Effect of ionic strength on intra-protein electron transfer reactions: The case study of charge recombination within the bacterial reaction center

Abstract

It is a common believe that intra-protein electron transfer (ET) involving reactants and products that are overall electroneutral are not influenced by the ions of the surrounding solution. The results presented here show an electrostatic coupling between the ionic atmosphere surrounding a membrane protein (the reaction center (RC) from the photosynthetic bacterium Rhodobacter sphaeroides) and two very different intra-protein ET processes taking place within it. Specifically we have studied the effect of salt concentration on: i) the kinetics of the charge recombination between the reduced primary quinone acceptor QA(-) and the primary photoxidized donor P(+); ii) the thermodynamic equilibrium (QA(-)↔QB(-)) for the ET between QA(-) and the secondary quinone acceptor QB. A distinctive point of this investigation is that reactants and products are overall electroneutral. The protein electrostatics has been described adopting the lowest level of complexity sufficient to grasp the experimental phenomenology and the impact of salt on the relative free energy level of reactants and products has been evaluated according to suitable thermodynamic cycles. The ionic strength effect was found to be independent on the ion nature for P(+)QA(-) charge recombination where the leading electrostatic term was the dipole moment. In the case of the QA(-)↔QB(-) equilibrium, the relative stability of QA(-) and QB(-) was found to depend on the salt concentration in a fashion that is different for chaotropic and kosmotropic ions. In such a case both dipole moment and quadrupole moments of the RC must be considered.

Perspective on the use of nanoparticles to improve LIBS analytical performance: nanoparticle enhanced laser induced breakdown spectroscopy (NELIBS)

“…LIBS and NELIBS were then used for detecting the Li content. 25,27 An enhancement of one order of magnitude was observed for Li emission lines at 671 nm when NPs were Fig. 4 LIBS and NELIBS of glasses.…”

“…After extensive dialysis, the native functionality was restored and all the cations were removed, except Li. LIBS and NELIBS were then used for detecting the Li content [25,27]. An enhancement of one order of magnitude was observed for Li emission lines at 671 nm when NPs were deposited, thus enabling the Li content quantification with the calibration curve method.…”