• Bulletin of the Korean Chemical Society
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• v.19 no.7
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• pp.776-779
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• 1998

Second-order rate constants have been measured spectrophotometrically for the addition reaction of a series of alicyclic amines to 3-butyn-2-one to yield their respective enamines at 25.0 'C. The reactivity of the amines increases with increasing the basicity of the amines. However, the Bronsted-type plot obtained exhibits a downward curvature as the basicity of the amines increases, i.e. βnuc decreases from 0.3 for low basic amines (pKa < 9) and to 0.1 for highly basic amines (pKa > 9). Such a curvature in the Bronsted-type plot is clearly indicative of a change in the reaction mechanism or transition state structure. From the corresponding reactions run in D2O, the magnitude of kinetic isotope effect (KIE) has been calculated to be about 0.8 for highly basic amines and 1.21 for weakly basic amines. The difference in the magnitude of KIE also supports a change in the reaction mechanism or transition state structure upon changing the basicity of the amines. Furthermore, the small KIE clearly suggests that H+ transfer is not involved in the rate-determining step, i.e. the addition reaction is considered to proceed via a stepwise mechanism in which the attack of the amines to the acetylene is the rate-determining step. The curvature in the Bronsted-type plot has been attributed to a change in the degree of bond formation between the amine and the acetylene.

• Bulletin of the Korean Chemical Society
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• v.19 no.9
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• pp.968-973
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• 1998

Solvolyses of para-substituted phenyl chloroformates in water, $D_2O,\;CH_3OD$, 50% $D_2O-CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol are investigated at 25.0 ℃. Product selectivities are reported for a wide range of ethanol-water and methanol-water solvent compositions. These data are interpreted using the Grunwald-Winstein relationship, Hammett equation, and quantum mechanical model. Grunwald-Winstein plots of the first-order rate constants for phenyl chloroformates with $Y_{Cl}$ (based on 1-adamantyl chloride) show marked dispersions into three separate curves for the three aqueous mixtures with a small m value and a rate maximum for aqueous alcohol solvents. To account for these results, third-order rate constants, $k_{ww},\;k_{aw},\;k_{wa}$, and $k_{aa}$ were calculated from the observed $k_{ww}\;and\;k_{aa}$ values together with $k_{aw}\;and\;k_{wa}$ calculated from the computer fit. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed carbonyl addition-elimination for para-substituted phenyl chloroformates solvolyses based on mass law and stoichiometric salvation effect studies. This study has shown that the quantum mechanical model predicts transition state variation correctly for $S_N2\;like\;S_AN$ reaction mechanism of para-substituted phenyl chloroformates.

• Bulletin of the Korean Chemical Society
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• v.17 no.6
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• pp.520-524
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• 1996

Solvolyses of phenyl chloroformate in water, D2O, CH3OD, 50% D2O-CH3OD, and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25.0 ℃. Product selectivities are reported at 25 ℃ for a wide range of ethanol-water and methanol-water solvent compositions. The Grunwald-Winstein plots of first-order rate constants for phenyl chloroformate with YCl (based on 2-adamantyl chloride) show marked dispersions into three separate lines for the three aqueous mixtures with a small m value (m< 0.2) and a rate maximum for aqueous alcohol solvents. Third-order rate constants, kww, kaw, kwa and kaa were calculated from the observed kww and kaa values together with kaw and kwa calculated from the intercept and slope of the plot of 1/S vs. [alcohol]/[water]. The calculated rate constants, kcalc and mol % of ester agree satisfactorily with those of the observed rate constants, kobs and mol % of ester, supporting the stoichiometric solvation effect analysis. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed and/or carbonyl addition for phenyl chloroformate solvolyses based on mass law and stoichiometric solvation effect studies.

• Journal of Radiopharmaceuticals and Molecular Probes
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• v.8 no.2
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• pp.113-118
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• 2022

Gadolinium neutron capture therapy (Gd-NCT) is a precision radiation therapy that kills cancer cells using the neutron capture reaction that occurs when ¹⁵⁷Gd hits thermal neutrons. ¹⁵⁷Gd has the highest thermal neutron capture cross section of 254,000 barns among stable isotopes in the periodic table. Another stable isotope, ¹⁵⁵Gd, also has a high thermal neutron trapping area (~ 60,700 barns), so gadolinium that exists in nature can be used as a Gd-NCT drug. Gd-NCT is a mixed kinetic energy of low-energy and high-energy ionizing particles, which can be uniformly distributed throughout the tumor tissue, thereby solving the disadvantage of heterogeneous dose distribution in tumor tissue. The Gd complexes of small-sized molecule are widely used as contrast agents for magnetic resonance imaging (MRI) in clinical practice. Therefore, these compounds can be used not only for diagnosis but also therapy when considering the concept of Gd-NCT. This multifunctional trial can look forward to new medical advance into NCT clinical practices. In this review, we introduce gadolinium compounds suitable for Gd-NCT and describe the necessity of image guided Gd-NCT.

• Bulletin of the Korean Chemical Society
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• v.23 no.1
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• pp.123-131
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• 2002

Solvolyses rate constant of 1- and 2- naphthoyl chlorides (1 and 2) are reported for aqueous binary mixtures with methanol, ethanol, fluorinated alcohol, acetonitrile and dioxane. Kinetic solvent isotope effects (KISE) in methanol and product selectivities (S) of 2-naphthoyl chloride (2) in alcohol-water are also reported. Dispersions in Grunwald-Winstein correlations $(r{\leq}0.901)$ are discussed by multiple regression analysis incorporating ionizing power $(Y_{Cl})$ scale and rate-rate profiles. Major causes for these phenomena are investigated as an aromatic ring solvation effects, in conjunction with weakly nucleophilic solvation effects ($S_N2$ character), for solvolyses of 1 and for solvolyses of 2, as dual reaction channels, described as $S_N1$-$S_N2$ and $S_AN$-$S_N2$ processes. Distinct border lines between the two pathways are derived from solvolyses rates of 2 in 18 solvent using the results of $log(k/k_o)=mY_{Cl}+lN_T+hI$ plot with values of 1.13 for m, 0.37 for l and 0.15 for h value in 5 aqueous fluorinated alcohol mixtures. Using rate-product correlation, the validity of a third order model based on a general base catalyzed by solvent and contribution from these rate constants, $k_{aa},\;k_{aw}$ and $k_{aw}$, are investigated for $S_AN$-$S_N2$ solvolyses of 2 favored in more rich alcohol media and gradual addition of water to alcohol solvent shows a great shift away from stoichiometric solvation to predominantly medium effects. Rate-rate correlation between solvolyses of 2 and trimethyl acetylchloride (5) with alkyl group in the 29 aqueous solvent mixtures shows appreciable linearity (slope = 0.84, r = 0.987), caused by the same pathway ($S_N1$-$S_N2$ process), even if this correlation coincides with appreciable dispersion (different solvation effect).

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2000.11a
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• pp.232-236
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• 2000

Multi-regression statistical analyses were applied for the water quality data of shallow alluvial ground water (n = 47) collected from the Youngdeok area, in order to quantitatively generalize the natural (non-anthropogenic) causes of regional water quality variation. Seven samples having the high contamination index ( $C_{a}$ > 3) reflect the striong effects by anthropogenic activity. Most of the alluvial groundwaters have acquired their quality primarily due to the dissolution of carbonate minerals. The results of multi-regression analysis show that chlorine is mainly derived from seawater effect. Sulfur isotopic compositions of dissolved sulfur and the S $O_4$/Cl ratio also enable us to discriminate the samples (n = 18) which are affected by atmospheric input of marine aerosol (sea-spray) and also by mixing between freshwater and seawater. Hydrogen and oxygen isotope data of the samples collected lie close to the local meteoric water line obtained from nearby Pohang city but has lower slope (5.45) on the $\delta$D-$^{18}$ O plot, indicating that alluvial groundwater was recharged from infiltrated meteoric water which has undergone some degree of kinetic evaporation. The estimated initial isotopic composition of the recharged water ($\delta$D = -74.8$^{0}$ /$_{00}$, $\delta$$^{18}$ O = -10.8$^{[-1000]}$ /$_{[-1000]}$ ) suggests that the alluvial ground water recharge largely occurs during summer storm events.s.s.

• Bulletin of the Korean Chemical Society
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• v.29 no.4
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• pp.790-794
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• 2008

Nucleophilic addition reaction of benzenethiols (PhSH) to 1-(2-nitrovinyl) benzenes ($\beta$ NS) in the presence of triethylamine (TEA) has been studied in acetonitrile at 25 ${^{\circ}C}$. The rate is first order with respect to [PhSH], [TEA] and [$\beta$ NS]. The reaction is found to proceed with the formation of ion-pair between benzenethiol and TEA. A suitable mechanism with the formation of an adduct between ion-pair and substrate in a slow step followed by its rearrangement to 1,2-addition product in a fast step has been proposed and corresponding rate law derived. From the rate law, the rate constants for the interaction between ion-pair and $\beta$NS have been evaluated. Interestingly, in both para-substituted substrates and benzenethiols the rate increases with the electron-withdrawing power of the substituents. The positive sign of $\rho_x$ in benzenethiols has been explained. The magnitude of cross-interaction constant, $\rho_{xy}$ is small (0.08). The magnitude of the Hammett $\rho_x$ values is higher than that of the Bronsted, $\beta_x$ values for benzenethiols. The kinetic isotope effect, $k_H/k_D$, is found to be greater than unity. A suitable transition state with simultaneous formation of $C_\beta$ -H and $B_\alpha$ -S bonds involving the ion-pair and $\beta$NS in a single concerted step has been proposed to account for these observations.

• Bulletin of the Korean Chemical Society
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• v.24 no.9
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• pp.1293-1302
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• 2003

Rate constants at various temperatures and activation parameters are reported for solvolyses of acyl chlorides (RCOCl), with R = Me, Et, i-Pr, t-Bu, cyclopentylmethyl, benzyl, thiophenylmethyl, 2-phenylethyl, diphenylmethyl, and phenylthiomethyl in 100% ethanol, 100% 2,2,2-trifluoroethanol (TFE), 80% v/v ethanol/ water and 97% w/w TFE/water. Additional rate constants for solvolyses with R = Me, t-Bu, and $PhCH_2$ are reported for TFE/water and TFE/ethanol mixtures, and for solvolyses with R = t-Bu, and PhCH2 are reported for 1,1,1,3,3,3-hexafluoropropan-2-ol/water mixtures, as well as selected kinetic solvent isotope effects (MeOH/MeOD and TFE). Taft plots show that electron withdrawing groups (EWG) decrease reactivity significantly in TFE, but increase reactivity slightly in ethanol. Correlation of solvent effects using the extended Grunwald-Winstein (GW) equation shows an increasing sensitivity to solvent nucleophilicity for EWG. The effect of solvent stoichiometry in assumed third order reactions is evaluated for TFE/ethanol mixtures, which do not fit well in GW plots for R = Me, and t-Bu, and it is proposed that one molecule of TFE may have a specific role as electrophile; in contrast, reactions of substrates containing an EWG can be explained by third order reactions in which one molecule of solvent (ethanol or TFE) acts as a nucleophile, and a molecule of ethanol acts as a general base catalyst. Isokinetic relationships are also investigated.

• Journal of Soil and Groundwater Environment
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• v.26 no.5
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• pp.29-38
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• 2021

This study investigated the mineralogical properties of bentonite and illite and evaluated the Cs sorption at various concentrations (C_w≈1-10⁵ ㎍/L). Bentonite samples, collected from South Korea and USA, majorly consisted of Ca- and Na-montmorillonite, showed large cation exchange capacity (CEC, 91.4 and 47.3 meq/100 g) and specific surface area (SSA, 46.1 and 39.7 m²/g). In contrast, illite sample (USA) had relatively low values for 14.4 meq/100g of CEC and 29.3 m²/g of SSA, respectively. Bentonite and illite had different non-linear sorption for Cs along with C_w. At low C_w<10 ㎍/L, illite showed higher sorption capacity than bentonite despite low CEC because of the existence of specific sorption sites at the weathered mineral edge. However, as C_w increased, bentonite represented high sorption capacity because the cation exchange between Cs and interlayer cations was effective at high C_w conditions. These results implicated that the Cs concentration is important to evaluate the sorption performance of bentonite and illite. Finally, the Cuadros' kinetic model for illitization using various K concentrations (2×10^-5 and 1.7×10^-3 mol/L) and temperature (100-200℃) showed that up to 50% of the montmorillonite in bentonite could be converted to illite, suggesting that the illitization should be considered to evaluate the sorption performance of the bentonite in deep geological disposal repository.

• Journal of the Korean Chemical Society
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• v.38 no.10
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• pp.753-762
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• 1994

Dephosphorylation of diphenyl- or isopropylphenyl-4-nitrophenylphosphinate (DPNPIN or IPNPIN) mediated by $OH^-$ or o-iodosobenzoate ion ($IB^-$) are relatively slow in aqueous solution. The reactions in CTAX micellar solutions are, however, very accelerated, because CTAX micelles can accommodate both reactants in their Stern layer in which they can easily react, while hydrophilic $OH^-$(or $IB^-$) and hydrophobic phosphinates are not mixed in water. Even though the concentrations (> $10^{-3}$ M) of $OH^-$(or $IB^-$) in CTAX solutions are much larger amounts than those ($6{\times}10^{-6}$ M) of phosphinates, the rate constants of the dephosphorylations are largely influenced by change of the concentration of the ions, which means that the reactions are not followed by the pseudo first order kinetics. In comparison to effect of the counter ions of CTAX in the reactions, CTACl is more effective on the dephosphorylation of DPNPIN (or IPNPIN) than CTABr due to easier expelling of $Cl^-$ ion by $OH^-$(or $IB^-$) ion from the micelle, because of easier solvation $Cl^-$ ion by water molecules. The reactivity of IPNPIN with $OH^-$(or $IB^-$) is lower than that of DPNPIN. The reason seems that the 'bulky' isopropyl group of IPNPIN hinders the attack of the nucleophiles. The mechanism of reaction of IPNPIN with IB- ion concluded as 'nucleophilic' instead of 'general basic' by a trapping experiment and a measured kinetic isotope effect.