Complex Sequence-Defined Heteropolymers Enable Controlled Film Growth in Layer-By-Layer Assembly

Digitally-encoded poly(phosphodiesters) (d-PPDE) with highly complex primary structures are evaluated for layer-by-layer (LbL) assembly. To be easily decoded by mass spectrometry (MS), these digital polymers contain many different monomers: 2 coding units allowing binary encryption, 1 cleavable spacer allowing controlled MS fragmentation, and 3 mass tags allowing fragment identification. These complex heteropolymers are therefore composed of 6 different motifs. Despite this strong sequence heterogeneity, it is found that they enable a highly controlled LbL film formation. For instance, a regular growth is observed when alternating the deposition of negatively-charged d-PPDE and positively-charged poly(allyl amine hydrochloride) (PAH). Yet, in this approach, the interdistance between consecutive coded d-PPDE layers remains relatively small, which may be an issue for data storage applications, especially for the selective decoding of the stored information. Using poly(sodium 4-styrene sulfonate) (PSS) as an intermediate non-coded polyanion, it is shown that a controlled interdistance between d-PPDE layers can be easily achieved, while still maintaining a regular LbL growth. Last but not least, it is found in this work that d-PPDE of relatively small molecular weight (i.e., significantly smaller than those of PAH and PSS) still enables a controlled LbL assembly. Nano-organized thin films containing digital layers are prepared by layer-by-layer deposition of digitally-encoded poly(phosphodiester)s with non-coded polyelectrolytes such as poly(allyl amine hydrochloride) and poly(sodium 4-styrene sulfonate). Despite the sequence heterogeneity of the digital polymer and the differences in molecular weight between coded and non-coded polyelectrolytes, a linear film growth is observed, thus resulting in the formation of well-segregated digital strata. image