Antibacterial ultrafiltration membrane with silver nanoparticle impregnation by interfacial polymerization for ballast water

Interfacial polymerization technology was employed to immobilize silver (Ag) nanoparticles on the surface of commercial polyethersulfone (PES) membrane to develop antibacterial and antifouling ultrafiltration membrane. Ag nanoparticles were prepared from the reduction of silver nitrate (AgNO₃) by sodium borohydride in the presence of polyethyleneimine (PEI) as the stabilizer. The encapsulated Ag nanoparticles in the PEI solution were embedded into the PEI membrane when trimesoyl chloride solution was used to crosslink the PEI solution with the PES membrane, forming Ag-polyamide (PA) networks through the interfacial polymerization reaction. Experimental results showed that the membrane prepared with 50 mmol/L of AgNO₃ and 20 mmol/L of PEI had the optimized antibacterial effect against Escherichia coli. Bacterial concentration and species were also investigated. Exiguobacterium aestuarii and Staphylococcus aureus which are gram-positive bacteria, needed significantly more time for the Ag-PA/PES membrane to kill the bacteria completely when compared to E.coli and Vibrio coralliilyticus which are gram-negative bacteria. This study showed that Ag nanoparticles impregnated in membrane surfaces were 100% effective in killing various types of marine bacteria and bacteria in the seawater collected off Sentosa Island in Singapore. These membranes exhibit excellent antibacterial and antifouling properties which can be used to kill bacteria in ballast water and seawater.     

Porous Microstructured Surfaces with pH‐Triggered Antibacterial Properties

New antibacterial films are designed with the capability to reversibly regulate their killing and repelling functions in response to variations in environmental pH. These systems consist of porous polystyrene surfaces as the main components and a copolymer bearing pH‐sensitive thiazole and triazole groups as the minor components. These pH‐sensitive groups, located on the surfaces, can be partially protonated at acidic pH levels, increasing the positive charge density of the surfaces and their antibacterial activity. Similarly, their bacterial adhesion and killing efficiencies in response to changes in pH are evaluated by analyzing the bacterial viability of Staphylococcus aureus bacteria on the surfaces under acidic and neutral pH values. It is demonstrated that after only 1 h of incubation with the bacterial suspension in acidic conditions, the surfaces killed the bacteria, while at pH = 7.4, some of the adhered bacteria are removed. Furthermore, the surface topography exerts an important role by intensifying this response.     

Controlled adhesion of Salmonella Typhimurium to poly(oligoethylene glycol methacrylate) grafts

Poly(oligoethylene glycol methacrylate), POEGMA, brushes were prepared by surface‐initiated atom transfer radical polymerization (SI‐ATRP) on gold‐coated silicon wafers. Prior to ATRP, the substrates were grafted by brominated aryl initiators via the electrochemical reduction of a noncommercial parent diazonium salt of the formula BF₄^?, ⁺N₂‐C₆H₄‐CH(CH₃)Br. The diazonium‐modified gold plates (Au‐Br) served as macroinitiators for ATRP of OEGMA which resulted in hydrophilic surfaces (Au‐POEGMA) that could be used for two distinct objectives: (i) resistance to fouling by Salmonella Typhimurium; (ii) specific recognition of the same bacteria provided that the POEGMA grafts are activated by anti‐Salmonella. The Au‐POEGMA plates were characterized by XPS, polarization modulation‐infrared reflection‐absorption spectroscopy (PM‐IRRAS) and contact angle measurements. Both Beer‐Lambert equation and Tougaard's QUASES software indicated a POEGMA thickness that exceeds the critical ～10 nm value necessary for obtaining a hydrophilic polymer with effective resistance to cell adhesion. The Au‐POEGMA slides were further activated by trichlorotriazine (TCT) in order to covalently bind anti‐Salmonella antibodies (AS). The antibody‐modified Au‐POEGMA specimens were found to specifically attach Salmonella Typhimurium bacteria. This work is another example of the diazonium salt/ATRP process to provide biomedical polymer surfaces. Copyright © 2011 John Wiley & Sons, Ltd.     

Polymer‐Based Surfaces Designed to Reduce Biofilm Formation: From Antimicrobial Polymers to Strategies for Long‐Term Applications

Contact‐active antimicrobial polymer surfaces bear cationic charges and kill or deactivate bacteria by interaction with the negatively charged parts of their cell envelope (lipopolysaccharides, peptidoglycan, and membrane lipids). The exact mechanism of this interaction is still under debate. While cationic antimicrobial polymer surfaces can be very useful for short‐term applications, they lose their activity once they are contaminated by a sufficiently thick layer of adhering biomolecules or bacterial cell debris. This layer shields incoming bacteria from the antimicrobially active cationic surface moieties. Besides discussing antimicrobial surfaces, this feature article focuses on recent strategies that were developed to overcome the contamination problem. This includes bifunctional materials with simultaneously presented antimicrobial and protein‐repellent moieties; polymer surfaces that can be switched from an antimicrobial, cell‐attractive to a cell‐repellent state; polymer surfaces that can be regenerated by enzyme action; degradable antimicrobial polymers; and antimicrobial polymer surfaces with removable top layers.     

Positively Charged Nanoaggregates Based on Zwitterionic Pillar[5]arene that Combat Planktonic Bacteria and Disrupt Biofilms

Bacterial biofilms are difficult to eradicate because they are less susceptible to antibiotics and more easily develop resistance. Therefore, there is an urgent need for new materials that can combat planktonic bacteria and disrupt established biofilms. To tackle this challenge, we design a multifunctional zwitterionic pillar[5]arene, which can self‐assemble into weakly positively charged nanoaggregates that exhibit antibacterial activity against Gram‐negative Escherichia coli (DH5α) and Gram‐positive Staphylococcus aureus (SH1000) bacterial strains in solution. In addition, the zwitterionic pillar[5]arene can efficiently disrupt pre‐existing Escherichia coli (DH5α) biofilms and kill the biofilm‐enclosed bacteria without rapid generation of resistance.     

A biofilm resistance surface yielded by grafting of antimicrobial peptides on stainless steel surface

Anti‐biofilm formation on the surface is a severe issue in medical implants, hull surface, and food industry. Antimicrobial peptide, magainin II, was covalently bound to stainless steel surfaces through multi‐step modification. The untreated and modified samples were analyzed by SEM‐EDS, XPS, and contact angle, respectively, which indicated the peptide was immobilized on the surfaces. The antimicrobial tests of modified samples were conducted using Staphylococcus aureus and Escherichia coli, and the results revealed that peptide modified surface decreased the biofilm and bacteria quantity of stainless steel surface.     

A modified polyvinylchloride surface with antibacterial and antifouling functions

Surfaces with antibacterial and hydrophilic properties are very attractive to cardiovascular applications. The objective of this study was to synthesize and immobilize a novel antibacterial and hydrophilic polymer onto surface of polyvinylchloride via an effective and mild surface coating technique. The surface coated with a terpolymer constructed with N‐vinylpyrrolidone, 3,4‐dichloro‐5‐hydroxy‐2(5H)‐furanone derivative, and succinimide residue was evaluated with cell adhesion, bacterial adhesion, and bacterial viability. 3T3 mouse fibroblast cells and two bacteria species were used to evaluate surface adhesion and antibacterial activity. Results showed that the polymer‐modified polyvinylchloride surface exhibited not only significantly decreased 3T3 fibroblast cell adhesion with a 66% to 87% reduction but also significantly decreased bacterial adhesion with 69% to 87% and 52% to 74% reduction of Pseudomonas aeruginosa and Staphylococcus aureus attachment, respectively, as compared with original polyvinylchloride. Furthermore, the modified polyvinylchloride surfaces exhibited significant antibacterial functions by inhibiting bacterial growth (75%‐84% and 78–94% inhibition of P aeruginosa and S aureus, respectively, as compared to original polyvinylchloride) and killing bacteria. These results demonstrate that covalent polymer attachment conferred antifouling and antibacterial properties to the polyvinylchloride surface.     

Halogenated Phenazines that Potently Eradicate Biofilms,MRSA Persister Cells in Non‐Biofilm Cultures,and Mycobacterium tuberculosis

Conventional antibiotics are ineffective against non‐replicating bacteria (for example, bacteria within biofilms). We report a series of halogenated phenazines (HP), inspired by marine antibiotic 1 , that targets persistent bacteria. HP 14 demonstrated the most potent biofilm eradication activities to date against MRSA, MRSE, and VRE biofilms (MBEC=0.2–12.5 μM), as well as the effective killing of MRSA persister cells in non‐biofilm cultures. Frontline MRSA treatments, vancomycin and daptomycin, were unable to eradicate MRSA biofilms or non‐biofilm persisters alongside 14 . HP 13 displayed potent antibacterial activity against slow‐growing M. tuberculosis (MIC=3.13 μM), the leading cause of death by bacterial infection around the world. HP analogues effectively target persistent bacteria through a mechanism that is non‐toxic to mammalian cells and could have a significant impact on treatments for chronic bacterial infections.     

Halogenated Phenazines that Potently Eradicate Biofilms,MRSA Persister Cells in Non‐Biofilm Cultures,and Mycobacterium tuberculosis

Conventional antibiotics are ineffective against non‐replicating bacteria (for example, bacteria within biofilms). We report a series of halogenated phenazines (HP), inspired by marine antibiotic 1 , that targets persistent bacteria. HP 14 demonstrated the most potent biofilm eradication activities to date against MRSA, MRSE, and VRE biofilms (MBEC=0.2–12.5 μM), as well as the effective killing of MRSA persister cells in non‐biofilm cultures. Frontline MRSA treatments, vancomycin and daptomycin, were unable to eradicate MRSA biofilms or non‐biofilm persisters alongside 14 . HP 13 displayed potent antibacterial activity against slow‐growing M. tuberculosis (MIC=3.13 μM), the leading cause of death by bacterial infection around the world. HP analogues effectively target persistent bacteria through a mechanism that is non‐toxic to mammalian cells and could have a significant impact on treatments for chronic bacterial infections.     

Contact Active Antimicrobial Coatings Prepared by Polymer Blending

Herein, contact active antimicrobial films are prepared by simply blending cationic amphiphilic block copolymers with commercial polystyrene (PS). The copolymers are prepared by combining atom transfer radical polymerization and “click chemistry.” A variety of copolymers are synthesized, and composed of a PS segment and an antimicrobial block bearing flexible side chain with thiazole and triazole groups, 4‐(1‐(2‐(4‐methylthiazol‐5‐yl)ethyl)‐1H‐1,2,3‐triazol‐4‐yl) butyl methacrylate (TTBM). The length of the TTBM block is varied as well as the alkylating agent. Different films are prepared from N,N‐dimethylformamide solution, containing variable PS‐b‐PTTBM/PS ratio: from 0 to 100 wt%. Remarkably, the blend films, especially those with 30 and 50 wt% of copolymers, exhibit excellent antimicrobial activities against Gram‐positive, Gram‐negative bacteria and fungi, even higher than films prepared exclusively from the cationic copolymers. Blends composed of 50 wt% of the copolymers present a more than 99.999% killing efficiency against the studied microorganisms. The better activity found in blends can be due to the higher roughness, which increases the surface area and consequently the contact with the microorganisms. These results demonstrate that the use of blends implies a reduction of the content of antimicrobial agent and also enhances the antimicrobial activity, providing new insights for the better designing of antimicrobial coatings.     

Wettability of poly(styrene‐co‐acrylate) ionomers improved by oxygen‐plasma source ion implantation

The surfaces of poly(styrene‐co‐acrylic acid) copolymers and their Na‐ and Cs‐neutralized ionomers were modified by O₂‐plasma source ion implantation (PSII) treatment to improve the surface wettability. The changes in the surface wettability, composition, and structure upon the PSII treatment were examined with contact‐angle measurements and X‐ray photoelectron spectroscopy. The untreated surfaces of the acid copolymers and ionomers exhibited different surface energies; this implied clearly that the type of ion species affects the surface hydrophilicity. Also, the PSII treatment induced oxygen‐containing groups to reside on the surface and ionic groups to come out toward the surface; this made the surfaces of the ionomers more hydrophilic as compared with that of the acid copolymers. The ionomers also showed slow hydrophobic recovery. Thus, it was suggested that the reduced mobility of the polymer chain because of the presence of ionic aggregates results in restricted reorientation of oxygen‐containing groups. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1791–1797, 2003     

具有“杀菌-释菌”功能转换的智能抗菌表面

细菌在生物材料表面的黏附和后续生物被膜的形成会引起一系列严重后果,因此赋予生物材料表面抗菌性能成为国内外科研工作者们的研究热点.然而目前常见的抗菌策略主要集中在杀死表面黏附的细菌,而忽略了死细菌在表面的积累所引起的如抗菌效率下降、二次污染等诸多问题.针对此,研究者们提出了"杀菌-释菌"功能转换的智能抗菌策略并以此发展了一系列智能抗菌表面.本专论基于我们课题组的研究成果,根据杀菌剂与材料表面结合方式的不同(永久固定杀菌剂、可重复负载杀菌剂和不需要杀菌剂),对近年来智能抗菌表面领域的研究进展进行了评述.这些智能抗菌表面能够在杀灭细菌后及时清除表面残留的死细菌,从而保持了长效抗菌功能.最后对该领域未来的研究方向进行了展望.     

Bacterial Autoimmune Drug Metabolism Transforms an Immunomodulator into Structurally and Functionally Divergent Antibiotics

Tapinarof is a stilbene drug that is used to treat psoriasis and atopic dermatitis, and is thought to function through regulation of the AhR and Nrf2 signaling pathways, which have also been linked to inflammatory bowel diseases. It is produced by the gammaproteobacterial Photorhabdus genus, which thus represents a model to probe tapinarof structural and functional transformations. We show that Photorhabdus transforms tapinarof into novel drug metabolism products that kill inflammatory bacteria, and that a cupin enzyme contributes to the conversion of tapinarof and related dietary stilbenes into novel dimers. One dimer has activity against methicillin‐resistant Staphylococcus aureus (MRSA) and vancomycin‐resistant Enterococcus faecalis (VRE), and another undergoes spontaneous cyclizations to a cyclopropane‐bridge‐containing hexacyclic framework that exhibits activity against Mycobacterium. These dimers lack efficacy in a colitis mouse model, whereas the monomer reduces disease symptoms.     

New Calcium‐Selective Smart Contrast Agents for Magnetic Resonance Imaging

Calcium plays a vital role in the human body and especially in the central nervous system. Precise maintenance of Ca²⁺ levels is very crucial for normal cell physiology and health. The deregulation of calcium homeostasis can lead to neuronal cell death and brain damage. To study this functional role played by Ca²⁺ in the brain noninvasively by using magnetic resonance imaging, we have synthesized a new set of Ca²⁺‐sensitive smart contrast agents (CAs). The agents were found to be highly selective to Ca²⁺ in the presence of other competitive anions and cations in buffer and in physiological fluids. The structure of CAs comprises Gd³⁺‐DO3A (DO3A=1,4,7‐tris(carboxymethyl)‐1,4,7,10‐tetraazacyclododecane) coupled to a Ca²⁺ chelator o‐amino phenol‐N,N,O‐triacetate (APTRA). The agents are designed to sense Ca²⁺ present in extracellular fluid of the brain where its concentration is relatively high, that is, 1.2–0.8 mM . The determined dissociation constant of the CAs to Ca²⁺ falls in the range required to sense and report changes in extracellular Ca²⁺ levels followed by an increase in neural activity. In buffer, with the addition of Ca²⁺ the increase in relaxivity ranged from 100–157 %, the highest ever known for any T₁‐based Ca²⁺‐sensitive smart CA. The CAs were analyzed extensively by the measurement of luminescence lifetime measurement on Tb³⁺ analogues, nuclear magnetic relaxation dispersion (NMRD), and ¹⁷O NMR transverse relaxation and shift experiments. The results obtained confirmed that the large relaxivity enhancement observed upon Ca²⁺ addition is due to the increase of the hydration state of the complexes together with the slowing down of the molecular rotation and the retention of a significant contribution of the water molecules of the second sphere of hydration.     

Antiviral and Antibacterial Polyurethanes of Various Modalities

We have prepared and characterized a new polyurethane-based antimicrobial material, N,N-dodecyl,methyl-polyurethane (Quat-12-PU). It exhibits strong antiviral and antibacterial activities when coated (as an organic solution or an aqueous nanosuspension) onto surfaces and antibacterial activity when electrospun into nanofibers. Quat-12-PU surfaces are able to kill airborne Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli bacteria, as well as inactivate the enveloped influenza virus (but not the non-enveloped poliovirus).     

3D‐Printed Titanium Cage with PVA‐Vancomycin Coating Prevents Surgical Site Infections (SSIs)

Many coating materials have been studied to prevent surgical site infections (SSIs). However, antibacterial coating on surfaces show weak adhesion using the traditional titanium (Ti) cage, resulting in low efficacy for preventing SSIs after spinal surgery. Herein, a 3D‐printed Ti cage combined with a drug‐releasing system is developed for in situ drug release and bacteria killing, leading to prevention of SSIs in vitro and in vivo. First, a 3D‐printed Ti cage is designed and prepared by the Electron Beam Melting (EBM) method. Second, polyvinyl alcohol (PVA) containing hydrophilic vancomycin hydrochloride (VH) is scattered across the surface of 3D‐printed porous Ti (Ti‐VH@PVA) cages. Ti‐VH@PVA cages show an efficient drug‐releasing profile and excellent bactericidal effect for three common bacteria after more than seven days in vitro. In addition, Ti‐VH@PVA cages exhibit reliable inhibition of inflammation associated with Staphylococcus aureus and effective bone regeneration capacity in a rabbit model of SSIs. The results indicate that Ti‐VH@PVA cages have potential advantages for preventing SSIs after spinal surgery.     

Photo-Controlled Gating of Selective Bacterial Membrane Interaction and Enhanced Antibacterial Activity for Wound Healing

Reversible biointerfaces are essential for on-demand molecular recognition to regulate stimuli-responsive bioactivity such as specific interactions with cell membranes. The reversibility on a single platform allows the smart material to kill pathogens or attach/detach cells. Herein, we introduce a 2D-MoS₂ functionalized with cationic azobenzene that interacts selectively with either Gram-positive or Gram-negative bacteria in a light-gated fashion. The trans conformation ( trans -Azo-MoS₂ ) selectively kills Gram-negative bacteria, whereas the cis form ( cis -Azo-MoS₂ ), under UV light, exhibits antibacterial activity against Gram-positive strains. The mechanistic investigation indicates that the cis -Azo-MoS₂ exhibits higher affinity towards the membrane of Gram-positive bacteria compared to trans -Azo-MoS₂ . In case of Gram-negative bacteria, trans -Azo-MoS₂ internalizes more efficiently than cis -Azo-MoS₂ and generates intracellular ROS to kill the bacteria. While the trans -Azo-MoS₂ exhibits strong electrostatic interactions and internalizes faster into Gram-negative bacterial cells, cis -Azo-MoS₂ primarily interacts with Gram-positive bacteria through hydrophobic and H-bonding interactions. The difference in molecular mechanism leads to photo-controlled Gram-selectivity and enhanced antibacterial activity. We found strain-specific and high bactericidal activity (minimal bactericidal concentration, 0.65 μg/ml) with low cytotoxicity, which we extended to wound healing applications. This methodology provides a single platform for efficiently switching between conformers to reversibly control the strain-selective bactericidal activity regulated by light.     

Recent Progress on Manganese-Based Nanostructures as Responsive MRI Contrast Agents

Manganese-based nanostructured contrast agents (CAs) entered the field of medical diagnosis through magnetic resonance imaging (MRI) some years ago. Although some of these Mn-based CAs behave as classic T₁ contrast enhancers in the same way as clinical Gd-based molecules do, a new type of Mn nanomaterials have been developed to improve MRI sensitivity and potentially gather new functional information from tissues by using traditional T₁ contrast enhanced MRI. These nanomaterials have been designed to respond to biological environments, mainly to pH and redox potential variations. In many cases, the differences in signal generation in these responsive Mn-based nanostructures come from intrinsic changes in the magnetic properties of Mn cations depending on their oxidation state. In other cases, no changes in the nature of Mn take place, but rather the nanomaterial as a whole responds to the change in the environment through different mechanisms, including changes in integrity and hydration state. This review focusses on the chemistry and MR performance of these responsive Mn-based nanomaterials.     

p‐Nitrobenzoic Acid Adsorption on Nanostructured Gold Surfaces Investigated by Combined Experimental and Computational Approaches

Adsorption of guest molecules on host surfaces can lead to dramatic changes in the spectral properties of the guest. One such effect is surface‐enhanced infrared absorption (SEIRA), observed when the guest is adsorbed on, for example, thin films, metal surfaces, or nanotubes. p‐Nitrobenzoic acid (p‐NBA) exhibits a SEIRA effect when adsorbed on Ag and Au. Herein, the IR spectra of p‐NBA adsorbed on a homemade rough Au surface, recorded in reflection mode with an angle of incidence of 16.5°, are reported. This SEIRA experiment reveals more bands than found by previous SEIRA studies. The intensities of both symmetric and asymmetric COO^? and NO₂ stretching, in‐plane CH, and C?C ring stretching modes are enhanced. Theoretical models constructed on the basis of density functional theory reveal the binding mode of p‐NBA to gold “particles”. The p‐NBA anion binds to gold much more strongly than the neutral form, and interaction via the carboxylic oxygen atoms is preferred over the nitro group–gold contact. A significant charge transfer during chemisorption is found, which is considered to be crucial in leading to a high SEIRA enhancement factor.     

Exchange of Methyl‐ and Azobenzene‐Terminated Alkanethiols on Polycrystalline Gold Studied by Tip‐Enhanced Raman Mapping

Mixed thiol self‐assembled monolayers (SAMs) presenting methyl and azobenzene head groups were prepared by chemical substitution from the original single‐component n‐decanethiol or [4‐(phenylazo)phenoxy]hexane‐1‐thiol SAMs on polycrystalline gold substrates. Static contact‐angle measurements were carried out to confirm a change in the hydrophobicity of the functionalized surfaces following the exchange reaction. The mixed SAMs presented contact‐angle values between those of the more hydrophobic n‐decanethiol and the more hydrophilic [4‐(phenylazo)phenoxy]hexane‐1‐thiol single‐component SAMs. By means of tip‐enhanced Raman spectroscopy (TERS) mapping experiments, it was possible to highlight that molecular replacement takes place easily and first at grain boundaries: for two different mixed SAM compositions, TERS point‐by‐point maps with <50 nm step sizes showed different spectral signatures in correspondence to the grain boundaries. An example of the substitution extending beyond grain boundaries and affecting flat areas of the gold surface is also shown.