• Proceedings of the Korean Vacuum Society Conference
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• 2012.08a
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• pp.71-71
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• 2012

Chemically modified graphene has been great interest for the application of printed electronics using solution prossesable technique. Here, we demonstrate a large area graphene exfoliation method with fewer defects on the basal plane by application of shear stress in solution to obtain high quality reduced graphene oxide (RGO). Moreover, we introduce a novel route to preparing highly concentrated and conductive RGO in various solvents by monovalent cation-${\pi}$ interaction. Noncovalent binding forces can be induced between a monopole (cation) and a quadrupole (aromatic ${\pi}$ system). The stability of this RGO dispersion was more sensitive to the strength of the cation-${\pi}$ interactions than to the cation-oxygen functional group interactions. The RGO film prepared without a post-annealing process displayed superior electrical conductivity of 97,500 S/m. Our strategy can facilitate the development of large scalable production methods for preparing printed electronics made from high-quality RGO nanosheets.

• Macromolecular Research
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• v.14 no.2
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• pp.199-204
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• 2006

Remarkably high and stable separation performance for olefin/paraffin mixtures was previously reported by facilitated olefin transport through ${\pi}$-complex membranes consisting of silver ions dissolved in poly(hexamethylenevinylene) (PHMV). In this study, the ${\pi}$-complex formation of $AgBF_4,\;AgClO_4\;and\;AgCF_{3}SO_3$ with PHMV and their ionic interactions were investigated. FT-Raman spectroscopy showed that the C=C stretching bands of PHMV shifted to a lower frequency upon incorporation of silver salt, but the degree of peak shift depended on the counter-anions of salt due to different complexation strengths. The symmetric stretching modes of anions indicated the presence of only free ions up to [C=C]:[Ag]=1:1, demonstrating the unusually high solubility of silver salt in PHMV. Above the solubility limit, the ion pairs and higher-order ionic aggregates started to form. The coordination number of silver ion for C=C of PHMV was in the order $AgBF_4$ > $AgClO_4$ > $AgCF_{3}SO_3$, but became similar at [C=C]:[Ag]=1:1. The different coordination number was interpreted in terms of the different transient crosslinks of silver cations in the complex, which may be related to both the interaction strength of the polymer/silver ion and the bulkiness of the counteranion.

• Bulletin of the Korean Chemical Society
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• v.34 no.12
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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.

• Journal of the Korean Applied Science and Technology
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• v.29 no.2
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• pp.278-285
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• 2012

Effects of ion species on the expansion behavior of Poly(styrene sufonic acid)(PSSA) hydrogel were investigated in aqueous solution of selected anions, cations and hydrophobic ions. The deexpansion extent of Poly(stylene sulfonic acid) gel follow the sequence $SCN^-$<$Br^-$<$Cl^-$<$F^-$ in low concentration solutions due to the destabilization of anions to hydrogen bond between ${SO_3}^-$ and water. The deexpansion in cations followed the sequence of counterion interactions between ${SO_3}^-$ and cations. It was discussed the effects of ions on the hydrogen bonding through ${SO_3}^-$ and phenyl ring in salt solutions. Other interactions, such as the cation-${\pi}$ interaction, hydrophobic interaction, and dispersion force, contributed to the ion specific swelling of PSSA hydrogel.

• Advances in nano research
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• v.6 no.4
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• pp.357-375
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• 2018

Two dimensional (2D) atomic layered nanomaterials exhibit some of the most striking phenomena in modern materials research and hold promise for a wide range of applications including energy and biomedical technologies. Graphene has received much attention for having extremely high surface area to mass ratio and excellent electric conductivity. Graphene has also been shown to maximize the activity of surface-assembled metal nanoparticle catalysts due to its unique characteristics of enhancing mass transport of reactants to catalysts. This paper specifically investigates the strategy of pre-formed nanoparticle self-assembly used for the formation of various metal nanoparticles supported on graphene families such as graphene, graphene oxide, and reduced graphene oxide and aims at understanding the interactions between ligand-capped metal nanoparticles and 2D nanomaterials. By varying the functional groups on the ligands between alkyl, aromatic, amine, and alcohol groups, different interactions such as van der Waals, ${\pi}-{\pi}$ stacking, dipole-dipole, and hydrogen bonding are formed as the 2D hybrids produced.

• Bulletin of the Korean Chemical Society
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• v.32 no.1
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• pp.162-168
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• 2011

Many ligands have been experimentally designed and tested for their activities as inhibitors against bacterial enoyl-ACP reductase (FabI), ENR. Here the binding energies of the reported ligands with the E. coli ENR-$NAD^+$ were calculated, analyzed and compared, and their molecular dynamics (MD) simulation study was performed. IDN, ZAM and AYM ligands were calculated to have larger binding energies than TCL and IDN has the largest binding energy among the considered ligands (TCL, S54, E26, ZAM, AYM and IDN). The contribution of residues to the ligand binding energy is larger in E. coli ENR-NAD+-IDN than in E. coli ENR-$NAD^+$-TCL, while the contribution of $NAD^+$ is smaller for IDN than for TCL. The large-size ligands having considerable interactions with residues and $NAD^+$ have many effective functional groups such as aromatic $\pi$ rings, acidic hydroxyl groups, and polarizable amide carbonyl groups in common. The cation-$\pi$ interactions have large binding energies, positively charged residues strongly interact with polarisable amide carbonyl group, and the acidic phenoxyl group has strong H-bond interactions. The residues which have strong interactions with the ligands in common are Y146, Y156, M159 and K163. This study of the reported inhibitor candidates is expected to assist the design of feasible ENR inhibitors.

• Bulletin of the Korean Chemical Society
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• v.27 no.4
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• pp.508-514
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• 2006

In this study, we have performed ab initio computer simulations to investigate the conformational and complexation characteristics of the trimethyl ether of p-tert-butylmonodeoxycalix[4]arene (6) with a potassium ion. The structures of different conformers of 6 and their potassium complexes were optimized by using ab initio RHF/6-31G and B3LYP/6-31G(d,p) methods. The relative stability of the various conformers of the uncomplexed 6 is in following order: cone (most stable) > 1-partial-cone ~ 2i-partial-cone > 2-partial-cone ~ 1,3-alternate > 3i-partial-cone. However, the relative stability of the conformational complexes of 6 with $K^+$ is in the following order: 2-partial cone ~ 1,3-alternate > cone > 3-partial cone > 1-partial cone (least stable). The highest binding strengths of 2-partial-cone and 1,3-alternate complexes originate from two strong cation-$\pi$ interactions and two strong cation-oxygen interactions in the complex of 6+$K^+$. Due to the cation-$\pi$ interactions, the calculated C-C bond distances in the arenes of the $K^+$-complexes are about 0.0048 $\AA$ longer than the values of their isolated hosts.

• Bulletin of the Korean Chemical Society
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• v.35 no.9
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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 $D_{fullerene}$.

• Bulletin of the Korean Chemical Society
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• v.31 no.3
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• pp.595-598
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• 2010

Ab initio and DFT molecular orbital calculations predict that acetyl radical reacts with acetylene through interactions primarily involving the SOMO of the radical and the in-plane ${\pi}$-bond of acetylene. An energy barrier (${\Delta}E_1$) of 39.6 kJ $mol^{-1}$ is predicted for the preferred anti arrangement of reactants at the CCSD(T)/cc-pVDZ//BHandHLYP/cc-pVDZ level of theory. NBO analysis reveals additional interactions between the radical SOMO and the nearby C-H ${\sigma}$-bond in acetylene worth about 10% of the total transition state interaction energy. This type of orbital interaction has not previously been observed in radical addition reactions involving C-C ${\pi}$-bonds.

• Bulletin of the Korean Chemical Society
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• v.32 no.9
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• pp.3255-3260
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• 2011

Two novel binuclear metal-organic coordination complexes $[Cd_2(L)_2(bpy)_2(H_2O)_2]{\cdot}6H_2O$ (1), $[Cd_2(L)_2(phen)_2-(H_2O)_2]{\cdot}2H_2O$ (2) (where L = 2-methylquinoline-3,4-dicarboxylate dianion, bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline) have been synthesized under hydrothermal conditions and characterized by single crystal Xray diffraction, spectral method (IR), elemental analysis and thermal gravimetric analysis (TGA). Both 1 and 2 consist of two Cd(II) atoms bridged by two monoatomic bridging carboxylate groups from two L ligands, and the second carboxylate group of each L is monodentately coordinated to Cd(II), creating a sevenmembered chelating ring. The coordination at each metal nucleus is completed by a water molecule and a chelating bidentate molecule. The 3D structures of the complexes are stabilized by ${\pi}-{\pi}$ stacking interactions and hydrogen-bonds.