Radical polymerization inside living cells

Abstract

Polymerisation reactions conducted inside cells must be compatible with the complex intracellular environment, which contains numerous molecules and functional groups that could potentially prevent or quench polymerisation reactions. Here we report a strategy for directly synthesising unnatural polymers in cells through free radical photo-polymerisation using a number of biocompatible acrylic and methacrylic monomers. This offers a platform to manipulate, track and control cellular behaviour by the in cellulo generation of macromolecules that have the ability to alter cellular motility, label cells by the generation of fluorescent polymers for long-term tracking studies, as well as the generation within cells of a variety of nanostructures. It is remarkable that free radical polymerisation chemistry can take place within such complex cellular environments and this demonstration opens up a multitude of new possibilities for how chemists can modulate cellular function and behaviour and for understanding cellular behaviour in response to the generation of free radicals.

Engineering stable radicals using photochromic triggers

“…A radical formation upon photochemical triggering can then be inferred, since a radical can easily result in a significant absorption shift [1][2][3]11,12 . The absorbance ratio (A 630 nm /A 330 nm , Fig.…”

“…R adicals that can be stabilized in chemical systems have played an important role in regulating chemical reactivity and material physical properties [1][2][3] . By delocalizing spin and blocking subsequent reactions, chemists have developed several molecular structures (e.g.…”

“…To produce stable radicals by light, we need to overcome the dilemmas in chemical design between the photoproduction and the stabilization factors. There are two facts that mostly hamper the above-mentioned hypothesis: (1) unpaired electrons produced upon photoirradiation can easily suffer from ultrafast back pairing relaxation; (2) there is lack of structural characteristics to stabilize radicals in chemical systems even if they are formed. Here we note that the photochromism, as a representative photochemical behavior, which can undergo rapid and efficient photocontrol process accompanied by dramatic π-electron rearrangement to change the apparent color [18][19][20][21][22][23] , may have potential to fulfill the task.…”

Einblick: Polymere und Medizin

“…Oben links: Nutzung von Crispr-Cas für responsive Hydrogele; 1) oben rechts: Protein und spezifische Liganden bilden Proteinröhrchen; 3) unten: In-Cellulo-Polymerisation. 4) mit Auswertung und Darstellung großer Datenmengen, die entscheidend für den Erkenntnisgewinn sind.…”

Iron‐Catalysed Radical Polymerisation by Living Bacteria

“…To date there have been a number of examples of cell‐mediated polymerisations but most have required catalysts or conditions that are toxic to biology or difficult to control. These include the production of polypyrrole, increasing charge transfer from fungi…”