Airborne antibiotic resistome and microbiome in pharmaceutical factories.

Antimicrobial resistance is considered to be one of the biggest public health problems, and airborne transmission is an important but under-appreciated pathway for the spread of antibiotic resistance genes (ARGs) in the environment. Previous research has shown pharmaceutical factories to be a major source of ARGs and antibiotic resistant bacteria (ARB) in the surrounding receiving water and soil environments. Pharmaceutical factories are hotspots of antibiotic resistance, but the atmospheric transmission and its environmental risk remain more concerns. Here, we conducted a metagenomic investigation into the airborne microbiome and resistome in three pharmaceutical factories in China. Soil (average: 38.45%) and wastewater (average: 28.53%) were major contributors of airborne resistome. ARGs (vanR/vanS, blaOXA, and CfxA) conferring resistance to critically important clinically used antibiotics were identified in the air samples. The wastewater treatment area had significantly higher relative abundances of ARGs (average: 0.64 copies/16S rRNA). Approximately 28.2% of the detected airborne ARGs were found to be associated with plasmids, and this increased to about 50% in the wastewater treatment area. We have compiled a list of high-risk airborne ARGs found in pharmaceutical factories. Moreover, A total of 1,043 viral operational taxonomic units were identified and linked to 47 family-group taxa. Different CRISPR-Cas immune systems have been identified in bacterial hosts in response to phage infection. Similarly, higher phage abundance (average: 2451.70 PPM) was found in the air of the wastewater treatment area. Our data provide insights into the antibiotic resistance gene profiles and microbiome (bacterial and non-bacterial) in pharmaceutical factories and reveal the potential role of horizontal transfer in the spread of airborne ARGs, with implications for human and animal health.

Potassium Poly(heptazine imide) Coupled with Ti3C2 MXene-Derived TiO2 as a Composite Photocatalyst for Efficient Pollutant Degradation.

The photocatalytic degradation of pollutants is an effective and sustainable way to solve environmental problems, and the key is to develop an efficient, low-cost, and stable photocatalyst. Polymeric potassium poly(heptazine imide) (K-PHI), as a new member of the carbon nitride family, is a promising candidate but is characterized by a high charge recombination rate. To solve this problem, K-PHI was in-situ composited with MXene Ti3C2-derived TiO2 to construct a type-II heterojunction. The morphology and structure of composite K-PHI/TiO2 photocatalysts were characterized via different technologies, including TEM, XRD, FT-IR, XPS, and UV-vis reflectance spectra. Robust heterostructures and tight interactions between the two components of the composite were verified. Furthermore, the K-PHI/TiO2 photocatalyst showed excellent activity for Rhodamine 6G removal under visible light illumination. When the weight percent of K-PHI in the original mixture of K-PHI and Ti3C2 was set to 10%, the prepared K-PHI/TiO2 composite photocatalyst shows the highest photocatalytic degradation efficiency as high as 96.3%. The electron paramagnetic resonance characterization indicated that the·OH radical is the active species accounting for the degradation of Rhodamine 6G.

Airborne antibiotic resistome and human health risk in railway stations during COVID-19 pandemic.

Antimicrobial resistance is recognized as one of the greatest public health concerns. It is becoming an increasingly threat during the COVID-19 pandemic due to increasing usage of antimicrobials, such as antibiotics and disinfectants, in healthcare facilities or public spaces. To explore the characteristics of airborne antibiotic resistome in public transport systems, we assessed distribution and health risks of airborne antibiotic resistome and microbiome in railway stations before and after the pandemic outbreak by culture-independent and culture-dependent metagenomic analysis. Results showed that the diversity of airborne antibiotic resistance genes (ARGs) decreased following the pandemic, while the relative abundance of core ARGs increased. A total of 159 horizontally acquired ARGs, predominantly confering resistance to macrolides and aminoglycosides, were identified in the airborne bacteria and dust samples. Meanwhile, the abundance of horizontally acquired ARGs hosted by pathogens increased during the pandemic. A bloom of clinically important antibiotic (tigecycline and meropenem) resistant bacteria was found following the pandemic outbreak. 251 high-quality metagenome-assembled genomes (MAGs) were recovered from 27 metagenomes, and 86 genera and 125 species were classified. Relative abundance of ARG-carrying MAGs, taxonomically assigned to genus of Bacillus, Pseudomonas, Acinetobacter, and Staphylococcus, was found increased during the pandemic. Bayesian source tracking estimated that human skin and anthropogenic activities were presumptive resistome sources for the public transit air. Moreover, risk assessment based on resistome and microbiome data revealed elevated airborne health risks during the pandemic.

The effects of the chemotherapy drug cyclophosphamide on the structure and functioning of freshwater communities under sub-tropical conditions: A mesocosm study.

Cyclophosphamide (CP) is a chemotherapy drug which is widely used in the treatment of neoplastic diseases and have often been detected in urban and hospital wastewater, and surface waters. However, at present the effects of CP on aquatic organisms and ecosystems are poorly understood. The main objective of the present study was to assess the effect of CP on the structure and functioning of a sub-tropical freshwater ecosystem (macroinvertebrates, zooplankton and phytoplankton) at environmental relevant concentrations. CP (0, 0.5, 5 and 50 µg/L) was applied weekly to 13,600 L mesocosms over a period of four weeks followed by a one month post exposure period. CP was found to dissipate much faster than previous reported in literature and the half-dissipation times were treatment dependent, being 2.2, 21.3 and 23.6 days in the lowest, middle and highest treatments respectively. Only treatment related effects were observed on the community structure at individual samplings with zooplankton (NOECcommunity = 0.5 µg/L) responding at lower concentrations than phytoplankton (NOECcommunity = 5 µg/L) and macroinvertebrates (NOECcommunity ≥ 50 µg/L). The dissolved organic carbon concentration was consistently higher in the 2 highest treatments, indicating a potential effect on food web interactions and/or the microbial loop. At the population level, consistent adverse effects were observed for the plankton taxa Pleuroxus laevis, Dissotrocha sp. and Oscillatoria sp. at all CP concentrations (NOEC <0.5 µg/L). Additionally, at the highest CP treatments 7% of all the taxa showed a clear short-term adverse effect. Based on comparison with literature data it can be concluded that these taxa have the highest CP sensitivity ever recorded and these findings indicate a potential CP risk to aquatic ecosystems at environmental relevant concentrations.

Imidacloprid treatments induces cyanobacteria blooms in freshwater communities under sub-tropical conditions.

Imidacloprid is one of the most used neonicotinoid insecticides all over the world and is considered as a contaminant of concern due to its high toxicity potential to aquatic organisms. However, the majority of the studies that have evaluated the effects of imidacloprid on aquatic organisms were conducted under temperate conditions. In the present study, a mesocosm experiment was conducted under sub-tropical conditions to assess the effects of imidacloprid on the structure (macroinvertebrates, zooplankton and phytoplankton) and functional endpoints of an aquatic ecosystem and to compare the results with similar temperate and (sub-)tropical mesocosm studies. Imidacloprid (0, 0.03, 0.3 and 3 µg/L) was applied to 13 mesocosms weekly over a period of 4 weeks, followed by a one month recovery period. At the community level a lowest NOECcommunity of 0.03 µg/L was calculated for the zooplankton, phytoplankton and macroinvertebrate communities. The highest sensitivity to imidacloprid (NOEC < 0.03 µg/L) were observed for Gerris sp., Diaptomus sp. and Brachionus quadridentatus. Imidacloprid induced population declines of the larger zooplankton species (Diaptomus sp. and Ostracoda) resulted in increased rotifer abundances and shifted the phytoplankton community to a graze resistant gelatinous cyanobacteria dominated ecosystem. These cyanobacteria blooms occurred at all different concentrations and could pose an important public health and environmental concern. Although there are some differences in species and community sensitivity between the present and the other (sub-)topical mesocosm studies, it can be observed that all show a similar general community response to imidacloprid. Under (sub-)tropical conditions, the toxic effects of imidacloprid occur at lower concentrations than found for temperate ecosystems.

The Ionic Liquid-H2O Interface: A New Platform for the Synthesis of Highly Crystalline and Molecular Sieving Covalent Organic Framework Membranes.

Covalent organic frameworks (COFs) are highly porous crystalline polymers with uniform pores and large surface areas. Combined with their modular design principle and excellent properties, COFs are an ideal candidate for separation membranes. Liquid-liquid interfacial polymerization is a well-known approach to synthesize membranes by reacting two monomers at the interface. However, volatile organic solvents are usually used, which may disturb the liquid-liquid interface and affect the COF membrane crystallinity due to solvent evaporation. Simultaneously, the domain size of the organic solvent-water interface, named the reaction zone, can hardly be regulated, and the diffusion control of monomers for favorable crystallinity is only achieved in the water phase. These drawbacks may limit the widespread applications of liquid-liquid interfacial polymerization to synthesize diverse COF membranes with different functionalities. Here, we report a facile strategy to synthesize a series of imine-linked freestanding COF membranes with different thicknesses and morphologies at tunable ionic liquid (IL)-H2O interfaces. Due to the H-bonding of the catalysts with amine monomers and the high viscosity of the ILs, the diffusion of the monomers was simultaneously controlled in water and in ILs. This resulted in the exceptionally high crystallinity of freestanding COF membranes with a Brunauer-Emmett-Teller (BET) surface area up to 4.3 times of that synthesized at a dichloromethane-H2O interface. By varying the alkyl chain length of cations in the ILs, the interfacial region size and interfacial tension could be regulated to further improve the crystallinity of the COF membranes. As a result, the as-fabricated COF membranes exhibited ultrahigh permeance toward water and organic solvents and excellent selective rejection of dyes.

An aqueous synthesis of porous PtPd nanoparticles with reversed bimetallic structures for highly efficient hydrogen generation from ammonia borane hydrolysis.

Fine construction of porous bimetallic nanomaterials with tunable components and structures is of great importance for their catalytic performance and durability. Herein, we present a facile and mild one-pot route for the preparation of porous PtPd bimetallic nanoparticles (NPs) with reversed structures in aqueous solution for the first time. To this end, a common ionic liquid (IL) 1-hexadecyl-3-methylimidazolium chloride ([C16mim]Cl) is utilized to direct the growth and assembly of porous structures of PtPd NPs. It is shown that the as-prepared porous Pt25Pd75 NPs have obvious hierarchical structures with nanoflowers as subunits and nanorods as basic units. The elemental components and structures of the porous PtPd NPs can be tuned by the precursor ratio and the [C16mim]Cl concentration. Furthermore, various porous PtPd bimetallic structures from Pd-on-Pt to Pt-on-Pd may be efficiently switched by controlling the concentration of glycine. Owing to their high specific surface area, porous hierarchical structures (including mesopores and micropores), and probable electronic effects between Pt and Pd, the porous Pt25Pd75 NPs (Pd-on-Pt structure) are found to exhibit prominent catalytic activity and high stability for hydrogen production from hydrolysis of ammonia borane.

Ionic Liquid-Modulated Synthesis of Porous Worm-Like Gold with Strong SERS Response and Superior Catalytic Activities.

Porous gold with well-defined shape and size have aroused extensive research enthusiasm due to their prominent properties in various applications. However, it is still a great challenge to explore a simple, green, and low-cost route to fabricate porous gold with a "clean" surface. In this work, porous worm-like Au has been easily synthesized in a one-step procedure from aqueous solution at room temperature under the action of ionic liquid tetrapropylammonium glycine ([N3333][Gly]). It is shown that the as-prepared porous worm-like Au has the length from 0.3 to 0.6 µm and the width of approximately 100-150 nm, and it is composed of lots of small nanoparticles about 6-12 nm in diameter. With rhodamine 6G (R6G) as a probe molecule, porous worm-like Au displays remarkable surface enhanced Raman scattering (SERS) sensitivity (detection limit is lower than 10-13 M), and extremely high reproducibility (average relative standard deviations is less than 2%). At the same time, owing to significantly high specific surface area, various pore sizes and plenty of crystal defects, porous worm-like Au also exhibits excellent catalytic performance in the reduction of nitroaromatics, such as p-nitrophenol and p-nitroaniline, which can be completely converted within only 100 s and 150 s, respectively. It is expected that the as-prepared porous worm-like Au with porous and self-supported structures will also present the encouraging advances in electrocatalysis, sensing, and many others.

Synthesis of various gold hierarchical architectures assisted by functionalized ionic liquids in aqueous solutions and their efficient SERS responses.

Developing a simple and green route for the controlled synthesis of hierarchical nanomaterials with anisotropic particles as subunits is highly desirable and technically important. Here, a functionalized ionic liquid (FIL) assisted strategy is developed for the preparation of hierarchical Au nanomaterials at room temperature. Various morphologies of Au products, including nanoplate-built flowers, nanobar-built flowers and nanourchins, have been well achieved using the current route in aqueous solutions of imidazolium ILs with different functional groups, such as 1-carboxymethy-3-methylimidazolium chloride ([CMmim]Cl), 1-hydroxylethyl- 3-methylimidazolium chloride ([HEmim]Cl), and 1-(3-aminopropyl)-3- methylimidazolium chloride ([APmim]Cl). The influence of these FILs on the morphology of Au products and their growth process has been studied systematically. It is shown that the functionalized ILs play important roles in the construction of these interesting Au hierarchies. The seed, IL concentration (within a certain range), reaction temperature have negligible influence, but stirring and anions of the ILs have important influences, on the product morphologies. Based on these results, the possible growth mechanism is proposed for the formation of different Au hierarchies. In addition, all the Au samples prepared with the assistance of the functionalized ILs, especially the nanoplate-built flowers, exhibit striking SERS sensitivity and high reproducibility.

Nanoreactors stable up to 200 °C: a class of high temperature microemulsions composed solely of ionic liquids.

It is a challenge to develop microemulsions which can serve as nanoreactors for the synthesis of nanoparticles and chemical reactions at high temperature. In this work, a class of novel high temperature microemulsions consisting solely of ionic liquids have been designed and prepared for the first time. It is found that nanoscale droplets formed in the ionic liquid microemulsions can be maintained up to 200 °C, and the size distribution of the droplets can be easily tuned by selection of the ionic liquids and varying compositions of the systems. By using such microemulsions as nanoreactors, porous metals such as Pt have been prepared at 180 °C without using any purposely added reductant.

Co-immobilization of cellulase and lysozyme on amino-functionalized magnetic nanoparticles: An activity-tunable biocatalyst for extraction of lipids from microalgae.

An activity-tunable biocatalyst for Nannochloropsis sp. cell-walls degradation was prepared by co-immobilization of cellulase and lysozyme on the surface of amino-functionalized magnetic nanoparticles (MNPs) employing glutaraldehyde. The competition between cellulase and lysozyme during immobilization was caused by the limited active sites of the MNPs. The maximum recovery of activities (cellulase: 78.9% and lysozyme: 69.6%) were achieved due to synergistic effects during dual-enzyme co-immobilization. The thermal stability in terms of half-life of the co-immobilized enzymes was three times higher than that in free form and had higher catalytic efficiency for hydrolysis of cell walls. Moreover, the co-immobilized enzymes showed greater thermal stability and wider pH tolerance than free enzymes under harsh conditions. Furthermore, the co-immobilized enzymes retained up to 60% of the residual activity after being recycled 6 times. This study provides a feasible approach for the industrialization of enzyme during cell-walls disruption and lipids extraction from Nannochloropsis sp.

Efficient Photoelectrochemical Reduction of Carbon Dioxide to Formic Acid: A Functionalized Ionic Liquid as an Absorbent and Electrolyte.

Photoelectrochemical (PEC) reduction of carbon dioxide (CO2 ) is a potential method for production of fuels and chemicals from a C1 feedstock accumulated in the atmosphere. However, the low solubility of CO2 in water, and complicated processes associated with capture and conversion, render CO2 conversion inefficient. A new concept is proposed in which a PEC system is used to capture and convert CO2 into formic acid. The process is assisted by an ionic liquid (1-aminopropyl-3-methylimidazolium bromide) aqueous solution, which functions as an absorbent and electrolyte at ambient temperature and pressure. Within this PEC reduction strategy, the ionic liquid plays a critical role in promoting the conversion of CO2 to formic acid and suppressing the reduction of H2 O to H2 . At an applied voltage of 1.7 V, the Faradaic efficiency for formic acid production is as high as 94.1 % and the electro-to-chemical efficiency is 86.2 %.

Density Functional Study of Trimetallic AuxPdyPtz (x + y + z = 7) Clusters and Their Interactions with the O2 Molecule.

Density functional theory calculations were performed to investigate the structural and energetic properties of trimetallic AuxPdyPtz clusters with x + y + z = 7. The possible stable geometrical configurations with their electronic states are determined. We analyze the chemical order, binding energies, vertical ionization potential, electron affinity, and HOMO-LUMO gaps as a function of the whole concentration range. The affinity of AuxPdyPtz clusters toward one O2 molecule is also evaluated in terms of the changes in geometry, adsorption energy, and charge transfer.

A facile synthesis of gold micro/nanostructures at the interface of 1,3-dibutylimidazolium bis(trifluoromethylsulfonyl)imide and water.

The development of a simple, template-free, and one-step strategy to synthesize nanostructured Au architectures with fascinating morphology is highly desirable and technically important due to their valuable applications in varied fields. In this work, the "green" strategy of "tunable ionic liquids-water (ILs-H2O) interfacial synthesis" developed previously by us is utilized for feasible synthesis of gold needle mushroom-like micro/nanostructures at the 1,3-dibutylimidazolium bis(trifluoromethylsulfonyl)imide ([C4bim][Tf2N]) - water interface and ambient conditions. The as-obtained gold needle mushrooms (AuNMs) have been characterized and analyzed systemically by scanning electron microscopy, X-ray powder diffraction, energy-dispersive X-ray spectroscopy, and transmission electron microscopy. It is shown that the as-prepared AuNMs can be used as substrates to perform surface enhanced Raman scattering (SERS) investigation with striking SERS sensitivity. By employing ILs with different alkyl chain lengths of the imidazolium cations and/or different nature of anions, Au nanomaterials with diverse morphologies can be easily prepared at different ILs-H2O interfaces. Based on the analysis of the control experiments, the growth and formation of AuNMs at the [C4bim][Tf2N]-H2O interface have been discussed.

Reversible Hydrophobic-Hydrophilic Transition of Ionic Liquids Driven by Carbon Dioxide.

Ionic liquids (ILs) with a reversible hydrophobic-hydrophilic transition were developed, and they exhibited unique phase behavior with H2O: monophase in the presence of CO2, but biphase upon removal of CO2 at room temperature and atmospheric pressure. Thus, coupling of reaction, separation, and recovery steps in sustainable chemical processes could be realized by a reversible liquid-liquid phase transition of such IL-H2O mixtures. Spectroscopic investigations and DFT calculations showed that the mechanism behind hydrophobic-hydrophilic transition involved reversible reaction of CO2 with anion of the ILs and formation of hydrophilic ammonium salts. These unique IL-H2O systems were successfully utilized for facile one-step synthesis of Au porous films by bubbling CO2 under ambient conditions. The Au porous films and the ILs were then separated simultaneously from aqueous solutions by bubbling N2, and recovered ILs could be directly reused in the next process.

Ionic liquids-water interfacial preparation of triangular Ag nanoplates and their shape-dependent antibacterial activity.

As a class of green and designable solvents, ionic liquids (ILs) have been used extensively in inorganic synthesis. In those schemes, ILs were usually used as reaction media to replace water and organic solvents, and/or used as stabilizer and capping agents to act like an amphiphilic molecule or polymer. However, the unique properties of ILs were not fully utilized in the area of material preparation. In this study, a new protocol of "ILs-water interfacial synthesis" was developed and used for the preparation of Ag nanomaterials. Taking the advantage of tunable property of ILs-water interface, Ag nanomaterials with different morphology such as triangular nanoplates, polygonal nanoplates, and nanoparticles could be facilely obtained. Growth mechanism of the triangular Ag nanoplates has been investigated from structural characterization and molecular dynamics (MD) simulation. It was shown that growth of the nanoplates was under kinetic control mainly due to high viscosity and ionicity of the ILs. Furthermore, the antimicrobial performance of these Ag samples was tested to study the influence of shape of the Ag nanomaterials on the antimicrobial activity and the related antimicrobial mechanism. The results suggested that the efficient antimicrobial activity of the triangular Ag nanoplates was ascribed to their sharp corners and edges and large areas of active (111) crystal plane, which leads to the higher amount of leaching Ag(+) ion.

Thermal-induced formation of a three-dimensional nanoplasmonic sensor from Ag nanocubes with high stability and reusability.

Nanoplasmonic sensors based on the localized surface plasmon resonance (LSPR) of noble metal nanoparticles have many advantages, such as real-time detection, no need for reagent labelling, and no use of complicated equipment. However, the nanoplasmonic sensors with two dimensional structures usually suffer from a low LSPR signal and thus low sensitivity due to the low density of the nanoparticles. In addition, complicated surface functionalization is always required to suppress the non-specific binding of the analyst to the substrate of the sensor, because the two types of surface, that is, metal and substrate surfaces, are simultaneously exposed to the reaction medium. To overcome these problems, an innovative thermal-induced method has been proposed in the present work, to construct three dimensional (3D) nanostructure of Ag nanocubes on both surfaces of the substrate by using the unique amphiphilic property of 2-diethylaminoethanethiol. The prepared nanoplasmonic sensor is highly sensitive due to the high density of 3D structure of the nanoparticles and the low non-specific binding since only one type of surface is exposed. To enhance the stability of the sensor, a thin SiO2 overlayer was formed on the surface without using an additional coupling agent. Furthermore, the Ni(II)-nitriloacetic acid (Ni(II)-NTA) complex was covalently bound on the surface, so that the regeneration and reuse of the sensor becomes easy. Therefore, the easy fabrication, high stability, and good reusability of this 3D LSPR sensor makes our method competitive for the development of nanoplasmonic sensors.

Tunable synthesis of Ag films at ionic liquid-aqueous interfaces.

A new concept of "tunable ionic liquid (IL)-H(2)O interfacial synthesis" is proposed and used practically in the synthesis of Ag films with various morphologies at the IL-H(2)O interface by employing ILs with different anions and/or different alkyl chain lengths.