A quantum-mechanical study of charge transfer in redox catalysis: Decomposition of hydrogen peroxide on copper ammoniates and iron porphyrin

Reactions of redox type at a catalyst are initiated by transfer of a charge q, with accompanying change in the electronic structure of the reagent. It is shown that quantum chemistry provides estimates of q sufficient for many qualitative and semiquantitative purposes, provided that the interaction is one of stationary coordination, or nearly so. The semiempirical approximation in the MO LCAO method is used with self-consistent charges in calculations for the decomposition of H₂O₂ on copper ammoniates. The results indicate indirectly that the reaction has a radical mechanism (q 1 e in stationary coordination). An approximate analytic formula for q is derived for a catalyst containing a large conjugated system (chelate or enzyme), in which a major part is played by the redox (catalytic) capacity of the system, which is defined as the derivative of the charge with respect to the Fermi level and which is easily calculated or determined empirically. This concept explains the high catalytic activity of such systems in redox processes. Detailed calculations are presented for the decomposition of H₂O₂ on iron porphyrin.     

Assessment of a Plantibody HB-01 Purification Strategy at Different Scales

Transgenic plant investigations focus on fine-regulation of the recombinant protein expression and purification strategies. In this article, preliminary experiments were done at analytical-scale to decide the best plantibody HB-01 purification strategy. Once it was assumed, the purification efficiency was assessed at different scales (10–600 kg of biomass). The plantibody purity measured by SDS-PAGE and LC-GF was over 90%, yielding 9.9 ± 6.2–18.6 ± 0.9 mg plantibody kg⁻¹ of biomass and 39.9 ± 7.9–48.7 ± 2.1% of recovery. Significant differences were not observed among these parameters at these scales. Plant DNA contents were <3.3 ng mg⁻¹ of plantibody, which is considered very low for the plantibody HB-01 application in the hepatitis B vaccine production.

     

Spatial trends of petroleum hydrocarbons in water and sediments

Seasonal changes in petroleum hydrocarbons in water and streambed sediment from selected oil-related areas of Ondo State, Nigeria have been examined using gravimetric and infrared methods. The highest and lowest total petroleum hydrocarbon concentrations (TPH) in water (sediments in brackets) gravimetrically were 3.49 mg L⁻¹ (199.3) mg kg⁻¹ and 0.003 mg L⁻¹ (81.0) mg kg⁻¹ while the concentrations found by IR were 24.0 mg L⁻¹ (135.0 mg kg⁻¹) and 14.0 mg L⁻¹ (33.0 mg kg⁻¹) respectively. The two seasons were positively correlated (α = 0.01) by both methods. The TPH level was well correlated with the sediment organic carbon (OC) during both seasons. The characteristic carbonyl (C=O) vibrations at 1650 cm⁻¹ and 1700 cm⁻¹ indicate oxidation of the oil residue. The study recommends further investigation into the type of organics present to evaluate their toxicity and appropriate remediation.      

Single molecule studies of calix[4]arene-linked perylene bisimide dimers: relationship between blinking, lifetime and/or spectral fluctuations

We recorded fluorescence time traces, and simultaneously either the fluorescence lifetime or the emission spectra from single perylene bisimide (PBI) dimers embedded in a polystyrene matrix. In these traces three distinct intensity levels can be distinguished, which reflect the photo-induced radicalisation of one of the perylene subunits. Differences in the energy transfer rate between the neutral PBI and the reversibly formed radical anion give rise to variations in the chronological order of the appearance of the intensity levels, which allowed us to categorise the time traces into three distinct groups: Type 1 blinking corresponds to a high energy transfer rate, type 2 blinking to fluctuations between large and small transfer rates (dynamic quenching), and type 3 blinking results from small energy transfer rates together with Coulomb blockade. The information that we obtain from the distributions of the fluorescence lifetimes at the various signal levels allows us to relate these differences to properties of the local polymer environment of the dimers.     

Pseudo Jahn-Teller origin of perovskite multiferroics, magnetic-ferroelectric crossover, and magnetoelectric effects: the d0-d10 problem

The conditions of multiferroicity in d(n) perovskites are derived from the pseudo Jahn-Teller effect, due to which ferroelectric displacements are triggered by vibronic coupling between ground and excited electronic states of opposite parity but same spin multiplicity; it takes place for some specific d(n) configurations and spin states only. In combination with the high-spin-low-spin crossover effect this leads to a novel phenomenon, the magnetic-ferroelectric (multiferroics) crossover which predicts magnetoelectric effects with exciting functionalities including electric magnetization and demagnetization.     

Vibronic effects and exchange interaction in dinuclear clusters

A study was made on exchange in dinuclear clusters, which contain centers having degenerate or pseudodegenerate states. The semiclassical approximation was used to examine the temperature dependence of the exchange parameters arising from the vibronic coupling.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 24, No. 6, pp. 641–647, November–December, 1988.