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    Effect of Hydrophobic Chain Length in Amphiphilic Chitosan Conjugates on Intracellular Drug Delivery and Smart Drug Release of Redox-Responsive Micelle

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    Three redox-sensitive nanocarriers were rationally designed based on amphiphilic low molecular weight chitosan-cystamine-octylamine/dodecylamin/cetylamine (LC-Cys-OA, LC-Cys-DA, LC-Cys-CA) conjugates containing disulfide linkage for maximizing therapeutic effect by regulating hydrophobic interaction. The resultant spherical micelles had the characteristics of low CMC, suitable size, excellent biosafety and desired stability. The drug-loaded micelles were fabricated by embedding doxorubicin (Dox) into the hydrophobic cores. The effect of hydrophobic chain lengths of amphiphilic conjugates on encapsulation capacity, redox sensitivity, trigger-release behavior, cellular uptake efficacy, antitumor effect and antimigratory activity of Dox-loaded micelles was systematically investigated. Studies found that Dox-loaded LC-Cys-CA micelle had superior loading capacity and enhanced redox sensitivity compared with the other two micelles. Release assay indicated that the three Dox-loaded micelles maintained sufficiently stability in normal blood circulation but rapidly disintegrated in tumor cells. More importantly, the LC-Cys-CA micelle with a longer hydrophobic chain length exhibited a higher accumulative Dox release percentage than the other two micelles. Additionally, an increase in hydrophobic chain lengths of amphiphilic conjugates improved cellular uptake efficiency, antitumor effect and antimigration activity of Dox-loaded micelles, which could be explained by enhanced loading ability and redox sensitivity. Our research was expected to provide a viable platform for achieving a desired therapeutic efficacy via the alteration of hydrophobic interaction

    Chemical Cues Released by Predators' Consumption of Heterospecific Prey Alter the Embryogenesis of Zebrafish

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    Environmentally cued hatching is prevalent, diverse, and crucial to many animals' survival. Fish embryos use a variety of chemical cues to initiate hatching to avoid potential predators, yet the function of chemical cues released from the predatory consumption of heterospecific prey is largely unknown. Zebra cichlids (Metriaclima estherae) are ferocious predators that can feed on medaka (Oryzias latipes), though it is impossible for this to occur in their natural habitat. Zebrafish (Danio rerio) embryos have been employed as experimental subjects due to their sensitivity to a variety of chemical signals. In this study, zebrafish embryos were subjected to three types of chemical signals: predator cues (PCs, released from cichlids), heterospecific cues (HCs, released from medaka), and heterospecific dietary cues (HDCs, released from cichlids that have ingested medaka). As a result, the hatching times of zebrafish embryos were accelerated by 6.8% and 12.6% by PCs and HDCs, respectively. PCs and HDCs cause significantly reduced morphology in zebrafish embryos, including regarding total length, eye length, dorsal fin length, trunk height, caudal fin height, and body cavity, and increase yolk sac height. The PCs and HDCs diminished the larvae's motion at 120 and 144 h post fertilization (hpf), which could be attributed to non-developmental embryogenesis. Overall, the impacts of HDCs on embryonic hatching, developmental morphology, and locomotor were more pronounced in comparison with PCs. Our findings demonstrate that predators' dietary cues, even those released after predation on heterospecific prey, can modify embryogenesis, highlighting the critical functions of chemical signals in predation risk assessment using embryos

    Aggregating <i>Synechococcus </i>contributes to particle organic carbon export in coastal estuarine waters: Its lineage features and assembly processes

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    The release and deposition of phytoplankton-derived particulate organic matter is crucial in marine carbon export, yet the roles of picoplankton in these processes were seldom considered. Therefore, this study aimed to shed light on the matter by investigating the aggregating (AG) lifestyle of Synechococcus, a main group of picoplankton, in the coastal waters of the Yellow River Estuary with ample sediments acting as ballast minerals. We revealed that AG Synechococcus constituted a substantial portion, maximally reaching up to 85.4 %, of the total Synechococcus population. Pearson correlations and random forest (RF) regression analyses found significant connections (p < 0.01) between AG Synechococcus and the content of particulate organic carbon (POC), which emphasized its underlying role in facilitating POC export in this region. Furthermore, by employing highthroughput sequencing of the RNA polymerase gene (rpoC1), it was demonstrated that S5.1 clade I exhibited a significantly higher proportion in the AG fraction than in the free-living (FL) fraction (p < 0.05). This suggests distinct inclinations in the phylogenetic preference for different Synechococcus lineages between different lifestyles in the studied area. Finally, we ascertained "small-world" and higher robustness attributes of aggregates formed through the co-occurrence construction between Synechococcus and heterotrophic bacteria, likely facilitated by the reciprocal exchange of carbon and nitrogen elements. Overall, these findings have implications for our understanding of the role of Synechococcus in the ecology and biogeochemistry of marine ecosystems, and they are significant for more accurately evaluating the contribution of picophytoplankton in ocean carbon export

    Climate and mineral accretion as drivers of mineral-associated and particulate organic matter accumulation in tidal wetland soils

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    Tidal wetlands sequester vast amounts of organic carbon (OC) and enhance soil accretion. The conservation and restoration of these ecosystems is becoming increasingly geared toward "blue" carbon sequestration while obtaining additional benefits, such as buffering sea-level rise and enhancing biodiversity. However, the assessments of blue carbon sequestration focus primarily on bulk SOC inventories and often neglect OC fractions and their drivers; this limits our understanding of the mechanisms controlling OC storage and opportunities to enhance blue carbon sinks. Here, we determined mineral-associated and particulate organic matter (MAOM and POM, respectively) in 99 surface soils and 40 soil cores collected from Chinese mangrove and saltmarsh habitats across a broad range of climates and accretion rates and showed how previously unrecognized mechanisms of climate and mineral accretion regulated MAOM and POM accumulation in tidal wetlands. MAOM concentrations (8.0 +/- 5.7gCkg(-1)) (+/- standard deviation) were significantly higher than POM concentrations (4.2 +/- 5.7gCkg(-1)) across the different soil depths and habitats. MAOM contributed over 51.6 +/- 24.9% and 78.9 +/- 19.0% to OC in mangrove and saltmarsh soils, respectively; both exhibited lower autochthonous contributions but higher contributions from terrestrial or marine sources than POM, which was derived primarily from autochthonous sources. Increased input of plant-derived organic matter along the increased temperature and precipitation gradients significantly enriched the POM concentrations. In contrast, the MAOM concentrations depended on climate, which controlled the mineral reactivity and mineral-OC interactions, and on regional sedimentary processes that could redistribute the reactive minerals. Mineral accretion diluted the POM concentrations and potentially enhanced the MAOM concentrations depending on mineral composition and whether the mineral accretion benefited plant productivity. Therefore, management strategies should comprehensively consider regional climate while regulating sediment supply and mineral abundance with engineering solutions to tap the OC sink potential of tidal wetlands

    Inversion and Evaluation of Oil Thickness Based on a C-Band Microwave Experiment

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    In the event of an offshore oil spill accident, timely acquisition of the oil spill area and volume is of great significance for scientific decision-making and emergency responses. The remote sensing acquisition breakthrough point pertaining to oil spill volume is the determination of oil film thickness (OFT). Several rules have been identified based on the empirical relationships between the oil film's normalized radar cross section (NRCS) obtained from C-band field experiments and the inversion of the OFT retrieved from synchronous optical images. Inversion formulas suitable for different OFT ranges under certain conditions are established. Following experimental data verification, our results show that the correlation coefficient is greater than 0.99, and the root mean square error (RMSE) is less than 15 mu m. The damping ratio (DR) of the spaceborne synthetic aperture radar (SAR) image is used as a bridge to establish the correlation between the optical OFT and the SAR-inverted OFT. The pixels of the SAR image are classified and substituted into different inversion formulas to obtain the OFT distributions in the SAR images. Then, the OFT distributions of the SAR-inverted and optical images are compared and evaluated. It is found that the OFT of the SAR image can explain the spatial distribution of the oil film. This study provides a new idea for spaceborne SAR OFT inversion

    Distribution, sources, and eco-risk of Current-Use Pesticides (CUPs) in the coastal waters of the northern Shandong Peninsula, China

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    This study investigated the spatial distributions and seasonal variations of 19 CUPs in the coastal areas of the Shandong Peninsula and its surrounding rivers and assessed their ecological risk. In freshwater and seawater, insecticides (chlorpyrifos, methoxychlor, and pyridaben), as well as fungicides (fenarimol) and herbicides (dichlobenil) were the main pollutants (Detection Frequency: 100 %). Spatially, during winter, the regional pollution levels of Sigma(19)CUPs in seawater showed a trend of Laizhou Bay (LZB, mean:4.13 ng L-1) > Yellow River Estuary (YRE, mean:2.57 ngL(-1)) > Bohai Bay (BHB, mean:2.21 ng L-1) > Yanwei Area (YWA, mean:1.94 ng L-1). The similarities of major substances between rivers and the marine environment suggest that river discharge is the main source of CUPs pollution in coastal areas. In summer, CUPs in rivers posed a high risk. In winter, the risk significantly decreased, indicating a moderate overall risk. Seawater exhibited a low risk in winter

    Carbon fluxes of China's coastal wetlands and impacts of reclamation and restoration

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    Coastal wetlands play an important role in regulating atmospheric carbon dioxide (CO2) concentrations and contribute significantly to climate change mitigation. However, climate change, reclamation, and restoration have been causing substantial changes in coastal wetland areas and carbon exchange in China during recent decades. Here we compiled a carbon flux database consisting of 15 coastal wetland sites to assess the magnitude, patterns, and drivers of carbon fluxes and to compare fluxes among contrasting natural, disturbed, and restored wetlands. The natural coastal wetlands have the average net ecosystem exchange of CO2 (NEE) of -577 g C m(-2) year(-1), with -821 g C m(-2) year(-1) for mangrove forests and -430 g C m(-2) year(-1) for salt marshes. There are pronounced latitudinal patterns for carbon dioxide exchange of natural coastal wetlands: NEE increased whereas gross primary production (GPP) and respiration of ecosystem decreased with increasing latitude. Distinct environmental factors drive annual variations of GPP between mangroves and salt marshes; temperature was the dominant controlling factor in salt marshes, while temperature, precipitation, and solar radiation were co-dominant in mangroves. Meanwhile, both anthropogenic reclamation and restoration had substantial effects on coastal wetland carbon fluxes, and the effect of the anthropogenic perturbation in mangroves was more extensive than that in salt marshes. Furthermore, from 1980 to 2020, anthropogenic reclamation of China's coastal wetlands caused a carbon loss of similar to 3720 Gg C, while the mangrove restoration project during the period of 2021-2025 may switch restored coastal wetlands from a carbon source to carbon sink with a net carbon gain of 73 Gg C. The comparison of carbon fluxes among these coastal wetlands can improve our understanding of how anthropogenic perturbation can affect the potentials of coastal blue carbon in China, which has implications for informing conservation and restoration strategies and efforts of coastal wetlands

    Carbon fluxes of China's coastal wetlands and impacts of reclamation and restoration

    No full text
    Coastal wetlands play an important role in regulating atmospheric carbon dioxide (CO2) concentrations and contribute significantly to climate change mitigation. However, climate change, reclamation, and restoration have been causing substantial changes in coastal wetland areas and carbon exchange in China during recent decades. Here we compiled a carbon flux database consisting of 15 coastal wetland sites to assess the magnitude, patterns, and drivers of carbon fluxes and to compare fluxes among contrasting natural, disturbed, and restored wetlands. The natural coastal wetlands have the average net ecosystem exchange of CO2 (NEE) of -577 g C m(-2) year(-1), with -821 g C m(-2) year(-1) for mangrove forests and -430 g C m(-2) year(-1) for salt marshes. There are pronounced latitudinal patterns for carbon dioxide exchange of natural coastal wetlands: NEE increased whereas gross primary production (GPP) and respiration of ecosystem decreased with increasing latitude. Distinct environmental factors drive annual variations of GPP between mangroves and salt marshes; temperature was the dominant controlling factor in salt marshes, while temperature, precipitation, and solar radiation were co-dominant in mangroves. Meanwhile, both anthropogenic reclamation and restoration had substantial effects on coastal wetland carbon fluxes, and the effect of the anthropogenic perturbation in mangroves was more extensive than that in salt marshes. Furthermore, from 1980 to 2020, anthropogenic reclamation of China's coastal wetlands caused a carbon loss of similar to 3720 Gg C, while the mangrove restoration project during the period of 2021-2025 may switch restored coastal wetlands from a carbon source to carbon sink with a net carbon gain of 73 Gg C. The comparison of carbon fluxes among these coastal wetlands can improve our understanding of how anthropogenic perturbation can affect the potentials of coastal blue carbon in China, which has implications for informing conservation and restoration strategies and efforts of coastal wetlands

    Improvement of the selectivity of a molecularly imprinted polymer-based potentiometric sensor by using a specific functional monomer

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    Potentiometric sensors based on the molecularly imprinted polymers (MIPs) as the receptors have been successfully developed for determination of various organic and biological species. However, these MIP receptors may suffer from problems of low selectivity. Especially, it would be difficult to distinguish the target analyte from its structurally similar interferents. In this work, we propose a novel strategy that using specific functional monomer to fabricate MIP with high selectivity towards the target molecule. The density functional theory calculations are used to investigate the interactions between the template and the functional monomer. The binding energy between the template and functional monomer can be used as the criterion for identifying the optimal monomer. As a proof-of-concept experiment, bisphenol A (BPA) is chosen as the template and the MIP is synthesized by the precipitation polymerization method using the specific allyl-beta-cyclodextrin (allyl-beta-CD) with high affinity towards BPA as the functional monomer. The high-affinity MIP is employed as the receptor for the construction of the potentiometric sensor. The proposed potentiometric sensor based on the MIP using allyl-beta-CD as the functional monomer shows an improved response performance in terms of selectivity and sensitivity compared to the conventional potentiometric sensor based on the MIP with the common monomer (i.e., methacrylic acid). This allyl-beta-CD MIP-based potentiometric sensor shows a detection limit of 0.29 mu M for BPA, which is about one order of magnitude lower than that obtained by the conventional MIP-based potentiometric sensor. We believe that utilizing a functional monomer with specific recognition ability towards target in the fabrication of MIP could provide an appealing way to construct highly selective MIP-based electrochemical and optical sensors

    Unveiling the fast adsorption and desorption of heavy metals on/off nanoplastics by real-time in-situ potentiometric sensing

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    Nanoplastics (<1 mu m) can serve as a transport vector of environmental pollutants (e.g., heavy metals) and change their toxicities and bioavailabilities. Up to date the behaviors of adsorption and desorption heavy metals on/off nanoplastics are largely unknown. Herein, polymeric membrane potentiometric ion sensors are proposed for in-situ assessment of the real-time kinetics of heavy metal adsorption and desorption on/off nanoplastics. Results show that nanoplastics can adsorb and release heavy metals in a fast manner, indicating their superior ability in transferring heavy metals. The adsorption behaviors are closely related to the characteristics of nanoplastics and background electrolytes. Particle aggregation and increases in salinity and acidity suppress the adsorption of heavy metals on nanoplastics. The desorption efficiencies of different heavy metals are Pb2+ (31 %) < Cu2+ (40 %) < Cd2+ (97 %). Our proposed method is applicable for the detection of the plastic pollutants with size <100 nm and of the samples with high salinities (e.g., seawater). This work would provide new insights into the assessment of environmental risks posed by nanoplastics and heavy metals

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