We present an electric field modulated absorption spectroscopy (Stark effect) study of isolated photosystem II reaction center complexes, including a preparation in which the inactive pheophytin H(B) was exchanged for 13(1)-deoxo-13(1)-hydroxy-pheophytin. The results reveal that the Stark spectrum of the Q(x) and Q(y) transitions of the pheophytins has a second-derivative line shape, indicating...

In photosynthesis absorbed sun light produces collective excitations (excitons) that form a coherent superposition of electronic and vibrational states of the individual pigments. Two-dimensional (2D) electronic spectroscopy allows a visualization of how these coherences are involved in the primary processes of energy and charge transfer. Based on quantitative modeling we identify the exciton-v...

An electrochemical study using transient techniques of a quinone-type natural product, horminone, has been performed in acetonitrile in the presence of two buffer solutions of pH = 17.2 and pH = 15.5. Using linear sweep voltammetry, it was found that at both pH values the reduction mechanism of horminone involves a monoelectronic charge-transfer step, followed by a protonation step and homogene...

We report abnormal magnetic field effects on electrogenerated chemiluminescence (MFEECL) based on triplet emission from the Ru(bpy)3Cl2-TPrA electrochemical system: the appearance of MFEECL after magnetic field ceases. In early studies the normal MFEECL have been observed from electrochemical systems during the application of magnetic field. Here, the abnormal MFEECL suggest that the activated ...

The chemistry of disulfide exchange in biological systems is well studied. However, the detailed mechanism of how oxidizing equivalents are derived to form disulfide bonds in proteins is not clear. In prokaryotic organisms, it is known that DsbB delivers oxidizing equivalents through DsbA to secreted proteins. DsbB becomes reoxidized by reducing quinones that are part of the membrane-bound elec...

Multiply-charged peptide cations comprised of two polypeptide chains (designated A and B) bound via a disulfide linkage have been reacted with SO2-* in an electrodynamic ion trap mass spectrometer. These reactions proceed through both proton transfer (without dissociation) and electron transfer (with and without dissociation). Electron transfer reactions are shown to give rise to cleavage along...

We report a scalable process for fabricating a multiple-layer hybrid photocathode, namely Cu2O/NiO/Cu2MoS4, for H2 generation in water. In pH 5 solution and under 1 sun illumination, the photocathode showed interesting photocatalytic properties. The onset photocurrent was recorded at +0.45 V vs. RHE, while at 0 V vs. RHE, a photocurrent density of 1.25 mA cm(-2) was obtained. It was found that ...

In this paper, the effect of surface area of reaction layers in gas diffusion electrodes on oxygen reduction reaction was investigated. For this purpose, various amounts (0.1, 0.2, 0.3, 0.4, 0.5, 1, 1.5 and zero %wt of total loading of reaction layer) of single walled carbon nanotube (SWCNT) were inserted in the reaction layer. The performance of gas diffusion electrodes for oxygen reduction re...

Photosynthetic organisms convert photoenergy to chemical energy with near-unity quantum efficiency. This occurs through charge transfer in the reaction center, which consists of two branches of pigments. In bacteria, both branches are energy-transfer pathways, but only one is also an electron transfer pathway. One barrier to a full understanding of the asymmetry is that the two branches contain...