세자리 Schiff Base의 Ni(II) 착물의 분석

채희남,최용국,Chae, Hee-Nam,Choi, Yong-Kook 한국분석과학회 1998 분석과학 Vol.11 No.5

Tridentate Schiff base ligands, $SIPH_2$, $SIPCH_2$, $HNIPH_2$, and $HNIPCH_2$ were prepared by the reactions of salicylaldehyde and 2-hydroxy-1-naphthaldehyde with 2-aminophenol and 2-amino-p-cresol. Ni(II) complexes of those ligands were synthesized. The structures and properties of ligands and their complexes were studied by elemental analysis, $^1H$-NMR, IR, UV-visible spectra, and thermogravimetric analysis. The mole ratio of Schiff base to the metal of complexes was found to be 1:1. Ni(II) complexes were contemplated to be hexa-coordinated octahedral configuration containing three water molecules. The redox process of ligands and complexes in DMSO solution containing 0.1 M TBAP as supporting electrolyte was investigated by cyclic voltammetry and differential pulse voltammetry with glassy carbon electrode. The redox process of the tridentate Schiff base ligands was totally irreversible. The redox process of Ni(II) complexes were quasi-reversible and diffusion-controlled as one electron by one step process Ni(II)/Ni(I). The reduction potentials of the Ni(II) complexes shifted in the positive direction in the order [$Ni(II)(HNIP)(H_2O)_3$]>[$Ni(II)(SIP)(H_2O)_3$]>[$Ni(II)(SIPC)(H_2O)_3$]>[$Ni(II)(HNIPC)(H_2O)_3$] and their dependence on ligands were not so high. Consequently the [$Ni(II)(HNIPC)(H_2O)_3$] complex among the synthesized Ni(II) complexes was found to be most stable in the DMSO solution. Salicylaldehyde와 2-hydroxy-1-naphthaldehyde를 2-aminophenol과 2-amino-p-cresol에 반응시켜 세자리 Schiff base 리간드($SIPH_2$, $SIPCH_2$, $HNIPH_2$, $HNIPCH_2$)들을 합성하였다. 이들 리간드를 Ni(II) 이온과 반응시켜 세자리 Schiff base Ni(II) 착물들을 합성 하였다. 이들 리간드와 그 착물들의 가상적인 구조와 특성을 원소분석, $^1H$-NMR, IR, UV-vis 분광법과 열 무게 분석법으로 알아보았다. Schiff base 리간드와 Ni(II) 착물의 몰비는 1:1로 결합하며, Ni(II)착물들은 3분자의 수화물이 배위된 6배위의 8면체 구조임을 알았다. 지지 전해질로서 0.1 M TBAP를 포함한 DMSO 용액에서 순환 전압전류법과 미분 펄스 전압전류법으로 세자리 Schiff base 리간드와 이들의 Ni(II) 착물들의 전기 화학적인 산화 환원 과정을 알아보았다. 세자리 Schiff base 리간드들의 전기 화학적 환원은 확산 지배적이고 비가역적으로 진행되었다. Ni(II) 착물의 전기화학적 환원과정은 1단계 1전자 반응으로 확산 지배적이고 준가역적으로 진행되었다. Ni(II) 착물들의 환원전위는 [$Ni(II)(HNIP)(H_2O)_3$]>[$Ni(II)(SIP)(H_2O)_3$]>[$Ni(II)(SIPC)(H_2O)_3$]>[$Ni(II)(HNIPC)(H_2O)_3$]순으로 양전위 방향으로 이동하였으며, 리간드의 영향은 크게 받지 않았다. 이들 결과로 부터 본 연구에서 합성한 Ni(II)착물은 [$Ni(II)(HNIPC)(H_2O)_3$] 착물이 DMSO용매에서 가장 안정함을 알 수 있다.

HPLC용 Schiff Base 컬럼과 Glow Discharge 검출기의 개발에 관한 기초연구 I

강미라,김은수,신정숙,박현국,양정성,이상천,Kang, Mi-Ra,Kim, Eun-Soo,Shin, Jung-Sook,Park, Hyun-Kook,Yang, Jung-Sung,Lee, Sang C. 한국분석과학회 1995 분석과학 Vol.8 No.3

본 연구는 중금속 이온의 신속한 현장분석을 위하여 HPLC용 Schiff Base 컬럼과 Glow Discharge 검출기의 개발에 관한 연구결과를 정리한 것이다. 현재 사용한 컬럼의 소재로는 hydrazide Schiff base 리간드인 N, N'-oxalybis(salicylaldehydrazone) (OBSH), N, N'-malonylbis (salicylaldehydrazone) (MBSH), 그리고 N, N'-succinylbis(salicylaldehydrazone) (SBSH)들과 HPLC 컬럼용 고분자 수지인 poly(styrene divinylbenzene)를 혼합하여 그 특성을 관찰하고 앞으로의 HPLC용 컬럼으로서의 응용성을 살펴보았다. 다음으로 중금속 이온들의 효과적인 검출을 수행할 수 있는 검출기의 필요성에 따라 현재 본 연구실에서 새로 개발한 Hollow Cathode Glow Discharge-Atomic Emission Spectrometry(HCGD-AES)를 사용하여 금속이온의 검출을 수행하였다. 이때 리간드-수지 혼합 컬럼을 통하여 용리된 용리액 중의 구리, 루비듐, 납, 수은 등의 금속이온 검출을 시도하였고, 실험결과를 토대로 Schiff Base를 사용한 컬럼이 금속이온에 따라 선택성을 보여 주고 있음을 살필 수 있었다. 또한 금속이온의 검출을 위한 HPLC용 검출기의 개발을 글로우 방전을 이용하여 추진하고 있으며 이에 대한 기초실험 결과를 정리하였다. Schiff base ligand columns and glow discharge detector have been developed for the trace analysis of metal ions desolved in water. Various types of hydrazide Schiff base ligands have been used and, additionally, they were examined as a filling material of a HPLC column. The hydrazide Schiff base ligands used were N, N'-oxalybis(salicylaldehydrazone) (OBSH), N, N'-malonylbis(salicylaldehydrazone) (MBSH), and N, N'-succinylbis(salicylaldehydrazone) (SBSH). A mixture of Schiff base ligand and poly(styrene divinylbenzene) was examined and it showed a smooth flow of solution. The OBSH-polymer column demonstrated different effluent factors for different metal ions. Metal ions in eluates were detected by Hollow Cathode Glow Discharge-Atomic Emission Spectrometry(HCGD-AES). HCGD-AES showed good sensitivity and selectivity. This is only the preliminary results of new OBSH-polymer column and glow discharge detector.

$NOTDH_2$ Schiff Base를 가진 전이금속(II) 착물의 합성과 구조분석

오정근,최용국,Oh, Jeong-Geun,Choi, Yong-Kook 한국분석과학회 1999 분석과학 Vol.12 No.6

2-hydroxy-1-naphthaldehyde와 aromatic amine으로부터 $N_2O_2$형의 네자리 schiff base 리간드인 Bis(2-hydroxy-1-naphtyllidine)-o-toluene-diimine;[$NOTDH_2$]를 합성하였다. 이 리간드와 cobalt(II), nickel(II) 및 copper(II) Acetate들과 반응시켜 schiff base 전이금속(II) 착물들을 합성하였으며 원소분석, IR, UV-vis, NMR 분광법 및 TGA로부터 착물들의 구조를 확인하였다. 중심 금속인 전이금속(II) 이온은 $N_2O_2$형의 주개원자를 갖는 네자리 리간드의 페놀에 있는 산소와는 이온결합을, aromatic amine의 질소와는 배위결합을 형성하여 비이온성의 착물을 형성하였다. $N_2O_2$형의 네자리 Schiff Base 전이금속(II) 착물에서 리간드와 금속이온들은 전이금속(II) 이온과 1:1로 결합하며 Cu(II)착물들은 4배위 구조임을 알았으며, Co(II) Ni(II)착물들은 2분자의 수화물이 배위된 6배위 착물 구조임을 알았다. Co(II), Ni(II), and Cu(II) complexes with tetradentate schiff base-$NOTDH_2$, were synthesized. The structures of these complexes were characterized by elemental analysis, IR, UV-visible, NMR spectra, and thermogravimetric analysis. The mole ratio of schiff base($NOTDH_2$) to the metal(II) at complexes was found to be 1:1. Cu(II) complexes were four-coordinated configuration, while Co(II) and Ni(II) complexes were hexacoordinated configuration containing two water molecules and all complexes were non-ionic compounds.

Inhibition of corrosion of aluminum in alkaline solution by a novel azo-schiff base: Experiment and theory

Arjomandi, Jalal,Moghanni-Bavil-Olyaei, Hamed,Parvin, Mohammad Hadi,Lee, Jin Yong,Chul Ko, Kyoung,Joshaghani, Mohammad,Hamidian, Kourosh Elsevier 2018 JOURNAL OF ALLOYS AND COMPOUNDS Vol.746 No.-

<P><B>Abstract</B></P> <P>The inhibition effect of a Schiff base with several functional groups on the corrosion of aluminum in alkaline solution is studied by experimental techniques and density function theory (DFT) calculations. The Schiff base are characterized by <SUP>1</SUP>HNMR, <SUP>13</SUP>CNMR, FT-IR, and CHN elemental analysis. In addition, different electrochemical and corrosion techniques such as weight loss, tafel polarization, electrochemical impedance spectroscopy (EIS) and optical microscopy images are performed to analyze the inhibiting performances. In the Tafel measurements the cathodic Tafel slopes values incurred small changes with increasing the inhibitor concentration, which revealed that the inhibitor was adsorbed on the aluminum surface. The inhibition efficiencies are calculated from weight loss measurement and electrochemical tests. The adsorption of the inhibitor onto the aluminum surface follows the Langmuir adsorption isotherm with the free adsorption energy of −8.66 kJ mol<SUP>−1</SUP>. The calculated adsorption energies and the amount of charge transfer obtained by DFT calculation revealed that corrosion inhibition effectively occurs with chemisorption, where new NAl bonds are formed between of N atoms in azo (–NN–) group and Al surface atoms, which is confirmed from <I>ab initio</I> molecular dynamics (AIMD) simulation.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Novel Schiff base were synthesized as inhibitor for Al corrosion in alkaline. </LI> <LI> The Schiff base were characterized by <SUP>1</SUP>HNMR, <SUP>13</SUP>CNMR, FT-IR, and CHN. </LI> <LI> The inhibition effect of Schiff base were studied by experimental and DFT. </LI> <LI> The adsorption of inhibitor on Al surface follows Langmuir adsorption isotherm. </LI> <LI> The corrosion inhibitions is chemisorptions which confirmed by AIMD simulation. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Experimental and theoretical studies of the schiff base (<i>Z</i>)-1-(thiophen-2-yl- methyleneamino) propane-2-ol

Berhanu, Asnake Lealem,Sharma, Neha,Mohiuddin, Irshad,Malik, Ashok Kumar,Aulakh, Jatinder Singh,Lee, Jechan,Kim, Ki-Hyun Elsevier 2020 Journal of molecular structure Vol.1200 No.-

<P><B>Abstract</B></P> <P>In this study, a quantum chemical model was developed to better account for the properties of a Schiff base, (<I>Z</I>)-1-(thiophen-2-yl-methyleneamino) propane-2-ol, which is derived from thiophene-2-carboxy aldehyde and 1-amino-2-propanol. To predict its molecular structure, the assignment of the vibrational wavelength (for FT-IR) and chemical shift (for <SUP>1</SUP>HNMR) of (<I>Z</I>)-1-(thiophen-2-yl-methyleneamino) propane-2-ol was performed experimentally and theoretically. All of the theoretical calculations were performed using the Gaussian 09 program package. The theoretically and experimentally obtained results were in good agreement (R<SUP>2</SUP> ≥ 0.99). The energies of the highest occupied and lowest unoccupied molecular orbitals were estimated using B3LYP (Becke three-parameter hybrid functional combined with Lee–Yang–Parr correlation functional)/6-311++G (d, p). Optimization of the structure of (<I>Z</I>)-1-(thiophen-2-yl-methyleneamino) propane-2-ol provided information concerning the stable form of the geometry of the molecule, stoichiometry of the complexes, and thermodynamic parameters (e.g., energy and entropy). The results indicate that the Schiff base formed stable complexes with Ni<SUP>2+</SUP>. The energy of the complex was much lower than that of the free Schiff base. The charge distribution values of each atom in the Schiff base were in agreement with the Pauling scale for electronegativity and vibrational wavelength.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Experimental and Theoretical study of (Z)-1-(thiophen-2-yl-methyleneamino) propane-2-ol was investigated. </LI> <LI> The vibrational FTIR wavelength and chemical shift (for <SUP>1</SUP>HNMR) were studied with DFT studies. </LI> <LI> (Z)-1-(thiophen-2-yl-methyleneamino) propane-2-ol formed a more stable complex with Ni<SUP>2+</SUP>. </LI> <LI> Bond lengths and bond angles were calculated to characterize its strength. </LI> <LI> HOMO -LUMO energy gap of the Schiff base was calculated. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Synthesis and Characterization of Schiff Base Metal Complexes and Reactivity Studies with Malemide Epoxy Resin

Lakshmi, B.,Shivananda, K.N.,Prakash, Gouda Avaji,Isloor, Arun M.,Mahendra, K.N. Korean Chemical Society 2012 Bulletin of the Korean Chemical Society Vol.33 No.2

A novel malemide epoxy containing Co(II), Ni(II) and Cu(II) ions have been synthesized by curing malemide epoxy resin (MIEB-13) and Co(II), Ni(II) and Cu(II) complexes of macrocyclic bis-hydrazone Schiff base. The Schiff base was synthesized by reacting 1,4-dicarbnyl phenyl dihydrazide with 2,6-diformyl-4-methyl phenol. The Schiff base and its Co(II), Ni(II) and Cu(II) complexes have been characterized by elemental analyses, spectral (IR, $^1H$ NMR, UV-vis., FAB mass, ESR), thermal and magnetic data. The curing reaction of maleimide epoxy compound with metal complexes was studied as curing agents. The stability of cured samples was studied by thermo-gravimetric analyses and which have excellent chemical (acid/alkali/solvent) and water absorption resistance. Further, the scanning electron microscopy (SEM) and definitional scanning colorimetric (DSC) techniques were confirmed the phase homogeneity of the cured systems.

Synthesis and Characterization of Schiff Base Metal Complexes and Reactivity Studies with Malemide Epoxy Resin

B. Lakshmi,K. N. Shivananda,Gouda Avaji Prakash,Arun M Isloor,K. N. Mahendra 대한화학회 2012 Bulletin of the Korean Chemical Society Vol.33 No.2

A novel malemide epoxy containing Co(II), Ni(II) and Cu(II) ions have been synthesized by curing malemide epoxy resin (MIEB-13) and Co(II), Ni(II) and Cu(II) complexes of macrocyclic bis-hydrazone Schiff base. The Schiff base was synthesized by reacting 1,4-dicarbnyl phenyl dihydrazide with 2,6-diformyl-4-methyl phenol. The Schiff base and its Co(II), Ni(II) and Cu(II) complexes have been characterized by elemental analyses,spectral (IR, 1H NMR, UV-vis., FAB mass, ESR), thermal and magnetic data. The curing reaction of maleimide epoxy compound with metal complexes was studied as curing agents. The stability of cured samples was studied by thermo-gravimetric analyses and which have excellent chemical (acid/alkali/solvent) and water absorption resistance. Further, the scanning electron microscopy (SEM) and definitional scanning colorimetric (DSC) techniques were confirmed the phase homogeneity of the cured systems.

A Novel Linking Schiff-Base Type Ligand (L: py-CH=N-C₆H₄-N=CH-py) and Its Zinc Coordination Polymers:Preparation of L, 2-Pyridin-3-yl-1H-benzoimidazol, trans-[Zn(H₂O)₄L₂].(NO₃)₂

Kim, Han-Na,Lee, Hee-K.,Lee, Soon-W. Korean Chemical Society 2005 Bulletin of the Korean Chemical Society Vol.26 No.6

A long, bis(monodentate), linking Schiff-base ligand L (py-CH=N-$C_6H_4$-N=CH-py) was prepared from 1,4-phenylenediamine and 3-pyridinecarboxaldehyde by the Schiff-base condensation. Ligand L has two terminal pyridyl groups capable of coordinating to metals through their nitrogen atoms. In contrast, the same reaction between 1,2-phenylenediamine and 3-pyridinecarboxaldehyde produced a mixture of imidazol isomers (2-pyridin-3-yl-1H-benzoimidazole), which are connected to one another by the N-H…N hydrogen bonding to form a tetramer. From Zn($NO_3)_2{\cdot}6H_2O$ and ligand L under various conditions, one discrete molecule, trans- [Zn($H_2O)_4L_2]{\cdot}(NO_3)_2{\cdot}(MeOH)_2$, and two 1-D zinc polymers, [Zn$(NO_3)(H_2O)_2(L)]{\cdot}(NO_3){\cdot}(H_2O)_2$ and [Zn(L) (OBC)($H_2O$)], were prepared. In ligand L, the N$\ldots$N separation between the terminal pyridyl groups is 13.994 $\AA$, with their nitrogen atoms at the meta positions (3,3’) in a trans manner. The corresponding N$\ldots$N separations in its compounds range from 13.853 to 14.754 $\AA$.

Proteomic and Morphologic Evidence for Taurine-5-Bromosalicylaldehyde Schiff Base as an Efficient Anti-Mycobacterial Drug

( Wenyong Ding ),( Houli Zhang ),( Yuefei Xu ),( Li Ma ),( Wenli Zhang ) 한국미생물생명공학회(구 한국산업미생물학회) 2019 Journal of microbiology and biotechnology Vol.29 No.8

Mycobacterium tuberculosis, a causative pathogen of tuberculosis (TB), still threatens human health worldwide. To find a novel drug to eradicate this pathogen, we tested taurine-5- bromosalicylaldehyde Schiff base (TBSSB) as an innovative anti-mycobacterial drug using Mycobacterium smegmatis as a surrogate model for M. tuberculosis. We investigated the antimicrobial activity of TBSSB against M. smegmatis by plotting growth curves, examined the effect of TBSSB on biofilm formation, observed morphological changes by scanning electron microscopy and transmission electron microscopy, and detected differentially expressed proteins using two-dimensional gel electrophoresis coupled with mass spectrometry. TBSSB inhibited mycobacterial growth and biofilm formation, altered cell ultrastructure and intracellular content, and inhibited cell division. Furthermore, M. smegmatis adapted itself to TBSSB inhibition by regulating the metabolic pathways and enzymatic activities of the identified proteins. NDMA-dependent methanol dehydrogenase, NAD(P)H nitroreductase, and amidohydrolase AmiB1 appear to be pivotal factors to regulate the M. smegmatis survival under TBSSB. Our dataset reinforced the idea that Schiff base-taurine compounds have the potential to be developed as novel anti-mycobacterial drugs.

A Novel Linking Schiff-Base Type Ligand (L: py-CH=N-C6H4-N=CH-py) and Its Zinc Coordination Polymers: Preparation of L, 2-Pyridin-3-yl-1H-benzoimidazol, trans-[Zn(H2O)4L2]·(NO3)2·(MeOH)2,

이순원,Hee K. Lee,Han Na Kim 대한화학회 2005 Bulletin of the Korean Chemical Society Vol.26 No.6

A long, bis(monodentate), linking Schiff-base ligand L (py-CH=N-C6H4-N=CH-py) was prepared from 1,4-phenylenediamine and 3-pyridinecarboxaldehyde by the Schiff-base condensation. Ligand L has two terminal pyridyl groups capable of coordinating to metals through their nitrogen atoms. In contrast, the same reaction between 1,2-phenylenediamine and 3-pyridinecarboxaldehyde produced a mixture of imidazol isomers (2-pyridin-3-yl-1H-benzoimidazole), which are connected to one another by the N-H…N hydrogen bonding to form a tetramer. From Zn(NO3)2•6H2O and ligand L under various conditions, one discrete molecule, trans-[Zn(H2O)4L2]•(NO3)2•(MeOH)2, and two 1-D zinc polymers, [Zn(NO3)(H2O)2(L)]•(NO3)•(H2O)2 and [Zn(L) (OBC)(H2O)], were prepared. In ligand L, the N갤N separation between the terminal pyridyl groups is 13.994 Å, with their nitrogen atoms at the meta positions (3,3’) in a trans manner. The corresponding N갤N separations in its compounds range from 13.853 to 14.754 Å.