• Carbon letters
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• 제10권2호
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• pp.114-122
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• 2009

Crushed, depitted peach stones were impregnated activated with 50% $H_3PO_4$ followed by pyrolysis at $500^{\circ}C$. Two activated carbons were produced, one under its own evolved gases during pyrolysis, and the second conducted with air flow throughout the carbonization stage. Physicochemical properties were investigated by several procedures; carbon yield, ash content, elemental chemical analysis, TG/DTG and FTIR spectra. Porosity characteristics were determined by the conventional $N_2$ adsorption at 77 K, and data analyzed to get the major texture parameters of surface area and pore volume. Highly developed activated carbons were obtained, essentially microporous, with slight effect of air on the porous structure. Oxygen was observed to be markedly incorporated in the carbon matrix during the air treatment process. Cation exchange capacity towards Cu (II) and Cd (II) was tested in batch single ion experimental mode, which proved to be slow and a function of carbon dose, time and initial ion concentration. Copper was up taken more favorably than cadmium, under same conditions, and adsorption of both cations was remarkably enhanced as a consequence of the air treatment procedure. Sequestration of the metal ions was explained on basis of the combined effect of the oxygen functional groups and the phosphorous-containing compounds; both contributing to the total surface acidity character.

• Bulletin of the Korean Chemical Society
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• 제29권1호
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• pp.117-121
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• 2008

Pseudo-first-order rate constants (kobsd) have been measured spectrophotometrically for nucleophilic substitution reactions of 5-nitro-8-quinolyl benzoate (5) with alkali metal ethoxides, EtO?M+ (M+ = Li+, Na+ and K+) in anhydrous ethanol (EtOH) at 25.0 0.1 C. The plots of kobsd vs. [EtO?M+] exhibit upward curvatures, while the corresponding plots for the reactions of 5 with EtO?Na+ and EtO?K+ in the presence of complexing agents, 15-crown-5-ether and 18-crown-6-ether are linear with rate retardation. The reactions of 5 with EtO?Na+ and EtO?Li+ result in significant rate enhancements on additions of Na+ClO4, indicating that the M+ ions behave as a catalyst. The dissociated EtO and ion-paired EtOM+ have been proposed to react with 5. The second-order rate constants for the reactions with EtO (kEtO) and EtOM+ (kEtOM+) have been calculated from ion-pairing treatments. The kEtO and kEtOM+ values decrease in the order kEtONa+ > kEtOK+ > kEtOLi+ > kEtO, indicating that ion-paired EtOM+ species are more reactive than the dissociated EtO ion, and Na+ ion exhibits the largest catalytic effect. The M+ ions in this study form stronger complex with the transition state than with the ground state. Coordination of the M+ ions with the O and N atoms in the leaving group of 5 has been suggested to be responsible for the catalytic effect shown by the alkali metal ions in this study.

• Bulletin of the Korean Chemical Society
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• 제35권8호
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• pp.2438-2442
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• 2014

A kinetic study is reported for $S_NAr$ reaction of 1-fluoro-2,4-dinitrobenzene (5a) and 1-chloro-2,4-dinitrobenzene (5b) with alkali-metal ethoxides (EtOM, M = Li, Na, K and 18-crown-6-ether complexed K) in anhydrous ethanol. The second-order rate constant increases in the order $k_{EtOLi}$ < $k_{EtO^-}$ < $k_{EtONa}$ < $k_{EtOK}$ < $k_{EtOK/18C6}$ for the reaction of 5a and $k_{EtOLi}$ < $k_{EtONa}$ < $k_{EtO^-$ < $k_{EtOK}$ < $k_{EtOK/18C6}$ for that of 5b. This indicates that $M^+$ ion behaves as a catalyst or an inhibitor depending on the size of $M^+$ ion and the nature of the leaving group ($F^-$ vs. $Cl^-$). Substrate 5a is more reactive than 5b, although the $F^-$ in 5a is ca. $10pK_a$ units more basic than the $Cl^-$ in 5b, indicating that the reaction proceeds through a Meisenheimer complex in which expulsion of the leaving group occurs after the rate-determining step (RDS). $M^+$ ion would catalyze the reaction by increasing either the nucleofugality of the leaving group through a four-membered cyclic transition state or the electrophilicity of the reaction center through a ${\pi}$-complex. However, the enhanced nucleofugality would be ineffective for the current reaction, since expulsion of the leaving group occurs after the RDS. Thus, it has been concluded that $M^+$ ion catalyzes the reaction by increasing the electrophilicity of the reaction center through a ${\pi}$-complex between $M^+$ ion and the ${\pi}$-electrons in the benzene ring.

• 한국생물정보학회:학술대회논문집
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• 한국생물정보시스템생물학회 2003년도 제2차 연례학술대회 발표논문집
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• pp.5-5
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• 2003

The purple acid phosphatases comprise a family of binuclear metal-containing enzymes. The metal centre contains one ferric ion and one divalent metal ion. Spectroscopic studies of the monomeric, ${\sim}$36 kDa mammalian purple acid phosphatases reveal the presence of an Fe(III)Fe(II) centre in which the metals are weakly antiferromagnetically coupled, whereas the dimeric, ${\sim}$110 000 kDa plant enzymes contain either Fe(III)Zn(II) or Fe(III)Mn(II). The three dimensional structures of the red kidney bean and pig enzymes show very similar arrangements of the metal ligands but some significant differences beyond the immediate vicinity of the metals. In addition to the catalytic domain, the plant enzyme contains a second domain of unknown function. A search of sequence databases was undertaken using a sequence pattern which includes the conserved metal-binding residues in the plant and animal enzymes. The search revealed the presence in plants of a 'mammalian-type' low molecular weight purple acid phosphatase, a high molecular weight form in some fungi, and a homologue in some bacteria. The catalytic mechanism of the enzyme has been investigated with a view to understanding the marked difference in specificity between the Fe-Mn sweet potato enzyme, which exhibits highly efficient catalysis towards both activated and unactivated phosphate esters, and other PAPs, which hydrolyse only activated esters. Comparison of the active site structures of the enzymes reveal some interesting differences between them which may account for the difference. The implications fur understanding the physiological functions of the enzymes will be discussed.

• 한국전기전자재료학회논문지
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• 제26권3호
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• pp.227-231
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• 2013

Electrodeionization is a hybrid separation process of electrodialysis and ion exchange to produce high purity water under electric field. This article provides a fabrication result of hole patterned metal electrode for elecrodeionization system. The hole patterns have been fabricated by nanosphere lithography (NSL). The technique utilizes the self-assembled nanospheres as lens-mask patterns and collimated laser beam source. The hole patterns have a periodic array structure. The images of hole pattern on metal electrode prepared were observed by SEM. We believe that the periodic hole patterned metal electrode structure is a useful device applicable for metal mat electrode in electrodeionization system.

• 한국자기공명학회논문지
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• 제21권4호
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• pp.139-144
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• 2017

Ni(II) containing coenzyme F430 catalyzes the reduction of $CO_2$ in methanogen. Macrocyclic Ni(II) complexes with N,O shiff bases have been received a great attention since metal ions play an important role in the catalysis of reduction. The reducing power of metal complexes are supposed to be dependent on oxidoreduction state of metal ion and structural properties of macrocyclic ring moiety that can enhance electrochemical properties in catalytic process. Six different ${\alpha}$-oximinoketone compounds, precursor of macrocyclic ligands used in $CO_2$ reduction coenzyme F430 model complexes, were synthesized with yields over 90% and characterized by NMR. The molecular geometries of ${\alpha}$-oximinoketone analogues were fully optimized at Beck's-three-parameter hybrid (B3LYP) method in density functional theory (DFT) method with $6-31+G^*$ basis set using the ab initio program. In order to understand molecular planarity and substitutional effects that may enhance reducing power of metal ion are studied by computing the structure-dependent $^{13}C$-NMR chemical shift and comparing with experimental results.

• 대한화학회지
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• 제57권6호
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• pp.712-720
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• 2013

Microwave assisted syntheses of Zn(II), Cd(II) and Hg(II) complexes with 3-aminopyridine (3AP) and nitrite ($NO_2{^-}$) ions have been reported. The metal complexes were characterized by elemental analyses, molar conductance, IR, Far-IR, electronic, NMR ($^1H$, $^{13}C$), thermal and electron impact mass spectral studies. The spectroscopic studies reveal the composition, the nature of nitrite ligand in the complexes, electronic transitions, chemical environments of C and H atoms thermal degradation of the complexes. On the basis of characterization data, distorted tetrahedral geometry is suggested for Zn(II), Cd(II) and Hg(II) complexes. The organic ligand (3AP) and their metal complexes were screened against gram negative pathogenic bacteria and fungi in vitro. The results are compared with our previous report J. Korean Chem. Soc. 2013, 57, 341 on 4-aminopyridine and nitrite ion complexes of the same metal ions.

• Bulletin of the Korean Chemical Society
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• 제34권5호
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• pp.1525-1529
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• 2013

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the nucleophilic substitution reactions of 2-pyridyl thionobenzoate (5b) with alkali-metal ethoxides (EtOM, $M^+=Li^+$, $Na^+$, $K^+$, and 18-crown-6-ether complexed $K^+$) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. $[EtOM]_o$ curve upward regardless of the nature of the $M^+$ ions, while those of $k_{obsd}/[EtO^-]_{eq}$ vs. $[EtO^-]_{eq}$ are linear with a positive intercept. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the ion-paired EtOM is more reactive than the dissociated $EtO^-$, and $M^+$ ions catalyze the reactions in the order $K^+$ < $Na^+$ < $Li^+$ < 18C6-complexed $K^+$. The plot of log $k_{EtOM}$ vs. $1/r_{Stokes}$ results in an excellent linear correlation, indicating that the reactions are catalyzed by the solvated $M^+$ ions but not by the bare $M^+$ ions. The reactions of 5b with EtOM have been concluded to proceed through a six-membered cyclic TS, in which the solvated $M^+$ ions increase the electrophilicity of the reaction center and the nucleofugality of the leaving group.

• 대한화학회지
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• 제57권3호
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• pp.341-351
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• 2013

Zn(II), Cd(II) and Hg(II) complexes with a general composition[$M(L)_2(X)_2$], where L=4-aminopyridine (4AP) and $X=NO_2{^-}$ were prepared under microwave irradiation. The metal complexes were characterized by elemental analyses, molar conductance, IR, Far-IR, electronic, NMR ($^1H$, $^{13}C$), XPS spectral and thermal studies. The spectroscopic studies reveal the composition, different modes of bonding, electronic transition, different chemical environment of C and H atoms and the electronic state of the metal atoms. On the basis of the characterization data, tetrahedral geometry is suggested for all the complexes. The free ligand (4-aminopyridine) and their metal complexes were screened against phytopathogenic fungi and bacteria in vitro and the activities were compared.

• 공업화학
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• 제19권1호
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• pp.1-16
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• 2008

산화티탄은 가장 많이 연구된 반도체 산화물로 환경 정화와 에너지 생산에 응용이 크게 기대되고 있다. 공기와 물 속의 유해 유기물을 제거하고 물분해를 통한 수소 생산은 대표적인 응용 분야이다. 산화티탄의 저렴한 가격, 낮은 독성, 화학적 및 열적 안정성은 잘 알려진 장점이다. 그러나, 산화티탄의 단점은 가시광 영역에서 광촉매 활성이 낮다는 점이다. 이러한 문제점을 해결하기 위하여, 귀금속, 금속, 양이온, 음이온 도핑 방법으로 산화티탄의 표면과 전기적 구조를 변형시켜 가시광 영역에서 광촉매 활성을 높이기 위한 연구가 많이 진행되고 있다. 이번 총설에서는 산화티탄의 가시광 감응을 유도하는 방법에 대한 광범위한 정보를 정리하였다.