Digital micelles of encoded polymeric amphiphiles for direct sequence reading and ex vivo label-free quantification

Dendritic Quaternary‐Encoded Oligourethanes for Data Encryption

“…Linear sequence‐encoded oligourethanes of T ‐ 00000000 ‐ dPEG , T ‐ 11110000 ‐ dPEG , and T ‐ 01001011 ‐ dPEG were first synthesized (Scheme S1 and Figures S1–S7), [23] in which 0 bit and 1 bit denoted the benzene ring of monomeric units without or with a methyl group, respectively. These digital oligourethanes had the following structural features: i) photoresponsive nitrobenzyl carbamate derivative was employed as a trigger motif; ii) 1,6‐azaquinone methide elimination spontaneously occurred once the photoresponsive capping agent was removed; [22a, 24] iii) a PEG dendron was introduced to render the resulting digital oligourethanes amphiphilic, which can simultaneously bypass interferences from the matrix used in MALDI‐ToF analysis and enhance the MS signals of the fragments with the PEG dendron residues [23] . As shown in Figure 1a, using T ‐ 01001011 ‐ dPEG as an example, cascade depolymerization starts with the exposure of the terminal aniline moieties under UV irradiation, which then spontaneously activates the cascade cleavage of neighboring N ‐arylcarbamate moieties via 1,6‐azaquinone methide elimination and decarboxylation reactions.…”

“…These digital oligourethanes had the following structural features: i) photoresponsive nitrobenzyl carbamate derivative was employed as a trigger motif; ii) 1,6-azaquinone methide elimination spontaneously occurred once the photoresponsive capping agent was removed; [22a, 24] iii) a PEG dendron was introduced to render the resulting digital oligourethanes amphiphilic, which can simultaneously bypass interferences from the matrix used in MALDI-ToF analysis and enhance the MS signals of the fragments with the PEG dendron residues. [23] As shown in Figure 1a, using T-01001011-dPEG as an example, cascade depolymerization starts with the exposure of the terminal aniline moieties under UV irradiation, which then spontaneously activates the cascade cleavage of neighboring N-arylcarbamate moieties via 1,6azaquinone methide elimination and decarboxylation reactions. This process continuously proceeded until complete depolymerization of all repeating units.…”

Digital synthetic polymers for information storage

“…10b). 51 This direct code-reliant quantification technique can furthest avoid alteration of surface properties, background interference, inattentive cleavage of conjugated labels or spontaneous/triggered degradation that may be caused by traditional fluorescent and isotopic labelling approach, providing the actual spatiotemporal biodistribution of polymeric nanomedicine. Monomer sequences and chain lengths of precisely encoded OU amphiphiles can significantly impact their solution self-assembling behaviours, leading to digital micelles with different morphologies and sizes, like spheres, rods, and worms (Fig.…”

“…24 Remarkably, the barcode amplifications or other pre-analysis treatments are generally eliminated over the direct sequencereading of digital synthetic macromolecules. 24 Heretofore, a variety of digital synthetic macromolecules, such as poly(triazole amide)s, 32,33 polyphosphates, 24,[34][35][36][37][38][39][40][41] polyurethanes, [42][43][44][45][46][47][48][49][50][51][52] poly-(succinimide thioether)s, [53][54][55][56] poly(alkoxyamine amide)s, 57 have been created via multistep reactions, 23,58 copolyesters, 28 oligopeptides, 59 oligo(monothioacetal)s 60 and others, 61 opening up new avenues for molecular data storage.…”

Controlled Self‐Assembly of Discrete Amphiphilic Oligourethanes with a Cascade Self‐Immolative Motif

“…Taking terminals rather than 2C 18 alkyl groups were observed, which was ascribed to the strong affinity of dPEG toward Na + ions. [15][16] Moreover, discrete oligourethanes with Nnaphthylcarbamate backbones had higher signal-to-noise patterns than those oligourethanes containing N-phenylcarbamate backbones due to the lower bond energy. [15,20] After elucidating the unique degradation behavior of discrete oligourethanes, we next investigated their selfassembly behavior in aqueous solutions.…”