Zero-dimensional hybrid tin halides with stable broadband light emissions.

Considering the instability and toxicity of 3D Pb-based perovskite nanocrystals, lead-free low-dimensional organic-inorganic hybrid metal halides have attracted widespread attention as potential substitutes. Herein, two new tin-based 0D halides [H4BAPP]SnBr5·Br and [H4BAPP]SnCl5·Cl·H2O (BAPP = 1,4-bis(3-aminopropyl)piperazine) were synthesized successfully based on [SnX5]3- as an emission center. Typically, [H4BAPP]SnBr5·Br and [H4BAPP]SnCl5·Cl·H2O display broadband yellow and yellow-green light emissions originating from the radiative recombination of self-trapped excitons (STEs). The photoluminescence quantum yields (PLQYs) of the two compounds were calculated to be 19.27% and 2.36%, respectively. Furthermore, the excellent chemical and thermal stability and broadband light emissions reveal their potential application in solid-state white lighting diodes.

Near-Unity Green Luminescent Hybrid Manganese Halides as X-ray Scintillators.

The increasing demands in optoelectronic applications have driven the advancement of organic-inorganic hybrid metal halides (OIMHs), owing to their exceptional optical and scintillation properties. Among them, zero-dimensional (0D) low-toxic manganese-based scintillators have garnered significant interest due to their exceptional optical transparency and elevated photoluminescence quantum yields (PLQYs), making them promising for colorful light-emitting diodes and X-ray imaging applications. In this study, two OIMH single crystals of (Br-PrTPP)2MnBr4 (Br-PrTPP = (3-bromopropyl) triphenylphosphonium) and (Br-BuTPP)2MnBr4 (Br-BuTPP = (4-bromobutyl) triphenylphosphonium) were prepared via a facile saturated crystallization method. Benefiting from the tetrahedrally coordinated [MnBr4]2- polyhedron, both of them exhibited strong green emissions peaked at 517 nm owing to the d-d electron transition of Mn2+ with near-unity PLQYs of 99.33 and 86.85%, respectively. Moreover, benefiting from the high optical transparencies and remarkable luminescence properties, these manganese halides also exhibit excellent radioluminescent performance with the highest light yield of up to 68,000 photons MeV-1, negligible afterglow (0.4 ms), and linear response to X-ray dose rate with the lowest detection limit of 45 nGyair s-1. In X-ray imaging, the flexible film made by the composite of (Br-PrTPP)2MnBr4 and PDMS shows an ultrahigh spatial resolution of 12.78 lp mm-1, which provides a potential visualization tool for X-ray radiography.

Mixotrophic culture of bait microalgae for biomass and nutrients accumulation and their synergistic carbon metabolism.

Microalgae cannot meet the bait demand for aquaculture due to light intensity limitation and other disadvantageous conditions. This research selected 6 mixotrophic microalgae, and the optimal strains and organic carbon were screened. The results showed that Thalassiosira pseudonana and Chlorella sp. are suitable for mixotrophic culture. The maximum cell density of Thalassiosira pseudonana was found to be 1.67 times than that of the photoautotrophic group when glycerol was added. The maximum cell density of Chlorella sp. with acetic acid was 1.69 times than that of the photoautotrophic group. When the concentration of acetic acid was 5.0 g·L-1 and the concentration of KNO3 was 0.2 g·L-1, the maximum biomass of Chlorella sp. could reach 3.54 × 107 cells·mL-1; the maximum biomass of Thalassiosira pseudonana was 5.53 × 106 cells·mL-1 with 10.0 g·L-1 glycerol and 0.2 g·L-1 KNO3. Metabolomic analysis further revealed that mixotrophic bait microalgae could promote the accumulation of lipids and amino acids.

Salinity fluctuation influences the toxicity of 1-octyl-3-methylimidazolium chloride ([C8mim]Cl) to a marine diatom Phaeodactylum tricornutum.

In this work, a marine diatom (Phaeodactylum tricornutum) was exposed to 1-octyl-3-methylimidazolium chloride ([C8mim]Cl) for 96 h at three different salinities (25, 35, and 45 ‰) for investigating their interactive effects. Results showed that values of EC10 and EC50 at 96 h of exposure were 0.29, 1.06, 2.01 µg L-1 and 7.21, 7.71, 7.25 mg L-1 when the salinities were 25, 35, and 45 ‰, respectively, meaning that salinity fluctuation affected the toxicity of [C8mim]Cl to this diatom. Changes in chlorophyll a contents and chlorophyll fluorescence parameters suggested that [C8mim]Cl and salinity fluctuation had a significant interactive effect on the algal photosynthesis. In addition, soluble protein content and activities of antioxidant enzymes in algal cells changed significantly. Increased malondialdehyde contents indicated that the combined stresses could induce excessive production of reactive oxygen species leading to oxidative damage to the algal cells.

Interactive effects of polymethyl methacrylate (PMMA) microplastics and salinity variation on a marine diatom Phaeodactylum tricornutum.

Until now, knowledge about the interactive effects of microplastics and environmental factors on primary producers is quite limited. In this work, a marine diatom (Phaeodactylum tricornutum) was exposed to polymethyl methacrylate (PMMA) microplastics at different salinities (25, 35, and 45‰) for 10 days in order to study their interactive effects. Results showed that growth of P. tricornutum was negatively affected by PMMA microplastics and salinity variation with a minimum EC50 value of 91.75 mg L-1. Photosynthetic activity of P. tricornutum was also inhibited by the two factors, and their interactive effects on chlorophyll fluorescence parameters (Fv/Fm and ΦPSII) were significant. In the algal cells, soluble protein accumulated, activities of two antioxidant enzymes changed, and malondialdehyde (MDA) content increased when this diatom was exposed to the microplastics at different salinities. These data would help to evaluate the risks of microplastics to primary producers under different environmental factors.

Molecular response mechanisms of silkworm (Bombyx mori L.) to the toxicity of 1-octyl-3-methylimidazole chloride based on transcriptome analysis of midguts and silk glands.

In a previous study, silkworm larvae were used as a novel model to assess the biotoxicity of ILs, which showed that ILs could cause significant physiological and biochemical changes in midguts and silk glands of the larvae, and result in the death of larvae. In order to investigate the toxicity of 1-octyl-3-methylimidazole chloride ([C8mim]Cl) to the larvae at molecular level, RNA-sequencing technology was used to construct transcriptomic profiles of midguts and silk glands in this work. Results showed that a lot of differentially expressed genes (DEGs) were effectively screened out through bioinformatics software based on the transcriptome data and reference genome. To give more detail, 5118 and 2211 DEGs (926 and 822 DEGs) were obtained in the midguts (silk glands) when the larvae were exposed to [C8mim]Cl for 6 and 12 h, respectively, relative to the controls. In addition, gene ontology (GO) analysis suggested that the DEGs could be divided into three categories (i.e., biological process, cellular component, and molecular function), and were involved in multiple organelle functions and complex biological processes. Kyoto encyclopedia of genes and genomes (KEGG) analysis showed that the DEGs were enriched in a variety of pathways, such as signal transduction, apoptosis, glycolysis, peroxisome, autophagy, hippo signaling pathway, arginine and proline metabolism. Results of quantitative real-time PCR and histopathological observation indicated that molecular mechanism of the larvae against [C8mim]Cl toxicology may be attributed to cell apoptosis regulation via both the mitochondrial pathway and the death receptor-initiated pathway. Thus, these results provided useful data for exploring the toxicity of ILs to insects at molecular level.

Cultivation of Chlorella sorokiniana in a bubble-column bioreactor coupled with cooking cocoon wastewater treatment: effects of initial cell density and aeration rate.

Previous studies have documented that Chlorella sorokiniana could grow well on cooking cocoon wastewater (CCW) with a maximum biomass of 0.49 g/L. In order to further enhance the biomass production and nutrient removals, a bubble-column bioreactor was designed and performed to cultivate C. sorokiniana in CCW, and two main cultivation parameters were investigated in this work. Results showed that a maximum algal biomass, specific growth rate, and biomass productivity of 2.83 g/L, 0.854 d-1, and 476.25 g/L/d, respectively, were achieved when this alga was cultivated in the bioreactor with an initial cell density of 0.8 g/L and an aeration rate of 3.34 L air/L culture/min; meanwhile, removal efficiencies of ammonium, total nitrogen, total phosphorus, and chemical oxygen demand reached 97.96, 85.66, 97.96, and 86.43%, respectively, which were significantly higher than that obtained in our previous studies. Moreover, chemical compositions in the algal cells varied with the changes of cultivation conditions (i.e., initial cell density and aeration rate). Thus, it is concluded that (1) the bubble-column bioreactor was suitable for cultivation of C. sorokiniana coupled with the CCW treatment and (2) initial cell density and aeration rate affected the biomass production, nutrient removals and chemical compositions of this alga.

Oxidative stress responses caused by dimethyl phthalate (DMP) and diethyl phthalate (DEP) in a marine diatom Phaeodactylum tricornutum.

A marine diatom (Phaeodactylum tricornutum) was exposed to different concentrations of dimethyl phthalate (DMP) and diethyl phthalate (DEP) for 96 h within a batch-culture system to investigate their toxicities. Results showed that P. tricornutum could remove DMP and DEP effectively with removal rates of 0.20-0.30 and 0.14-0.21 mg L-1 h-1, respectively. In addition, DMP and DEP significantly inhibited the photosynthesis and chlorophyll a biosynthesis of P. tricornutum with 96-h EC50 values of 390.5 mg L-1 and 74.0 mg L-1, respectively. Results of reactive oxygen species (ROS) level suggested that the two PAEs could induce excessive ROS production in the diatom. Moreover, activities of antioxidant enzymes (i.e., SOD and POD) in the diatom increased with the increase of DMP and DEP concentrations. The results will help to understand the toxic mechanisms of PAEs, and provide strong evidences for evaluating their ecological risks in the marine environment.

A feasibility study of using silkworm larvae as a novel in vivo model to evaluate the biotoxicity of ionic liquids.

Ionic liquids (ILs) have been reported to be a potential water and soil pollutant, whose toxicity has gained much attention in recent years. In this work, silkworm larvae were used as a novel in vivo model to assess the biotoxicity of ILs, which were performed by three steps. The first step was to determine the susceptibility of different silkworm strains to ILs. Data showed that Jingsong×haoyue was the most susceptible one among three silkworm strains (Jingsong×haoyue, P50, and Yi16) for evaluating the biological effects of ILs. The second step was to compare the toxicity of ILs with different structures using the larvae of Jingsong×haoyue. It was found that three representative ILs, 1-octyl-3-methylimidazole chloride ([C8mim]Cl), N-octyl-3-methylpyridine chloride ([C8mpy]Cl), and 1-octyl-3-methylimidazole tetrafluoroborate ([C8mim]BF4), had significant toxic effects on the growth and development of the larvae with 24 h median lethal concentration (24 h-LC50) values of 112.3, 156.3, and 68.9 µg g-1, respectively, indicating that the types of anions and cations had impacts on the toxicity of ILs. The last step was targeted at investigating responses of the larvae to the exposure of ILs. It was observed that remarkable physiological and biochemical responses occurred in different tissues of the larvae. For example, activities of superoxide dismutase (SOD), catalase (CAT), and peroxidase (POD) in different tissues increased significantly to form an active protective mechanism for alleviating the toxic effects of ILs. Additionally, an increase of malondialdehyde (MDA) contents was found in the larvae. The data suggested that ILs could induce lipid peroxidation and cellular damage, which may be the main reason for toxicity of ILs to the larvae. Therefore, silkworm larvae could be used as a susceptible and reliable in vivo model to evaluate the toxicity of ILs, and the results are helpful to reveal their toxic mechanism to insects.

Using a freshwater green alga Chlorella pyrenoidosa to evaluate the biotoxicity of ionic liquids with different cations and anions.

With the extensive use of ionic liquids (ILs) in various industrial fields, their potential toxicity to aquatic ecosystem has attracted considerable attention. In this work, biotoxicity of ILs with different cations and anions was evaluated by using a freshwater green alga Chlorella pyrenoidosa. Results showed that 1-butyl-3-methylimidazolium chloride ([C4mim]Cl), 1-octyl-3-methylimidazolium chloride ([C8mim]Cl), 1-octyl-3-methylimidazolium nitrate ([C8mim]NO3), 1-octyl-3-methylimidazolium tetrafluoroborate ([C8mim]BF4), and 1-dodecyl-3-methylimidazolium chloride ([C12mim]Cl) had a significant inhibition on the algal growth with EC50 values of 23.48, 4.72, 3.80, 4.44, and 0.10 mg L-1 at the 72 h of exposure, respectively. These data suggested that the toxicity of ILs increased with the increase of side alkyl chain length, while anions had little influences on their toxicity to this alga. Moreover, changes in chlorophyll a content and chlorophyll fluorescence parameters (Fv/Fm and ΦPSII) indicated that the five ILs could damage the photosynthetic system of this alga resulting in the decrease of photosynthetic efficiency. The increased soluble protein content and antioxidase activity could be considered as an active response mechanism of this alga against the exposure of ILs. Content of malondialdehyde (MDA) in this alga increased significantly when it was exposed to ILs, suggesting that reactive oxygen species (ROS) were accumulated in the algal cells, which would cause injury of the algal biofilm and chloroplast. Therefore, results obtained in this work would help to explain the possible underlying toxic mechanisms of ILs to C. pyrenoidosa, and provide a significant theoretical support for assessing the toxicity of ILs to aquatic organisms.

Impacts of four ionic liquids exposure on a marine diatom Phaeodactylum tricornutum at physiological and biochemical levels.

With the increasing applications in various industrial areas, toxicity of ionic liquids (ILs) has gained much attention in recent years. In this work, 1-octyl-3-methylimidazolium nitrate ([C8mim]NO3), 1-octyl-3-methylimidazolium chloride ([C8mim]Cl), N-octyl-3-metylpyridinium chloride ([C8mpy]Cl) and N-octyl-3-metylpyridinium bromide ([C8mpy]Br) were used to investigate the impacts of different types of cations and anions on their toxicity to a marine diatom Phaeodactylum tricornutum. Results showed that the four ILs had poor degradability under the culture conditions used in this study, and significantly inhibited the growth of this diatom with 96-h EC50 values of 24.0, 33.6, 16.1 and 14.4mgL-1 for [C8mim]NO3, [C8mim]Cl, [C8mpy]Cl and [C8mpy]Br, respectively. The data indicated that types of cations and anions would affect the toxicity of ILs to this diatom. Additionally, photosynthesis of this diatom was inhibited because significant decrease of chlorophyll a content and damage of PSII reaction centers were observed when it was exposed to the four ILs. Remarkable physiological and biochemical responses occurred in the cells of this diatom to alleviate the damaging effects of the four ILs. For example, content of soluble protein and activities of superoxide dismutase (SOD) and catalase (CAT) in the cells of this diatom increased significantly to form a protective mechanism against the toxicity of ILs, although they decreased in the cultures with high concentrations of ILs (≥20mgL-1). Thus, these results would not only provide strong evidences for evaluating the ecological risks and toxicity of ILs to marine ecosystem, but also help for understanding their toxic mechanisms to marine diatoms.

Feasibility of Growing Chlorella sorokiniana on Cooking Cocoon Wastewater for Biomass Production and Nutrient Removal.

The feasibility of microalgae cultivation using cooking cocoon wastewater (CCW) collected from a silk production factory was investigated in this work. Results showed that Chlorella sorokiniana grew well on the CCW whether it was autoclaved or not. After 7-day cultivation, the biomass increased by 1.57, 2.78, 3.33, and 3.14 times, and by 3.65, 4.03, 3.27, and 2.82 times when this alga was cultivated in the raw CCW (R-CCW) and autoclaved CCW (A-CCW) at the initial dry cell densities of 0.01, 0.04, 0.08, and 0.16 g/L, respectively. The algal photosynthetic growth was not affected when this alga grew on the R-CCW at an initial dry cell density of ≥ 0.04 g/L, while it was significantly inhibited when the initial dry cell density was 0.01 g/L. Additionally, this alga could remove nutrients rapidly from the CCW, and the removal efficiency increased with the increase of initial dry cell density. Thus, it was concluded that the CCW could be used as a good-quality medium for the algal growth, which is worthy of further study and promotion.

Biomass production and biochemical profiles of a freshwater microalga Chlorella kessleri in mixotrophic culture: Effects of light intensity and photoperiodicity.

In this work, different light conditions (light intensity and photoperiodicity) were set up to investigate the impact of light on growth, chemical compositions and fatty acid profiles of Chlorella kessleri in mixotrophic cultures. Results indicated that C. kessleri could absorb and utilize glucose rapidly when light intensity was ≤ 90 µE m-2 s-1, and a maximum algal biomass of 1.17 g L-1 was obtained in the cultures with 2 g L-1 glucose at a light intensity and light/dark (L/D) cycle of 90 µE m-2 s-1 and 20L:4D, respectively. Additionally, this alga would accumulate a large amount of chlorophyll a (about 30 mg g-1) in the mixotrophic cultures under a low light intensity (≤90 µE m-2 s-1), and the algal chemical compositions changed with light intensity and photoperiodicity. Results of fatty acid profiles suggested that the algal biomass could be used as animal feeds or a good-quality biodiesel feedstock.

Cultivation of Chlorella vulgaris on anaerobically digested swine manure with daily recycling of the post-harvest culture broth.

In this work, a cultivation system with daily recycling of the post-harvest culture broth was set up and performed in order to reuse the water and nutrients in pretreated anaerobically digested swine manure, which was used as media to cultivate Chlorella vulgaris (UTEX 2714) at different recycling ratios. Results showed that the alga grew well in the system with an accumulative algal biomass and productivity of 1.68-3.47g/L and 234.1-532.2mg/L/d, respectively, at the end of the cultivation. Additionally, chemical compositions in this alga varied with the change of recycling ratios, and the highest productivities of carbohydrate, protein and lipids (76.4, 257.2 and 183.7mg/L/d, respectively) were obtained in the system with a recycling ratio of 1/4 or 1/6. Fatty acid profiles indicated that this alga could be used as a good-quality biodiesel feedstock with a biodiesel productivity of 9.65-40.1mg/L/d.

Carbon-dependent alleviation of ammonia toxicity for algae cultivation and associated mechanisms exploration.

Ammonia toxicity in wastewater is one of the factors that limit the application of algae technology in wastewater treatment. This work explored the correlation between carbon sources and ammonia assimilation and applied a glucose-assisted nitrogen starvation method to alleviate ammonia toxicity. In this study, ammonia toxicity to Chlorella sp. was observed when NH3-N concentration reached 28.03mM in artificial wastewater. Addition of alpha-ketoglutarate in wastewater promoted ammonia assimilation, but low utilization efficiency and high cost of alpha-ketoglutarate limits its application in wastewater treatment. Comparison of three common carbon sources, glucose, citric acid, and sodium bicarbonate, indicates that in terms of ammonia assimilation, glucose is the best carbon source. Experimental results suggest that organic carbon with good ability of generating energy and hydride donor may be critical to ammonia assimilation. Nitrogen starvation treatment assisted by glucose increased ammonia removal efficiencies and algal viabilities.

Co-cultivation of microalgae in aquaponic systems.

Aquaponics is a sustainable system for the future farming. In aquaponic systems, the nutrient-rich wastewater generated by the fish provides nutrients needed for vegetable growth. In the present study, the role of microalgae of Chlorella sp. in the floating-raft aquaponic system was evaluated for ammonia control. The yields of algal biomass, vegetable, and removal of the key nutrients from the systems were monitored during the operation of the aquaponic systems. When the systems were in full operation, the algae production was about 4.15±0.19g/m2·day (dry basis) which is considered low because the growth conditions are primarily tailored to fish and vegetable production. However, it was found that algae had a positive effect on balancing pH drop caused by nitrifying bacteria, and the ammonia could be controlled by algae since algae prefer for ammonia nitrogen over nitrate nitrogen. The algae are more efficient for overall nitrogen removal than vegetables.

An innovative intermittent-vacuum assisted thermophilic anaerobic digestion process for effective animal manure utilization and treatment.

Intermittent-vacuum stripping (IVS) was developed as a pretreatment for thermophilic anaerobic digestion (TAD) to improve methanogenesis and hydrolysis activity through preventing free ammonia and hydrogen sulfide (H2S) inhibition from liquid swine manure (LSM). Over 98% of ammonia and 38% organic nitrogen were removed in 60min from 55°C to 85°C with vacuum pressure (from 100.63±3.79mmHg to 360.91±7.39mmHg) at initial pH 10.0 by IVS. Thermophilic methanogenesis and hydrolysis activity of pretreated LSM increased 52.25% (from 11.56±1.75% to 17.60±0.49%) in 25days and 40% (from 10days to 6days) in bio-methane potential assay. Over 80% H2S and total nitrogen were removed by IVS assistance, while around 70% nitrogen was recycled as ammonium sulfate. Therefore, IVS-TAD combination could be an effective strategy to improve TAD efficiency, whose elution is more easily utilized in algae cultivation and/or hydroponic system.