• Bulletin of the Korean Chemical Society
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• v.25 no.11
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• pp.1635-1640
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• 2004

The cyclophanes 1a-d containing two benzo[b]furan rings connected by various bridges have been prepared and their binding behaviors with N-benzylphenethylammonium cation 2 were examined by NMR titration method. The successive alkylation reactions of 4-hydroxyl groups and then 2-hydroxyl groups of 2,4-dihydroxybenzophenonse gave macrocycles 5a-c. Photoirradiation of the macrocycles 5a-c with 350 nm mercury lamp followed by dehydration afforded the cyclophanes 1a-c. Hydrolysis of two ester groups pendant on a bridge of 1b produced the carboxyl group-containing cyclophane 1d. The cyclophane 1a having a p-xylene bridge showed 1 : 1 binding with 2 with the binding constant of $36{\pm}6M^{-1}$ in 3 : 1 $CDCl_3$/methanol-$d_4$ solvent, while 1b and 1c which have neutral flexible bridges exhibited no appreciable binding with 2. The disodium salt of 1d showed much higher binding affinity for 2 forming 1 : 1 and 1 : 2 complexes.

• Bulletin of the Korean Chemical Society
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• v.29 no.1
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• pp.197-201
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• 2008

Conformational heterogeneity of directly linked multiporphyrin arrays with larger molecular length retards their utilities in practical applications such as two-photon absorption and molecular photonic wire. In this regard, here we adopted a way to overcome the conformational heterogeneity through hydrogen bonding by selective binding of meso aryl substituents of porphyrins (host) with urea (guest) to form helical structure. Using steady-state and time-resolved spectroscopy, we observed the enhanced fluorescence quantum yield by ~1.8 to 2.4 times, enhanced anisotropy values and the disappearance of fast fluorescence decay component in the host-guest helical forms. In addition, the enhanced nonlinear optical responses of helical arrays infer the extended inter-porphyrin electronic coupling due to a significant change in dihedral angle between the neighboring porphyrin moieties. The current host-guest strategy will provide a guideline to improve the structural homogeneity of the photonic wire.

• Proceedings of the Korean Environmental Sciences Society Conference
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• 2003.11a
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• pp.155-158
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• 2003

New porphyrin square (1) was prepared by reaction of porphyrin containing pyridine and Re$(CO)_5Cl$ in THF/toluene solvent. 2-(Methylene15-crown-5)-nicotinoly ester(2) was synthesized by reaction of 2-(Hydroxymethyl-15-crown-5 and nicotinoly chloride in $CH_2Cl_2$. In fluorescence quenching studies luminescence was quenched by addition of the guest(2) into host(l). In the host-guest system we could obtain binding constant (K= $1.13{\times}10^{7}M^{-1}$) at decreasing concentration of (2). But the luminescence was dramatically increased after $Na^{+}$ was added into the host-guest system.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2003.08a
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• pp.133-136
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• 2003

New porphyrin square (1) was prepared by reaction of porphyrin containing pyridine and $Re(CO)_5Cl$ in THF/toluene solvent. 2-(Methylenel5-crown-5)-nicotinoly ester(2) was synthesized by reaction of 2-(Hydroxymethyl-15-crown-5 and nicotinoly chloride in $CH_2Cl_2$. In fluorescence quenching studies luminescence was quenched by addition of the guest(2) into host(l). In the host-guest system we could obtain binding constant (K=$1.13{\times}10^7M^{-1}$) at decreasing concentration of (2). But the luminescence was dramatically increased after $Na^+$ was added into the host-guest system.

• Korean Chemical Engineering Research
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• v.55 no.5
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• pp.704-710
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• 2017

Although the desalination technique using gas hydrate formation is at a development stage compared to the commercially well-established reverse osmosis (RO), it still draws attention because of its simplicity and moderate operational conditions especially when using refrigerants for guest gases. In this study, DFT (density functional theory)-based molecular modeling was employed to explain the energetics of the gas hydrate formation using HFC (hydrofluorocarbon) and HCFC (hydrochlorofluorocarbon) refrigerants. For guest gases, R-134a, R-227ea, R-236fa, and R-141b were selected and three cavity structures ($5^{12}$, $5^{12}6^2$, and $5^{12}6^4$) composed of water molecules were constructed. The geometries of guest gas, cavity, and cavity encapsulating guest gas were optimized by molecular modeling respectively and their located energies were then used for the calculation of binding energy between the guest gas and cavity. Finally, the comparison of binding energies was used to propose which refrigerant is more favorable for the gas hydrate formation energetically. In conclusion, R-236fa was the best choice in terms of thermodynamic spontaneity, less toxicity, and low solubility in water.

• Bulletin of the Korean Chemical Society
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• v.21 no.11
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• pp.1119-1124
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• 2000

$\beta-Cyclodextrin$ derivatives connected with diaza-18-crown-6 through flexible bridges (R) at the secondary face 1a-c (1a: R = $-(CH_2)4-;$ 1b: R = $-CH_2CH_2OCH_2CH2-;$ 1c: R = $-(CH_2)8-)$ have been prepared. The associa tion constants of 1 with (2-naphthoxy)alkylammonium ions (2a: alkyl = butyl; 2b: alkyl = octyl) were determined by induced circular dichroism (ICD) spectroscopy and it was found that the derivatization of $\beta-CD$ with the diazacrown resulted in enhanced binding with 2, compared to the native $\beta-CD.$ ICD Characteristics of the host-guest complexes indicate that a part of the alkylammonium moiety of 2 is protruded from the secondary side of the $\beta-CD$ cavity, and the guest molecules 2a and 2b move to the secondary and primary side, respectively, to make the binding of the ammonium group with the diaza-18-crown-6 moiety more feasible. The energy accompanied by the relocation of the guest molecules inside $\beta-CD$ moiety is compensated by the interaction energy between the ammonium ion and diazacrown ether.

• Bulletin of the Korean Chemical Society
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• v.22 no.11
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• pp.1248-1254
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• 2001

The conformations and energies of p-tert-butylcalix[4]crown-6-ether (1) and its alkyl ammonium complexes have been calculated by ab initio HF/6-31G quantum mechanics method. The cone conformation was found to be most stable for free host 1. We hav e determined the binding site of these host-guest complexes focusing on the crown-6-ether or p-tert-butylcalix[4]arene pocket of the cone conformation of host molecule 1. The primary binding site of host 1 for the recognition of alkyl ammonium guests was confirmed to be the central part of the crown moiety of cone conformation. The complexation energy calculations revealed that the ammonium cation without alkyl group showed the highest complexation efficiency when combined with host 1, that is in satisfactory agreement with the experimental results.

• Bulletin of the Korean Chemical Society
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• v.30 no.2
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• pp.505-508
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• 2009

• Bulletin of the Korean Chemical Society
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• v.29 no.5
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• pp.953-958
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• 2008

A novel anthraquinone diamino-bridged bis($\beta$ -cyclodextrin) 2 was synthesized. The inclusion complexation behaviors of the native $\beta$ -cyclodextrin 1 and the novel bis($\beta$ -cyclodextrin) 2 with guests, such as acridine red (AR), neutral red (NR), ammonium 8-anilino-1-naphthalenesulfonate (ANS), sodium 2-(p-toluidinyl) naphthalenesulfonate (TNS) and rhodamine B (RhB) were investigation by fluorescence, circular dichroism and 2D NMR spectroscopy. The spectral titrations were performed in phosphate buffer (pH 7.20) at 25 ${^{\circ}C}$ to give the complex stability constants (Ks) and Gibbs free energy changes (−${\Delta}G^0$) for the stoichiometric 1:1 inclusion complexation of host 1 and 2 with guests. The results indicated that the novel bis($\beta$ -cyclodextrin) 2 greatly enhanced the original binding affinity of the native $\beta$ -cyclodextrin 1. Typically, bis($\beta$ -cyclodextrin) 2 showed the highest binding constant towards ANS up to 34.8 times higher than that of 1. The 2D NMR spectra of bis($\beta$ -cyclodextrin) 2 with RhB and TNS were performed to confirm the binding mode. The increased binding affinity and molecular selectivity of guests by bis($\beta$ -cyclodextrin) 2 were discussed from the viewpoint of the size/shape-fit concept and multipoint recognition mechanism.

• Mass Spectrometry Letters
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• v.7 no.1
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• pp.16-20
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• 2016

Characterization of intact protein structures in the gas phase using electrospray ionization combined with ion mobility mass spectrometry has become an important tool of research. However, the biophysical properties that govern the structures of protein ions in the gas phase remain to be understood. Here, we investigated the impact of host-guest complexation of ubiquitin (Ubq) with macrocyclic host molecules, cucurbit[n]urils (CB[n]s, n = 6, 7), on its structure in the gas phase. We found that CB[n] complexation induces the formation of compact Ubq ions. Both CB[6] and CB[7] exhibited similar effects despite differences in their binding properties in solution. In addition, CB[n] attachment prevented Ubq from unfolding by collisional activation. Based on the experimental results, we suggest that CB[n]s prevent unfolding of Ubq during transfer to the gas phase to promote the formation of compact protein ions. Furthermore, interaction with positively charged residues per se is suggested to be the most important factor for the host-guest complexation effect.