• Bulletin of the Korean Chemical Society
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• 제34권7호
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• pp.2099-2104
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• 2013

We present here an efficient and simple method for preparation of highly active Pd heterogeneous catalyst (CNT-Pd), specifically by reaction of dichlorobis(triphenylphosphine)palladium ($Pd(PPh_3)_2Cl_2$) with thiolated carbon nanotubes (CNTs). The as-prepared CNT-Pd catalysts demonstrated an excellent catalytic activity for the carbon-carbon (C-C) cross-coupling reactions (i.e. Suzuki, Stille, and decarboxylative coupling reactions) under mild conditions. The CNT-Pd catalyst could easily be removed from the reaction mixture; additionally, in the decarboxylative coupling of iodobenzene and phenylpropiolic acid, it showed a six-times recyclability, with no loss of activity. Moreover, once its activity had decreased by repeated recycling, it could easily be reactivated by the addition of phosphine ligands. The remarkable recyclability of the decarboxylative coupling reaction is attributable to the high degree of dispersion of Pd catalysts in CNTs. Aggregation of the Pd catalysts is inhibited by their strong adhesion to the thiolated CNTs during the chemical reactions, thereby permitting their recycling.

• Bulletin of the Korean Chemical Society
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• 제31권2호
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• pp.303-308
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• 2010

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl benzoate (5a), 4-nitrophenyl 4-methoxybenzoate (5b), and 4-nitrophenyl 4-hydroxybenzoate (5c) with alkali metal ethoxides, $EtO^-M^+$ ($M^+=Li^+$, $Na^+$ and $K^+$) in anhydrous ethanol (EtOH) at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [$EtO^-M^+$] exhibit upward curvatures in all cases, indicating that $M^+$ ions catalyze the reactions and ionpaired $EtO^-M^+$ species are more reactive than dissociated $EtO^-$. Second-order rate constants for reactions with dissociated $EtO^-$ and ion-paired $EtO^-M^+$ (i.e., $k_{EtO^-}$ and $k_{EtO^-M^+}$, respectively) have been calculated from ion-pair treatment for the reactions of 5a and 5b. However, such ion-pair treatment has failed to determine $k_{EtO^-}$ and $k_{EtO^-M^+}$ values for the reactions of 5c. It has been concluded that reactions of 5a and 5b are catalyzed by one metal ion, which increases electrophilicity of the reaction center through coordination on the carbonyl oxygen. In contrast, reactions of 5c have been suggested to involve two metal ions, i.e., the one coordinated on the carbonyl oxygen increases the electrophilicity of the reaction center while the other one associated on the phenoxy oxygen decreases the charge repulsion between the anionic reagents (i.e., $EtO^-$ and deprotonated 5c). It has been found that the rate equation derived from the mechanism involving two metal ions fits nicely to the kinetic results obtained for the reactions of 5c.

• Journal of Microbiology and Biotechnology
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• 제18권5호
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• pp.885-888
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• 2008

In this work, we demonstrate that glycolytic intermediates can serve as efficient energy sources to regenerate ATP during continuous-exchange cell-free (CECF) protein synthesis reactions. Through the use of an optimal energy source, approximately 10 mg/ml of protein was generated from a CECF protein synthesis reaction at greatly reduced reagent costs. Compared with the conventional reactions utilizing phosphoenol pyruvate as an energy source, the described method yields 10-fold higher productivity per unit reagent cost, making the techniques of CECF protein synthesis a more realistic alternative for rapid protein production.

• Bulletin of the Korean Chemical Society
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• 제35권7호
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• pp.2130-2134
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• 2014

A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl isonicotinate (7) with a series of cyclic secondary amines in MeCN. The plots of $k_{obsd}$ vs. [amine] curve upward for the reactions with weakly basic amines (e.g., morpholine, 1-(2-hydroxyethyl)piperazine, and piperazine) but are linear for those with strongly basic amines (e.g., piperidine and 3-methylpiperidine). The curved plots for the reactions with the weakly basic amines are typical for reactions reported previously to proceed through uncatalyzed and catalyzed routes with two intermediates (e.g., a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$). In contrast, the linear plots for the reactions with the strongly basic amines indicate that the catalytic route (i.e., the deprotonation process to yield $T^-$ from $T^{\pm}$ by a second amine molecule) is absent. The Br${\o}$nsted-type plots for $Kk_2$ and $Kk_3$ (i.e., the rate constants for the uncatalyzed and catalyzed routes, respectively) exhibit excellent linear correlations with ${\beta}_{nuc}$ = 0.99 and 0.69, respectively. The effect of amine basicity on the reaction mechanism is discussed in detail.

• Bulletin of the Korean Chemical Society
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• 제32권3호
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• pp.964-972
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• 2011

This work investigated the difference between $Fe^{2+}$ autoxidation-induced and Fenton-type cleavage of pBR322 plasmid DNA. $^{\cdot}OH$ generation reactions in the absence and presence of $H_2O_2$ under various conditions were also investigated. Although both the $Fe^{2+}$ autoxidation and Fenton-type reactions showed DNA cleavage and $^{\cdot}OH$ generation, there were significant differences in their efficiencies and reaction rates. The rate and efficiency of the cleavage reaction were higher in the absence of 1.0 mM of $H_2O_2$ than in its presence in 20 mM phosphate buffer. In contrast, the $^{\cdot}OH$ generation reaction was more prominent in the presence of $H_2O_2$ and showed a pH-independent, fast initial reaction rate, but the rate was decreased in the absence of $H_2O_2$ at across the entire tested pH range. Studies using radical scavengers on DNA cleavage and $^{\cdot}OH$ generation reactions in both the absence and presence of $H_2O_2$ confirmed that both reactions spontaneously involved the active oxygen species $^{\cdot}OH$, ${O_2}^{\cdot-}$, $^1O_2$ and $H_2O_2$, indicating that a similar process may participate in both reactions. Based on the above observations, a new mechanism for the $Fe^{2+}$ autoxidation-induced DNA cleavage reaction is proposed.

• Bulletin of the Korean Chemical Society
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• 제25권10호
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• pp.1538-1544
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• 2004

Fragmentations and proton transfer reactions of mono-, di-, and triethanolamines were studied using FTMS. It was found that the most abundant fragment ion was $[M-CH_2OH]^+$. The $[M-CH_2OH-H_2O]^+$ was observed in the mass spectra of diethanolamine and triethanolamine. By increasing the ion trapping time in the ICR cell, the $[M+H]^+$ and $[M+H-H_2O]^+$ ions were notably increased for all the samples while the $[M+H-2H_2O]^+$ was observed in the mass spectra of diethanolamine and triethanolamine. The proton transfer reactions between the fragment ions and neutral molecules occurred predominantly by increasing the ion trapping time. The rate constants for the proton transfer reactions were calculated from experimental results. The proton transfer reaction of $CHO^+$ was the fastest one, which is consistent with the heats of reaction. The rate constants for proton transfer reactions of triethanolamine were much slower than those of ethanolamine and diethanolamine because of the steric hindered structure of triethanolamine. The plausible structures of observed ions and heats of reaction for proton transfer were calculated with AM1 semiempirical method.

• Bulletin of the Korean Chemical Society
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• 제9권1호
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• pp.55-59
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• 1988

The gaseous carbon dioxide has been irradiated with Co-60 gamma-radiation in the presence and absence of various alcohols, and the radiolysis products analyzed by gas chromatography. Experimental results indicate that no detectable amount of carbon monoxide is formed when pure carbon dioxide is irradiated. By adding small quantities of alcohols to carbon dioxide, however, considerable amount of carbon monoxide, ketones, alcohols and other organic products have been detected. By adding 0.1% of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-l-propanol, 2-butanol, and 2-methyl-2-propanol, G(CO) values obtained are 4.4, 4.5, 5.2, 4.4, 5.2, 5.0, 4.7 and 4.1, respectively. These high yields of carbon monoxide suggest that the oxidation reactions of carbon monoxide may be suppressed by scavenging oxygen atom with the alcohols. The main radiolytic decomposition reactions of the alcohols present in small quantity in carbon dioxide may be supposed to be the reactions with the oxygen atom produced by the radiolysis of carbon dioxide. The decomposition reactions seems to follow pseudo-first order kinetics with respect to the alcohols. The decomposition rate measured with 2-propanol is the fastest and that with 2-methyl-2-propanol the slowest. The mechanisms of the radiolytic decomposition reactions of the alcohols present in carbon dioxide are discussed on the basis of the experimental results of the present study.

• Bulletin of the Korean Chemical Society
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• 제18권8호
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• pp.868-873
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• 1997

Nucleophilic substitution reactions of 1-phenylethyl chlorides (1-PEC; YC6H4CH(CH3)Cl) with phenoxides (XC6H4O-) and thiophenoxides (XC6H4S-) are investigated theoretically using the PM3 method. The Bronsted α and β values are greater for the phenoxides indicating a more advanced reaction in the transition state (TS) than for the thiophenoxides. This is supported by a greater magnitude of ρX (- 6.4 ∼ - 7.4) and ρXY (- 0.76) for the phenoxides than for the thiophenoxides (ρX = - 3.6 ∼ - 4.4 and ρXY = - 0.60). The percentage bond order changes, %Δn≠, suggest that the extents of bond making and breaking are similar for the phenoxides and hence the TS is symmetrical, but bond making is somewhat greater than bond cleavage for the thiophenoxides indicating an unsymmetrical TS. The reactions in the gas phase for both nucleophile series proceed by a SN2 mechanism with a tight TS and negative charge development on the reaction center carbon, Cα. The reactions in water investigated with model systems of benzyl and 1-phenylethyl chlorides using the Cramer-Truhlar solvation model (PM3-SM3) indicate that the reactions of 1-PEC are far more complex due to enhanced stabilization of the carbocation by the methyl substitution for a benzylic hydrogen.

• Bulletin of the Korean Chemical Society
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• 제22권7호
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• pp.669-672
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• 2001

Pseudo-first-order rate constants have been measured spectrophotometrically for the title reactions. The plot of kobs vs the concentration of alkali metal ethoxides is linear for the reactions performed in the presence of complexing age nt, 18-crown-6 ether, but curved upwardly for the corresponding reactions performed in the absence of the complexing agent, indicating that the alkali metal ions studied in this study behave as a catalyst. The catalytic effect was found to increase in the order Li+ << K+ ${\leq}$ Na+. Second-order rate constants were determined for the reactions with dissociated free ethoxide (kEtO-) and with ion paired alkali metal ethoxides (kEtO-M+ ) from ion pairing treatments. The magnitude of catalytic effect (kEtO-M+/kEtO-) was found to be 2.3, 9.5 and 8.7 for the reaction of 8-(5-nitroquinolyl) 2-furoate, while 1.4, 3.6 and 4.2 for that of 4-nitrophenyl 2-furoate, indicating that the catalytic effect is larger in the reaction of the former substrate than in that of the latter one. The larger catalytic effect was attributed to two possible complexing sites with alkali metal ions in the former substrate.

• Bulletin of the Korean Chemical Society
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• 제22권7호
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• pp.673-677
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• 2001

Pseudo-first-order rate constants have been measured spectrophotometrically for the reactions of 8-(5-nitroquinolyl) 3-furoate with alkali metal ethoxides in anhydrous ethanol. The plot of kobs vs the concentration of alkali metal ethox ides is linear for the reactions performed in the presence of a complexing agent, 18-crown-6 ether, but exhibits upward curvatures for the corresponding reactions performed in the absence of the complexing agent, indicating that the alkali metal ions in this study behave as catalysts. Second-order rate constants were determined for the reactions with dissociated free ethoxide (kEtO-) and with ion paired alkali metal ethoxides (kEtO-M + ) from ion pairing treatments. The magnitude of catalytic effect (kEtO-M + /kEtO-) was found to be 1.7, 3.4 and 2.5 for the reaction of 8-(5-nitroquinolyl) 3-furoate, while 1.4, 3.6 and 4.2 for that of 4-nitrophenyl 2-furoate, 1.8, 3.7 and 2.4 for that of 8-(5-nitroquinolyl) benzoate, and 2.0, 9.8 and 9.3 for that of 8-(5-nitroquinolyl) 2-furoate with EtO- Li+ , EtO- Na+ and EtO- K+ , respectively. A 5-membered chelation at the leaving group is suggested to be responsible for the catalytic effect shown by alkali metal ions.