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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Nanocomposite liposomes are relatively stable in weak basic solutions but effectively release porphyrins at acidic pH, as indicated by the difference in fluorescence.
Cobalt-mimochrome VI*a (CoMC6*a), a synthetic mini-enzyme with a cobalt porphyrin active site, is developed as a biomolecular catalyst for electrocatalytic CO 2 reduction in water. The catalytic turnover number reaches ∼14 000 for CO production with a selectivity of 86 : 5 over H 2 production under the same conditions. Varying the applied potential and the p K a of the proton donor was used to gain insight into the basis for selectivity. The protected active site of CoMC6*a is proposed to enhance selectivity for CO 2 reduction under conditions that typically favor H 2 production by related catalysts. CoMC6*a activity and selectivity change only marginally under air, indicating excellent oxygen tolerance.
Charge transfer rate constants were calculated for the carotenoid-porphyrin-C 60 (CPC 60 ) molecular triad dissolved in explicit tetrahydrofuran. The calculation was based on mapping the all-atom anharmonic Hamiltonian of this system onto the spin-boson Hamiltonian. The mapping was based on discretizing the spectral density from the time correlation function of the donor–acceptor potential energy gap, as obtained from all-atom molecular dynamics simulations. Different spin-boson Hamiltonians were constructed for each of the possible transitions between the three excited electronic states in two different triad conformations. The rate constants of three possible transitions were calculated via the quantum-mechanically exact Fermi’s golden rule (FGR), as well as a progression of more approximate expressions that lead to the classical Marcus expression. The advantage of the spin-boson approach is that once the mapping is established, the quantum-mechanically exact FGR and the hierarchy of approximations are known in closed form. The classical Marcus charge transfer rate constants obtained with the spin-boson Hamiltonians were found to reproduce those obtained from all-atom simulations with the linearized semiclassical approximation, thereby confirming the equivalence of the two approaches for this system. Furthermore, within the spin-boson Hamiltonian, we also found that the quantum-mechanically exact FGR rate constants were significantly enhanced compared to the classical Marcus theory rate constants for two out of three transitions in one of the two conformations under consideration. The results confirm that mapping to the spin-boson model can yield accurate predictions for charge transfer rate constants in a system as complex as CPC 60 dissolved in tetrahydrofuran.
Significance Electronic waste, also called e-waste, is rapidly becoming a major industrial hazard because of the increased use of circuits and screens. With the right technology, however, this waste could become a sustainable source for precious metals. Such a solution requires selectivity toward the precious metals, as this characteristic is even more important than capacity. A porphyrin-based porous polymer with selective binding shows remarkable selectivity and a reductive mechanism, a combination which makes for record-high recycling of precious metals––particularly gold––from e-waste.
High-valent Fe IV =O species are common intermediates in biological and artificial catalysts. Heme and nonheme S=1 Fe IV =O sites have been synthesized and studied for decades but little quantitative experimental comparison of their electronic structures has been available, due to the lack of direct methods focused on the iron. This study allows a rigorous determination of the electronic structure of a nonheme Fe IV =O center and its comparison to an Fe IV =O heme site using 1s2p resonant inelastic X-ray scattering (RIXS) and Fe L-edge X-ray absorption spectroscopy (XAS). Further, variable temperature magnetic circular dichroism (VT-MCD) of the ligand field transitions, combined with nuclear resonance vibrational spectroscopy of the two S=1 Fe IV =O systems show that the equatorial ligand field decreases from a nonheme to a heme Fe IV =O site. Alternatively, RIXS and Fe L-edge XAS combined with MCD show that the Fe dπ orbitals are unperturbed in the Fe IV =O heme relative to the nonheme site because the strong axial Fe-O bond uncouples the Fe dπ orbitals from the porphyrin π-system. As a consequence, the thermodynamics and kinetics of the H-atom abstraction reactions are actually very similar for heme compound II and nonheme Fe IV =O active sites.
As part of a program to develop the fundamental science of synthetic bacteriochlorins — analogues of Nature’s light-harvesting pigments in anoxygenic photosynthesis — 11 synthetic free base bacteriochlorins have been examined by single-crystal X-ray diffraction analysis. In each bacteriochlorin, each pyrroline ring contains a gem-dimethyl group to block adventitious (aerobic) dehydrogenation. The structural features of the bacteriochlorins (tetrahydroporphyrins) are compared with the less saturated counterparts, chlorins (dihydroporphyrins) and porphyrins. Only slight structural perturbation accrues due to the presence of the gem-dimethyl groups. Furthermore, the results presented herein may aid in understanding metal chelation processes and underpin the development of functional solid-state molecular assemblies.
Abstract It remains unclear how the collective strong coupling of cavity-confined photons to the electronic transitions of molecular chromophore leverages the distinct properties of the polaritonic constituents for future technologies. In this study, we design, fabricate, and characterize multiple types of Fabry-Pérot (FP) mirco-resonators containing copper(II) tetraphenyl porphyrin (CuTPP) to show how cavity polariton formation affects radiative relaxation processes in the presence of substantial non-Condon vibronic coupling between two of this molecule’s excited electronic states. Unlike the prototypical enhancement of Q state radiative relaxation of CuTPP in a FP resonator incapable of forming polaritons, we find the light emission processes in multimode cavity polariton samples become enhanced for cavity-exciton energy differences near those of vibrations known to mediate non-Condon vibronic coupling. We propose the value of this detuning is consistent with radiative relaxation of Herzberg-Teller polaritons into collective molecular states coupled to the cavity photon coherently. We contrast the feature stemming from light emission from the HT polariton state with those that occur due to polariton-enhanced light absorption. Our results demonstrate the landscape of molecular and photonic interactions enabled by cavity polariton formation using complex chromophores and how researchers can design resonators to leverage these interactions to characterize and control polaritonic properties.
Meteorites pigments identification as porphyrins for extraterrestrial life evidence, noting sample analyses of Orgueil, Murray, Cold Bokkeveld and Mokoia carbonaceous chondrites
Detection and spectral examination of trace porphyrin complexes by demetallation with methanesulfonic acid and spectrofluorometry, compared to absorption spectrophotometry
Porphyrin in Fig Tree shale and Onverwacht chert from Swaziland System sediments, noting age of three billion years and importance in abiogenesis research
Apollo 11 lunar fines porphyrin-like pigments content demonstrated by fluorescence spectrometry and analytical demetallation, suggesting rocket exhaust source
Determining presence of porphyrins in Apollo 11 and 12 soil samples by fluorescence spectrometry and analytical demetallation
Porphyrins and amino acids chemical bonding under geochemically plausible conditions, considering diagenesis of biogenic compounds and life processes prebiotic chemical evolution
Porphyrin-like pigments in Apollo 12 lunar soil sample 12023, using spectral analysis involving fluorescence, absorption and magnetic circular dichroism spectrometry
Apollo 12 lunar surface fines examination noting absence of porphyrins
A variety of nitrogen compounds have been synthesized by a static Fischer-Tropsch type reaction from CO, D2 and ND3, with Ni-Fe and Al2O3 catalysts. In this reaction, the gas is heated to 500-700 C for about 0.5 hr, and then cycled through lower temperatures (100-400 C) for 1-14 days. Products were analyzed by mass spectrometry in conjunction with gas chromatography and other chromatographic techniques. Compounds produced include alkyl cyanides, pyrroles, porphyrin-like compounds, guanidines, hydantoin, uracil and its derivatives, thymine, adenine, guanine, xanthine, melamine, as well as alkanes, alkenes and aromatic hydrocarbons. Such reactions may have been involved in the production of interstellar molecules, organic compounds in meteorites, and prebiotic organic matter on planets.
An Apollo 17 surface fines sample 75081,78, collected from Station 5, was extracted and examined fluorometrically. No porphyrins were found with fluorometric methods capable of detecting 2 times 10 to the minus 14th moles/g of Ni-mesoporphyrin IX in the sample. Also aromatic hydrocarbons were undetected.
The visible and infrared spectra and thermal behavior of the bis-pyridal-magnesium-tetrabenz-porphyrin molecule proposed as the carrier of the diffuse interstellar bands were measured. Of the six band coincidences reported by Johnson (1977), only one, 4430 A, occurs in these experiments. This coincidence requires a special environment, not likely to occur in interstellar space but the infrared spectrum does not support Johnson's vibrational scheme. These spectroscopic and thermal measurements contradict the hypothesis that this molecule causes the diffuse bands.