• Bulletin of the Korean Chemical Society
• /
• v.14 no.5
• /
• pp.561-567
• /
• 1993

The twelve macrocycle (L) complexes of cadmium(II) nitrate have been synthesized: $CdL(NO_3)_2$. All the complexes have been indentified by elemental analysis, electric conductivity measurements, IR and NMR spectroscopic techniques. The molar electric conductivities of the complexes in water and acetonitrile solvent were in the range of 236.8-296.1 $cm^2{\cdot}mol^{-1}{\cdot}ohm^{-1}$ at 25$^{\circ}$C. The characteristic peaks of macrocycles affected from Cd(II) were shifted to lower frequencies as compared with uncomplexed macrocycles. A complex with 1,4,8,11-tetrakis(methylacetato)-1,4,8,11-tetraaza cyclodecane (L4) exhibited two characteristic bands such as strong stretching (1646 $cm^{-1})$, and weaker symmetric stretching band (1384 $cm^{-1})$. NMR studies indicated that all nitrogen donor atoms of macrocycles have greater affinity to cadmium(II) metal ion than do the oxygen atoms. The $^{13}$C-resonance lines of methylene groups neighboring the donor atom such as N and S were shifted to a direction of high magnetic field and the order of chemical shifts were $L_1 < L_2 < L_3 < L_6 < L_4$. Also the chemical shifts values were larger than those of methylene groups bridgeheaded in side-armed groups. This result seems due to not only the strong interaction of Cd(Ⅱ) with nitrogen donors according to the HSAB theory, but weak interaction of Cd(Ⅱ) and COO- ions or sulfur which is enhanced by the flexible methylene spacing group in side-armed groups. Thus, each additional gem-methyl pairs of L_3, L_4\;and\; L_6$ macrocycles relative to $L_1, L_2,\;and\;L_5$ leads to an large enhancement in Cd(II) affinity. ^{13}C$-NMR spectrum of the complex with $L_{12}$ (1,5,9,13-tetracyclothiacyclohexadecane-3,11-diol) reveals the presence of two sets of three resonance lines, and intensities of the each resonance line have the ratio of 1 : 2 : 2. This molecular conformation is predicted as structure of tetragonal complex to be formed by coordinating two sulfur atoms and the other two sulfur atoms which is affected by OH-groups.

• Applied Chemistry for Engineering
• /
• v.8 no.5
• /
• pp.796-803
• /
• 1997

The PVT and $^2H$-NMR characteristic of main-chain dimer liquid crystals having structures such as ${\alpha}$, ${\omega}$-bis[4,4'-cyanobiphenyl) oxy] alkane(CBA-10) were studied. In this work, V-T curves obtained from isobaris measurements on various pressures, volume changes were observed at the nematic-isotropic and nematic-crystal phase transition. The volume changes at the transition exhibit slight odd-even effect with respect to the number of methylene unit n. The values of the$({\Delta}S_{tr})_V$ obtained at the NI transition for CBA-10 was $12.6J/mol{\cdot}K$. The values of $({\Delta}S_{CN})_V$ for the CN transition was estimated on the basis of DSC data : $65.3J/mol{\cdot}K$. For both transition, it was found that the correction about the volume change is significant, ranging from 40 to 60% of the total transition entropy observed under constant pressure. The RIS analysis of the spectra was performed so as to elucidate the conformational characteristics of the spacer in the nematic phase. The conformational entropy changes at both CN and NI interphases were estimated on the basis of the nematic conformations taken from the conformation map as well as those derived from the simulation. The estimated conformational entropy change values were then compared with the corresponding constant-volume entropies obtained from PVT measurements. The correspondence between both entropy values was found to be quite good in consideration of the uncertainties involved in both experiment and calculations.

• BMB Reports
• /
• v.34 no.1
• /
• pp.1-7
• /
• 2001

Structural and physical properties of type wild type and various selected mutants of the vnd/NK-2 homeodomain, the protein product of the homeobox, and the implication in genetic disease are reviewed. The structure, dynamics and thermodynamics have been Investigated by NMR and by calorimetry. The interactions responsible for the nucleotide sequence-specific binding of the homeodomain to its consensus DNA binding site have been identified. There is a strong correlation between significant structural alterations within the homeodomain or its DNA complex and the appearance of genetic disease. Mutations in positions known to be important in genetic disease have been examined carefully For example, mutation of position 52 of vnd/NK-2 results in a significant structural modification and mutation of position 54 alters the DNA binding specificity and amity The $^{15}N$ relaxation behavior and heteronuclear Overhauser effect data was used to characterize and describe the protein backbone dynamics. These studies were carried out on the wild type and the double mutant proteins both in the free and in the DNA bound states. Finally, the thermodynamic properties associated with DNA binding are described for the vnd/NK-2 homeodomain. These thermodynamic measurements reinforce the hypothesis that water structure around a protein and around DNA significantly contribute to the protein-DNA binding behavior. The results, taken together, demonstrate that structure and dynamic studies of proteins combined with thermodynamic measurements provide a significantly more complete picture of the solution behavior than the individual studies.

• Journal of the Korean Chemical Society
• /
• v.55 no.4
• /
• pp.612-619
• /
• 2011

Lanthanide(III) complexes of 1,2-diphenyl-4-butyl-3,5-pyrazolidinedione(phenylbutazone, PB) have been synthesized and characterized by elemental analyses, molar conductance measurements, IR, UV-Vis. and NMR spectra. The spectral data reveal that the PB acts as a bidentate and mono-ionic ligand coordinating through both the carbonyl oxygens of the pyrazolidinedione ring. The molar conductance data suggest that the complexes are non-electrolytes. The thermal behaviour of the complexes was studied by TG and DTG in air atmosphere and the results provide information about dehydration, thermal stability and thermal decomposition. The final products are found to be the corresponding metal oxides. The thermodynamic parameters and kinetic parameters were evaluated for the dehydration and decomposition stages. The negative entropy values of the decomposition stages indicate that the activated complexes have a more ordered structure than the reactants and that the reactions are slower than normal. Based on these studies, the complexes have been formulated as $[Ln(PB)_3]{\cdot}5H_2O$(Ln=La and Ce) and $[Ln(PB)_3(H_2O)_2]{\cdot}2H_2O$(Ln=Pr, Nd and Sm).

• Applied Chemistry for Engineering
• /
• v.30 no.4
• /
• pp.435-444
• /
• 2019

In this study, two types of nonionic saccharide biosurfactants, GP-6 and GP-7, were prepared from coconut oil and the structure of resulting products was investigated by FT-IR, $^1H-NMR$ and $^{13}C-NMR$ spectrophotometer. The interfacial properties of GP-6 and GP-7 were found to be excellent from interfacial property measurements such as critical micelle concentration, static and dynamic surface tensions, interfacial tension, emulsification power, wetting property and foam stability. Detergency test evaluated by using a Terg-o-tometer showed moderately good detergency compared to that of conventional surfactants used in detergent formulations. Biodegradability, acute oral toxicity, acute dermal irritation and acute eye irritation tests revealed that both surfactants possess excellent mildness and superior environmental compatibility indicating the potential applicability to detergent products formulations. In particular, GP-6 can be considered as a strong candidate in detergent formulations since it is more surface active, mild and readily biodegradable than GP-7.

• Mycobiology
• /
• v.40 no.2
• /
• pp.142-144
• /
• 2012

During the search for neuraminidase inhibitors from medicinal fungi, we found that the culture broth of Phellinus linteus exhibited potent inhibitory activity. Solvent partition, Sephadex LH-20 column chromatography, and high-performance liquid chromatography (HPLC) were performed for purification of two active substances from the culture broth. According to $^1H$ NMR measurements and comparison of HPLC retention times with those of authentic compounds, their chemical structures were identified as hispidin and hypholomine B. Compounds (hispidin) 1 and 2 (hypholomine B) inhibited neuraminidase, with $IC_{50}$ values of 13.1 and 0.03 ${\mu}M$, respectively.

• Bulletin of the Korean Chemical Society
• /
• v.34 no.7
• /
• pp.2131-2137
• /
• 2013

In this work, the key intermediate, 4-amino-4'-(2-amino-4-anilino-1,3,5-triazine-6-yl)-aminostilbene-2,2'-disulfonic acid, was prepared from 4-(2-amino-4-anilino-1,3,5-triazine-6-yl)amino-4'-nitrostilbene-2,2'-disulfonate by using Tin(II) chloride as the reducing agent. Using this intermediate, nineteen new asymmetrically substituted bistriazinylstilbene fluorescent brightening agents were synthesized. Chemical structures of the obtained compounds 5a-s were analyzed by proton NMR spectrum. The physical properties of the new compounds 5a-s were characterized by fastness test and whiteness measurement test and the obtained data were compared to measurements obtained from CI 86.

• Textile Coloration and Finishing
• /
• v.23 no.3
• /
• pp.163-168
• /
• 2011

In this article, we synthesized an azo dye rotaxane containing bis(8-hydroxyquinoline) group and its polymeric metal complex with zinc. The azo dye rotaxane exhibits high pH sensitivity, solvatochromism and zinc (II) ion sensings in aqueous solution. These behaviors came from the tautomeric equilibrium between azo-hydrazone tautomers and the formation of extended conjugation. The structure of polymeric zinc complexed dye rotaxane was confirmed with NMR and FT-IR measurements. The existence of CD rings, provided by dye rotaxane formation, was found to be very beneficial in improving aqueous solubility of polymeric metal complex.

• Macromolecular Research
• /
• v.11 no.6
• /
• pp.418-424
• /
• 2003

Exfoliated poly(methyl methacrylate-co-styrene) [P(MMA-co-ST)]/silicate nanocomposites were synthesized through a multistep emulsion polymerization. The methyl methacrylate monomers were polymerized first and then the styrene monomers were polymerized. The nanocomposites had core-shell structures consisting of PMMA (core) and PS (shell); these structures were confirmed by $^1$H NMR spectroscopy and TEM, respectively. P(MMA-co-ST) copolymers showed two molecular weight profiles and two glass transition temperatures (T$_{g}$) in GPC and DMA measurements. At 30 $^{\circ}C$, the nanocomposites exhibited 83 and 91 % increases in their storage moduli relative to the neat copolymer because the silicate layers were dispersed uniformly in the polymer matrix.x.

• 한국정보디스플레이학회:학술대회논문집
• /
• 2003.07a
• /
• pp.475-477
• /
• 2003

Orientation of E7 liquid crystals (LCs) confined to 200 nm-diameter cylindrical cavities of Anodisc membranes are investigated by FTIR dichroism techniques. The cavity walls of the confining pores are chemically modified with different aliphatic acids ($C_nH_{2n+1}COOH$, n=5, 6, 7, 9). From the FTIR spectra of aliphatic acid treated alumina Anodsic membranes, we found the salt formation between -COOH group of aliphatic acid and Anodisc membrane. From the FTIR spectra of LC filled Anodisc membranes, we found abrupt alignment direction change of LC molecules between n=6 and 7 for 2% aliphatic acid treated Anodisc membranes, from parallel to perpendicular direction to the cavity walls. But 4% aliphatic acid treated Anodisc membranes, alignment direction of LC molecules changed between n=5 and n=6, from parallel to perpendicular direction. The same trend was observed for $^2H-NMR$ measurements.