• Bulletin of the Korean Chemical Society
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• 제24권9호
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• pp.1393-1395
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• 2003

• 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.

• 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.

• 한국결정학회지
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• 제11권1호
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• pp.28-33
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• 2000

The slow of 2,3-bis(2-pyridyl)pyarzine(bpp) with Ag(CF₃CO₂) produces crystalline product suitable for X-ray crystallography. Crystallographic characterization of the crystal (C/sub 32/H/sub 20/-F/sub 6/N/sub 8/O₄Ag₂: triclinic P1, a=8.518(5)Å, b=9.546(2)Å, c=10.632(1)Å, α=81.11(1)°, β=87.61(3)°, γ=75.66(3)°, V=827.5(5)ų, Z=1, R=0.0431) has provided that the complex is a cyclic dimer [Ag(bpp)(CF₃CO₂)]₂. Each bpp ligand connects two tetrahedral silver(I) ions in a tridentate mode (Ag-N, 2.26()-2.43(2)Å), and the trifluoroacetato anion is bonded to each silver(I) atom in a monodentate fashion (Ag-O, 2.38(1); 2.39(2) Å). The skeletal cyclic dimer is stable up to 212℃, and drastically decomposes around this temperature.

• Bulletin of the Korean Chemical Society
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• 제19권9호
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• pp.993-999
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• 1998

Acid catalyzed hydrolysis of 1-phenoxyethyl propionate, Ⅰ, has been studied using the PM3 method in the gas phase. The first step of the reaction is the protonation of basic sites, three different oxygens in Ⅰ, producing three protonated species Ⅱ, Ⅲ and Ⅳ. All possible reaction pathways have been studied from each protonated structure. Changes in the reaction mechanisms have also been discussed from the results obtained by varying a nucleophile from a water monomer to a water dimer to a complex between one water molecule and an intermediate product (propionic acid or phenol) produced in the preceding unimolecular dissociation processes. Minimum energy reaction pathway is 2-W among the possible pathways, in which water dimer acts as an active catalyst and therefore facilitates the formation of a six-membered cyclic transition state. Lower barrier of 2-W is ascribed to an efficient bifunctional catalytic effect of water molecules. PM3-SM3.1 single point calculations have been done at the gas-phase optimized structure (SM3.1/PM3//PM3) to compare theoretical results to those of experimental work.

• Bulletin of the Korean Chemical Society
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• 제20권6호
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• pp.643-647
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• 1999

Hydropalladium carboxylates, formed from π-allylpalladium chloride dimer plus carboxylic acids, have been shown to catalyze cyclization of structurally diverse enediynes to form the corresponding six- or five-membered rings depending upon the reaction conditions. Some enediynes having an Oxygen linker in an appropriate position under the similar condition yielded the corresponding cyclopropanation products in highly stereoselective manner. A study using deuterated formic acid has proven that the alkylpalladium intermediates formed in our conditions were reduced by the pendant formate ligand. The dienediyne 10 yielded only the tricyclic product 12 in 67% yield, although it was expected to frrm the cyclic product 11. All these cyclizations seemed to occur via the corresponding alkylpalladium intermediates I. which could proceed to the corresponding cyclic products depending on the reaction conditions and the substrates. The study using ceuterated formic acid could provide an important information to understand the present cyclization mechanism. Overall the present study could play an important role in developing new synthetic methodologies for constructing complex polycyclic compounds.

• Bulletin of the Korean Chemical Society
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• 제32권12호
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• pp.4321-4326
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• 2011

A new series of heteroleptic cyclometalated iridium(III) complexes has been synthesized and characterized by absorption, emission and cyclic voltammetry studies: $(pqx)_2Ir(acac)$ (1), $(dmpqx)_2Ir(acac)$ (2) and $(dfpqx)_2Ir(acac)$ (3) where pqx=2-phenylquinoxalinate, dmpqx=2-(2,4-dimethoxyphenyl)quinoxalinate, dfpqx=2-(2,4-difluorophenyl) quinoxalinate and acac=acetylacetonate anion. The reaction of excess acetylacetone with ${\mu}$-chloride-bridged dimeric iridium complex, $[(C\^N)_2Ir({\mu}-Cl)]_2$, gives a complex 1 and an unusual hydridoiridium(III) complex, $(pqx)IrH(acac)_2$ (4). The complex 1, 2 and 3 show their emissions in an orangered region (${\lambda}_{PL,max}$ = 583-616 nm), and the emission maxima can be tuned by the change of substituent at phenyl ring of 2-phenylquinoxaline ligand. The phosphorescent line shape indicates that the emissions originate predominantly from $^3MLCT$ states with little admixture of ligand-based $^3({\pi}-{\pi}^*)$ excited states. The structures of complex 3 and 4 are additionally characterized by a single crystal X-ray diffraction method. The complex 3 shows a distorted octahedral geometry around iridium(III) metal ion. A strong trans influence of the phenyl ring is examined. In complex 4, there are two discrete molecules which are mirror images each other at the ratio of 1:1 in an unit cell. We propose that the phosphorescent complex 1, 2 and 3 are possible candidates for the phosphors in OLEDs applications.

• 한국생물물리학회:학술대회논문집
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• 한국생물물리학회 1996년도 정기총회 및 학술발표회
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• pp.19-19
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• 1996

Cyclic AMP receptor protein (CRP) from E. Coli plays a key role in regulation of the expression of more than 20 genes of the bacterium. CRP binds in the presence of cAMP to a specific target site near the promoter of each gene under its regulation. CRP is a dimer (Mr～47,000) of two identical subunits. There are two binding domains in the CRP monomer, one for the binding of the cAMP and the other for the binding of specific DNA sequences. (omitted)