Self-Promoted Hydroxyl Radical Releasing Magnetic Zn@Fe Particles.

Semiconductor photocatalysts, such as TiO2 and ZnO, have garnered significant attention for their ability to generate hydroxyl radicals, offering various practical applications. However, the reliance on UV light to facilitate electron-hole separation for hydroxyl radical production poses limitations. In this study, a novel approach is presented utilizing Zn@Fe core/shell particles capable of generating hydroxyl radicals without external energy input. The generation process involves electron donation from Zn to O2 , resulting in the formation of radical species . O2 - /H2 O2 , followed by Fe-catalyzed conversion of H2 O2 into hydroxyl radicals through the Fenton reaction. The release of . OH imparts good antimicrobial and antiviral properties to the Zn@Fe particles. Furthermore, the inclusion of Fe confers magnetic properties to the material. This dual functionality holds promise for diverse potential applications for the Zn@Fe particles.

Redox Active Zn@MOFs as Spontaneous Reactive Oxygen Species Releasing Antimicrobials.

The rapid development of antimicrobial resistance (AMR) among infectious pathogens has become a major threat and challenge in healthcare systems globally. A strategy distinct from minimizing the overuse of antimicrobials involves the development of novel antimicrobials with a mode of action that prevents the development of AMR microbial strains. Reactive oxygen species (ROS) are formed as a natural byproduct of the cellular aerobic metabolism. However, it becomes pathological when ROS is produced at excessive levels. Exploiting this phenomenon, research on redox-active bactericides has been demonstrated to be beneficial. Materials that release ROS via photodynamic, thermodynamic, and photocatalytic interventions have been developed as nanomedicines and are used in various applications. However, these materials require external stimuli for ROS release to be effective as biocides. In this paper, we report novel zinc-based metal organic framework (Zn@MOF) particles that promote the spontaneous release of active ROS species. The synthesized Zn@MOF spontaneously releases superoxide anions and hydrogen peroxide, exhibiting a potent antimicrobial efficacy against various microbes. Zn@MOF-incorporated plastic films and coatings show excellent, long-lasting antimicrobial potency even under continuous microbial challenge and an aging process. These disinfecting surfaces maintain their antimicrobial properties even after 500× surface wipes. Zn@MOF is also biocompatible and safe on the skin, illustrating its broad potential applications in medical technology and consumer care applications.

Nanostructured Surfaces with Multimodal Antimicrobial Action.

Self-disinfecting surfaces are a current pressing need for public health and safety in view of the current COVID-19 pandemic, where the keenly felt worldwide repercussions have highlighted the importance of infection control, frequent disinfection, and proper hygiene. Because of its potential impact upon real-world translation into downstream applications, there has been much research interest in multiple disciplines such as materials science, chemistry, biology, and engineering. Various antimicrobial technologies have been developed and currently applied on surfaces in public spaces, such as elevator buttons and escalator handrails. These technologies are mainly based on conventional methods of grafting quaternary ammonium salts (QACs) such as benzalkonium chloride or the immobilization of metal species of silver or copper. However, neither the long-term efficacy nor the fast-killing properties have been proven, and the future repercussions from extended use, such as environmental hazards and the induction of MDR development, is unknown. Nanostructured surfaces with excellent antimicrobial activities have been claimed to be the next generation of self-disinfecting surfaces with various promising applications and passive antimicrobial mechanisms, without the potential repercussions of active ingredient overuse. In this Account, we briefly introduce the concept of mechanobactericidal action realized by these nanostructured surfaces first discovered on cicada wings. The elimination of microbes on the surface was actualized by the physical rupture of the microbe cell wall by nanoprotusions, without any involvement of chemical species. By mimicking the physical features of naturally occurring biocidal surfaces, the fabrication of nanostructures on various substrates such as titania, silicon, and polymers has been well described. Observations of the dependence of their antimicrobial efficacy on physical characteristics such as height, density, and rigidity have also been documented. However, the complex fabrication of such nanostructures remains the main drawback preventing its widespread application. We outline our efforts in fabricating a series of zinc-based nanostructured materials with facile and generally applicable wet chemistry methods, including nanodaggered zeolitic imidazolate frameworks (ZIF-L) and ZnO nanoneedles. In our investigations, we discovered that there were additional modes of action that contributed to the excellent biocidal activities of our materials. The impact of surface chemistry and charge was partially responsible for the selectivity and efficacy of ZIF-L-coated surfaces, where the positively charged surfaces were able to attract and adhere negatively charged bacteria to the surface. The combination of semiconductor ZnO nanoneedles on electron-donating substrates allowed for the generation of reactive oxygen species (ROS), realizing the remote killing of bacteria unadhered to the nanostructured surface. Additionally, we demonstrate several real-life applications of the synthesized materials, underscoring the importance of materials development suited for scale-up and eventual translation to potential applications and commercial end products.

Nanostructured Copper Surface Kills ESKAPE Pathogens and Viruses in Minutes.

In the search for a fast contact-killing antimicrobial surface to break the transmission pathway of lethal pathogens, nanostructured copper surfaces were found to exhibit the desired antimicrobial properties. Compared with plain copper, these nanostructured copper surfaces with Cu(OH)2 nano-sword or CuO nano-foam were found to completely eliminate pathogens at a fast rate, including clinically isolated drug resistant species. Additionally these nanostructured copper surfaces demonstrated potential antiviral properties when assessed against bacteriophages, as a viral surrogate, and murine hepatitis virus, a surrogate for SARS-CoV-2. The multiple modes of killing, physical killing and copper ion mediated killing contribute to the superior and fast kinetics of antimicrobial action against common microbes, and ESKAPE pathogens. Prototypes for air and water cleaning with current nanostructured copper surface have also been demonstrated.

Recent Advances of Zinc-based Antimicrobial Materials.

Zinc has been widely utilized as an antimicrobial material, often in the form of complexes or zinc oxide nanoparticles. The efficacy of zinc complexes are often due to the synergistic effect of both the zinc ions and the attached organic ligands. In contrast, the nanoparticle effect of ZnO, and the photocatalytic generation of reactive oxygen species (ROS) has been postulated to be the effective mechanism of ZnO as a biocide. Recently, new forms of zinc-based biocidal materials have been reported with distinct antimicrobial mechanisms. This minireview summarizes these recent advances, including zinc-based nano-arrays, MOF-based ROS release and zinc composites that can self-generate ROS.

Evaluation of the ZnO Nanopillar Surface for Disinfection Applications.

Much attention has been devoted to the synthesis and antimicrobial studies of nanopatterned surfaces. However, factors contributing to their potential and eventual application, such as large-scale synthesis, material durability, and biocompatibility, are often neglected in such studies. In this paper, the ZnO nanopillar surface is found to be amenable to synthesis in large forms and stable upon exposure to highly accelerated lifetime tests (HALT) without any detrimental effect on its antimicrobial activity. Additionally, the material is effective against clinically isolated pathogens and biocompatible in vivo. These findings illustrate the broad applicability of ZnO nanopillar surfaces in the common equipment used in health-care and consumer industries.

Antibiotic resistance mitigation: the development of alternative general strategies.

Antibiotic resistance has become one of the major, deadly threats to public health worldwide. This paper highlights several recent works, which may initiate the development of comprehensive approaches to mitigate antibiotic resistance. The new strategies demonstrate efficiency and efficacy, with very little probability of inducing drug resistance, paving the way for further breakthroughs in drug discovery for infection control.

Nitrogen-Linked Hexaazatrinaphthylene Polymer as Cathode Material in Lithium-Ion Battery.

Nitrogen-linked hexaazatrinaphthylene polymer (N2 -HATN) as organic cathode material with low HOMO-LOMO gap was synthesized and was observed to possess reversible high capacity and unexpected long-term cycling stability. The pre-treated N2 -HATN and pRGO combination demonstrated good structure compatibility and the resultant cathode exhibited a constant increment of capacity during the redox cycles. The initial capacity at 0.05 A g-1 was 406 mA h-1 g-1 , and increased to 630 mA h-1 g-1 after 70 cycles. At 0.5 A g-1 discharging rate, the capacity increased from an initial value of 186 mA h-1 g-1 to 588 mA h-1 g-1 after 1600 cycles. The pseudocapacitance-type behavior is postulated to be attributed to the structure compatibility between the active material and pRGO.

Microbicide surface nano-structures.

The prevention of infectious diseases is a global challenge where multidrug-resistant bacteria or "superbugs" pose a serious threat to worldwide public health. Microtopographic surfaces have attracted much attention as they represent a biomimetic and nontoxic surface antibacterial strategy to replace biocides. The antimicrobial effect of such natural and biomimetic surface nanostructures involves a physical approach which eradicates bacteria via the structural features of the surfaces without any release of biocides or chemicals. These recent developments present a significant proof-of-concept and a powerful tool in which cellular adhesion and death caused by a physical approach, can be controlled by the micro/nanotopology of such surfaces. This represents an innovative direction of development of clean, effective and nonresistant antimicrobial surfaces. The minireview will cover novel approaches for the construction of nanostructures on surfaces in order to create antimicrobial surface in an environmentally friendly, nontoxic manner.

A nanoporous sulfur-bridged hexaazatrinaphthylene framework as an organic cathode for lithium ion batteries with well-balanced electrochemical performance.

Some inherent drawbacks of organic cathode materials include low conductivity and high solubility in electrolytes, which lead to low rate capability and low cycling stability. Herein, a novel nanoporous sulfur-bridged hexaazatrinaphthylene (NSHATN) framework has been developed. The sulfur-bridged aromatic framework has good electrical conductivity and is insoluble in electrolytes. The well-defined nanoporous structure with the pore size dominant at 1.26 nm endows the framework with good ionic conductivity. With that, the NSHATN cathode for lithium ion batteries gives well-balanced electrical performances in capacity, cycling stability and rate capability.

Redox Active Metal- and Covalent Organic Frameworks for Energy Storage: Balancing Porosity and Electrical Conductivity.

Porous redox-active metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have emerged as electrode materials for energy storage devices. These porous frameworks have different levels of intrinsic properties such as low solubility, high ionic conductivity (porosity) and low electrical conductivity, all of which are critical parameters when utilised as electrode materials. This Minireview focuses on recent developments of using porous MOFs/COFs as redox active electrode materials for energy storage and strategies to improve their electrochemical performance.

Ultrafast Killing and Self-Gelling Antimicrobial Imidazolium Oligomers.

Infectious diseases and the increasing threat of worldwide pandemics have underscored the importance of antibiotics and hygiene. Intensive efforts have been devoted to developing new antibiotics to meet the rapidly growing demand. In particular, advancing the knowledge of the structure-property-activity relationship is critical to expedite the design and development of novel antimicrobial with the needed potential and efficacy. Herein, a series of new antimicrobial imidazolium oligomers are developed with the rational manipulation of terminal group's hydrophobicity. These materials exhibit superior activity, excellent selectivity, ultrafast killing (>99.7% killing within 30 s), and desirable self-gelling properties. Molecular dynamic simulations reveal the delicate effect of structural changes on the translocation motion across the microbial cell membrane. The energy barrier of the translocation process analyzed by free energy calculations provides clear kinetic information to suggest that the spontaneous penetration requires a very short timescale of seconds to minutes for the new imidazolium oligomers.

Imidazolium salts and their polymeric materials for biological applications.

Imidazolium salts, distinct from their parent imidazoles, are made up of a discrete cation and anion pair, and have found widespread utility as ionic liquids. A lesser known function of such imidazolium salts includes the application of these salts in biological systems, and several areas of bio-applications, including antitumour, antimicrobial, antioxidant and bioengineering applications, will be presented and discussed in this review. The wide-ranging applications and versatility of these imidazolium salts stem from the ease of their structural variation, in which properties such as amphiphilicity, lipophilicity and solubility can be tuned.

Short imidazolium chains effectively clear fungal biofilm in keratitis treatment.

Fungal keratitis is a leading cause of ocular morbidity throughout the world. However, current therapies against fungal keratitis are often ineffective. Herein, we have developed the amphiphilic main-chain imidazolium polymer (PIM-45) and oligomer (IBN-1) materials that can efficiently inhibit the growth of fungi with low minimal inhibition concentration (MIC) values and clear the fungal biofilm, while displaying minimal hemolysis. In vivo keratitis treatment indicates that topical solutions of these polyimidazolium salts (PIMSs) are safe and as effective as that of amphotericin B, the most commonly used agent for the treatment of Candida albicans (C. albicans) keratitis. Compared to the costly and unstable amphotericin B and fluconazole, PIM-45 and IBN-1 are easy to prepare, inexpensive and stable. They can be stored in phosphate-buffered saline (PBS) solutions with long shelf life for routine topical use.

Main-chain imidazolium oligomer material as a selective biomimetic antimicrobial agent.

Human health has been challenged by multi-drug-resistant microorganisms for several decades. Herein, we have developed a main-chain imidazolium oligomer (IBN-1) material to combat broad spectrum of pathogenic strains, including drug-resistant Klebsiella pneumoniae, Vancomycin-resistant enterococcus, Methicillin-resistant Staphylococcus aureus and fluconazole-resistant yeast Cryptococcus neoformans, while displaying minimal hemolysis (HC(50)/MIC values over 3000) and a very high therapeutic index of 37 for killing S. aureus under inflammatory conditions in vivo.

Magnetic nanoparticles entrapped in siliceous mesocellular foam: a new catalyst support.

γ-Fe(2)O(3) nanoparticles were formed inside the cage-like pores of mesocellular foam (MCF). These magnetic nanoparticles showed a uniform size distribution that could be easily controlled by the MCF pore size, as well as by the hydrocarbon chain length used for MCF surface modification. Throughout the entrapment process, the pore structure and surface area of the MCF remained intact. The resulting magnetic MCF facilitated the immobilization of biocatalysts, homogeneous catalysts, and nanoclusters. Moreover, the MCF allowed for facile catalyst recovery by using a simple magnet. The supported catalysts exhibited excellent catalytic efficiencies that were comparable to their homogeneous counterparts.

Carbon dioxide mediated stereoselective copper-catalyzed reductive coupling of alkynes and thiols.

A simple protocol for the stereoselective copper-catalyzed hydrothiolation of alkynes under a CO(2) atmosphere has been developed. The stereoselectivity is determined by the presence/absence of a CO(2) atmosphere. The reaction system is robust and utilizes inexpensive, readily available substrates. A cyclic alkene/carboxylate copper complex intermediate is proposed as the key step in determining the stereoselectivity, and an equivalent amount of water is found to play an active role as a proton donor.

Functional porous organic polymers for heterogeneous catalysis.

Porous organic polymers (POPs), a class of highly crosslinked amorphous polymers possessing nano-pores, have recently emerged as a versatile platform for the deployment of catalysts. The bottom-up approach for porous organic polymer synthesis provides the opportunity for the design of polymer frameworks with various functionalities, for their use as catalysts or ligands. This tutorial review focuses on the framework structures and functionalities of catalytic POPs. Their structural design, functional framework synthesis and catalytic reactions are discussed along with some of the challenges.

Metal-free imidazolium salts inhibit the growth of hepatocellular carcinoma in a mouse model.

Imidazolium salts (IMSs) are precursors to N-heterocyclic carbenes (NHCs), which are routinely used as ligands or organo-catalysts in synthetic chemistry. We recently identified several IMSs as anti-fibrotic agents in liver fibrosis, which often has a consequence in the oncogenesis of hepatocellular carcinoma (HCC). Here, we investigate the potential anti-tumor property of three IMSs (named IBN-1, IBN-9, and DPIM) in HCC cell lines and in a xenograft mouse model. Our results showed that both IBN-1 and IBN-9 significantly inhibited the cell proliferation and arrested HCC cells in the G1-phase, whereas DPIM did not have any anti-tumor activity. When tested in a Huh7 HCC xenograft mouse model, IBN-1 reduced the tumor volume by 31% (P<0.05), however accompanied by a 9% loss in body weight (P<0.005), suggesting a general toxicity. In contrast, IBN-9 significantly reduced the tumor volume by 45% (P<0.05) and 60% (P<0.01) at doses of 0.6 and 1.5 g/l in drinking water, respectively, without any loss in body weight. Our in vitro and in vivo data suggested that IBN-1 and IBN-9 inhibited the growth of HCC by suppressing the expression of Survivin and Cyclin-dependent kinases. The current study provides a proof of concept for using the metal-free IMSs to develop novel anti-cancer agents.