NOVEL AMPHIPHILIC MICROGELS FABRICATED VIA
ON-CHIP POLYMERISATION
Bingyuan Lu
1
, Mark D. Tarn
1
, Nicole Pamme
1*
and Theoni K. Georgiou
2
1
Department of Chemistry, University of Hull, UK
2
Department of Materials, Imperial College London, UK
ABSTRACT
We report the on-chip polymerisation of hydrophobic microgels from precursor droplets, and their
downstream synthesis to pH-responsive amphiphilic microgels for drug delivery. This elegant platform
offers superior control over microgel properties, including size, crosslinking density and
hydrophobic/hydrophilic properties. The encapsulation and release of hydrophilic (Trypan Blue) and
hydrophobic (Sudan Red) dyes based on the microgel shrinking/swelling properties was also studied.
KEYWORDS: Amphiphilic microgels, On-chip polymerisation, Drug release, pH responsiveness
INTRODUCTION
Microgels are 3-dimensionally crosslinked polymer microparticles that can be used as drug delivery
vehicles [1]. They can be responsive to specific stimuli such as pH, temperature and electric fields,
depending on the types functional groups present. Conventional bulk synthesis methods yield microgels
in large size distributions (coefficient of variation (CV) 5-30 %) and offer only limited control over the
internal chemistry. Droplet microfluidics can overcome these issues by enabling the generation of
monodispersed droplets (CV ~3 %) that, when loaded with precursors, can be polymerised downstream
[2]. Nonetheless, the synthesis of amphiphilic microgels, useful for both hydrophilic and hydrophobic
drug delivery, is typically achieved in a two-step modification that provides poor control over the
hydrophobic/hydrophilic ratio and crosslinking density [3]. We have previously demonstrated the
synthesis of amphiphilic microgels, based on hydrophilic chains and hydrophobic crosslinks, with
controlled hydrophobicity from droplets generated on-chip followed by off-chip polymerisation [4].
Here, we report a far superior process for the synthesis of pH-responsive amphiphilic acrylic acid-
butyl acrylate-ethylene glycol dimethacrylate (AA-BuA-EGDMA) microgels, in which hydrophobic
droplets generated on-chip undergo immediate polymerisation within the microchannels. The microgels
were rendered amphiphilic via a simple one-step hydrolysation process. This elegant platform offers
superior control over microgel properties, including their size, hydrophilic/hydrophobic ratio, and
crosslinking density. Furthermore, these microgels, unlike in our previous study, also contain
hydrophobic groups in the backbone chains on the microgel and not only at the crosslinks.
Figure 1: (a) Exploded schematic of the microfluidic device, featuring a flow focusing junction and serpentine
channel in the top layer (10 μm deep, 30 μm wide), and the serpentine channel (50 μm deep, 800 μm wide, 2 m
long) mirrored in the bottom layer. (b) Photograph of the microfluidic chip fabricated in glass. (c) Schematic
showing the principle of droplet generation with in situ UV polymerisation to form microgels.
EXPERIMENTAL
A flow-focusing glass chip was used for droplet generation and polymerisation, which featured two
layers (Fig. 1a,b): a top layer containing a flow-focusing junction and serpentine channel (30 μm deep, 10
μm wide), with the serpentine channel mirrored in the bottom layer (60 μm deep, 800 μm wide). The
1044 978-0-9798064-8-3/μTAS 2015/$20©15CBMS-0001 19
th
International Conference on Miniaturized
Systems for Chemistry and Life Sciences
October 25-29, 2015, Gyeongju, KOREA