• Bulletin of the Korean Chemical Society
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• v.14 no.5
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• pp.599-602
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• 1993

Micellization process of dodecyltrimethylammonium bromide (DTAB) was studied by using the aromatic probe (benzene) which dissolved in aqueous DTAB solutions. Proton NMR chemical shift measurements of DTAB and DTAB-benzene system showed that benzene molecules solubilized near the micelle-water interface and that the solubilization sites within the micelles are different as the DTAB concentration is passing through 32.0 mM (hereafter we refer this concentration as the second CMC). The change of solubilization sites is also confirmed by abrupt changes of the chemical shifts and relaxation rates of benzene protons in DATB-benzene system at this concentration. It was revealed from the electrical conductivity and viscosity measurements that the solubilization of benzene caused the DTAB micelles to swell out and that the micelles prepared after the second CMC had a greater swelling effect than those prepared before the second CMC. The transition point which reflects the saturation of benzene molecules on the solubilization sites of micelles was observed at one benzene/micellized DTAB mole ratio from the electrical conductivity measurements. Along the different concentration of DTAB solution, this transition point is appeared clearly after the second CMC. From these results it is suggested that the shapes and/or sizes of DTAB micelles of the spherical micelle region prepared after the second CMC are different from those prepared before the second CMC.

• Bulletin of the Korean Chemical Society
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• v.18 no.6
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• pp.653-656
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• 1997

The new unsymmetric $N_6$ ligand 1-amino-13-(2-pyridyl)-3,6,9,12-tetraazatridecane (aptatd) containing one pyridyl group has been synthesized and characterized by EA, IR, and NMR. Its proton association constants $(log K_H^n)$ and stability constants $(log K_{ML})$ for Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), and Zn(Ⅱ) ions were determined at 298.1 K and ionic strength 0.100 mol $dm^{-3}$ (KNO₃) in aqueous solution by potentiometry: log $K_H^1$=8.80, log $K_H^2$=8.49, log $K_H^3$=6.84, log $K_H^4$=4.17, log $K_H^5$=3.47; log $K_{ML}(Co^{2+})$=18.00, log $K_{ML}(Ni^{2+})$=21.31, log $K_{ML}(Cu^{2+})$=23.62, log $K_{ML}(Zn^{2+})$=15.60. The X-ray structure of its nickel(Ⅱ) complex [Ni(aptatd)]$(ClO_4)_2$ are reported: orthorhombic space group Pbca, a=15.715(1) Å, b=14.280(2) Å, c=19.443(2) Å, V=4363.4 (9) ų with Z=8. The geometry around nickel is a distorted octahedron with the pyridine nitrogen atom being cis to the nitrogen atom of the terminal primary amine.

• Journal of Electrochemical Science and Technology
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• v.12 no.4
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• pp.387-397
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• 2021

Deep eutectic solvents have been established as feasible metal electroplating solvent alternatives over traditional toxic aqueous plating baths. However, water, either added intentionally or unintentionally, can significantly influence the solvent's physical properties and performance, thereby hindering its industry application. In this study, the hygroscopicity, or the ability to absorb moisture from the environment, of synthesized ethaline (1:2 choline chloride:ethylene glycol) was investigated. The kinematic viscosity, electrical conductivity, electrochemical window, and water content of ethaline were monitored over a 2-week period. Karl Fischer titration tests showed that ethaline exposed to the atmosphere displayed significant hygroscopicity compared to its unexposed counterpart. ¹H NMR spectroscopy revealed that water vapor was readily absorbed at the surface due to the hydrophilic groups present in the ethaline molecule. Water uptake resulted in the decrease in viscosity, increase in electrical conductivity and narrowing of the electrochemical window of ethaline. Solution heating at 100℃ removed the absorbed moisture and allowed the recovery of the solvent's initial properties.

• Nuclear Engineering and Technology
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• v.53 no.12
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• pp.4033-4041
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• 2021

To better understand the permeability of uranium sandstone, improve the leaching rate of uranium, and explore the change law of pore structure characteristics and blocking mechanism during leaching, we systematically analyzed the microstructure of acid-leaching uranium sandstone. We investigated the variable rules of pore structure characteristics based on nuclear magnetic resonance (NMR). The results showed the following: (1) The uranium concentration change followed the exponential law during uranium deposits acid leaching. After 24 h, the uranium leaching rate reached 50%. The uranium leaching slowed gradually over the next 4 days. (2) Combined with the regularity of porosity variation, Stages I and II included chemical plugging controlled by surface reaction. Stage I was the major completion phase of uranium displacement with saturation precipitation of calcium sulfate. Stage II mainly precipitated iron (III) oxide-hydroxide and aluminum hydroxide. Stage III involved physical clogging controlled by diffusion. (3) In the three stages of leaching, the permeability of the leaching solution changed with the pore structure, which first decreased, then increased, and then decreased.

• Analytical Science and Technology
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• v.14 no.2
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• pp.159-166
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• 2001

A humic acid(HA, Aldrich Co) sample was subjected to ultrafiltration for molecular size fractionation and three fractions of different nominal size($F_1$: 1,000-10,000 daltons; $F_2$: 10,000-50,000 daltons; $F_3$: 100,000-300,000 daltons) were obtained. The structural characteristics of the size-fractionated HA were analyzed using their IR and solid state C-13 NMR spectral data, and the carboxylate group contents of the humic acids were determined using their pH titration data. The $^7F_0-{^5}D_0$ excitation spectra of Eu(III) complexes of the size-fractionated mgHA in aqueous solution were acquired($[Eu(III)]=1.0{\times}10^{-4}mol\;L^{-1}$, $(HA)=470-970mg\;L^{-1}$) at pH 5.0 using a pulsed tunable laser system, in which metal binding properties of the size-fractionated HA were elucidated and compared on another. Characterization of the IR and C-13 NMR spectral data indicated that the fraction($F_3$) with molecules of larger size were primarily aliphatic, while the fractions($F_1$, $F_2$) with smaller molecules of less than 50,000 daltons were predominantly aromatic. Titration data were consistent with an increase in the number of carboxylate groups per unit mass as molecular size became smaller. The $^7F_0-{^5}D_0$ excitation spectral data of Eu(III)-humate complexes showed that the peak maxima on these spectra were shifted toward lower energies with increasing molecular size of HA, indicating the higher degree of bindings of the Eu in the molecules of larger size. We also discussed the relationship of the lower energy shifts of the maximum peaks with increasing the molecular size of HA with the structural differences of the size-fractionated HA.

• Analytical Science and Technology
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• v.13 no.4
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• pp.494-503
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• 2000

A 21-residue peptide corresponding to amino acids 84-104 of $p16^{INK4A}$, the tumor suppressor, has been synthesized and its structure was studied by Circular Dichroism, $^1H$ NMR spectroscopy and molecular modeling. A p16-derived peptide (84-104 amino acids) forming stable complex with CDK4 and CDK6 inhibits the ability of CDK4/6 to phosphorylate pRb in vitro, and blocks cell-cycle progression through G1/S phase as shown in the function of the full-length p16. Its NMR spectral data including NOEs, $^3J_{NH-H{\alpha}}$ coupling constants, $C_{\alpha}H$ chemical shift, the average amplitude of amide chemical shift oscillation and temperature coefficients indicate that the secondary structure of a p16-derived peptide is similar to that of the same region of full-length p16, which consists of helix-turn-helix structure. The 3-D distance geometry structure based on NOE-hased distance and torsion angle restraints is characterized by ${\gamma}$-turn conformation between residues $Gly^{89}-Leu^{91}$(${\varphi}_{i+1}=-79.8^{\circ}$, ${\varphi}_{i+1}=60.2^{\circ}$) as evidenced in a single crystal structure for the corresponding region of p18 or p19, but is undefined at both the N and C termini. This compact and rigid ${\gamma}$-turn region is considered to stabilize the structure of p16-derived peptide and serve as a site recognizing cyelin dependent kinase, and this well-defined ${\gamma}$-turn structure could be utilized for the design of anti-cancer drug candidates.

• Journal of Korea Foresty Energy
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• v.17 no.1
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• pp.56-70
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• 1998

This study was carried out to investigate the structural characteristics of kraft lignin and the wood degrading characteristics, the productivity of ligninolytic enzymes and the enzymatic degradation of kraft lignin by white-rot fungi. To purify kraft lignin, precipitation of kraft pulping black liquors of pitch pine meal was done by titration with lN $H_{2}SO_{4}$ reaching to pH 2, and isolation of the precipitates done by centrifugation. The isolated precipitates from pitch pine were redissloved in lN NaOH, reprecipitated by titration with lN $H_{2}SO_{4}$, washed with deionized water, and kept ofr analysis after freeze drying. Fractionation of the precipitates in solution by successive extraction with $CH_{2}Cl_{2}$ and MeOH, and the fractionates were named SwKL, SwKL I, SwKL II, and SwKL III for pitch pine kraft lignin. The more molecular weights of kraft lignin increased, the less phenolic hydroxyl groups and the more aliphatic hydroxyl groups. Because as the molecular weights increased, the ratio of etherified guaiayl/syringyl(G/S ratio) and the percentage were increased. The spectra obtained by 13C NMR and FTIR assigned by comparing the chemical shifts of various signals with shifts of signals from autherized ones reported. The optimal growth temperature and pH of white-rot fungi in medium were $28^{\circ}C$ and 4.5-5.0, respectively. Especially, in temperature and pH range, and mycelial growth, the best white-rot fungus selected was Phanerochaete chrysosporium for biodegradation. For the degradation pathways, the ligninolytic fungus jcultivated with stationary culture using medium of 1% kraft lignin as a substrate for 3 weeks at $28^{\circ}C$. The weight loss of pitch pine kraft lignin was 15.8%. The degraded products extracted successively methoanol, 90% dioxane and diethyl ether. The ether solubles were analyzed by HPLC. Kraft lignin degradation was initiated in $\beta$-O-4 bonds of lignin by the laccase from Phanerochaete chrysosporium and the degraded compounds were produced from the cleavage of $C\alpha$-$C\beta$ linkages at the side chains by oxidation process. After $C\alpha$-$C\beta$ cleavage, $C\alpha$-Carbon was oxidized and changed into aldehyde and acidic compounds such as syringic acid, syringic aldehyde and vanilline. And the other compound as quinonemethide, coumarin, was analyzed. The structural characteristics of kraft lignin were composed of guaiacyl group substituted functional OHs, methoxyl, and carbonyl at C-3, -4, and -5 and these groups were combinated with $\alpha$ aryl ether, $\beta$ aryl ether and biphenyl. Kraft lignin degradation pathways by Phanerochaete chrysosporium were initially accomplished cleavage of $C\alpha$-$C\beta$ linkages and $C\alpha$ oxidation at the propyl side chains and finally cleavage of aromatic ring and oxidation of OHs.

• Journal of the Korean Chemical Society
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• v.55 no.3
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• pp.444-453
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• 2011

VO(II), ZrO(II), Hf(IV), $UO_2$(II), Sn(II), V(V)$O_3$, Ru(III), Cd(II), Ho(III) and Yb(III) complexes of N'-(2-hydroxybenzyl)-2-(phenylamino)acetohydrazide ($H_2L^1$, 1) and N'-((3-hydroxy-naphthalen-2-yl)methylene)-2-(phenylamino)-acetohydrazide ($H_2L^2$, 13) have been synthesized and characterized by elemental analyses, $^1H$ NMR, IR, UV-Vis, conductance, thermal analyses (DTA and TG). The spectral data showed that the ligands behave as neutral bidentate, monobasic bidentate, monobasic tridentate or bibasic tridentate ligand bonded to the metal ions through the azomethine nitrogen atoms, phenolic hydroxyl group in protonated or deprotonated form and enolic or ketonic carbonyl group. The ligands and their metal complexes exhibit higher antifungal and antibacterial inhibitory effects than parent ligands and the solution of metal ions. Most of metal complexes exhibit higher antifungal activity than standard antifungal drug (amphotricene B). It is also clear that the ligands and their metal complexes have higher antifungal activity than antibacterial activity.

• Elastomers and Composites
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• v.43 no.4
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• pp.271-280
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• 2008

Aromatic polyhydroxyamides (PHAs) having bulky groups and ether linkages in the polymer main chain were synthesized by the low temperature solution polycondensation reaction. FT-IR, $^{1}H-NMR$, DSC, and TGA were used to study the properties of these polymers. The PHAs were converted into polybenzoxazoles (PBOs) by a thermal cyclization reaction, and endothermic peaks were observed in the range of $220{\sim}400^{\circ}C$. The introduction of the ether and bulky groups in the main chain improved the solubility of the PHAs in aprotic solvents such as DMSO and DMF, but the PBOs were nearly insoluble in common solvents. All the PBOs, except for PBO 5 with 2,6-dimethylphenoxy pendant and 2,3-dihydroxyquinoxaline ring, and PBO 6 with 2,6-dimethylphenoxy pendant and 2,3-dihydroxyquinoxaline ring, exhibited $T_g's$ in the range from 149 to $217^{\circ}C$ by DSC. The thermogravimetric analyses indicated that most of the PBOs were thermally stable up to $400^{\circ}C$ in nitrogen. Maximum weight loss temperatures of PHA 5 and PBO 5 with 2,6-dimethylphenoxy pendant and 2,3-dihydroxyquinoxaline ring were $707^{\circ}C$ and $683^{\circ}C$, respectively, which were the hightest temperatures among the corresponding copolymers. The PBOs in nitrogen exhibited relatively high char yields in the range of $63{\sim}70%$ at $900^{\circ}C$.

• Applied Chemistry for Engineering
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• v.10 no.1
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• pp.6-11
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• 1999

Dialkylamine (di-)nitrobenzoates as vapor corrosion inhibitor were synthesized with dialkylamines and (di-)nitrobenzoic acids. The compounds were analyzed by elemental analyzer, FT-IR and $^1H$-NMR spectrophotometer. Corrosion inhibition of synthetic compounds and additives [$(NH_4)_2CO_3$, $NaHCO_3$] against ferrous and non-ferrous metal was investigated by potentiostatic method [1% (w/v) corrosion inhibitor in 1M $Na_2SO_4$ aqueous solution] respectively. For corrosion inhibition of ferrous metal, dialkylamine 4-nitrobenzoates were better inhibitor than dialkylamine 3, 5-dinitrobenzoates, the passivating current density ($i_p$) of dialkylamine 4-nitrobenzoate was shown $4.78mA/cm^2$. While, for non-ferrous metal, dialkylamine 3, 5-dinitrobenzoates were better, those of dipropylamine 3, 5-dinitrobenzoate and hexamethyleneimine 3, 5-dinitrobenzoate were shown 36 and $37mA/cm^2$. Additive effect of $(NH_4)_2CO_3$ and $NaHCO_3$ for corrosion inhibition of ferrous metal was excellent but that of non-ferrous metal was not. Optimum ratios of diethylamine 4-nitrobenzoate with $(NH_4)_2CO_3$ and $NaHCO_3$ were 4 : 6 and 5 : 5 (V/V), and passivating current densities ($i_p$) of the mixtures were shown 0.26 and $0.85mA/cm^2$, respectively.