Bioinspired nanostructured surfaces for antimicrobial and antifouling applications

Because zinc oxide (ZnO) nanomaterials are used in antifouling and antibacterial solutions, understanding their toxic effects on different aquatic organisms is essential. In the present study, we evaluated the toxicity of ZnO nanoparticles of 10 to 30 nm (ZnONPI) and 80 to 200 nm (ZnONPII), ZnO nanorods (width 80 nm, height 1.7 µm) attached to the support substrate (glass, ZnONRG) and not attached (ZnONRS), as well as Zn2+ ions at concentrations ranging from 0.5 to 100 mg/L. Toxicity was evaluated using the microalga Dunaliella salina, the brine shrimp Artemia salina, and the marine bacterium Bacillus cereus. The highest toxicity was observed for ZnONPs (median lethal concentration [LC50] ~15 mg/L) and Zn2+ ions (LC50 ~13 mg/L), whereas the lowest toxicity found for ZnO nanorods (ZnONRG LC50 ~60 mg/L; ZnONRS LC50 ~42 mg/L). The presence of the support substrate in case of ZnO nanorods reduced the associated toxicity to aquatic organisms. Smaller ZnONPs resulted in the highest Zn2+ ion dissolution among tested nanostructures. Different aquatic organisms responded differently to ZnO nanomaterials, with D. salina and B. cereus being more sensitive than A. salina. Toxicity of nanostructures increased with an increase of the dose and the time of exposure. Supported ZnO nanorods can be used as a low-toxicity alternative for future antimicrobial and antifouling applications. Environ Toxicol Chem 2020;39:1343-1354. © 2020 SETAC.

The breadth and importance of polymerized ionic liquids (PILs) are steadily expanding, and this review updates advances and trends in syntheses, properties, and applications over the past five to six years. We begin with an historical overview of the genesis and growth of the PIL field as a subset of materials science. The genesis of ionic liquids (ILs) over nano to meso length-scales exhibiting 0D, 1D, 2D, and 3D topologies defines colloidal ionic liquids, CILs, which compose a subclass of PILs and provide a synthetic bridge between IL monomers (ILMs) and micro to macro-scale PIL materials. The second focus of this review addresses design and syntheses of ILMs and their polymerization reactions to yield PILs and PIL-based materials. A burgeoning diversity of ILMs reflects increasing use of nonimidazolium nuclei and an expanding use of step-growth chemistries in synthesizing PIL materials. Radical chain polymerization remains a primary method of making PILs and reflects an increasing use of controlled polymerization methods. Step-growth chemistries used in creating some CILs utilize extensive cross-linking. This cross-linking is enabled by incorporating reactive functionalities in CILs and PILs, and some of these CILs and PILs may be viewed as exotic cross-linking agents. The third part of this update focuses upon some advances in key properties, including molecular weight, thermal properties, rheology, ion transport, self-healing, and stimuli-responsiveness. Glass transitions, critical solution temperatures, and liquidity are key thermal properties that tie to PIL rheology and viscoelasticity. These properties in turn modulate mechanical properties and ion transport, which are foundational in increasing applications of PILs. Cross-linking in gelation and ionogels and reversible step-growth chemistries are essential for self-healing PILs. Stimuli-responsiveness distinguishes PILs from many other classes of polymers, and it emphasizes the importance of segmentally controlling and tuning solvation in CILs and PILs. The fourth part of this review addresses development of applications, and the diverse scope of such applications supports the increasing importance of PILs in materials science. Adhesion applications are supported by ionogel properties, especially cross-linking and solvation tunable interactions with adjacent phases. Antimicrobial and antifouling applications are consequences of the cationic nature of PILs. Similarly, emulsion and dispersion applications rely on tunable solvation of functional groups and on how such groups interact with continuous phases and substrates. Catalysis is another significant application, and this is an historical tie between ILs and PILs. This component also provides a connection to diverse and porous carbon phases templated by PILs that are catalysts or serve as supports for catalysts. Devices, including sensors and actuators, also rely on solvation tuning and stimuli-responsiveness that include photo and electrochemical stimuli. We conclude our view of applications with 3D printing. The largest components of these applications are energy related and include developments for supercapacitors, batteries, fuel cells, and solar cells. We conclude with our vision of how PIL development will evolve over the next decade.

Electroactive polymers (EAPS) are a unique class of materials that are extensively applied as sensors for chemical and mechanical stimuli. Due to their high strain ability and low moduli they can form various shapes. These characteristics allow them to be used as sensors and to interact with cells, for example, for tissue engineering applications and drug delivery. Based on the charge they carry, they can be categorized in to two types: ionic and electronic EAPs. This chapter will discuss the major types of electroactive materials that are used for sensing drug delivery, tissue regeneration, and antimicrobial and antifouling applications.

Copper formulations have been used for decades for antimicrobial and antifouling applications. With the development of nanoformulations of copper that are more effective than their ionic and microsized analogues, a key regulatory question is whether these materials should be treated as new or existing materials. To address this issue, here we compare the magnitude and mechanisms of toxicity of a series of Cu species (at concentration ranging from 2 to 250 μg/mL), including nano Cu, nano CuO, nano Cu(OH)2 (CuPro and Kocide), micro Cu, micro CuO, ionic Cu(2+) (CuCl2 and CuSO4) in two species of bacteria (Escherichia coli and Lactobacillus brevis). The primary size of the particles studied ranged from 10 nm to 10 μm. Our results reveal that Cu and CuO nanoparticles (NPs) are more toxic than their microsized counterparts at the same Cu concentration, with toxicities approaching those of the ionic Cu species. Strikingly, these NPs showed distinct differences in their mode of toxicity when compared to the ionic and microsized Cu, highlighting the unique toxicity properties of materials at the nanoscale. In vitro DNA damage assays reveal that both nano Cu and microsized Cu are capable of causing complete degradation of plasmid DNA, but electron tomography results show that only nanoformulations of Cu are internalized as intact intracellular particles. These studies suggest that nano Cu at the concentration of 50 μg/mL may have unique genotoxicity in bacteria compared to ionic and microsized Cu.

Biomimetic catechol-functionalized hydrogels have attracted substantial attention due to their potential in a variety of biomedical applications, such as tissue repair and regeneration, drug delivery, and antimicrobial and antifouling applications. In this study, a one-pot strategy for fabrication of functional catecholic hydrogels using dopamine as a photoinitiator was developed. Under UV irradiation in an acidic solution, dopamine generates free radicals, likely semiquinone radicals, to trigger the addition polymerization, following pseudo-first-order kinetics. The dopamine-initiated photopolymerization provides a straightforward and facile approach and, in addition, prevents the undesirable oxidation to catecholic groups. Superhydrophilic sulfobetaine methacrylate (SBMA) was applied for developing biocompatible hydrogels. 1H nuclear magnetic resonance, UV-vis spectroscopy, gel permeation chromatography, and rheological studies were conducted to explore the polymerization mechanism and optimal experimental conditions in terms of pH, UV doses, and the concentration of dopamine. The unique properties of the resultant catechol-functionalized pSBMA hydrogels were demonstrated by enhanced mechanical properties through metal-catechol complexation, self-healing and injectable capability, high adhesiveness, and fouling resistance. Consequently, the synthetic strategy to design catecholic hydrogels can leverage the use of dopamine in a variety of applications.

Inhibition of bacteria adhesion and biofilm formation using a precisely structured nitric oxide-releasing coating with repeatedly renewing antimicrobial and antifouling ability

It is well-established that the structural, morphological and performance characteristics of nanoscale materials critically depend upon the dispersion state of the nanofillers that is, in turn, largely determined by the preparation protocol. In this report, we review synthetic strategies that capitalise on the in situ generation of nanoparticles on and within polymeric materials, an approach that relies on the chemical transformation of suitable precursors to functional nanoparticles synchronous with the build-up of the nanohybrid systems. This approach is distinctively different compared to standard preparation methods that exploit the dispersion of preformed nanoparticles within the macromolecular host and presents advantages in terms of time and cost effectiveness, environmental friendliness and the uniformity of the resulting composites. Notably, the in situ-generated nanoparticles tend to nucleate and grow on the active sites of the macromolecular chains, showing strong adhesion on the polymeric host. So far, this strategy has been explored in fabrics and membranes comprising metallic nanoparticles (silver, gold, platinum, copper, etc.) in relation to their antimicrobial and antifouling applications, while proof-of-concept demonstrations for carbon- and silica-based nanoparticles as well as titanium oxide-, layered double hydroxide-, hectorite-, lignin- and hydroxyapatite-based nanocomposites have been reported. The nanocomposites thus prepared are ideal candidates for a broad spectrum of applications such as water purification, environmental remediation, antimicrobial treatment, mechanical reinforcement, optical devices, etc.

Inverse infusion processed hierarchical structure towards superhydrophobic coatings with ultrahigh mechanical robustness

In marine environments or industrial water systems, microorganisms are likely to adhere onto surfaces and form biofilms. Such biofouling creates significant adverse effects, e.g., increases flow friction by roughening surfaces. Previous studies demonstrated the effectiveness of surface microstructures on the prevention of biofouling, which is also closely associated with the surface energy and wettability. Unfortunately, the study of the anti-biofouling property of the micro- and nanostructured surfaces with regulated surface wettability is underperformed at present. In this paper, we report on the bio-adhesions of various cell types on nanoengineered surfaces with dense-array nanostructures whose physical and chemical properties are systematically controlled for the prevention of biofouling. Two nanopatterns (pillar and grating) with varying three-dimensionalities (e.g., structural heights are varied from 50 to 500 nm while the pattern periodicity is fixed at 230 nm) are tested in both hydrophilic and hydrophobic surface conditions. The structural tips are especially sharpened (<10 nm in tip radius) to minimize the cell contact to the substrate and potentially biofouling. The experimental results show that cells were much smaller and their proliferation significantly lower on taller nanostructures in both hydrophilic and hydrophobic surface conditions. Cells were found levitated by sharp tips and easily peeled off, i.e., their adherence to the sharp-tip tall nanostructures was relatively weak regardless of the surface wettability. The ability to control adherence and growth of cells by nanoscale surface topographies can empower the micro- and nanotechnology-based materials, devices, and systems for anti-biofouling and anti-microbial applications. The knowledge obtained through this investigation will also be useful in engineering problems that involve contact with biological substances and in the development of energy efficient surfaces for green tribology.

The impact of the reaction environment on the formation of the polycrystalline layer and its biomedical (antimicrobial) applications were analyzed in detail. Copper oxide layers were synthesized using an electrodeposition technique, with varying additives influencing the morphology, thickness, and chemical composition. Scanning electron microscopy (SEM) images confirmed the successful formation of polyhedral structures. Unmodified samples (CuL) crystallized as a mixture of copper oxide (I) and (II), with a thickness of approximately 1.74 μm. The inclusion of the nonconductive polymer polyvinylpyrrolidone (PVP) during synthesis led to a regular and compact CuO-rich structure (CuL-PVP). Conversely, adding glucose resulted in forming a Cu2O-rich nanostructured layer (CuL-D(+)G). Both additives significantly reduced the sample thickness to 617 nm for CuL-PVP and 560 nm for CuL-D(+)G. The effectiveness of the synthesized copper oxide layers was demonstrated in their ability to significantly reduce the T4 phage titer by approximately 2.5-3 log. Notably, CuL-PVP and CuL-D(+)G showed a more substantial reduction in the MS2 phage titer, achieving about a 5-log decrease. In terms of antibacterial activity, CuL and CuL-PVP exhibited moderate efficacy against Escherichia coli, whereas CuL-D(+)G reduced the E. coli titer to undetectable levels. All samples induced similar reductions in Staphylococcus aureus titer. The study revealed differential susceptibilities, with Gram-negative bacteria being more vulnerable to CuL-D(+)G due to its unique composition and morphology. The antimicrobial properties were attributed to the redox cycling of Cu ions, which generate ROS, and the mechanical damage caused by nanostructured surfaces. A crucial finding was the impact of surface composition rather than surface morphology on antimicrobial efficacy. Samples with a dominant Cu2O composition exhibited potent antibacterial and antiviral properties, whereas CuO-rich materials showed predominantly enhanced antiviral activity. This research highlights the significance of phase composition in determining the antimicrobial properties of copper oxide layers synthesized through electrodeposition.

Microbial biofilms are associated with drastically enhanced resistance to most of the antimicrobial agents and with frequent treatment failures, generating the search for novel strategies which can eradicate infections by preventing the persistent colonization of the hospital environment, medical devices or human tissues. Some of the current approaches for fighting biofilms are represented by the development of novel biomaterials with increased resistance to microbial colonization and by the improvement of the current therapeutic solutions with the aid of nano (bio)technology. This special issues includes papers describing the applications of nanotechnology and biomaterials science for the development of improved drug delivery systems and nanostructured surfaces for the prevention and treatment of medical biofilms. Nanomaterials display unique and well-defined physical and chemical properties making them useful for biomedical applications, such as: very high surface area to volume ratio, biocompatibility, biodegradation, safety for human ingestion, capacity to support surface modification and therefore, to be combined with other bioactive molecules or substrata and more importantly being seemingly not attracting antimicrobial resistance. The use of biomaterials is significantly contributing to the reduction of the excessive use of antibiotics, and consequently to the decrease of the emergence rate of resistant microorganisms, as well as of the associated toxic effects. Various biomaterials with intrinsic antimicrobial activity (inorganic nanoparticles, polymers, composites), medical devices for drug delivery, as well as factors influencing their antimicrobial properties are presented. One of the presented papers reviews the recent literature on the use of magnetic nanoparticles (MNP)-based nanomaterials in antimicrobial applications for biomedicine, focusing on the growth inhibition and killing of bacteria and fungi, and, on viral inactivation. The anti-pathogenic activity of the most common types of metallic/metal oxide nanoparticles, as well as the photocontrolled targeted drug-delivery system and the development of traditional Chinese herbs nanoparticles are some of the highlights of another paper of this issue. The applications of synthetic, biodegradable polymers for the improvement of antiinfective therapeutic and prophylactic agents (i.e., antimicrobial and anti-inflammatory agents and vaccines) activity, as well as for the design of biomaterials with increased biocompatibility and resistance to microbial colonization are also discussed, as well as one of the most recent paradigms of the pharmaceutical field and nanobiotechnology, represented by the design of smart multifunctional polymeric nanocarriers for controlled drug delivery. These systems are responding to physico-chemical changes and as a result, they can release the active substances in a controlled and targeted manner. The advantages and limitations of the main routes of polymerization by which these nanovehicles are obtained, as well as the practical appllications in the field of drug nanocarriers are presented. The authors describe the therapeutic applications of dendrimers, which are unimolecular, monodisperse nanocarriers with unique branched tree-like globular structure. The applications of nanotechnology for the stabilization and improved release of anti-pathogenic natural or synthetic compounds, which do not interfere with the microbial growth, but inhibit different features of microbial pathogenicity are also highlighted. We expect this special issue would offer a comprehensive update and give new directions for the design of micro/nano engineered materials to inhibit microbial colonization on the surfaces or to potentiate the efficiency of the current/ novel/alternative antimicrobial agents by improving their bioavailability and pharmacokinetic features.

Electrochemical modification of high contact stainless steel 304 surfaces for antimicrobial applications