Damage-Free Silica Coating for Colloidal Nanocrystals Through a Proactively Water-Generating Amidation Reaction at High Temperature.

Silica is a promising shell coating material for colloidal nanoparticles due to its excellent chemical inertness and optical transparency. To encapsulate high-quality colloidal nanocrystals with silica shells, the silane coupling hydrolysis is currently the most effective approach. However, this reaction requires water, which often adversely affects the intrinsic physicochemical properties of nanocrystals. Achieving a damage-free silica encapsulation process to nanocrystals by hydrolysis is a huge challenge. Here, a novel strategy is developed to coat colloidal nanocrystals with a denser silica shell via a proactively water-generating reaction at high temperature. In this work, water molecules are continuously and proactively released into the reaction system through the amidation reaction, followed by in situ hydrolysis of silane, completely avoiding the impacts of water on nanocrystals during the silica coating process. In this work, water sensitive perovskite nanocrystals (CsPbBr3 ) are selected as the typical colloidal nanocrystals for silica coating. Notably, this high-temperature in situ encapsulation technology greatly improves the optical properties of nanocrystals, and the silica shells exhibit a denser structure, providing nanocrystals with better protection. This method overcomes the challenge of the influence of water on nanocrystals during the hydrolysis process, and provides an important reference for the non-destructive encapsulation of colloidal nanocrystals.

Ternary Rotational Polyanion Coupling Enables Fast Li Ion Dynamics in Tetrafluoroborate Ion Doped Antiperovskite Li2OHCl Solid Electrolyte.

Li-rich antiperovskite (LiRAP) hydroxyhalides are emerging as attractive solid electrolyte (SEs) for all-solid-state Li metal batteries (ASSLMBs) due to their low melting point, low cost, and ease of scaling-up. The incorporation of rotational polyanions can reduce the activation energy and thus improve the Li ion conductivity of SEs. Herein, we propose a ternary rotational polyanion coupling strategy to fasten the Li ion conduction in tetrafluoroborate (BF4 -) ion doped LiRAP Li2OHCl. Assisted by first-principles calculation, powder X-ray diffraction, solid-state magnetic resonance and electrochemical impedance spectra, it is confirmed that Li ion transport in BF4 - ion doped Li2OHCl is strongly associated with the rotational coupling among OH-, BF4 - and Li2-O-H octahedrons, which enhances the Li ion conductivity for more than 1.8 times with the activation energy lowering 0.03 eV. This work provides a new perspective to design high-performance superionic conductors with multi-polyanions.

Fluorine Passivation Inhibits "Particle Talking" Behaviors under Thermal and Electrical Conditions of Pure Blue Mixed Halide Perovskite Nanocrystals.

Owing to outstanding optoelectronic properties, lead halide perovskite nanocrystals (PNCs) are considered promising emitters for next-generation displays. However, the development of pure blue (460-470 nm) perovskite nanocrystal light-emitting diodes (PNC-LEDs), which correspond to the requirements of Rec. 2020 standard, lag far behind that of their green and red counterparts. Here, pure blue CsPb(Br/Cl)3 nanocrystals with remarkable optical performance are demonstrated by a facile fluorine passivation strategy. Prominently, the fluorine passivation on halide vacancies and strong bonding of Pb-F intensely enhance crystal structure stability and inhibit "particle talking" behaviors under both thermal and electrical conditions. Fluorine-based PNCs with high resistance of luminescence thermal quenching retain 70% of photoluminescent intensity when heated to 343 K, which can be attributed to the elevated activation energy for carrier trapping and unchanged grain size. Fluorine-based PNC-LEDs also exhibit stable pure blue electroluminescence (EL) emission with sevenfold promoted luminance and external quantum efficiencies (EQEs), where the suppression of ion migration is further evidenced by a lateral structure device with applied polarizing potential.

Stable Lead-Free Tin Halide Perovskite with Operational Stability >1200 h by Suppressing Tin(II) Oxidation.

Sn-based perovskites are the most promising alternative materials for Pb-based perovskites to address the toxicity problem of lead. However, the development of SnII -based perovskites has been hindered by their extreme instability. Here, we synthesized efficient and stable lead-free Cs4 SnBr6 perovskite by using SnF2 as tin source instead of easily oxidized SnBr2 . The SnF2 configures a fluorine-rich environment, which can not only suppress the oxidation of Sn2+ in the synthesis, but also construct chemically stable Sn-F coordination to hinder the electron transfer from Sn2+ to oxygen within the long-term operation process. The SnF2 -derived Cs4 SnBr6 perovskite shows a high photoluminescence quantum yield of 62.8 %, and excellent stability against oxygen, moisture, and light radiation for 1200 h, representing one of the most stable lead-free perovskites. The results pave a new pathway to enhance the optical properties and stability of lead-free perovskite for high-performance light emitters.

Dietary conjugated linoleic acid modulates morphology, selective immune parameters, and gene expressions in the intestine of grass carp.

Conjugated linoleic acid (CLA) has been shown to exhibit anti-inflammatory properties in the intestine in mammals. However, the effect of CLA on intestinal immune response in fish is still unknown. Therefore, a 65-day growth trial was conducted to investigate the effects of dietary conjugated linoleic acid (CLA) on morphology, selective immune parameters, and gene expressions in the intestine of grass carp. Seven isonitrogenous and isolipidic diets were formulated as follows: 0 (control), 0.5 (CLA0.5), 1 (CLA1), 1.5 (CLA1.5), 2 (CLA2), 2.5 (CLA2.5), and 3 (CLA3) g CLA per 100g of feed. RESULTS: showed that dietary supplementation of 1.5-3% CLA significantly (P < 0.05) increased the fold and enterocyte heights in the PI and MI of grass carp. Complement 3 (C3) and immunoglobulin M (IgM) contents in three intestinal segments were significantly (P < 0.05) higher in fish fed with CLA1.5 to CLA2.5 diets compared to fish fed the control diet. CLA1.5 to CLA2.5 diets significantly (P < 0.05) increased the mRNA expression levels of anti-inflammatory cytokines (IL-10 and TGFß1) and significantly (P < 0.05) reduced the mRNA expression levels of pro-inflammatory cytokines (IL-1ß, IL-8, and TNF-α) in the PI, MI, and DI. This improved expression of anti-inflammatory cytokines and the inhibited expression of pro-inflammatory cytokines in the intestine of grass carp, might be mediated via TLR4/NF-κB-signaling pathway. Our results suggested that CLA1.5 to CLA2 diets improved intestinal morphology, increased the expression of anti-inflammatory cytokines, and inhibited the expression of pro-inflammatory cytokines in the intestine of grass carp. In conclusion, dietary supplementation of 1.5%-2% CLA show the anti-inflammatory therapeutic potential in the intestine of grass carp. The anti-inflammatory therapeutic potential of CLA might be mediated via TLR4/NF-κB-signaling pathway.

Scanning tunneling microscopy investigations of unoccupied surface states in two-dimensional semiconducting ß-√3 × âˆš3-Bi/Si(111) surface.

Two-dimensional surface structures often host a surface state in the bulk gap, which plays a crucial role in the surface electron transport. The diversity of in-gap surface states extends the category of two-dimensional systems and gives us more choices in material applications. In this article, we investigated the surface states of ß-√3 × âˆš3-Bi/Si(111) surface by scanning tunneling microscopy. Two nearly free electron states in the bulk gap of silicon were found in the unoccupied states. Combined with first-principles calculations, these two states were verified to be the Bi-contributed surface states and electron-accumulation-induced quantum well states. Due to the spin-orbit coupling of Bi atoms, Bi-contributed surface states exhibit free-electron Rashba splitting. The in-gap surface states with spin splitting can possibly be used for spin polarized electronics applications.

Soil mineral alters the effect of Cd on the alkaline phosphatase activity.

The toxicity of heavy metals (HMs) to soil enzymes is directly influenced by the status of the enzyme (free vs. immobilized on minerals) and the duration of exposure. However, little information is available on the interaction effect of HMs, mineral, and exposure time on soil enzyme activities. We investigated the interaction mechanism of alkaline phosphatase (ALP) with minerals (montmorillonite and goethite) and the response of free and immobilized ALP to cadmium (Cd) toxicity under different exposure times. The adsorption isotherms of ALP on both minerals were L-type. The maximum adsorption capacity of goethite for ALP was 3.96 times than montmorillonite, although both had similar adsorption constant (K). Goethite showed a greater inhibitory effect on ALP activity than montmorillonite. The toxicity of Cd to free- and goethite-ALP was enhanced with increasing exposure time, indicating a time-dependent inhibition. However, Cd toxicity to montmorillonite-ALP was not affected by the exposure time. The inhibition of Cd to soil enzyme activity is influenced by the properties of mineral complexes and the duration of exposure. A further understanding of the time pattern of HMs toxicity is helpful for accurately assessing the hazards of HMs to soil enzyme activity.

Highly Luminescent and Ultrastable CsPbBr3 Perovskite Quantum Dots Incorporated into a Silica/Alumina Monolith.

We successfully prepared QDs incorporated into a silica/alumina monolith (QDs-SAM) by a simple sol-gel reaction of an Al-Si single precursor with CsPbBr3 QDs blended in toluene solution, without adding water and catalyst. The resultant transparent monolith exhibits high photoluminescence quantum yields (PLQY) up to 90 %, and good photostability under strong illumination of blue light for 300 h. We show that the preliminary ligand exchange of didodecyl dimethyl ammonium bromide (DDAB) was very important to protect CsPbBr3 QDs from surface damages during the sol-gel reaction, which not only allowed us to maintain the original optical properties of CsPbBr3 QDs but also prevented the aggregation of QDs and made the monolith transparent. The CsPbBr3 QDs-SAM in powder form was easily mixed into the resins and applied as color-converting layer with curing on blue light-emitting diodes (LED). The material showed a high luminous efficacy of 80 lm W-1 and a narrow emission with a full width at half maximum (FWHM) of 25 nm.

Enhancing the Stability of CH3NH3PbBr3 Quantum Dots by Embedding in Silica Spheres Derived from Tetramethyl Orthosilicate in "Waterless" Toluene.

Methylammonium lead halide perovskites suffer from poor stability because of their high sensitivity to moisture. Inorganic material coatings of SiO2 are preferred for coupling with perovskites to improve their stability, whereas the conventional SiO2 formation method is unsuitable because it requires water. Here, a simple SiO2 generation method based on the high hydrolysis rate of tetramethyl orthosilicate in analytical-grade toluene was developed to avoid the addition of water and catalyst. As a result, SiO2-encapsulated CH3NH3PbBr3 quantum dots (MAPB-QDs/SiO2) were fabricated without decreasing the quantum yield. Photostability tests indicated that the MAPB-QDs/SiO2 samples were markedly more stable than the unencapsulated MAPB-QDs. The photoluminescence (PL) of the MAPB-QDs/SiO2 powders was maintained at 94.10% after 470 nm LED illumination for 7 h, which was much higher than the remnant PL (38.36%) of the pure MAPB-QD sample under a relative humidity of 60%. Similar test results were observed when the MAPB-QDs/SiO2 powders were incorporated into the poly(methyl methacrylate) films. The enhanced photostability is ascribed to the SiO2 barriers protecting the MAPB-QDs from degradation.

General Method for the Synthesis of Ultrastable Core/Shell Quantum Dots by Aluminum Doping.

Semiconductor quantum dots (QDs) have attracted extensive attention in various applications because of their unique optical and electronic properties. However, long-term photostability remains a challenge for their practical application. Here, we present a simple method to enhance the photostability of QDs against oxidation by doping aluminum into the shell of core/shell QDs. We demonstrate that Al in the coating shell can be oxidized to Al2O3, which can serve as a self-passivation layer on the surface of the core/shell QDs and effectively stop further photodegradation during long-term light irradiation. The prepared CdSe/CdS:Al QDs survived 24 h without significant degradation when they were subjected to intense illumination under LED light (450 nm, 0.35 W/cm(2)), whereas conventional CdSe/CdS QDs were bleached within 3 h.

Removal of toxic metals using iron sulfide particles: A brief overview of modifications and mechanisms.

Growing mechanization has released higher concentrations of toxic metals in water and sediment, which is a critical concern for the environment and human health. Recent studies show that naturally occurring and synthetic iron sulfide particles are efficient at removing these hazardous pollutants. This review seeks to provide a concise summary of the evolution in the production of iron sulfide particles, specifically nanoparticles, through the years. This review presents an outline of the synthesis process for the most dominant forms of iron sulfide: mackinawite (FeS), pyrite (FeS2), pyrrhotite (Fe1-x S), and greigite (Fe3S4). The review confirms that both natural forms of iron sulfide and modified forms of iron sulfide are highly effective at removing different heavy metals and metalloids from water. Concurrently, this review reveals the interaction mechanism between toxic metals and iron sulfide, along with the impact of conditions for remedy and rectification. None the less, modifications and future investigations into the synthesis of novel iron sulfides, their use to adsorb diverse environmental pollutants, and their fate after injection into polluted aquifers, remain crucial to maximizing pollution control.

Perovskite Nanocrystals In Situ Encapsulated in TiO2 Microspheres for Stable CO2 Photoreduction in Water.

Photoreduction of carbon dioxide (CO2) into fuels presents a promising approach to mitigate global warming and energy crises. Halide perovskite nanocrystals (NCs) with prominent optoelectronic properties have triggered substantial attention as photocatalysts but are limited by the charge recombination and instability. Here, we develop stable CsPbBr3/titania microspheres (TMs) by in situ growth of CsPbBr3 NCs inside mesoporous TMs through solid-state sintering, which significantly improves the stability of perovskite NCs, making them applicable in water with efficient CO2 photoreduction performance. Notably, the CsPbBr3/TMs demonstrates a 6.73- and 9.23-fold increase in the rate of CH4 production compared to TMs and CsPbBr3, respectively. The internal electric field facilitates S-scheme charge transfer, enhancing the separation of electron-hole pairs, as evidenced by X-ray photoelectron spectroscopy and electron paramagnetic resonance analysis, which is pivotal for the selective photoreduction of CO2. These insights pave the way for the design of CsPbBr3-based photocatalysts with superior efficiency and stability.

A simple method for the synthesis of copper nanoparticles from metastable intermediates.

Copper nanoparticles have attracted a wide attention because of their low cost and high specific surface area. At present, the synthesis of copper nanoparticles has the problems of complicated process and environmentally unfriendly materials like hydrazine hydrate and sodium hypophosphite that would pollute water, harm human health and may even cause cancer. In this paper, a simple and low-cost two-step synthesis method was used to prepare highly stable and well-dispersed spherical copper nanoparticles in solution with a particle size of about 34 nm. The prepared spherical copper nanoparticles were kept in solution for one month without precipitation. Using non-toxic l-ascorbic acid as the reducing and secondary coating agent, polyvinylpyrrolidone (PVP) as the primary coating agent, and NaOH as the pH modulator, the metastable intermediate CuCl was prepared. Due to the characteristics of the metastable state, copper nanoparticles were rapidly prepared. Moreover, to improve the dispersibility and antioxidant, the PVP and l-ascorbic acid were used to coat the surface of copper nanoparticles. Finally, the mechanism of the two-step synthesis of copper nanoparticles was discussed. This mechanism mainly relies on the two-step dehydrogenation of l-ascorbic acid to obtain copper nanoparticles.

Inverted semitransparent perovskite nanocrystal light-emitting diodes with a conjugated polymer as an electron transport layer.

Perovskite nanocrystals have attracted much attention due to their unique optical and electronic properties. Much progress has also been made in the development of light-emitting diodes based on perovskite nanocrystals in the past years. However, compared with the widely reported opaque perovskite nanocrystal light-emitting diodes, semitransparent perovskite nanocrystal light-emitting diodes are rarely studied, which affects the potential application of perovskite nanocrystals in the translucent display field in the future. Here, poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN), a conjugated polymer, was used as an electron transport layer to fabricate the inverted opaque and semitransparent perovskite light-emitting diodes. The maximum external quantum efficiency and luminance were improved from 0.13% and 1041 cd m-2 to 2.07% and 12 540 cd m-2, respectively, through device optimization in opaque light-emitting diodes. The corresponding semitransparent device also demonstrated high transmittance (average 61% from 380 to 780 nm) and high brightness of 1619 and 1643 cd m-2 for the bottom and top sides, respectively.

Sequential exposures of single walled carbon nanotubes and heavy metal ions to macrophages induce different cytotoxicity.

The probability of occupational exposure rises with the increasing production and biomedical application of carbon nanotubes (CNTs). Thus, the risk of co-exposure of nanomaterials with environmental pollutants is also increasing. Although many studies have focused on the combined toxicity of nanomaterials and pollutants, more attention has been paid to the toxicity of nanomaterials after adsorbing pollutants or the toxicity of nanomaterials and pollutants exposed simultaneously. Few studies have been conducted on the toxicity and toxicity mechanisms of nanomaterials and environmental pollutants following sequential exposure. In this study, we employed THP-1 cells to investigate how pristine single walled CNTs (p-SWCNTs) and oxidized single walled CNTs (SWCNT-COOHs) pretreatments at a non-lethal dose of 10 µg/mL affect cell responses to metal ions (i. e., Pb2+, Cu2+, and Cr(VI)). We found that p-SWCNTs caused more significant damage to cell membrane integrity than SWCNT-COOHs, which led to higher metallothionein (MT) levels and increased transport of metal ions into cells. Pretreatment of p-SWCNTs in cells significantly increased the cytotoxicity of Pb2+, Cu2+, and Cr(VI) by 2-4-fold, whereas SWCNT-COOHs pretreated cells showed no noteworthy changes in response to heavy metals, which were further confirmed by the cellular reactive oxygen species (ROS) assays. These findings indicate that understanding the effects of the exposure sequence of engineered nanomaterials and environmental pollutants on their toxicity provides an excellent complement to combined toxicity evaluation.

Interface defects repair of core/shell quantum dots through halide ion penetration.

The interface defects of core-shell colloidal quantum dots (QDs) affect their optoelectronic properties and charge transport characteristics. However, the limited available strategies pose challenges in the comprehensive control of these interface defects. Herein, we introduce a versatile strategy that effectively addresses both surface and interface defects in QDs through simple post-synthesis treatment. Through the combination of fine chemical etching methods and spectroscopic analysis, we have revealed that halogens can diffuse within the crystal structure at elevated temperatures, acting as "repairmen" to rectify oxidation and significantly reducing interface defects within the QDs. Under the guidance of this protocol, InP core/shell QDs were synthesized by a hydrofluoric acid-free method with a full width at half-maximum of 37.0 nm and an absolute quantum yield of 86%. To further underscore the generality of this strategy, we successfully applied it to CdSe core/shell QDs as well. These findings provide fundamental insights into interface defect engineering and contribute to the advancement of innovative solutions for semiconductor nanomaterials.

Effects of Extract from Mangifera indica Leaf on Monosodium Urate Crystal-Induced Gouty Arthritis in Rats.

The leaves of Mangifera indica L. (Anacardiaceae) is used as a medicinal material in traditional herb medicine for a long time in India, China, and other Eastern Asian countries. Our present study investigated the therapeutic effects of the ethanol extract from Mangifera indica (EMI) in rat with monosodium urate (MSU) crystals-induced gouty arthritis. Effects of EMI (50, 100, and 200 mg/kg, p.o.) administrated for 9 days on the ankle swelling, synovial tumor necrosis factor-alpha (TNF-α), and interleukin-1beta (IL-1ß) levels were assessed in MSU crystal rat. Data from our study showed that rat with gouty arthritis induced by MSU crystal demonstrated an elevation in ankle swelling, synovial TNF-α, IL-1ß mRNA, and protein levels. Oral administration of 100 and 200 mg/kg EMI for 9 days reversed the abnormalities in ankle swelling, synovial TNF-α, IL-1ß mRNA, and protein levels. The results indicated that the beneficial antigouty arthritis effect of EMI may be mediated, at least in part, by inhibiting TNF-α and IL-1ß expression in the synovial tissues. Our study suggests that Mangifera indica and its extract may have a considerable potential for development as an anti-gouty arthritis agent for clinical application.

Simultaneous reduction and sequestration of hexavalent chromium by magnetic ß-Cyclodextrin stabilized Fe3S4.

In this study, ß-Cyclodextrin (CD) modified Fe3S4 nanomaterials were synthesized by a one-step facile strategy and investigated for the removal of Cr(VI). The resulted CD-Fe3S4 exhibited enhanced removal efficiency toward Cr(VI) than bared Fe3S4 with a maximum capacity of 220.26 mg·g-1 as the molar ratio of CD-to-Fe3S4 at 0.2. The effective performance of CD-Fe3S4 toward Cr(VI) could well maintain under oxic conditions and a wide pH range of aqueous solution. A high selectivity for Cr(VI) was achieved in the presence of coexisting cations and anions. More significantly, a single treatment step of CD-Fe3S4 effectively removed chromium from actual electroplating wastewater to the detection limit of 0.004 mg·L-1 that far below the WHO limitation of Cr (VI) (<0.05 mg·L-1) combing with the rapid magnetic separation without adjusting the pH value of wastewater at 7. The effective removal of Cr (VI) by CD-Fe3S4 involved a complex process of surface adsorption/reduction, and solution homogenous reduction and subsequent sequestration of Cr(III) achieving the effective removal of aqueous total Cr. The superior Cr (VI) removal capability and facial separation of CD-Fe3S4 attained its prominent potential application as an effective material for the Cr(VI) removal.

Magnetic Adsorbents for Wastewater Treatment: Advancements in Their Synthesis Methods.

The remediation of water streams, polluted by various substances, is important for realizing a sustainable future. Magnetic adsorbents are promising materials for wastewater treatment. Although numerous techniques have been developed for the preparation of magnetic adsorbents, with effective adsorption performance, reviews that focus on the synthesis methods of magnetic adsorbents for wastewater treatment and their material structures have not been reported. In this review, advancements in the synthesis methods of magnetic adsorbents for the removal of substances from water streams has been comprehensively summarized and discussed. Generally, the synthesis methods are categorized into five groups, as follows: direct use of magnetic particles as adsorbents, attachment of pre-prepared adsorbents and pre-prepared magnetic particles, synthesis of magnetic particles on pre-prepared adsorbents, synthesis of adsorbents on preprepared magnetic particles, and co-synthesis of adsorbents and magnetic particles. The main improvements in the advanced methods involved making the conventional synthesis a less energy intensive, more efficient, and simpler process, while maintaining or increasing the adsorption performance. The key challenges, such as the enhancement of the adsorption performance of materials and the design of sophisticated material structures, are discussed as well.

Suppressing thermal quenching of lead halide perovskite nanocrystals by constructing a wide-bandgap surface layer for achieving thermally stable white light-emitting diodes.

Lead halide perovskite nanocrystals as promising ultrapure emitters are outstanding candidates for next-generation light-emitting diodes (LEDs) and display applications, but the thermal quenching behavior of light emission has severely hampered their real-world applications. Here, we report an anion passivation strategy to suppress the emission thermal quenching behavior of CsPbBr3 perovskite nanocrystals. By treating with specific anions (such as SO4 2-, OH-, and F- ions), the corresponding wide-bandgap passivation layers, PbSO4, Pb(OH)2, and PbF2, were obtained. They not only repair the surface defects of CsPbBr3 nanocrystals but also stabilize the phase structure of the inner CsPbBr3 core by constructing a core-shell like structure. The photoluminescence thermal resistance experiments show that the treated sample could preserve 79% of its original emission intensity up to 373 K, far superior to that (17%) of pristine CsPbBr3. Based on the thermally stable CsPbBr3 nanocrystals, we achieved temperature-stable white LED devices with a stable electroluminescence spectrum, color gamut and color coordinates in thermal stress tests (up to 373 K).