• Applied Biological Chemistry
• /
• 제41권8호
• /
• pp.611-612
• /
• 1998

The transition state analog for metal catalyzed hydrolysis of an ester through cooperative interactions between metal ions as Lewis acid and peroxide was discussed.

• 대한화학회지
• /
• 제68권3호
• /
• pp.139-145
• /
• 2024

This study aims to elucidate the mechanism involved in the hydrolysis of the hexacyanoferrate(III) complex ion (Fe(CN)₆^3-) and the mechanism leading to the formation of Prussian blue (Fe^III₄[Fe_II(CN)₆]₃·xH₂O, PB) in acidic aqueous solutions at moderately elevated temperatures. Hydrolysis constitutes a crucial step in generating PB through the widely used single-source or precursor method. Recent PB syntheses predominantly rely on the single-source method, where hexacyanoferrate(II/III) is the exclusive reactant, as opposed to the co-precipitation method employing bare metal ions and hexacyanometalate ions. Despite the widespread adoption of the single-source method, mechanistic exploration remains largely unexplored and speculative. Utilizing UV-vis spectrophotometry, negative-ion mode liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS), and a devised reaction, this study identifies crucial intermediates, including aqueous Fe^2+/3+ ions and hydrocyanic acid (HCN) in the solution. These two intermediates eventually combine to form thermodynamically stable PB. The findings presented in this research significantly contribute to understanding the fundamental mechanism underlying the acid-catalyzed hydrolysis of the hexacyanoferrate(III) complex ion and the subsequent formation of PB, as proposed in the sequential mechanism introduced herein. This finding might contribute to the cost-effective synthesis of PB by incorporating diverse metal ions and potassium cyanide.

• 한국환경과학회지
• /
• 제5권5호
• /
• pp.579-583
• /
• 1996

본 연구는 날로 더해가는 오염의 직접간접 원인인 고분자성 제품류의 분해 촉진에 사용될 촉매 개발의 일차적 연구로서, 구리 촉매작용에 의한 아미드 결합의 분해 반응을 수행하였다. 가시광선 스펙트럼의 변화를 측정함으로써 반응을 추적하였다. 아미드 리간드를 포함하는 구리 화합물에서 수용액의 pH의 증가에 따라, 온도의 증가에 따라 아미드의 반응속도가 증가한다. 반응속도는 구리 화합물에 대하여 1차 반응으로 밝혀졌다. 반응의 중간체로 구리-히드록시 화합물이 관여하는 반응 메카니즘을 제시하였다. 분해 반응 메카니즘의 확실한 이해를 통하여 펩티드 결합의 분해 반응에 사용될 좋은 촉매 개발에의 응용이 기대 된다.

• Applied Biological Chemistry
• /
• 제48권2호
• /
• pp.115-119
• /
• 2005

DNA 모델 화합물인 bis(p-nitrophenyl)phosphate(BNPP)에 대한 2핵 닉켈(II) 착 화합물, ${\mu}-aquapentaaqua[{\mu}-3,6-bis(6'-methyl-2'-pyridyl)pyridazine]chlorodinickel(II)$ trichloride trihydrate(APNT)의 촉매 가수분해 반응성을 검토하였다. APNT의 산 해리 상수는 각각 $pKa_1=7.9$ 및 $pKa_2=9.6$이었으며 BNPP의 가수분해반응 결과, pH 7.0과 $50^{\circ}C$에서 무 촉매인 경우에 비하여 가수분해 속도를 약 37만 배 가량 촉진시킴을 확인하였다. 그리고 pH-rate profile로부터 실험 사실을 합리적으로 설명할 수 있는 APNT에 의한 BNPP의 촉매 가수분해 반응에 대한 일련의 catalytic cycle을 제안하였다. 따라서 반응의 각 단계에서 2핵 닉켈(II) 착 화합물의 금속 이온들은 phosphoryl group의 전달 속도를 촉진하였고 물 분자는 친핵체와 양성자 전달체로 작용하였다.

• Journal of Pharmaceutical Investigation
• /
• 제20권3호
• /
• pp.145-152
• /
• 1990

Zirconium pyrithione complex was prepared by reaction of sodium-pyrithione solution and zirconyl chloride solution. The physico-chemical properties of the complex was examined by means of IR, XRD, DSC and NMR. And the stability of Zr-complex was investigated on the basis of accelerated stability analysis under conditions of temp. elevation, UV radiation and pH dependence. The result indicates that the ratio of the ligand to metal in Zr-pyrithione complex was determined 4:1, and its stability constant was $4.643{\times}10^4$. The rate order of decomposition of the complex was apparent first-order reaction of which rate constant and the decomposition rate was not only accelerated by effect of heat and UV radiation but was catalyzed by specific acid-base catalysis considered the pH dependence for the hydrolysis of the complex and the suspension was most stable over the range pH 4-8 indicating that solvent catalysis is the primary made of reaction in this region.

• 한국지하수토양환경학회지:지하수토양환경
• /
• 제20권1호
• /
• pp.56-64
• /
• 2015

Acid mine drainage occurrence is a serious environmental problem by mining industry, it usually contains high levels of metal ions, such as iron, copper, zinc, aluminum, and manganese, as well as metalloids of which arsenic is generally of the greatest concern. An indigenous plant extract was used to produce calcium carbonate from Canavalia ensiformis as effective biomaterial, and its ability to form the calcium carbonate under stable conditions was compared to that of purified urease. X-ray diffraction and scanning electron microscopy were employed to elucidate the mechanism of calcium carbonate formation from the crude plant extracts. The results revealed that urease in the plant extracts catalyzed the hydrolysis of urea in liquid state cultures and decreased heavy metal amounts in the contaminated soil. The heavy metal amounts were decreased in the leachate from the treated mine soil; 31.7% of As, 65.8% of Mn, 50.6% of Zn, 51.6% of Pb, 45.1% of Cr, and 49.7% of Cu, respectively. The procedure described herein is a simple and beneficial method of calcium carbonate biomineralization without cultivation of microorganisms or further purification of crude extracts. This study suggests that crude plant extracts of Canavalia ensiformis have the potential to be used in place of purified forms of the enzyme during remediation of heavy metal contaminated soil.

• Membrane and Water Treatment
• /
• 제9권6호
• /
• pp.405-419
• /
• 2018

Persulfates (i.e., peroxymonosulfate and peroxydisulfate) are capable of oxidizing a wide range of organic compounds via direct reactions, as well as by indirect reactions by the radical intermediates. In aqueous solution, persulfates undergo self-decomposition, which is accelerated by thermal, photochemical and metal-catalyzed methods, which usually involve the generation of various radical species. The chemistry of persulfates has been studied since the early twentieth century. However, its environmental application has recently gained attention, as persulfates show promise in in situ chemical oxidation (ISCO) for soil and groundwater remediation. Persulfates are known to have both reactivity and persistence in the subsurface, which can provide advantages over other oxidants inclined toward either of the two properties. Besides the ISCO applications, recent studies have shown that the persulfate oxidation also has the potential for wastewater treatment and disinfection. This article reviews the chemistry regarding the hydrolysis, photolysis and catalysis of persulfates and the reactions of persulfates with organic compounds in aqueous solution. This article is intended to provide insight into interpreting the behaviors of the contaminant oxidation by persulfates, as well as developing new persulfate-based oxidation technologies.

• Journal of Microbiology and Biotechnology
• /
• 제16권2호
• /
• pp.272-279
• /
• 2006

The gene encoding Thermus sp. T351 alkaline phosphatase (T351 APase) was cloned and sequenced. The gene consisted of 1,503 bp coding for a protein with 500 amino acid residues including a signal peptide. The deduced amino acid sequence of T351 APase showed relatively low similarity to other Thermus APases. The T351 APase gene was expressed under the control of the T7lac promoter on the expression vector pET-22b(+) in Escherichia coli BL21 (DE3). The expressed enzyme was purified by heat treatment, and $UNO^{TM}$ Q and $HiTrap^{TM}$ Heparin HP column chromatographies. The purified enzyme exhibited high activity at extremely alkaline pHs, reaching a maximum at pH 12.0. The optimum temperature of the enzyme was $80^{\circ}C$, and the half-life at $85^{\circ}C$ was approximately 103 min. The enzyme activity was found to be dependent on metal ions: the addition of $Mg^{2+}$ and $CO^{2+}$ increased the activity, whereas EDTA inhibited it. With p-nitrophenyl phosphate as the substrate, T351 APase had a Michaelis constant ($K_{m}$) of $3.9{\times}10^{-5}M$. The enzyme catalyzed the hydrolysis of a wide variety of phosphorylated compounds.