Characterization and reactivity study of non-heme high-valent iron–hydroxo complexes

A terminal Fe^IIIOH complex, [Fe^III(L)(OH)]²⁻ (1), has been synthesized and structurally characterized (H₄L = 1,2-bis(2-hydroxy-2-methylpropanamido)benzene). The oxidation reaction of 1 with one equiv. of tris(4-bromophenyl)ammoniumyl hexachloroantimonate (TBAH) or ceric ammonium nitrate (CAN) in acetonitrile at −45 °C results in the formation of a Fe^IIIOH ligand radical complex, [Fe^III(L˙)(OH)]⁻ (2), which is hereby characterized by UV-visible, ¹H nuclear magnetic resonance, electron paramagnetic resonance, and X-ray absorption spectroscopy techniques. The reaction of 2 with a triphenylcarbon radical further gives triphenylmethanol and mimics the so-called oxygen rebound step of Cpd II of cytochrome P450. Furthermore, the reaction of 2 was explored with different 4-substituted-2,6-di-tert-butylphenols. Based on kinetic analysis, a hydrogen atom transfer (HAT) mechanism has been established. A pK_a value of 19.3 and a BDFE value of 78.2 kcal/mol have been estimated for complex 2.

One-electron oxidation of an Fe^III–OH complex (1) results in the formation of a Fe^III–OH ligand radical complex (2). Its reaction with (C₆H₅)₃C˙ results in the formation of (C₆H₅)₃COH, which is a functional mimic of compound II of cytochrome P450.     

Hydrolysis and amine-capping in a glycol solvent as a route to soluble maghemite gamma-Fe2O3 nanoparticles

The preparation of capped metal oxide nanoparticles through the hydrolysis of metal salts is made arduous by the difficulty of dissolving long organic chain capping agents in water; by performing the reaction in propylene glycol under reflux, instead of water, we are able to hydrolyse FeCl3 in the presence of n-octylamine to obtain (repeatedly) soluble, monodisperse approximately 5 nm gamma-Fe2O3 particles that display a tendency to aggregate into superlattices.     

An empirical fit to estimated neutron emission cross sections from proton induced reactions

Neutron emission cross section for various elements from⁹Be to²⁰⁹Bi have been calculated using the hybrid model code ALICE-91 for proton induced reactions in the energy range 25 MeV to 105 Me V. An empirical expression relating neutron emission cross section to target mass number and incident proton energy has been obtained. The simple expression reduces the computation time significantly. The trend in the variation of neutron emission cross sections with respect to the target mass number and incident proton energy has been discussed within the framework of the model used.     

Cerium(IV) ammonium nitrate catalyzed synthesis of α-dehydro-β-amino esters

α-Dehydro-β-amino esters have been synthesized regioselectively from acetates of Baylis-Hillman adducts with amines in the presence of a catalytic amount of ceric ammonium nitrate (CAN) in good yield. The regioselectivity does not differ with respect to the polarity of the solvent.     

A facile and versatile protocol for the one-pot PhI(OAc)2 mediated divergent synthesis of quinazolines from 2-aminobenzylamine

In this present work iodobenzenediacetate (PIDA) has been found to be the key reagent in absence or presence of catalytic amount of molecular iodine (I₂)/zinc chloride (ZnCl₂) to construct quinazoline scaffold from 2-aminobenzylamine and a variety of easily available aldehydes, aryl and aliphatic amines, aliphatic and aryl alcohols and nitriles. This protocol provides mild and robust conditions along with great versatility to synthesize 2-substituted quinazolines from diverse starting materials in good to excellent yields. The developed protocol is also well applicable to reactants containing ease to oxidation prone functional groups.     

Nanocrystals,Nanorods and other Nanostructures of Nickel,Ruthenium, Rhodium and Iridium prepared by a Simple Solvothermal Procedure

The solvothermal decomposition of nickel acetate in n-octylamine medium at 250 °C gives rise to nickel nanostructures while in a hydrocarbon medium NiO nanostructures are obtained. It has been possible to obtain nickel nanorods of 12–15 nm diameter by this means. By carrying out the reaction at a slightly higher temperature, ultra-thin single-crystalline sheets of nickel are obtained. The nanorods and the thin sheets, with the FCC structure, are both ferromagnetic at room temperature, with the nanorods exhibiting high coercivities. It has been possible to obtain ruthenium, rhodium and iridium nanostructures by carrying out the decomposition of the respective metal acetylacetonates in a hydrocarbon (decalin or toluene) or an amine (n-octylamine or oleylamine) around 300 °C. Nanorod formation is favored by linear long-chain amines. The method described by us to prepare the nanostructures of nickel, ruthenium, rhodium and iridium is simple and straightforward compared to the literature procedures, the preparation of single-crystalline thin sheets of nickel by such a solution route being noteworthy. The nanostructures prepared in the amine media could be readily dispersed in hydrocarbon solvents. Dedicated to Professor Dr. Günther Schmid     

Multimodal approaches of the hydroalcoholic extract of Diospyros peregrina fruits in diabetic therapy

The matured fruits of Diospyros peregrina possess significant antidiabetic activity. The present investigation was undertaken to evaluate the target of action of the hydroalcoholic extract of D. peregrina fruit in diabetic pathophysiology. The extract was tested in vitro for inhibition of glucose absorption by α-amylase inhibition assay, glucose uptake study by isolated rat hemidiaphragm method and free radical scavenging activity by DPPH method. The extract exhibited significant α-amylase inhibition (IC?? 136.5 μg mL?1), peripheral glucose utilisation and radical scavenging (IC?? 167.5 μg mL?1) activity. From the results, it may be concluded that the hydroalcoholic extract of D. peregrina fruit can counteract diabetes by multiple mechanisms, namely inhibition of carbohydrate absorption, improving peripheral glucose utilisation and antioxidant defence.