Computer simulation for effect of Pr(III) on Ca(II) speciation in human interstitial fluid

A multiphase model of metal ion speciation in human interstitial fluid was constructed and the effect of Pr(III) on Ca(II) speciation was studied. Results show that free Ca2+, [Ca(HCO3)], and [Ca(Lac)] are the main species of Ca(II). Because of the competition of Pr(III) for ligands with Ca(II), the percentages of free Ca2+, [Ca(Lac)], and [Ca(His)(Thr)H-3] increase gradually and the percentages of CaHPO4(aq) and [Ca(Cit)(His)H-2] decrease gradually with the increase in the total concentration of Pr(III). However, the percentages of [Ca(HCO3)] and CaCO3(aq) first increase and then begin to decrease when the total concentration of Pr(III) exceeds 6.070 x 10(-4) M.

A mechanistic model of algal photoinhibition induced by photodamage to Photosystem-II

Photoinhibition is a central problem for the understanding of plasticity in photosynthesis vs. irradiance response. It effectively reduces the photosynthetic rate. In this contribution, we present a mechanistic model of algal photoinhibition induced by photodamage to photosystem-II. Photosystem-IIs (PSIIs) are assumed to exist in three states: open, closed and inhibited. Photosynthesis is closely associated with the transitions between the three states. The present model is defined by four parameters: effective cross section of PSII, number of PSIIs, turnover time of electron transfer chains and the ratio of rate constant of damage to that of repair of D1 proteins in PSIIs. It gives a photosynthetic response curve of phytoplankton to irradiance (PI-curve). Without photoinhibition, the PI-curve is in hyperbola with the first three parameters. The PI-curve with photoinhibition can be simplified to the same form as the hyperbola by replacing either the number of PSIIs with the number of functional PSIIs or the turnover time of electron transfer chains with the average turnover time.

The Unexpected Preference for the fac-Isomer with the Tris(5-ester-substituted-2,2′-bipyridine) Complexes of Ruthenium(II)

The synthesis of a number of new 2,2'-bipyridine ligands, functionalized with bulky ester side groups is reported (L2 - L8). Their reaction with [Ru(DMSO)4Cl2] gives rise to tris-chelate ruthenium(II) metal complexes which show an unusually high proportion of the fac-isomer, as judged by 1H NMR following conversion to the ruthenium(II) complex of 2,2'-bipyridine-5-carboxylic acid methyl ester (L1). The initial reaction appears to have thermodynamic control with the steric bulk of the ligands causing the third ligand to be labile under the reaction conditions used, giving rise to disappointing yields and allowing rearrangement to the more stable facial form. DFT studies indicate that this does not appear to be as a consequence of a metal centered electronic effect. The two isomers of [Ru(L1)3](PF6)2 were separated into the two individual forms using silica preparative plate chromatographic procedures, and the photophysical characteristics of the two forms compared. The results appear to indicate that there is no significant difference in both their room temperature electronic absorption and emission spectra or their excited state lifetimes at 77K.

Distribution of Uranium Contamination in Weathered Fractured Saprolite/Shale and Ground Water

The objective of this study was to determine how structure, stratigraphy, and weathering influence fate and transport of contaminants (particularly U) in the ground water and geologic material at the Department of Energy (DOE) Environmental Remediation Sciences Department (ERSD) Field Research Center (FRC). Several cores were collected near four former unlined adjoining waste disposal ponds. The cores were collected, described, analyzed for U, and compared with ground water geochemistry from surrounding multilevel wells. At some locations, acidic U-contaminated ground water was found to preferentially flow in small remnant fractures weathering the surrounding shale (nitric acid extractable U [UNA] usually <50 mg kg–1) into thin (