The nature of crystal facet effect of TiO2-supported Pd/Pt catalysts on selective hydrogenation of cinnamaldehyde: electron transfer process promoted by interfacial oxygen species.

Supported noble metal nanocatalysts typically exhibit strong crystal plane dependent catalytic behavior, but their working mechanism is still unclear. Herein, using anatase TiO2 with well-exposed crystal facets of {101}, {100} and {001} as a prototype support, Pd- and Pt-based supported TiO2 nanocatalysts (TiO2-Pd and TiO2-Pt) were prepared by chemical reduction with NaBH4 as reducer, and they showed a distinct metal-dependent crystal facet effect in the selective hydrogenation of cinamaldehyde (CAL). For Pd-based nanocatalysts, most Pd species on the {100} plane of TiO2 are present in the oxidized form with positive charges and unexpectedly show higher reactivity than the Pd species in the zero-valence state on the {101} and {001} planes. On the contrary, Pt species on all three crystal planes of TiO2 show zero-valence state, with relatively low conversion, but much better selectivity for hydrogenation of a CO bond than Pd-based catalysts. Well-designed experiments manipulating the stability and type of surface oxygen species confirmed that the essence of the crystal facet effect of the catalyst support actually creates a unique nanoconfined interface at the molecular level to construct a surface p-band intermediate state (PBIS), which provides a new alternative channel for surface electron transfer and consequently accelerates the reaction kinetics.

Single primer site-specific nested PCR for accurate and rapid genome-walking.

Genome-walking is a molecular tool used to unveil uncharacterized DNA regions flanking a known DNA, which has been widely used in bioscience and related areas. This study developed a reliable and efficient PCR-based genome-walking approach, named as single primer site-specific nested PCR (SPN-PCR). A SPN-PCR set sequentially consists of three single-primer nested PCR amplifications. The primary relaxed thermal cycle promotes outmost nested site-specific primer (NSSP) to partially combine with numerous places on DNA template, synthesizing many single-stranded DNAs (ssDNA). Among them, the target ssDNA is exponentially amplified in the subsequent stringent cycles, as its 3' part possesses the outmost NSSP complement; but a non-target ssDNA cannot be amplified, because it does not possess such a complement. Stringent secondary and tertiary PCRs also exclusively enrich this target DNA. Finally, the target DNA product becomes predominant. The feasibility of SPN-PCR was validated by genome-walking several selected genes from two divergent species.

Biofilm on the pipeline wall is an important transmission route of resistome in drinking water distribution system.

Due to the intensive use of antibiotics, the drinking water distribution system (DWDS) has become one of the hotspots of antibiotic resistance. However, little is known about the role of biofilm in the aspect of spreading resistance in DWDS. In present study, four lab-scale biological annular reactors (BAR) were constructed to investigate the transmission of ARGs exposed to a certain amount of antibiotic (sulfamethoxazole) synergistic disinfectants. It was emphasized that pipe wall biofilm was an important way for ARGs to propagate in the pipeline, and the results were quantified by constructing an operational taxonomic unit (OTU) network map. The network analysis results showed the biofilm contribution to waterborne bacteria was finally estimated to be 51.45% and 34.27% in polyethylen (PE) pipe and ductile iron (DI) pipe, respectively. The proportion of vertical gene transfer (VGT) in biofilm was higher than that in water, and the occurrence of this situation had little relationship with the selection of pipe type. Overall, this study revealed how biofilm promoted the transmission of resistome in bulk water, which can provide insights into assessing biofilm-associated risks and optimizing pipe material selection for biofilm control in DWDS.

The mixed-order chlorine decay model with an analytical solution and corresponding trihalomethane generation model in drinking water.

Ensuring effective drinking water disinfection, remaining a certain amount of residual chlorine, and controlling disinfection by-product formation were very important for guarantying water quality safety and protecting public health; thus, the chlorine decay model and corresponding disinfection by-product formation model were necessary. This paper proposed a mixed-order chlorine bulk decay model (two parameters) based on Taylor's formula and derived its analytical solution. The accuracy of the mixed-order model was evaluated by comparing it with the nth-order model. To optimize the model and reduce the number of parameters required to be calibrated, the relationship of parameters with temperature, initial chlorine concentration, TOC and inorganic substance (ammonia nitrogen and iodide ion) was explored. The result proved that one of the parameters could be regarded as temperature dependent only. Meanwhile, the temperature equation of the model parameters was established by the Arrhenius formula. Subsequently, this paper selected trihalomethane as the target and study the linear relationship between chlorine consumption and trihalomethane formation. The results indicated that the liner slope had little correlation with initial chlorine concentration and temperature. On this basis, the corresponding trihalomethane model was built and its performance was proven to be good. The modeling developed in this work could be applied to drinking water distribution systems for residual chlorine and trihalomethane prediction, and provided a reference for the decision involving water quality.

Deciphering the distribution and microbial secretors of extracellular polymeric substances associated antibiotic resistance genes in tube wall biofilm.

Antibiotics and disinfectants have both been proposed to exert selective pressures on the biofilm as well as affecting the emergence and spread of antibiotic resistance genes (ARGs). However, the transfer mechanism of ARGs in drinking water distribution system (DWDS) under the coupling effect of antibiotics and disinfectants has not been completely understood. In the current study, four lab-scale biological annular reactors (BARs) were constructed to evaluate the effects of sulfamethoxazole (SMX) and NaClO coupling in DWDS and reveal the related mechanisms of ARGs proliferation. TetM was abundant in both the liquid phase and the biofilm, and redundancy analysis showed that the total organic carbon (TOC) and temperature were significantly correlated with ARGs in the water phase. There was a significant correlation between the relative abundance of ARGs in the biofilm phase and extracellular polymeric substances (EPS). Additionally, the proliferation and spread of ARGs in water phase were related to microbial community structure. Partial least-squares path modeling showed that antibiotic concentration may influence ARGs by affecting MGEs. These findings help us to better understand the diffusion process of ARGs in drinking water and provide a theoretical support for technologies to control ARGs at the front of pipeline.

Tetraalkoxysilane-Assisted Self-Emulsification Templating for Controlled Mesostructured Silica Nanoparticles.

Although mesoporous silica nanoparticles (MSNs) have been intensively investigated, their mesostructure and formation mechanism are still a topic of debate. Here, we show that MSNS are generated at the interface of the biphasic water-surfactant-triethanolamine-tetraalkoxysilane (TAOS) quaternary system. The spontaneous microemulsification of the hydrophobic TAOS generates microdroplets and direct micelles that both determine the particle size and the pore size. We confirmed also that the dendritic morphology with conical pores is an intermediate species, which readily transforms into regular MSNs concomitantly with the collapse of the microemulsion due to the continuous consumption of TAOS. The prominent effect of the microemulsion on the mechanism growth as a primary template is thoroughly investigated and named here tetraalkoxysilane-assisted self-emulsification templating.

A study on the role of plasmonic Ti3C2Tx MXene in enhancing photoredox catalysis.

Engineering the spatial separation and transfer of photogenerated charge carriers has been one of the most enduring research topics in the field of photocatalysis due to its crucial role in determining the performances of photocatalysts. Herein, as a proof-of-concept, Ti3C2Tx MXene is coupled with a typical heterojunction of TiO2@CdS through a co-assembly strategy to boost electron pumping towards improving the photocatalytic efficiency. In addition to the band alignment-mediated electron transfer in TiO2@CdS-Ti3C2Tx heterojunctions, the plasmon-induced electric field enhancement of Ti3C2Tx is found to cooperate with the electron-reservoir role of Ti3C2Tx to extract photoinduced electrons. The synergistic dual functions of Ti3C2Tx promote multichannel electron transfer in TiO2@CdS-Ti3C2Tx hybrids to improve the photocatalytic efficiency. These results intuitively show that there is a wide scope to manipulate the spatial separation and transfer of photoinduced electrons by cultivating the fertile ground of Ti3C2Tx toward boosting the efficiency of solar-to-chemical conversion.

Mach-Zehnder interferometer based integrated-photonic acetone sensor approaching the sub-ppm level detection limit.

The detection of acetone in the gaseous form in exhaled breath using an integrated sensor can provide an effective tool for disease diagnostics as acetone is a marker for monitoring human metabolism. An on-chip acetone gas sensor based on the principle of Mach-Zehnder interferometer is proposed and demonstrated. The sensing arm of the device is activated with a composite film of polyethyleneimine and amido-graphene oxide as the gas-sensitive adsorption layer. The composite film demonstrates good selectivity to acetone gas, can be used repeatedly, and is stable in long-term use. Room temperature operation has been demonstrated for the sensor with high sensitivity under a 20 ppm acetone environment. The detection limit can reach 0.76 ppm, making it feasible to be used for the clinical diagnosis of diabetes and the prognosis of heart failure.

Chiral Optofluidics with a Plasmonic Metasurface Using the Photothermal Effect.

Plasmonic metasurfaces with the photothermal effect have been increasingly investigated for optofluidics. Meanwhile, along with the expanding application of circularly polarized light, a growing number of investigations on chiral plasmonic metasurfaces have been conducted. However, few studies have explored the chirality and the thermal-induced convection of such systems simultaneously. This paper aims to theoretically investigate the dynamics of the thermally induced fluid convection of a chiral plasmonic metasurface. The proposed metasurface exhibits giant circular dichroism in absorption and thus leads to a strong photothermal effect. On the basis of the multiphysical analysis, including optics, thermodynamics, and hydrodynamics, we propose a concept of chiral spectroscopy termed optofluidic circular dichroism. Our results show that different fluid velocities of thermally induced convection appear around a chiral plasmonic metasurface under different circularly polarized excitation. The chiral fluid convection is induced by an asymmetric heat distribution generated by absorbed photons in the plasmonic heater. This concept can be potentially used to induce chiral fluid convection utilizing the chiral photothermal effect. Our proposed structure can potentially be used in various optofluidics applications related to biochemistry, clinical biology, and so on.

Antibiotic resistance genes are enriched with prolonged age of refuse in small and medium-sized landfill systems.

Landfills are sites for the disposal of waste over decades. The dynamics of contaminants during landfill treatment influence the functions and environmental risks of the landfill systems, but the patterns of these dynamics are not fully characterized, especially for antibiotic resistant genes (ARGs), an emerging contaminant of global concern. Here, seventeen typical ARG subtypes were quantitatively investigated in refuse samples from small and medium-sized landfills with ages of <3 years, ~5 years, and 8-10 years. The abundance of ARGs, including tetM, tetX, blaPER, emrB, sul1 and sul2, increased significantly (p < 0.05), approaching 8- to 304-fold on average, from refuse of < 3years to that of 8-10 years, while there was no obvious change (p > 0.05) in abundance for other ARGs, including tetQ, tetW, ampC, blaCTX-M, blaSHV, emrA, mefA, qnrD, qnrS, and mexF. Accordingly, resistance to tetracyclines, macrolides, and sulfonamides increased with landfill age, while resistance to ß-lactams and quinolones remained unchanged. The increase in ARG abundance with increasing refuse age was probably related with the increased horizontal gene transfer (HGT) (indicated by the increased abundance of mobile gene elements) and the enhanced co-selective pressure (suggested by the increased contents of heavy metals). These results indicated a potential risk from ARG enrichment with an increase in refuse age in small and medium-sized landfills, which should be managed to ensure landfill safety.

Schottky Junctions with Bi Cocatalyst for Taming Aqueous Phase N2 Reduction toward Enhanced Solar Ammonia Production.

Solar-powered N2 reduction in aqueous solution is becoming a research hotspot for ammonia production. Schottky junctions at the metal/semiconductor interface have been effective to build up a one-way channel for the delivery of photogenerated electrons toward photoredox reactions. However, their applications for enhancing the aqueous phase reduction of N2 to ammonia have been bottlenecked by the difficulty of N2 activation and the competing H2 evolution reaction (HER) at the metal surface. Herein, the application of Bi with low HER activity as a robust cocatalyst for constructing Schottky-junction photocatalysts toward N2 reduction to ammonia is reported. The introduction of Bi not only boosts the interfacial electron transfer from excited photocatalysts due to the built-in Schottky-junction effect at the Bi/semiconductor interface but also synchronously facilitates the on-site N2 adsorption and activation toward solar ammonia production. The unidirectional charge transfer to the active site of Bi significantly promotes the photocatalytic N2-to-ammonia conversion efficiency by 65 times for BiOBr. In addition, utilizing Bi to enhance the photocatalytic ammonia production can be extended to other semiconductor systems. This work is expected to unlock the promise of engineering Schottky junctions toward high-efficiency solar N2-to-ammonia conversion in aqueous phase.

Outbreak of a novel disease caused by Staphylococcus pseudintermedius in raccoon dogs (Nyctereutes procyonoides).

This study reports outbreak of a new disease caused by Staphylococcus pseudintermedius (S. pseudintermedius) in raccoon dogs. The disease occurred in a breeding farm of raccoon dogs in Guan County of Shandong Province in China in August of 2019. 47% (425/896) of the raccoon dogs showed some abnormal symptoms; 17.6% (75/425) of which had severe skin and soft tissue infections (SSTIs), dyspnoea and severe pathological lesions in lungs, livers, etc; and 4.2% (18/425) of which died within 4 weeks. The pathogen of the disease was identified as S. pseudintermedius by mass spectrometer detection, animal pathogenicity tests, microscopic examination and biochemical reaction tests. Its nucleotide homology of 16S rRNA gene was 100% with that of other published strains, and its genotype was between the American and Brazilian strains from other animals. The isolated S. pseudintermedius strain from the diseased raccoon dogs could cause ulceration and suppuration in the skins and severe pathological lesions not only in raccoon dogs, but also in mice; and it is confirmed as a methicillin-resistant S. pseudintermedius (MRSP) strain by the amplification of mecA gene; and 12 sensitive drugs were screened by drug sensitivity tests. Full attention should be paid to the great economic loss and the potential zoonotic risk caused by the S. pseudintermedius in raccoon dogs, and this study can provide a reference for the clinical diagnosis and treatment of this new disease.

Broadband Tamm plasmon-enhanced planar hot-electron photodetector.

Here, we propose a planar hot-electron photodetector based on broadband Tamm plasmon resonance using a TiN layer, n-type doped Si layer, and seven pairs of DBRs. Simulation results show high absorption (94.2%) with a full width at half maximum of 239.3 nm, which is 2.9 times that of the Au/DBR configuration. We predict that the photoresponsivity can reach 26.1 mA W-1 at 1140 nm. Since the planar nanofilms for TP resonance are facile to fabricate, this work promotes hot-electron applications in broadband photodetection and other broadband light-harvesting applications.

Planar hot-electron photodetector utilizing high refractive index MoS2 in Fabry-Pérot perfect absorber.

Hot electron photodetection (HEPD) excited by surface plasmon can circumvent bandgap limitations, opening pathways for additional energy harvesting. However, the costly and time-consuming lithography has long been a barrier for large-area and mass production of HEPD. In this paper, we proposed a planar and electron beam lithography-free hot electron photodetector based on the Fabry-Pérot (F-P) resonance composed of Au/MoS2/Au cavity. The hot electron photodetector has a nanoscale thickness, high spectral tunability, and multicolour photoresponse in the near-infrared region due to the increased round-trip phase shift by using high refractive index MoS2. We predict that the photoresponsivity can achieve up to 23.6 mA W-1 when double cavities are integrated with the F-P cavity. The proposed hot electron photodetector that has a nanoscale thickness and planar stacking is a perfect candidate for large-area and mass production of HEPD.

Trehalose suppresses cadmium-activated Nrf2 signaling pathway to protect against spleen injury.

Cadmium (Cd), as a kind of ubiquitous and highly toxic heavy metal pollutants, has been known to result in immunotoxicity in animals. As a multifunctional bioactivity disaccharide, trehalose (Tre) is characterized by antioxidative, antiapoptotic, and accelerating autophagy. In this study, Sprague-Dawley (SD) rats were fed with cadmium chloride (CdCl2) and/or Tre to explore the molecular mechanisms of Tre-protected against spleen injury caused by Cd exposure. Firstly, the results showed that Tre partially recovered splenic pathological changes induced by Cd exposure. Secondly, Tre dramatically declined the level of methane dicarboxylic aldehyde (MDA) and elevated the level of total antioxidant capacity (T-AOC) to weaken oxidative stress caused by Cd exposure in spleen tissue. Moreover, the results showed that Tre significantly suppressed Cd-induced the nuclear translocation of nuclear factor erythroid 2-related factor 2 (Nrf2) and up-regulated the protein expression of nuclear Nrf2. Thirdly, Tre remarkably reduced the protein expression of sequestosome 1 (p62/SQSTM1) and microtubule-associated protein light chain 3II (LC-3II) to restore autophagy inhibition induced by Cd exposure. Finally, the results of TUNEL and the expression of apoptosis marker proteins showed that Tre significantly inhibited Cd-induced apoptosis in spleen tissue to exert its protective effects. In summary, the results indicated that Tre modulated Nrf2 signaling pathway, which interacted with apoptosis and autophagy to against Cd-induced spleen injury, providing potential therapeutic strategies for the prevention and treatment of Cd-related immune system diseases.

Alleviation of cadmium-induced oxidative stress by trehalose via inhibiting the Nrf2-Keap1 signaling pathway in primary rat proximal tubular cells.

Nuclear factor erythroid 2-related factor 2 (Nrf2) is a transcription factor that regulates a cluster of oxidative stress-inducible genes in cells. Here, we aimed to investigate whether trehalose (Tre) protects primary rat proximal tubular (rPT) cells against cadmium (Cd)-induced oxidative stress via Nrf2 antioxidant pathway. Data showed that Tre treatment inhibited Nrf2 nuclear translocation and restored the decline in Kelch-like ECH-associated protein 1 (Keap1) protein level in Cd-exposed rPT cells. Moreover, Cd-activated Nrf2 target genes, including phase II detoxifying enzymes, that is, NAD(P)H quinone oxidoreductase 1 and heme oxygenase-1, direct antioxidant proteins, that is, glutathione peroxidase, superoxide dismutase, catalase, and glutathione biosynthesis-related proteins, that is, glutamatecysteine ligase catalytic subunit, glutamate cysteine ligase modifier subunit, and glutathione reductase, were all downregulated by co-treatment with Tre. Collectively, these findings demonstrate that Tre treatment alleviates Cd-induced oxidative stress in rPT cells by inhibiting the Nrf2-Keap1 signaling pathway.