ABSTRACT
Irradiation of dichloroethane solutions of different bile acids with diacetoxy(iodobenzene) and iodine followed by treatment of the resulting raw mixture with MCPBA led to the 41-50% yields of the corresponding dehomologated alcohols in an uncomplicated one-pot protocol that can be completed in less than one day of work.
Subject(s)
Alcohols/chemical synthesis , Bile Acids and Salts/chemistry , Alcohols/chemistry , Iodine/chemistry , Iodobenzenes/chemistry , Molecular StructureABSTRACT
Atrazine (ATZ) is an herbicide that has been considered an environmental pollutant worldwide. ATZ contaminates groundwaters and can persist in soils for up to a year causing several environmental and health problems. This study aimed to investigate ATZ degradation catalyzed by manganese porphyrins as biomimetic cytochrome P450 models. We used PhIO, PhI(OAc)2, H2O2, t-BuOOH, m-CPBA, or Oxone® as oxidant under mild conditions and evaluated a range of manganese porphyrins as catalyst. Concerning oxidant, iodosylbenzene provided the best result-ATZ degradation catalyzed by one of the studied manganese porphyrins in acetonitrile was as high as 47%. We studied the same catalyst/oxidant systems in natural water from a Brazilian river as solvent and obtained up to 100% ATZ degradation when iodobenzene diacetate was the oxidant, regardless of the manganese porphyrin. Besides the already known ATZ degradation products, we also identified unexpected degradation compounds (ring-opening products). Toxicity tests showed that the latter products were capable of proliferate blood cells because they did not show toxicity under the evaluated conditions.
Subject(s)
Atrazine/chemistry , Biodegradation, Environmental , Leukocytes, Mononuclear/drug effects , Porphyrins/chemistry , Water Pollutants, Chemical/chemistry , Water Purification/methods , Acetonitriles/chemistry , Biomimetics , Brazil , Catalysis , Cell Survival/drug effects , Herbicides , Humans , Iodobenzenes/chemistry , Manganese/chemistry , Oxidants/chemistry , Peroxides/chemistry , Pesticides/chemistry , Toxicity TestsABSTRACT
Two unnatural steroid sapogenins bearing a furospirostane side chain were prepared starting from the readily available spirostane sapogenins, tigogenin and diosgenin following a synthetic protocol that included: (i) introduction of a carbonyl group at position C-23, (ii) diacetoxyiodobenzene-induced F-ring contraction and (iii) LiAlH4 reduction of the newly emerged methoxycarbonyl moiety. The structures of the new compounds were corroborated by NMR and X-ray studies.
Subject(s)
Acetates/chemistry , Diosgenin/chemistry , Iodobenzenes/chemistry , Sapogenins/chemical synthesis , Spirostans/chemistry , Crystallography, X-Ray , Hydrolysis , Magnetic Resonance Spectroscopy , Molecular ConformationABSTRACT
INTRODUCTION: In this report, we propose the application of the p-iodophenol-enhanced luminol chemiluminescent technique to the determination of peroxidase (myeloperoxidase and/or platelet peroxidase) activity in blasts of minimally differentiated acute myeloblastic leukemia (AML-M0) and acute megakaryoblastic leukemia (AML-M7). METHODS: The frozen blast cells from 29 patients were thawed and submitted to the optimized protocol. RESULTS: All cases of AML-M7 and AML-M I exhibited integrated light emission greater than 73(10(2) mV x s), which was the arbitrary cutoff point set for the discrimination between AML and acute lymphoblastic leukemia (ALL) (mean + 3 x s.d. of ALL samples, n = 10). In addition, five out of seven cases of AML-MO showed results above the cutoff point. CONCLUSION: This highly sensitive enhanced chemiluminescent technique may be applied to discriminate between ALL and AML-M7 or AML-MI cases, and most AML-M0 cases. It is very simple, cheap and easy to perform compared to other procedures used to measure MPO activity in AML-leukemias including AML-M7 and AML-M0.
Subject(s)
Iodobenzenes/chemistry , Leukemia, Megakaryoblastic, Acute/diagnosis , Leukemia, Myeloid, Acute/diagnosis , Luminescent Measurements/methods , Luminol/chemistry , Precursor Cell Lymphoblastic Leukemia-Lymphoma/diagnosis , Bone Marrow Cells/enzymology , Bone Marrow Cells/immunology , Bone Marrow Cells/metabolism , Diagnosis, Differential , Humans , Immunohistochemistry , Immunophenotyping , Leukemia, Megakaryoblastic, Acute/pathology , Leukemia, Myeloid, Acute/pathology , Luminol/metabolism , Peroxidase/analysis , Peroxidase/metabolism , Precursor Cell Lymphoblastic Leukemia-Lymphoma/pathologyABSTRACT
Two samples of montmorillonite (one of Brazilian origin, BNC1 clay, and the other STX-1, supplied by the Clay Mineral Society Repository (University of Missouri, USA) were allowed to react with biomimetic metalloporphyrins of Fe(III) and Mn(III) in cationic form. The compounds were characterized by several techniques, showing that the metalloporphyrins molecules were adsorbed at the surface of the clay platelet crystals. The catalytic activities of the intercalated complexes for the oxidation of alkane were dependent upon the concentration of the porphyrin immobilized in the clay and factors such as the metal ion species in the porphyrins, choice of solvent, and concentration of the iodosylbenzene oxidant. Good selectivity to cyclohexanol instead of cyclohexanone was observed for the catalytic oxidation of cyclohexane by iodosylbenzene.