SURFACE-ENHANCED RAMAN-SCATTERING STUDIES OF METALLOPORPHYRINS ON SILVER SOLS, MELLFS, AND ELECTRODES - EVIDENCE FOR REVERSIBLE PHOTOINDUCED DEMETALATION OF A SILVER(II) PORPHYRIN

A series of metalloporphyrins of the type M(TMPyP) (where M = Ag(II), Zn(II), Cu(II) and TMPyP = meso-tetrakis(4-N-methylpyridyl)porphyrin) have been investigated in solution and on the surface of silver sols, electrodes, and MELLFs (metal liquidlike films). Similar spectra were recorded on all three surfaces but significant differences in detailed behavior were found. In particular, a novel, reversible, and rapid photoinduced demetalation reaction has been observed for the AgII(TMPyP)/MELLF system. An apparently similar demetalation reaction for the same metalloporphyrin was observed on Ag electrodes but this reversed at a very much slower rate. No demetalation of Ag(II)(TMPyP) was observed with Ag sols nor with any of the other metalloporphyrins at any of the surfaces investigated. The implications of the findings in relation to the nature of the MELLF environment are briefly considered.

UV VIS AND RESONANCE RAMAN SPECTROELECTROCHEMICAL PROPERTIES OF TRANSITION-METAL CENTERS IMMOBILIZED WITHIN A POLY(AMINO ACID) MATRIX - ILLUSTRATED WITH AN IRON PORPHYRIN

An iron prophyrin complex has been immobilized on the surfaces of platinum, silver, and indium doped-tin oxide coated glass by using the poly(gamma-ethyl L-glutamate)-N-(3-aminopropyl)imidazole derivative 1 as a linking agent, thus allowing-the surface-enhanced resonance Raman and UV-VIS absorption spectra and electrochemical properties of the porphyrin to be studied in solvents in which it is not normally soluble.

CONTRIBUTION OF RESONANCE RAMAN EXCITATION SPECTROSCOPY FOR PROBING ELECTRONICALLY EXCITED-STATES - NATURE OF A PORPHYRIN-DNA EXCIPLEX

The resonance Raman spectra of a water-soluble metalloporphyrin Cu(TMpy-P4), complexed with a synthetic nucleic acid, poly(dA-dT), were measured by using excitation wavelengths located within the B (Soret) transition of the porphyrin (417-470 nm), while its excited state was synchronously pumped with 545-nm pulsed excitation corresponding to the Q transition. In the presence of pump pulses, the aqueous solution of the Cu(TMpy-P4).poly(dA-dT) complex exhibits resonance Raman bands at 1558 and 1353 cm-1 that are not observed in the absence of pump pulses. These new features were previously assigned to electronically excited Cu(TMpy-P4), stabilized by forming an exciplex with the A-T sites of the nucleic acid. Here we present resonance Raman excitation profiles (RREP) of both the excited and ground states of the complex, and we experimentally confirm the very short lifetime of the exciplex. To our knowledge this is the first time that a RREP of a very short lived (ca. 20 ps) intermediate excited state has been obtained with a two-color experiment. We use this to help to characterize the nature of the porphyrin-AT specific complex formed in the porphyrin excited state.

Controlling the response characteristics of luminescent porphyrin plastic film sensors for oxygen

Two porphyrins, platinum(II) octaethylporphyrin (Pt-OEP) and palladium(II) octaethylporphyrin (Pd-OEP), are incorporated into a wide variety of different encapsulating matricies and tested as oxygen sensors, The excited state lifetimes of the two porphyrins are quite different, 0.091 ms for Pt-OEP and 0.99 ms for Pd-OEP, and Pt-OEP-based oxygen sensors are found to be much less sensitive than Pd-OEP-based ones to quenching by oxygen, Two major response characteristics of an oxygen sensor are (i) its sensitivity toward oxygen and (ii) its response and recovery times when exposed to an alternating atmosphere of nitrogen and air. The response characteristics of a rang of Pt-OEP, and Pd-OEP-based oxygen sensors were determined using cellulose acetate butyrate (CAB), poly(methyl methacrylate) (PMMA), and PMMA/CAB polymer blends as the encapsulating media. Pt-OEP and Pd-OEP oxygen sensors have better response characteristics (i.e., more sensitive and lower response and recovery times) when CAB is used as the encapsulating medium rather than PMMA. For both Pt-OEP- and Pd-OEP-based oxygen sensors, in either polymer, increasing the level of tributyl phosphate plasticizer improves the response characteristics of the final oxygen-sensitive film. Pt-OEP in different unplasticized PMMA/CAB blended films produced a range of oxygen sensors in which the response characteristics improved with increasing level of CAB present.

Altered porphyrin excretion and histopathology of greylag geese (Anser anser) exposed to soil contaminated with lead and arsenic in the Guadalquivir Marshes, southwestern Spain

Greylag geese (Anser anser) in the Guadalquivir Marshes (southwestern Spain) can be exposed to sources of inorganic pollution such as heavy metals and arsenic from mining activities or Pb shot used for hunting. We have sampled 270 fecal excreta in different areas of the marshes in 2001 to 2002 to evaluate the exposure to Pb, Zn, Cu, Mn, and As and to determine its relationship with soil ingestion and with the excretion of porphyrins and biliverdin as biomarkers. These effects and the histopathology of liver, kidney, and pancreas were also studied in 50 geese shot in 2002 to 2004. None of the geese had ingested Pb shot in the gizzard. This contrasts with earlier samplings before the ban of Pb shot for waterfowl hunting in 2001 and the removal of Pb shot in points of the Doñana National Park (Spain) in 1999 to 2000. The highest exposure through direct soil ingestion to Pb and other studied elements was observed in samples from Entremuros, the area of the Doñana Natural Park affected by the Aznalcóllar mine spill in 1998. Birds from Entremuros also more frequently showed mononuclear infiltrates in liver and kidney than birds from the unaffected areas, although other more specific lesions of Pb or Zn poisoning were not observed. The excretion of coproporphyrins, especially of the isomer I, was positively related to the fecal As concentration, and the ratio of coproporphyrin III/I was positively related to fecal Pb concentration. Biliary protoporphyrin IX concentration was also slightly related to hepatic Pb concentration. This study reflects biological effects on terrestrial animals by the mining pollution in Doñana that can be monitored with the simple noninvasive sampling of feces.

Selective Hydrogenation of alpha,beta-Unsaturated Aldehydes and Ketones using Novel Manganese Oxide and Platinum Supported on Manganese Oxide Octahedral Molecular Sieves as Catalysts

The selective hydrogenation of ,-unsaturated aldehydes and ketones has been studied using ketoisophorone and cinnamaldehyde as model substrates using manganese oxide octahedral molecular sieve (OMS-2) based catalysts. For the first time, OMS-2 has been shown to be an efficient and selective hydrogenation catalyst. High selectivities for either the CC or CO double bond at approximate to 100% conversion were achieved by using OMS-2 and platinum supported on OMS-2 catalysts. Density functional theory (DFT) calculations showed that the dissociation of H2 on OMS-2 was water assisted and occurred on the surface Mn of OMS-2(001) that had been modified by an adsorbed H2O molecule. The theoretically calculated activation barrier was in good agreement with the experimentally determined value for the hydrogenation reactions, indicating that H2 dissociation on OMS-2 is likely to be the rate-determining step. A significant increase in the rate of reaction was observed in the presence of Pt as a result of the enhancement of H2 dissociative adsorption and subsequent reaction on the Pt or spillover of the hydrogen to the OMS-2 support. The relative adsorption strengths of ketoisophorone and cinnamaldehyde on the OMS-2 support compared with the Pt were found to determine the product selectivity.

Preparation and characterisation of palladium, platinum and manganese di(organo)carbene complexes from quinolinone and quinolinium precursors

A series of palladium, platinum and manganese di(organo) carbene complexes have been prepared from 4-chloro-N-methylquinolinone by processes that involve alkylation before or after attachment to the metal unit; the nucleophilic heteroatoms necessary for eventual carbene formation and stabilisation are separated from the C-donor atom by three bonds.

A Microscopic Study of Iron and Manganese Oxide Distribution in Soils from East Tennessee (U.S.A.)

Soils and saprolites developed from interbedded shales and limestones of the Conasauga Group are widespread in the Valley and Ridge Province of East Tennessee. Thin sections from four soil profiles were examined by petrographic and scanning electron microscopy including backscatter electron and energy-dispersive X-ray analyses. Iron and manganese released by weathering had migrated differentially downward and precipitated as crystalline and noncrystalline oxides. Oxides were observed as nodules, granular particulates, pore fillings, and coatings on other minerals, packing voids, vesicles, channels, and chambers. Iron oxides formed predominantly as coatings on packing-void walls and on laminated clays in vesicles and channels. Manganese oxides occurred as an early replacement phase of packing voids and of fracture-filling carbonate minerals. Iron oxides were dominant in moderately well-drained and oxidized horizons of the soil solum, whereas manganese oxides were abundant in the oxidized and moderately leached saprolite zone where the water table fluctuates seasonally. Therefore, a manganese enrichment zone, on a bulk soil basis, occurred generally below the iron oxide zone in the soil profile. Such differential migration and accumulation of iron and manganese have been controlled by localized soil microenvironments. Micromorphologic features observed in this study are important in land-use evaluation for hazardous waste disposal. © 1990.

Microstructure, mechanical properties and fractography of heat-treated manganese steel

A Fe-8.46%Mn-0.24%Nb-0.038%C (wt.%) manganese steel was investigated. The steel has a 100% bcc structure after heat treatment at 850°C for 1.5 h, water quenching or air cooling. Martensite interlocked microstructure consisting of fine martensite plates/needles with different spatial orientations was found. Austenite forms, in small amounts, after a 600°C reheating treatment. Scanning electron microscopy images and energy dispersive spectrometry of the fracture surfaces revealed both ductile and brittle types of failure and precipitates. Deep quenching after the heat treatments does not change the phase composition or the hardness. NbC is formed in the steel, in high number densities. It plays a role in the impact fracture process, by acting as void nucleation sites, facilitating ductile fracture with dimples appearing on the fracture surface.

Manganese Superoxide Dismutase Is a Promising Target for Enhancing Chemosensitivity of Basal-Like Breast Carcinoma

AIMS: Although earlier reports highlighted a tumor suppressor role for manganese superoxide dismutase (MnSOD), recent evidence indicates increased expression in a variety of human cancers including aggressive breast carcinoma. In the present article, we hypothesized that MnSOD expression is significantly amplified in the aggressive breast carcinoma basal subtype, and targeting MnSOD could be an attractive strategy for enhancing chemosensitivity of this highly aggressive breast cancer subtype.

RESULTS: Using MDA-MB-231 and BT549 as a model of basal breast cancer cell lines, we show that knockdown of MnSOD decreased the colony-forming ability and sensitized the cells to drug-induced cell death, while drug resistance was associated with increased MnSOD expression. In an attempt to develop a clinically relevant approach to down-regulate MnSOD expression in patients with basal breast carcinoma, we employed activation of the peroxisome proliferator-activated receptor gamma (PPARγ) to repress MnSOD expression; PPARγ activation significantly reduced MnSOD expression, increased chemosensitivity, and inhibited tumor growth. Moreover, as a proof of concept for the clinical use of PPARγ agonists to decrease MnSOD expression, biopsies derived from breast cancer patients who had received synthetic PPARγ ligands as anti-diabetic therapy had significantly reduced MnSOD expression. Finally, we provide evidence to implicate peroxynitrite as the mechanism involved in the increased sensitivity to chemotherapy induced by MnSOD repression.

INNOVATION AND CONCLUSION: These data provide evidence to link increased MnSOD expression with the aggressive basal breast cancer, and underscore the judicious use of PPARγ ligands for specifically down-regulating MnSOD to increase the chemosensitivity of this subtype of breast carcinoma.

Conserved histidine of metal transporter AtNRAMP1 is crucial for optimal plant growth under manganese deficiency at chilling temperatures

Manganese (Mn) is an essential nutrient required for plant growth, in particular in the process of photosynthesis. Plant performance is influenced by various environmental stresses including contrasting temperatures, light or nutrient deficiencies. The molecular responses of plants exposed to such stress factors in combination are largely unknown. 

Screening of 108 Arabidopsis thaliana (Arabidopsis) accessions for reduced photosynthetic performance at chilling temperatures was performed and one accession (Hog) was isolated. Using genetic and molecular approaches, the molecular basis of this particular response to temperature (GxE interaction) was identified. 

Hog showed an induction of a severe leaf chlorosis and impaired growth after transfer to lower temperatures. We demonstrated that this response was dependent on the nutrient content of the soil. Genetic mapping and complementation identified NRAMP1 as the causal gene. Chlorotic phenotype was associated with a histidine to tyrosine (H239Y) substitution in the allele of Hog NRAMP1. This led to lethality when Hog seedlings were directly grown at 4 degrees C. 

Chemical complementation and hydroponic culture experiments showed that Mn deficiency was the major cause of this GxE interaction. For the first time, the NRAMP-specific highly conserved histidine was shown to be crucial for plant performance.

Selective Hydrogenation of Halogenated Arenes using porous Manganese Oxide (OMS-2) and Platinum supported OMS-2 Catalysts

Porous manganese oxide (OMS-2) and platinum supported on OMS-2 catalysts have been shown to facilitate the hydrogenation of the nitro group on chloronitrobenzene to give chloroaniline with no dehalogenation. Complete conversion was obtained within 2 h at 25 [degree]C and, although the rate of reaction increased with increasing temperature up to 100 [degree]C, the selectivity to chloroaniline remained at 99.0%. Use of Pd/OMS-2 or Pt/Al2O3 resulted in significant dechlorination even at 25 [degree]C and 2 bar hydrogen pressure giving selectivity to chloroaniline of 34.5% and 77.8%, respectively, at complete conversion. This demonstrates the potential of using platinum group metal free catalysts for the selective hydrogenation of halogenated aromatics. Two pathways were observed for the analogous nitrobenzene hydrogenation depending on the catalyst used. The hydrogenation of nitrobenzene was found to follow a direct pathway to aniline and nitrosobenzene over Pd/OMS-2 in contrast to the OMS and Pt/OMS-2 catalysts which resulted in formation of nitrosobenzene, azoxybenzene and azobenzene/hydrazobenzene intermediates before complete conversion to aniline. These results indicate that for the Pt/OMS-2 the hydrogenation proceeds predominantly over the support with the metal acting to dissociate the hydrogen. In the case of the Pd/OMS-2 both the hydrogenation and the hydrogen adsorption occur on the metal sites.