• Journal of the Korean Chemical Society
• /
• v.62 no.1
• /
• pp.14-18
• /
• 2018

The complexes $[Zn(L)(H_2O)_2]{\cdot}2NO_2$ (1) and $[Zn(L)(NO_3)_2]$ (2) (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo $[14,4,0^{1.18},0^{7.12}]$docosane) have been synthesized and structurally characterized. The compound 1 crystallizes in the monoclinic system $P2_1/c$ with a = 8.74650(10), b = 18.6880(3), c = $7.96680(10){\AA}$, ${\beta}=109.1920(10)^{\circ}$, $V=1229.84(3){\AA}^3$, Z = 2. The compound 2 crystallizes in the monoclinic system P1 with a = 8.1292(5), b = 8.9244(5), c = $9.1398(5){\AA}$, ${\alpha}=68.035(2)$, ${\beta}=70.109(2)$, ${\gamma}=75.649(3)^{\circ}$, $V=572.70(6){\AA}^3$, Z = 1. The crystal structures of the compounds 1 and 2 show a distorted octahedral coordination geometry around the zinc(II) ion, with four secondary amines and two oxygen atoms of the two water and two nitrate ligands at the axial position. The TGA behaviors of the complexes are significantly affected by the nature of the tetraaza macrocycle and the axial ligands.

• Bulletin of the Korean Chemical Society
• /
• v.17 no.9
• /
• pp.854-857
• /
• 1996

Absorption and luminescence spectra of Eu3+ (aquo) and the two different 1: 3 Eu3+: ligand systems in aqueous solutions are measured under mild acidic pH condition. The oxydiacetate (ODA) and dipicolinate (DPA) ligands, forming the similar geometric complexes, are used in this work. The three intensity parameters, Ωλ (λ=2, 4, and 6) are empirically determined by applying the Judd-Ofelt theorem to the oscillator strengths of the six absorption bands arising from the ground 7F0 state. Among the three intensity parameters, the Ω2 is found to response markedly to a miner change in the ligand environment via the 7F0→5D0 transition. In addition, the relative oscillator strengths of the four luminescence bands in the visible region, assigned to the 5D0→7FJ (J=1, 2, 3 and 4) transitions are obtained to investigate their sensitivity to the ligand environment. Among the four bands, the 610 nm band, attributed to the 5D0→7F2 transition, shows hypersensitivity in the luminescence.

• BMB Reports
• /
• v.44 no.3
• /
• pp.170-175
• /
• 2011

We identified a bovine $B_{12}$ trafficking chaperone bCblC in Bos taurus that showed 88% amino acid sequence identity with a human homologue. The protein bCblC was purified from E. coli by over-expression of the encoding gene. bCblC bound cyanocobalamin (CNCbl), methylcobalamin (MeCbl) and adenosylcobalamin (AdoCbl) in the base-off states and eliminated the upper axial ligands forming aquo/hydroxocobalamin ($OH_2$/OHCbl) under aerobic conditions. A transition of $OH_2$/OHCbl was induced upon binding to bCblC. Interestingly, bCblC-bound $OH_2$/OHCbl did not react with reduced glutathione (GSH), while the reaction of free$OH_2$/OHCbl with GSH resulted in the formation of glutathionylcobalamin (GSCbl) and glutathione disulfide (GSSG). Furthermore we found that bCblC eliminates the GSH ligand of GSCbl forming $OH_2$/OHCbl. The results demonstrated that bCblC is a $B_{12}$ trafficking chaperone that binds cobalamins and protects $OH_2$/OHCbl from GSH, which could be oxidized to GSSG by free $OH_2$/OHCbl.

• Bulletin of the Korean Chemical Society
• /
• v.13 no.1
• /
• pp.54-59
• /
• 1992

Spectroscopic measurements and theoretical calculations are performed for the four 1 : 3 Sm(III) : ligand solutions. The ligands included in this study are oxidiacetate, iminodiacetate, methyliminodiacetate and dipicolinate. The oscillator strengths for the $4f{\to}4f$ multiplet-to-multiplet transitions are empirically determined from the absorption spectra. The intensity parameters ${\Omega}_{\lambda}\;({\lambda}=2,\;4,\;6)$ of $Sm^{3+}$(aquo) and ${SmL_3}^{3-}$ complexes are also evaluated by applying the Judd-Ofelt theorem to the observed oscillator strengths. The values of the intensity parameters are compared and discussed in term of structural properties of the complexes. In addition, the fluorescence spectra are reported for the Sm(III) complex systems under mild alkaline condition. The excitation from the $^6H_{5/2}$ ground state to any excited states lying above the emitting energy level $(^4G_{5/2})$ produces four fluorescence bands, following nonradiative transitions from a certain excited state to the $^4G_{5/2}$ state. The ratios of oscillator strengths of ${SmL_3}^{3-}$ complexes to that of $Sm^{3+}$(aquo) are also evaluated from the fluorescence spectra and compared to the results obtained from the absorption bands.

• Journal of the Korean Chemical Society
• /
• v.54 no.6
• /
• pp.687-695
• /
• 2010

Complexes of thiocyanato(L)cobaloximes where L is urea, acetamide, semicrabazide and formamide were synthesized and characterized. The reaction of thiocyanato (L) cobaloximes (SCNCo$(DH)_2$(L)) with benzyl (aquo) cobaloxime $PhCH_2Co(DH)_2(OH_2)$ was found to produce a series of thiocyanato bridged dicobaloximes of a general formula of $PhCH_2Co(DH)_2SCNCo(DH_2)(L)$. Evidence for formulation as dicobaloximes containing thiocyanato ligand bridges was obtained from infrared data which show $20-45cm^{-1}$ increase in vCN upon formation of the dicobaloxime from the corresponding terminal thiocyanocobaloxime (SCNCo$(DH)_2$(L)). Further characterization of these two series was done on the basis of ($^1H$,$^{13}C$)NMR, LCMS and elemental analysis. Anti-microbial activity of thiocyanato(L)cobaloximes and thiocyanato bridged dicobaloximes were screened against E. Coli. The DNA-binding behaviors of both monomers and dimers were investigated by spectroscopic methods and viscosity measurements. The results indicated that the dimer complexes bind with calf-thymus DNA in an intercalative mode via the terminal benzyl ring into the base pairs of DNA. It was observed that the monomer complexes did not interact with DNA. Fluorescence spectra for the interaction between thiocyanato bridged dicobaloximes and DNA were also studied.