Chlorosomes are the largest and most efficient light-harvesting antennae found in nature, and they are constructed from hundreds of thousands of self-assembled bacteriochlorophyll (BChl) c, d, or e pigments. Because they form very large and compositionally heterogeneous organelles, they had been the only photosynthetic antenna system for which no detailed structural information was available. In our approach, the structure of a member of the chlorosome class was determined and compared with the wild type (WT) to resolve how the biological light-harvesting function of the chlorosome is established. By constructing a triple mutant, the heterogeneous BChl c pigment composition of chlorosomes of the green sulfur bacteria Chlorobaculum tepidum was simplified to nearly homogeneous BChl d. Computational integration of two different bioimaging techniques, solid-state NMR and cryoEM, revealed an undescribed syn-anti stacking mode and showed how ligated BChl c and d self-assemble into coaxial cylinders to form tubular-shaped elements. A close packing of BChls via pi-pi stacking and helical H-bonding networks present in both the mutant and in the WT forms the basis for ultrafast, long-distance transmission of excitation energy. The structural framework is robust and can accommodate extensive chemical heterogeneity in the BChl side chains for adaptive optimization of the light-harvesting functionality in low-light environments. In addition, syn-anti BChl stacks form sheets that allow for strong exciton overlap in two dimensions enabling triplet exciton formation for efficient photoprotection.
We perform a thorough comparative investigation of the excitation energies of the anionic and neutral forms of the green fluorescent protein (GFP) chromophore in the gas phase using a variety of first-principle theoretical approaches commonly used to access excited state properties of photoactive molecules. These include time-dependent density functional theory (TDDFT), complete-active-space second-order perturbation theory (CASPT2), equation-of-motion coupled cluster (EOM-CC), and quantum Monte Carlo (QMC) methods. We find that all approaches give roughly the same vertical excitation for the anionic form, while TDDFT predicts an excitation for the neutral chromophore significantly lower than the highly correlated methods. Our findings support the picture emerging from the extrapolation of the Kamlet-Taft fit of absorption experimental data in solution and indicate that the protein gives rise to a considerable bathochromic shift with respect to vacuum. These results also open some questions on the interpretation of photodestruction spectroscopy experiments in the gas phase as well as on the accuracy of previous theoretical calculations in the more complex protein environment.
We present an extensive investigation of the vertical excitations of the anionic and neutral forms of wild-type green fluorescent protein using time-dependent density functional theory (TDDFT), multiconfigurational perturbation theory (CASPT2), and quantum Monte Carlo (QMC) methods within a quantum mechanics/molecular mechanics (QM/MM) scheme. The protein models are constructed via room-temperature QM/MM molecular dynamics simulations based on DFT and are representative of an average configuration of the chromophore-protein complex. We thoroughly verify the reliability of our structures through simulations with an extended QM region, different nonpolarizable force fields, as well as partial reoptimization with the CASPT2 approach. When computing the excitations, we find that wave function as well as density functional theory methods with long-range corrected functionals agree in the gas phase with the extrapolation of solution experiments but fail in reproducing the bathochromic shift in the protein, which should be particularly significant in the neutral case. In particular, while all methods correctly predict a shift in the absorption between the anionic and neutral forms of the protein, the location of the theoretical absorption maxima is significantly blue-shifted and too close to the gas-phase values. These results point to either an intrinsic limitation of nonpolarizable force-field embedding in the computation of the excitations or to the need to explore alternative protonation states of amino acids in the close vicinity of the chomophore.
Density functional theory has been used to investigate the nature of the oxidizing agent in the Fenton reaction. Starting from the primary intermediate [FeII(H2O)5H2O2]2+, we show that the oxygen-oxygen bond breaking mechanism has a small activation energy and could therefore demonstrate the catalytic effect of the metal complex. The O-O bond cleavage of the coordinated H2O2, however, does not lead to a free hydroxyl radical. Instead, the leaving hydroxyl radical abstracts a hydrogen from an adjacent coordinated water leading to the formation of a second Fe-OH bond and of a water molecule. Along this reaction path the primary intermediate transforms into the [FeIV(H2O)4(OH)2]2+ complex and in a second step into a more stable high valent ferryl-oxo complex [FeIV(H2O)5O]2+. We show that the energy profile along the reaction path is strongly affected by the presence of an extra water molecule located near the iron complex. The alternative intermediate [FeII(H2O)4(OOH-)(H3O+)]2+ suggested in the literature has been also investigated, but it is found to be unstable against the primary intermediate. Our results support a picture in which an FeIV-oxo complex is the most likely candidate as the active intermediate in the Fenton reaction, as indeed first proposed by Bray and Gorin already in 1932.
Nanoporous graphene and related atomically thin layered materials are promising candidates in reverse electrodialysis research owing to their remarkable ionic conductivity and high permselectivity. The synthesis of atomically thin nanoporous membranes with a narrow pore size distribution, however, remains challenging. Here, we report the fabrication of nanoporous carbon membranes via the thermal crosslinking of core-rim structured monomers, that is, polycyclic aromatic hydrocarbons. The mechanically robust, centimetre-sized membrane has a pore size of 3.6 ± 1.8 nm and a thickness of 2.0 ± 0.5 nm. When applied to reverse electrodialysis, the nanoporous carbon membrane offers a high short-circuit current with an output power density of 67 W m −2 , which is about two orders of magnitude beyond that of the classic ion-exchange membranes and current prototype nanoporous membranes reported in the literature. Crosslinked and atomically thin porous polycyclic aromatic hydrocarbon membranes therefore represent new scaffolds that will revolutionize the rapidly developing fields of sustainable energy and membrane technology.
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