In Situ Synthesis of Photoactive Polymers on a Living Cell Surface via Bio‐Palladium Catalysis for Modulating Biological Functions

Abstract

Cell surface engineering with functional polymers is an effective strategy to modulate cell activity. Here, a bio‐palladium catalyzed polymerization strategy was developed for in situ synthesis of conjugated polymers on living cell surfaces. Through Sonagashira polymerization, photoactive polyphenyleneethynylene (PPE) is synthesized on the cell surface via cell‐generated bio‐Pd catalyst. The in situ formed PPE is identified by excellent light‐harvest capacity and blue fluorescence on the surfaces of E. coli and C. pyrenoidosa. Besides imaging microbes for tracing the polymerization process, PPE also exhibits enhanced antibacterial activity against E. coli. It can also augment the ATP synthesis of C. pyrenoidosa through enlarging the light absorption and accelerating the cyclic electron transport of the algae. With this bio‐metal catalyzed polymerization method, functional polymers can be synthesized in situ on the living cell surface.

Whole‐Cell‐Based Photosynthetic Biohybrid Systems for Energy and Environmental Applications

“…[54] Nevertheless, modification usually requires a large excess of reactive polymers owing to low conjugation efficiency of polymers to cell surface caused by exogenous repulsion. To solve this key issue, Qi et al [55] have taken a novel measure in constructing conjugated polymerbased biohybrid system, by means of in-situ polymerization strategy. Considering the cell surface generally exists multiple Pd binding sites such as carboxyl, amino and phosphate groups, [56] the cell surface of C. pyrenoidosa could be modified with photoactive polyphenyleneethynylene (PPE) via Sonagashira polymerization catalyzed by the in-situ formed surface bio-Pd catalysts.…”

“…Considering the cell surface generally exists multiple Pd binding sites such as carboxyl, amino and phosphate groups, [56] the cell surface of C. pyrenoidosa could be modified with photoactive polyphenyleneethynylene (PPE) via Sonagashira polymerization catalyzed by the in-situ formed surface bio-Pd catalysts. [55] The in-situ synthesized light-harvesting polymer PPE regulated the electron-transport pathways and led to an elevated cyclic electron transport and enhanced activity of PSI for producing more ATP (Figure 7c).…”

“…(c) In-situ synthesis of PPE on the cell surface through bio-Pd catalyzed Sonogashira polymerization and the accompanied improvement of ATP synthesis in C. pyrenoidosa. Reproduced from Ref [55]. with permission from Wiley-VCH.…”

Supramolecular Polymerization Powered by Escherichia coli : Fabricating a Near-Infrared Photothermal Antibacterial Agent in Situ

“…For bacteria, a transmembrane redox potential generated by procaryote respiration not only supports biological functions, [1,2] but also can be employed as an energy source for various artificial applications, such as bioelectrosynthesis, initiation of polymerization, and microbial fuel cells. [3][4][5][6][7][8][9][10] Notably, the reducing ability of bacteria originated from this redox potential has been applied in the in situ fabrication of biomedical materials at the place where it functions. [7,8,11] Compared with the conventional biomedical materials which are generally readily constructed and then transported to the working area, in an in situ fabrication strategy, targeting ability could be realized and the transporting process could be omitted, thus improving the specificity and adaptivity of biomedical materials.…”

“…[3][4][5][6][7][8][9][10] Notably, the reducing ability of bacteria originated from this redox potential has been applied in the in situ fabrication of biomedical materials at the place where it functions. [7,8,11] Compared with the conventional biomedical materials which are generally readily constructed and then transported to the working area, in an in situ fabrication strategy, targeting ability could be realized and the transporting process could be omitted, thus improving the specificity and adaptivity of biomedical materials. [12][13][14][15][16][17] As an integration of polymer science and supramolecular chemistry, supramolecular polymers exhibit superiority in various biomedical applications [18][19][20][21][22][23][24][25] such as drug delivery, [26][27][28][29][30] bioimaging and diagnosis, [31,32] phototherapy, [33][34][35] and tissue engineering.…”