4.6 Article

Electroactive Nanogel Formation by Reactive Layer-by-Layer Assembly of Polyester and Branched Polyethylenimine via Aza-Michael Addition

Journal

LANGMUIR
Volume 37, Issue 37, Pages 10902-10913

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.langmuir.1c01070

Keywords

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Funding

  1. YOK 100/2000 scholarship
  2. Scientific and Technological Research Council of Turkey (TUBITAK) 2214A International Doctoral Research Fellowship Programme

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The research demonstrates the formation of a nanogel coating on a gold surface using reactive layer-by-layer assembly, which exhibits multilayered structure, uniform distribution, and good electrochemical properties. The nanogel coating based on rLBL reactions effectively drives mass and charge transfer, making it suitable for applications in soft biointerfaces.
We here demonstrate the utilization of reactive layer-by-layer (rLBL) assembly to form a nanogel coating made of branched polyethylenimine (BPEI) and alkyne containing polyester (PE) on a gold surface. The rLBL is generated by the rapid aza-Michael addition reaction of the alkyne group of PE and the -NH2 groups of BPEI by yielding a homogeneous gel coating on the gold substrate. The thickness profile of the nanogel revealed that a 400 nm thick coating is formed by six multilayers of rLBL, and it exhibits 50 nm roughness over 8 mu m distance. The LBL characteristics were determined via depth profiling analysis by X-ray photoelectron spectroscopy, and it has been shown that a 70-100 nm periodic increase in gel thickness is a consequence of consecutive cycles of rLBL. A detailed XPS analysis was performed to determine the yield of the rLBL reaction: the average yield was deduced as 86.4% by the ratio of the binding energies at 286.26 eV, (C CN-C bond) and 283.33 eV, (C C triple bond). The electrochemical characterization of the nanogels ascertains that up to the six-multilayered rLBL of BPEI-PE is electroactive, and the nanogel permeability had led to drive mass and charge transfer effectively. These results promise that nanogel formation by rLBL films may be a straightforward modification of electrodes approach, and it exhibits potential for the application of soft biointerfaces.

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