• 약학회지
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• 제28권2호
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• pp.101-127
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• 1984

The study of interaction between riboflavin derivatives and biologically active substances was reviewed. With combination of spectroscopic methods such as NMR, UV, Fluorescence and IR, informations about interaction mechanism including hydrogen bond formation, conformation of association complex, and association constant were obtained. 1. Riboflavin associated with adenine but not with other bases found in the nucleic acids. -CONHCO- group was included in the formation of hydrogen bond with adenine. 2. Riboflavin interacted with alcohol to make a 1 : 1 association complex through the 3N-imino and 2C-carbonyl group of the isoalloxazine ring and the hydroxyl group of the alcohols. 3. Riboflavin associated with salicylates to produce the cyclic hydrogen-bonded dimer. The strongest complex was formed with salicylic acid, a weaker one with aspirin, and an even weaker one with salicylamide. 4. Other bio-active substances, orotic acid and inhibitors such as phenol, trichloroacetic acid and indol also formed hydrogen bond with riboflavin. 5. Reduced riboflavin showed strong self-association to produce the cyclic hydrogen-bonded complex and it associated with adenine and with cytosine to form 1 : 3 complex.

• Archives of Pharmacal Research
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• 제8권3호
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• pp.109-117
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• 1985

The interaction of salicylic acid (S. A.), salicylamide (S,M) with nucleic acid base derivatives such as 9-ethyl adenine (A), 1-cyclohexyl uracil (U), 2', 3'-benzylidine-5' trityl-cytidine (C), gaunosine-2', 3', 5'-isobutylate (G) has been spectroscopically investigated to determine the binding mechanism. NMR and IR spectra were measured in nonpolar solvents. The association constant K of the formation of complex was calculated from the IR spectra. Compounds S. A. and A form a 1:1 or 1:2 cyclic hydrogen-bonded complex depending on the sample concentration. Compounds S. A. and U form a 1:1 or 1:2 hydrogen-bonded complex on the sample concentration. Compounds S. A. and C form a 2:1 hydrogen-bonded complex at low concentration (0.0016M). Compound S. A. binds compound G, but its binding does not completely break the self-association of compound G, Compound S. M. binds compounds A. U. C. G. very weakly.

• Bulletin of the Korean Chemical Society
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• 제11권5호
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• pp.367-371
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• 1990

The near-IR spectra of thioacetamide were recorded for the investigation of hydrogen bonding between thioacetamide (TA) and N,N-dimethylalkylamides (DMF, DMA, DMP) in chloroform over the range of 5$^{\circ}C$ to 55$^{\circ}C$. The ${\nu}_{\alpha}$ + amide II combination band has been resolved into contributions from monomeric TA, 1:1 hydrogen bonded complex and 1:2 complex by the parameterized matrix modeling method. The association constants ($K_c$) of the complex have been obtained at various temperatures and used to determine the thermodynamic parameters for the hydrogen bonding by the usual Van't Hoff method. It was found that N,N-dimethylalkylamide forms less stable hydrogen bonded complex with TA in chloroform than in carbon tetrachloride.

• 대한화학회지
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• 제68권2호
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• pp.65-73
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• 2024

The halide-acetylene anions, X^--HCCH (X = F, Cl, and Br) have been studied by using several different ab initio and DFT methods to determine structures, hydrogen-bond energies, vibrational frequencies of the anion complexes. Although the halide-acetylene complexes all have linear equilibrium structures, it is found that the fluoride complex is characterized with distinctively different structure and interactions compared to those of the chloride and bromide complexes. The performance of various density functionals on describing ionic hydrogen-bonded complexes is assessed by examining statistical deviations with respect to high level ab initio CCSD(T) results as reference. The density functionals employed in the present work show considerably varying degrees of performance depending on the properties computed. The performances of each density functional on geometrical parameters related with the hydrogen bond, hydrogen-bond energies, and scaled harmonic frequencies of the anion complexes are examined and discussed based on the statistical deviations.

• Bulletin of the Korean Chemical Society
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• 제20권9호
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• pp.1067-1072
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• 1999

Structures of unprotonated [(NH3)n+(n = 1-6)] and protonated [NH4+(NH3)n-1(n = 1-6)] ammonia cluster cations have been optimized with ab initio Hartree-Fock (HF) and second-order MФller-Plesset (MP2)/6-31+G ** levels and the harmonic vibrational frequencies have also been evaluated. In unprotonated cluster cations, NH3+ forms as a central core of the first ammonia solvation shell. In protonated cluster cations, NH4+ forms as a central core. In unprotonated dimer and trimer cations, there are two types of isomers (hydrogen-bonded and head-to-head interactions). In both cluster cations, the hydrogen-bonded isomers are more stable. In the hydrogen-bonded dimer cation, the proton transfer reaction takes place from (NH3-HN+H2) to (NH4+-NH2). But in the other unprotonated cluster cations, the proton transfer does not take place. In unprotonated pentamer and hexamer, a NH3+ core has both interactions in a complex. On the other hand, in unprotonated tetramer a core has only the hydrogen-bonded type combined with neutral ammonia molecules. With increasing cluster cation size, the bond lengths [R(NN)] between two nitrogen atoms and the distances [R(N ...H)] of the hydrogen-bond increase reg-ularly. In the calculated infra-red absorption bands for ammonia cluster cations, the characteristic peaks of the bridged NH vibration of the hydrogen-bonded clusters appear near 2500 cm-1 . With increasing size, the peaks shift from 2306 cm-1 to 2780 cm-1 .

• 대한화학회지
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• 제38권5호
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• pp.345-350
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• 1994

클로로포름과 사염화탄소 속에서 티오아세트아미드(TA)와 pyridine(Py), quinoline(Qu), and acridine(Ac)간의 수소 결합에 대한 열역학적 상수들을 조사하기 위해 5$^{\circ}C$ 에서 55$^{\circ}C$까지 TA의 $v_{a^+}$ Amide II조합띠를 사용하였다. 이 조합띠는 두 개의 Lorentzian-Gauss 곱함수의 띠로 분해되며, 각각은 TA단위체 및 수소결합을 이룬 TA의 복합체임이 확인되었다. 온도 및 농도에 따른 이 조합띠의 변화로부터 TA의 수소 결합에 대한 여러가지 열역학적 상수들을 구하였다. 클로로포름에서 TA 와 pyridine, quinoline, acridine의 수소결합 엔탈피는 각각 -7.6 kJ/mol, -6.5 kJ/mol, -5.4 kJ/mol이었고, 사염화탄소에서 TA 와 pyridine, quinoline의 결합 엔탈피는 각각 -13.3kJ/mol, -12.0kJ/mol이었다.

• Bulletin of the Korean Chemical Society
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• 제27권12호
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• pp.2028-2036
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• 2006

The combined ab initio and vibrational predissociation (VP) spectroscopic studies on methylammonium-$(water)_4$ complex aimed at understanding the hydration behavior of an amphiphilic ion core are described. The ab initio calculations predicted eleven low-energy isomers forming cyclic, tripod, chain, and caged structures, and their relative stabilities, total hydration energies and thermodynamic functions at 298 K and 150 K. The excellent correlation between the observed VP spectra and ab initio spectra for bonded N-H, bonded O-H and free O-H stretches suggested co-existence of five cyclic isomers and two non-cyclic isomers in ion beam at 150 K, consistent with the trends of calculated Gibbs free energies.

• 대한화학회지
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• 제39권11호
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• pp.837-841
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• 1995

사염화탄소 속에서 티오프로피온아미드(TPA)와 triethylphosphine oxide(TEPO), triethylphosphine oxide(TPPO), trimethylphosphate(TMP), 그리고 tributyl phosphate(TBP)간의 수소 결합에 대한 열역학적 상수들을 근적외선 분광법을 이용하여 구하였다. TPA의 .nu./.alpha./+amide 2 조합띠는 TPA 단위체 및 수소 결합을 이룬 TPA의 띠로 이루어져 있음이 확인되어 이 띠를 두 개의 Lorentzian-Gaussian 곱함수의 띠로 분해하였다. 온도 및 농도의 변화에 따른 이 조합띠의 변화기로부터 TPA와 TEPO, TPPO, TMP, TBP의 수소 결합 엔탈피는 각각 -21.4, -16.8, -12.8, -12.9kJ/mol이었다. 이 결과는 치환기의 inductive effect 및 steric effect로 설명할 수 있다.

• Bulletin of the Korean Chemical Society
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• 제32권10호
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• pp.3634-3640
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• 2011

We have performed quantum mechanical calculations to study the geometries and binding energies of biologically important, cyclic hydrogen-bonded complexes, such as formic acid + $H_2O$, formamidine + $H_2O$, formamide + $H_2O$, formic acid dimer, formamidine dimer, formamide dimer, formic acid + formamide, formic acid + formamidine, formamide + formamidine, and barrier heights for the double proton transfer in these complexes. Various ab initio, density functional theory, multilevel methods have been used. Geometries and energies depend very much on the level of theory. In particular, the transition state symmetry of the proton transfer in formamidine dimer varies greatly depending on the level of theory, so very high level of theory must be used to get any reasonable results.

• Bulletin of the Korean Chemical Society
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• 제28권3호
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• pp.386-390
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• 2007

By use of a simple two-point extrapolation scheme estimating the correlation energies of the molecules along with the basis sets specifically targeted for extrapolation, we have shown that the MP2 basis set limit binding energies of large hydrogen-bonded complexes can be accurately predicted with relatively small amount of computational cost. The basis sets employed for computation and extrapolation consist of the smallest correlation consistent basis set cc-pVDZ and another basis set made of the cc-pVDZ set plus highest angular momentum polarization functions from the cc-pVTZ set, both of which were then augmented by diffuse functions centered on the heavy atoms except hydrogen in the complex. The correlation energy extrapolation formula takes the (X+1)-3 form with X corresponding to 2.0 for the cc-pVDZ set and 2.3 for the other basis set. The estimated MP2 basis set limit binding energies for water hexamer, hydrogen fluoride pentamer, alaninewater, phenol-water, and guanine-cytosine base pair complexes of nucleic acid by this method are 45.2(45.9), 36.1(37.5), 10.9(10.7), 7.1(6.9), and 27.6(27.7) kcal/mol, respectively, with the values in parentheses representing the reference basis set limit values. A comparison with the DFT results by B3LYP method clearly manifests the effectiveness and accuracy of this method in the study of large hydrogen-bonded complexes.