제강슬래그를 이용한 다공성 블록 제조

김진수 안동대학교 대학원 2006 국내석사

Synthesis and Characterization of MV2O6-xClx(M=Sr,Ba)

배성희 안동대학교 대학원 1996 국내석사

BaV2O6-xNx, Sr3(Ca3)V2O8-xNx의 합성과 그 구조

한선미 안동대학교 대학원 1995 국내석사

1, 1, 3, 4-tetramethyl-1-sila-cyclopentadiene의 합성

황혜숙 성균관대학교 대학원 화학과 무기화학전공 1983 국내석사

Model complexes of active sites in carbonic anhydrase to facilitate the hydration of carbon dioxide to carbonate

박동국 국민대학교일반대학원 화학과 무기화학전공 2016 국내박사

A rapid global warming and climate change need global efforts to reduce the concentration of atmospheric carbon dioxide. Carbon capture and storage technology (CCS) can help mitigate CO2 emissions from large emitters such as steel plants, cement plants and thermoelectric power plants. However, CO2 is an inert and unreactive molecule that is thermodynamically stable, which means it difficult to capture and separate. The chemical absorption of CO2 using a monoethanolamine (amines) solvent is currently the most widely accepted commercial approach. However, desorption of CO2 for recovery of the solvent requires a large parasitic high supply of energy. Therefore, alternative process for CO2 absorption has been recently proposed to replace the amine solvents with an eco-friendly biocatalyst. The proposed eco-friendly biocatalyst mainly used carbonic anhydrase (CA). CA is a ubiquitous enzyme that catalyzes the conversion CO2 to bicarbonate or vice versa. The use of CA for CO2 capture can potentially overcome the limitations of amine solvents. In spite of unparalleled advantages, it is difficult to apply to commercial CO2 capture processes because of expensive production costs, short life time, temperature and pH sensitive and so on. In order to overcome such potential limitations of CA, this thesis study the small molecules that was designed for mimicking CA. Thus, Chapter 1 reviewed overall introduction related to CA. Chapter 2, 3 and 4 explored with respect to the especially functionalized CA mimicking catalysts, respectively. Chapter 5 summarized the previous chapters. Chapter 1 Introduction to implementation of carbonic anhydrase model complexes in carbon capture process This chapter reviewed the general CCS processes at first. In particular, this chapter focused on a biocatalyst to replace the chemical absorbents (such as amines) in the post-combustion CO2 capture. Also, CA among the biocatalyst and the previously reported CA mimicking catalysts sufficiently reviewed in order to apply to the development of following studies. Chapter 2 Kinetic study of catalytic CO2 hydration by carbonic anhydrase model complexes with various metal cation Each of CA mimicking complexes containing Tris(2-pyridylmethyl)amine (TPA) as a N4 ligand that have Zn2+, Ni2+ and Cu2+ was synthesized and characterized, which measured the effect on CO2 hydration rate according to the type of metal ion, respectively. At first, the pKa that represent intrinsic proton donating ability of water molecule bound each complex identify a tendency to increase in order of [(TPA)Cu(OH2)] < [(TPA)Ni(OH2)] < [(TPA)]Zn(OH2)] (pKa values of [(TPA)Cu(OH2)], [TPA]Ni(OH2)] and [TPA]Zn(OH2)] are 6.0, 7.6 and 8.0, respectively). Probably, this trend results from the difference in electronegativity of metal ions. The catalytic rate constants (kobs) on CO2 hydration reaction using stopped-flow spectrophotometry show a tendency to increase in order of [(TPA)Ni(OH2)] < [(TPA)Cu(OH2)] < [(TPA)Zn(OH2)]. kobs values of [(TPA)Ni(OH2)], [(TPA)Cu(OH2)] and [(TPA)Zn(OH2)] are 526.4 < 542.3 < 645.7, respectively. Although [(TPA)Ni(OH2)] is easy to deprotonate water molecule, substitution reaction (like bicarbonate release step) of bicarbonate by water molecule is not easy. But, [(TPA)Zn(OH2)] being the highest pKa value showed the fastest CO2 hydration rate. Thus, Zn2+ of CA showed that advantage of bicarbonate release step is greater than advantage of deprotonation step of water molecule. Chapter 3 Synthesis and catalytic reactivity of a Zn(II) complex, mimicking second coordination environment of CA enzyme The zinc complex using 6-(((pyridin-2-ylmethyl)(pyridin-3-ylmethyl)amino)methyl) pyridin -2-ol ligand (TPA-OH) mimicking Thr-199 existing in second coordination sphere of the CA was synthesized. The [(TPA-OH)Zn(OH2)] was investigated in comparison with [(TPA)Zn(OH2)]. The pKa value was measured by potentiometric pH titration method in order to determine the acidity of the [(TPA-OH)Zn(OH2)]. The pKa value of [(TPA-OH)Zn(OH2)] and [(TPA)Zn(OH2)] was 6.8 and 8.0, respectively. The CO2 hydration rate of [(TPA-OH)Zn(OH2)] and [(TPA)Zn(OH2)] was measured by stopped flow spectrophotometer and the measured rate constants is 648.4 and 730.6 M-1•s-1, respectively. The [(TPA-OH)Zn(OH2)] exists in intramolecular hydrogen bond network through mimicking Thr-199, so the [(TPA-OH)Zn(OH2)] showed a lower pKa value than the [(TPA)Zn(OH2)]. In addition, CO2 hydration of [(TPA-OH)Zn(OH2)] rate was also found to increase. Chapter 4 Experimental investigations on nucleophilic reaction by diverse carbonic anhydrase model Zn(II) complex with Tris(2-benzimidazolylmethyl-4-hydroxy) amine derivatives This study synthesized CA model complex using Tris(2-benzimidazolymethyl)amine derivative ligand (TBA) similar to environment around zinc ion of CA. [(TBA)Zn(OH2)] using Tris(2-benzimidazolymethyl)amine ligand mimic CA active site. [(HTBA)Zn(OH2)] using Tris(2-benzimidazolylmethyl-4-hydroxy)amine (HTBA) ligand mimic CA active site and Thr-199 existing in second coordination sphere to make hydrogen bond interaction around zinc bound water. [(STBA)Zn(OH2)] using Tris(2-benzimidazolylmethyl-6-sulfonic acid)amine (STBA) ligand and [(NTBA)Zn(OH2)] using Tris(2-benzimidazolylmethyl-6-nitro)amine (NTBA) ligand were synthesized to investigate the effect about the functional change of CA via change of electronic property of ligand. All of complexes measure the kinetic of ester hydrolysis using p-NPA to determine the ability of nucleophilic attack and catalytic efficiency. As the Km value of [(HTBA)Zn(OH2)] is 2.61 mM, the complex showed higher constant than 2.39 mM of [(TBA)Zn(OH2)] in comparison with ester hydrolysis rate. The kcat value of [(HTBA)Zn(OH2)] and [(TBA)Zn(OH2)] showed 13.48 M-1•s-1 and 10.06 M-1•s-1, respectively. The result of Km value is to prevent the formation of enzyme-substrate complex by interference of access of substrate into zinc bound hydroxide because hydroxyl group in [(HTBA)Zn(OH2)] is located at the entrance of the active site. But, kcat / Km value of [(HTBA)Zn(OH2)] have excelled rather than [(TBA)Zn(OH2)]. This result can occur easily bicarbonate release due to destabilization by electrostatic repulsion between hydroxyl group and carboxyl group produced by ester hydrolysis reaction. In comparison with ester hydrolysis kinetic of [(NTBA)Zn(OH2)], [(STBA)Zn(OH2)] and [(TBA)Zn(OH2)], [(NTBA)Zn(OH2)] showed the higher Km value than 2.37 mM of [(STBA)Zn(OH2)] as [(NTBA)Zn(OH2)] is 2.16 mM,. kcat / Km value of [(NTBA)Zn(OH2)] is 17.76 M-1•s-1 and [(STBA)Zn(OH2)] is 15.16 M-1•s-1. [(STBA)Zn(OH2)] and [(NTBA)Zn(OH2)] having electron withdrawing group such as sulfonyl group and nitro group were found that enzyme-substrate complex is more easily formed because Km value of [(TBA)Zn(OH2)] than [(STBA)Zn(OH2)] and [(NTBA)Zn(OH2)] is low, which easily formed enzyme-substrate complex when nitro group being the stronger electron withdrawing than sulfonyl group was introduced. kcat / Km value of [(STBA)Zn(OH2)] and [(NTBA)Zn(OH2)] than [(TBA)Zn(OH2)] showed the more excellent catalytic efficiency. Chapter 5 overall conclusions This chapter summarized previous chapters. And the results can provide qualitative insights for the design of improved small molecule as CO2 capture catalysts. Key word: Carbon dioxide, Carbonic anhydrase, hydration, Zinc complex, CCS, model complex, kinetic

Supramolecular chemistry using cucurbit[8]uril

김수영 포항공과대학교 2004 국내박사

Transition metal mediated cycloaddition reactions and syntheses of tetrakis(tricarbonylorganothiomanganese) compounds

홍순혁 Graduate School, Seoul National University 1999 국내박사

Ferrocenyl silane 유도체의 반응 및 특성 연구

김진식 경기대학교 대학원 1997 국내석사

Ferrocene은 η^5 착화합물로서 π전자가 비편재화되어 있어 안정한 샌드위치 화합물이다. 이 안정한 ferrocene을 활성화시키기 위하여 n-BuLi 또는 t-BuLi를 사용하여 monolithioferrocene과 dilithioferrocene의 반응성이 큰 중간체를 합성하였다. 이 합성된 monolithioferrocene과 dilithioferrocene을 silane 또는 silacyclopentadiene을 반응시켜 ferrocenyl silane과 ferrocenyl silacyclopentadiene유도체를 합성하였다. 합성된 ferrocenyl 화합물은 ^1H, ^(13)C-NMR 등으로 확인하였다. Ferrocene 이 ferrocenyl silane과 ferrocenyl disilane유도체가 되었을 때 비교해보면, ferrocene의 Cp 고리의 ^1H-NMR은 4.15ppm이었으나, ferrocenyl silane에서는 4.06ppm과 4.28ppm으로 splitting이 일어났으며, ferrocene의 ^(13)C-NMR에서 Cp 고리의 탄소가 모두 동등하므로 68.05ppm에서 singlet으로 나타났고, ferrocenyl silane에서는 Cp 고리의 탄소가 71.01ppm, 72.744ppm, 그리고 Cp-Si는 70.59ppm에서 나타났다. Ferrocene is the stable sandwitch compound which the π-electrons are delocalized in the Cp ring. The reactive intermediates, such as monolithioferrocene and dilithioferrocene synthesized by reacting ferrocene with n-BuLi or t-BuLi, can be converted to ferrocenyl silanes and ferrocenyl silacyclopentadiene by adding silanes and silacyclopentadiene, respectively. All of the ferrocenyl silicon compounds were identified by ^1H-NMR, ^(13)C -NMR and IR spectrum. Comparing ferrocene with ferrocenyl silane derivate, the carbon peak of Cp ring of ferrocene was appeared at 4.15ppm, but that of ferrocenyl silane was splitted at 4.06ppm and 4.28ppm in ^1H-NMR spectrum. In the case of ^(13)C-NMR spectrum, the carbon peak of Cp ring of ferrocene was only appeared at 68.05ppm, and that of ferrocenyl silane was shown at the 71.01ppm, 72.41ppm and 70.05ppm respectively.

비대칭 테트라아자애뉼렌의 Ni(II), Cu(II), Pd(II) 착물과 리간드의 합성, 결정구조 및 촉매활성

김동일 慶北大學校 大學院 2004 국내박사

The new asymmetrical monobenzotetraazaannulene complexes, 3-(p-[Y]benzoyl)-2,4,9,11- tetramethyl-1,5,8,12-mono[X]benzotetraazacyclo[14]tetradecinato(2-)nickel(II) (X or Y = CH_(3), H, Cl, NO_(2), OCH_(3)) and 3,10-di(ρ-[Y]benzoyl)-2,4,9,11-tetramethyl-1,5,8,12-monobenzoytetra- azacyclo[14]tetradecinato(2-)nickel(II), -copper(II), -palladium(II) complexes, 3,11-di(ρ-[Y] benzoyl)-2,4,10,12-tetramethyl-1,5,9,13-monobenzoytetraazacyclo[15]tetradecinato(2-)nickel(II), and the free ligands, 5,8-dihydro-2,4,9,11-tetramethyl-1,5,8,12- monobenzotetraazacyclo [14]- tetradecine and 5,9-dihydro-2,4,10,12-tetramethyl-1,5,9,13-monobenzotetraazacyclo[15]tetradecine by demetallation method of 2,4,9,11-tetramethyl-1,5,8,12-monobenzotetraazacyclo[14]-tetradecinato(2-)nickel(II) and 2,4,10,12-tetramethyl-1,5,9,13 -monobenzotetraazacyclo[15]tetradecinato(2-)nickel(II) complex,5,8-dihydro-3,10-di(ρ-[Y]benzoyl)-2,4,9,11 -tetramethyl-1,5,8,12-monobenzotetraazacyclo[14]tetradecine have been synthesized and characterized by element analysis, UV-visible, EI-mass, IR, ^(1)H- and ^(13)C-NMR, and cyclovoltammetry. The ^(1)H-NMR spectra of benzoylated complexes showed that methyl proton peaks moved to upfield and the other proton peaks shifted to downfield owing to shielding and deshielding effect by benzoylation. The ^(1)H-NMR peak of the methine site of monobenzoylated nickel(II) complexes was affected by the substituents on benzene ring of macrocyclic ring stronger than those of benzoyl group. The Hammett plot for amine and ethylene peaks of free ligands had positive linear slopes as OCH_(3) < CH_(3) < H < Cl < NO_(2) on dibenzoyl group. In the ^(13)C-NMR spectra, the C=O peaks of dibenzoylated complexes and free ligands showed range of 198 ∼ 201 ppm. Also, the methine peaks were moved to downfield about 15 ppm by benzoylation. The electronic absorption spectra showed a χ → χ^(*) by the ligand and a ligand to metal charge transfer (LMCT) by the interaction between metal and ligand for the all complexes while monobenzoylated nickel(II) complexes with nitro group on benzene ring of the macrocycle ring had two χ → χ^(*) and a LMCT, and dibenzoylated free ligands had only a χ → χ^(*)(. Also, the χ → χ^(*) and LMCT of complexes with benzoyl group moved to long wave because of the increasing χ-conjugation effect by benzoylation. The LMCT of complexes was moved to the long wave order palladium(II) <nickel(II) < copper(II) due to the different interactions between metal and nitrogen atoms of ligand. Also, Hammett plots for complexes and free ligands by benzoylation were showed a linear positive or negative slopes as substituents of benzoyl group. Electrochemical characteristics of compounds were carried out by cyclic voltammetry in DMSO solutions. The cyclic voltammograms of the complexes were observed two one-electron irreversible oxidation processes by ligand based and one reversible reduction potential by metal based in the range +1.1 ∼ -3.0 V. The Hammett plots showed negative or positive slopes as substituents (OCH_(3), CH_(3) H, Cl and NO_(2)) for the 1st and 2nd oxidation potentials by ligand based and reduction potentials by metal based. The 14- or 15-membered copper(II) and palladium(II) complexes were electropolymerized by cycling from +1.0 ∼ -2.0 V in acetonitrile solutions giving thin films on the glassy carbon electrode surface similar to nickel(II) complexes. The surface modified electrodes showed strong electrocatalytic activities for substrates such as dioxygen, hydrazine and catechol with substituents in phosphate buffer solution (pH = 7.0, 25 ℃). For the reduction for dioxygen, the catalytic activity of 14-member copper(II) complex was higher than the others complexes in the range of 0 ∼ -1.0 V. While the oxidation for hydrazine showed that 15-membered palladium(II) complex had the most catalytic activity in the range of +1.0 ∼ 0 V. The oxidation for catechol were showed similar to catalytic activity both copper and palladium complexes in the range of +1.0 ∼ -0.6 V. Hydrocarbon oxidations catalyzed by monobenzoylated tetraaza[14]annulene nickel(II) complexes have been investigated by substituents on both complexes and styrenes. The total conversion(%) were increased as CH_(3) < H < Cl < NO_(2) for the substituted complexes but decreased following OCH_(3) > CH_(3) > H > F > Cl for the substituted styrene. The 15-membered complexes were higher total conversion yields than those of 14-membered complexes. The metal ion effect on the catalytic activity of complex was increased in the order of Pd(II) < Ni(II) < Cu(II). The conversion(%) were affected by electron density of both catalysts and derived styrenes. The structures of the complexes and ligands were solved using single crystal X-ray diffraction methods. The crystal structure data showed that the bond lengths between a metal (nickel, copper, palladium) and nitrogen of ethylenediamine group for the 14-membered complexes were shorter than that between a metal and nitrogen of phenylenediamine, owing to the difference of basicities for ethylenediamine (pK_(b1) = 4.11, pK_(b2) = 6.92) and phenylenediamine (pK_(b1) = 9.39, pK_(b2) = 12.19). While the bond lengths of a metal and nitrogen of phenylenediamine for the 15-membered complexes were shorter than those of a metal and nitrogen of propylenediamine owing to the ring strain of propylenediamine group. The protons of free ligands were bonded to nitrogens of both ethylenediamine and propylenediamine due to bigger than basicity of phenylenediamine. The bond lengths of a metal and nitrogen both 14- and 15-membered tetraazaannulene complexes increased in the order Ni(II) < Cu(II) < Pd(II) owing to metal ion radius effect. The coordination environment around the central metal(II) atom for the 14- and 15-membered complex showed a square planar and a square pyramid geometry, respectively. The dibenzoyl group of tetraaza[14 or 15]annulenenickel(II) complexes were showed almost cis-perpendicular for the plane of four nitrogen atoms and a nickel atom but trans-perpendicular for the dibenzoylated tetraaza[14]annulenepalladium(II) complex. While the benzoyl group of free ligand was cis distortion to the same direction with benzen of macrocycle ring for the plane of four nitrogen atoms. These results could explain about the shielding and deshielding effect for the NMR spectrum.

Re(=NC6H5)(PPh₃)(PR₃) Cl₃(PR₃=PMe₃,P(OMe)₃)의 합성과 구조

김영웅 成均館大學校 1994 국내석사