English

Probing Molecular Structures of Antifouling Polymer/Liquid Interfaces In Situ

• Zhang Chengcheng ^†, ,
• Crisci Ralph ^†, ,
• Chen Zhan ^,

• Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, USA

• These authors contributed equally to this work.

Author Bio: Professor Zhan Chen was born on June 4, 1966. He received his BS degree in Chemistry from Peking University in 1988, MS degree in Physics from Chinese Academy of Sciences in 1991, PhD degree in Chemistry from the University of California at Berkeley in 1998 and did his postdoctoral research in Lawrence Berkeley National Laboratory between 1998 and 2000. He then worked at the University of Michigan as an assistant professor (2000–2005), an associate professor with tenure (2005–2009), and was promoted to a full professor with tenure in 2009. Currently he is a professor of chemistry, macromolecular science and engineering, biophysics, and applied physics at the University of Michigan. Professor Chen's research is focused on the molecular level understanding of structures of polymers and biological molecules at interfaces. His fundamental research has been extensively supported by a variety of Federal funding agencies such as National Science Foundation, National Institutes of Health, Office of Naval Research, Army Research Office, Defense Threat Reduction Agency, etc. He has also widely collaborated with companies such as Dow Chemical, BASF, P & G, Intel, IBM, BMS, Sanofi, Texas Instruments, etc. on applied research. Professor Chen received the Beckman Young Investigator Award, Dow Corning Professorship, National Science Foundation CAREER Award, and Japan Society for the Promotion of Science Invitation Fellowship. He is a senior editor of Langmuir and an associate editor-in-chief of Chinese Chemical Letters. Professor Chen is a Fellow of American Association for the Advancement of Science (AAAS) and a Fellow of Royal Society of Chemistry (RSC). He published 280 peer reviewed research articles and gave more than 330 invited talks at various institutions and conferences;

Corresponding author: Chen Zhan, zhanc@umich.edu

• Received Date: 07 October 2019
  Accepted Date: 25 November 2019
  Revised Date: 23 November 2019
  Available Online: 15 October 2020
• Fund Project:

  The project was supported by the Office of Naval Research, USA (N00014-16-1-3115 and N00014-19-1-2171)

Abstract: Marine organisms such as plants, algae or small animals can adhere to surfaces of materials that are submerged in ocean. The accumulation of these organisms on surfaces is a marine biofouling process that has considerable adverse effects. Marine biofouling on ship hulls can cause severe fuel consumption increase. Investigations on antifouling polymers are therefore becoming important research topics for marine vessel operations. Antifouling polymers can be applied as coating layers on the ship hull, protecting it against the settlement and growth of sea organisms. Polyethylene glycol (PEG) is a hydrophilic polymer that can effectively resist the accumulation of marine organisms. PEG-based antifouling coatings have therefore been extensively researched and developed. However, the inferior stability of PEG makes it subject to degradation, rendering it ineffective for long-term services. Zwitterionic polymers have also emerged as promising antifouling materials in recent years. These polymers consist of both positively charged and negatively charged functional groups. Various zwitterionic polymers have been demonstrated to exhibit exceptional antifouling properties. Previously, surface characterizations of zwitterionic polymers have revealed that strong surface hydration is critical for their antifouling properties. In addition to these hydrophilic polymers, amphiphilic materials have also been developed as potential antifouling coatings. Both hydrophobic and hydrophilic functional groups are incorporated into the backbones or sidechains of these polymers. It has been demonstrated that the antifouling performance can be enhanced by precisely controlling the sequence of the hydrophobic-hydrophilic functionalities. Since biofouling generally occurs at the outer surface of the coatings, the antifouling properties of these coatings are closely related to their surface characteristics in water. Therefore, understanding of the surface molecular structures of antifouling materials is imperative for their future developments. In this review, we will summarize our recent advancements of antifouling material surface analysis using sum frequency generation (SFG) vibrational spectroscopy. SFG is a surface-sensitive technique which can provide molecular information of water and polymer structures at interfaces in situ in real time. The antifouling polymers we will review include zwitterionic polymer brushes, mixed charged polymers, and amphiphilic polypeptoids. Interfacial hydration studies of these polymers by SFG will be presented. The salt effect on antifouling polymer surface hydration will also be discussed. In addition, the interactions between antifouling materials and protein molecules as well as algae will be reviewed. The above research clearly established strong correlations between strong surface hydration and good antifouling properties. It also demonstrated that SFG is a powerful technique to provide molecular level understanding of polymer antifouling mechanisms.

Key words:
• Antifouling materials
•  /  Sum frequency generation vibrational spectroscopy
•  /  Interfacial hydration
•  /  Zwitterionic polymer
•  /  Salt effect
•  /  Protein interaction

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