Plasma-initiated Polymerization Research Articles

Electric Field Effect of the Plasma-Initiated Polymerization of Methyl Methacrylate: A Negatively Charged Long-Lived Radical.

Plasma-initiated polymerization (PIP) is generally attributed to a radical process due to its inhibiting property. However, its unique polymerization behaviors like long-lived radical and solvent effect do not comply well with the traditional radical mechanism. Herein, the PIP of methyl methacrylate (MMA) was conducted in a high-voltage DC electric field to investigate the charged nature of its radicals. Consequently, the polymerization presented a preferential distribution of polymers at the anode but not the cathode, revealing the negatively charged nature of the growing radicals. An acceleration phenomenon, accompanied by the growth in molecular weights and the reduction in molecular weight distributions (Ð), was observed at the voltages above 16 kV, suggesting the dissociation of ion pairs of growing radicals. The PIP yielded PMMA with analogous chemical and steric structures to those of PMMA from traditional radical initiation, whether in the presence or absence of the external electric field. This work offers new insights into the PIP of vinyl monomers, wherein a one-electron transfer reaction is inferred to be involved in the monomer activation.

Ion-Selective Potentiometry with Plasma-Initiated Covalent Attachment of Sensing Membranes onto Inert Polymeric Substrates and Carbon Solid Contacts.

The physical delamination of the sensing membrane from underlying electrode bodies and electron conductors limits sensor lifetimes and long-term monitoring with ion-selective electrodes (ISEs). To address this problem, we developed two plasma-initiated graft polymerization methods that attach ionophore-doped polymethacrylate sensing membranes covalently to high-surface-area carbons that serve as the conducting solid contact as well as to polypropylene, poly(ethylene-co-tetrafluoroethylene), and polyurethane as the inert polymeric electrode body materials. The first strategy consists of depositing the precursor solution for the preparation of the sensing membranes onto the platform substrates with the solid contact carbon, followed by exposure to an argon plasma, which results in surface-grafting of the in situ polymerized sensing membrane. Using the second strategy, the polymeric platform substrate is pretreated with argon plasma and subsequently exposed to ambient oxygen, forming hydroperoxide groups on the surface. Those functionalities are then used for the initiation of photoinitiated graft polymerization of the sensing membrane. Attenuated total reflection-Fourier transform infrared spectroscopy, water contact angle measurements, and delamination tests confirm the covalent attachment of the in situ polymerized sensing membranes onto the polymeric substrates. Using membrane precursor solutions comprising, in addition to decyl methacrylate and a cross-linker, also 2-(diisopropylamino)ethyl methacrylate as a covalently attachable H+ ionophore and tetrakis(pentafluorophenyl)borate as ionic sites, both plasma-based fabrication methods produced electrodes that responded to pH in a Nernstian fashion, with the high selectivity expected for ionophore-based ISEs.

Significantly enhanced sedimentation and adsorption of clay materials by plasma-initiated polymerization

Except for the high adsorption capacity, the color of the adsorbent suspension and the solid-liquid separation characteristics are also essential factors for adsorption material in wastewater management. Here, a novel carboxymethyl chitosan grafted magnetic montmorillonite (CMC@MMt) adsorbent-material with large metal ions uptake capacity, transparent solution, excellent turbidity, and low cytotoxicity in human hepatic cells (HepG2 cells) was successfully synthesized by plasma technology. The adsorption performance for different metal ions, the turbidity property, and the toxicity of CMC@MMt were evaluated by systematic studies. The results indicate that adding of CMC could enhance the adsorption capacity because of NH2, COOH, and OH functional groups. Especially the turbidity property of montmorillonite was also improved due to the enlarged grain size and the polarity reduction. This research will promote the application of clay mineral-based material in environmental pollution control, such as preconcentration and immobilization of heavy metal ions.

Bulk Polymerization of PEGDA in Spruce Wood Using a DBD Plasma-Initiated Process to Improve the Flexural Strength of the Wood–Polymer Composite

The chemical treatment of wood has been shown to increase its mechanical strength by forming composites with a variety of polymers. Polyethylene glycol diacrylate (PEGDA) has commonly been used as a polymer reinforcement to increase the strength and resistance of spruce wood for various applications, such as protection from weathering. In this study, PEGDA was impregnated into wood samples and polymerized by dielectric barrier discharge (DBD) plasma to form wood–polymer composites (WPCs). The kinetic rate order of PEGDA was explored using FT-IR quantitative analysis and the DBD plasma-initiated polymerization was determined to be second order. The strength of the wood samples was then determined by a three-point flexural test. The PEGDA-treated spruce wood samples showed improved flexural strength versus the untreated wood samples. The WPCs were also made using a UV treatment method and were then compared to the DBD plasma-treated samples. The results showed that the DBD plasma-treated samples yielded superior flexural strength relative to the UV-treated samples. We accredited this difference in strength to the plasma process and its ability to penetrate into the various layers of the wood and initiate polymerization, as opposed to UV light that can only penetrate superficially, initiating polymerization in only the first few layers of the wood surface.

Plasma-initiated graft polymerization of carbon nanoparticles as nano-based drug delivery systems

Plasma-initiated free radical polymerization was used to engineer carbon nanoparticles (CNPs) with tailored chemical and physical properties. Following surface modification, CNPs were loaded with a highly effective anti-infection agent called metal-free Russian propolis ethanol extract (MFRPEE), thus, creating nano-based drug delivery systems (NBDDSs). The loading of MFRPEE onto grafted CNPs occurred naturally through both electrostatic interactions and hydrogen bonding. When constructed under optimal experimental conditions, the NBDDSs were stable under physiologic conditions, and demonstrated enhanced anti-biofilm activity when compared with free MFRPEE. Mechanistic studies revealed that the enhanced anti-infectious activity of the NBDDSs was attributed to the modified surface chemistry of grafted CNPs. More specifically, the overall positive surface charge on grafted CNPs, which stems from quaternary ammonium polymer brushes covalently bound to the CNPs, provides NBDDSs with the ability to specifically target negatively charged components of biofilms. When studying the release profile of MFRPEE from the modified CNPs, acidic components produced by a biofilm triggered the release of MFRPEE bound to the NBDDS. Once in its free form, the anti-infectious properties of MFRPEE became activated and damaged the extracellular polymeric matrix (EPM) of the biofilm. Once the architecture of the biofilm became compromised, the EPM was no longer capable of protecting the bacteria encapsulated within the biofilm from the anti-infectious agent. Consequently, exposure of bacteria to MFRPEE led to bacterial cell death and biofilm inactivation. The results obtained from this study begin to examine the potential application of NBDDSs for the treatment of healthcare-associated infections (HCAIs).

Active and selective removal of U(VI) from contaminated water by plasma-initiated polymerization of aniline/GO

The development of new enrichment material for U(VI) enrichment with high selectivity is of great importance for both the pollution management and efficient recycling of U(VI). In order to explore the effect of –NH2 functional groups in U(VI) extraction, we here used the plasma technique to prepare Aniline/GO (AGO) composites, as raw-GO has no nitrogen element and aniline has a large number of –NH2 functional groups. The effect of –NH2 functional groups in the U(VI) enrichment is evaluated by comparison of enrichment performance of raw-GO with and without the addition of –NH2 group, GO with plasma treatment is also under consideration. Effect of Aniline/GO weight ratio and different environmental factors are all studied. The results revealed that the –NH2 functional groups could enhance the U(VI) enrichment capacity and selectivity, especially at pH 3–7 with a weight ratio (2.5–7.5) of aniline to GO. The 5AGO composite showed excellent enrichment ability (341.5 mg/g, pH = 5.0, T = 298 K), anti-interference ability, selectivity, recycling ability and low cytotoxicity in human cells. The enhanced selectivity is attributed to the strong coordination between the nitrogen donor atoms and U(VI). This research provides a direction for the design of effective U(VI) extraction materials from seawater.

Nanoscale Zerovalent Iron Immobilized on Functionalized Nonwoven Cotton Fabric for As(V) Adsorption

A functionalized nonwoven cotton fabric-Fe(0) (denoted as FNCF-ZVI) as a novel adsorbent material was synthesized in two main steps for water treatment of arsenate ions. Firstly, the Fe(III)-immobilized chelating fabric with iminodiacetic acid (IDA) functional groups was synthesized through an epoxy group–containing glycidyl methacrylate (GMA) grafted to the nonwoven cotton fabric (NCF) via plasma-initiated emulsion graft polymerization. Subsequently, the obtained Fe(III)-immobilized FCNF was followed by a reduction of Fe(III) into Fe(0) to obtain stabilized nanoscale zerovalent iron (ZVI) on the surface of FNCF. FNCF-ZVI was applied for arsenic(V) removal in batch experiments at different pH values (2.00–9.00) and concentrations ranging between 1 and 500 mg/L As(V). The FNCF-ZVI had a positive impact on the absorption of As(V) species under acidic conditions, and the highest adsorption was seen at a pH value of 3.00. The adsorption equilibrium of adsorbent was reached in 420 min with initial solution concentrations at 1 mg/L, 10 mg/L, and 50 mg/L, and the process better fitted to the nonlinear pseudo-second-order model than to the nonlinear pseudo-first-order model. The resulting FNCF-ZVI showed a high maximum adsorption capacity of 158.73 mg/g at 35 °C for As(V) adsorption, and the adsorption data fitted the Freundlich isotherm model. Regeneration studies displayed that after 3 times usage, the adsorption capacity can remain up to 86%. It has been observed that ZVI nanoparticles have superior adsorption capacity compared to Fe(III) under their optimum conditions.

Plasma-Initiated Graft Polymerization of Acrylic Acid onto Fluorine-Doped Tin Oxide as a Platform for Immobilization of Water-Oxidation Catalysts.

The discovery of new and versatile strategies for the immobilization of molecular water-oxidation catalysts (WOCs) is crucial for developing clean energy conversion devices [e.g., (photo)electrocatalytic cells for water splitting]. The traditional approach for surface attachment to transparent conductive oxides [e.g., fluorine doped tin oxide (FTO)] is via synthetic modification of the ligand architecture to incorporate functional groups such as carboxylic acids (-COOH) or phosphonates (-PO3H2) prior to immobilization. However, challenges arising from desorption and the cumbersome derivatizations steps have limited the scope and applications of surface-bound WOCs. Herein, we report the successful immobilization of underivatized Ru(II)-based WOCs (Ru-Cat1 = [Ru(tpy) (bpy) (H2O)]2+ (tpy = 2,2':6'2″-terpyridine and bpy = 2,2'-bipyridine) and Ru-Cat2 = [Ru(Mebimpy) (bpy) (H2O)]2+ (Mebimpy = 2,6-bis(1-methylbenzimidazol-2-yl) pyridine)) and the Ru(II) polypyridyl chromophore Ru-C3 = [Ru(bpy)3]2+ onto a FTO plasma-grafted poly(acrylic acid) surface (PAA|FTO). Various characterization techniques such as attenuated total reflectance Fourier transform infrared spectroscopy, scanning electron microscopy, atomic force microscopy, and cyclic voltammetry measurements provide evidence for the plasma-induced grafted PAA|FTO film and immobilization. Surface stability and electrocatalytic properties of these new hybrid composite films upon cycling were investigated at different pH values. Immobilized Ru-Cat1 and Ru-Cat2 onto PAA|FTO displayed pH-dependent (RuIII/RuII) couples and onset potentials indicative of PCET (proton-coupled electron transfer) reactions. Based on cyclic voltammetry results and spectroscopic monitoring, the immobilized WOCs Ru-Cat1 and Ru-Cat2 exhibited a higher surface stability in neutral aqueous solutions relative to Ru-C3 upon electrochemical oxidation. We attribute the surface PCET and stability to the presence of a water ligand in the coordination sphere of immobilized Ru-Cat1 and Ru-Cat2 which can H-bond with negatively charged carboxylate groups of the cross-linked PAA brushes. Our findings demonstrate that the plasma-grafted polymeric network onto FTO offers a versatile platform to directly anchor unmodified homogeneous WOCs or chromophores for potential applications in solar-to-fuel energy conversion.

Plasma-initiated polymerization of N-isopropylacrylamide and functionalized with dopamine for the adhesion to Hela cells

Temperature-responsive films of poly(N-isopropylacrylamide) (PNIPAM) were facilely fabricated by one-step plasma-initiated polymerization and then functionalized by self-polymerization of dopamine on the surface. High retention of the monomer structure and temperature-responsive properties in PNIPAM films were confirmed. After plasma-initiated polymerization, PNIPAM films formed protrusions and ridges surfaces. Moreover, cross-linker of N,N′-methylenebisacrylamide with different dosage was introduced into the systems to effectively modulate the roughness of PNIPAM films and to supply better adhesive surface. Furthermore, in cell culture, satisfactory survival rate of the attached Hela cells was obtained on PNIPAM films, and the cell viability was improved further on PNIPAM/PDA films. The results indicated that such films might be applicable in medical treatment and tissue engineering, due to their adjusted adhesion ability and less toxicity to cells.

Novel cotton fabric adsorbent for efficient As(V) adsorption.

A novel amine functionalized nonwoven cotton fabric (EDA-GMA-g-NCF) adsorbent material for As(V) adsorption was prepared by using plasma-initiated graft polymerization of glycidyl methacrylate (GMA) onto nonwoven cotton fabric (NCF) and then its modification with ethylenediamine (EDA). The resultant nonwoven cotton fabric adsorbent was examined by using FT-IR, SEM, and XPS techniques. As(V) adsorption experiments were performed in batch mode as a function of pH, contact time, initial concentration, coexisting ions, ionic strength, and tap water applications. Ethylenediamine carrying nonwoven cotton fabric-based functional adsorbent showed efficient, rapid As(V) removal with high adsorption capacity. The experimental data shows that adsorption mechanism fits to the Langmuir isotherm, and adsorption kinetic follows a pseudo-second-order model. Between pH 2-8 range, nonwoven cotton fabric adsorbent is effective at pH 3 for As(V) adsorption. The maximum adsorption capacity of the nonwoven cotton fabric for As(V) was 217.39mg/g. The adsorbent could be easily regenerated at least ten cycles with 3% HNO3 solution. EDA-GMA-g-NCF was also efficient for tap water applications with high percent As(V) removal. Thermodynamic parameters show that the As(V) adsorption process was spontaneous and exothermic. Graphical abstract Preparation of cotton fabric adsorbent and As(V) treatment process.

A Plasma-Initiated Graft Polymerization of Methyl Methacrylate in the Presence of a Reverse ATRP Catalyst

A plasma-initiated graft polymerization of methyl methacrylate (MMA) was carried out on the high-density polyethylene (HDPE) surface in the presence of the reverse atom transfer radical polymerization (RATRP) catalyst of CuCl2/2,2′-bipyridine (bpy). The polymerization kinetics presented a linear relation with polymerization time. A well-defined PMMA brush was fabricated on the surface, evidenced by the linear growth of molecular weights with conversions and narrow polymer dispersity (Ð = 1.31). Graft amounts were indicated to increase proportionally with the increase of conversions and molecular weights. Subsequently, a solvent-responsive surface was prepared by the block copolymerization of 2-hydroxyethyl methacrylate (HEMA) on the PMMA grafted surface. The polymerization is suggested to proceed via a RATRP mechanism, when plasma radicals could behave similarly as conventional radicals in forming dormant species.

Plasma-initiated graft polymerization as an immobilization platform for metal free Russian propolis ethanol extracts designed specifically for biomaterials

The antibacterial and anti-biofilm activities of propolis have been intensively reported. However, the application of this folk remedy as a means to prevent biomedical implant contamination has yet to be completely evaluated. In response to the significant resistant and infectious attributes of biofilms, biomaterials engineered to possess specific chemical and physical properties were immobilized with metal free Russian propolis ethanol extracts (MFRPEE), a known antibacterial agent. The results obtained from this study begin to examine the application of MFRPEE as a novel alternative method for the prevention of medical and biomedical implant infections. When constructed under specific experimental conditions, immobilized biomaterials showed excellent stability when subjected to simulated body fluid and fetal bovine serum. The ability of immobilized biomaterials to specifically target pathogens (both Gram-positive and Gram-negative biofilm forming bacteria), while promoting tissue cell growth, renders these biomaterials as potential candidates for clinical applications.

Preparation and characterization of ethylenediamine modified glycidyl methacrylate-grafted nonwoven cotton fabric adsorbent

In this study, plasma-initiated graft polymerization of glycidyl methacrylate (GMA) onto nonwoven cotton fabric (NCF) and its modification with ethylenediamine (EDA) was performed. To determine the optimum conditions for plasma treatment, a comprehensive analysis of different parameters such as plasma power, applied pressure, applied plasma gas, and exposure time were conducted using both air- and Ar-plasma. The concentration of radicals generated on the NCF surface after plasma treatment was examined using ESR spectroscopy. The effects of plasma pretreatment conditions, namely GMA concentration, grafting temperature, and grafting time were investigated. Plasma treated NCF has been grafted with GMA (GMA-g-NCF) was functionalized with ethylenediamine (EDA-GMA-g-NCF) to develop an efficient arsenic adsorbent. NCF, GMA-g-NCF and EDA-GMA-g-NCF samples were characterized by using FTIR, SEM, EDX, XPS, elemental analysis, TGA, and contact angle.

Plasma initiated graft polymerization of 2-methacryloyloxyethyl phosphorylcholine on silicone elastomer surfaces to enhance bio(hemo)compatibility

Poly-2-methacryloyloxyethyl phosphorylcholine (pMPC) was grafted from the silicone elastomer (SE) surface by plasma-initiated polymerization to alter the surface properties. Argon plasma was used to activate the SE surface, and the amount of peroxide produced on the surface was determined by 1,1-diphenyl-2-picryl-hydrazyl. Successful grafting of pMPC from the SE surface was verified by attenuated total reflection-Fourier transform infrared spectroscopy and elemental analysis. The surface morphology of cells adhered to pMPC-grafted SE also differed from that of cells adhered to unmodified and Ar-plasma-treated SE surfaces due to the homogenous graft polymerization of pMPC. Biological analyses of pMPC-grafted SE revealed that, at the polymer surface, protein adsorption of bovine serum albumin was significantly reduced, and that the surface exhibited anti-coagulant activity in human whole blood and decreased platelet adhesion. In summary, the grafting of pMPC on SE significantly enhanced the bio(hemo)-compatibility of SE.

Hydrophobic Coatings on Cotton Obtained by in Situ Plasma Polymerization of a Fluorinated Monomer in Ethanol Solutions.

Plasma polymerization using hydrophobic monomers in the gas phase is a well-known technology to generate hydrophobic coatings. However, synthesis of functional hydrophobic coatings using plasma technology in liquids has not yet been accomplished. This work is consequently focused on polymerization of a liquid fluorinated monomer on cotton fabric initiated by atmospheric plasma in a dielectric barrier discharge configuration. Functional hydrophobic coatings on cotton were successfully achieved using in situ atmospheric plasma-initiated polymerization of fluorinated monomer dissolved in ethanol. Gravimetric measurements reveal that the amount of polymer deposited on cotton substrates can be modulated with the concentration of monomer in ethanol solution, and cross-linking reactions occur during plasma polymerization of a fluorinated monomer even without the presence of a cross-linking agent. FTIR and XPS analysis were used to study the chemical composition of hydrophobic coatings and to get insights into the physicochemical processes involved in plasma treatment. SEM analysis reveals that at high monomer concentration, coatings possess a three-dimensional pattern with a characteristic interconnected porous network structure. EDX analysis reveals that plasma polymerization of fluorinated monomers takes place preferentially at the surface of cotton fabric and negligible polymerization takes place inside the cotton fabric. Wetting time measurements confirm the hydrophobicity of cotton coatings obtained although equilibrium moisture content was slightly decreased. Additionally, the abrasion behavior and resistance to washing of plasma-coated cotton has been evaluated.

Plasma-initiated polymerization of chitosan-based CS-g-P(AM-DMDAAC) flocculant for the enhanced flocculation of low-algal-turbidity water

In this work, a highly efficient and environmentally friendly chitosan-based graft flocculant, namely, acrylamide- and dimethyl diallyl ammonium chloride-grafted chitosan [CS-g-P(AM-DMDAAC)], was prepared successfully through plasma initiation. FTIR results confirmed the successful polymerization of CS-g-P(AM-DMDAAC) and P(AM-DMDAAC). P(AM-DMDAAC) was the copolymer of acrylamide- and dimethyl diallyl ammonium chloride. SEM results revealed that a densely cross-linked network structure formed on the surface. XRD results verified that the ordered crystal structure of chitosan in CS-g-P(AM-DMDAAC) was changed into an amorphous structure after plasma-induced polymerization. The flocculation results of low-algal-turbidity water further showed the optimal flocculation efficiency of turbidity removal rate, COD removal rate, and Chl-a removal rate were 99.02%, 96.11%, and 92.20%, respectively. The flocculation efficiency of CS-g-P(AM-DMDAAC) were significantly higher than those obtained by cationic polyacrylamide (CPAM) and Polymeric aluminum and iron (PAFC). This work provided a valuable basis for the design of eco-friendly naturally modified polymeric flocculants to enhance the flocculation of low-algal-turbidity water.

Functionalized Denture Resins as Drug Delivery Biomaterials to Control Fungal Biofilms.

Colonization and biofilm-formation of Candida species on denture surfaces cause Candida-associated denture stomatitis (CADS), a recurring fungal infection that affects up to 67% of denture wearers. We grafted poly(2-hydroxyethyl methacrylate) (PHEMA) onto poly(methyl methacrylate) (PMMA)-based denture resins through plasma-initiated grafting polymerization. The effects of reaction conditions on grafting and the physical properties of the resulting resins were evaluated. The grafted resins showed significantly increased drug binding capability toward clotrimazole, one of the most widely used antifungal drugs. The mechanisms for the enhancement in drug binding were discussed. The new clotrimazole-containing resins provided sustained drug release for longer than 28 days, and the released drugs demonstrated potent, long-term biofilm-controlling effects against Candida, pointing to an attractive strategy in controlling CADS and related fungal infections.

Controlling fungal biofilms with functional drug delivery denture biomaterials

Candida-associated denture stomatitis (CADS), caused by colonization and biofilm-formation of Candida species on denture surfaces, is a significant clinical concern. We show here that modification of conventional denture materials with functional groups can significantly increase drug binding capacity and control drug release rate of the resulting denture materials for potentially managing CADS. In our approach, poly(methyl methacrylate) (PMMA)-based denture resins were surface grafted with three kinds of polymers, poly(1-vinyl-2-pyrrolidinone) (PNVP), poly(methacrylic acid) (PMAA), and poly(2-hydroxyethyl methacrylate) (PHEMA), through plasma-initiated grafting polymerization. With a grafting yield as low as 2wt%, the three classes of new functionalized denture materials showed significantly higher drug binding capacities toward miconazole, a widely used antifungal drug, than the original PMMA denture resin control, leading to sustained drug release and potent biofilm-controlling effects against Candida. Among the three classes of functionalized denture materials, PNVP-grafted resin provided the highest miconazole binding capability and the most powerful antifungal and biofilm-controlling activities. Drug binding mechanisms were studied. These results demonstrated the importance of specific interactions between drug molecules and functional groups on biomaterials, shedding lights on future design of CADS-managing denture materials and other related devices for controlled drug delivery.

Core/shell silicon/polyaniline particles via in-flight plasma-induced polymerization

Although silicon nanoparticles have potential applications in many relevant fields, there is often the need for post-processing steps to tune the property of the nanomaterial and to optimize it for targeted applications. In particular surface modification is generally necessary to both tune dispersibility of the particles in desired solvents to achieve optimal coating conditions, and to interface the particles with other materials to realize functional heterostructures. In this contribution we discuss the realization of core/shell silicon/polymer nanoparticles realized using a plasma-initiated in-flight polymerization process. Silicon particles are produced in a non-thermal plasma reactor using silane as a precursor. After synthesis they are aerodynamically injected into a second plasma reactor into which aniline vapor is introduced. The second plasma initiates the polymerization reactor leading to the formation of a 3–4 nm thick polymer shell surrounding the silicon core. The role of processing conditions on the properties of the polymeric shell is discussed. Preliminary results on the testing of this material as an anode for lithium ion batteries are presented.

N-trimethylchitosan/alginate layer-by-layer self assembly coatings act as "fungal repellents" to prevent biofilm formation on healthcare materials.

Fungal biofilm formation on healthcare materials is a significant clinical concern, often leading to medical-device-related infections, which are difficult to treat. A novel fungal repellent strategy is developed to control fungal biofilm formation. Methylacrylic acid (MAA) is grated onto poly methyl methacrylate (PMMA)-based biomaterials via plasma-initiated grafting polymerization. A cationic polymer, trimethylchitosan (TMC), is synthesized by reacting chitosan with methyl iodide. Sodium alginate (SA) is used as an anionic polymer. TMC/SA multilayers are coated onto the MAA-grafted PMMA via layer-by-layer self-assembly. The TMC/SA multilayer coatings significantly reduce fungal initial adhesion, and effectively prevent fungal biofilm formation. It is concluded that the anti-adhesive property of the surface is due to its hydrophilicity, and that the biofilm-inhibiting action is attributed to the antifungal activity of TMC as well as the chelating function of TMC and SA, which may have acted as fungal repellents. Phosphate buffered saline (PBS)-immersion tests show that the biofilm-modulating effect of the multilayer coatings is stable for more than 4 weeks. Furthermore, the presence of TMC/SA multilayer coatings improves the biocompatibility of the original PMMA, offering a simple, yet effective, strategy for controlling fungal biofilm formation.