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Qing Dai (Naturalis Indigo) is a traditional Chinese medicine (TCM) used as a topical agent in moderate psoriasis, targeting interleukin-17 (IL-17). In this study, it was prepared from the aerial parts of Strobilanthes cusia. Three undescribed indole alkaloid derivatives, indigodoles A-C, along with seven known compounds were isolated from this preparation of Qing Dai and their structures were elucidated from spectroscopic data, including NMR, MS, UV, IR, optical rotation, and CD. As well, most compounds were tested against IL-17. Indigodole C and tryptanthrin could significantly inhibit IL-17 production of Th17 cells. In addition, indigodole A and indirubin showed notably anti-IL-17 gene expression in dose-dependent effects without cytotoxicities toward Th17 and Jurkat cells, respectively. Overall, our studies indicate that the aforementioned indole alkaloids could contribute to anti-IL 17 properties of Qing Dai.

Recently, anodic aluminum oxide (AAO) membranes with ordered and monodispersed nanopores have attracted significant attention because the pore sizes and lengths of the AAO membranes can be systematically controlled by changing the anodization parameters. Asymmetries of geometry, wettability, charge, and polarity in nanoporous AAO membranes are now highly desired for applications such as drug delivery, membrane filtration, and catalysis. Although the asymmetries in AAO membranes have been widely studied, AAO membranes whose nanopores simultaneously possess more than two asymmetric properties still need to be developed. In this work, we present a simple method to fabricate asymmetric AAO membranes by combining the post-treatments with the three-step anodization method. The asymmetries of the AAO membranes simultaneously possessing larger nanopores with higher hydrophobicity and smaller nanopores with lower hydrophobicity are characterized by scanning electron microscopy, water contact angle measurements, an...

Semiconductor photocatalysis can be operated over a narrow pH range for wastewater treatment. In this study, a simulated solar-light-mediated bismuth tungstate (SSL/Bi2WO6) process is found to be effective for norfloxacin degradation over a narrow pH range. To broaden the operating pH range of the SSL/Bi2WO6 process, an NH4+ buffer system and an Fe3+ salt were introduced under extremely basic and acidic pH conditions, respectively. The NH4+ buffer system continuously supplied hydroxyl ions to generate ·OH radicals and prevented acidification of the solution, resulting in improved norfloxacin removal and mineralization removal under alkaline conditions. In contrast, the Fe3+ salt offered an additional homogeneous photo-sensitization pathway. The former treatment assisted in norfloxacin decay and the latter increased the collision frequency between the photo-generated hole and hydroxyl ions. Moreover, the effect of parameters such as pH and Fe3+ dosage was optimized.

Degradation of diphenamid (DPA) was examined by a novel process through sulfite activation by Fe impregnated N-doped TiO2 (FeN-TiO2) under visible LED (Vis LED). The FeN-TiO2 was synthesized using an impregnation method and characterized by various techniques. The mechanism of sulfite activation by FeN-TiO2 under Vis LED was proposed. The reaction mechanisms were further elucidated by investigating the XPS spectra of the catalysts before and after the reaction. Thirty intermediates were identified and twenty-four of them are newly reported. A new pathway was reported for the first time in the DPA studies through the rupture of benzene ring linkage. A higher mineralization degree was achieved using the FeN-TiO2/sulfite/Vis LED process, which is not in accordance with previous reports on sulfite-based processes. The absence of sulfate adducts could provide a rational explanation of the higher mineralization degree during DPA degradation. Based on reusability test, the DPA degradation efficiency increased after successive usage of the catalyst. After the complete degradation of DPA, the leached Fe-ions were found to be negligible and sulfite was completely depleted. Considering several factors such as the cheap source of sulfite (an air pollutant waste from flue-gas desulfurization process), low cost of Fe, negligible leaching of Fe-ions, and high energy efficiency of Vis LED light, the FeN-TiO2/sulfite/Vis LED process could be a practical and green technology for the removal of wastewater contaminants.

It is of fundamental significance to rationally design the potent toluene-oxidation nanocatalysts for alleviating the release of toluene, one hazardous volatile organic compound, from industrial processes, oil products and fitments materials. The manganese oxide has been developed as the extremely robust combustion materials for a wide spectra of application involving methane combustion, CO oxidation and so forth, but still has been haunted with the poor behavior for toluene combustion. Herein, we successfully demonstrate a one-step scenario wherein the well-structured LaMnO3 perovskites are in situ assembled over δ-MnO2 for the first time. Various characterizations unravel that the LaMnO3 perovskites interact with δ-MnO2 to result in good catalytic toluene combustion behavior at the Mn/La ratio of 15. Boosted active phase-carrier interplays, improved redox abilities, and tuned Mn4+/Mn3+ couples ultimately result in the decent toluene combustion property with the full toluene oxidation at 275 °C and T90 at 258 °C. The nanostructured scalable MnO2-based materials are promising catalyts that can be extended to degrade alkane, alcohols, aldehydes and benzene series.

A novel coral-like perovskite nanostructured layer was grown on a compact perovskite foundation layer by the facile surface modification with dimethylformamide/isopropanol (DMF/IPA) as co-solvent. Surface morphological characterizations with SEM and XRD analyses revealed a growing mechanism of the new morphology, which was composed of the perovskite decomposition and recrystallization, excessive-PbI2 extraction, and sequential formation of coral-like nanostructured perovskite layer. The coral-like perovskite nanostructures resulted in significant light scattering, enhancing the light-harvesting efficiency, and thus augmenting the photocurrent density. Moreover, the geometric configuration of the perovksite solar cells was changed from planar to bulk heterojunction, which results in the acceleration of charge separation and extraction due to the high surface area at the interface between the obtained perovskite and hole-transport layers. The optimal perovskite solar cell exhibited an impressive power conversion efficiency (PCE) of 19.47%, as compared to that of the pristine cell (17.19%).

Versatile photoresponsive gels based on tripodal low molecular weight gelators (LMWGs) are reported. A cyclohexane‐1,3,5‐tricarboxamide (CTA) core provides face‐to‐face hydrogen bonding and a planar conformation, inducing the self‐assembly of supramolecular polymers. The CTA core was substituted with three arylazopyrazole (AAP) arms. AAP is a molecular photoswitch that isomerizes reversibly under alternating UV and green light irradiation. The E isomer of AAP is planar, favoring the self‐assembly, whereas the Z isomer has a twisted structure, leading to a disassembly of the supramolecular polymers. By using tailor‐made molecular design of the tripodal gelator, light‐responsive organogels and hydrogels were obtained. Additionally, in the case of the hydrogels, AAP was coupled to the core through hydrazones, so that the hydrogelator and, hence, the photoresponsive hydrogel could also be assembled and disassembled by using dynamic covalent chemistry.

A series of CuxCoy catalysts were successfully synthesized by deposition–precipitation with urea method and their catalytic performance was investigated for methanol decomposition to hydrogen. These as-prepared samples were characterized by ICP-OES, XRD, SEM, BET, H2-TPR and XPS. The characterization results indicate that the bimetallic catalysts exhibit better dispersion and reducibility as compared with the monometallic catalysts, and the strong interaction between copper and cobalt can promote the formation of Cu+. Among the fabricated materials, the Cu0.5Co0.5 presents the best catalytic activity and H2 selectivity. Moreover, its catalytic performance is higher than the commercial catalyst at the same test conditions. The catalytic performance of bimetallic CuxCoy catalytic is better than that of monometallic catalysts. Meanwhile, the optimized catalyst prepared exhibits excellent catalytic activity and selectivity compared with the commercial catalysts at the same reaction conditions, which is due to the coexist of Cu+ and Cu2+ after reduction.

The interaction between magnetite and aqueous Fe(II) profoundly impacts the mineral recrystallization, trace-metal sequestration, and contaminant reduction. The iron ions in natural magnetite are extensively substituted by other cations. It is still unclear whether the substitution with thermodynamically favorable redox repairs (e.g., Co2+/Co3+) plays a vital role in the reducing capability of the coupled system. Herein, a series of Co-substituted magnetite samples (Fe3−xCoxO4, 0.00 ≤ x ≤ 1.00) were synthesized and tested for the reductive removal of Cr(VI) in the presence of Fe(II). Fe3−xCoxO4 had a spinel structure with the preferential occupancy of Co2+ on octahedral sites. No visible variation in the BET surface area was observed, whereas the surface site density increased gradually with Co substitution. Cr(VI) was found first adsorbed on the Fe3−xCoxO4 surface and then reduced to Cr(III) by the structural Fe2+ and the absorbed Fe(II), accompanied by the oxidation of bulk Fe2+ and surface Fe(II) in Fe3−xCoxO4 without phase transformation. The Cr(III) was precipitated on the Fe3−xCoxO4 surface with Fe(III), or substituted octahedral Fe in Fe3−xCoxO4. Both the reaction kinetics and the electron transfer efficiency revealed that Co substitution significantly improved the reactivity of Fe3−xCoxO4/Fe(II) towards Cr(VI) reduction. This was ascribed to the presence of the redox pairs Co2+/Co3+ and Fe2+/Fe3+ accelerating electron transfer from the Fe3−xCoxO4 interface to Cr(VI).

The mechanical properties of nucleic acids underlie biological processes ranging from genome packaging to gene expression, but tracing their molecular origin has been difficult due to the structural and chemical complexity. We posit that concepts from machine learning can help to tackle this long-standing challenge. Here, we demonstrate the feasibility and advantage of this strategy through developing a structure-mechanics statistical learning scheme to elucidate how local rigidity in double-stranded (ds)DNA and dsRNA may lead to their global flexibility in bend, stretch, and twist. Specifically, the mechanical parameters in a heavy-atom elastic network model are computed from the trajectory data of all-atom molecular dynamics simulation. The results show that the inter-atomic springs for backbone and ribose puckering in dsRNA are stronger than those in dsDNA, but are similar in strengths for base-stacking and base-pairing. Our analysis shows that the experimental observation of dsDNA being easier to bend but harder to stretch than dsRNA comes mostly from the respective B- and A-form topologies. The computationally resolved composition of local rigidity indicates that the flexibility of both nucleic acids is mostly due to base-stacking. But for properties like twist-stretch coupling, backbone springs are shown to play a major role instead. The quantitative connection between local rigidity and global flexibility sets foundation for understanding how local binding and chemical modification of genetic materials effectuate longer-ranged regulatory signals., The mechanical properties of nucleic acids underlie biological processes ranging from genome packaging to gene expression. We devise structural mechanics statistical learning method to reveal their molecular origin in terms of chemical interactions.

In this study, we prepared organic photovoltaics (OPVs) featuring an active layer comprising double bulk heterojunction (BHJ) structures, featuring binary blends of a polymer donor and concentration gradients of two small-molecule acceptors. After forming the first BHJ structure by spin-coating, the second BHJ layer was transfer-printed onto the first using polydimethylsiloxane stamps. A specially designed selenium heterocyclic small-molecule acceptor (Y6-Se-4Cl) was employed as the second acceptor in the BHJ. X-ray photoelectron spectroscopy revealed that the two acceptors formed a gradient concentration profile across the active layer, thereby facilitating charge transportation. The best power conversion efficiencies (PCEs) for the double-BHJ-structured devices incorporating PM6:Y6-Se-4Cl/PM6:Y6 and PM6:Y6-Se-4Cl/PM6:IT-4Cl were 16.4 and 15.8%, respectively; these values were higher than those of devices having one-BHJ structures based on PM6:Y6-Se-4Cl (15.0%), PM6:Y6 (15.4%), and PM6:IT-4Cl (11.6%), presumably because of the favorable vertical concentration gradient of the selenium-containing small-molecule Y6-Se-4Cl in the active layer as well as some complementary light absorption. Thus, combining two BHJ structures with a concentration gradient of the two small-molecule acceptors can be an effective approach for enhancing the PCEs of OPVs.

A multiple-time programmable (MTP) twin-bit memory cell with metal floating gate coupled by n-well program gate is proposed and implemented by standard CMOS logic processes. Equipped with high programming gate coupling ratio controlled well by overlap area design, a twin bit cell with a pair of symmetric floating gates is successfully demonstrated. In addition, this memory also shows good endurance and low disturbance during the P/E cycling tests.

Nowadays, the power conversion efficiency of organometallic mixed halide perovskite solar cells (PSCs) is beyond 25%. To fabricate highly efficient and stable PSCs, the performance of metal oxide charge transport layers (CTLs) is one of the key factors. The CTLs are employed in PSCs to separate the electrons and holes generated in the perovskite active layer, suppressing the charge recombination rate so that the charge collection efficiency can be increased at their respective electrodes. In general, engineering of metal oxide electron transport layers (ETLs) is found to be dominated in the research community to boost the performance of PSCs due to the resilient features of ETLs such as excellent electronic properties, high resistance to thermal temperature and moisture, ensuring good device stability as well as their high versatility in material preparation. The metal oxide hole transport layers in PSCs are recently intensively studied. The performance of PSCs is found to be very promising by using optimized hole transport materials. This review concisely discusses the evolution of some prevalent metal oxide charge transport materials (CTMs) including TiO2, SnO2, and NiOx, which are able to yield high-performance PSCs. The article begins with introducing the development trend of PSCs using different types of CTLs, pointing out the important criteria for metal oxides being effective CTLs, and then a variety of preparation methods for CTLs as employed by the community for high-performance PSCs are discussed. Finally, the challenges and prospects for future research direction toward scalable metal oxide CTM-based PSCs are delineated.

We experimently and theoretically investigate temporal structures of ${{\mathrm{N}}_{2}}^{+}$ lasing at the wavelengths of 391 and 428 nm. Our results show that the resonant interaction of a femtosecond laser with ${{\mathrm{N}}_{2}}^{+}$ ions with a picosecond dipole relaxation time will induce a long-lasting polarization, which exists in cases of both absorption and amplification of the external seed. The induced polarization will be amplified in population-inverted ${{\mathrm{N}}_{2}}^{+}$ ions, giving rise to the retarded radiation (i.e., ${{\mathrm{N}}_{2}}^{+}$ lasing). The temporal profile of the retarded radiation is closely related to the dipole relaxation time, population inversion density, and propagation length. The combined experimental and theoretical study reveals the physical origin of the retarded seed amplification in ${{\mathrm{N}}_{2}}^{+}$ ions.

We demonstrate the hybrid integration of a lithium niobate microring resonator with a silicon nitride waveguide in the vertical configuration to achieve efficient light coupling. The microring resonator is fabricated on a lithium niobate on insulator (LNOI) substrate using photolithography assisted chemo-mechanical etching (PLACE). A fused silica cladding layer is deposited on the LNOI ring resonator. The silicon nitride waveguide is further produced on the fused silica cladding layer by first fabricating a trench in the fused silica while using focused ion beam (FIB) etching for facilitating the evanescent coupling, followed by the formation of the silicon nitride waveguide on the bottom of the trench. The FIB etching ensures the required high positioning accuracy between the waveguide and ring resonator. We achieve Q-factors as high as 1.4 × 107 with the vertically integrated device.

The pollution of heavy metals and organic compounds has received increased attention in recent years. In the current study, a novel biochar-based iron oxide composite (FeYBC) was successfully synthesized using pomelo peel and ferric chloride solution through one-step process at moderate temperature. Results clearly demonstrate that FeYBC exhibited more efficient removal of Cr(VI) and/or phenol compared with the pristine biochar, and the maximum adsorption amounts of Cr(VI) and phenol by FeYBC could reach 24.37 and 39.32 mg g−1, respectively. A series of characterization data suggests that several iron oxides such as Fe2O3, Fe0, FeOOH and Fe3O4 were formed on the FeYBC surface as well as oxygen-containing groups. Thermodynamics study indicates that Cr(VI) and phenol adsorption by FeYBC were endothermic and exothermic processes, respectively. Langmuir adsorption isotherm and pseudo-second order models could better explain the Cr(VI) and phenol adsorption behaviors over FeYBC. The Cr(VI) adsorption might be primarily achieved through the ion exchange and surface complexation and reduction, whereas the π–π interaction and electron donor–acceptor complex mainly contributed to phenol adsorption. The findings indicate that the biochar-based iron oxide composites material was an efficient adsorbent for the remediation of industrial effluents containing Cr(VI) and phenol.

The understanding of nonlinear light–matter interactions at the nanoscale has fueled worldwide interest in upconversion emission for imaging, lasing, and sensing. Upconversion lasers with anti-Stokes-type emission with various designs have been reported. However, reducing the volume and lasing threshold of such lasers to the nanoscale level is a fundamental photonics challenge. Here, we demonstrate that the upconversion efficiency can be improved by exploiting single-mode upconversion lasing from a single organo-lead halide perovskite nanocrystal in a resonance-adjustable plasmonic nanocavity. This upconversion plasmonic nanolaser has a very low lasing threshold (10 μJ cm⁻²) and a calculated ultrasmall mode volume (∼0.06 λ³) at 6 K. To provide the unique feature for lasing action, a temporal coherence signature of the upconversion plasmonic nanolasing was determined by measuring the second-order correlation function. The localized-electromagnetic-field confinement can be tailored in titanium nitride resonance-adjustable nanocavities, enhancing the pump-photon absorption and upconverted photon emission rate to achieve lasing. The proof-of-concept results significantly expand the performance of upconversion nanolasers, which are useful in applications such as on-chip, coherent, nonlinear optics, information processing, data storage, and sensing.

Frontiers in Earth Science 9, 1-17 (2021). doi:10.3389/feart.2021.599986, Published by Frontiers Media, Lausanne

We demonstrate monolithic integration of an electro-optically (EO) tunable microring laser on lithium niobate on insulator (LNOI) platform. The device is fabricated by photolithography assisted chemo-mechanical etching (PLACE), and the pump laser is evanescently coupled into the erbium (Er3+) doped LN microring laser using an undoped LN waveguide mounted above the microring. The quality factor of the LN microring resonator is measured as high as 1.54x10^5 at the wavelength of 1542 nm. Lasing action can be observed at a pump power threshold below 3.5 mW using a 980 nm continuous-wave pump laser. Finally, tuning of the laser wavelength is achieved by varying the electric voltage on the microelectrodes fabricated in the vicinity of microring waveguide, showing an EO coefficient of 0.33 pm/V., Comment: 4 pages, 4 figures

Two-photon absorption spectra are difficult to observe using direct absorption spectroscopy especially in the near-infrared region. Cavity ring-down spectroscopy is a promising absorption spectroscopy technique which has been widely applied to linear and saturated single-photon absorption spectra. In the present study, we report the observation of a possible two-photon absorption in the near-infrared using cavity ring-down spectroscopy, namely a two-photon resonance of methane. Using an optical frequency comb, the single-photon wavenumber of the double-quantum transition has been determined to be 182 207 682.645 MHz with a standard deviation of 75 kHz.

Polyploidy occurs prevalently and plays an important role during plant speciation and evolution. This phenomenon suggests polyploidy could develop novel features that enable them to adapt wider range of environmental conditions compared with diploid progenitors. Bread wheat (Triticum aestivum L., BBAADD) is a typical allohexaploid species and generally exhibits greater salt tolerance than its tetraploid wheat progenitor (BBAA). However, little is known about the underlying molecular basis and the regulatory pathway of this trait. Here, we show that the histone acetyltransferase TaHAG1 acts as a crucial regulator to strengthen salt tolerance of hexaploid wheat. Salinity-induced TaHAG1 expression was associated with tolerance variation in polyploidy wheat. Overexpression, silencing, and CRISPR-mediated knockout of TaHAG1 validated the role of TaHAG1 in salinity tolerance of wheat. TaHAG1 contributed to salt tolerance by modulating reactive oxygen species (ROS) production and signal specificity. Moreover, TaHAG1 directly targeted a subset of genes that are responsible for hydrogen peroxide production, and enrichment of TaHAG1 triggered increased H3 acetylation and transcriptional upregulation of these loci under salt stress. In addition, we found the salinity-induced TaHAG1-mediated ROS production pathway is involved in salt tolerance difference of wheat accessions with varying ploidy. Our findings provide insight into the molecular mechanism of how an epigenetic regulatory factor facilitates adaptability of polyploidy wheat and highlights this epigenetic modulator as a strategy for salt tolerance breeding in bread wheat.

Background Electrophysiological sensing of cardiomyocytes (CMs) in optogenetic preparations applies various techniques, such as patch-clamp, microelectrode array, and optical mapping. However, challenges remain in decreasing the cost, system dimensions, and operating skills required for these technologies. Objective This study developed a low-cost, portable impedance plethysmography (IPG)-based electrophysiological measurement of cultured CMs for optogenetic applications. Methods To validate the efficacy of the proposed sensor, optogenetic stimulation with different pacing cycle lengths (PCL) was performed to evaluate whether the channelrhodopsin-2 (ChR2)-expressing CM beating rhythm measured by the IPG sensor was consistent with biological responses. Results The experimental results show that the CM field potential was synchronized with external optical pacing with PCLs ranging from 250 ms to 1000 ms. Moreover, irregular fibrillating waveforms induced by CM arrhythmia were detected after overdrive optical pacing. Through the combined evidence of the theoretical model and experimental results, this study confirmed the feasibility of long-term electrophysiological sensing for optogenetic CMs. Conclusion This study proposes an IPG-based sensor that is low-cost, portable, and requires low-operating skills to perform real-time CM field potential measurement in response to optogenetic stimulation. Significance This study demonstrates a new methodology for convenient electrophysiological sensing of CMs in optogenetic applications.

Integrity of rails is the foundation of safe rail transportation. It is critical to detect internal rail flaws in time, and one popular solution to this issue is ultrasonic techniques. On the other hand, long short-term memory (LSTM) has been proven in text classification to which we think the ultrasonic rail flaw detection can be quite similar. In this context, this paper proposes a novel text-style sequential modeling method for ultrasonic rail flaw data and a LSTM-based deep learning model for rail flaw detection. Comparative experiments proved the feasibility and remarkable computational efficiency of the proposed modeling method and model.

We design a compact three-dimensional (3D) micromixer based on the Baker’s transformation concept and fabricate it in fused silica by ultrafast laser direct writing. One of the issues in the micromixer is the unbalanced mixing efficiencies between the center and boundary areas of the microfluidic channel. We overcome this problem by periodically exchanging the microstreams in the center and near the boundary which gives rise to improved mixing efficiency and uniformity. The performance of the fabricated micromixer is examined by mixing a blue and a yellow ink solution, showing efficient mixing with a high throughput.

The combination of a bulk 3D perovskite layer and a reduced dimensional perovskite layer (perovskite quantum wells (PQWs)) is demonstrated to enhance the performance of perovskite solar cells (PSCs) significantly in terms of stability and efficiency. This perovskite hierarchy has attracted intensive research interest; however, the in-depth formation mechanism of perovskite quantum wells on top of a 3D perovskite layer is not clearly understood and is therefore the focus of this study. Along with ex situ morphology and photophysical characterization, the time-resolved grazing-incidence wide-angle X-ray scattering (TS-GIWAXS) technique performed in this study provides real-time insights on the phase-transition during the organic cation (HTAB ligand molecule) coating and PQWs/3D architecture formation process. A strikingly strong ionic reaction between the 3D perovskite and the long-chain organic cation leads to the quick formation of an ordered intermediate phase within only a few seconds. The optimal PQWs/3D architecture is achieved by controlling the HTAB casting, which is assisted by time-of-flight SIMS characterization. By controlling the second ionic reaction during the long-chain cation coating process, along with the fluorinated poly(triarylamine) (PTAA) as a hole-transport layer, the perovskite solar cells demonstrate efficiencies exceeding 22% along with drastically improved device stability.

In this investigation, raw water (RW), settled water (SW), and filtered water (FW) collected from a drinking water treatment plant were fractionated into 24 natural organic matter (NOM) fractions with varying molecular weights and hydrophobicity. The yields of disinfection byproducts (DBPs) obtained during the chlorination of the NOM fractions were explored. Results revealed that the 0–1 kDa, 5–10 kDa, and hydrophobic DBP precursors dominated RW. Hydrophobic fractions cannot be effectively removed, which contributed to the high DBP precursors remaining in the FW. The optional optical parameters, including UVA (UV340, UV360, and UV380), UVB (UV280, UV300, and UV310), and UVC (UV254, UV260, and UV272), were analyzed to determine the DBP yields during chlorination of different NOM fractions. Results revealed that UVC could be applied to indicate the regulated DBP yields of the humified precursors. Contrary to the generally accepted view, for biologically derived precursors, their regulated DBPs and dichloroacetonitrile correlated better with UVA (e.g. UV340). Moreover, PARAFAC analysis was applied to decompose an array of 24 EEM spectra. Good linear correlations were found between the PARAFAC components and most DBP yields. Furthermore, four fluorescence parameters were proposed via a modified fluorescence picking method, which can serve as excellent surrogates of PARAFAC components. These fluorescence parameters were found to be effective in indicating most DBP yields. Finally, the fluorescence intensity at excitation wavelength/emission wavelength = 310/416 nm was found to be a promising built-in parameter for the real-time monitoring of DBP precursors, regardless of the humification degree of the precursors.

Lead halide perovskite materials have recently received considerable attention for achieving an economic and tunable laser owing to their solution-processable feature and promising optical properties. However, most reported perovskite-based lasers operate with a large lasing-mode volume, resulting in a high lasing threshold due to the inefficient coupling between the optical gain medium and cavity. Here, we demonstrate a continuous-wave nanolasing from a single lead halide perovskite (CsPbBr3) quantum dot (PQD) in a plasmonic gap-mode nanocavity with an ultralow threshold of 1.9 Wcm-2 under 120 K. The calculated ultrasmall mode volume (∼0.002 λ3) with a z-polarized dipole and the significantly large Purcell enhancement at the corner of the nanocavity inside the gap dramatically enhance the light-matter interaction in the nanocavity, thus facilitating lasing. The demonstration of PQD nanolasing with an ultralow-threshold provides an approach for realizing on-chip electrically driven lasing and integration into on-chip plasmonic circuitry for ultrafast optical communication and quantum information processing.

A systematic study of nonsequential double ionization (NSDI) of alkaline-earth metal atoms with mid-infrared femtosecond pulses is reported. We find that the measured NSDI yield shows a strong target dependence and it is more suppressed for alkaline-earth metal with higher ionization potential. The observation is attributed to the differences in the recollision induced excitation and ionization cross sections of alkaline-earth metals. This work indicates that NSDI of alkaline-earth metals can be generally understood within recollision picture and sheds light on ultrafast control of electron correlation and dynamics of ionic excited states during NSDI of atoms with complex structures.

This study aims at systematically examining the potential of removing the emerging pollutant sulfamethoxazole (SMX) from aqueous solution under photo-assisted peroxymonosulfate (PMS) activation by Fe(II). The residual SMX was determined by HPLC analysis. The concentration of Fe(II) ([Fe(II)]) was monitored during SMX degradation. Fe(II) and PMS cooperated with each other for faster SMX photodegradation; a relatively lower or higher molar ratio between Fe(II) and PMS led to lower SMX removal efficiency due to the insufficient radicals or scavenging effect. A fixed reaction ratio of [Fe(II)]Δ : [PMS]0 with 1.6 : 1 at the first 5 min was detected for reactions with [Fe(II)]0 ≥ 0.5 mM or [PMS]0 ≤ 0.25 mM. The pH level of around 6.0 was recommended for optimal SMX removal under the treatment process UVA + Fe(II) + PMS. Six transformation products were detected through UPLC/ESI-MS analysis, and four of the proposed intermediates were newly reported. Concentrations of the intermediates were proposed based on the isoxazole-ring balance and the Beer–Lambert law. Total Organic Carbon (TOC) reduction was mainly attributed to the loss of benzene ring, N–S cleavage, and isoxazole ring opening during SMX degradation. The contributions of reactive species OH˙ and SO4˙− were determined based on quench tests. The acute toxicity of SMX to the rotifers was eliminated after the proposed treatment, demonstrating that the process was effective for SMX treatment and safe to the environment.

Metal halide perovskites having three-dimensional crystal structures are being applied successfully in various optoelectronic applications. To address their most challenging issues—instability and toxicity—without losing efficiency, lower-dimensional perovskites appear to be promising alternatives. Recently, two-dimensional (2D) perovskite solar cells have been developed exhibiting excellent photostability and moisture-stability, together with moderate device efficiency. This review summarizes the photophysical properties and operating mechanisms of 2D perovskites as well as recent advances in their applications in solar cell devices. Also presented is an agenda for the next-stage development of stable perovskite materials for solar cell applications, highlighting the issues of stability and toxicity that require further study to ensure commercialization.

Fully inorganic perovskites based on Bi3+ and Sb3+ are emerging as alternatives that overcome the toxicity and low stability of their Pb-based perovskite counterparts. Nevertheless, thin film fabri...

In this study, we synthesized a series of small-molecule benzotrithiophenes (BTTs) and used them as hole transporting materials (HTMs) in perovskite solar cells (PSCs). The asymmetric benzo[2,1-b:-...

Single-atom catalysts (SACs) have shown superior activity and/or selectivity for many energy- and environment-related reactions, but their stability at high site density and under reducing atmosphere remains unresolved. Herein, we elucidate the intrinsic driving force of a Pd single atom with high site density (up to 5 wt %) under reducing atmosphere, and its unique catalytic performance for hydrogenation reactions. In situ experiments and calculations reveal that Pd atoms tend to migrate into the surface vacancy-enriched MoC surface during the carburization process by transferring oxide crystals to carbide crystals, leading to the surface enrichment of atomic Pd instead of formation of particles. The Pd-1/alpha-MoC catalyst exhibits high activity and excellent selectivity for liquid-phase hydrogenation of substituted nitroaromatics (>99 %) and gas-phase hydrogenation of CO(2)to CO (>98 %). The Pd-1/alpha-MoC catalyst could endure up to 400 degrees C without any observable aggregation of single atoms.

We report on a comparative study of strong-field ionization of alkaline-earth-metal atoms by intense femtosecond laser pulses from near-infrared to midinfrared wavelengths. By collecting the ionization signals only produced within the central portion of the laser focus, the focus volume effect is largely reduced and the saturation intensities for different alkaline-earth-metal atoms are reliably determined, which permits us to directly test the strong-field-ionization theories. We demonstrate that the Perelomov-Popov-Terent'ev model accurately predicts the experimental ionization yields and saturation intensities in general for arbitrary values of the Keldysh parameter, while the Ammosov-Delone-Krainov simulations agree with the experiments for the tunneling-ionization regime and also for the regime when the Keldysh parameter is around 1. Our work presents benchmark data for strong-field ionization of alkaline-earth metals over a broad range of laser parameters and confirms the validity of Keldysh's picture for such atoms.

In this paper, We propose a general Riemannian proximal optimization algorithm with guaranteed convergence to solve Markov decision process (MDP) problems. To model policy functions in MDP, we employ Gaussian mixture model (GMM) and formulate it as a nonconvex optimization problem in the Riemannian space of positive semidefinite matrices. For two given policy functions, we also provide its lower bound on policy improvement by using bounds derived from the Wasserstein distance of GMMs. Preliminary experiments show the efficacy of our proposed Riemannian proximal policy optimization algorithm., 12 pages, 1 figures

In this paper, a comparative study on removal of the emerging pollutant phenazone (PNZ) by two treatment processes UVA/Fe(II)/persulfate (PS) and UVA/Fe(II)/peroxymonosulfate (PMS) was conducted. The two processes showed high efficiency in PNZ degradation, followed by a reasonable mineralization. The treatment system with PMS was found to be more efficient for PNZ degradation than that with PS due to the larger amounts of radicals generated. While the treatment process UVA/Fe(II)/PS showed higher ΔTOC/ΔSMX (TOC removal per unit of PNZ decay) than UVA/Fe(II)/PMS process. The sulfate and hydroxyl radicals played dominant roles in PNZ degradation in the UVA/Fe(II)/PS and UVA/Fe(II)/PMS process, respectively. Six and seven intermediates during PNZ degradation by UVA/Fe(II)/PS and UVA/Fe(II)/PMS process were detected, respectively. Among the detected intermediates, six of them are found for the first time. It takes shorter time for toxicity elimination by UVA/Fe(II)/PS process than UVA/Fe(II)/PMS, possibly due to the lower Kow values of hydroxylated products. The results demonstrate that UVA/Fe(II)/PMS process is more efficient in PNZ degradation, while UVA/Fe(II)/PS is more efficient in detoxification of PNZ. The two sulfate radicals based processes have good potentials in degradation, mineralization and detoxification of the emerging contaminants such as PNZ.

Swiftly deciphering soil organic matter (SOM) composition is critical for research on soil degradation and restoration. Recent advances in analytical techniques (e.g., optical methods and mass spectrometry) have expanded our understanding of the composition, origin, and evolution of SOM. In particular, the use of Fourier transform ion cyclotron resonance mass spectrometers (FTICR-MS) makes it possible to interpret SOM compositions at the molecular level. In this review, we discuss extraction, enrichment, and purification methods for SOM using FTICR-MS analysis; summarize ionization techniques, FTICR-MS mechanisms, data analysis methods, and molecular compositions of SOM in different environments (providing new insights into its origin and evolution); and discuss factors affecting its molecular diversity. Our results show that digenesis, combustion, pyrolysis, and biological metabolisms jointly contribute to the molecular diversity of SOM molecules. The SOM thus formed can further undergo photodegradation during transportation from land to fresh water (and subsequently oceans), resulting in the formation of dissolved organic matter (DOM). Better understanding the molecular features of DOM therefore accelerates our understanding of SOM evolution. In addition, we assess the degradation potential of SOM in different environments to better inform soil remediation methods. Finally, we discuss the merits and drawbacks of applying FTICR-MS on the analysis of SOM molecules, along with existing gaps in knowledge, challenges, and new opportunities for research in FTICR-MS applications and SOM identification.

The search for high efficiency and low-cost catalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is vital to overall water splitting. In this work, on the basis of first-principles calculations, we screened a series of late transition metal atoms supported on a C9N4 monolayer (TM@C9N4, where TM represents Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir, and Pt) as electrocatalysts for both the HER and OER. Our results demonstrate that the TM atoms can be bonded with the nitrogen atoms around the hole to form stable structures, and the bonded TM atoms are stable against diffusion. Co@C9N4 exhibits high catalytic activity toward the HER. In particular, the N active sites in the Co@C9N4, Ni@C9N4, and Pt@C9N4 systems demonstrate relatively high performance for the HER. However, Co@C9N4 and Pt@C9N4 exhibit low OER activities with large overpotentials. Among the ten cases of TM@C9N4 considered here, only Ni@C9N4 performs as a promising bifunctional electrocatalyst with N and Ni atoms as catalytic active sites for the HER and OER, with a calculated hydrogen adsorption Gibbs free energy (ΔGH*) of -0.04 eV and an OER overpotential (ηOER) of 0.31 V. The results demonstrate that TM@C9N4 is a promising single-atom catalytic system, which can be used as the non-noble metal bifunctional electrocatalyst for overall water splitting.

Dissolution of lithium polysulfide (LiPS) into the electrolyte during discharging, causing shuttling of LiPS from the cathode to the lithium (Li) metal, is mainly responsible for the capacity decay and short battery life of lithium-sulfur batteries (LSBs). Herein, we designed a separator comprising polypropylene (PP) coated with MoO3 nanobelts (MNBs), prepared through facile grinding of commercial MoO3 powder. The formation of Li2Sn-MoO3 during discharging inhibited the polysulfide shuttling; during charging, Li passivated LixMoO3 facilitated ionic transfer during the redox reaction by decreasing the charge transfer resistance. This dual-interaction mechanism of LiPS-with both Mo and the formation of LixMoO3-resulted in a substantially high initial discharge capacity at a very high current density of 5C, with 29.4% of the capacity retained after 5000 cycles. The simple fabrication approach and extraordinary cycle life observed when using this MNB-coated separator suggest a scalable solution for future commercialization of LSBs.

Highly active single-atom catalysts (SACs) have recently been intensively studied for their potential in the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Due to the existence of many such SAC systems, a general understanding of the trend and designing principle is necessary to discover an optimal SAC system. In this work, by using density functional theory (DFT), we investigated a series of late single transition metals (TM = Fe, Co, Ni, Cu, and Pd) anchored on various N doped graphenes (xN-TM, x = 1-4) as electrocatalysts for both the HER and OER. Solvent effects were taken into account using an implicit continuum model. Our results reveal that the catalytic activity of SACs is determined by the local coordination number of N and TM in the catalysts. Among the considered catalysts, a low-coordinated Co site, i.e. a triple-coordinated Co, exhibits a high catalytic activity toward the HER with a calculated hydrogen adsorption free energy of -0.01 eV, whereas a high-coordinated Co center, i.e. a quadruple-coordinated Co is a promising candidate for the OER with a low computed overpotential of -0.39 V, which are comparable to those of noble metal catalysts, indicating superior HER and OER performance of N-Co co-doped graphenes. The results shed light on the potential applications of TM and N co-doped graphenes as efficient single-atom bifunctional catalysts for water splitting, thereby functioning as promising candidates for hydrogen/oxygen production.

Ni nanoclusters were confined inside an alumina matrix through Ni–Al layered double hydroxide (NiAl-LDH) decomposition methods and studied in one-pot cellobiose conversion to hexitols. The TEM results indicated that very tiny Ni particles with a mean particle size of 0.95 nm were successfully incorporated in the Al2O3 matrix on the 5%NiAl-MMO catalysts. However, the performance was unexpectedly low with a 10% hexitol yield due to the strong interaction between Ni and Al, leading to the formation of NiAl2O4 and the low availability of Ni0 active species. Interestingly, a small amount of Pt dopant (0.5 wt%) dramatically improved the hexitol yield up to 88.8%, for an eight-fold improvement, on a 0.5%Pt5%NiAl-MMO catalyst. DFT simulations revealed that the Pt dopants showed greater reduction of the H2 activation barrier on small Ni clusters compared with that on larger Ni particles while at the same time increasing the Pt surface contents. The activated protons not only benefited the consequential hydrogenation step of glucose, but also contributed to the improved hydrolysis of celloboise. Compared with their counterparts of traditional impregnated alumina-supported PtNi catalysts, the confined PtNi-MMO catalyst showed a greater potential in biomass conversion in aqueous phase reactions.

Easy-to-obtain magnetic bentonite-chitosan hybrid beads (Bn-CTS) were prepared by immobilizing bentonite within a porous structure of chitosan beads to achieve a hybrid adsorption effect for the removal of cesium ion (Cs+) from water. The hybrid adsorbent, which had a porous structure and abundant binding sites contributed by both chitosan and bentonite, ensured superb adsorption characteristics. The paramagnetic character of the beads enabled their facile separation for recycling. The chitosan/bentonite ratio, pH and contact time were optimized to achieve the optimal Cs+ efficiency, and the adsorption kinetics and isotherms were thoroughly discussed. The adsorption kinetics obeyed the pseudo-second-order model, and the best fitted equation for equilibrium data was the Langmuir isotherm model. The maximum adsorption capacity of the bentonite-chitosan beads was 57.1 mg g−1. The adsorbent had excellent selectivity towards Cs+ adsorption in the presence of abundant cations (Li+, Na+, K+ and Mg2+). The adsorbent was able to be recycled by treating the beads with 0.1 mol L−1 of MgCl2 to quantitatively desorb Cs+ from the beads. Overall, the magnetic bentonite-chitosan beads can be used as a highly efficient adsorbent for radioactive waste disposal and management.

The paper reports a microwave assisted rapid synthesis of NiCo2O4@CNTs composite for the first time. Ultrafine NiCo2O4 nanoparticles approximately 6–10 nm in size dispersed uniformly along the CNTs walls are obtained. Interestingly, nanosheets structure is formed in the absence of CNTs. The distinctive morphology difference is attributed to the different nucleating and growing mechanisms. Due to the small NiCo2O4 nanoparticle size derived from microwave enabled fast synthesis and the unique 1D nanostructure, the NiCo2O4@CNTs composites materials exhibit more excellent lithium storage performance than that of counterparts.

The NiZrAl mixed metal oxides catalysts with varied Zr/Al ratio were derived from the layered double hydroxides (LDH) through the thermal decomposition. The different techniques such as TG, XRD, N2 adsorption/desorption, XPS, TPR, H2 chemisorption, SEM and TEM etc. were applied to study the thermal decomposition behaviors of the corresponding LDH, crystalline phases changes before and after reaction, the porous structure, chemical state of surface element, reducibility, properties of active phase metallic Ni and the morphology. The results showed that the LDH structure could be kept during the experimental range from 0.1 to 1.0, although high Zr/Al ratio made the structure feature weaken. The porous structure of the calcined catalysts exhibited an significant change when Zr/Al ratio reached 0.5. Both Ni dispersion and surface increased linearly with the increased Zr/Al, however, more amount of surface Ni was reduced and less amount of coke was formed over the sample NiZr0.5Al. It consequently gave the best conversion to gaseous products and the highest selectivity of hydrogen by promoting the water gas shift reaction and suppressing the CO methanation reaction.

In this work, we study the structure transformations of cylinder-forming polystyrene-block-polydimethylsiloxane (PS31k-b-PDMS14.5k) confined in cylindrical nanopores. PS-b-PDMS nanotubes, nanospheres, and curved nanodiscs are ingeniously prepared by a facile template wetting strategy using anodic aluminum oxide (AAO) templates. Quantitative analyses of the structure transformations from nanospheres to curved nanodiscs are also conducted, showing that the lengths of the curved nanodiscs can be controlled by adjusting the annealing temperature and time. Furthermore, the PDMS domains of the nanostructures can be selectively etched using HF solutions, generating porous PS nanostructures. This work not only offers versatile routes to prepare block copolymer nanostructures with controlled shapes but also provides a deeper understanding of the structure transformation of block copolymers in confined geometries.

Product image search in E-commerce systems is a challenging task, because of a huge number of product classes, low intra-class similarity and high inter-class similarity. Deep metric learning, based on paired distances independent of the number of classes, aims to minimize intra-class variances and inter-class similarity in feature embedding space. Most existing approaches strictly restrict the distance between samples with fixed values to distinguish different classes of samples. However, the distance of paired samples has various magnitudes during different training stages. Therefore, it is difficult to directly restrict absolute distances with fixed values. In this paper, we propose a novel Equidistant and Equidistributed Triplet-based (EET) loss function to adjust the distance between samples with relative distance constraints. By optimizing the loss function, the algorithm progressively maximizes intra-class similarity and inter-class variances. Specifically, 1) the equidistant loss pulls the matched samples closer by adaptively constraining two samples of the same class to be equally distant from another one of a different class in each triplet, 2) the equidistributed loss pushes the mismatched samples farther away by guiding different classes to be uniformly distributed while keeping intra-class structure compact in embedding space. Extensive experimental results on product search benchmarks verify the improved performance of our method. We also achieve improvements on other retrieval datasets, which show superior generalization capacity of our method in image search.

Pyrite (FeS2) is an abundant sulfide-associated iron mineral that exists in the earth. In this study, the pyrite/oxone process was demonstrated to be an effective approach for the catalytic degradation of propanil, where more than 90% decay ([propanil]0 = 0.01 mM) was achieved within 15 min. Typically, the effects of various experimental parameters, including catalyst loading, oxone dosage, propanil concentration, and initial solution pH, were examined. Two optimal reaction pH values were observed at pH 9.1 and pH 2.9. The generated SO4－ and OH were verified to be the dominant reactive radicals and primarily responsible for the propanil degradation. Both Fe(II) regeneration and sulfur conversion play an important role in oxone activation mechanism and effectively aid the catalytic activity of pyrite. Different co-existing natural water constituents exert dissimilar effects on the pyrite/oxone process. Additionally, the reusability test of pyrite exhibited a reasonable catalytic activity. The pyrite/oxone process was proven efficient in terms of propanil mineralization. A series of reaction intermediates was detected via four major degradation pathways. Overall, the pyrite/oxone process could be a promising approach for the removal of organic compounds in water.

Advances in the ultra-high-resolution mass spectroscopy lead to a deep insight into the molecular characterization of natural organic matter (NOM). Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) has been used as one of the most powerful tools to decipher NOM molecules. In FTICR-MS analysis, the matrix effects caused by the co-occurring inorganic substances in water samples greatly affect the ionization of NOM molecules. The inherent complexity of NOM may hinder its component classification and formula assignment. In this study, basic principles and recent advances for sample separation and purification approaches, ionization methods, and the evolutions in formula assignment and data exploitation of the FTICR-MS analysis were reviewed. The complementary characterization methods for FTICR-MS were also reviewed. By coupling with other developed/developing characterization methods, the statistical confidence for inferring the NOM compositions by FTICR-MS was greatly improved. Despite that the refined separation procedures and advanced data processing methods for NOM molecules have been exploited, the big challenge for interpreting NOM molecules is to give the basic structures of them. Online share of the FTICR-MS data, further optimizing the FTICR-MS technique, and coupling this technique with more characterization methods would be beneficial to improving the understanding of the composition and property of NOM.

Metal-organic frameworks (MOFs) derived metal@porous carbon showed good performance in peroxymonosulfate (PMS) activation for refractory organic chemical degradation from aqueous. However, the effect of structure and physical-chemical properties of metal@porous carbon on PMS activation and its involved reaction mechanism were still unclear. Herein, Fe@porous carbon derived from MOF MIL-53(Fe) was used as target, to discuss the role of NH2-group incorporation on the development of structure and physical-chemical properties of obtained Fe@porous carbon, and reaction mechanism for PMS activation. The incorporation of NH2-group significantly decreased the synthesis temperature of Fe@porous carbon and increased the encapsulation of Fe0 in the porous carbon. Furthermore, the addition of nitrogen in porous carbon and rigid encapsulation structure reduced the defects of the Fe@porous carbon. These improvements of the structure and chemical properties were favored for enhancement of the catalytic activity and stability of the obtained Fe@porous carbon in the activation of PMS. Electron paramagnetic resonance (EPR) experiments indicated that SO4 −, OH and 1O2 were involved. The radical pathway involving SO4 − and OH was the prevailing pathway while the nonradical pathway involving 1O2 was the recessive pathway. Based on intermediate identification, the degradation pathway of acyclovir (ACV) was proposed as SO4 − and OH derived process, and eight of intermediates were first reported. It was interesting to note that iron species, carbon structure, and nitrogen element in the catalysts derived from MIL-53(Fe) or NH2-MIL-53(Fe) clearly showed different role and reaction pathway. This work not only provided an efficient Fe@N-doped porous carbon for activation PMS to degrade refractory organic chemicals for water purification, but also suggested a valuable insight for the design of metal@porous carbon derived from MOF.

A novel ternary nanocomposite MoS2/MoO3/polypyrrole (PPy) has been fabricated. MoO3 nanoparticle-decorated few-layered MoS2 nanosheets were first prepared via the exfoliation of partially oxidized MoS2. In situ oxidation polymerization was then used to fabricate the ternary nanocomposites. We show the synergetic effects provided by the ternary composites via investigating the electrochemical performance of supercapacitors using the nanocomposites as the electrodes. Furthermore, the morphology evolution during the synthesis of the MoO3 nanoparticle-decorated MoS2 nanosheets was also examined. This not only allows the understanding of the formation mechanism but also leads to the surprising discovery of unprecedented amorphous carbon (a-C) layers intercalated in between the MoS2 nanosheets. We therefore propose a mechanism to explain the formation of such a-C layer and demonstrate that the a-C plays a critical role in the supercapacitor performance. Finally, we demonstrate that the cycle life and capacitance of PPy are enhanced via the addition of MoS2/MoO3 with an excellent Csp of 352 F g−1 and electrochemical stability with Csp retention up to 105% after 2000 cycles.