Oriented (Local) Electric Fields Drive the Millionfold Enhancement of the H‐Abstraction Catalysis Observed for Synthetic Metalloenzyme Analogues

This contribution follows the recent remarkable catalysis observed by Groves et al. in hydrogen‐abstraction reactions by a) an oxoferryl porphyrin radical‐cation complex [Por^?+Fe^IV(O)L_ax] and b) a hydroxoiron porphyrazine ferric complex [PyPzFe^III(OH)L_ax], both of which involve positively charged substituents on the outer circumference of the respective macrocyclic ligands. These charge‐coronated complexes are analogues of the biologically important Compound I (Cpd I) and synthetic hydroxoferric species, respectively. We demonstrate that the observed enhancement of the H‐abstraction catalysis for these systems is a purely electrostatic effect, elicited by the local charges embedded on the peripheries of the respective macrocyclic ligands. Our findings provide new insights into how electrostatics can be employed to tune the catalytic activity of metalloenzymes and can thus contribute to the future design of new and highly efficient hydrogen‐abstraction catalysts.     

Substitution of aqua ligands fromcis-diaqua-bis(bipyridyl) ruthenium(II) by 1, 10-phenanthroline in aqueous medium

The kinetics of aqua ligand substitution fromcis-[Ru(bipy)₂(H₂O)₂]²⁺ by 1, 10-phenanthroline (phen) have been studied spectrophotometrically in the 35 to 50°C temperature range. We propose the following rate law for the reaction within the 3.65 to 5.5 pH range:

Surfactant chain-length-dependent modulation of the prototropic transformation of a biological photosensitizer: norharmane in anionic micelles

A photophysical study of norharmane (NHM), an efficient cancer cell photosensitizer, has been undertaken in well-characterized biomimetic micellar nanocavities formed by anionic surfactants of varying chain length, namely, sodium decyl sulfate (S10S), sodium dodecyl sulfate (S12S), and sodium tetradecyl sulfate (S14S), using steady-state and time-resolved fluorescence spectroscopy. The effect of the hydrophobic chain length on the structural dynamism of the fluorophore has been reported. Experimental results demonstrate that the equilibrium of this dynamism is sensitive to the environment. Variation in the surfactant chain length plays an important role in promoting a specific prototropic form of the probe molecule. A striking feature of the present study is that an increase in the surfactant chain length (hydrophobicity) favors the cationic species of NHM. This has been rationalized on the basis of changes in the local pH and the aggregation number of the micelles. A fluorescence quenching study of the micelle-bound probe using ionic quencher Cu2+ corroborates this.     

The reaction kinetics of NiCl2 in silica-alumina gel matrix

Insitu isothermal reduction of NiCl₂ by dextrose in silica-alumina gel matrix has been carried out between 800 and 950 °C under nitrogen atmosphere. The predominant mechanism of reaction is found to be nucleation and growth. X-ray diffraction (XRD) analyses of reacted samples confirm the presence of metallic Ni, nickel aluminate and finely dispersed alumina in the reacted samples. The average particle size of nickel has been determined by transmission electron micrograph (14 nm) as well as XRD (17±2 nm).     

Fluorescence resonance energy transfer from tryptophan in human serum albumin to a bioactive indoloquinolizine system

The interaction between a bioactive molecule, 3-acetyl-4-oxo-6,7-dihydro-12H indolo-[2,3-a] quinolizine (AODIQ), with human serum albumin (HSA) has been studied using steady-state absorption and fluorescence techniques. A 1:1 complex formation has been established and the binding constant (K) and free energy change for the process have been reported. The AODIQ-HSA complex results in fluorescence resonance energy transfer (FRET) from the tryptophan moiety of HSA to the probe. The critical energy-transfer distance (R ₀) for FRET and the Stern-Volmer constant (K _sv) for the fluorescence quenching of the donor in the presence of the acceptor have been determined. Importantly, K _SV has been shown to be equal to the binding constant itself, implying that the fluorescence quenching arises only from the FRET process. The study suggests that the donor and the acceptor are bound to the same protein at different locations but within the quenching distance.     

Relativistic Ornstein–Uhlenbeck Process

We wish to shed some light on the problem of thermodynamic irreversibility in the relativistic framework. Therefore, we propose a relativistic stochastic process based on a generalization of the usual Ornstein–Uhlenbeck process: we introduce a relativistic version of the Langevin equation with a damping term which has the correct Galilean limit. We then deduce relativistic Kramers and Fokker–Planck equations and a fluctuation-dissipation theorem is derived from them. Finally, numerical simulations are used to check the equilibrium distribution in momentum space and to investigate diffusion in physical space.     

Reaction of 2-(arylazo)pyridine complexes of type [OsX2L2] (X = Cl or Br) with heterocyclic bases (B): spectra and electrochemistry of [OsX(B)L2]ClO4·H2O

Summary The synthesis and characterization of a series of complexes of the type [OsX(B)L₂] ⁺ (X = Cl or Br, B = pyridine (py) and pyrazine (pyz), L = 2-(phenylazo)pyridine (L¹) or 2-(m-tolylazo)pyridine (L²)) is described. The cations have been isolated as crystalline perchlorate monohydrates after purification by column chromatography. The diamagnetic compounds display several spin-allowed and spin-forbidden m.l.c.t. transitions in the visible region. The metal-centred oxidations and ligand-based reductions of the complexes are studied electrochemically in MeCN. Two consecutive one-electron oxidations corresponding to Os^III/Os^II and Os^IV/Os^III couples occur at ca. 1.3 and ca. 2.3 V versus s.c.e. respectively. Four successive azo-reductions are observable in the potential range -0.4 to -2.4V.     

An investigation into flow mode transition and pressure fluctuations for fluidized dense-phase pneumatic conveying of fine powders

This paper presents the results of an ongoing investigation into the fluctuations of pressure signals due to solids-gas flows for dense-phase pneumatic conveying of fine powders.Pressure signals were obtained from pressure transducers installed along different locations of a pipeline for the fluidized dense-phase pneumatic conveying of fly ash(median particle diameter 30μm;particle density 2300kg/m~3;loosepoured bulk density 700kg/m~3) and white powder(median particle diameter 55 u.m;particle density1600kg/m~3;loose-poured bulk density 620kg/m~3) from dilute to fluidized dense-phase.Standard deviation and Shannon entropy were employed to investigate the pressure signal fluctuations.It was found that there is an increase in the values of Shannon entropy and standard deviation for both of the products along the flow direction through the straight pipe sections.However,both the Shannon entropy and standard deviation values tend to decrease after the flow through bend(s).This result could be attributed to the deceleration of particles while flowing through the bends,resulting in dampened particle fluctuation and turbulence.Lower values of Shannon entropy in the early parts of the pipeline could be due to the non-suspension nature of flow(dense-phase),i.e.,there is a higher probability that the particles are concentrated toward the bottom of pipe,compared with dilute-phase or suspension flow(high velocity),where the particles could be expected to be distributed homogenously throughout the pipe bore(as the flow is in suspension).Changes in straight-pipe pneumatic conveying characteristics along the flow direction also indicate a change in the flow regime along the flow.