Metalloporphyrins catalyse the photo-reduction of water to H2

McLendon, George; Miller, Deborah S.

doi:10.1039/c39800000533

Cited by 59 publications

(33 citation statements)

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“…The particular advantage of the Zn-porphyrin (ZnP) cofactor in the context of our experiments is that it is redox-inactive in its ground state but becomes a strong reductant/oxidant on UV-visible (UV-vis) excitation (45,46). ZnP-RIDC3 was prepared in high purity according to established protocols for other cytochromes (47) and displayed the expected absorption and emission features for a ZnP species (Soret maximum at 426 nm, emission maxima at 594 and 645 nm; Fig.…”

Section: +mentioning

confidence: 99%

Exceptionally stable, redox-active supramolecular protein assemblies with emergent properties

Brodin

Carr

Sontz

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

104

107

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The designed assembly of proteins into well-defined supramolecular architectures not only tests our understanding of proteinprotein interactions, but it also provides an opportunity to tailor materials with new physical and chemical properties. Previously, we described that RIDC3, a designed variant of the monomeric electron transfer protein cytochrome cb 562 , could self-assemble through Zn 2+ coordination into uniform 1D nanotubes or 2D arrays with crystalline order. Here we show that these 1D and 2D RIDC3 assemblies display very high chemical stabilities owing to their metal-mediated frameworks, maintaining their structural order in ≥90% (vol/vol) of several polar organic solvents including tetrahydrofuran (THF) and isopropanol (iPrOH). In contrast, the unassembled RIDC3 monomers denature in ∼30% THF and 50% iPrOH, indicating that metal-mediated self-assembly also leads to considerable stabilization of the individual building blocks. The 1D and 2D RIDC3 assemblies are highly thermostable as well, remaining intact at up to ∼70°C and ∼90°C, respectively. The 1D nanotubes cleanly convert into the 2D arrays on heating above 70°C, a rare example of a thermal crystalline-to-crystalline conversion in a biomolecular assembly. Finally, we demonstrate that the Zn-directed RIDC3 assemblies can be used to spatiotemporally control the templated growth of small Pt 0 nanocrystals. This emergent function is enabled by and absolutely dependent on both the supramolecular assembly of RIDC3 molecules (to form a periodically organized structural template) and their innate redox activities (to direct Pt 2+ reduction).protein self-assembly | supramolecular coordination chemistry | nanomaterials | biomaterials | inorganic nanoparticles T he enormous structural and chemical diversity of proteins makes them highly attractive building blocks for functional materials. Supramolecular protein assemblies constitute the major components of cellular machinery, and many of them [e.g., 0D ferritin (1), 1D silicatein filaments (2, 3), 2D S-layers (4)] have also found a number of applications in nano-and biotechnology (2, 4, 5). Such protein assemblies are typically highly ordered, yet they possess dynamic structures that respond to external stimuli (6). Distinctively, protein assemblies are innately functional: the individual building blocks of these assemblies often perform specific chemical functions. For instance, the monomeric components of silicatein filaments or ferritin cages each have catalytic sites that process the precursors (SiO 2 or Fe 2+ ) for the downstream biomineralization processes (1, 3). On self-assembly, these individual components can be significantly stabilized (allowing them to withstand the extracellular environment and perform their functions) (7), and their chemical function takes on an entirely different context within the supramolecular architecture (acting as the template for biomineralization in the cases of silicatein and ferritin). Thus, they display emergent properties, both structurally and functionally.Such a...

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Section: +mentioning

confidence: 99%

Exceptionally stable, redox-active supramolecular protein assemblies with emergent properties

Brodin

Carr

Sontz

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

104

107

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“…For example, a Fe-containing porphyrin cycle is responsible for the adsorption of O 2 and CO 2 in haemoglobin, while light absorption in chlorophyll takes place in a Mg-containing porphyrin cycle. Not surprisingly, porphyrins have been investigated as active molecular centres for articial photosynthesis, 1,[23][24][25] and solar cells. [26][27][28] Rosseinsky and coworkers synthesized PMOFs with Al at the metal nodes (Al-PMOF) which were found to be water-stable.…”

Section: Introductionmentioning

confidence: 99%

Porphyrin-based metal-organic frameworks for solar fuel synthesis photocatalysis: band gap tuning via iron substitutions

et al. 2017

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Photocatalysts based on metal-organic frameworks (MOFs) are very promising due to a combination of high tuneability and convenient porous structure. Introducing porphyrin units within MOFs is a potential route to engineer these natural photosynthesis molecular catalysts into artificial photosynthesis heterogeneous catalysts. Using computer simulations based on density functional theory, we explore how to modify the electronic structure of porphyrin-based MOFs to make them suitable for the photocatalysis of solar fuel synthesis via water splitting or carbon dioxide reduction. In particular, we have investigated the effect that Fe substitutions have on the electronic properties of porphyrin-based metal organic frameworks. By aligning the electron levels with a vacuum reference, we show that Fe at the porphyrin metal centre has the effect of slightly raising the position of the valence band edge, whereas Fe at the octahedral metal node has the ability to significantly lower the position of the conduction band edge on the absolute scale. Iron is therefore a very useful dopant to engineer the band structure and alignment of these MOFs. We find that the porphyrin-based structure with Al in the octahedral sites and Zn in the porphyrin centres has a band gap that is slightly too wide to take advantage of visible-light solar radiation, while the structure with Fe in the octahedral sites has bandgaps that are too narrow for water splitting photocatalysis. We then show that the optimal composition is achieved by partial substitution of Al by Fe at the octahedral sites, while keeping Zn at the porphyrin centres. Our study demonstrates that porphyrinbased MOFs can be engineered to display intrinsic photocatalytic activity in solar fuel synthesis reactions.

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“…21 Recently, Finikova et al 22 discovered that palladium complexes of meso aryl tetranaphthoporphyrins phosphoresce at room tempera ture (quantum yield ϕ = 2-3%, λ max = 900-1000 nm), their phosphorescence being very sensitive to the oxygen concentration in solution. For instance, the Stern-Volmer constant for the palladium complex of 5,10,15,20 tetra phenyltetranaphtho [2,3]porphyrin is ~20 000 Torr -1 s -1 . Compound 2 and its derivatives exhibit interesting acid base 23 and electrochemical 24 properties, which make them promising for use as sensors for small molecules and ions.…”

Section: Introductionmentioning

confidence: 99%

“…Electronic absorption spectra in pyridine: (1) zinc meso tetraphenylporphyrinate, (2) zinc meso tetraphenyltetrabenzo porphyrinate (3), and (3) zinc meso tetraphenyltetranaphtho[2,3]porphyrinate.…”

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confidence: 99%

meso-Aryltetrabenzoporphyrins. Synthesis and properties

2008

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The most considerable achievements in the synthesis and investigations of meso aryl tetrabenzoporphyrins and their metal complexes are reviewed. The choice of the route to, and the properties of, these compounds depends on the nature and number of meso aryl substituents. The reviewed synthetic methods are compared. Selected physicochemical and spectroscopic properties of meso aryltetrabenzoporphyrins are analyzed.

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Metalloporphyrins catalyse the photo-reduction of water to H2

Cited by 59 publications

References 0 publications

Exceptionally stable, redox-active supramolecular protein assemblies with emergent properties

Exceptionally stable, redox-active supramolecular protein assemblies with emergent properties

Porphyrin-based metal-organic frameworks for solar fuel synthesis photocatalysis: band gap tuning via iron substitutions

meso-Aryltetrabenzoporphyrins. Synthesis and properties

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