Sequence isomerism in uniform polyphosphoesters programmes self-assembly and folding

Abstract

Perfectly sequence-defined macromolecules have been synthesised through the phosphoramidite method. Sequence isomerism determines self-assembly giving a raft of unusual nanostructures.

Chain Entropy Beats Hydrogen Bonds to Unfold and Thread Dialcohol Phosphates inside Cyanostar Macrocycles To Form [3]Pseudorotaxanes

“…Substituent-mediated recognition of organophosphates underpins processes across biology and chemistry, yet the role of the substituents is poorly understood . The biorecognition of oligonucleotides, , R 1 –PO 4 – –R 1 (R 1 = hydroxyl-substituted ribose/deoxyribose sugars), and phospholipids, , R 3 –PO 4 – –R 4 (e.g., R 3 = ester-linked fatty acids, R 4 = 4° ammonium) are critical for life − and human health while chiral phosphates, R 5 –R 5* –PO 4 – , (e.g., R 5 –R 5* = BINOL) enable organic catalysis. , Synthetic organophosphates , are also functional targets, such as designer polyphosphates for information storage, − self-assembly, − and templates for rotaxane synthesis . Despite this broad diversity of usage, and beyond dihydrogen phosphate anions − (H 2 PO 4 – ), most studies of organophosphate recognition have focused on ATP. − Recognition targets are growing with more aimed at phosphorylated biomolecules, − phosphate-rich phytate, − dyes, insecticides, herbicides, neurotoxins, and phosphoryl nerve agents. − However, the binding of disubstituted phosphates (R–PO 4 – –R), , where R = alkyl, benzyl, phenyl, and propargyl, is rare, which is limited by the synthetic difficulty for disubstituted organophosphate.…”

Sequence-complementarity dependent co-assembly of phosphodiester-linked aromatic donor-acceptor trimers

“…The magnesium-containing buffer was employed since the presence of the divalent cation can have dramatic effects upon the selfassembly of oligophosphates. [20,28] The yellow solutions gave absorption spectra characteristic of their respective aromatic units (250 -350 nm for DAN, 370-400 nm for NDI), with the buffer systems making minimal difference. Both DAN-NDI-DAN and NDI-DAN-NDI gave purple solutions at 250 μM in water, TBE, or TAMg (Fig.…”

“…The phosphodiester backbone of nucleic acids provides an attractive platform for the creation of sequence-defined molecules because of the outstanding efficiency of the automated phosphoramidite synthesis which permits creation of polymers of >100 monomer units long. [19,20] DA interactions have been integrated into DNA itself, [21] and the phosphodiester backbone has been used in development of various π-stacked folded and self-assembled systems, generating significant complexity from oligomers as short as trimers. [22][23][24] Since aromatic donor and acceptor units are complementary in a supramolecular sense, they reflect the hydrogen-bonded complementarity of nucleobases, and their sequence in a chain could therefore be used to control self-assembly.…”

Synthesis and sequencing of informational poly(amino phosphodiester)s

“…20 These polymers are prepared by solid-phase phosphoramidite polymer chemistry (PPC); a versatile method that can be used for synthesis of biological (i.e. DNA and RNA), 21 abiological 19 , [22][23][24] and bio-hybrid macromolecules. [25][26][27][28] In all d-PPDE we have studied so far, the coded side-chains are attached to a main-chain carbon atom.…”