Conjugated Molecules Based Multi-Component Artificial Photosynthesis System for Producing Multi-Objective Products.

The development of artificial photosynthesis systems that mimics natural photosynthesis can help address the issue of energy scarcity by efficiently utilizing solar energy. Here, it presents liposomes-based artificial photosynthetic nanocapsules (PSNC) integrating photocatalytic, chemical catalytic, and biocatalytic systems through one-pot method. The PSNC contains 5,10,15,20-tetra(4-pyridyl) cobalt-porphyrin, tridipyridyl-ruthenium nitrate, oligo-pphenyl-ethylene-rhodium complex, and creatine kinase, efficiently generating oxygen, nicotinamide adenine dinucleotide (NADH), and adenosine triphosphate with remarkable enhancements of 231%, 30%, and 86%, compared with that of molecules mixing in aqueous solution. Additionally, the versatile PSNC enables simulation of light-independent reactions, achieving a controllable output of various target products. The regenerated NADH within PSNC further facilitates alcohol dehydrogenase, yielding methanol with a notable efficiency improvement of 37%. This work introduces a promising platform for sustainable solar energy conversion and the simultaneous synthesis of multiple valuable products in an ingenious and straightforward way.

Increased Nitrogenase Activity in Solar-Driven Biohybrids Containing Non-photosynthetic Bacteria and Conducting Polymers.

A conductive polymer-based photosynthetic biohybrid is constructed to enhance biological nitrogen fixation by increasing nitrogenase activity in the non-photosynthetic bacterium Azotobacter Chroococcum (A. Chroococcum). The light-harvesting cationic poly(fluorene-alt-phenylene) (PFP) electrostatically binds to the surface of the bacteria and possesses satisfactory conductivity to facilitate electron transfer to the bacterium, promoting the nitrogen fixation pathway through redox proteins on the surface of the bacteria when under illumination. Therefore, the nitrogenase activity, hydrogen, NH4 + -N and L-amino acids production are increased by 260 %, 37 %, 44 %, and 47 %, respectively. The expression levels of nifD and nifK encoding molybdenum-iron (MoFe) protein and relevant nitrogen-fixing proteins are up-regulated. These photoactive conductive polymer-bacteria biohybrids provide a new method for improving the biological nitrogen fixation capability of non-photosynthetic nitrogen-fixing bacteria.

9,9'-Bifluorenylidene-Core Perylene Diimide Acceptors for As-Cast Non-Fullerene Organic Solar Cells: The Isomeric Effect on Optoelectronic Properties.

Two different non-fullerene small-molecule acceptors, m-PIB and p-PIB, based on 9,9'-bifluorenylidene (BF) and perylene diimide (PDI) were designed and synthesized. Four ß-substituted PDIs were linked to BF in different positions. Based on DFT analysis, derivative p-PIB exhibited reduced intramolecular twisting between the PDI moieties, more delocalized wave function, and sufficiently wider π-electron delocalization than that of m-PIB. The absorption ability of p-PIB was enhanced due to increased intermolecular interactions. By blending p-PIB with poly{4,8-bis[5-(2ethylhexyl)thiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene-co-3-fluorothieno[3,4-b]-thiophene-2-carboxylate} (PTB7-Th), organic solar cells (OSCs) based on p-PIB obtained a maximum power conversion efficiency of 5.95 % without any treatments. Due to the improved and balanced hole and electron mobilities, the short-circuit current and fill factor of OSCs based on PTB7-Th and p-PIB were significantly increased. The AFM and TEM results revealed that the PTB7-Th:p-PIB film had favorable nanoscale phase separation and formed a bicontinuous interpenetrating network.

Photosynthetic Polymer Dots-Bacteria Biohybrid System Based on Transmembrane Electron Transport for Fixing CO2 into Poly-3-hydroxybutyrate.

Organic semiconductor-microbial photosynthetic biohybrid systems show great potential in light-driven biosynthesis. In such a system, an organic semiconductor is used to harvest solar energy and generate electrons, which can be further transported to microorganisms with a wide range of metabolic pathways for final biosynthesis. However, the lack of direct electron transport proteins in existing microorganisms hinders the hybrid system of photosynthesis. In this work, we have designed a photosynthetic biohybrid system based on transmembrane electron transport that can effectively deliver the electrons from organic semiconductor across the cell wall to the microbe. Biocompatible organic semiconductor polymer dots (Pdots) are used as photosensitizers to construct a ternary synergistic biochemical factory in collaboration with Ralstonia eutropha H16 (RH16) and electron shuttle neutral red (NR). Photogenerated electrons from Pdots promote the proportion of nicotinamide adenine dinucleotide phosphate (NADPH) through NR, driving the Calvin cycle of RH16 to convert CO2 into poly-3-hydroxybutyrate (PHB), with a yield of 21.3 ± 3.78 mg/L, almost 3 times higher than that of original RH16. This work provides a concept of an integrated photoactive biological factory based on organic semiconductor polymer dots/bacteria for valuable chemical production only using solar energy as the energy input.

Solar-powered multi-organism symbiont mimic system for beyond natural synthesis of polypeptides from CO2 and N2.

Developing artificial symbionts beyond natural synthesis limitations would bring revolutionary contributions to agriculture, medicine, environment, etc. Here, we initiated a solar-driven multi-organism symbiont, which was assembled by the CO2 fixation module of Synechocystis sp., N2 fixation module of Rhodopseudomonas palustris, biofunctional polypeptides synthesis module of Bacillus licheniformis, and the electron transfer module of conductive cationic poly(fluorene-co-phenylene) derivative. The modular design broke the pathway to synthesize γ-polyglutamic acid (γ-PGA) using CO2 and N2, attributing to the artificially constructed direct interspecific substance and electron transfer. So, the intracellular ATP and NADPH were enhanced by 69 and 30%, respectively, and the produced γ-PGA was enhanced by 104%. The strategy was further extended to produce a commercial antibiotic of bacitracin A. These achievements improve the selectivity and yield of functional polypeptides with one click by CO2 and N2, and also provide an innovative strategy for creating photosynthetic systems on demand.

Solar-Driven Producing of Value-Added Chemicals with Organic Semiconductor-Bacteria Biohybrid System.

Photosynthetic biohybrid systems exhibit promising performance in biosynthesis; however, these systems can only produce a single metabolite and cannot further transform carbon sources into highly valuable chemical production. Herein, a photosynthetic biohybrid system integrating biological and chemical cascade synthesis was developed for solar-driven conversion of glucose to value-added chemicals. A new ternary cooperative biohybrid system, namely bacterial factory, was constructed by self-assembling of enzyme-modified light-harvesting donor-acceptor conjugated polymer nanoparticles (D-A CPNs) and genetically engineered Escherichia coli (E. coli). The D-A CPNs coating on E. coli could effectively generate electrons under light irradiation, which were transferred into E. coli to promote the 37% increment of threonine production by increasing the ratio of nicotinamide adenine dinucleotide phosphate (NADPH). Subsequently, the metabolized threonine was catalyzed by threonine deaminase covalently linking with D-A CPNs to obtain 2-oxobutyrate, which is an important precursor of drugs and chemicals. The 2-oxobutyrate yield under light irradiation is increased by 58% in comparison to that in dark. This work provides a new organic semiconductor-microorganism photosynthetic biohybrid system for biological and chemical cascade synthesis of highly valuable chemicals by taking advantage of renewable carbon sources and solar energy.

Bacteria-Mediated Intracellular Click Reaction for Drug Enrichment and Selective Apoptosis of Drug-Resistant Tumor Cells.

Functionalized biocarriers that can perform bio-orthogonal reactions in tumor cells may provide solutions to overcome the efflux of the chemotherapeutic agent from drug-resistant tumor cells. Herein, we report the enrichment of therapeutic drugs in tumor cells through intracellular click reaction with functionalized bacteria. Specifically, an intracellular bioactive drug enrichment template (OPV@Escherichia coli) is constructed by combining positively charged oligo(phenylene-vinylene)-alkyne (OPV-C≡CH) with E. coli via electrostatic interaction. After the cell uptake of OPV@E. coli and Cu(II)-based complex, Cu(I) generated in situ can catalyze the bio-orthogonal click reaction to covalently anchor the azide-bearing molecules of cyanine 5 (Cy5-N3) and paclitaxel (PTX-N3) on OPV@E. coli. These molecules and their functions were retained and enriched inside the drug-resistant tumor cells A549T, which can label cells with fluorescent probes and selectively induce the apoptosis of drug-resistant tumor cells.

Integrating molecular rigidity and chirality into thermally activated delayed fluorescence emitters for highly efficient sky-blue and orange circularly polarized electroluminescence.

By integrating high molecular rigidity and stable chirality, two pairs of D*-A type circularly polarized thermally activated delayed fluorescence (CP-TADF) emitters with an almost absolute quasi-equatorial conformer geometry and excellent photoluminescence quantum efficiencies (PLQYs) are developed, achieving state-of-the-art electroluminescence performance among blue and orange circularly polarized organic light-emitting diodes (CP-OLEDs).