High-Performance Nanofiltration Membrane with Dual Resistance to Gypsum Scaling and Biofouling for Enhanced Water Purification.

Nanofiltration (NF) technology is pivotal for ensuring a sustainable and reliable supply of clean water. To address the critical need for advanced thin-film composite (TFC) polyamide (PA) membranes with exceptional permselectivity and fouling resistance for emerging contaminant purification, we introduce a novel high-performance NF membrane. This membrane features a selective polypiperazine (PIP) layer functionalized with amino-containing quaternary ammonium compounds (QACs) through an in situ interfacial polycondensation reaction. Our investigation demonstrated that precise QAC functionalization enabled the construction of the selective PA layer with increased surface area, enhanced microporosity, stronger electronegativity, and reduced thickness compared to the control PIP membrane. As a result, the QAC NF membrane exhibited an approximately 51% increase in water permeance compared to the control PIP membrane, while achieving superior retention capabilities for divalent salts (>99%) and emerging organic contaminants (>90%). Furthermore, the incorporation of QACs into the PIP selective layer was proved to be effective in mitigating mineral scaling by allowing selective passage of scale-forming cations, while simultaneously exhibiting strong antimicrobial properties to combat biofouling. The in situ QAC incorporation strategy presented in this study provides valuable guidelines for the fit-for-purpose design of the selective PA layer, which is crucial for the development of high-performance NF membranes for efficient water purification.

Ultrafast Electronic Dynamics in Anisotropic Indirect Interlayer Excitonic States of Monolayer WSe2/ReS2 Heterojunctions.

Understanding ultrafast electronic dynamics of the interlayer excitonic states in atomically thin transition metal dichalcogenides is of importance in engineering valleytronics and developing excitonic integrated circuits. In this work, we experimentally explored the ultrafast dynamics of indirect interlayer excitonic states in monolayer type II WSe2/ReS2 heterojunctions using time-resolved photoemission electron microscopy, which reveals its anisotropic behavior. The ultrafast cooling and decay of excited-state electrons exhibit significant linear dichroism. The ab initio theoretical calculations provide unambiguous evidence that this linear dichroism result is primarily associated with the anisotropic nonradiative recombination of indirect interlayer excitonic states. Measuring time-resolved photoemission energy spectra, we have further revealed the ultrafast evolution of excited-state electrons in anisotropic indirect interlayer excitonic states. The findings have important implications for controlling the interlayer moiré excitonic effects and designing anisotropic optoelectronic devices.

Unraveling the Structure and Reactivity Patterns of the Indole Radical Cation in Regioselective Electrochemical Oxidative Annulations.

Oxidation-induced strategy for inert chemical bond activation through highly active radical cation intermediate has exhibited unique reactivity. Understanding the structure and reactivity patterns of radical cation intermediates is crucial in the mechanistic study and will be beneficial for developing new reactions. In this work, the structure and properties of indole radical cations have been revealed using time-resolved transient absorption spectroscopy, in situ electrochemical UV-vis, and in situ electrochemical electron paramagnetic resonance (EPR) technique. Density functional theory (DFT) calculations were used to explain and predict the regioselectivity of several electrochemical oxidative indole annulations. Based on the understanding of the inherent properties of several indole radical cations, two different regioselective annulations of indoles have been successfully developed under electrochemical oxidation conditions. Varieties of furo[2,3-b]indolines and furo[3,2-b]indolines were synthesized in good yields with high regioselectivities. Our mechanistic insights into indole radical cations will promote the further development of oxidation-induced indole functionalizations.

Bright and Dark Quadrupolar Excitons in the WSe_{2}/MoSe_{2}/WSe_{2} Heterotrilayer.

Transition metal dichalcogenide heterostructures have been extensively studied as a platform for investigating exciton physics. While heterobilayers such as WSe_{2}/MoSe_{2} have received significant attention, there has been comparatively less research on heterotrilayers, which may offer new excitonic species and phases, as well as unique physical properties. In this Letter, we present theoretical and experimental investigations on the emission properties of quadrupolar excitons (QXs), a newly predicted type of exciton, in a WSe_{2}/MoSe_{2}/WSe_{2} heterotrilayer device. Our findings reveal that the optical brightness or darkness of QXs is determined by horizontal mirror symmetry and valley and spin selection rules. Additionally, the emission intensity and energy of both bright and dark QXs can be adjusted by applying an out-of-plane electric field, due to changes in hole distribution and the Stark effect. These results not only provide experimental evidence for the existence of QXs in heterotrilayers but also uncover their novel properties, which have the potential to drive the development of new exciton-based applications.

Electroactive Ultrafiltration Membrane for Simultaneous Removal of Antibiotic, Antibiotic Resistant Bacteria, and Antibiotic Resistance Genes from Wastewater Effluent.

To combat the spread of antibiotic resistance into the environment, we should adequately manage wastewater effluent treatment to achieve simultaneous removal of antibiotics, antibiotic resistant bacteria (ARB), and antibiotic resistance genes (ARGs). Herein, we fabricate a multifunctional electroactive poly(vinylidene fluoride) ultrafiltration membrane (C/PVDF) by phase inversion on conductive carbon cloth. The membrane possesses not only excellent retention toward ARB and ARGs but also exhibits high oxidation capacity as an electrode. Notably, sulfamethoxazole degradation involving hydroxylation and hydrolysis by the anode membrane is predominant, and the degradation efficiency is up to 81.5% at +4 V. Both electro-filtration processes exhibit significant ARB inactivation, anode filtration is superior to cathode filtration. Moreover, the degradation of intracellular ARGs (iARGs) located in the genome is more efficient than those located in the plasmid, and these degradation efficiencies at -2 V are higher than +2 V. The degradation efficiencies of extracellular ARGs (eARGs) are opposite and are lower than iARGs. Compared with regular filtration, the normalized flux of electroactive ultrafiltration membrane is improved by 18.0% at -2 V, 15.9% at +2 V, and 30.4% at +4 V during treating wastewater effluent, confirming its antifouling properties and feasibility for practical application.

Electrochemical biosensing of circulating microRNA-21 in cerebrospinal fluid of medulloblastoma patients through target-induced redox signal amplification.

Monitoring of cerebrospinal fluid (CSF) microRNAs (miRs) offers a promising option for the diagnosis and management of patients with central nervous system tumors. However, the sensitive detection of miRs in clinical CSF samples has been hindered by the ultra-low abundance of target miRs. Here, we report an electrochemical biosensor for the highly sensitive label-free detection of CSF miR-21 relying on target-induced redox signal amplification (eTIRSA). The biosensor was developed by covalently assembling the capture stands partially complementary to miR-21 on the gold nanoparticle-coated glassy carbon electrode. In the presence of miR-21, the short capture stand hybridized with the partial bases of miR-21, allowing the rest sequence of the target molecule to further bind with a long guanine-rich sequence which could specifically adsorb a number of methylene blue indicators, thus generating an amplified electrochemical redox signal, typically at a working potential of - 0.19 V (vs. SCE). The response of the surface-bound methylene blue indicators was positively correlated to the concentration of miR-21, providing a dynamic range of 0.5-80 pM and a limit of detection down to 56 fM. Moreover, the eTIRSA biosensor had high specificity with single-base resolution and exhibited good performance for label-free quantification of miR-21 in medulloblastoma cell extracts and clinical CSF samples and for accurate discrimination of medulloblastoma against non-cancer controls, indicating its potential application in CSF miR-based liquid biopsy of brain cancers.

Ultrafast Electron Cooling and Decay in Monolayer WS2 Revealed by Time- and Energy-Resolved Photoemission Electron Microscopy.

A comprehensive understanding of the ultrafast electron dynamics in two-dimensional transition metal dichalcogenides (TMDs) is necessary for their applications in optoelectronic devices. In this work, we contribute a study of ultrafast electron cooling and decay dynamics in the supported and suspended monolayer WS2 by time- and energy-resolved photoemission electron microscopy (PEEM). Electron cooling in the Q valley of the conduction band is clearly resolved in energy and time, on a time scale of 0.3 ps. Electron decay is mainly via a defect trapping process on a time scale of several picoseconds. We observed that the trap states can be produced and increased by laser illumination under an ultrahigh vacuum, and the higher local optical-field intensity led to the faster increase of trap states. The enhanced defect trapping could significantly modify the carrier dynamics and should be paid attention to in photoemission experiments for two-dimensional materials.

High Performance Nanofiltration Membrane for Effective Removal of Perfluoroalkyl Substances at High Water Recovery.

We demonstrate the fabrication of a loose, negatively charged nanofiltration (NF) membrane with tailored selectivity for the removal of perfluoroalkyl substances with reduced scaling potential. A selective polyamide layer was fabricated on top of a poly(ether sulfone) support via interfacial polymerization of trimesoyl chloride and a mixture of piperazine and bipiperidine. Incorporating high molecular weight bipiperidine during the interfacial polymerization enables the formation of a loose, nanoporous selective layer structure. The fabricated NF membrane possessed a negative surface charge and had a pore diameter of ∼1.2 nm, much larger than a widely used commercial NF membrane (i.e., NF270 with pore diameter of ∼0.8 nm). We evaluated the performance of the fabricated NF membrane for the rejection of different salts (i.e., NaCl, CaCl2, and Na2SO4) and perfluorooctanoic acid (PFOA). The fabricated NF membrane exhibited a high retention of PFOA (∼90%) while allowing high passage of scale-forming cations (i.e., calcium). We further performed gypsum scaling experiments to demonstrate lower scaling potential of the fabricated loose porous NF membrane compared to NF membranes having a dense selective layer under solution conditions simulating high water recovery. Our results demonstrate that properly designed NF membranes are a critical component of a high recovery NF system, which provide an efficient and sustainable solution for remediation of groundwater contaminated with perfluoroalkyl substances.

Photocatalytic Reactive Ultrafiltration Membrane for Removal of Antibiotic Resistant Bacteria and Antibiotic Resistance Genes from Wastewater Effluent.

Biological wastewater treatment is not effective in removal of antibiotic resistant bacteria (ARB) and antibiotic resistance genes (ARGs). In this study, we fabricated a photocatalytic reactive membrane by functionalizing polyvinylidene fluoride (PVDF) ultrafiltration (UF) membrane with titanium oxide (TiO2) nanoparticles for the removal of ARB and ARGs from a secondary wastewater effluent. The TiO2-modified PVDF membrane provided complete retention of ARB and effective photocatalytic degradation of ARGs and integrons. Specifically, the total removal efficiency of ARGs (i.e., plasmid-mediated floR, sul1, and sul2) with TiO2-modified PVDF membrane reached ∼98% after exposure to UV irradiation. Photocatalytic degradation of ARGs located in the genome was found to be more efficient than those located in plasmid. Excellent removal of integrons (i.e., intI1, intI2, and intI3) after UV treatment indicated that the horizontal transfer potential of ARGs was effectively controlled by the TiO2 photocatalytic reaction. We also evaluated the antifouling properties of the TiO2-UF membrane to demonstrate its potential application in wastewater treatment.

Improvement of cerebral blood perfusion in certain cerebral regions after cranioplasty could be monitored via tympanic membrane temperature changes.

OBJECTIVE: Delayed neurological deficit was often observed in patients underwent craniectomy, which could be improved by cranioplasty. Little is known about hemodynamic improvement before and after cranioplasty. METHODS: Cerebral blood perfusion, tympanic membrane temperature (TMT), neuropsychological and cognitive function were assessed in eleven craniectomy patients before and after cranioplasty. RESULTS: Before cranioplasty, the cerebral blood volume (CBV) on the decompressed side was significantly lower than that of the contralateral side. The cranioplasty led to instant improvement (7 days after cranioplasty) of cerebral perfusion at the cranioplasty side in the frontal lobe, parietal lobe, temporal lobe, mesencephalon, basal ganglia and thalamus, but not the occipital lobe and epencephalon. Interestingly, CBV of the thalamus and basal ganglia gradually decreased to pre-surgical status 6 months later while the frontal lobe, parietal lobe, temporal lobe, mesencephalon remained well perfused. Meanwhile, the TMT changes acquired positive correlation with the perfusion of temporal lobe and mesencephalon as well as the GCS and MMSE score. CONCLUSION: The cranioplasty remarkably improves neurological and cognitive function by ameliorating cerebral perfusion in certain regions. The TMT could be used as a non-invasive method to monitor the cerebral perfusion improvement after the cranioplasty.

Qualitatively and quantitatively assessing the aggregation ability of sludge during aerobic granulation process combined XDLVO theory with physicochemical properties.

Inexact mechanism of aerobic granulation still impedes optimization and application of aerobic granules. In this study, the extended Derjaguin, Landau, Verwey, and Overbeek (XDLVO) theory and physicochemical properties were combined to assess the aggregation ability of sludge during aerobic granulation process qualitatively and quantitatively. Results show that relative hydrophobicity of sludge and polysaccharide content of extracellular polymeric substances (EPS) increased, while electronegativity of sludge decreased during acclimation phase. After 20days' acclimation, small granules began to form due to high aggregation ability of sludge. Since then, coexisted flocs and granules possessed distinct physicochemical properties during granulation and maturation phase. The relative hydrophobicity decreased while electronegativity increased for flocs, whereas that for granules presented reverse trend. Through analyzing the interaction energy using the XDLVO theory, small granules tended to self-grow rather than self-aggregate or attach of flocs due to poor aggregation ability between flocs and granules during the granulation phase. Besides, remaining flocs were unlikely to self-aggregate owing to poor aggregation ability, low hydrophobicity and high electronegativity.

Bioelectrochemical Chromium(VI) Removal in Plant-Microbial Fuel Cells.

Plant-microbial fuel cell (PMFC) is a renewable and sustainable energy technology that generates electricity with living plants. However, little information is available regarding the application of PMFC for the remediation of heavy metal contaminated water or soil. In this study, the potential for the removal of heavy metal Cr(VI) using PMFC was evaluated, and the performance of the PMFC at various initial Cr(VI) contents was investigated. The Cr(VI) removal efficiency could reached 99% under various conditions. Both the Cr(VI) removal rates and the removal efficiencies increased with the increasing initial Cr(VI) concentration. Furthermore, the long-term operation of the PMFC indicated that the system was stable and sustainable for Cr(VI) removal. The mass balance results and XPS analysis results demonstrate that only a small amount of soluble Cr(III) remained in the PMFC and that most Cr(III) precipitated in the form of the Cr(OH)3(s) or was adsorbed onto the electrodes. The PMFC experiments of without acetate addition also show that plants can provide carbon source for MFC through secrete root exudates and bioelectrochemical reduction of Cr(VI) was the main mechanism for the Cr(VI) removal. These results extend the application fields of PMFC and might provide a new insight for Cr(VI) removal from wastewater or soil.

Application of a weak magnetic field to improve microbial fuel cell performance.

Microbial fuel cells (MFCs) have emerged as a promising technology for wastewater treatment with concomitant energy production but the performance is usually limited by low microbial activities. This has spurred intensive research interest for microbial enhancement. This study demonstrated an interesting stimulation effect of a static magnetic field (MF) on sludge-inoculated MFCs and explored into the mechanisms. The implementation of a 100-mT MF accelerated the reactor startup and led to increased electricity generation. Under the MF exposure, the activation loss of the MFC was decreased, but there was no increased secretion of redox mediators. Thus, the MF effect was mainly due to enhanced bioelectrochemical activities of anodic microorganisms, which are likely attributed to the oxidative stress and magnetohydrodynamic effects under an MF exposure. This work implies that weak MF may be applied as a simple and effective approach to stimulate microbial activities for various bioelectrochemical energy production and decontamination applications.

Regulation of quorum sensing for the manipulation of conjugative transfer of antibiotic resistance genes in wastewater treatment system.

The emergence and transmission of antibiotic resistance genes (ARGs) through plasmid-mediated conjugation has become a significant worldwide public health threat. Biofilms are widely recognized as the primary reservoirs for ARGs, providing favorable conditions for horizontal gene transfer. Quorum sensing (QS) plays a critical role in bacterial biofilm formation, which further influences the spread of bacterial resistance. In this study, we examined the effects of vanillin, a QS inhibitor (QSI), at subinhibitory concentrations (sub-MICs) ranging from 0 - 0.1 g/L, on the transfer of ARGs between Escherichia coli and Pseudomonas aeruginosa. Our findings indicated that vanillin at sub-MICs inhibited the conjugative transfer frequency of the RP4 plasmid. This inhibition was supported by the downregulation of plasmid transfer genes. The suppression of conjugation can mainly be attributed to the inhibition of biofilm formation, the synthesis of extracellular polymeric substances (EPS), and the secretion of virulence factors, all of which are regulated by the bacterial QS system. On the other hand, the levels of ROS and cell membrane permeability were not primary explanations for this phenomenon. Furthermore, vanillin also reduced the conjugative transfer frequency of ARGs in wastewater effluent, providing a potential approach to alleviate bacterial resistance in water environments. These findings underscore the regulatory role of QSI in controlling ARGs transfer and have significant implications for manipulating the dissemination of bacterial resistance in the environment.

Regulation of intracellular process by two-component systems: Exploring the mechanism of plasmid-mediated conjugative transfer.

Plasmid-mediated conjugative transfer facilitates the dissemination of antibiotic resistance, yet the comprehensive regulatory mechanisms governing this process remain elusive. Herein, we established pure bacteria and activated sludge conjugation system to investigate the regulatory mechanisms of conjugative transfer, leveraging metformin as an exogenous agent. Transcriptomic analysis unveiled that substantial upregulation of genes associated with the two-component system (e.g., AcrB/AcrA, EnvZ/Omp, and CpxA/CpxR) upon exposure to metformin. Furthermore, downstream regulators of the two-component system, including reactive oxygen species (ROS), cytoplasmic membrane permeability, and adenosine triphosphate (ATP) production, were enhanced by 1.7, 1.4 and 1.1 times, respectively, compared to the control group under 0.1 mg/L metformin exposure. Moreover, flow sorting and high-throughput sequencing revealed increased microbial community diversity among transconjugants in activated sludge systems. Notably, the antibacterial potential of human pathogenic bacteria (e.g., Bacteroides, Escherichia-Shigella, and Lactobacillus) was augmented, posing a potential threat to human health. Our findings shed light on the spread of antibiotic resistance bacteria and assess the ecological risks associated with plasmid-mediated conjugative transfer in wastewater treatment systems.

miR-124-3p and miR-194-5p regulation of the PI3K/AKT pathway via ROR2 in medulloblastoma progression.

Medulloblastoma (MB), a prevalent pediatric central nervous system tumor, is influenced by microRNAs (miRNAs) that impact tumor initiation and progression. However, the specific involvement of miRNAs in MB tumorigenesis remains unclear. Using single-cell RNA sequencing, we identified ROR2 expression in normal human fetal cerebellum. Subsequent analyses, including immunofluorescence, quantitative real-time PCR (qRT-PCR), and Western blot, assessed ROR2 expression in MB tissues and cell lines. We investigated miR-124-3p and miR-194-5p and their regulatory role in ROR2 expression through the dual-luciferase reporter, qRT-PCR, and western blot assays. Mechanistic insights were gained through functional assays exploring the impact of miR-124-3p, miR-194-5p, and ROR2 on MB growth in vitro and in vivo. We observed significantly reduced miR-124-3p and miR-194-5p expression and elevated ROR2 expression in MB tissues and cell lines. High ROR2 expression inversely correlated with overall survival in WNT and SHH subgroups of MB patients. Functionally, overexpressing miR-124-3p and miR-194-5p and inhibiting ROR2 suppressed in vitro malignant transformation and in vivo tumorigenicity. Mechanistically, miR-124-3p and miR-194-5p synergistically regulated the ROR2/PI3K/Akt pathway, influencing MB progression. Our findings indicate that miR-124-3p and miR-194-5p function as tumor suppressors, inhibiting MB progression via the ROR2/PI3K/Akt axis, suggesting a key mechanism and therapeutic targets for MB patients.

Preparation of Aromatic and Heterocyclic Amines by the Electrophilic Amination of Functionalized Diorganozincs with Polyfunctional O-2,6-Dichlorobenzoyl Hydroxylamines.

We report a catalyst-free electrophilic amination, which enables the synthesis of aromatic and heterocyclic amines. By subjecting diarylzinc or diheteroarylzinc compounds to readily accessible O-2,6-dichlorobenzoyl hydroxylamines in the presence of MgCl2 in dioxane at a temperature of 60 °C (8-16 h). This new electrophilic amination allowed an expedited synthesis of two pharmaceutically significant compounds: vortioxetine is a key intermediate of delamanid. This approach offers opportunities for the streamlined synthesis of amine-based molecules in the pharmaceutical industry.

Intermodal interferometer based on a fluid-filled two-mode photonic crystal fiber for sensing applications.

A fluid-filled two-mode photonic crystal fiber (PCF)-based intermodal interferometer and its sensing characteristics are demonstrated and investigated. The interferometer works from the interference between LP(01) and LP(11) core modes of the fluid-filled PCF. Solutions to enhance the temperature sensitivity of the interferometer are also discussed. Via choosing a higher fluid-filled length ratio of PCF, a sensitivity of more than -340 pm/°C at 1480 nm is achieved, which is the highest value for a PCF intermodal interferometer-based sensor, to our best knowledge. Furthermore, there exist significant differences in temperature and strain sensitivity for two different interference dips, thus the interferometer can be used as a dual-parameter sensor with a compact structure through matrix demodulation.

Determination of the fate of antibiotic resistance genes and the response mechanism of plants during enhanced antibiotic degradation in a bioelectrochemical-constructed wetland system.

Chloramphenicol (CAP) has a high concentration and detection frequency in aquatic environments due to its insufficient degradation in traditional biological wastewater treatment processes. In this study, bioelectrochemical assistant-constructed wetland systems (BES-CWs) were developed as advanced processes for efficient CAP removal, in which the degradation and transfer of CAP and the fate of antibiotic resistance genes (ARGs) were evaluated. The CAP removal efficiency could reach as high as 90.2%, while the removed CAP can be partially adsorbed and bioaccumulated in plants, significantly affecting plant growth. The vertical gene transfer and horizontal gene transfer increased the abundance of ARGs under high voltage and CAP concentrations. Microbial community analysis showed that CAP pressure and electrical stimulation selected the functional bacteria to increase CAP removal and antibiotic resistance. CAP degradation species carrying ARGs could increase their opposition to the biotoxicity of CAP and maintain system performance. In addition, ARGs are transferred into the plant and upward, which can potentially enter the food chain. This study provides an essential reference for enhancing antibiotic degradation and offers fundamental support for the underlying mechanism and ARG proliferation during antibiotic biodegradation.