2435-53-2Relevant articles and documents
Spin-State-Dependent Redox-Catalytic Activity of a Switchable Iron(II) Complex
Gural'skiy, Il'ya A.,Shylin, Sergii I.,Ksenofontov, Vadim,Tremel, Wolfgang
, p. 3125 - 3131 (2017)
The spin state of catalytically active 3d metal centers plays a significant role in their activity in enzymatic processes and organometallic catalysis. Here the catalytic activity of an FeII coordination compound that can undergo a cooperative switch between low-spin (LS) and high-spin (HS) states is reported. Catalytic measurements in the temperature range 291–318 K revealed a drastic drop of the catalytic activity on conversion of the metal centers from the LS to the HS form. For thermoswitchable complex [Fe(NH2trz)3]Br2 (NH2trz = 4-amino-1,2,4-tiazole; Tup = 305 K), the activation energy is found to be considerably lower for the LS state (158 kJ mol–1) compared to the HS state (305 kJ mol–1). M?ssbauer analysis revealed that this is related to higher conversion of the LS complex on oxidation. Comparisons with another polymorph of [Fe(NH2trz)3]Br2 (Tup = 301 K) and [Fe(NH2trz)3](ClO4)2 (Tup = 240 K) are made. These results show the potential of spin-crossover compounds to compare the catalytic activity of different spin states of the same material when other means of differentiation are limited.
Effect of oxalate and pH on photodegradation of pentachlorophenol in heterogeneous irradiated maghemite System
Lan, Qing,Cao, Meiyuan,Ye, Zhijun,Zhu, Jishu,Chen, Manjia,Chen, Xuequan,Liu, Chengshuai
, p. 198 - 206 (2016/07/06)
Photochemical degradation in the system of iron oxides and oxalic acid (OX) is the important reaction for detoxification of organic pollutants in natural environments, including surface soils, surface water, and even aerosols, and it was more effective at low pH according to previous studies. However, in this study, the photodegradation of pentachlorophenol (PCP) proceeded rapidly at different pH conditions in the system with maghemite and OX under UV light illumination. It was observed that the removal of PCP was 77.7% ± 0.90%, 79.9% ± 0.80% and 74.3% ± 1.50% at initial pH of 3.5, 5.0 and 7.0, respectively. To explore the degradation mechanism, the interaction of OX and maghemite were systematically studied as a function of pH. The presence of OX of 1.2 mM effectively decreased the iso-electric point (iep) of the maghemite from 5.6 to 1.8. The maximum adsorption amount of maghemite adsorbing OX increased with increasing pH value from 208 mmol kg-1 at pH = 3.5 to 293 mmol kg-1 at pH = 9.0. However, PCP (0.0375 mM) inhibited the adsorption of oxalic acid at pH = 3.5 and pH = 5.0 but promoted it at pH = 7.0 and pH = 9.0. When the initial content of OX was 1.2 mM, the highly active compounds of Fe(C2O4)33- as Fe(III) and Fe(C2O4)22- as Fe(II) were the dominant species at different pH. The formation of H2O2 also relied on the value of pH and the concentration range of H2O2 during PCP degradation was 0-1.67 mg L-1, 0-1.16 mg L-1 and 0-0.16 mg L-1at initial pH of 3.5, 5.0 and 7.0, respectively. The low pH conditions favored the iron cycling, the H2O2 generation and the broken of aromatic ring of PCP, so as to enhance the degradation rates of PCP. At the high pH conditions, due to the slowdown of the iron cycling and the decreased amount of H2O2 formation, the direct photolysis was responsible for the enhanced degradation of PCP. The foundation of high photochemical efficiencies of OX and maghemite for PCP degradation at large-scale pH conditions improves the photochemical mechanisms of OX-iron oxide system and is of important for understanding the transformation of organic pollutants in light environments.
A unique nickel system having versatile catalytic activity of biological significance
Chattopadhyay, Tanmay,Mukherjee, Madhupama,Mondal, Arindam,Maiti, Pali,Banerjee, Arpita,Banu, Kazi Sabnam,Bhattacharya, Santanu,Roy, Bappaditya,Chattopadhyay,Mondai, Tapan Kumar,Nethaji, Munirathinam,Zangrando, Ennio,Das, Debasis
scheme or table, p. 3121 - 3129 (2010/05/14)
A new dinuclear nickel(ll) complex, [Ni2(LH2)(H 2O)2(OH)(NO3)](NO3)3 (1), of an "end-off" compartmental ligand 2,6-bis(N-ethylpiperazine- iminomethyl)-4-methyl-phenolato, has been synthesized and structurally characterized. The X-ray single crystal structure analysis shows that the piperazine moieties assume the expected chair conformation and are protonated. The complex 1 exhibits versatile catalytic activities of biological significance, viz. catecholase, phosphatase, and DNA cleavage activities, etc. The catecholase activity of the complex observed is very dependent on the nature of the solvent. In acetonitrile medium, the complex is inactive to exhibit catecholase activity. On the other hand, in methanol, it catalyzes not only the oxidation of 3,5-ditert-buty !catechol (3,5-DTBC) but also tetrachlorocatechol (TCC), a catechol which is very difficult to oxidize, under aerobic conditions. UV-vis spectroscopic investigation shows that TCC oxidation proceeds through the formation of an intermediate. The intermediate has been characterized by an electron spray ionizaton-mass spectrometry study, which suggests a bidentate rather than a monodentate mode of TCC coordination in that intermediate, and this proposition have been verified by density functional theory calculation. The complex also exhibits phosphatase (with substrate p-nitrophenylphosphate) and DNA cleavage activities. The DNA cleavage activity exhibited by complex 1 most probably proceeds through a hydroxyl radical pathway. The bioactivity study suggests the possible applications of complex 1 as a site specific recognition of DNA and/or as an anticancer agent.