Fast Degradation Research Articles

Contact-Electro-Catalysis Through Electret Behavior to Facilitate Electron Transfer.

Contact-electro-catalysis (CEC) usually uses polymer dielectrics as its catalysts under mechanical stimulation conditions, which although has a decent catalytic dye degradation effect still warrants performance improvement. A carrier separation promotion strategy based on an internal electric field by polarization can effectively improve ferroelectric material performance in photocatalysis and piezocatalysis. Therefore, carrier separation as a necessary process of CEC also can be promoted and is largely expected to improve CEC performance theoretically. However, the carrier separation enhancement by the internal electric field strategy has not been achieved in the CEC experiment yet, because of the difficulty of building an internal electric field in an inert polymer dielectric. Herein, a polytetrafluoroethylene (PTFE) dielectric was charged through an electret process, which was believed to establish an internal electric field for CEC catalysts proved by KPFM, XPS, and triboelectric nanogenerator voltage output analysis. The fastest degradation rate of methyl orange reached over 90% at 1.5 h, while the hydroxyl free radical (•OH) yield of the PTFE electret was nearly three times that of the original PTFE. Density functional theory (DFT) calculations verified that the potential barrier of interatomic electron transfer between PTFE and H2O was reduced by 37% under the internal electric field. The electret strategy used herein to optimize the PTFE catalyst provides a base for the use of other general plastics in CEC and facilitates the production of easily prepared, easily recyclable, and inexpensive polymer dielectric catalysts that can promote large-scale pollutant degradation via CEC.

Phase engineered enhancement of photocatalytic and Opto-magnetic properties of CuO nanoparticles through fluorine and gadolinium doping

The present study comprises co-doping of CuO nanoparticles with gadolinium (Gd) and fluorine (F) using the sol-gel method to achieve phase stabilization and tune their physicochemical properties. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses revealed successful incorporation of the dopants and the stabilization of the CuO phase with increasing Gd content. Morphological studies revealed grain refinement and an enhanced surface-to-volume ratio upon co-doping. Average particle size decreased from 194 nm to 138 nm for pure and 5%F to 126 nm, 101 nm, and 81 nm for, 1mol%, 2mol% and 3mol% Gd along with 5mol% F co-doped CuO nanoparticles. Increasing the Gd ratio also tuned the band structure and significantly improved the optical properties of the CuO nanoparticles. Additionally, a transition from weak ferromagnetic ordering to paramagnetic behavior is observed. Coercivity decreased to 2.5 Oe for Cu0.97Gd0.03F0.05O0.95 as opposed to 396.3 Oe for CuF0.05O0.95. Photocatalytic activity studies using rhodamine B (Rh B) as a model probe revealed a pronounced enhancement in degradation kinetics with increasing gadolinium (Gd) doping, culminating in around 2.9 times faster degradation rate for 3 % Gd-doped CuO nanoparticles compared to pure CuO nanoparticles. After 3 h of UV light irradiation, the photodegradation efficiency of Cu0.97Gd0.03F0.05O0.95 was 94 %, which is significantly higher than the 80 % and 69 % efficiency of CuF0.05O0.95 and CuO, respectively. These remarkable optical, magnetic, and photocatalytic properties of the co-doped nanoparticles offer promising candidacy for various applications, including photocatalysis, solar energy harvesting, magnetic switching, and magnetic sensing.

Degradation kinetics of PLA/hemp biocomposites: Tradeoff between nucleating action and pro-hydrolytic effect of natural fibers

Natural fibers are not only a sustainable alternative to synthetic reinforcement materials, but can also be used to produce truly sustainable biocomposites with fast degradation kinetics. Indeed, due to their hygroscopicity, lignocellulosic fibers allow water and/or degrading organisms from the external environment to penetrate inside the host matrix and trigger its hydrolysis. The latter is the rate-limiting step for the degradation of bio-polyesters, which exhibit unacceptably slow degradation kinetics at ambient temperature and humidity. However, fibers also promote crystallization of the host matrix and thus slow down its degradation kinetics. To better understand and potentially control the degradation kinetics of biocomposites, here we investigate the ability of hemp shives, a hygroscopic by-product of hemp fiber production, to accelerate the hydrolysis of poly (lactic acid) (PLA). The degradation kinetics and degree of crystallinity of PLA are monitored in water and mature compost as a function of fiber content, which was varied across the percolation threshold (Φc) to study the effect of fiber interconnectivity. Above Φc, the fibers accelerate PLA hydrolysis in water despite their nucleating effect. Conversely, in compost the shielding effect of fiber-induced crystallinity prevails, and the fibers eventually slow down the degradation kinetics of PLA.

Achieving thermodynamic stability of single-crystal ultrahigh-nickel cathodes via an alcohol-assisted mechanical fusion

Elevating the operating voltage is an effective approach to improve the reversible capacity of ultra-high nickel layered oxide cathode LiNixCoyMnzO2 (NCM, x ≥ 0.8) and solve the “range anxiety” confusion of electric vehicles. However, the undesirable surface reconstruction induced by the high cut-off voltage has a fatal impact on the thermodynamic stability of the material, inevitably leading to fast capacity degradation. Herein, a mechanical fusion aided by alcohol is suggested to create a stable olivine structure for the single-crystal (SC) ultrahigh-nickel cathode LiNi0.92Co0.04Mn0.04O2. The addition of nanoparticles effectively bridges the void of SC-NCM, builds an ideal particle grading, and significantly raises the cost efficiency, as well as promotes the cycling stability and safety of the full cell. Remarkably, the layered/olivine mixture forms a perfect shield by lowering the surface area between the NCM cathode and electrolyte, hence mitigating side reactions and contributing to an incredibly thin and stable cathode/electrolyte interface. Furthermore, the thermodynamic stability of highly delithiated NCM is improved, as both the particle cracks and structural degradation are simultaneously postponed. Consequently, the maximum temperature of the single-crystal LiNi0.92Co0.04Mn0.04O2@LiFePO4‖graphite pouch full cell is dramatically reduced from 599.4 to 351.4 °C, and the full cell achieves 88.2% capacity retention after 800 cycles, demonstrating excellent thermal stability and cycling stability. This facile strategy provides a feasible technical reference for further exploiting the ultrahigh-capacity, high-safety, and long-life Ni-rich cathode for commercial application of lithium-ion batteries (LIBs).

Effects of Non-Uniform Temperature Distribution on the Degradation of Liquid-Cooled Parallel-Connected Lithium-Ion Cells

Our previous work on an air-cooled stack of five pouch-format lithium-ion (Li-ion) cells showed that non-uniform temperature can cause accelerated degradation, especially of the middle cell. In this work, a stack of five similar cells was cycled at a higher C-rate and water-cooled to create a larger temperature gradient for comparison with the air-cooled stack. It was hypothesized that the larger temperature gradient in the water-cooled stack would exacerbate the degradation of the middle cell. However, the results showed that the middle cell degraded slightly slower than the side cells in the water-cooled stack. This trend is opposite to that in the air-cooled stack. This difference could be attributed to the combined effects of a smaller temperature rise and larger temperature gradient in the water-cooled stack than in the air-cooled stack. Post-mortem analysis of cycled cells and a fresh cell showed that the degradation mainly came from the anode. Increased lithium plating and decreased porosity in the side cells are possible mechanisms for the faster degradation compared with the middle cell. It was also found that all the cells in the water-cooled stack experienced a phenomenon of capacity drop and recovery after a low C-rate reference performance test and extended rest. This phenomenon can be attributed to lithium diffusion between the anode active area and the anode overhang area.

Preliminary Assessment of On-Orbit Radiometric Calibration Challenges in NOAA-21 VIIRS Reflective Solar Bands (RSBs)

The National Oceanic and Atmospheric Administration (NOAA) 21 Visible Infrared Imaging Radiometer Suite (VIIRS) was successfully launched on 10 November 2022. To ensure the required instrument performance, a series of Post-Launch Tests (PLTs) were performed and analyzed. The primary calibration source for NOAA-21 VIIRS Reflective Solar Bands (RSBs) is the Solar Diffuser (SD), which retains the prelaunch radiometric calibration standard from prelaunch to on-orbit. Upon reaching orbit, the SD undergoes degradation as a result of ultraviolet solar illumination. The rate of SD degradation (called the H-factor) is monitored by a Solar Diffuser Stability Monitor (SDSM). The initial H-factor’s instability was significantly improved by deriving a new sun transmittance function from the yaw maneuver and one-year SDSM data. The F-factors (normally represent the inverse of instrument gain) thus calculated for the Visible/Near-Infrared (VISNIR) bands were proven to be stable throughout the first year of the on-orbit operations. On the other hand, the Shortwave Infrared (SWIR) bands unexpectedly showed fast degradation, which is possibly due to unknown substance accumulation along the optical path. To mitigate these SWIR band gain changes, the NOAA VIIRS Sensor Data Record (SDR) team used an automated calibration software package called RSBautoCal. In March 2024, the second middle-mission outgassing event to reverse SWIR band degradation was shown to be successful and its effects are closely monitored. Finally, the deep convective cloud trends and lunar collection results validated the operational F-factors. This paper summarizes the preliminary on-orbit radiometric calibration updates and performance for the NOAA-21 VIIRS SDR products in the RSB.

In Situ Encapsulation of SnS2/MoS2 Heterojunctions by Amphiphilic Graphene for High-Energy and Ultrastable Lithium-Ion Anodes.

Lithium-ion batteries with transition metal sulfides (TMSs) anodes promise a high capacity, abundant resources, and environmental friendliness, yet they suffer from fast degradation and low Coulombic efficiency. Here, a heterostructured bimetallic TMS anode is fabricated by in situ encapsulating SnS2/MoS2 nanoparticles within an amphiphilic hollow double-graphene sheet (DGS). The hierarchically porous DGS consists of inner hydrophilic graphene and outer hydrophobic graphene, which can accelerate electron/ion migration and strongly hold the integrity of alloy microparticles during expansion and/or shrinkage. Moreover, catalytic Mo converted from lithiated MoS2 can promote the reaction kinetics and suppress heterointerface passivation by forming a building-in-electric field, thereby enhancing the reversible conversion of Sn to SnS2. Consequently, the SnS2/MoS2/DGS anode with high gravimetric and high volumetric capacities achieves 200 cycles with a high initial Coulombic efficiency of >90%, as well as excellent low-temperature performance. When the commercial Li(Ni0.8Co0.1Mn0.1)O2 (NCM811) cathode is paired with the prelithiated SnS2/MoS2/DGS anode, the full cells deliver high gravimetric and volumetric energy densities of 577Wh kg-1 and 853Wh L-1, respectively. This work highlights the significance of integrating spatial confinement and atomic heterointerface engineering to solve the shortcomings of conversion-/alloying typed TMS-based anodes to construct outstanding high-energy LIBs.

Biological performance of a bioabsorbable magnesium-magnesium phosphate cement interbody fusion cage in a porcine lumbar interbody fusion model: a feasibility study.

The aim of the study was to evaluate the feasibility of a bioabsorbable cage consisting of magnesium and magnesium phosphate cement (MPC) in a porcine lumbar interbody fusion model. Twelve male Ba-Ma mini pigs underwent lumbar discectomy and fusion with an Mg-MPC cage or a PEEK cage at the L3/L4 and L4/L5 level. Computed tomography (CT) scans were made to evaluate the distractive property by comparing average disc space height (DSH) before and at 6, 12, and 24 weeks after the operation. After the lumbar spines were harvested at 6 or 24 weeks after the operation, micro-CT examination was conducted to analyze the fusion rate, and stiffness of motion segments was investigated through mechanical tests. A histological study was performed to evaluate the tissue type, inflammation, and osteolysis in the intervertebral space. CT scans showed no significant difference between the two groups in average DSH at each time point. Micro-CT scans revealed an equal fusion rate in both groups (0% at 6 weeks, 83.3% at 24 weeks). Both groups showed time-dependent increases in stability, the Mg-MPC cages achieved an inferior stiffness at 6 weeks and a comparable stiffness at 24 weeks. Histologic evaluation showed the presence of newly formed bone in both groups. However, empty spaces were observed at the interface or around the Mg-MPC cages. Compared with the PEEK cages, the Mg-MPC cages achieved comparable distraction, fusion rate, and spinal stability at 24 weeks after the operation. However, due to inferior stiffness at the early stage and fast degradation, further modification of material composition and design are necessary.

Atomic oxygen erosion mechanism of polyimide via reactive molecular dynamics simulation and density functional theory calculation

Atomic oxygen (AO) causes serious oxidative degradation on polymeric materials in the space environment, yet understanding its reaction mechanism is a challenging task. Herein, we primarily investigate the reaction sites and reaction paths of pure polyimide material to AO erosion and propose a modification strategy involving electron-withdrawing groups to enhance the material's resistance to AO with density functional theory (DFT) and reactive force field molecular dynamics (ReaxFF MD). DFT calculations reveal that AO erosion is an electrophilic reaction, which preferentially interacts on the benzene ring with pronounced electron density distribution on the third part of the polyimide molecule. ReaxFF MD simulations validate this finding and provide additional reaction pathways that are divided into the early-stage reactions and later secondary reactions. In the early stage, only small number of AOs take part in the reactions that include the formation of CO bonds and ring opening processes. These reactions are relatively slow and majorly determine the AO resistance of the material. In the subsequent stage, AO predominantly reacts with reactive species and radicals generated from earlier reactions, leading to fast degradation. With these findings, we propose a strategy to enhance the AO resistance by introducing electron-withdrawing functional groups in the polyimides. As exemplified, the polyimide with -CF3 group shows 21.1% lower erosion yield than unmodified polymer. The present study gives a deep insight for the mechanism of AO erosion on polyimide by exploring its reaction sites and provides valuable theoretical guidance for improving the material's resistance to erosion.

Application of novel dual-ligand co metal-organic framework/graphene oxide for electrocatalytic oxidative degradation of bisphenol A in marine wastewater

The adjustment of the electron distribution of 2D metal-organic frameworks (2D-MOFs), as a hot anode candidate for electrocatalytic oxidation, is crucial for its application. In this work, a new electron distribution was achieved with dual-ligand connection and graphene oxide (GO) loading and the complex of dual-ligand 2D-MOF/GO (Co-IH/GO) exhibit faster electron transfer efficiency (Rct = 62.5) and more active sites (ID/IG = 1.01). Co-IH/GO demonstrated excellent electrocatalytic performance and achieved 100 % electrocatalytic degradation of bisphenol A (BPA) within 10 min. In addition, superior properties of stability, temperature tolerance, and pH tolerance were achieved, after 5 cycles of degradation, the catalyst was able to maintain 100 % degradation efficiency, Capable of maintaining good degradation performance over a temperature range of 25 °C–45 °C and a wide pH range of pH = 5–11. Both experimental and electron paramagnetic resonance analysis results indicated that 1O2 acted as the dominant active substrate. With the involvement of Cl− in marine wastewater, activated chlorine was also generated during the reaction, which contributed to fast BPA degradation. Furthermore, the established dual-ligand 2D-MOF/GO electrocatalytic system exhibited superior activity for the degradation of dyes and complex microflora, while the solar-driven degradation experiment shed light on the independence of fossil and stationary sources of energy.

Structure, morphology, and properties of aliphatic polyurethane elastomers from bio‐based 1,3‐propanediol

AbstractThe utilization of biomass resources in the production of bio‐based or bio‐recycled polyurethanes (PUs) enhances the sustainable development and eco‐friendliness of PU. Herein, a series of new bio‐based aliphatic poly(propylene dicarboxylate) diols were synthesized using bio‐based 1,3‐propanediol (bio‐PDO) and aliphatic dicarboxylic acids with different chain lengths. These bio‐based polyester diols and 1,4‐butanediol (BDO) reacted with 4,4′‐dicyclohexylmethane diisocyanate to produce aliphatic PU elastomers (PUEs). The study aimed to evaluate the impact of the structure of poly(propylene dicarboxylate) diols on the architecture, morphology, mechanical properties, and degradation of PUEs, thereby expanding the application of bio‐PDO. The results indicate a strong correlation between the degree of microphase separation, tensile properties, and degradation behavior of the synthesized PUEs and the number of methylene groups in the repeating unit of the poly(propylene dicarboxylate) diols. Notably, the PUE derived from poly(propylene pimelate) diol demonstrates the highest level of microphase separation and superior elasticity properties because of the high flexibility of the polyester. On the other hand, PUE prepared from poly(propylene succinate) diol exhibits the fastest degradation performance due to its high density of ester groups. Bio‐PDO based polyester diols show significant potential as raw materials for PUEs with biodegradable and adjustable mechanical properties.Highlights Poly(propylene dicarboxylate) diols were prepared from bio‐based 1,3‐propanediol. The poly(propylene dicarboxylate) diols based polyurethane elastomers (PUEs) have high tensile strength (>22 MPa) and elongation at break (>920%). The morphology, mechanical properties and degradation of PUEs are highly related to the structure of the poly(propylene dicarboxylate) diols. The increasing repeating unit length of the poly(propylene dicarboxylate) diols increases elastic recovery of PUEs.

Hydrothermally synthesized MoS2 NFs toward efficient supercapacitor and fast photocatalytic degradation of MB

Hydrothermally synthesized MoS2 NFs toward efficient supercapacitor and fast photocatalytic degradation of MB

Biodegradation of the cyanobacterial toxin anatoxin-a by a Bacillus subtilis strain isolated from a eutrophic lake in Saudi Arabia.

Anatoxin-a (ATX-a) is a neurotoxin produced by some species of cyanobacteria. Due to its water solubility and stability in natural water, it could pose health risks to human, animals, and plants. Conventional water treatment techniques are not only insufficient for the removal of ATX-a, but they also result in cell lysis and toxin release. The elimination of this toxin through biodegradation may be a promising strategy. This study examines for the first time the biodegradation of ATX-a to a non-toxic metabolite (Epoxy-ATX-a) by a strain of Bacillus that has a history of dealing with toxic cyanobacteria in a eutrophic lake. The Bacillus strain AMRI-03 thrived without lag phase in a lake water containing ATX-a. The strain displayed fast degradation of ATX-a, depending on initial toxin concentration. At the highest initial concentrations (50 & 100µg L- 1), total ATX-a degradation took place in 4 days, but it took 6 & 7 days at lower concentrations (20, 10, and 1µg L- 1, respectively). The ATX-a biodegradation rate was also influenced by the initial toxin concentration, reaching its maximum value (12.5µg L- 1 day- 1) at the highest initial toxin concentrations (50 & 100µg L- 1). Temperature and pH also had an impact on the rate of ATX-a biodegradation, with the highest rates occurring at 25 and 30 ºC and pH 7 and 8. This nontoxic bacterial strain could be immobilized within a biofilm on sand filters and/or sludge for the degradation and removal of ATX-a and other cyanotoxins during water treatment processes, following the establishment of mesocosm experiments to assess the potential effects of this bacterium on water quality.

Intrinsic doping and ageing of indium oxide thin films

Indium oxide (In2O3) is one of the most used materials for the synthesis of transparent electronics devices and currently tin-doped indium oxide (ITO) dominates the field of Transparent Conductive Oxides for most applications, from ICT to photovoltaics. In this work we present a study on the responses of indium oxide upon the formation, and stabilization, of point defects induced with different methods. After the deposition of In2O3 thin films via RF magnetron sputtering, treatments such as Ion Implantation (I.I.), Ultraviolet (UV) irradiation and Sun exposure were employed to generate oxygen vacancies as intrinsic dopants. Both I.I. and UV irradiations significantly improved the electrical conductivity of films, increasing the carrier density by up to 3 orders of magnitude. Moreover, after I.I. also the crystalline quality of the films was enhanced.To monitor the stability of oxygen vacancies upon exposure to ambient atmosphere, the ageing of samples was followed and recorded for a couple of weeks, reporting a fast and strong degradation of electrical properties. As a facile strategy to counteract the sheet resistance increase, samples were encapsulated in an ultra-thin (≈10 nm) SiO2 layer deposited via sputtering. Irradiated and encapsulated films retained a much lower sheet resistance throughout the observation time, preserving the samples conductivity.

Biodegradation of mixed litter-derived dissolved organic matter with varying evenness in a temperate freshwater wetland.

Litter-derived dissolved organic matter (DOM) plays an essential role in biogeochemical cycles. In wetlands, species relative abundance and its change have great influences on input features of litter-derived DOM, including chemical characteristics per se and functional diversity of chemical characteristics. Functional diversity is an important factor controlling organic matter biodegradation, but little is known in terms of the DOM. We mixed litter leachates of four macrophytes with a constant concentration (20mg DOC L-1) but varying dominant species and volume ratios, i.e. 15:1:1:1 (low-evenness), 5:1:1:1 (mid-evenness), and 2:1:1:1 (high-evenness), generating a gradient of chemical characteristics and functional diversity (represented by functional dispersion index FDis). Based on a 42-d incubation, we measured degradation dynamics of these DOM mixtures, and analyzed potential determinants. After 42days of incubation, the high-evenness treatments, along with mid-evenness treatments sometimes, had most degradation, while the low-evenness treatments always had least degradation. The degradation of mixtures related significantly to not only the volume-weighted mean chemical characteristics but also FDis. Furthermore, the FDis even explained more variation of degradation. The non-additive mixing effects, synergistic effects (faster degradation than predicted) in particular, on degradation of DOM mixtures were rather common, especially in the high- and mid-evenness treatments. Remarkably, the mixing effects increased linearly with the FDis values (r2adj. = 0.426). This study highlights the critical role of functional diversity in regulating degradation of mixed litter-derived DOM. Resulting changes in chemistry and composition of litter leachates due to plant community succession may exert substantial influences on biogeochemical cycling.

The problem of anthropogenic microfibres in karst systems: Assessment of water and submerged sediments

A new worrying micropollutant threathens natural environments: the microfibres (MFs). Natural, regenerated and synthetic MFs have been detected in different environments, as well as in organisms. While synthetic MFs are generally detected in microplastic analyses, natural and regenerated MFs are not taken into account, or are wrongly considered plastics. They are generally considered biodegradable even if their degradation processes in ecosystems are poorly known. Their potential faster degradation could release toxic compounds, and their characteristics could led to a long-term accumulation in the environment. Understanding their dangerousness and the possible impact they could have on ecosystems is fundamental for environment conservation. We collected and investigated water and submerged sediment samples in different caves and springs of the Classical Karst Region (NE Italy), rich in protected habitats and species. MFs were analysed via microscopy and spectroscopy. MFs were found in all samples, highlighting pollution in surface and subterranean habitats of the karst system. MF concentration was higher in submerged sediments respect to waters, highlighting an accumulation of MFs over time. Big microfibres were less abundant, and MF amount increased with the decrease in the considered size. More than 80% of fibres were fluorescent under UV light. Fluorescent MFs were especially transparent, while non-fluorescent ones were mainly black and blue. Most MFs were cellulosic, and synthetic MFs represent only 15–22%, highlighting a significant gap between the MF composition detected in natural environments and the global production of synthetic textiles in recent times. Synthetic MFs were more abundant in waters. Our results improve the knowledge on micropollutants in karst environments, laying the foundations for future research. MF pollution monitoring in karst areas must become a priority for species protection, habitat conservation, and waters management, improving analyses on a larger number of aquatic environments, taking into account the ecological connections between surface and subterranean habitats.

Trypsin-encoding gene function of efficient star polycation nanomaterial-mediated dsRNA feeding delivery system of Grapholita molesta.

Grapholita molesta is an important and harmful fruit pest worldwide, with widespread feeding hosts. Trypsin, an indispensable hydrolytic digestive protease in the insect gut, is crucial in digestion, growth and development. We analyzed the characteristics of the trypsin-encoding genes, screened for the optimal dose of RNAi mediated by nanocarriers, and investigated various indices of larval growth and development of G. molesta. Gut content (GC) and RNase A degraded double-stranded RNA (dsRNA), with a faster degradation rate at higher concentrations. Star polycation (SPc) nanomaterials protected dsGFP from degradation by anion-cation binding and did not migrate through agarose gel. The key conserved motifs of the trypsin-encoding genes were similar, exhibiting high homology with those in other lepidopteran insects. An interference efficiency of ≈70% was achieved with SPc nanomaterial-mediated RNA interference with 0.05 μg dsRNA. The efficiency of continuous interference was stable. Trypsin activity, body weight of 8-day-old larvae, pupal weight and emergence rate were significantly reduced, and the larval stage was significantly prolonged. The investigated trypsin gene is a key target gene in the growth and development of G. molesta. We investigated the efficiency and convenience of feeding SPc nanomaterials in a functional study of insects. Our results provide valuable data for the development of efficient trypsin-targeting pesticides. © 2024 Society of Chemical Industry.

Photodegradation of bisphenol A (BPA) in coastal aquaculture waters: Influencing factors, products, and pathways

Bisphenol A (BPA), an endocrine-disrupting contaminant, is ubiquitous in the environment due to its presence in plastics, wastewater, and agricultural runoff. This study investigated the photodegradation behavior of BPA in coastal aquaculture waters near Qingdao, China. Lower salinity promoted BPA photodegradation, while higher salinity has an inhibitory effect, suggesting slower degradation in seawater compared to ultrapure water. Triplet-excited dissolved organic matter (3DOM*) was identified as the primary mediator of BPA degradation, with additional contributions from hydroxyl radicals (•OH), singlet oxygen (1O2), and halogen radicals (HRS). Alepocephalidae aquaculture water exhibited the fastest degradation rate, likely due to its high DOM and nitrate/nitrite (NO3−/NO2−) content, which are sources of 3DOM* and •OH. A positive correlation existed between NO3−/NO2− concentration and the BPA degradation rate. Ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS) analysis identified the primary BPA photodegradation products, formed mainly through oxidative degradation, hydroxyl substitution, nitration, and chlorination pathways. Elucidating these photodegradation mechanisms provides valuable insights into the environmental fate and potential ecological risks of BPA in aquaculture environments. This knowledge can inform strategies for marine environmental protection and the development of sustainable practices.

Chondroitin Sulfate Derivative Cross-Linking of Decellularized Heart Valve for the Improvement of Mechanical Properties, Hemocompatibility, and Endothelialization.

Tissue-engineered heart valve (TEHV) has emerged as a prospective alternative to conventional valve prostheses. The decellularized heart valve (DHV) represents a promising TEHV scaffold that preserves the natural three-dimensional structure and retains essential biological activity. However, the limited mechanical strength, fast degradation, poor hemocompatibility, and lack of endothelialization of DHV restrict its clinical use, which is necessary for ensuring its long-term durability. Herein, we used oxidized chondroitin sulfate (ChS), one of the main components of the extracellular matrix with various biological activities, to cross-link DHV to overcome the above problems. In addition, the ChS-adipic dihydrazide was used to react with residual aldehyde groups, thus preventing potential calcification. The results indicated notable enhancements in mechanical properties and resilience against elastase and collagenase degradation in vitro as well as the ability to withstand extended periods of storage without compromising the structural integrity of valve scaffolds. Additionally, the newly cross-linked valves exhibited favorable hemocompatibility in vitro and in vivo, thereby demonstrating exceptional biocompatibility. Furthermore, the scaffolds exhibited traits of gradual degradation and resistance to calcification through a rat subcutaneous implantation model. In the rat abdominal aorta implantation model, the scaffolds demonstrated favorable endothelialization, commendable patency, and a diminished pro-inflammatory response. As a result, the newly constructed DHV scaffold offers a compelling alternative to traditional valve prostheses, which potentially advances the field of TEHV.

Stimuli-Responsive mRNA Vaccines to Induce Robust CD8+ T Cell Response via ROS-Mediated Innate Immunity Boosting.

The messenger RNA (mRNA) vaccines hold great significance in contagion prevention and cancer immunotherapy. However, safely and effectively harnessing innate immunity to stimulate robust and durable adaptive immune protection is crucial, yet challenging. In this study, we synthesized a library of stimuli-responsive bivalent ionizable lipids (srBiv iLPs) with smart molecular blocks responsive to esterase, H2O2, cytochrome P450, alkaline phosphatase, nitroreductase, or glutathione (GSH), aiming to leverage physiological cues to trigger fast lipid degradation, promote mRNA translation, and induce robust antitumor immunity via reactive oxygen species (ROS)-mediated boosting. After subcutaneous immunization, esterase-responsive vaccine (eBiv-mVac) was rapidly internalized and transported into the draining lymph nodes. It then underwent fast decaging and self-immolative degradation in esterase-rich antigen-presenting cells, releasing sufficient mRNA for antigen translation and massive reactive quinone methides to elevate ROS levels. This resulted in broad activation of innate immunity to boost T cell response, prompting a large number of primed antigen-specific CD8+ T cells to circulate and infiltrate into tumors (>1000-fold versus unvaccinated control), thereby orchestrating innate and adaptive immunity to control tumor growth. Moreover, by further combining our vaccination strategy with immune checkpoint blockade, we demonstrated a synergism that significantly amplified the magnitude and function of antigen-specific CD8+ T cells. This, in turn, caused potent systemic antitumor efficacy and prolonged survival with high complete response rate in xenograft and metastasis models. Overall, our generalized stimuli-responsive mRNA delivery platform promises a paradigm shift in the design of potent vaccines for cancer immunotherapy, as well as effective and precise carriers for gene editing, protein replacement, and cell engineering.