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Biofouling is a serious problem in the medical, marine, and several other industrial fields as it poses significant health risks and financial losses. Therefore, there is a great need to endow surfaces with antifouling and antimicrobial properties to mitigate biofouling. For long-term biofouling resistance, a unifunctional antimicrobial or non-adhesive surface is insufficient for preventing biofilm formation. To overcome this limitation, non-adhesive and antimicrobial dual-functional surfaces are highly desirable. Zwitterionic polymers have been used extensively as one of the best antifouling materials for surface modification. Being a super hydrophilic polymer, zwitterionic polymers need a strong binding agent to maintain attachment to the surface for long-term applications. In this thesis work, new strategies have been explored for surface modification to covalently graft zwitterionic polymers using mussel-inspired dopamine chemistry and prebiotic chemistry for long-term antifouling and antimicrobial applications. In the first project, a facile surface modification technique using dopamine chemistry was developed to prepare a super hydrophilic coating with both antifouling and antimicrobial properties. Catechol containing adhesive monomer dopamine methacrylamide (DMA) was copolymerized with bioinspired zwitterionic 2-methacryloyloxyethyl phosphorylcholine (MPC) monomer, and the synthesized copolymers were covalently grafted onto the amino (−NH2) rich polyethylenimine (PEI)/polydopamine (PDA) codeposited surface to obtain a stable antifouling surface. The resulting surface was used for in situ deposition of antimicrobial silver nanoparticles (AgNPs), facilitated by the presence of catechol groups of the coating. This dual functional coating significantly reduced the adhesion of both Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus bacteria and showed excellent resistance to bovine serum albumin adsorption. This bioinspired and efficient surface modification strategy with dual functional coating promises its potential application in implantable biomedical devices. In the second project, a smart surface was developed which can not only kill the attached microbials but also can release the dead cells and foulants from the surface under a particular incitement on demand. In this project, sugar responsive self-cleaning coating was developed by forming covalent boronic ester bonds between catechol groups from polydopamine and benzoxaborole pendant from zwitterionic and cationic polymers. To incorporate antifouling property and enhance biocompatibility of the coating, zwitterionic compound MPC was chosen and benzoxaborole pendant containing zwitterionic polymer poly (MPC-st-MAABO) (MAABO: 5-Methacrylamido-1,2-benzoxaborole) was synthesized. Additionally, to impart antibacterial properties to the surface, quaternary ammonium containing cationic polymer poly (2-(methacryloyloxy)ethyl trimethylammonium (META)-st-MAABO)) was synthesized. These synthesized polymers were covalently grafted to PDA coated surface by forming a strong cyclic boronic ester complex with catechol group of PDA layer endowing the surface with bacteria contact-killing property and capturing specific protein. After the addition of cis-diol containing competitive molecules i.e. sugars, this boronic ester complex with catechol group of PDA was replaced and attached polymer layer cleaved from the surface resulting in the release of both absorbed protein and live/killed bacteria electrostatically attached to the polymer layer. This dynamic self-cleaning surface can be a promising material for biomedical applications avoiding the gathering of dead cells and debris which is typically encountered on traditional biocidal surfaces. In practice macro or micro scratches or damages can happen to the coating which can act as an active site for microbial deposition and destroy the antifouling or antibacterial functionality of the coating. In the third project, an excellent biocompatible and multifunctional coating with antifouling, antibacterial and self-healing property was developed. Prebiotic chemistry inspired self-polymerization of AMN was used as a primary coating layer which act as a primer to graft vitamin B5 analogous methacrylamide polymer poly(B5AMA) and zwitterionic compound MPC containing polymer poly (MPC-st-B5AMA) by forming strong hydrogen bond. B5AMA having multiple polar groups into the structure acted as an intrinsic self-healing material and showed excellent antifouling property against protein and bacteria maintaining a good hydration layer. To impart the antibacterial property into the coating AgNps has also been incorporated which showed more that 90% killing efficiency against both gram-positive and gram-negative bacteria with significant reduction of their adhesion on the surface. Incorporation of self-healing property into the fouling repelling and antibacterial coating can significantly extend the durability of the multifunctional coating making it promising for biomedical applications. Three different surface modification techniques explored in this thesis, not only demonstrates excellent antifouling and antibacterial property but also provides fundamental insights into the facile development of multifunctional coating in various biomedical applications.
Biofouling on marine vessels and bacterial growth on biomedical surfaces bring huge economic loss to our society. Traditional antifouling and antibacterial surfaces contain toxic substances or antibiotics, which can threaten the environments and raise the risk of inducing drug-resistance strains. In the long-term evolution process of natural organisms, they present multiple functions through the joint action of their own morphology, structure, and other factors to achieve the maximum adaptation to the environment. Many of natural organisms have developed antifouling and antibacterial strategies. Inspired by these strategies, lots of artificial surfaces have been fabricated and tested. They are highly efficient and environmental-compatibility, and they have potential to achieve enhanced antifouling capabilities and desirable properties by combining the characteristics of novel materials. This book focuses on the research and application of bioinspired antifouling surfaces in the two major fields—marine industry and biomedical field. It is intended for mechanical manufacturing and biomedical researchers, professionals and students.
There are three major challenges for the design of patterned surfaces for biointerfacial applications: (i) durability of antibacterial/antifouling mechanisms, (ii) mechanical durability, and (iii) lifetime of the master mold for mass production of patterned surfaces. In this dissertation, we describe our contribution for the development of each of these challenges. The bioinspired surface, Sharklet AFTM, has been shown to reduce bacterial attachment via a biocide-free structure-property relationship effectively. Unfortunately, the effectiveness of polymer-based sharkskin surfaces is challenged over the long term by both eventual bacteria accumulation and a lack of mechanical durability. To address these common modes of failure, hard, multifunctional, antifouling, and antibacterial shark-skin patterned surfaces were fabricated via a solvent-assisted imprint patterning technique. A UV-crosslinkable adhesive material was loaded with titanium dioxide (TiO2) nanoparticles (NPs) from which shark skin microstructures were imprinted on a polyethylene terephthalate substrate. Furthermore, hard, multifunctional, antifouling, and antibacterial shark skin patterned surfaces were fabricated using inks comprised of zirconium dioxide (ZrO2) NPs and TiO2 NPs. The ZrO2 NPs provide an extremely hard and durable matrix in the final structure, while the TiO2 NPs provide active antibacterial functionality in the presence of UV light via photooxidation. The dynamic water contact angle, mechanical, antibacterial, and antifouling characteristics of the shark skin patterned surfaces were investigated as a function of TiO2 content. We then demonstrated the multifunctional shark skin system's suitability for use as an antifouling biosensor. Lastly, we described the design of a durable, hard master mold for pattern transfer. The lifetime of many of the current molds is limited by a lack of mechanical durability as well as cost. In this study, ZrO2 NPs were imprinted on a variety of substrates using a solvent-assisted patterning technique and subsequently annealed to increase the mechanical durability of the mold. Polymer replications were demonstrated using the hard ZrO2 mold with thermal and UV nanoimprinting lithography techniques, and injection molding. After up to 115,000 injection molding cycles, there was no delamination or breakage in the ZrO2 mold. The high hardness and durability, as demonstrated through the many replication cycles, suggests that the ZrO2 mold has excellent potential for use in the mass production of patterned polymer replicas. We also explored the nanopatterning of stainless steel using the ZrO2 mold. The solution-processability and simple patterning technique of ZrO2 NPs enable large-area and cost-effective fabrication of the hard molds which can be used for the variety of nano and micro-replication technologies.
This book reviews the development of antifouling surfaces and materials for both land and marine environments, with an emphasis on marine anti biofouling. It explains the differences and intrinsic relationship between antifouling in land and marine environments, which are based on superhydrophobicity and superhydrophilicity respectively. It covers various topics including biomimetic antifouling and self-cleaning surfaces, grafted polymer brushes and micro/nanostructure surfaces with antifouling properties, as well as marine anti biofouling. Marine anti biofouling includes both historical biocidal compounds (tributyltin, copper and zinc) and current green, non-toxic antifouling strategies. This book is intended for those readers who are interested in grasping the fundamentals and applications of antifouling. Feng Zhou is a professor at the State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences.
Biosynthetic Polymers for Medical Applications provides the latest information on biopolymers, the polymers that have been produced from living organisms and are biodegradable in nature. These advanced materials are becoming increasingly important for medical applications due to their favorable properties, such as degradability and biocompatibility. This important book provides readers with a thorough review of the fundamentals of biosynthetic polymers and their applications. Part One covers the fundamentals of biosynthetic polymers for medical applications, while Part Two explores biosynthetic polymer coatings and surface modification. Subsequent sections discuss biosynthetic polymers for tissue engineering applications and how to conduct polymers for medical applications. Comprehensively covers all major medical applications of biosynthetic polymers Provides an overview of non-degradable and biodegradable biosynthetic polymers and their medical uses Presents a specific focus on coatings and surface modifications, biosynthetic hydrogels, particulate systems for gene and drug delivery, and conjugated conducting polymers
Anti-biofouling is very important in many applications ranging from marine coatings to biomedical devices. The poor bio-compatibility of medical devices with human body causes undesired effects. Therefore, to achieve long-term stability of implanted medical devices the task is to modify the surfaces of medical devices so as to resist protein and make them compatible. In this thesis, the objective is to study a universal dip-coating method based on a zwitterionic polymer-DOPA conjugate for its anti-biofouling performance.
Biomimetic and bioinspired membranes are the most promising type of membrane for multiple usage scenarios, including commercial separation applications as well as water and wastewater treatment technologies. In recent years, aquaporin biomimetic membranes (ABMs) for water purification have raised considerable interest. These membranes display uniquely favorable properties and outstanding performances, such as diverse interactions, varied selective transport mechanisms, superior stability, high resistance to membrane fouling, and distinct adaptability. Biomimetic membranes would make a significant contribution to alleviate water stress, environmental threats, and energy consumption.
Antibiofouling Membranes for Water and Wastewater Treatment: Principles and Applications covers most recent advances, challenges, and industrial applications of antibiofouling membranes to help in reducing cost and increasing sustainability of long term-filtration performance of membranes in water and wastewater treatment. This book will provide a compact source of relevant and timely information on antibiofouling membranes and will be of great interest to scientists, engineers, industry R&D personnel, and graduate students engaged in the development, engineering scale-up, and applications of antibiofouling membranes, as well as other readers who are interested in microfiltration, membrane bioreactor, ultrafiltration, nanofiltration, reverse osmosis, and related topics. Covers scientific and engineering principles of antibiofouling membranes for water and wastewater treatment Unravels the structure-preparation-property-application relationship of antibiofouling membranes Provides advanced design strategies of antibiofouling membrane materials Summarizes and critically discusses antibiofouling membrane materials based on biocidal nanomaterials and quaternary ammonium compounds Focuses on the state-of-the-art applications of antibiofouling membranes for water and wastewater treatment
Bioinspired Materials for Medical Applications examines the inspiration of natural materials and their interpretation as modern biomaterials. With a strong focus on therapeutic and diagnostic applications, the book also examines the development and manipulation of bioinspired materials in regenerative medicine. The first set of chapters is heavily focused on bioinspired solutions for the delivery of drugs and therapeutics that also offer information on the fundamentals of these materials. Chapters in part two concentrate on bioinspired materials for diagnosis applications with a wide coverage of sensor and imaging systems With a broad coverage of the applications of bioinspired biomaterials, this book is a valuable resource for biomaterials researchers, clinicians, and scientists in academia and industry, and all those who wish to broaden their knowledge in the allied field. Explores how materials designed and produced with inspiration from nature can be used to enhance man-made biomaterials and medical devices Brings together the two fields of biomaterials and bioinspired materials Written by a world-class team of research scientists, engineers, and clinicians