A recent experiment has probed the electron transfer kinetics in the early stage of photosynthesis in Rhodobacter sphaeroides for the reaction center of wild type and different mutants [Science 316, 747 (2007)]. By monitoring the changes in the transient absorption of the donor-acceptor pair at 280 and 930 nm, both of which show non-exponential temporal decay, the experiment has provided a strong evidence that the initial electron transfer kinetics is modulated by the dynamics of protein backbone. In this work, we present a model where the electron transfer kinetics of the donor-acceptor pair is described along the reaction coordinate associated with the distance fluctuations in a protein backbone. The stochastic evolution of the reaction coordinate is described in terms of a non-Markovian generalized Langevin equation with a memory kernel and Gaussian colored noise, both of which are completely described in terms of the microscopics of the protein normal modes. This model provides excellent fits to the transient absorption signals at 280 and 930 nm associated with protein distance fluctuations and protein dynamics modulated electron transfer reaction, respectively. In contrast to previous models, the present work explains the microscopic origins of the non-exponential decay of the transient absorption curve at 280 nm in terms of multiple time scales of relaxation of the protein normal modes. Dynamic disorder in the reaction pathway due to protein conformational fluctuations which occur on time scales slower than or comparable to the electron transfer kinetics explains the microscopic origin of the non-exponential nature of the transient absorption decay at 930 nm. The theoretical estimates for the relative driving force for five different mutants are in close agreement with the experimental estimates obtained using electrochemical measurements.
In a long 130 years of its journey in service to mankind, the power transformer has grown in many aspects; ratings, performance, technology, aesthetics and ecofriendliness. Today, the transformer industry is witnessing the era of shifting from petroleum based mineral oils that are depleting, environmentally unfavorable, and proven dangerous to natural esters (vegetable oil based) that are renewable, environmentally friendly, and non-hazardous. The market and regulatory pressures to reduce liability risk exposure of mineral-oil-filled distribution and power transformers are increasing. In addition, there are demands to improve equipment efficiency and adopt more "earth-friendly" options in our power systems. In the last two decades there has been a resurgence of usage of natural ester insulating liquids for their "GREEN" and Safety credentials. These renewable resources have good dielectric properties and are compatible for use in power transformers. This paper evaluates and relates the new natural ester oil with existing mineral oil technology in terms of environmental concern, fire safety, physio-chemical properties, thermal performance, and dielectric performance. It also covers key modifications in design, manufacturing and operation to help assure excellent functionality and long life. In brief, this paper provides transformer designers and users about the advantages and challenges of "Green Insulating Liquid". Due to the voluminous properties that are compared and discussed, this paper is presented in two parts: Part 1 discusses on key properties and standards for the two liquids. Part 2 emphasizes on additional key properties and material compatibility related to electrical design. Based on evidence discussed in both parts, it is concluded that natural esters are acceptable for both new transformers and for retro filling existing units.
Light scattering and viscometric measurements on weak polyelectrolytes show two important aspects of counterion condensation, namely, non-monotonic variation in the polyelectrolyte size with the increase in the electrostatic strength, and, monovalent counterion selectivity in determining the nature of collapse transition at high electrostatic strengths. Here, we present a self-consistent variational theory for weak polyelectrolytes which includes the effects of the polarizability of monovalent counterions. Our theory reproduces several experimental findings including non-monotonic conformational size with the variation in the electrostatic strength and a shift from a continuous to a discontinuous collapse transition with the increase in the dipole strength of condensed ions. At low dipole strength and high electrostatic strength, our theory predicts a series of solvent quality driven size transitions spanning the re-entrant poor, theta and good solvent regimes. At high dipole strength, the size remains that of a compact globule independent of solvent quality. The dipole strength of the ion-pair formed due to counterion condensation, which depends on the size and polarizability of the monovalent counterions, is found to be an important molecular parameter in determining the nature of collapse transition, and the size of the collapsed state at high electrostatic strength.
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