Chemical Synergic Stabilization of High Br-Content Mixed-Halide Wide-Bandgap Perovskites for Durable Multi-Terminal Tandem Solar Cells with Minimized Pb Leakage.

High Br-content mixed-halide perovskites with wide-bandgap (WBG) of 1.6-2.0 eV have showcased vast potential to be used in tandem solar cells. However, they often suffer from severe halide segregation, phase separation and ion migration issues, which would accelerate the decomposition of perovskites films, deteriorate the photovoltaic performance and even aggravate the lead leakage from damaged devices. Here, we report a novel chemical synergic interaction strategy to mitigate the abovementioned issues. A small amount of cationic ß-cyclodextrin, composed of multiple ammonium cations, chlorine ions and abundant hydroxyl functional groups, was introduced into WBG perovskites, which effectively stabilized the halide ions and homogenized the phase distribution, comprehensively passivated the defects,and efficiently immobilized the Pb2+ ions. Encouragingly, the cationic ß-cyclodextrin was universal and useful for different WBG perovskites, which favorably boosted the efficiencies by 10%-36% and extended the device operational stability to 2680 h. The integrated four-terminal or six-terminal all-perovskite tandem solar cells exhibited efficiencies up to 24.39% and 22.42%, respectively. We demonstrated the cationic ß-cyclodextrin-assisted internal chemical encapsulation effectively prevented the Pb leakage from severely damaged devices with only 5.63 ppb Pb leaching out. The target tandem solar cells with cationic ß-cyclodextrin modification also realized a Pb sequestration efficiency of 93.4%.

Physiological response of mussel to rayon microfibers and PCB's exposure: Overlooked semi-synthetic micropollutant?

Rayon microfibers, micro-sized semi-synthetic polymers derived from cellulose, have been frequently detected and reported as "micropollutants" in marine environments. However, there has been limited research on their ecotoxicity and combined effects with persistent organic pollutants (POPs). To address these knowledge gaps, thick-shell mussels (Mytilus coruscus) were exposed to rayon microfibers at 1000 pieces/L, along with polychlorinated biphenyls (PCBs) at 100 and 1000 ng/L for 14 days, followed by a 7-day recovery period. We found that rayon microfibers at the environmentally relevant concentration exacerbated the irreversible effects of PCBs on the immune and digestive systems of mussels, indicating chronic and sublethal impacts. Furthermore, the results of 16 s rRNA sequencing demonstrated significant effects on the community structure, species richness, and diversity of the mussels' intestinal microbiota. The branching map analysis identified the responsive bacteria to rayon microfibers and PCBs belonging to the Proteobacteria, Actinobacteriota, and Bacteroidota phyla. Despite not being considered a conventional plastic, the extensive and increasing use of rayon fibers, their direct toxicological effects, and their interaction with POPs highlight the need for urgent attention, investigation, and regulation to address their contribution to "micropollution".

Two-Second-Annealed 2D/3D Perovskite Films with Graded Energy Funnels and Toughened Heterointerfaces for Efficient and Durable Solar Cells.

The 2D/3D perovskite heterostructures have been widely investigated to enhance the efficiency and stability of perovskite solar cells (PSCs). However, rational manipulation of phase distribution and energy level alignment in such 2D/3D perovskite hybrids are still of great challenge. Herein, we successfully achieved spontaneous phase alignment of 2D/3D perovskite heterostructures by concurrently introducing both 2D perovskite component and organic halide additive. The graded phase distribution of 2D perovskites with different n values and 3D perovskites induced favorable energy band alignment across the perovskite film and boosted the charge transfer at the relevant heterointerfaces. Moreover, the 2D perovskite component also acted as a "band-aid" to simultaneously passivate the defects and release the residual tensile stress of perovskite films. Encouragingly, the blade-coated PSCs based on only ≈2 s in-situ fast annealed 2D/3D perovskite films with favorable energy funnels and toughened heterointerfaces achieved promising efficiencies of 22.5 %, accompanied by extended lifespan. To our knowledge, this is the highest reported efficiency for the PSCs fabricated with energy-saved thermal treatment just within a few seconds, which also outperformed those state-of-the-art annealing-free analogues. Such a two-second-in-situ-annealing technique could save the energy cost by up to 99.6 % during device fabrication, which will grant its low-coast implementation.

Targeted passivation and optimized interfacial carrier dynamics improving the efficiency and stability of hole transport layer-free narrow-bandgap perovskite solar cells.

Narrow-bandgap mixed Sn-Pb perovskite solar cells (PSCs) have showcased great potential to approach the Shockley-Queisser limit. Nevertheless, the practical application and long-term deployment of mixed Sn-Pb PSCs are still largely impeded by the rapid oxidation of Sn2+ ions and under-optimized carrier transport layer (CTL)/perovskite interfaces that would inevitably incur serious interfacial charge recombination and device performance degradation. Herein, we successfully removed the hole transport layer (HTL) by incorporating a small amount of organic phosphonic acid molecules into perovskites, which could preferably interact with Sn2+ ions (relative to Pb2+ analogues) at the grain boundaries (GBs) throughout the perovskite film thickness via coordination bonding, thus effectively retarding the oxidation of Sn2+, passivating the defects and suppressing the non-radiative recombination. Targeted modification effectively reinforced built-in potential by ∼100 mV, and favorably induced energy level cascade, thus accelerating spatial charge separation and facilitating the hole extraction from perovskite layer to underlying conductive electrodes even in the absence of HTL. Consequently, enhanced power conversion efficiencies up to 20.21% have been achieved, which is the record efficiency for the HTL-free mixed Sn-Pb PSCs, accompanied by a decent photovoltage of 0.87 V and improved long-term stability over 2400 h.

Ocean acidificationf affects the bioenergetics of marine mussels as revealed by high-coverage quantitative metabolomics.

Ocean acidification has become a major ecological and environmental problem in the world, whereas the impact mechanism of ocean acidification in marine bivalves is not fully understood. Cellular energy allocation (CEA) approach and high-coverage metabolomic techniques were used to investigate the acidification effects on the energy metabolism of mussels. The thick shell mussels Mytilus coruscus were exposed to seawater pH 8.1 (control) and pH 7.7 (acidification) for 14 days and allowed to recover at pH 8.1 for 7 days. The levels of carbohydrates, lipids and proteins significantly decreased in the digestive glands of the mussels exposed to acidification. The 14-day acidification exposure increased the energy demands of mussels, resulting in increased electron transport system (ETS) activity and decreased cellular energy allocation (CEA). Significant carry-over effects were observed on all cellular energy parameters except the concentration of carbohydrates and cellular energy demand (Ec) after 7 days of recovery. Metabolomic analysis showed that acidification affected the phenylalanine, tyrosine and tryptophan biosynthesis, taurine and hypotaurine metabolism, and glycine, serine and threonine metabolism. Correlation analysis showed that mussel cell energy parameters (carbohydrates, lipids, proteins, CEA) were negatively/positively correlated with certain differentially abundant metabolites. Overall, the integrated biochemical and metabolomics analyses demonstrated the negative effects of acidification on energy metabolism at the cellular level and implicated the alteration of biosynthesis and metabolism of amino acids as a mechanism of metabolic perturbation caused by acidification in mussels.

Sex-specific digestive performance of mussels exposed to warming and starvation.

As global climate change has dramatically impacted the ocean, severe temperature elevation and a decline in primary productivity has frequently occurred, which has affected the structure of coastal biomes. In this study, the sex-specific responses to temperature change and food availability in mussels were determined in terms of digestive performance. The thick-shelled mussels Mytilus coruscus (male and female) were exposed to different temperature and nutritional conditions for 30 days. The results showed that the digestive enzymes of mussels were significantly affected by temperature, food, sex, and their interactions. High temperature (30°C) and starvation significantly decreased amylase, lysozyme, and pepsase activities of female mussels, while trypsin and trehalase did not change significantly at the experimental end. The activity of amylase, trypsin, and trehalase was significantly reduced in males at high temperature (30°C) under starvation treatment, but high temperature (30°C) elevated pepsase. Unsurprisingly, starvation caused the reduction of lysozyme and pepsase under 25°C in males. Amylase, lipase, and trehalase were higher in female mussels compared with males, while the enzymatic activities of lysozyme, pepsase, and trypsin were higher in male mussels than females. Principal component analysis showed that different enzyme activity indexes were separated in male and female mussels, indicating that male and female mussels exhibited significantly different digestive abilities under temperature and food condition change. The study clarified sex-specific response difference in mussel digestive enzymes under warming and starvation and provided guidance for the development of mussel aquaculture (high temperature management and feeding strategy) under changing marine environments.

Is microplastic an oxidative stressor? Evidence from a meta-analysis on bivalves.

Microplastic pollution is a major threat to the marine environment attracting attention from scientific and public communities. Although we have sufficient evidence that microplastic is ubiquitous in all ecosystems, the question of the harmfulness of microplastic exposure is still under debate. Filter feeders like bivalves are commonly exposed to microplastics in water and sediments and thus can serve as excellent biological indicators for microplastic pollution. A relatively rich toxicological literature has been focusing on microplastic effects on bivalves but we have yet to reach an agreement on the toxic effects and mechanisms of microplastics. Here, we conducted a meta-analysis and bibliometrics analysis of the microplastic studies in bivalves. The bibliometric analysis (used to evaluate the general research trends) showed that the investigation of microplastic distribution in the marine environment and the molecular mechanisms of microplastic toxicity are the two major hot spots of research. Based on analyses of ecologically and environmentally relevant microplastics concentrations, particle sizes and polymer types, we discuss the physiological effects of microplastics on bivalves, and the severity and direction of the effects at the cellular, tissue, organ and organismal levels. The meta-analysis results show that microplastics can induce time-dependent oxidative stress in bivalves. Generally, the activities of antioxidant enzymes, such as glutathione peroxidase (GPx), glutathione-S-transferase (GST) and superoxide dismutase (SOD) increased during short-term exposure but declined after long-term exposure to microplastics. Non-linear response of GPx, GST and SOD enzymes to MP exposure over time indicate that these enzymes are not good biomarkers of MPs effects in marine bivalves. The tissue glutathione levels and catalase (CAT activity) showed an increase during both short- and long term MP exposures and thus can be used as oxidative stress biomarkers of sublethal MPs effects in marine bivalves.

Microplastics and food shortage impair the byssal attachment of thick-shelled mussel Mytilus coruscus.

Microplastics (MPs) have become a ubiquitous emerging pollutant in the global marine environment. The potential toxic effects of MPs and interactions of MP pollution with other stressors such as food limitation on marine organisms' health are not yet well understood. This study investigated the effects of three-week exposure to different MPs and food shortage on the physical defense mechanisms (byssus production and properties) of Mytilus coruscus. Starvation significantly reduced the number of byssus threads, and combined exposure to MPs and food shortage suppressed the adhesion ability and condition index of mussels. The length of the byssus threads was not affected by all experimental exposures. Transcript levels of genes encoding key proteins involved in byssus formation (the mussel foot proteins mfp-1, -2, -3, -4, -5 and -6, and prepolymerized collagen proteins preCOL-D, -P and -NG) were altered by interactions between the MPs and food shortage. These findings show that insufficient food supply can exacerbate the adverse effects of MPs on mussel defense which might have implications for survival and fitness of mussels under food limited conditions (e.g. in winter) in polluted coastal habitats.

Oxidative stress induced by nanoplastics in the liver of juvenile large yellow croaker Larimichthys crocea.

There are many toxicological studies on microplastics, but little is known about the effect of nanoplastics (NPs). Here, we evaluated the oxidative stress responses induced by NPs (10, 104 and 106 particles/l) in juvenile Larimichthys crocea during 14-d NPs exposure followed by a 7-d recovery. After exposure, the activities of antioxidant enzymes (SOD, CAT, GPx) and MDA levels increased in the liver of fish at the highest NPs concentration. SOD and CAT activities remained elevated above the baseline after recovery under high-concentration NPs but returned to the baseline in two other NP treatments. Although lipid peroxidation in liver was reversible, juvenile fish in NPs treatments exhibited a lower survival rate than the control during both exposure and recovery. Furthermore, IBR value and PCA analysis showed the potential adverse effects of NPs. Considering that NPs can reduce the survival of fish juveniles, impacts of NPs on fishery productivity should be considered.

Enhanced immunity and hemocytes proliferation by three immunostimulants in tri-spine horseshoe crab Tachypleus tridentatus.

Tachypleus amebocyte lysate (TAL) is crucial in medical testing, but its industry in China has been restricted due to the decline of horseshoe crab population in recent years. Exploring methods of enhancing immunity and rapid hemocytes proliferation is urgent for the industrial horseshoe crab culture. In this study, ß-glucan (G), peptidoglycan (P), and squalene (S) were injected to horseshoe crabs at two concentrations (5 and 10 mg/kg), in order to compare their effects on total hemocyte count (THC), reactive oxygen species (ROS), and non-specific immune enzyme activities. Results showed that the THC, superoxide dismutase (SOD), catalase (CAT), and total antioxidant capacity (T-AOC) were significantly increased by three immunostimulants at different points of time; ROS was significantly increased except at two squalene groups; lysozyme (LZM) and alkaline phosphatase (AKP) activity were increased except at low dose (5 mg/kg) squalene group; malondialdehyde (MDA) activity was decreased in all treatments; and hemocyanin concentration (HC) changed little during the experiment. At the 48th hour, THC, ROS, SOD, CAT, T-AOC, LZM, and AKP activities were significantly higher in the two peptidoglycan groups than those in the control group; the low dose ß-glucan and squalene groups showed significantly higher SOD and CAT, but their THC and AKP were not significantly different from those of the control group. In general, all three immunostimulants stimulated the hemolymph parameters of horseshoe crabs, notably, peptidoglycan could significantly increase the THC and enzyme activities, suggesting that peptidoglycan can be developed as an efficient immunostimulant for horseshoe crabs.

Gonadal antioxidant responses to seawater acidification and hypoxia in the marine mussel Mytilus coruscus.

This study investigated the combined effects of seawater acidification and hypoxia on the antioxidant response in gonads of the thick shell mussel Mytilus coruscus. Mussels were collected along the Shengsi Island, East China Sea, where oxygen and pH fluctuations frequently occur in summer. Mussels were exposed to three pH (8.1, 7.7, and 7.3) and two dissolved oxygen (DO) levels (6 and 2 mg L-1) for 21 days followed by a 10-day recovery period (pH 8.1 and DO 6 mg L-1). Gonad surface area (GSA) and activity of superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPX), glutathione (GSH), glutathione S-transferase (GST), and malondialdehyde (MDA) in gonad were measured at days 21 and 31. Complex and enzyme-specific responses were observed after the 21-day exposure period. Overall, PCA analysis revealed a stronger effect of pH than DO. Integrated biomarker response (IBR) analysis demonstrated that low pH and DO decreased mussel's antioxidant system and increased oxidative damage with potential consequences for gonad development. Mussels exposed to low pH and DO were only partly able to recover a normal enzymatic activity after 10-day recovery period. This suggests that mussels exposed to short-term pH and DO fluctuations event in the field may suffer lasting negative impacts.

Optical determination of Shockley-Read-Hall and interface recombination currents in hybrid perovskites.

Metal-halide perovskite solar cells rival the best inorganic solar cells in power conversion efficiency, providing the outlook for efficient, cheap devices. In order for the technology to mature and approach the ideal Shockley-Queissier efficiency, experimental tools are needed to diagnose what processes limit performances, beyond simply measuring electrical characteristics often affected by parasitic effects and difficult to interpret. Here we study the microscopic origin of recombination currents causing photoconversion losses with an all-optical technique, measuring the electron-hole free energy as a function of the exciting light intensity. Our method allows assessing the ideality factor and breaks down the electron-hole recombination current into bulk defect and interface contributions, providing an estimate of the limit photoconversion efficiency, without any real charge current flowing through the device. We identify Shockley-Read-Hall recombination as the main decay process in insulated perovskite layers and quantify the additional performance degradation due to interface recombination in heterojunctions.