• Journal of Pharmaceutical Investigation
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• v.18 no.2
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• pp.89-97
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• 1988

A series of novel water-soluble paracyclophanes containing two diphenyl ether skeletons and two bridging aliphatic chains of various length were designed and prepared to develop artificial host compounds which might provide efficient hydrophobic field. They were 1,5,19,23-tetraaza-12,30-dioxa[5,1.5.1] paracyclophane (6), 1,6,20,25-tetraaza-13,32-dioxa[6.1.6.1]paracyclophane (7), 1,7,21,27-tetraaza-14,34-dioxa[7.1.7.1]paracyclophane (8) and 1,8,22,29-tetraaza-15,36-dioxa[8.1.8.1]paracyclophane (9). As the corresponding acyclic analogue, 4,4'-dimethylaminodiphenyl ether (11) was synthesized for the comparative study of further host-guest interaction.

• Electrical & Electronic Materials
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• v.10 no.10
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• pp.989-994
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• 1997

In a Guest-Host cell the orientational ordering of dyes doped into liquid crystals has been investigated. To evaluate the influence of the host liquid crystals on the ordering of the dyes we have measured precisely the ordering parameters of the liquid crystals by using the dichroic ratio of the absorbances for infrared light polarized parallel and perpendicular to the diector. Our experimental results show that the ordering of the dyes can be expressed as a function of not only the molecular structure of the dyes but also the order parameter of the liquid crystals. These functions are dependent on the kinds of the liquid crystals and the dyes. Particularly the combination such as anthraquinone dyes doped into cyanobiphenyl liquid crystals show a very high ordering parameter. This is considered due to a strong intermolecular interaction between the dipoles of both liquid crystals and dyes.

• Bulletin of the Korean Chemical Society
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• v.30 no.1
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• pp.145-148
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• 2009

Nucleotides are the building blocks of nucleic acids and essential for many cellular functions. In this study, ultrasonic absorption spectra of $\beta$-cyclodextrin ($\beta$-CD) and adenosine 5'-monophosphate (AMP) in aqueous solution were measured over the broad frequency range 0.1-40 MHz with emphasis on the low-frequency range below 1 MHz. Here we show that the interaction of $\beta$-CD and AMP complies with a typical spectrum of a single relaxation process. We determined reliable rate (kb) and equilibrium (K) constants and a standard volume change ($\Delta$V) of the reaction. They are $k_b=2.3{\times}{{10^{-6}}_s}^{-1},\;K=89M^{-1},\;and\;{\Delta}V=13.8(10^{-6}m^3mol^{-1})$, respectively.

• Bulletin of the Korean Chemical Society
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• v.29 no.3
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• pp.590-594
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• 2008

The inclusion complexes of cyclodextrins (CDs) with flavones in aqueous solution were investigated by phase solubility measurements. The effect of b -cyclodextrin (b -CD), heptakis (2,6-di-O-methyl) b -cyclodextrin (DM-b -CD) and 2-hydroxypropyl-b -cyclodextrin (HP-b -CD) on the aqueous solubility of three flavones, namely, chrysin, apigenin and luteolin was investigated, respectively. Solubility enhancements of all flavones obtained with three CDs followed the rank order: HP-b -CD > DM-b -CD > b -CD, and besides, CDs show higher stability constant on luteolin than that on others flavones. 1H-nuclear magnetic resonance (NMR) spectroscopy and molecular modeling was used to help establish the model of interaction of the CDs with luteolin. NMR spectroscopic analysis suggested that A-C ring, and part of the B ring of luteolin display favorable interaction with the CDs, which was also confirmed by docking studies based on the molecular simulation. The observed augmentation of solubility of luteolin by three CDs was explained by the difference of electrostatic interaction of each complex, especially hydrogen bonding.

• Bulletin of the Korean Chemical Society
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• v.11 no.6
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• pp.521-527
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• 1990

The binding characteristics and analytical applications of anilinium ion complexes with 18-crown-6 were studied by polarography and NMR. First, the electrochemical reduction of the 10 species of mono and dimethylsubstituted anilinium ion complexes with 18-crown-6 as host in methanol are examined. The addition of 18-crown-6 to anilinium guest solution the polarographic waves remain well defined but shifted toward more negative potentials, indicating the complex formation. The values of formation constants, log Κ for 10 species of methylsubstituted anilinium ion complexes with 18-crown-6 varies from 2.7 to 4.8 in methanol at $25^{\circ}C$. The stability order of complexes for 18-crown-6 is anilinilum > 4-methyl > 3,4-dimethyl > 3-methyl > 3,5-dimethyl > 2,4-dimethyl > 2,5-dimethyl > 2,3-dimethyl > 2-methyl > 2,6-dimethylanilinium ion. The steric hindrance shows significant effect. Second, Proton NMR was used to elucidate their interaction characteristics. From the results of so called NMR titration techniques, the behaviors of binding sites on complexation, and the stoichiometry and stability order of complex were obtained. And the later results show the satisfactory agreement with the quantitative values obtained by polarography. Finally, the individual determinations of anilinium ion mixtures were also accomplished by addition of 18-crown-6. In some mixtures of methyl or dimethylanilinium ions the reduction peaks of differential pulse method appeared into one unresolved wave attributed to the small difference of half-wave potential, ${\Delta}E_{1/2}$. In the presence of 18-crown-6, the polarographic waves were resolved into individual maxima because of the shift toward more negative direction by the difference of selectivity of anilinium ions with 18-crown-6. It may be concluded that quantitative analysis of methylanilinium ion mixture make possible because the half-wave potential shift by the selectivity difference due to the steric hindrance between methyl group and 18-crown-6 on complexation.

• Proceedings of the Korean Society of Dyers and Finishers Conference
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• 2011.03a
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• pp.35-35
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• 2011

The design and preparation of novel dye rotaxanes have gained much interest recently, since such structure usually exhibits peculiar spectral and optical changes. In spite of the promising results to date, increasing pressure remains to develop novel supramolecular structures based on stimuli-responsive systems. This presentation covers the study of inclusion complexes of cyclodextrins and various chromophores, with an emphasis on our most recent outcome of anisotropic hydrogel. In this system, physical gelation prepared from simple mixture of CD and a azo dye is completed through specific host-guest interaction. The obtained hydrogel exhibits respective morphological transitions based on supramolecular assembly and dissociation, leading to either precipitation or a sol-to-gel transition. It can identify different classes of metal ions, and, among them, naked-eye differentiation of lead ion is possible due to the coordination-induced unthreading of dye molecules. Accompanying structural changes were verified by numerous characterization techniques, including 2D-ROESY, HR-MAS, UV-Visible absorption, small-angle X-ray scattering, and induced circular dichroism measurements. Such properties discussed here will find useful in analytical applications, such as metal ion sensing and removal applications.

• Macromolecular Research
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• v.14 no.6
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• pp.603-609
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• 2006

Tricyanopyrrolidene chromophores were prepared in order to compare their macroscopic nonlinear optical (NLO) properties with a conjugated structure through the long molecular axis. A thiophene or phenyl ring was tethered to an ethylenic bond; it may act as a lateral moiety to disrupt the planarity of a chromophore and lessen the electrostatic interaction. Thin film composites of these chromophores dissolved in amorphous polycarbonate (APC) were fabricated. Real time pole and probe method was employed to investigate the change of electro-optic (EO) signal during poling. The EO properties and their relaxation behaviors of the guest-host systems containing newly synthesized chromophores were investigated in detail.

• The Journal of the Acoustical Society of Korea
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• v.36 no.6
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• pp.387-393
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• 2017

The dynamic interactions between benzoic acid derivative ($pH{\approx}7.0$)(guest) and ${\beta}$-cyclodextrin (${\beta}$-CD)(host) were investigated in an aqueous solutions in terms of ultrasonic absorption in the frequency range 0.2 MHz ~ 50 MHz with emphasis on the low-frequency range below 1 MHz at $25^{\circ}C$. We show that the interaction of ${\beta}$-CD and benzoic acid derivative complies with a typical spectrum of a single relaxation process around a few MHz. The ultrasonic relaxation observed in these solutions was due to a perturbation of a chemical equilibrium related to a reaction of an inclusion complex formed by the host and guest. The rate constant ($k_b=7.48{\times}10^6M^{-1}s^{-1}$) and equilibrium constant ($K=68.6M^{-1}$) were determined from the concentration dependences of benzoic acid on the relaxation frequency. The standard volume change (${\Delta}V=10.6{\times}10^{-6}m^3mol^{-1}$) of the reaction was also computed from the maximum absorption per wavelength. It was found that the hydrophobicity of guest molecules played an important role in the formation of the inclusion complex.

• Analytical Science and Technology
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• v.5 no.3
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• pp.239-247
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• 1992

The complexations and selectivities of the 10 species of mono- and dimethylsubstituted anilinium ions with 18-crown-6 in methanol are examined at dropping mercury electrode. The stability constants of these complexes varies drastically due to the steric hindrance by the positions and numbers of methyl groups. And the analyses of the isomeric mixtures of methylanilinium, which are impossible to detect due to the overlapped peaks in normal conditions, were also accomplished by the additions of 18-crown-6 as the supporting complexing agent using the selective complexations by the steric hindrance effects. As results in case of the difference of stability, ${\Delta}log\;K$ were about 0.7~1.3, it was possible to confirm the existence of two species qualitatively. Otherwise when ${\Delta}log\;K$ were large than 1.6, the quantitative determinations of each species could be accomplished sucessfully. From these results it is deduced that the selective recongnition of the positions and numbers of methyl groups as the steric hindrance in anililniums by 18-crown-6 cause the large variation of the magnitudes of negative shift of reduction waves for guest ions in mixtures.

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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• pp.160.1-160.1
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• 2014

Using a density functional theory calculation including van der Waals (vdW) corrections, we report that $H_2$ adsorption in a cubic-crystalline microporous metal-organic framework (MOF-5) leads to volume shrinkage, which is in contrast to the intuition that gas adsorption in a confined system (e.g., pores in a material) increases the internal pressure and then leads to volumetric expansion. This extraordinary phenomenon is closely related to the vdW interactions between MOF and $H_2$ along with the $H_2$-$H_2$ interaction, rather than the Madelung-type electrostatic interaction. At low temperatures, $H_2$ molecules adsorbed in the MOF-5 form highly symmetrical interlinked nanocages that change from a cube-like shape to a sphere-like shape with $H_2$ loading, helping to exert centrosymmetric forces and hydrostatic (volumetric) stresses from the collection of dispersive interactions. The generated internal negative stress is sufficient to overcome the stiffness of the MOF-5 which is a soft material with a low bulk modulus (15.54 GPa).