• Bulletin of the Korean Chemical Society
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• 제35권12호
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• pp.3495-3501
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• 2014

A novel crystal, the mono-protonated metformin acetate (1), was obtained and characterized by elemental analysis, IR spectroscopy and X-ray crystallography. It was found that one of the imino group in the metformin cation was protonated along with the proton transfer from the secondary amino group to the other imino group. Its crystal structure was then compared with the previously reported diprotonated metformin oxalate (2). The difference between them is that the mono-protonated metformin cations can be linked by hydrogen bonding to form dimers while the diprotonated metformin cations cannot. Both of them are stabilized by intermolecular hydrogen bonds to assemble a 3-D supermolecular structure. The four potential tautomer of the mono-protonated metformin cation (tautomers 1a, 1b, 1c and 1d) were optimized and their single point energies were calculated by Density Functional Theory (DFT) B3LYP method based on the Polarized Continuum Model (PCM) in water, which shows that the most likely existed tautomer in human cells is the same in the crystal structure. Based on the optimized structure, their Wiberg bond orders, Natural Population Analysis (NPA) atomic charges, molecular electrostatic potential (MEP) maps were calculated to analyze their electronic structures, which were then compared with the corresponding values of the diprotonated metformin cation (cation 2) and the neutral metformin (compound 3). Finally, the possible tautomeric mechanism of the mono-protonated metformin cation was discussed based on the observed phenomena.

• Bulletin of the Korean Chemical Society
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• 제30권3호
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• pp.556-560
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• 2009

Aggregation behavior of three kinds of benzindocarbocyanine dyes in aqueous methanol solution was studied by UV-Vis absorption spectrum. The results indicated that the three dyes all existed monomer-dimer equilibrium in aqueous methanol solution (concentration range $10^{−5}\;to\;10^{−6}$ M) at 25.0$\sim$41.0 ${^{\circ}C}$ for Dye 1, 28.0$\sim$49.0 ${^{\circ}C}$ for Dye 2 and 26.0$\sim$47.0 ${^{\circ}C}$ for Dye 3. The fundamental property of the three dyes as the dimeric association constant KD, the dimeric free energy ${\Delta$}G_D, the dimeric entropy ${\Delta$}S_D, and the dimeric enthalpy ${\Delta$}H_D were determined. The ${\Delta$}H_D of three dyes: Dye 1, Dye 2 and Dye 3 was -42.5, -15.1 and -18.9 kJ/mol, respectively. The experimental observations were the subject of a theoretical study including the ground-state geometries which were fully optimized using DFT at B3LYP/6-31G level. The effect of dye molecule structure on ${\Delta$}H_D was discussed by theoretical calculations.

• Bulletin of the Korean Chemical Society
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• 제31권5호
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• pp.1349-1354
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• 2010

The geometries and isomerization of the alkylidene silylenoid $H_2C$ = SiLiF as well as its insertion reactions with R-H (R = F, OH, $NH_2$) have been systematically investigated at the B3LYP/6-311+$G^*$ level of theory. The potential barriers of the three insertion reactions are 97.5, 103.3, and 126.1 kJ/mol, respectively. Here, all the mechanisms of the three reactions are identical to each other, i.e., an intermediate has been formed first during the insertion reaction. Then, the intermediate could dissociate into the substituted silylene ($H_2C$ = SiHR) and LiF with a barrier corresponding to their respective dissociation energies. Correspondingly, the reaction energies for the three reactions are -36.4, -24.3, and 3.7 kJ/mol, respectively. Compared with the insertion reaction of $H_2C$ = Si: and R-H (R = F, OH and $NH_2$), the introduction of LiF makes the insertion reaction occur more easily. Furthermore, the effects of halogen (F, Cl, Br) substitution and inorganic salts employed on the reaction activity have also been discussed. As a result, the relative reactivity among the three insertion reactions should be as follows: H-F > H-OH > H-$NH_2$.

• Journal of Electrochemical Science and Technology
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• 제8권1호
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• pp.43-52
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• 2017

In this paper, for the first time, the electroanalytical study of Triethylenediamine, TEDA was done on a typically graphene modified carbon paste electrode (Gr/CPE) in pH=10.5 of phosphate buffer solutions (PBS). The surface morphology of the bare and modified electrodes was characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The electro-oxidation of TEDA was investigated at the surface of modified electrode. The results revealed that the oxidation peak current of TEDA at the surface of Gr/CPE is 2.70 times than that shown at bare-CPE. A linear calibration plot was observed in the range of 1.0 to 202.0 ppm. In this way, the detection limit was found to be 0.18 ppm. The method was then successfully applied to determination of TEDA in aqueous samples obtained from two kinds of activated carbon from the masks of war. On the other hand, density functional theory (DFT) method at B3LYP/6-311++G** level of theory and a conductor-like Polarizable Continuum Model (CPCM) was used to calculate the $pK_a$ values of TEDA. The energies of lowest unoccupied molecular orbital ($E_{LUMO}$) and highest occupied molecular orbital ($E_{HOMO}$), gap energy (${\Delta}E$) and some thermodynamic parameters such as Gibbs free energy of TEDA and its conjugate acid ($HT^+$) were calculated. The results of calculated $pK_a$ were found to be in good agreement with the experimental values.

• Bulletin of the Korean Chemical Society
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• 제34권10호
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• pp.2889-2894
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• 2013

A new complex [$Ni(phen)(C_9H_8Br_2NO_3)_2{\cdot}2CH_3OH{\cdot}2H_2O$] [phen: 1,10-phenanthroline $C_9H_8Br_2NO_3$: 3,5-dibromo-L-tyrosine] was synthesized and characterized by IR, elemental analysis and single crystal X-ray diffraction. X-ray crystallography shows that Ni(II) ion is six-coordinated. The Ni(II) ion coordinates with four nitrogen atoms and two oxygen atoms from three ligands, forming a mononuclear Ni(II) complex. The crystal crystallizes in the Orthorhombic system, space group $P2_12_12$ with a = 12.9546 ${\AA}$, b = 14.9822 ${\AA}$, c = 9.9705 ${\AA}$, V = 1935.2 ${\AA}$, Z = 1, F(000) = 1008, S = 0.969, ${\rho}_{calcd}=1.742g{\cdot}cm^{-3}$, ${\mu}=4.688mm^{-1}$, $R_1$ = 0.0529 and $wR_2$ = 0.0738 for 3424 observed reflections (I > $2{\sigma}(I)$). Theoretical study of the title complex was carried out by density functional theory (DFT) method and the B3LYP method employing the $6-3l+G^*$ basis set. The energy gap between HOMO and LUMO indicates that this complex is prone to interact with DNA. CCDC: 908041.