Chiral Imprinting of Diblock Copolymer Single-Chain Particles

Abstract

This Article reports the molecular imprinting of polymer single-chain particles that have a radius ∼3.7 nm. For this, the template L-phenylalanine anilide or L-ΦAA and a diblock copolymer PtBA-b-P(CEMA-r-CA) were used. Here, PtBA denotes poly(tert-butyl acrylate), and P(CEMA-r-CA) denotes a random block consisting of cinnamoyloxyethyl methacrylate (CEMA) and carboxyl-bearing (CA) units. In CHCl(3)/cyclohexane (CHX) with 64 vol % of CHX or at f(CHX) = 64%, a block-selective solvent for PtBA, PtBA-b-P(CEMA-r-CA) formed spherical micelles. The core consisted of the insoluble P(CEMA-r-CA) block and L-ΦAA, which complexed with the CA groups. Pumping slowly this micellar solution into stirred CHCl(3)/(CHX) at f(CHX) = 64% triggered micelle dissociation into single-chain micelles, which comprised presumably a solubilized PtBA tail and a collapsed P(CEMA-r-CA)/L-ΦAA head. Because the solvent reservoir was under constant UV irradiation, the photo-cross-linkable units in the P(CEMA-r-CA) head cross-linked, and the single-chain micelles were converted into cross-linked single-chain micelles or tadpoles. Synchronizing the micelle addition and photoreaction rates allowed the preparation, from this protocol, of essentially pure tadpoles at high final polymer concentrations. Imprinted tadpoles were procured after L-ΦAA was extracted from the tadpole heads. Under optimized conditions, the produced imprinted tadpoles had exceptionally high binding capacity and high selectivity for L-ΦAA. In addition, the rates of L-ΦAA release from and rebinding by the particles were high.

Advances in single chain technology

“…127 The selective binding of L-phenylalanine anilide (natural amino acid) vs. D-phenylalanine anilide (synthetic organic compound) by these SCNPs was investigated. 127 The selective binding of L-phenylalanine anilide (natural amino acid) vs. D-phenylalanine anilide (synthetic organic compound) by these SCNPs was investigated.…”

Advances in Click Chemistry for Single-Chain Nanoparticle Construction

“…I agree with the suggested changes, that can be made easily by the editorial office. [7,22,28,29], poly(styrene) [3,22,23,[30][31][32], poly(haloalkyl styrene) [3,33], poly(4-N-Boc-vinylaniline) [33], poly(sodium 4-styrenesulfonate) [22], poly(N-alkyl acrylamide) [22,34,35] Atom transfer radical polymerization ATRP Poly(alkyl methacrylates) [14], poly(alkyl acrylates) [11,12], poly(styrene) [36], poly(N-hydroxyethyl acrylamide) [37] Nitroxide mediated radical polymerization NMP Poly(alkyl methacrylates) [9,[38][39][40], poly(alkyl acrylates) [40], poly(styrene) [2,38,40], poly(haloalkyl styrene) [40], poly(fluorene) [41] Ring opening metathesis polymerization ROMP Poly(-caprolactone) [38], poly(carbonates) [42] poly(norbornenes) [13,43,44] * For SCNP copolymer and terpolymer precursors, only the nature of the main component is indicated.…”

“…Ultra-fine (7.4 nm in size) L-phenylalanine anilide-imprinted polymer single-chain nanoparticles have been synthesized by Njiang et al [7] in 2012. Interestingly, the L-phenylalanine anilide-imprinted nanoparticles showed a higher sorption capacity for L-phenylalanine anilide (238 mol/g) than for D-phenylalanine anilide (132 mol/g) and the rate constant for L-phenylalanine anilide release was found to be inversely proportional to the squared radius of the particles.…”

“…This is a consequence of the polydisperse nature (in size and composition) of current synthetic polymers showing a distribution of molar mass when compared to the perfectly monodisperse nature and precise chemical sequence of natural biomacromolecules. Even so, due to their exceptional properties, unimolecular polymeric nanoparticles have been evaluated as rheology agents [2,3], enzyme mimics [4,5], drug/siRNA/peptide nanocarriers [6][7][8][9], image contrast agents [3,[10][11][12], sensors [13], catalytic systems in water [14], and smart gels [15]. As illustrated in Figure 1, synthesis of single-chain nanoparticles relies on the use of a combination of three main different techniques [3].…”

Ferrocenyl amphiphilic Janus dendrimers as redox‐responsive micellar carriers

“…[1][2][3] and are attracting wide attention owing to their combination of properties of the constituting blocks in a unique way. [12] The self-assembly structure and functions of stimuliresponsive JDs based on specific non-covalent interactions have been widely investigated in functional materials by means of different external stimuli, such as solvent polarity, [13,14] redox, [3,[15][16][17][18][19][20][21] temperature, [22][23][24][25] pH [26][27][28][29][30][31] and electrochemistry. [12] The self-assembly structure and functions of stimuliresponsive JDs based on specific non-covalent interactions have been widely investigated in functional materials by means of different external stimuli, such as solvent polarity, [13,14] redox, [3,[15][16][17][18][19][20][21] temperature, [22][23][24][25] pH [26][27][28][29][30][31] and electroc...…”