Thermoresponsive hydrophobic copolymer brushes modified porous monolithic silica for high-resolution bioseparation

Abstract

Thermoresponsive hydrophobic copolymer, poly(N-isopropylacrylamide-co-n-butyl methacrylate)[P(IPAAm-co-BMA)], brushes were prepared on porous monolithic silica rods through surface-initiated atom transfer radical polymerization (ATRP). The monolithic silica surface was modified with the ATRPinitiator [(chloromethyl)phenylethyl]trimethoxysilane (CPTMS) via silanization performed by flowing a CPTMS toluene solution into the monolithic silica rod column. ATRP was performed by flowing a reaction solution containing IPAAm and BMA monomers, and ATRP catalyst CuCl/CuCl 2 /tris[2-(N,Ndimethylamino)ethyl]amine in 2-propanol into the monolithic silica. Characterization by CHN elemental analysis, X-ray photoelectron spectroscopy (XPS), and gel permeation chromatography revealed that dense P(IPAAm-co-BMA) brushes were formed on the monolith surface. Chromatographic analysis using benzoic acids and insulin peptides indicated that the brush-modified monolithic silica was able to separate these analytes with high resolution and in short analysis times, owing to the effective interaction between the modified polymer brushes and the analyte. These results indicated that the present P(IPAAm-co-BMA) brush modified monolithic silica is an effective separation tool for analyzing bio-related molecules. Fig. 1 Scheme for preparation of P(IPAAm-co-BMA)-brush-grafted monolithic silica rod (A) and silica beads (B) using surface-initiated ATRP.This journal is

Thermoresponsive-polymer-based materials for temperature-modulated bioanalysis and bioseparations

“…97 Monolithic silica modified with hydrophobized thermoresponsive polymer P(IPAAm-co-BMA) brushes rapidly and effectively separated benzoic acids and phenol. 98 A mixture of insulin fragments, i.e., insulin chain A, insulin chain B, and insulin, was separated using a P(IPAAm-co-BMA)-brush-modified monolithic silica column. 98 The analysis time for thermoresponsive ion-exchange chromatography can be significantly reduced by using a monolithic silica rod column; for example, the separation of an adenosine nucleotide mixture, i.e., AMP, ADP, and ATP, on a column packed with beads modified with thermoresponsive cationic copolymer P(IPAAm-co-DMAEMA-co-tBAAm) brushes requires a long separation time (approximately 100 min).…”

“…98 A mixture of insulin fragments, i.e., insulin chain A, insulin chain B, and insulin, was separated using a P(IPAAm-co-BMA)-brush-modified monolithic silica column. 98 The analysis time for thermoresponsive ion-exchange chromatography can be significantly reduced by using a monolithic silica rod column; for example, the separation of an adenosine nucleotide mixture, i.e., AMP, ADP, and ATP, on a column packed with beads modified with thermoresponsive cationic copolymer P(IPAAm-co-DMAEMA-co-tBAAm) brushes requires a long separation time (approximately 100 min). In contrast, using a monolithic silica rod column modified with the same thermoresponsive cationic copolymer brushes achieves separation of the adenosine nucleotide mixture in 5 min.…”

Challenges and Advances in the Fabrication of Monolithic Bioseparation Materials and their Applications in Proteomics Research

“…Stimuli‐responsive surfaces play a significant role in diverse applications, such as biocatalyst system and drug delivery. Two kinds of thermoresponsive polymeric brushes, poly( N ‐isopropylacrylamide‐ co ‐acrylic acid‐ co ‐ tert ‐butylacrylamide) and poly( N ‐isopropylacrylamide‐ co ‐ n ‐butyl methacrylate), were immobilized onto monolithic silica columns via surface‐initiated ATRP, respectively, and then used for high‐speed separation of peptides ( Figure ).…”

Thermoresponsive hydrophobic copolymer grafted on agar microspheres for all‐aqueous bioseparations

“…They have drawn tremendous attention in various fields [1,2], including biosensors and diagnostic systems [3], cell culture [4], drug delivery [5,6], and bioseparation [7,8]. In chromatography, the use of thermoresponsive materials enable efficient separations that are controlled only by temperature avoiding changes in mobile phase [9]. As a green technology, this all-aqueous bioseparation is favorable to preserve the activity of biomolecules, especially poly(Nisopropylacrylamide) (PNIPAAm) has been developed for various separation applications because it possesses the ability of reversible phase transition with a lower critical solution Article Related Abbreviations: AAm, acrylamide; ATRP, atom transfer radical polymerization; BiBB, 2-bromine butyryl bromine; LCST, lower critical solution temperature; LMA, lauryl methacrylate; NIPAAm, N-isopropylacrylamide; PNIPAAm, poly(N-isopropylacrylamide) temperature (LCST) of 32 • C in all-aqueous solutions [10].…”