Dual-Coating of Fluorinated Polydimethylsiloxane/Fluorinated SiO2 Nanoparticles for Superhydrophobic and High-Efficiency Bacteriostatic Surface.

A simple two-step spray method is used to prepare superhydrophobic and bacteriostatic surfaces, involving dual-coating with polydimethylsiloxane-normal-fluorine (PDMS-NF) or branched-fluorine (PDMS-BF) in combination with fluorinated silica nanoparticles (FSiO2 -NPs) using a spray technique. This approach has the potential to create surfaces with both water-repellent and antimicrobial properties, which could be useful in a variety of applications. It is noteworthy that the dual-coating on cotton fabric exhibited an impressive dual-scale roughness and achieved superhydrophobicity with a water contact angle of 158° and a hysteresis of less than 3°. Additionally, the coating was subjected to an ultra-high concentration of bacteria (109 CFU/mL) and was still able to inhibit more than 80 % of attachment, demonstrating its effectiveness as a bacteriostatic surface.

The Synergistic Effect of Graphene Oxide in Epoxy Resin on Photocured Coating Films with Anticorrosion and Antibacterial Properties.

In this work, graphene oxide (GO) and epoxy-functionalized graphene oxide (GOSi) are chosen as additives and incorporated into epoxy resin (EP) for nanocomposite photo-coating films (GO/EP and GOSi/EP series). Compared to GO/EP, the GOSi/EP nanocomposite demonstrates strong binding and excellent dispersibility, highlighting covalent bonding between GOSi and the epoxy coating. Furthermore, GOSi/EP-based films demonstrated superior thermal stability and adhesion performance on galvanized steel plates. The corrosion performance of the coated galvanized steel is investigated using electrochemical impedance spectroscopy (EIS) and polarization curve analysis (Tafel). The effectiveness of corrosion protection is evaluated based on a combination of photoreactivity, crosslinking density, dispersity, and adhesion properties. Out of all the treated films, the film based on 0.1GOSi/EP exhibited the highest percentage of inhibition (98.89%) and demonstrated superior long-term anticorrosion stability. In addition, the 0.1GOSi/EP based formulation showed remarkable antibacterial activity against S. aureus, resulting in a 92% reduction. This work demonstrates the development of a facile, environmentally friendly functionalized graphene oxide/epoxy photocured film with superior dual functionalities in both anticorrosion and antibacterial properties. These advancements hold promising potential for impactful practical applications.

Effect of Codeposition of Polydopamine with Polyethylenimine or Poly(ethylene glycol) Coatings on Silver Nanoparticle Synthesis.

This study investigated the effects of polydopamine (PDA), PDA/polyethylenimine (PEI), and PDA/poly(ethylene glycol) (PEG) deposition on silver nanoparticle (AgNP) formation. PEI or PEG with different molecular weights was mixed with dopamine at different concentrations to obtain various PDA/PEI or PDA/PEG codepositions. These codepositions were soaked in silver nitrate solution to observe AgNPs generated on the surface and then to examine the catalytic activity of AgNPs for the reduction of 4-nitrophenol to 4-aminophenol. Results revealed that AgNPs on PDA/PEI or PDA/PEG codepositions were smaller and more dispersed than those on PDA coatings. Codeposition with 0.5 mg/mL polymer and 2 mg/mL dopamine generated the smallest AgNPs in each codeposition system. The content of AgNPs on PDA/PEI codeposition first increased and then decreased with an increase in the PEI concentration. PEI with a molecular weight of 600 (PEI600) generated a higher AgNP content than did PEI with a molecular weight of 10000. The AgNP content did not change with the concentration and molecular weight of PEG. Except for the codeposition with 0.5 mg/mL PEI600, codepositions produced less silver than did the PDA coating. The catalytic activity of AgNPs on all codepositions was better than that on PDA. The catalytic activity of AgNPs on all codepositions was related to the size of AgNPs. Smaller AgNPs exhibited more satisfactory catalytic activity. The codeposition with 0.5 mg/mL PEI600 had the highest rate constant (1.64 min-1). The systematic study provides insight into the relationship between various codepositions and AgNP generation and demonstrates that the composition of these codepositions can be tuned to increase their applicability.

Rapid Biocidal Activity of N-Halamine-Functionalized Polydopamine and Polyethylene Imine Coatings.

Microorganisms easily adhere to the surface of substrates and further form biofilms, which present problems in various fields. Therefore, the development of surfaces with antimicrobial adhesion or viability is a promising approach. In this study, we were committed to develop a rapid sterilizing coating. First, polyester fibers were immersed into a mixing solution of dopamine (PDA) and polyethyleneimine (PEI) for forming the co-deposition of PDA and PEI coatings. After this, the co-deposition of PDA and PEI coatings was immersed in a solution of household bleach for chlorination. We found that the nitrogens of PDA and PEI could be chlorinated repeatedly and that the oxidative chlorine content increased with the increasing PEI concentration upon co-deposition. Next, the efficacy of the co-deposition of chlorinated PDA and PEI coatings in eliminating Staphylococcus aureus and Escherichia coli was investigated. We found that the antibacterial ability of the coatings increased with increasing PEI content. In addition, the chlorinated co-deposition coatings had significantly improved antibacterial properties compared to the unchlorinated ones. The chlorinated co-deposition coatings inactivated >99.99% of S. aureus and >99.9% of E. coli after contact of less than 10 min. Therefore, chlorination of a PDA/PEI co-deposition surface is a feasible method for use in antibacterial coatings.

Conjugation of monocarboxybetaine molecules on amino-poly-p-xylylene films to reduce protein adsorption and cell adhesion.

A surface that resists protein adsorption and cell adhesion is highly desirable for many biomedical applications such as blood-contact devices and biosensors. In this study, we fabricated a carboxybetaine-containing surface and evaluated its antifouling efficacy. First, an amine-containing substrate was created by chemical vapor deposition of 4-aminomethyl-p-xylylene-co-p-xylylene (Amino-PPX). Aldehyde-ended carboxybetaine molecules were synthesized and conjugated onto Amino-PPX. The carboxybetaine-PPX surface greatly reduced protein adsorption and cell adhesion. The attachment of L929 cells on the carboxybetaine-PPX surface was reduced by 87% compared to the cell adhesion on Amino-PPX. Furthermore, RGD peptides could be conjugated on carboxybetaine-PPX to mediate specific cell adhesion. In conclusion, we demonstrate that a surface decoration with monocarboxybetaine molecules is useful for antifouling applications.

UV-crosslinking of chitosan/spent coffee ground composites for enhanced durability and multifunctionality.

Spent coffee grounds (SCGs) have numerous applications and are often blended with polymers to create composites. However, SCGs are physically trapped within the polymer matrix, lacking strong chemical bonding. Therefore, this study has developed a new method for UV crosslinking composites using phenyl azide to address the issue of SCG leakage and limited durability of the composites. The main approach involves grafting phenyl azide onto chitosan, which is then combined with SCGs. When exposed to UV light, the SCGs become covalently linked to the chitosan chains. This method not only resolves the problem of chitosan's porous material fragility but also prevents SCG detachment, surpassing the performance of glutaraldehyde-crosslinked composites. Regarding applications, CS/SCG composites exhibit rapid heating and photothermal stability, making them suitable for use as thermal pads in evaporative water purification, enabling for the collection of pure water from contaminated sources. Furthermore, SCGs have the ability to adsorb metal ions, significantly enhancing the Cu2+ adsorption capacity of CS/SCG composites compared to pure CS, with an increase of more than twofold. This research not only presents a practical solution for stabilizing fillers within polymer matrices but also demonstrates the reusability of SCGs.

Fabrication of poly(N-isopropylacrylamide) films containing submicrometer grooves for constructing aligned cell sheets.

Transplantation of cell sheets including an intact extracellular matrix is one tissue-engineering strategy for tissue regeneration. Temperature-responsive substrates based on poly(N-isopropylacrylamide) (PNIPAAm) have been used to harvest intact cell sheets by temperature change. In this work, we immobilized PNIPAAm on plastic substrates by a UV-activated azide-based cross-linking mechanism. We demonstrated that the UV-cross-linked PNIPAAm films could respond to temperature changes and be used for cell-sheet fabrication. Next, grooved PNIPAAm substrates were fabricated by imprinting from grooved poly(dimethylsiloxane) (PDMS) molds (800 nm in groove width and 500 nm in depth). C2C12 cells formed aligned cell sheets on the grooved PNIPAAm surface. The aligned cell sheet could be transferred to a gelatin substrate without losing cell alignment. We expect that this simple time-saving technique for the fabrication of grooved PNIPAAm substrates will benefit from the application of cellular alignment in tissue-engineering products.

Biomimetic surfaces: Insights on the role of surface topography and wetting properties in bacterial attachment and biofilm formation.

The study explores the impact of biomimetic surfaces on bacterial attachment and biofilm formation. Specifically, it investigates the effects of topographic scale and wetting behavior on the attachment and growth of Staphylococcus aureus and Escherichia coli on four different biomimetic surfaces: rose petals, Paragrass leaves, shark skin, and goose feathers. Using soft lithography, epoxy replicas with surface topographies similar to those of the natural surfaces were created. The static water contact angles of the replicas exceeded the hydrophobic threshold of 90°, while the hysteresis angles were found to be in the order of goose feathers, shark skin, Paragrass leaves, and rose petals. The results showed that bacterial attachment and biofilm formation were the lowest on rose petals and the highest on goose feathers, regardless of the bacterial strain. Additionally, the study revealed that surface topography had a significant impact on biofilm formation, with smaller feature sizes inhibiting biofilm formation. Hysteresis angle, rather than static water contact angle, was identified as a critical factor to consider when evaluating bacterial attachment behavior. These unique insights have the potential to lead to the development of more effective biomimetic surfaces for the prevention and eradication of biofilms, ultimately improving human health and safety.

Developing Transparent and Conductive PolyHEMA Gels Using Deep Eutectic Solvents.

Poly(2-hydroxyethyl methacrylate) (polyHEMA) hydrogels are commonly used in biomaterials such as contact lenses. However, water evaporation from these hydrogels can cause discomfort to wearers, and the bulk polymerization method used to synthesize them often results in heterogeneous microstructures, reducing their optical properties and elasticity. In this study, we synthesized polyHEMA gels using a deep eutectic solvent (DES) instead of water and compared their properties to traditional hydrogels. Fourier-transform infrared spectroscopy (FTIR) showed that HEMA conversion in DES was faster than in water. DES gels also demonstrated higher transparency, toughness, and conductivity, along with lower dehydration, than hydrogels. The compressive and tensile modulus values of DES gels increased with HEMA concentration. A DES gel with 45% HEMA showed excellent compression-relaxation cycles and had the highest strain at break value in the tensile test. Our findings suggest that DES is a promising alternative to water for synthesizing contact lenses with improved optical and mechanical properties. Furthermore, DES gels' conduction properties may enable their application in biosensors. This study presents an innovative approach to synthesizing polyHEMA gels and provides insights into their potential applications in the biomaterials field.

A Rapidly and Highly Self-Healing Poly(Sulfobetaine Methacrylate) Hydrogel with Stretching Properties, Adhesive Properties, and Biocompatibility.

This study focuses on the preparation of stretchable zwitterionic poly(sulfobetaine methacrylate) (PSBMA) hydrogels. To address the weak mechanical properties of chemically crosslinked PSBMA hydrogels, a physical crosslinking method utilizing hydrophobic interactions to crosslink hydrogels to approach tough properties is developed. Here, sodium dodecyl sulfate (SDS)-based micelle is used as a physical crosslinker to prepare physically crosslinked PSBMA (PSBMAphy ) hydrogels, and ethylene glycol dimethylacrylate (EGDMA) is used to prepare a control group of chemically crosslinked PSBMA (PSBMAchem ) hydrogels. The mechanical properties of the two hydrogels are compared, and PSBMAphy hydrogels exhibit greater flexibility than the PSBMAchem hydrogels. When the PSBMAphy hydrogels are subjected to external forces, the micelles act as dynamic crosslinking sites, allowing the stress to disperse and prevent the hydrogel from breaking. In addition, the PSBMAphy hydrogels have nearly 100% self-healing properties within 2.5 min. The PSBMAphy hydrogels exhibit usable adhesive properties to porcine skin and subcutis. MTT and hemolysis tests show that the PSBMAphy hydrogels have excellent biocompatibility and hemocompatibility. This study proposes that the multifunctional PSBMAphy hydrogels with micelles will be potential to carry drugs for use in drug delivery systems in the future.

Self-Assembly of Shark Scale-Patterned Tunable Superhydrophobic/Antifouling Structures with Visual Color Response.

The stacked riblet-like shark scales, also known as dermal denticles, allow them to control the boundary layer flow over the skin and to reduce interactions with any biomaterial attached, which guide the design of antifouling coatings. Interestingly, shark scales are with a wide variation in geometry both across species and body locations, thereby displaying diversified antifouling capabilities. Inspired by the multifarious denticles, a stretchable shark scale-patterned silica hollow sphere colloidal crystal/polyperfluoroether acrylate-polyurethane acrylate composite film is engineered through a scalable self-assembly approach. Upon stretching, the patterned photonic crystals feature different short-term antibacterial and long-term anti-biofilm performances with a distinguished color response under varied elongation ratios. To gain a better understanding, the dependence of elongation ratio on antiwetting behaviors, antifouling performances, and structural color changes has also been investigated in this research.

High viability of cells encapsulated in degradable poly(carboxybetaine) hydrogels.

In this study, we report a degradable poly(carboxybetaine) (pCB) hydrogel, produced via a thiol-disulfide exchange reaction for cell encapsulation. A pCB dithiol was synthesized as a cross-linker and reacted with a pyridyl dithiol-containing CB copolymer to form a hydrogel. We evaluated the biocompatibility of the pCB-based hydrogel via encapsulation of three cell types, including NIH3T3 fibroblasts, MG63 osteoblast-like cells, and HepG2 hepatocarcinoma cells. Up to 90% of cells retained their viability in the pCB hydrogel even at low cell-seeding densities under serum-free conditions after a 9-day culture. Results are compared with a degradable poly(ethylene glycol) methacrylate (PEGMA) hydrogel, which showed very low cell viability under serum-free condition after a 3-day culture. We incorporated an RGD peptide into the CB hydrogel using a cysteine-terminated cross-linker, which was shown to promote cell proliferation.

Tunable micropatterned substrates based on poly(dopamine) deposition via microcontact printing.

A simple technique was developed to fabricate tunable micropatterned substrates based on mussel-inspired surface modification. Polydopamine (PDA) was developed on polydimethylsiloxane (PDMS) stamps and was easily imprinted to several substrates such as glass, silicon, gold, polystyrene, and poly(ethylene glycol) via microcontact printing. The imprinted PDA retained its unique reactivity and could modulate the chemical properties of micropatterns via secondary reactions, which was illustrated in this study. PDA patterns imprinted onto a cytophobic and nonfouling substrates were used to form patterns of cells or proteins. PDA imprints reacted with nucleophilic amines or thiols to conjugate molecules such as poly(ethylene glycol) for creating nonfouling area. Gold nanoparticles were immobilized onto PDA-stamped area. The reductive ability of PDA transformed silver ions to elemental metals as an electroless process of metallization. This facile and economic technique provides a powerful tool for development of a functional patterned substrate for various applications.

Enhancing the antibacterial property of chitosan through synergistic alkylation and chlorination.

Chitosan exhibits moderate antimicrobial properties. Here, we enhanced the antimicrobial properties of chitosan through alkylation and chlorination and evaluated the effect of alkylation on chitosan's hydrophobicity, bacterial attachment, chlorination, biocidal property, and stability. First, chitosan films were prepared through casting and were then immersed in a hexanal solution of different concentrations. The aldehyde groups of hexanal reacted with the amino group in chitosan through a Schiff base reaction. Next, the hexanal-modified chitosan films were soaked in 10 % bleach to form N-halamine. The results demonstrated that the surface became more hydrophobic, and chitosan films with increased hexanal-grafting concentrations exhibited less bacterial attachment. However, the degree of chlorination decreased as the degree of alkylation increased, further reducing the diameter of the zone of inhibition. Nevertheless, all chlorinated samples could kill ~5 log of Staphylococcus aureus and Escherichia coli within 30 min. Unlike previous results for chlorinated chitosan, in this study, alkylation before chlorination enhanced antibacterial properties and bactericidal ability and decelerated the degradation of chlorinated samples. The results of a systematic evaluation indicated that a hexanal-grafting concentration of approximately 80 mM maintains the equilibrium of the various properties of chitosan. Alkylated and chlorinated chitosan has considerable potential application as mask filter layers.

Polycarboxybetaine-Based Hydrogels for the Capture and Release of Circulating Tumor Cells.

Circulating tumor cells (CTCs) are indicators for the detection, diagnosis, and monitoring of cancers and offer biological information for the development of personalized medicine. Techniques for the specific capture and non-destructive release of CTCs from millions of blood cells remain highly desirable. Here, we present a CTC capture-and-release system using a disulfide-containing poly(carboxybetaine methacrylate) (pCB) hydrogel. The non-fouling characteristic of pCB prevents unwanted, nonspecific cell binding, while the carboxyl functionality of pCB is used for the conjugation of anti-epithelial cell adhesion molecule (anti-EpCAM) antibodies for the capture of CTCs. The results demonstrated that the anti-EpCAM-conjugated pCB hydrogel captured HCT116 cells from blood, and the capture ratio reached 45%. Furthermore, the captured HCT116 cells were released within 30 min from the dissolution of the pCB hydrogel by adding cysteine, which breaks the disulfide bonds of the crosslinkers. The cells released were viable and able to grow. Our system has potential in the development of a device for CTC diagnosis.

A hemostatic keratin/alginate hydrogel scaffold with methylene blue mediated antimicrobial photodynamic therapy.

Uncontrollable bleeding and infection are two of the most common causes of trauma-related death. Yet, developing safe materials with high hemostatic and antibacterial effectiveness remains a challenge. Keratin-based biomaterials have been reported to exhibit the functions of enhancing platelet binding and activating and facilitating fibrinogen polymerization. In this study, we designed a hemostatic material with good biodegradability, biocompatibility, hemostatic ability, and antibacterial function to solve the shortcomings of common hemostatic materials. Methylene blue-loaded keratin/alginate composite scaffolds were prepared by the freeze-gelation method. The composite scaffolds exhibited over 1600% liquid absorption, well-interconnected pores, good biocompatibility, and biodegradability. We find that the keratin/alginate composite scaffolds' synergistic action may significantly reduce hemostasis time. To prevent infection, the drug-loaded scaffolds generated high burst release by absorbing wound exudate in the early stages of wound healing. The results obtained by the antimicrobial photoinactivation assay in vitro suggest that an antimicrobial photodynamic effect might be triggered, thereby preventing the fast growth of colonies.

Surface modification with poly(sulfobetaine methacrylate-co-acrylic acid) to reduce fibrinogen adsorption, platelet adhesion, and plasma coagulation.

Zwitterionic sulfobetaine methacrylate (SBMA) polymers were known to possess excellent antifouling properties due to high hydration capacity and neutral charge surface. In this study, copolymers of SBMA and acrylic acid (AA) with a variety of compositions were synthesized and were immobilized onto polymeric substrates with layer-by-layer polyelectrolyte films via electrostatic interaction. The amounts of platelet adhesion and fibrinogen adsorption were determined to evaluate hemocompatibility of poly(SBMA-co-AA)-modified substrates. Among various deposition conditions by modulating SBMA ratio in the copolymers and pH of the deposition solution, poly(SBMA(56)-co-AA(44)) deposited at pH 3.0 possessed the best hemocompatibility. This work demonstrated that poly(SBMA-co-AA) copolymers adsorbed on polyelectrolyte-base films via electrostatic interaction improve hemocompatibility effectively and are applicable for various substrates including TCPS, PU, and PDMS. Furthermore, poly(SBMA-co-AA)-coated substrate possesses great durability under rigorous conditions. The preliminary hemocompatibility tests regarding platelet adhesion, fibrinogen adsorption, and plasma coagulation suggest the potential of this technique for the application to blood-contacting biomedical devices.

Biomimetic Mineralization of Tannic Acid-Supplemented HEMA/SBMA Nanocomposite Hydrogels.

This study developed a tannic acid (TA)-supplemented 2-hydroxyethyl methacrylate-co-sulfobetaine methacrylate (HEMA-co-SBMA) nanocomposite hydrogel with mineralization and antibacterial functions. Initially, hybrid hydrogels were synthesized by incorporating SBMA into the HEMA network and the influence of SBMA on the chemical structure, water content, mechanical properties, and antibacterial characteristics of the hybrid HEMA/SBMA hydrogels was examined. Then, nanoclay (Laponite XLG) was introduced into the hybrid HEMA/SBMA hydrogels and the effects evaluated of the nanoclay on the chemical structure, water content, and mechanical properties of these supplemented hydrogels. The 50/50 hybrid HEMA/SBMA hydrogel with 30 mg/mL nanoclay showed outstanding mechanical properties (3 MPa) and water content (60%) compared to pure polyHEMA hydrogels. TA then went on to be incorporated into these hybrid nanocomposite hydrogels and its effects investigated on biomimetic mineralization. Scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) showed that bone-like spheroidal precipitates with a Ca/P ratio of 1.67% were observed after 28 days within these mineralized hydrogels. These mineralized hydrogels demonstrated an almost 1.5-fold increase in compressive moduli compared to the hydrogels without mineralization. These multifunctional hydrogels display good mechanical and biomimetic properties and may have applications in bone regeneration therapies.

Upconversion Nanoparticles Encapsulated with Molecularly Imprinted Amphiphilic Copolymer as a Fluorescent Probe for Specific Biorecognition.

A fluorescent probe for specific biorecognition was prepared by a facile method in which amphiphilic random copolymers were encapsulated with hydrophobic upconversion nanoparticles (UCNPs). This method quickly converted the hydrophobic UCNPs to hydrophilic UNCPs. Moreover, the self-folding ability of the amphiphilic copolymers allowed the formation of molecular imprinting polymers with template-shaped cavities. LiYF4:Yb3+/Tm3+@LiYF4:Yb3+ UCNP with up-conversion emission in the visible light region was prepared; this step was followed by the synthesis of an amphiphilic random copolymer, poly(methacrylate acid-co-octadecene) (poly(MAA-co-OD)). Combining the UCNPs and poly(MAA-co-OD) with the templates afforded a micelle-like structure. After removing the templates, UCNPs encapsulated with the molecularly imprinted polymer (MIP) (UCNPs@MIP) were obtained. The adsorption capacities of UCNPs@MIP bound with albumin and hemoglobin, respectively, were compared. The results showed that albumin was more easily bound to UCNPs@MIP than to hemoglobin because of the effect of protein conformation. The feasibility of using UCNPs@MIP as a fluorescent probe was also studied. The results showed that the fluorescence was quenched when hemoglobin was adsorbed on UCNPs@MIP; however, this was not observed for albumin. This fluorescence quenching is attributed to Förster resonance energy transfer (FRET) and overlap of the absorption spectrum of hemoglobin with the fluorescence spectrum of UCNPs@MIP. To our knowledge, the encapsulation approach for fabricating the UCNPs@MIP nanocomposite, which was further used as a fluorescent probe, might be the first report on specific biorecognition.

Well-Dispersed Silver Nanoparticles on Cellulose Filter Paper for Bacterial Removal.

In this study, a polydopamine (PDA) and polyethyleneimine (PEI)-assisted approach was developed to generate well-distributed PDA/PEI/silver (PDA/PEI/Ag) nanocomplexes on the surfaces of commercial cellulose filter papers to achieve substantial bacterial reduction under gravity-driven filtration. PDA can bind to cellulose paper and act as a reducer to produce silver nanoparticles (AgNPs), while PEI can react with oxidative dopamine and act as a dispersant to avoid the aggregation of AgNPs. The successful immobilization of PDA/PEI/Ag nanocomplexes was confirmed by scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) were used as pathogen models to test the efficacy of the PDA/PEI/Ag nanocomplex-incorporated filter papers. The PDA/PEI/Ag nanocomplex-incorporated filter papers provided a substantial bacterial removal of up to 99% by simple gravity filtration. This work may be useful to develop a feasible industrial production process for the integration of biocidal AgNPs into cellulose filter paper and is recommended as a local-condition water-treatment technology to treat microbial-contaminated drinking water.