DNA Lipoplex‐Based Light‐Harvesting Antennae

Abstract

Natural light‐harvesting complexes are operated through the well‐designed self‐assembly of pigments with large protein complexes in a thylakoid lipid bilayer. However, a long‐range, directed transfer of excitation energy has not been achieved in artificial systems because the nanoscale arrangement of chromophores into stable micrometer‐scale structures is highly challenging. Here the multiscale assembly of chromophores for excited energy transfer through the arrangement of chromophores on nanoscale DNA templates followed by their incorporation into larger multilamellar lipid structures is reported. Single‐strand 10 nucleotide DNA molecules containing a terminal residue linked with three different chromophores are hybridized with their complementary 30 nucleotide matrix DNA strand. Due to the short DNA sequences, the energy transfer of the DNA‐templated chromophore arrays is limited at 4 °C. However, the incorporation of DNA‐templated chromophores into lipid‐DNA complexes dramatically increases both of the efficiencies and antenna effects of the single and two‐step energy transfers at room temperature through the structural stabilization and the secondary assembly of DNA between the interstitial spaces of multilamellar lipid structures. The findings suggest that the supramolecular alignment of DNA‐templated chromophores, which has never been explored previously, can be a very promising route toward directed, long‐range light harvesting.

Highly Robust Multilamellar Lipid Vesicles Generated through Intervesicular Self-assembly Mediated by Hydrolyzed Collagen Peptides

“…Recently, we reported that some oppositely charged globular proteins can induce the structural changes of pre-formed charged lipid nanovesicles into multilamellar structures through polyionic interaction under certain conditions [18,19]. Our approach is similar to nucleic acid-lipid ionic complexation, where negatively charged nucleic acids are intercalated into the interstitial space of cationic lipid vesicles to generate closely packed arrays through spontaneous phase conversion [20][21][22]. However, protein-lipid complexation is technically more challenging as the precise control of the intermolecular interaction between proteins and the lipid membranes of nanovesicles is complicated because of the low and heterogeneous surface charge density of proteins.…”

DNA-organized artificial LHCs – testing the limits of chromophore segmentation

“…[13][14][15][16][17][18][19][20][21][22] In such systems, light is collected by precisely arranged donor chromophores and the absorbed energy is transferred to a suitable acceptor. [23][24][25][26][27][28][29][30] The light-harvesting properties resulting from the supramolecular assembly of phenanthrene and pyrene molecules within the scaffold of the DNA duplexes was demonstrated before. 17 In this type of LHC, the phenanthrene units serve as donor chromophores.…”

Nanostructured Semiconductor Photoelectrodes Complexed with Natural Photosystems I and II for Bias-Free Tandem Biophotovoltaics

“…Accordingly, biomimetic approaches have been attempted using natural photosystems as an efficient light-harvesting model to develop photoelectronic and photochemical materials. , The synthesis and supramolecular self-assembly of pigments have been extensively reported using graft copolymers, dendrimers, and biological macromolecules (e.g., DNA, peptides, proteins, viruses, and lipid vesicles) as templates that guide the organization of pigments on the nanoscale. − However, it is very challenging and time-consuming to fabricate such sophisticated supramolecules for efficient energy transfer, as found in natural light-harvesting antennae, in a reasonable yield.…”