Greater Bioaccessibility of Silver Nanoparticles in Earthworm than in Soils.

The buildup of silver nanoparticles (AgNPs) in soil has raised mounting concerns on their impact on human health. Human are exposed to AgNPs in soils via hand-to-mouth activities (direct exposure) and food consumption (indirect exposure). However, the bioaccessibility of AgNPs under these exposure scenarios remains largely unknown. We used a physiologically based extraction test (PBET) to assess Ag bioaccessibility in AgNP-containing soils and in earthworms (Pheretima guillemi) cultured in these soils. Silver bioaccessibility was 1.2 - 8.4% and 8.1 - 78.7% upon direct exposure and indirect exposure, respectively. These results indicated greater Ag bioaccessibility in earthworms than in soils. Moreover, particle size decreased upon direct exposure, but remained constant upon indirect exposure in wetland soil, as revealed by single particle inductively coupled plasma-mass spectrometry (spICP-MS) analysis. Our results highlight the importance of indirect exposure to NPs.

Analysis of risk factors and development of a nomogram prediction model for renal tubular acidosis in primary Sjogren syndrome patients.

OBJECTIVE: To investigate the risk factors of renal tubular acidosis (RTA) in patients with primary Sjögren's syndrome (pSS) and create a personalized nomogram for predicting pSS-RTA patients. METHOD: Data from 99 pSS patients who underwent inpatient treatment at our hospital from January 2012 to January 2024 were retrospectively collected and analyzed. Bootstrap resampling technique, single-factor, and multi-factor logistic regression analyses were used to explore the risk factors for pSS-RTA. A nomogram was developed based on the results of the multivariate logistic model. The model was evaluated through receiver operating characteristic curve, C-index, calibration curve, and decision curve analysis. In addition, we graded the severity of pSS-RTA patients and used univariate analysis to assess the relationship between pSS-RTA severity and risk factors. RESULTS: A multivariate logistic regression analysis revealed that concurrent thyroid disease, long symptom duration, subjective dry mouth, and positive RF were independent risk factors for pSS-RTA patients. Based on them, a personalized nomogram predictive model was established. With a p-value of 0.657 from the Hosmer-Lemeshow test, the model demonstrated a good fit. The AUC values in the training and validation groups were 0.912 and 0.896, indicating a strong discriminative power of the nomogram. The calibration curves for the training and validation groups closely followed the diagonal line with a slope of 1, confirming the model's reliable predictive ability. Furthermore, the decision curve analysis showed that the nomogram model had a net benefit in predicting pSS-RTA, emphasizing its clinical value.This study did not find an association between the severity of pSS-RTA and risk factors. DISCUSSION: We developed a nomogram to predict RTA occurrence in pSS patients, and it is believed to provide a foundation for early identification and intervention for high-risk pSS patients.

Microplastic co-exposure elevates cadmium accumulation in mouse tissue after rice consumption: Mechanisms and health implications.

Rice cadmium (Cd) and microplastics are prevalent contaminants, posing a co-exposure threat to humans by means of dietary intake. To assess whether co-exposure of microplastics affects the bioavailability of rice Cd, mice were exposed to Cd-contaminated rice with microplastic co-exposure. We found that polyethylene (PE), polystyrene (PS), polypropylene (PP), and polyamide (PA) microplastic co-exposure via diet consumption (2 µg g-1) caused 1.17-1.38-fold higher Cd accumulation in tissue of mice fed by Cd-rice. For mice with co-exposure of PE microplastics, the higher rice-Cd bioavailability corresponded to colonization of Lactobacillus reuteri (38.9 % vs 17.5 %) in the gut compared to control mice, which caused higher production of gut metabolites particularly peptides, likely causing a 'side effect' of elevating Cd solubility in the intestinal lumen. In addition, abundance of sphingosine 1-phosphate in the gut of mice was reduced under PE microplastic exposure, which may reduce intracellular calcium ions (Ca2+) in enterocytes and form a weaker competition in pumping of intracellular Ca2+ and Cd2+ across the basolateral membrane of enterocytes, leading to higher Cd2+ transport efficiency. The results suggest elevated Cd exposure risk from rice consumption with microplastic co-exposure at environmentally relevant low concentrations.

Growth, Enzymatic, and Transcriptomic Analysis of xyr1 Deletion Reveals a Major Regulator of Plant Biomass-Degrading Enzymes in Trichoderma harzianum.

The regulation of plant biomass degradation by fungi is critical to the carbon cycle, and applications in bioproducts and biocontrol. Trichoderma harzianum is an important plant biomass degrader, enzyme producer, and biocontrol agent, but few putative major transcriptional regulators have been deleted in this species. The T. harzianum ortholog of the transcriptional activator XYR1/XlnR/XLR-1 was deleted, and the mutant strains were analyzed through growth profiling, enzymatic activities, and transcriptomics on cellulose. From plate cultures, the Δxyr1 mutant had reduced growth on D-xylose, xylan, and cellulose, and from shake-flask cultures with cellulose, the Δxyr1 mutant had ~90% lower ß-glucosidase activity, and no detectable ß-xylosidase or cellulase activity. The comparison of the transcriptomes from 18 h shake-flask cultures on D-fructose, without a carbon source, and cellulose, showed major effects of XYR1 deletion whereby the Δxyr1 mutant on cellulose was transcriptionally most similar to the cultures without a carbon source. The cellulose induced 43 plant biomass-degrading CAZymes including xylanases as well as cellulases, and most of these had massively lower expression in the Δxyr1 mutant. The expression of a subset of carbon catabolic enzymes, other transcription factors, and sugar transporters was also lower in the Δxyr1 mutant on cellulose. In summary, T. harzianum XYR1 is the master regulator of cellulases and xylanases, as well as regulating carbon catabolic enzymes.

Reduced dietary Ca, Cu, Zn, Mn, and Mg bioavailability but increased Fe bioavailability with polyethylene microplastic ingestion in a mouse model: Changes in intestinal permeability and gut metabolites.

Microplastics emerge as a new environmental and human health crisis. Minimal research exists on effects of microplastic ingestion on the oral bioavailability of minerals (Fe, Ca, Cu, Zn, Mn, and Mg) in the gastrointestinal tract via impacting intestinal permeability, mineral transcellular transporters, and gut metabolites. Here, mice were exposed to polyethylene spheres of 30 and 200 µm (PE-30 and PE-200) in diet (2, 20, and 200 µg PE g-1) for 35 d to determine the microplastic effects on mineral oral bioavailability. Results showed that for mice fed diet amended with PE-30 and PE-200 at 2-200 µg g-1, Ca, Cu, Zn, Mn, and Mg concentrations in the small intestine tissue were 43.3-68.8 %, 28.6-52.4 %, 19.3-27.1 %, 12.9-29.9 %, and 10.2-22.4 % lower compared to control mice, suggesting hampered bioavailability of these minerals. In addition, Ca and Mg concentrations in mouse femur were 10.6 % and 11.0 % lower with PE-200 at 200 µg g-1. In contrast, Fe bioavailability was elevated, as suggested by significantly (p < 0.05) higher Fe concentration in the intestine tissue of mice exposed to PE-200 than control mice (157-180 vs. 115 ± 7.58 µg Fe g-1) and significantly (p < 0.05) higher Fe concentrations in liver and kidney with PE-30 and PE-200 at 200 µg g-1. Following PE-200 exposure at 200 µg g-1, genes coding for duodenal expression of tight junction proteins (e.g., claudin 4, occludin, zona occludins 1, and cingulin) were significantly up-regulated, possibility weakening intestinal permeability to Ca, Cu, Zn, Mn, and Mg ions. The elevated Fe bioavailability was possibly related to microplastic-induced greater abundances of small peptides in the intestinal tract, which inhibited Fe precipitation and elevated Fe solubility. Results showed that microplastic ingestion may cause Ca, Cu, Zn, Mn, and Mg deficiency but Fe overload via altering intestinal permeability and gut metabolites, posing a threat to human nutrition health.

Microplastics affect arsenic bioavailability by altering gut microbiota and metabolites in a mouse model.

Microplastics exposure is a new human health crisis. Although progress in understanding health effects of microplastic exposure has been made, microplastic impacts on absorption of co-exposure toxic pollutants such as arsenic (As), i.e., oral bioavailability, remain unclear. Microplastic ingestion may interfere As biotransformation, gut microbiota, and/or gut metabolites, thereby affecting As oral bioavailability. Here, mice were exposed to arsenate (6 µg As g-1) alone and in combination with polyethylene particles of 30 and 200 µm (PE-30 and PE-200 having surface area of 2.17 × 103 and 3.23 × 102 cm2 g-1) in diet (2, 20, and 200 µg PE g-1) to determine the influence of microplastic co-ingestion on arsenic (As) oral bioavailability. By determining the percentage of cumulative As consumption recovered in urine of mice, As oral bioavailability increased significantly (P < 0.05) from 72.0 ± 5.41% to 89.7 ± 6.33% with PE-30 at 200 µg PE g-1 rather than with PE-200 at 2, 20, and 200 µg PE g-1 (58.5 ± 19.0%, 72.3 ± 6.28%, and 69.2 ± 17.8%). Both PE-30 and PE-200 exerted limited effects on pre- and post-absorption As biotransformation in intestinal content, intestine tissue, feces, and urine. They affected gut microbiota dose-dependently, with lower exposure concentrations having more pronounced effects. Consistent with the PE-30-specific As oral bioavailability increase, PE exposure significantly up-regulated gut metabolite expression, and PE-30 exerted greater effects than PE-200, suggesting that gut metabolite changes may contribute to As oral bioavailability increase. This was supported by 1.58-4.07-fold higher As solubility in the presence of up-regulated metabolites (e.g., amino acid derivatives, organic acids, and pyrimidines and purines) in the intestinal tract assessed by an in vitro assay. Our results suggested that microplastic exposure especially smaller particles may exacerbate the oral bioavailability of As, providing a new angle to understand health effects of microplastics.

Threats to Terrestrial Plants from Emerging Nanoplastics.

Nanoplastics are ubiquitous in ecosystems and impact planetary health. However, our current understanding on the impacts of nanoplastics upon terrestrial plants is fragmented. The lack of systematic approaches to evaluating these impacts limits our ability to generalize from existing studies and perpetuates regulatory barriers. Here, we undertook a meta-analysis to quantify the overall strength of nanoplastic impacts upon terrestrial plants and developed a machine learning approach to predict adverse impacts and identify contributing features. We show that adverse impacts are primarily associated with toxicity metrics, followed by plant species, nanoplastic mass concentration and size, and exposure time and medium. These results highlight that the threats of nanoplastics depend on a diversity of reactions across molecular to ecosystem scales. These reactions are rooted in both the spatial and functional complexities of nanoplastics and, as such, are specific to both the plastic characteristics and environmental conditions. These findings demonstrate the utility of interrogating the diversity of toxicity data in the literature to update both risk assessments and evidence-based policy actions.

Microplastics altered soil microbiome and nitrogen cycling: The role of phthalate plasticizer.

Microplastics are emerging contaminants that are increasingly detected in soil environment, but their impact on soil microbiota and related biogeochemical processes remains poorly understood. In particular, the mechanisms involved (e.g., the role of chemical additives) are still elusive. In this study, we found that plasticizer-containing polyvinyl chloride (PVC) microplastics at 0.5% (w/w) significantly increased soil NH4+-N content and decreased NO3--N content by up to 91%, and shaped soil microbiota into a microbial system with more nitrogen-fixing microorganisms (as indicated by nifDHK gene abundance), urea decomposers (ureABC genes and urease activity) and nitrate reducers (nasA, NR, NIT-6 and napAB genes), and less nitrifiers (amoC gene and potential nitrification rate). Exposure to plasticizer alone had a similar effect on soil nitrogen parameters but microplastics of pure PVC polymer (either granule or film) had little effect over 60 days, indicating that phthalate plasticizer released from microplastics was the main driver of effects observed. Furthermore, a direct link between phthalate plasticizer, microbial taxonomic changes and altered nitrogen metabolism was established by the isolation of phthalate-degrading bacteria involved in nitrogen cycling. This study highlights the importance of chemical additives in determining the interplay of microplastics with microbes and nutrient cycling, which needs to be considered in future studies.

Biomass Schiff base polymer-derived N-doped porous carbon embedded with CoO nanodots for adsorption and catalytic degradation of chlorophenol by peroxymonosulfate.

The development of highly active and multifunctional carbocatalysts modified with heteroatoms or metal species is crucial for practical environmental remediation applications. In this study, nitrogen-doped porous carbon embedded with highly dispersed CoO nanodots (CoO-N-C) was successfully prepared from a biomass-derived Schiff base polymer for the first time. The morphology analysis shows that CoO nanodots were embedded in the N doped carbon layer with size of ∼6.5 nm. CoO-N-C catalyst exhibited excellent 4-CP adsorption efficiency as well as excellent catalytic performance in the activation of peroxymonosulfate (PMS) for 4-CP degradation. Total organic carbon (TOC) removal was close to 99.7% and involved a combination of adsorption and degradation processes. Singlet oxygen (1O2) was found to be the dominant oxidative species for 4-CP degradation. The underlying mechanism of these processes were elucidated, and it was found that the introduction of CoO nanodots in CoO-N-C not only enhanced radical catalytic processes, but also significantly enhanced the non-radical catalytic processes of PMS activation. This derived from the synergistic effect between the embedded CoO nanodots and doped nitrogen for the increase of electron density on carbon surface of catalyst, thereby accelerating the electron transfer process for PMS activation and improving the catalytic performance.

Effects of soil environmental factors and UV aging on Cu2+ adsorption on microplastics.

Microplastics (MPs) in natural environments have attracted lots of attention. Although the quantity of MPs present in terrene is much higher than that in aquatic environment, few studies have investigated the chemical behavior of MPs in terrestrial environment. This study investigate the Cu2+ (as a model heavy metal) adsorption capacity of six kinds of MPs (polyamide-6 (PA), polyethylene (PE), polystyrene (PS), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA)) in batch adsorption experiments and the effects of different soil environmental factors, including pH and the presence of cations and low-molecular-weight organic acids (LMWOAs), as well as ultraviolet (UV) aging. The Cu2+ adsorption capacities of PA and PMMA were higher than those of other MPs and their maximum equilibrium adsorption capacities (estimated by the Langmuir adsorption equation) were 323.6 µg/g ± 38.2 and 41.03 ± 1.78 µg/g, respectively. The Cu2+ adsorption on MPs was affected by pH, and the greatest amount of Cu2+ adsorbed on PA and PMMA was observed at pH = 6 and pH = 7, respectively. The presence of Ca2+ or Mg2+ inhibited Cu2+ adsorption by MPs, due to competition for the adsorption sites. Moreover, Cu2+ adsorption by MPs was affected by various types of LMWOAs. The Cu2+ adsorption on PA was significantly reduced by citric acid, followed by oxalic acid, and oxalic acid was particularly evident for Cu2+ adsorption on PMMA. UV aging (200 h) had different effect on Cu2+ adsorption on MPs and it depends on the change of carbonyl index. Results demonstrate that soil environmental factors can change the ability of different MPs to adsorb Cu2+ and affect the transport of pollutants as carriers.

Influence of bacterial extracellular polymeric substances on the sorption of Zn on γ-alumina: A combination of FTIR and EXAFS studies.

Extracellular polymeric substances (EPS) isolated from bacteria, are abound of functional groups which can react with metals and consequently influence the immobilization of metals. In this study, we combined with Zn K-edge Extended X-ray Absorption Fine Structure (EXAFS), Fourier Transform Infrared (FTIR) spectroscopy, and High-Resolution Transmission Electron Microscopy (HRTEM) techniques to study the effects of EPS isolated from Bacillus subtilis and Pseudomonas putida on Zn sorption on γ-alumina. The results revealed that Zn sorption on aluminum oxide was pH-dependent and significantly influenced by bacterial EPS. At pH 7.5, Zn sorbed on γ-alumina was in the form of Zn-Al layered doubled hydroxide (LDH) precipitates, whereas at pH 5.5, Zn sorbed on γ-alumina was as a Zn-Al bidentate mononuclear surface complex. The amount of sorbed Zn at pH 7.5 was 1.3-3.7 times higher than that at pH 5.5. However, in the presence of 2 g L-1 EPS, regardless of pH conditions and EPS source, Zn + EPS + γ-alumina ternary complex was formed on the surface of γ-alumina, which resulted in decreased Zn sorption (reduced by 8.4-67.8%) at pH 7.5 and enhanced Zn sorption (increased by 10.0-124.7%) at pH 5.5. The FTIR and EXAFS spectra demonstrated that both the carboxyl and phosphoryl moieties of EPS were crucial in this process. These findings highlight EPS effects on Zn interacts with γ-alumina.

Mechanistic understanding of reduced AgNP phytotoxicity induced by extracellular polymeric substances.

A knowledge gap concerning the potential effects of extracellular polymeric substances (EPS), a common organic material but highly variable in their composition of microbial origin, on the fate and phytotoxicity of silver nanoparticles (AgNP) still remains. A 48-h root elongation toxicity test showed that AgNP toxicity to wheat Triticum aestivum L. was dramatically alleviated by EPS isolated from Pseudomonas putida, as revealed by 7-59% increase in relative root elongation (RRE), 8-99% increase in root weight, 27-32% decrease in malondialdehyde (MDA) content and 11-43% decrease in H2O2 content compared to the treatment with AgNP in the absence of EPS. This was coincident with 7-69% decrease in root Ag concentrations. Our results showed that EPS could protect wheat seedlings from AgNP toxicity by reducing dissolved Ag concentration ([Ag]diss) and by forming AgNP-EPS complex. The FTIR spectra further showed that the amide, carboxyl, and phosphoryl functional groups of EPS were involved in binding with AgNP and/or Ag(+). All these processes worked simultaneously to reduce AgNP bioavailability, and subsequently mitigate AgNP toxicity. These findings highlight the importance of EPS in AgNP biogeochemistry in the terrestrial environment. EPS could be highly useful in developing strategies to counteract the phytotoxicty of metal-based nanoparticles in crops.

A Therapeutic Uricase with Reduced Immunogenicity Risk and Improved Development Properties.

Humans and higher primates are unique in that they lack uricase, the enzyme capable of oxidizing uric acid. As a consequence of this enzyme deficiency, humans have high serum uric acid levels. In some people, uric acid levels rise above the solubility limit resulting in crystallization in joints, acute inflammation in response to those crystals causes severe pain; a condition known as gout. Treatment for severe gout includes injection of non-human uricase to reduce serum uric acid levels. Krystexxa® is a hyper-PEGylated pig-baboon chimeric uricase indicated for chronic refractory gout that induces an immunogenic response in 91% of treated patients, including infusion reactions (26%) and anaphylaxis (6.5%). These properties limit its use and effectiveness. An innovative approach has been used to develop a therapeutic uricase with improved properties such as: soluble expression, neutral pH solubility, high E. coli expression level, thermal stability, and excellent activity. More than 200 diverse uricase sequences were aligned to guide protein engineering and reduce putative sequence liabilities. A single uricase lead candidate was identified, which showed low potential for immunogenicity in >200 human donor samples selected to represent diverse HLA haplotypes. Cysteines were engineered into the lead sequence for site specific PEGylation and studies demonstrated >95% PEGylation efficiency. PEGylated uricase retains enzymatic activity in vitro at neutral pH, in human serum and in vivo (rats and canines) and has an extended half-life. In canines, an 85% reduction in serum uric acid levels was observed with a single subcutaneous injection. This PEGylated, non-immunogenic uricase has the potential to provide meaningful benefits to patients with gout.

Biofilms and extracellular polymeric substances mediate the transport of graphene oxide nanoparticles in saturated porous media.

Understanding the fate and transport of graphene oxide nanoparticles (GONPs) in the subsurface environments is of crucial importance since they may pose potential risks to the environment and human health. However, little is known about the significance of biofilm on mobility of GONPs in the subsurface. Here we investigated the transport of GONPs in saturated sand coated with Bacillus subtilis (Gram-positive) and Pseudomonas putida (Gram-negative) biofilms, and their secreted extracellular polymeric substances (EPS) under environmentally relevant ionic strengths (1-50mM NaCl) at pH 7.2. Our results showed that irrespective of bacteria type, greater retention of GONPs occurred in biofilm-coated sand compared to clean sand, likely attributed to the increased surface roughness and physical straining. However, EPS showed negligible influence on GONPs transport, which was inconsistent with the findings in the presence of biofilms, while they exhibited comparable ζ-potentials. The different retention phenotype of GONPs in the presence of EPS was induced by hydration effect and steric repulsion. A two-site kinetic retention model well-described the transport of GONPs in porous media covered with different surface coatings, which proves the applicability of mathematical model in predicting nanoparticles' mobility in the subsurface environments, when considering the potential effects of biofilm and EPS.

Synthesis and crystal structures of two coordination polymers and a binuclear cadmium(II) complex containing 3- and 4-aminobenzoate ligands.

Due to their wide range of coordination modes and versatile conformations when binding to metal atoms, multicarboxylate ligands are of interest in the design of metal-organic frameworks (MOFs). Three Cd(II) complexes, namely catena-poly[diammonium [[chloridocadmium(II)]-di-µ-chlorido-[chloridocadmium(II)]-bis(µ-3-aminobenzoato)-κ(3)N:O,O';κ(3)O,O':N]], {(NH4)[CdCl2(C7H6NO2)]}n, (I), catena-poly[[[aquacadmium(II)]-bis(µ-4-aminobenzoato)-κ(3)N:O,O';κ(3)O,O':N] monohydrate], {[Cd(C7H6NO2)2(H2O)]·H2O}n, (II), and di-µ-acetato-κ(4)O:O'-bis[(4-aminobenzoato-κ(2)O,O')(2,2'-bipyridine-κ(2)N,N')cadmium(II)], [Cd2(CH3COO)2(C7H6NO2)2(C10H8N2)2], (III), with different stuctural forms are reported. Complex (I) has a one-dimensional ladder structure, with strong N-H···O and weak N-H···Cl hydrogen bonds linking the cations and anions in the three-dimensional supramolecular structure. Complex (II) has a one-dimensional chain structure. Extensive O-H···O and N-H···O hydrogen bonds between the anionic ligands and the solvent water molecules and π-π stacking interactions between the centroids of the benzene rings lead to the three-dimensional supramolecular structure. Complex (III) is a binuclear molecule which is extended into a three-dimensional supramolecular structure via strong N-H···O and weak C-H···O hydrogen bonds.

Equivalent models of indanol isomers adsorption on cellulose tribenzoate.

The adsorption isotherm data of (R)- and (S)-1-indanol and of their racemic mixture on cellulose tribenzoate were measured by frontal analysis. The experimental data for each enantiomers were fitted to the single-component bilangmuir isotherm model. The competitive experimental data were fitted to the ideal adsorption solution model (IAS), the real adsorption solution model (RAS), and the bilangmuir thermodynamically consistent model (BTC). The mass transfer kinetic parameters were estimated from systematic comparisons between the experimental single-component band profiles and profiles calculated using the general rate model (GR) of chromatography coupled with the generalized Maxwell-Stefan equation (GMS). The validation of the isotherm model and of the mass transfer kinetic model was made by comparing the experimental band profiles obtained for solutions of the two enantiomers and those calculated with the competitive GR-GMS model. The excellent agreement observed proves that a combination of the BTC isotherm model and the GMS kinetic model, using the best values of the BTC and GMS parameters estimated from single component experiments, allows an excellent prediction of the binary isotherm and the binary mass transfer kinetics.

Hyperexponential and nonmonotonic retention of polyvinylpyrrolidone-coated silver nanoparticles in an Ultisol.

The increasing application of engineered nanoparticles (ENPs) has heightened the concern that these ENPs would eventually be released to the environment and may enter into life cycle of living beings. In this regard, it is essential to understand how these ENPs transport and retain in natural soils because they are considered to be a major repository for ENPs. Herein, transport and retention of polyvinylpyrrolidone (PVP)-coated silver nanoparticles (PVP-AgNPs) were investigated over a wide range of physicochemical factors in water-saturated columns packed with an Ultisol rich in clay-size particles. Higher mobility of PVP-AgNPs occurred at larger soil grain size, lower solution ionic strength and divalent cation concentration, higher flow rate, and greater PVP concentrations. Most breakthrough curves (BTCs) for PVP-AgNPs exhibited significant amounts of retardation in the soil due to its large surface area and quantity of retention sites. In contrast to colloid filtration theory, the shapes of retention profiles (RPs) for PVP-AgNPs were either hyperexponential or nonmonotonic (a peak in particle retention down-gradient from the column inlet). The BTCs and hyperexponential RPs were successfully described using a 1-species model that considered time- and depth-dependent retention. Conversely, a 2-species model that included reversibility of retained PVP-AgNPs had to be employed to better simulate the BTCs and nonmonotonic RPs. As the retained concentration of species 1 approached the maximum solid-phase concentration, a second mobile species (species 2, i.e., the same PVP-AgNPs that are reversibly retained) was released that could be retained at a different rate than species 1 and thus yielded the nonmonotonic RPs. Some retained PVP-AgNPs were likely to irreversibly deposit in the primary minimum associated with microscopic chemical heterogeneity (favorable sites). Transmission electron microscopy and energy-dispersive X-ray spectroscopy analysis suggested that these favorable sites were positively charged sites on montmorillonite edges and goethite surfaces in the soil. Overall, our study highlights that the transport and especially retention of PVP-AgNPs are highly sensitive to the physicochemical factors, but mathematical modeling can accurately predict the fate of these ENPs in porous media which is important for better understanding the fate of these ENPs in point of exit and in the environment.

Reducing the bioavailability of PCBs in soil to plant by biochars assessed with triolein-embedded cellulose acetate membrane technique.

Coupling with triolein-embedded cellulose acetate membrane (TECAM) technique, hydroxypropyl ß-cyclodextrins (HPCD) extraction method, and the greenhouse pot experiments, the influences of biochars on polychlorinated biphenyls (PCBs) bioavailability in soil to plant (Brassica chinensis L. and Daucus carota) were investigated. Addition of 2% biochars to soils significantly reduced the uptake of PCBs in plant, especially for di-, tri- and tetra-chlorobiphenyls. PCBs concentrations in the roots of B. chinensis and D. carota were reduced for 61.5-93.7%, and 12.7-62.4%, respectively in the presence of biochars. The kinetic study showed that in the soils amended with/without biochars, PCBs concentrations accumulated in TECAM, as well as in the HPCD extraction solution, followed significant linear relationships with those in plant roots. Application of biochars to soil is a potentially promising method to reduce PCBs bioavailability whereas TECAM technique can be a useful tool to predict the bioavailability of PCBs in soil.

The role of surface charge density in cationic liposome-promoted dendritic cell maturation and vaccine-induced immune responses.

Cationic liposomes have emerged as a novel adjuvant and antigen delivery system to enhance vaccine efficacy. However, the role of surface charge density in cationic liposome-regulated immune responses has not yet been elucidated. In the present study, we prepared a series of DOTAP/DOPC cationic liposomes with different surface densities by incorporating varying amounts of DOPC (a neutral lipid) into DOTAP (a cationic lipid). The results showed that DOTAP/DOPC cationic liposome-regulated immune responses relied on the surface charge density, and might occur through ROS signaling. The liposomes with a relatively high charge density, such as DOTAP/DOPC 5:0 and 4:1 liposomes, potently enhanced dendritic cell maturation, ROS generaion, antigen uptake, as well as the production of OVA-specific IgG2a and IFN-γ. In contrast, low-charge liposomes, such as DOTAP/DOPC 1:4 liposome, failed to promote immune responses even at high concentrations, confirming that the immunoregulatory effect of cationic liposomes is mostly attributable to their surface charge density. Moreover, the DOTAP/DOPC 1:4 liposome suppressed anti-OVA antibody responses in vivo. Overall, maintaining an appropriate surface charge is crucial for optimizing the adjuvant effect of cationic liposomes and enhancing the efficacy of liposome-based vaccines.

Heterogeneous adsorption of 1-indanol on cellulose tribenzoate and adsorption energy distribution of the two enantiomers.

The distributions of the adsorption energies (AED) of two enantiomers, (R)-1- indanol and (S)-1-indanol, on a chiral stationary phase were measured and the results are discussed. The chiral phase used is made of cellulose tribenzoate coated on porous silica. The AEDs were determined using the expectation maximization method, a numerical method that uses directly the raw experimental isotherm data, inverts this set of data into an AED, and introduces no arbitrary information in the calculation. However, it uses the Langmuir equation as the local isotherm. The experimental data fit very well to the bi-Langmuir isotherm model for the more retained enantiomer. Our results show that the AEDs of these two enantiomers have no energy modes that would be identical (same mean energy, mode profile, and mode area), in contrast to numerous cases previously studied, e.g., that of the beta-blockers on a Cel7A column. This indicates a significantly different retention mechanism.