Development of Charged Polyampholyte Interfaces: Synthesis, Properties, and Antifouling Application

ACS Biomaterials Science & Engineering, vol. 11, pp. 6593–6604

Abstract

Biocompatible hydroxyapatite (HA) is a biomaterial widely used in the regeneration and replacement of dental and bone tissue. On these HA surfaces, complex multicellular communities known as biofilms are established by pathogenic microorganisms, contributing to 75% of all bacterial infections and presenting a significant public health concern. Among the various charged polymers, zwitterionic polymers are commonly used for antifouling applications due to their ability to form a strong hydration layer. In contrast, charged polymers like polyampholytes with both positively and negatively charged groups remain largely unexplored for this application. Polyampholytes can be modified to be neutral, cationic, or anionic, as they are composed of two monomers with opposite charges. In this study, we aim to investigate the preparation of polyampholytes with different charges through Reversible Addition–Fragmentation chain Transfer (RAFT) polymerization, coating these polymers onto HA discs and evaluating their antifouling capabilities using bacterial adhesion experiments. We synthesized charged polyampholytes using [2-(methacryloyloxy)ethyl]trimethylammonium chloride (MAETMA) and sodium- p -vinylbenzenesulfonate (VBS), which are cationic and anionic monomers, respectively, in a DI water/dioxane medium via RAFT polymerization. Next, HA discs were coated with a series of synthesized charged polymers, resulting in surfaces with systematically tuned net charges ranging from fully positive to fully negative, labeled as HAP1-HAP5. Cytotoxicity assessments using NIH-3T3 fibroblast cells confirmed the biocompatibility of the polymer-coated HA surfaces. To confirm the antifouling property, adherence studies of Streptococcus mutans ( S. mutans ), a bacterium that causes dental caries (tooth decay) and dental plaque, were analyzed using a scanning electron microscope (SEM). Among all samples, HAP3 exhibited the minimum bacterial adhesion and the most effective resistance to protein adsorption, significantly outperforming the uncoated HA control.

Authors 11

1. Anashwara Babu

   SRM Institute of Science and Technology

   Affiliation as printed

   Department of Chemistry, Faculty of Engineering and Technology

   SRM Institute of Science and Technology (SRMIST)

2. Gomathi Sivakumar

   SRM Institute of Science and Technology

   Affiliation as printed

   Department of Chemistry, Faculty of Engineering and Technology

   SRM Institute of Science and Technology (SRMIST)

3. Minjae Kim

   Seoul National University

   Affiliation as printed

   Department of Chemistry, College of Natural Sciences, Seoul National University, Gwanak-ro 1, Gwanak-gu, Seoul 08826, Republic of Korea

4. Deepika Chauhan

   Jawaharlal Nehru University

   Affiliation as printed

   Jawaharlal Nehru University

   School of Physical Sciences

5. Zlata Nagorna Aachen Leiden Academic Centre for Drug Research

   Leiden University

   Affiliation as printed

   Leiden Academic Centre for Drug Research, Einsteinweg 55, Leiden 2333 CC, The Netherlands

6. Pradip Kar

   Birla Institute of Technology, Mesra

   Affiliation as printed

   Birla Institute of Technology

   Department of Chemistry

   Department of Chemistry, Birla Institute of Technology, Mesra, Ranchi, Jharkhand 835215, India

7. Pijus K. Sasmal

   Jawaharlal Nehru University

   Affiliation as printed

   Jawaharlal Nehru University

   School of Physical Sciences

8. Joachim F. R. Van Guyse Aachen Leiden Academic Centre for Drug Research

   Leiden University

   Affiliation as printed

   Leiden Academic Centre for Drug Research, Einsteinweg 55, Leiden 2333 CC, The Netherlands

9. Susanta Banerjee

   Indian Institute of Technology Kharagpur

   Affiliation as printed

   Indian Institute of Technology Kharagpur

   Materials Science Centre

10. Yan Lee corresponding

    Seoul National University

    Affiliation as printed

    Department of Chemistry, College of Natural Sciences, Seoul National University, Gwanak-ro 1, Gwanak-gu, Seoul 08826, Republic of Korea

11. Samarendra Maji corresponding

    SRM Institute of Science and Technology

    Affiliation as printed

    Department of Chemistry, Faculty of Engineering and Technology

    SRM Institute of Science and Technology (SRMIST)