitative agreement in the low pressure limit.

• KEPCO Journal on Electric Power and Energy
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• 제6권3호
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• pp.297-303
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• 2020

The reaction of carbon dioxide with the amine-based absorbents which have various substituents in the molecule was described. In the case of MEA which is a representative primary amine, the absorption reaction was proceeded very fast while the regeneration reaction was took place slowly due to the strong bond strength between the absorbent and carbon dioxide. The more substituents on N atom of the absorbent, the slower the absorption reaction between carbon dioxide and the absorbent, which in turn causes faster the regeneration rate from the reaction intermediate, carbamate.

• Bulletin of the Korean Chemical Society
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• 제19권1호
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• pp.86-93
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• 1998

Trans-4-(9-anthrylethenyl)-4'-methyl-2,2'-bipyridine(t-aemb) and its bipyridyl Ru complex $[Ru(bpy)_2(t-aemb)](PF_6)_2$ (bpy=2,2'-bipyridine) 1 have been prepared and their excited state properties have been studied. t-Aemb exhibits solvent-dependent fluorescence and efficient trans→cis photoisomerization. 1 shows very weak fluorescence and its photochemically reactive. Fluorescence is wavelength-dependent. While the excitation into the MLCT band makes the complex fluorescent, direct absorption by the t-aemb ligand leads to the photoreaction of t-aemb ligand and no fluorescence is observed. 1 is considered to behave in part as bichromophoric molecule in which $[Ru(bpy)_3](PF_6)_2$ and anthryl group are covalently linked by ethenyl linkage. Because anthryl moiety is not effectively conjugated with bipyridylethenyl moiety due to steric hindrance, weak fluorescence can be explained due to the efficient energy or electron transfer.

• Bulletin of the Korean Chemical Society
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• 제20권4호
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• pp.427-430
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• 1999

The Grignard coupling reaction of bis(chloromethyl)diorganosilanes [(ClCH2)2SiR1R2: R1 = R2 = Me, la; R1 = Me, R2 = Ph, lb; R1 = R2 = Ph, lc] with diorganodichlorosilanes [(Cl2SiR3R4: R3 = R4 = Me, 2a; R3 = Me, R4 = Ph, 2b; R3 = R4 = Ph, 2c] at THE reflux temperature gave the intermolecular C-Si coupling product of 1,1,3,3-tetraorgano-1,3-disilacyclobutanes 3a-f in poor to moderate yields ranging from 7% to 50% along with polydiorganosilapropanes. The cyclization reaction of la-c with methyl-substituted dichlorosilanes 2a, b gave 1,3-disilacyclobutanes 3a-c, e, d in moderate yields (42-50%), while the same reaction with dichlorodiphenylsilane (2c) to 1,3-disilacyclobutanes 3d, f resulted in low yield (7-18%) probably due to the steric hindrance of two-phenyl groups on the silicon of 2c.

• Bulletin of the Korean Chemical Society
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• 제15권7호
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• pp.549-553
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• 1994

The 2-(dimethylaminomethyl)thiophene (dmamt) complexes with copper(II) chloride and bromide were prepared and characterized by optical, EPR, XPS spectroscopies and magnetic susceptibility measurements. The low-energy absorption band above 850 nm and the relatively small EPR hyperfine coupling constant ($A_{//}{\simeq}$125 G) indicate the pseudotetrahedral site symmetry around copper(II) ion both in Cu(dmamt)$Cl_2$ and Cu(dmamt)$Br_2$ complexes. The higher satellite to main peak intensity of Cu $2P_{3/2}$ core electron binding energy in XPS spectra also supports the pseudotetrahedral geometry around the copper(II) ions having $CuNSX_2$ chromophores. The distortion from square-planar to pseudotetrahedral symmetry is likely to arise from the steric hindrance of the bulky dmamt ligand in the complex. Magnetic susceptibility study shows that these compounds follow Curie-Weiss law in the temperature range of 77-300 K with positive Weiss constant exhibiting the ferromagnetic interaction between copper(II) ions in solid state.

• Bulletin of the Korean Chemical Society
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• 제12권3호
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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.

• Bulletin of the Korean Chemical Society
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• 제22권3호
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• pp.293-297
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• 2001

The purpose of this paper is to introduce the simplified linkage position determination method using tandem mass spectrometry combined with molecular modeling study. Using low energy tandem mass spectrometric experiments and molecular modeling, it has been suggested that significant differences in glycosidic bond cleavage may occur due not only to ionic considerations but also may have contributions from steric hindrance of the absorbance of collision energy, leading to a statistically higher bond cleavage for sterically crowded linkages. Permethylated derivatives of the linkage-isomeric trisaccharides give useful fragmentation ratios and productions, including a 3-linkage specific ion. The ratios of fragment ions are related to the ability of each linkage position in the oligosaccharide to absorb collisional energy.