Biofunctionalized block copolymer nanoparticles based on ring‐opening metathesis polymerization

Abstract

We present an approach to the synthesis of biofunctionalized block copolymer nanoparticles based on ring‐opening metathesis polymerization; these nanoparticles may serve as novel scaffolds for the multivalent display of ligands. The nanoparticles are formed by the self‐assembly of diblock copolymers composed of a hydrophobic block and a hydrophilic activated block that can be functionalized with thiolated ligands in aqueous media. The activated block enables control over the orientation of the displayed ligands, which may be sugars, peptides, or proteins engineered to contain cysteine residues at suitable locations. The nanoparticle diameter can be varied over a wide range through changes in the composition of the block copolymer, and biofunctionalization of the nanoparticles has been demonstrated by the attachment of a peptide previously shown to inhibit the assembly of anthrax toxin. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 928–939, 2006

ROMP Copolymers for Orthogonal Click Functionalizations

“…Here, these calculations showed the following composition for polymer 12 m:n:o = 9.8:4.7:10.5. Complete conversion could also be proven in the 19 F NMR spectrum due to complete disappearance of the signals corresponding to the pentafluorophenol ester ( Figure 6). For the alkyne to be suitable for CuAAC (copper-catalyzed azide−alkyne cycloaddition), the silyl protective group had to be cleaved quantitatively in order to ensure complete conversion to the corresponding triazole.…”

“…A mixture of compounds 2 (10 mg, 0.02 mmol, 1 equiv) and 7 (7 mg, 0.02 mmol, 1.1 equiv) in 0.6 mL of CDCl 3 was filled into a NMR tube, and 1 H NMR has been measured. Benzylamine (7 mg, 0.06 mmol, 3 equiv) was added, the NMR tube inverted once, and 1 H as well as 19 F NMR spectra were recorded every 5 min for 1 h.…”

Phosphonic acid‐based amphiphilic diblock copolymers derived from ROMP

“…This disappearance is in agreement with the formation of core-shell micelles in which the hydrophobic block is hidden in the micelle core in a nonsolvated state. [38][39][40] For the transformation to amphiphilic block copolymers, 5a-c, the phosphonate esters were cleaved by TMSiBr and then treated with methanol/dichloromethane mixture. Before deprotection, polymers 4a-c were soluble in DMF, chloroform, and DMSO; but after cleavage, the obtained polymers 5a-c became insoluble in these organic solvents.…”

Synthesis of well‐defined polymeric activated esters

“…59 All reactive polynorbornenes could be functionalized afterwards in a versatile manner. For example, Kiessling and coworkers 56 demonstrated the reaction with 3,6-disulfogalactose derivates could be used to prepare multivalent ligands for the development of a cellular binding assay for L-selectin, whereas Kane and coworkers 58 grafted amino end-functionalized hexaethylene glycol onto the reactive NHSNorb block resulting in amphiphilic diblock copolymers.…”

“…Following a similar route, Roberts and Sampson 57 prepared end-functionalized polymers with NHSNorb. Kane and coworkers 58 used NHSNorb to synthesize reactive diblock copolymers based on ROMP. Besides the NHS ester, pentafluorophenyl ester based norbornenes were also polymerized.…”