Interactions between iron, manganese, and the Al-Si eutectic in hypoeutectic Al-Si alloys

Sand-cast plates were used to determine the effect of iron and manganese concentrations on porosity levels in Al-9 pet Si-0.5 pet Mg alloys. Iron increased porosity levels. Manganese additions increased porosity levels in alloys with 0.1 pet Fe, but reduced porosity in alloys with 0.6 and I pet Fe. Thermal analysis and quenching were undertaken to determine the effect of iron and manganese on the solidification of the Al-Si eutectic. At high iron levels, the presence of large beta-Al5FeSi was found to reduce the number of eutectic nucleation events and increase the eutectic grain size. The preferential formation of alpha-Al15Mn3Si2 upon addition of manganese reversed these effects. It is proposed that this interaction is due to beta-Al5FeSi and the Al-Si eutectic having common nuclei. Porosity levels are proposed to be controlled by the eutectic grain size and the size of the iron-bearing intermetallic particles rather than the specific intermetallic phase that forms.

Phase equilibria in high MgO ferro- and silico-manganese smelting slags

Phase equilibria have been determined experimentally for pseudo-ternary sections of the form “MnO”- (CaO+MgO)-(SiO2+Al2O3) with a fixed Al2O3/SiO2 weight ratio of 0.17 and MgO/CaO weight ratios of 0.25 and 0.17 respectively for temperatures in the range 1473-1673 K. The primary phase fields present for the MgO/CaO weight ratio of 0.17 include manganosite (Mn,Mg,Ca)O; dicalcium silicate α-2(Ca,Mg,Mn)O·SiO2; merwinite 3CaO⋅(Mg,Mn)O⋅2SiO2; wollastonite [(Ca,Mg,Mn)O·SiO2]; diopside [(CaO,MgO,MnO,Al2O3)·SiO2]; tridymite (SiO2); tephroite [2(Mn,Mg)O·SiO2]; rhodonite [(Mn,Mg)O·SiO2] and melilite [2CaO·(MgO,MnO,Al2O3)·2(SiO2,Al2O3)]. For the section with MgO/CaO weight ratio of 0.25 the anorthite phase (CaO⋅Al2O3⋅2SiO2) is also present. The liquidus temperatures of ferro- and silico-manganese smelting slags have been determined. The liquidus temperatures at low MnO concentrations are shown to be principally dependent on the modified basicity weight ratio (CaO+MgO)/(SiO2+Al2O3).

Organic reactions in ionic liquids:A new method for the synthesis of alkyl aryl sulfones by alkylation of sodium arenesulfinates with unactivated alkyl chlorides

A new method is reported for the synthesis of alkyl aryl sulfones by alkylation of sodium arenesulfinates with unactivated alkyl chlorides using ionic liquid based on 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF 4) mixed with water (2:1) as reaction media. The ionic liquid can be reused and the procedure gives the sulfones in moderate yields.

Covalent attachment of chiral manganese(III) salen complexes onto functionalised hexagonal mesoporous silica and application to the asymmetric epoxidation of alkenes

Two modified Jacobsen-type catalysts were anchored onto an amine functionalised hexagonal mesoporous silica (HMS) using two distinct anchoring procedures: (i) one was anchored directly through the carboxylic acid functionalised diimine bridge fragment of the complex (CAT1) and (ii) the other through the hydroxyl group on the aldehyde fragment of the complex (CAT2), mediated by cyanuric chloride. The new heterogeneous catalyst, as well as the precedent materials, were characterised by elemental analyses, DRIFT, UV-vis, porosimetry and XPS which showed that the complexes were successfully anchored onto the hexagonal mesoporous silica. These materials acted as active heterogeneous catalysts in the epoxidation of styrene, using m-CPBA as oxidant, and α-methylstyrene, using NaOCl as oxidant. Under the latter conditions they acted also as enantioselective heterogeneous catalysts. Furthermore, when compared to the reaction run in homogeneous phase under similar experimental conditions, an increase in asymmetric induction was observed for the heterogenised CAT1, while the opposite effect was observed for the heterogenised CAT2, despite of CAT2 being more enantioselective than CAT1 in homogeneous phase. These results indicate that the covalent attachment of the Jacobsen catalyst through the diimine bridge leads to improved enantiomeric excess (%ee), whereas covalent attachment through one of the aldehyde fragments results in a negative effect in the %ee. Using α-methylstyrene and NaOCl as oxidant, heterogeneous catalyst reuse led to no significant loss of catalytic activity and enantioselectivity. © 2005 Elsevier Inc. All rights reserved.

Asymmetric epoxidation of alkenes by a chiral manganese(III) salen complex anchored onto a functionalised hexagonal mesoporous silica

A Jacobsen-type catalyst was anchored onto an amine functionalised hexagonal mesoporous silica (HMS) through the diimine bridge fragment of the complex. The new heterogeneous catalyst, as well as the precedent materials, were characterised by elemental analyses, FTIR-DRIFT, UV-vis, porosimetry and XPS which showed that the complex was successfully anchored. This material was active in the epoxidation of styrene and α-methylstyrene in dichloromethane at 0°C using, respectively, m-CPBA/NMO and NaOCl. With the former substrate no asymmetric induction was found in the epoxide, whereas with the latter substrate higher %ee was found than in homogeneous phase. Using the latter experimental conditions, catalyst reuse led to no significant loss of catalytic activity and enantioselectivity. © 2005 Elsevier B.V. All rights reserved.

Influence of hydrobiogeochemistry on transport of chromium through manganese -containing sediments: Experimental and modeling approaches

Chromium (Cr) is a metal of particular environmental concern, owing to its toxicity and widespread occurrence in groundwater, soil, and soil solution. A combination of hydrological, geochemical, and microbiological processes governs the subsurface migration of Cr. Little effort has been devoted to examining how these biogeochemical reactions combine with hydrologic processes influence Cr migration. This study has focused on the complex problem of predicting the Cr transport in laboratory column experiments. A 1-D reactive transport model was developed and evaluated against data obtained from laboratory column experiments. ^ A series of dynamic laboratory column experiments were conducted under abiotic and biotic conditions. Cr(III) was injected into columns packed with β-MnO 2-coated sand at different initial concentrations, variable flow rates, and at two different pore water pH (3.0 and 4.0). In biotic anaerobic column experiments Cr(VI) along with lactate was injected into columns packed with quartz sand or β-MnO2-coated sand and bacteria, Shewanella alga Simidu (BrY-MT). A mathematical model was developed which included advection-dispersion equations for the movement of Cr(III), Cr(VI), dissolved oxygen, lactate, and biomass. The model included first-order rate laws governing the adsorption of each Cr species and lactate. The equations for transport and adsorption were coupled with nonlinear equations for rate-limited oxidation-reduction reactions along with dual-monod kinetic equations. Kinetic batch experiments were conducted to determine the reduction of Cr(VI) by BrY-MT in three different substrates. Results of the column experiments with Cr(III)-containing influent solutions demonstrate that β-MnO2 effectively catalyzes the oxidation of Cr(III) to Cr(VI). For a given influent concentration and pore water velocity, oxidation rates are higher, and hence effluent concentrations of Cr(VI) are greater, at pH 4 relative to pH 3. Reduction of Cr(VI) by BrY-MT was rapid (within one hour) in columns packed with quartz sand, whereas Cr(VI) reduction by BrY-MT was delayed (57 hours) in presence of β-MnO 2-coated sand. BrY-MT grown in BHIB (brain heart infusion broth) reduced maximum amount of Cr(VI) to Cr(III) followed by TSB (tryptic soy broth) and M9 (minimum media). The comparisons of data and model results from the column experiments show that the depths associated with Cr(III) oxidation and transport within sediments of shallow aquatic systems can strongly influence trends in surface water quality. The results of this study suggests that carefully performed, laboratory column experiments is a useful tool in determining the biotransformation of redox-sensitive metals even in the presence of strong oxidant, like β-MnO2. ^

The relationship among serum levels of manganese superoxide dismutase and mitochondrial DNA 8-hydroxy-2'- deoxyguanosine, and dietary antioxidants intake in type 2 diabetes

Oxidative stress plays a key role in the development of Type 2 Diabetes (T2D). This cross-sectional study examined the relationship among serum levels of manganese superoxide dismutase (MnSOD), 8-hydroxy-2’-deoxyguanosine (8OHdG), dietary antioxidant intakes and glycemic control in African Americans (n=209) and Haitian Americans (n=234) with and without T2D. ^ African Americans had higher BMI (32.8 vs. 29.3 kg/m2), higher energy intake (2148 vs. 1770 kcal), and were more educated as compared to Haitian Americans; all variables were significant at p < .001. Serum levels of 8OHdG and MnSOD for African Americans (1691.0 ± 225.1 pg/ml, 2538.0 ± 1091.8 pg/ml; respectively) were significantly higher than for Haitian Americans (1626.2 ± 222.9, 2015.8 ± 656.3 pg/ml; respectively). 8OHdG was negatively correlated with MnSOD ( r = -.167, p < .001) in T2D. Having T2D was negatively correlated with MnSOD (r = -.337; p < .01) and positively correlated with 8OHdG (r = .500; p < .01). African Americans and Haitian Americans with T2D had fasting plasma glucose (FPG) levels of 143.0 ± 61.0 mg/dl and 157.6 ± 65.5 mg/dl, and A1C of 7.5 ± 1.8 % and 8.4 ± 2.4 %, respectively. African Americans and Haitian Americans without T2D had FPG levels of 95.8 ± 13.2 mg/dl and 98.7 ± 16.9 mg/dl, and A1C of 5.9 ± 0.4% and 6.0 ± 0.5%, respectively. Dietary intakes of vitamin C and vitamin D were negatively correlated with FPG (r = -.21; r = -.19, p < .05) respectively. Carotenoids negatively correlated with A1C (r = -.19, p < .05). Lower levels of MnSOD were associated with lower levels of zinc, r = .10, p < .05, and higher levels of carotenoids r = -.10, p < .05. Higher levels of 8OHdG were associated with lower levels of Vitamin D, r = -.14, p < .01, and carotenoids, r = -.09, p < .05. ^ The results demonstrate greater oxidative mtDNA damage in persons with T2D compared to those without T2D and in African Americans compared with Haitian Americans. The inverse relationship between dietary intake of antioxidants and oxidative stress implies a potential to reduce oxidative stress with diet. ^