STUDIES ON OLEFIN-COORDINATING TRANSITION-METAL CARBENE COMPLEXES .20. SYNTHESIS OF 1,3-CYCLOHEXADIENE(DICARBONYL) [ETHOXY(ARYL)-CARBENE]IRON COMPLEXES AND THEIR PHOSPHINE ADDUCTS - CRYSTAL-STRUCTURE OF C6H8(CO)2FEC(OC2H5)C6H4CH3-O

Reaction of 1,3-cyclohexadiene(tricarbonyl)iron (1) with ortho-substituted aryllithium reagents ArLi (Ar=o-CH3C6H4, o-CH3OC6H4, o-CF3C6H4) in ether at low temperature, and subsequent alkylation of the acylmetalates formed with Et3OBF4 in aqueous solution at 0-degrees-C or in CH2Cl2 at -60-degrees-C gave the 1,3-cyclohexadiene(dicarbonyl)[ethoxy(aryl)carbene]iron complexes (eta4-C6H8)(CO)2FeC(OC2H5)Ar (3, Ar = o-CH3C6H4; 4, Ar = o-CH3OC6H4), and the isomerized product (eta3-C6H8)(CO)2FeC(OC2H5)C6H4CF3-o (5), respectively, among which the structure of 3 has been established by an X-ray diffraction study. Complex 3 is monoclinic, space group P2(1) with a = 8.118(4), b = 7.367(4), c = 14.002(6) angstrom, beta = 104.09(3)-degrees, V = 812.2(6) angstrom3, Z = 2, D(c) = 1.39 g cm-3, R = 0.056, and R(w) = 0.062 for 976 observed reflections. Complexes 3 and 5 were converted into the chelated allyliron phosphine adducts(eta3-C6H8)(CO)2(PR31)FeC(OC2H5)Ar (6, Ar = o-CH3C6H4, R1 = Ph; 7, Ar = o-CH3C6H4, R1 = OPh; 9, Ar = o-CF3C6H4, R1 = Ph), by reaction with phosphines in petroleum ether at low temperatures.

INVESTIGATION OF MICROSTRUCTURE AT IRON TETRAPHENYLPORPHYRIN MODIFIED CLASSY CARBON ELECTRODE BY XPS

Microstructure of the glassy carbon surface modified with iron tetraphenyfporphyrin (FeTPP) by heat treatment has been studied by XPS,, DTA and TG. XPS spectra of Fe 2P_3\2 level in FeTPP and iron tetraphenylporphyriu/glassy carbon (FeTPP/GC) have shown that a bond can be formed between the glassy carbon surface and both the central metal iron ion and the macrocyclic, ligand, which loses its four phenyl groups during the beat treatment. The relationship between the surface mierostructure of FeTPP/GC and the...

Effect of iron on growth and lipid accumulation in Chlorella vulgaris

The economic feasibility of algal mass culture for biodiesel production is enhanced by the increase in biomass productivity and storage lipids. Effect of iron on growth and lipid accumulation in marine microalgae Chlorella vulgaris were investigated. In experiment I, supplementing the growth media with chelated FeCl3 in the late growth phase increased the final cell density but did not induce lipid accumulation in cells. In experiment II, cells in the late-exponential growth phase were collected by centrifugation and re-inoculated into new media supplemented with five levels of Fe3+ concentration. Total lipid content in cultures supplemented with 1.2 x 10(-5) mol L-1 FeCl3 was up to 56.6% biomass by dry weight and was 3-7-fold that in other media supplemented with lower iron concentration. Moreover, a simple and rapid method determining the lipid accumulation in C. vulgaris with spectrofluorimetry was developed. (c) 2007 Elsevier Ltd. All rights reserved.

Determination of multiple trace elements in seawater using chelation ion chromatography and ICP-MS

An off-line chelation system combined with ICP-MS technique was developed for the quantitative determination of trace elements in seawater, namely V, Co, Ni, Cu, Zn, Mo, Cd, Pb, U and rare earth elements(REEs). The system was built based on an ion chromatography equipped with MetPac((R)) CC-I chelation columns which had a strong selective chelation to these target elements within a pH range 5.2-5.6. Acidified seawater samples and NH4Ac(2 mol/L) were blended to meet suitable pH before being injected into the chelation column, thus target elements were retained while alkali and alkaline metals were excluded. Then chelated elements were eluted by HNO3 (1 mol/L) and samples were collected for ICP-MS analysis. Varying the ratio of input( gen. 200 mL) to output( gen. 5 mL), the target elements which were concentrated as 40 times as their concentrations were far beyond instrumental quantification limits. At last, a certificated seawater CASS-4 was introduced and our detected values were in good agreement with those certified values.

In vitro iron enrichment experiments in the Prydz Bay, the Southern Ocean: A test of the iron hypothesis

In "high nitrate, low chlorophyll" (HNLC) ocean regions, iron has been typically regarded as the limiting factor for phytoplankton production. This "iron hypothesis" needs to be tested in various oceanic environments to understand the role of iron in marine biological and biogeochemical processes. In this paper, three in vitro iron enrichment experiments were performed in Prydz Bay and at the Polar Front north of the Ross Sea, to study the role of iron on phytoplankton production. At the Polar Front of Ross Sea, iron addition significantly (P < 0.05, Student's t-test) stimulated phytoplankton growth. In Prydz Bay, however, both the iron treatments and the controls showed rapid phytoplankton growth, and no significant effect (P > 0.05, Student's t-test) as a consequence of iron addition was observed. These results confirmed the limiting role of iron in the Ross Sea and indicated that iron was not the primary factor limiting phytoplankton growth in Prydz Bay. Because the light environment for phytoplankton was enhanced in experimental bottles, light was assumed to be responsible for the rapid growth of phytoplankton in all treatments and to be the limiting factor controlling field phytoplankton growth in Prydz Bay. During the incubation experiments, nutrient consumption ratios also changed with the physiological status and the growth phases of phytoplankton cells. When phytoplankton growth was stimulated by iron addition, N was the first and Si was the last nutrient which absorption enhanced. The Si/N and Si/P consumption ratios of phytoplankton in the stationary and decay phases were significantly higher than those of rapidly growing phytoplankton. These findings were helpful for studies of the marine ecosystem and biogeochemistry in Prydz Bay, and were also valuable for biogeochemical studies of carbon and nutrients in various marine environments.

Oceanic iron fertilization: one of strategies for sequestration atmospheric CO2

Carbon cycle is connected with the most important environmental issue of Global Change. As one of the major carbon reservoirs, oceans play an important part in the carbon cycle. In recent years, iron seems to give us a good news that oceanic iron fertilization could stimulate biological productivity as CO2 sink of human-produced CO2. Oceanic iron fertilization experiments have verified that adding iron into high nutrient low chlorophyll (HNLC) seawaters can increase phytoplankton production and export organic carbon, and hence increase carbon sink of anthropogenic CO2, to reduce global warming. In sixty days, the export organic carbon could reach 10 000 times for adding iron by model prediction and in situ experiment, i.e. the atmospheric CO2 uptake and inorganic carbon drawdown in upper seawaters also have the same magnitude. Therefore, oceanic iron fertilization is one of the strategies for increasing carbon sink of anthropogenic CO2. The paper is focused on the iron fertilization, especially in situ ocean iron experiments in order that the future research is more efficient.

Antioxidant activity and cytoprotective effect of kappa-carrageenan oligosaccharides and their different derivatives

Antioxidant activity of kappa-carrageenan oligosaccharides (OM) and their chemical modification derivatives was investigated employing various established in vitro systems, such as reducing power, iron ion chelation, and total antioxidant activity using beta-carotene-linoleic acid system. The oversulfated (SD), lowly (LAD), and highly acetylated derivatives (HAD) in reducing power assay, the phosphorylated derivative (PD) in metal chelating assay, and oversulfated and phosphorylated derivatives in total antioxidant activity assay exhibited antioxidant activity higher than that of carrageenan oligosaccharides. The results indicated that the chemical modification of carrageenan oligosaccharides can enhance their antioxidant activity in vitro. The protective effects of the carrageenan oligosaccharides and their chemically modified derivatives against H2O2 and UVA (long-wave ultraviolet radiation) induced oxidative damage on rat thymic lymphocyte were investigated by measuring cell viability via 3-(4,5-dimethylthiazol-2yl)-2,5-diphenyltetrazolium bromide (MTT). Thymic lymphocyte exposure to H2O2 and UVA, a marked reduction in cell survival was observed, which was significantly prevented by carrageenan oligosaccharides and their derivatives (preincubated for 2 h) at 66.7-2000 mu g/mL. But both the carrageenan oligosaccharides and their different derivatives showed the similar protective effects on intracellular level. Taken together, these results suggest that carrageenan oligosaccharides and their derivatives show relevant antioxidant activity both in vitro and in a cell system. (C) 2005 Elsevier Ltd. All rights reserved.

Hydrogen ion reduction in the process of iron rusting

Since the acceptance of the electrochemical rusting mechanism, oxygen reduction has been considered the main cathodic process, while H+ reduction has been overlooked for the past four decades because oxygen can be readily renewed due to the thin layer Of Solution film formed during atmospheric corrosion. This study shows that measurable hydrogen call be detected at the surface opposite to the corroding side of the specimen during wet-dry cycles, and a clear correlation exists between the quantities of hydrogen permeated through iron sheet and weight loss. Results Suggest the intrinsic importance of H+ reduction that merits further investigation. (c) 2004 Elsevier Ltd. All rights reserved.

Effect of mechanical deformation on permeation of hydrogen in iron

Rate of hydrogen permeation was measured under static as well as dynamic mechanical deformation conditions, Cylindrical tensile test specimens were used for the study and hydrogen permeation was measured electrochemically, It was observed that the hydrogen diffusivity decreased as plastic deformation increased for the static deformation experiments while elastic deformation had no significant effect on diffusivity but increased the steady state permeation flux, For the dynamic loading experiment, an elastic deformation increased the hydrogen permeation rate almost linearly. Onset of plastic deformation led a sudden decrease of permeation rate and the reduced rate was rapidly recovered when the plastic deformation ceased. These rapid changes in the permeation rates were explained that the absorbed hydrogen was trapped by dislocations and creation rate and density of dislocations changed drastically when plastic deformation started and stopped.

Aminic nitrogen-bearing polydentate Schiff base compounds as corrosion inhibitors for iron in acidic media: A quantum chemical calculation

Quantum chemical calculations based on DFT method were performed on three polydentate Schiff base compounds (PSCs) used as corrosion inhibitors for iron in acid media to determine the relationship between the molecular structure of PSC and inhibition efficiency. The structural parameters, such as the frontier molecular orbital energy HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital), the charge distribution of the studied inhibitors, the absolute electronegativity (chi) values, and the fraction of electrons (Delta N) transfer from inhibitors to iron, were also calculated and correlated with inhibition efficiencies. The results showed that the inhibition efficiency of PSCs increased with the increase in E-HOMO and decrease in E-LUMO-E-HOMO; and the areas containing N atoms are most possible sites for bonding the metal iron surface by donating electrons to the metal. (C) 2007 Elsevier Ltd. All rights reserved.