Spartina alterniflora invasion benefits blue carbon sequestration in China.

Spartina alterniflora has rapidly and extensively encroached on China's coastline over the past decades. Among the coastal areas invaded by S. alterniflora, at most 93% are mudflats. However, the effect of S. alterniflora invasion on soil organic carbon (SOC) stocks of coastal mudflats has not been systematically studied on a national scale. Here, we quantified the nationwide changes in SOC stocks in coastal mudflats associated with S. alterniflora invasion between 1990 and 2020. We found that S. alterniflora invasion significantly enhanced SOC stocks in coastal China. Nonetheless, the benefit of S. alterniflora invasion of coastal SOC stock may be weakened by continuing human intervention. We found that S. alterniflora invading mudflats added 2.3 Tg SOC stocks to China's coastal blue carbon, while 1.78 Tg SOC stocks were lost mainly due to human activities, resulted in a net SOC stock gain of 0.52 Tg C. These findings overturned the traditionally thought that S. alterniflora invasion would reduce ecosystem services by highlighting that the historical invasion of S. alterniflora has broadly and consistently enhanced blue carbon stock in coastal China.

Protective and Flame-Retardant Bifunctional Epoxy-Based Nanocomposite Coating by Intercomponent Synergy between Modified CaAl-LDH and rGO.

Extensive utilization in various settings poses extra requirements of coatings beyond just anticorrosion properties. Herein, 8-hydroxyquinoline (8-HQ) intercalated CaAl-based layered double hydroxide (CaAl-8HQ-LDH) was loaded on reduced GO (rGO) through a one-pot hydrothermal reaction, which was employed as the nanofiller endowing the epoxy (EP/CaAl-8HQ LDH@rGO) with excellent flame-retardancy while ensuring efficient protection for mild steel. Results of electrochemical impedance spectroscopy (EIS) demonstrated the durability of the EP/CaAl-8HQ LDH@rGO-coated specimen, with the impedance at the lowest frequency (|Z|0.01Hz) maintained as 1.84 × 1010 Ω cm2 after 120 days of immersion in a 3.5 wt % NaCl solution. Even for the scratched EP/CaAl-8HQ LDH@rGO system, only a slight decline in |Z|0.01Hz was observed during 180 h of exposure to the NaCl solution, indicating a self-healing feature supported by salt spray tests. UL-94 burning tests revealed the V-0 rating for EP/CaAl-8HQ LDH@rGO with improved thermostability. Strong physical barrier from two-dimensional rGO and the release of 8-HQ from LDH interlayers accounted for the anticorrosive and self-healing properties. However, O2-concentration dilution and charring-layer promotion governed the flame-retardant behavior of the nanocomposite coating. The intercomponent synergy of nanofillers achieved in this work may provide a useful reference for designing multifunctional coatings.

A universal eco-friendly flame retardant strategy for polylactic acid fabrics and other polymer substrates.

Various polymer substrates have their particular combustion features, therefore, developing an effective universal flame retardant strategy for various polymer substrates is of great practical importance. Meanwhile, as substitutes for petroleum-based products, bio-based flame retardants and biodegradable polylactic acid (PLA) meet the requirements of sustainable development. In this work, a fully bio-based flame retardant coating (PAGS) was prepared using phytic acid (PA) and guanosine (GS). PAGS was used as a universal flame retardant coatings for polylactic acid (PLA) fabrics and other substrates, including cotton fabrics, polyethylene terephthalate (PET) fabrics, polyamide (PA) fabrics, polyurethane (PU) foams, polyethylene terephthalate (PET) films, and woods. The PAGS-treated substrates were able to self-extinguish and eliminate molten droplets. Similarly, the PAGS coating significantly suppressed the heat release of each substrate. The P-containing free radicals in the gas phase were able to interact with highly reactive H, HO and alkyl radicals, blocking the chain reaction during combustion. The flammable gas density was also diluted by nonflammable gases. The formed continuous porous and dense intumescent char layer hindered heat and oxygen. It is suggested that this work provides a simple and efficient flame retardant strategy for improving the fire safety of various polymer substrates.

Ferritin and iron supplements in gestational diabetes mellitus: less or more?

Iron metabolism has been found to be closely related to gestational diabetes mellitus (GDM). Excessive ferritin levels were shown to be related to an increased risk of GDM because of iron overload which may lead to insulin resistance and ß-cell injury by enhancing oxidative stress and inflammatory responses. On the contrary, insufficient ferritin levels can cause a number of obstetric complications, such as high incidence rates of anaemia and gestational hypertension. Therefore, high or low ferritin levels may have adverse effects on the mother and the foetus, putting clinicians in a dilemma when giving pregnant women iron supplements. This also explains why there have been more conflicting findings in the studies on dietary or oral iron supplementation during pregnancy. Hence, there is an urgent need for more evidence and strategies for appropriate recommendations for ferritin levels and iron supplementation during pregnancy to prevent iron insufficiency without causing iron overload and increasing the risk of GDM. Therefore, we gave an updated review on the association of GDM with ferritin metabolism, ferritin levels and iron supplementation based on the summary of the latest research.

P450-mediated dehydrotyrosine formation during WS9326 biosynthesis proceeds via dehydrogenation of a specific acylated dipeptide substrate.

WS9326A is a peptide antibiotic containing a highly unusual N-methyl-E-2-3-dehydrotyrosine (NMet-Dht) residue that is incorporated during peptide assembly on a non-ribosomal peptide synthetase (NRPS). The cytochrome P450 encoded by sas16 (P450Sas) has been shown to be essential for the formation of the alkene moiety in NMet-Dht, but the timing and mechanism of the P450Sas-mediated α,ß-dehydrogenation of Dht remained unclear. Here, we show that the substrate of P450Sas is the NRPS-associated peptidyl carrier protein (PCP)-bound dipeptide intermediate (Z)-2-pent-1'-enyl-cinnamoyl-Thr-N-Me-Tyr. We demonstrate that P450Sas-mediated incorporation of the double bond follows N-methylation of the Tyr by the N-methyl transferase domain found within the NRPS, and further that P450Sas appears to be specific for substrates containing the (Z)-2-pent-1'-enyl-cinnamoyl group. A crystal structure of P450Sas reveals differences between P450Sas and other P450s involved in the modification of NRPS-associated substrates, including the substitution of the canonical active site alcohol residue with a phenylalanine (F250), which in turn is critical to P450Sas activity and WS9326A biosynthesis. Together, our results suggest that P450Sas catalyses the direct dehydrogenation of the NRPS-bound dipeptide substrate, thus expanding the repertoire of P450 enzymes that can be used to produce biologically active peptides.

Coastal blue carbon in China as a nature-based solution toward carbon neutrality.

To achieve the Paris Agreement, China pledged to become "Carbon Neutral" by the 2060s. In addition to massive decarbonization, this would require significant changes in ecosystems toward negative CO2 emissions. The ability of coastal blue carbon ecosystems (BCEs), including mangrove, salt marsh, and seagrass meadows, to sequester large amounts of CO2 makes their conservation and restoration an important "nature-based solution (NbS)" for climate adaptation and mitigation. In this review, we examine how BCEs in China can contribute to climate mitigation. On the national scale, the BCEs in China store up to 118 Tg C across a total area of 1,440,377 ha, including over 75% as unvegetated tidal flats. The annual sedimental C burial of these BCEs reaches up to 2.06 Tg C year-1, of which most occurs in salt marshes and tidal flats. The lateral C flux of mangroves and salt marshes contributes to 1.17 Tg C year-1 along the Chinese coastline. Conservation and restoration of BCEs benefit climate change mitigation and provide other ecological services with a value of $32,000 ha-1 year-1. The potential practices and technologies that can be implemented in China to improve BCE C sequestration, including their constraints and feasibility, are also outlined. Future directions are suggested to improve blue carbon estimates on aerial extent, carbon stocks, sequestration, and mitigation potential. Restoring and preserving BCEs would be a cost-effective step to achieve Carbon Neutral by 2060 in China despite various barriers that should be removed.

Channel Modeling and Characteristics Analysis under Different 3D Dynamic Trajectories for UAV-Assisted Emergency Communications.

This study involved channel modeling and characteristics analysis of unmanned aerial vehicles (UAVs) according to different operating trajectories. Based on the idea of standardized channel modeling, air-to-ground (AG) channel modeling of a UAV was carried out, taking into consideration that both the receiver (Rx) and the transmitter (Tx) ran along different types of trajectories. In addition, based on Markov chains and a smooth-turn (ST) mobility model, the influences of different operation trajectories on typical channel characteristics-including time-variant power delay profile (PDP), stationary interval, temporal autocorrelation function (ACF), root mean square (RMS) delay spread (DS), and spatial cross-correlation function (CCF)-were studied. The multi-mobility multi-trajectory UAV channel model matched well with actual operation scenarios, and the characteristics of the UAV AG channel could be analyzed more accurately, thus providing a reference for future system design and sensor network deployment of sixth-generation (6G) UAV-assisted emergency communications.

Improving the hygroscopicity and flame retardancy of polyamide 6 fabrics by surface coating with ß-FeOOH and sulfamic acid.

The combustion of polyamide 6 (PA6) fabrics releases toxic smoke, which will pollute the environment and threaten human life and health. Herein, a novel eco-friendly flame-retardant coating was constructed and applied to PA6 fabrics. Needle-like ß-FeOOH with a high surface area was firstly constructed onto the surface of PA6 fabrics by the hydrolysis of Fe3+, sulfamic acid (SA) was then introduced by a facile dipping and nipping method. The growth of ß-FeOOH also endowed the PA6 fabrics with certain hydrophilicity and moisture permeability, resulting in improved comfortability. The limiting oxygen index (LOI) of the prepared PA6/Fe/6SA sample was increased to 27.2% from 18.5% of control PA6 sample, and the damaged length was reduced to only 6.0 cm from 12.0 cm of control PA6 sample. Meanwhile, the melt dripping was also eliminated. The heat release rate and total heat release values of the PA6/Fe/6SA sample were decreased to 318.5 kW/m2 and 17.0 MJ/m2, respectively, compared with those of control PA6 (494.7 kW/m2 and 21.4 MJ/m2). The analysis results indicated that nonflammable gases diluted flammable gases. The observation of char residues demonstrated that the stable char layer was formed, which effectively inhibited the transfer of heat and oxygen. The organic solvent-free coating does not contain any conventional halogens/phosphorus elements, which provides a useful methodology to produce environmentally friendly flame-retardant fabrics.

Channel Characterization and Modeling for 6G UAV-Assisted Emergency Communications in Complicated Mountainous Scenarios.

Regarding the new demands and challenges of sixth-generation (6G) mobile communications, wireless networks are undergoing a significant shift from traditional terrestrial networks to space-air-ground-sea-integrated networks. Unmanned aerial vehicle (UAV) communications in complicated mountainous scenarios are typical applications and have practical implications, especially in emergency communications. In this paper, the ray-tracing (RT) method was applied to reconstruct the propagation scenario and then acquire the wireless channel data. Channel measurements are also conducted in real mountainous scenarios for verification. By setting different flight positions, trajectories, and altitudes, channel data in the millimeter wave (mmWave) band was obtained. Important statistical properties, such as the power delay profile (PDP), Rician K-factor, path loss (PL), root mean square (RMS) delay spread (DS), RMS angular spreads (ASs), and channel capacity were compared and analyzed. The effects of different frequency bands on channel characteristics at 3.5 GHz, 4.9 GHz, 28 GHz, and 38 GHz bands in mountainous scenarios were considered. Furthermore, the effects of extreme weather, especially different precipitation, on the channel characteristics were analyzed. The related results can provide fundamental support for the design and performance evaluation of future 6G UAV-assisted sensor networks in complicated mountainous scenarios.

Negatively charged nano-hydroxyapatite can be used as a phosphorus fertilizer to increase the efficacy of wollastonite for soil cadmium immobilization.

Improper application of phosphorus (P) fertilizer during soil cadmium (Cd) immobilization reduces the efficiency of fertilizer and Cd remediation. In this study, we synthesized three types of nano-hydroxyapatite (NHAP) with different surface charges as slow-release P fertilizers during Cd immobilization. We also evaluated the effects of wollastonite application with or without NHAP addition, in comparison with triple superphosphate (TSP) or bulk hydroxyapatite, on Cd accumulation in Amaranthus tricolor L. The results showed that adding wollastonite significantly reduced P availability (23.5%) in the soil, but it did not inhibit plant P uptake. In wollastonite-amended soil, the application of negatively/positively charged NHAP significantly increased plant biomass by 643-865% and decreased Cd uptake by 74.8-75.1% compared to the unamended soil as well as showed greater efficiency than those with TSP. This was ascribed to the increased soil pH (from 3.94 to 6.52-6.63) and increased abundance of organic acids (including citric acid, malic acid, lactic acid, and acetic acid) secreted by plants. In addition, the P-preferring bacterial class Bacteroidia was specific to soils amended with both wollastonite and NHAP-. These results suggest that NHAP- may be an appropriate P fertilizer for soil Cd immobilization using wollastonite.

Nitrogen and phosphorus addition exerted different influences on litter and soil carbon release in a tropical forest.

Terrestrial soils release large amount of carbon dioxide (CO2) each year, which are mainly derived from litter and soil carbon (C) decomposition. Nutrient availability, especially nitrogen (N) and phosphorus (P), plays an important role in both litter and soil C decomposition. Therefore, understanding the underlying mechanism is crucial for mitigating CO2 emission and climate changes. Here, we assessed patterns of litter and soil C decomposition after 11 yrs. in-situ N and P addition in a tropical forest where corn leaves or corn roots were added as litter C. The total CO2 efflux was quantified and partitioned using 13C isotope signatures to determine the sources (litter or soil C) every three months. In addition, Changes in C-degrading enzyme activities: ß-1,4-glucosidase (BG), phenol oxidase (PHO) and peroxidase (PER), and microbial biomarkers were assessed to interpret the underlying mechanism. Total C-release was enhanced up to17% by the long-term N addition but inhibited up to 15% by P addition. Precisely, N addition only accelerated the litter decomposition and increased about 42% and 6% of the litter C release at 0-5 cm and 5-10 cm soil depths, respectively; while P addition only impeded the soil C decomposition and decreased about 9% and 11% of the soil C release at 0-5 cm and 5-10 cm, respectively. The enhanced C release under N addition might be attributed to the enhanced microbial biomass, the ratio of fungi to bacteria and C-degrading enzyme activities. However, P addition resulted in the reverse result in microbial properties and C-degrading enzyme activities, associated with a decreased C release. Our study suggests that the long-term N and P addition selectively affected the litter and soil C decomposition because of their different physiochemical properties and this tendency might be more pronounced in tropical forests exposed to increasing atmospheric N deposition in the future. The study indicates that the different patterns of litter and soil C decomposition under climate change should be taken account in the future C management strategies.

Adaptive optimal output regulation for wheel-legged robot Ollie: A data-driven approach.

The dynamics of a robot may vary during operation due to both internal and external factors, such as non-ideal motor characteristics and unmodeled loads, which would lead to control performance deterioration and even instability. In this paper, the adaptive optimal output regulation (AOOR)-based controller is designed for the wheel-legged robot Ollie to deal with the possible model uncertainties and disturbances in a data-driven approach. We test the AOOR-based controller by forcing the robot to stand still, which is a conventional index to judge the balance controller for two-wheel robots. By online training with small data, the resultant AOOR achieves the optimality of the control performance and stabilizes the robot within a small displacement in rich experiments with different working conditions. Finally, the robot further balances a rolling cylindrical bottle on its top with the balance control using the AOOR, but it fails with the initial controller. Experimental results demonstrate that the AOOR-based controller shows the effectiveness and high robustness with model uncertainties and external disturbances.

Long-term fertilization modifies the mineralization of soil organic matter in response to added substrate.

The turnover of SOC in soils is strongly influenced by the availability of substrate and nutrients, especially nitrogen (N) and phosphorus (P). Here, we assessed how long-term fertilization modified SOM mineralization in response to added substrate in a tropical forest. We carried out a 90-day incubation study in which we added two structurally similar compounds which differed in microbial metabolic availability: corn cellulose or corn starch to soils collected from a long-term (11 years) factorial N and P fertilization experiment site in a tropical forest in south China. We measured total soil mineralization rate (CO2 efflux) to characterize SOM mineralization and using 13C isotope signatures to determine the source of the CO2 (original soil C or added substrate) and assessed changes in extracellular enzyme activities: acid phosphomonoesterase (AP), ß-1,4-glucosidase (BG), ß-1,4- N-acetaminophen glucosidase (NAG), phenol oxidase (PHO) and peroxidase (PER), and microbial biomarkers to determine whether nutrient stoichiometry and decomposer communities explain differences in SOM mineralization rates. Total C mineralization increased substantially with substrate addition, particularly cellulose (5.38, 7.13, 5.58 and 5.37 times for N, P, NP fertilization and CK, respectively) compared to no substrate addition, and original soil C mineralization was further enhanced in long-term N (3.40% and 5.18% for cellulose and starch addition, respectively) or NP (35.11% for cellulose addition) fertilized soils compared to control treatment. Enzyme activities were stimulated by the addition of both substrates but suppressed by P-fertilization. Addition of both substrates increased microbial investment in P-acquisition, but only starch addition promoted C investment in N-acquisition. Finally, fungal abundance increased with substrate addition to a greater extent than bacterial abundance, particularly in cellulose-amended soils, and the effect was amplified by long-term fertilization. Our findings indicate that SOM mineralization might be enhanced in N and P enrichment ecosystems, since the litter input can liberate microbes from C limitation and stimulate SOM mineralization if N and P are sufficient. Our study further demonstrates that structurally similar substrates can have distinct effects on SOM mineralization and the extent of SOM mineralization is strongly dependent on elemental stoichiometry, as well as the resource requirements of microbial decomposers.

Serum epidermal growth factor-like domain 7 serves as a novel diagnostic marker for early hepatocellular carcinoma.

BACKGROUND: Epidermal growth factor-like domain 7 (Egfl7), a recently identified secreted protein, was significantly increased in patients with HCC by our previous studies. However, its efficacy in the diagnosis of early HCC remains unknown. In this study, we therefore evaluate the efficacy of serum Egfl7 for early HCC diagnosis and compare it with alpha-fetoprotein (AFP). METHODS: Serum Egfl7 levels in testing cohort (1081 participants) and validation cohort (476 participants) were measured by a sandwich enzyme-linked immunoassay (ELISA). The cut-off value of Egfl7 was determined by Youden's index and the efficacies of Egfl7 and AFP in diagnosing early HCC were estimated by receiver operating characteristic (ROC). RESULTS: Serum Egfl7 was significantly elevated in patients with early HCC than all non-HCC controls in whatever Testing Cohort or Validation Cohort. In the Testing Cohort, ROC curves showed the optimum cut-off value of Egfl7 was 2610 ng/mL and Egfl7 showed a significantly higher sensitivity than AFP in discriminating early HCC from healthy individuals (77.4% vs. 65.3%, P = 0.0013) but the area under ROC (AUROC) and accuracy of Egfl7 and AFP were similar (0.860 vs. 0.868, P = 0.704; 80.2% vs. 83.8%, P = 0.184). In distinguishing patients with early HCC from patients with chronic liver disease (CLD), the AUROC, sensitivity, specificity and accuracy of Egfl7 were 0.800, 75.2, 71.7 and 73.5%, which were all significantly higher than AFP (0.675, 61.8, 62.0 and 61.9% in order). Egfl7 also showed a significant higher sensitivity and accuracy than AFP (76.6% vs. 64.0%, P = 0.0031; 79.9% vs. 66.1%, P < 0.0001) in differentiating early HCC patients from non-HCC individuals. Additionally, 70.8% of early HCC patients with negative AFP could be diagnosed by Egfl7 and the combined use of Egfl7 and AFP increased the sensitivity to 91.0%. These results were confirmed by a validation cohort. CONCLUSION: Egfl7 is a valuable serum marker in the diagnosis of early HCC and could complement the efficacy of AFP, especially in distinguishing early HCC from CLD and identifying patients with AFP-negative early HCC.

N1­methylnicotinamide ameliorates insulin resistance in skeletal muscle of type 2 diabetic mice by activating the SIRT1/PGC­1α signaling pathway.

Insulin resistance is one of important factors causing type 2 diabetes; therefore, regulating insulin sensitivity is considered a beneficial therapeutic approach against type 2 diabetes. The present study aimed to determine the effects of N1­methylnicotinamide (MNAM) on insulin resistance (IR) in skeletal muscle from a mouse model of type 2 diabetes mellitus (T2DM), and to investigate the regulatory mechanisms of the sirtuin 1 (SIRT1)/peroxisome proliferator­activated receptor γ coactivator­1α (PGC­1α) signaling pathway. C57BL/6 mice were fed a normal diet with or without 1% MNAM and ob/ob mice were also fed a normal diet with or without 0.3 or 1% MNAM. Blood glucose, insulin levels, insulin resistance (IR), sensitivity indices and triglyceride (TG) content were detected using ELISAs. The expression of gluconeogenesis­related, insulin signaling­related and SIRT1/PGC­1α pathway­related proteins was analyzed using reverse transcription­quantitative PCR (RT­qPCR) and western blotting. In vitro, C2C12 cells were used to establish an IR muscle cell model by 0.75 mM palmitic acid (PA) treatment (PA group). The IR cell model was subsequently supplemented with 1 mM MNAM (PM group) or 1 mM MNAM + 30 µM SIRT1 inhibitor, EX527 (PME group). After treatment the glucose levels and insulin signaling­related proteins were detected by ELISAs and western blotting, respectively. Furthermore, the expression levels of SIRT1/PGC­1α signaling pathway­related mRNA and proteins under MNAM treatment were detected by RT­qPCR and western blotting. MNAM reduced body weight gain in T2DM mice, decreased fasting blood glucose and fasting insulin levels, and inhibited IR. MNAM also regulated insulin signal transduction and promoted glucose utilization in skeletal muscle, and reduced lipid deposition. Thus, MNAM improved IR in the skeletal muscle of T2DM mice. Following application of a SIRT1 inhibitor, the effects of MNAM on the increased glucose utilization in insulin­resistant myocytes and the insulin signaling pathway were suppressed. The mechanism of action was associated with activation of the SIRT1/PGC­1α signaling pathway, which promoted the activation of the insulin receptor substrate IRS1/PI3K/AKT pathway.

N1-Methylnicotinamide Improves Hepatic Insulin Sensitivity via Activation of SIRT1 and Inhibition of FOXO1 Acetylation.

OBJECTIVE: To explore the effects of N1-methylnicotinamide (MNAM) on insulin resistance and glucose metabolism in obese type 2 diabetes mellitus (T2DM) mice and regulatory mechanisms of the NAD-dependent deacetylase sirtuin-1 (SIRT1)/forkhead box protein O1 (FOXO1) pathway. METHODS: Blood glucose and insulin levels were examined in mice. HE and oil red O staining were used to observe the effects of MNAM on liver lipid deposition in ob/ob mice. Real-time PCR and Western blotting were used to detect expression of gluconeogenesis, insulin signaling-related proteins, and SIRT1/FOXO1 pathway-related proteins. L-O2 cells were cultured as a model of insulin resistance, and MNAM and SIRT1 inhibitors were administered in vivo. Residual glucose and insulin signaling-related proteins were detected and the mechanisms associated with the SIRT1/FOXO1 signaling pathway in insulin resistance explored. RESULTS: MNAM can effectively reduce levels of fasting blood glucose and insulin, improve liver morphology, and reduce lipid accumulation in obese type 2 diabetes mellitus mice. MNAM also downregulates the key proteins in the gluconeogenesis pathway in the liver, upregulates Sirt1 expression, and reduces acetylation of the FOXO1 protein. In vitro, MNAM could promote the glucose uptake capacity of L-O2 cells induced by palmitic acid (PA), a saturated fatty acid that induces IR in various scenarios, including hepatocytes, improving insulin resistance. As Sirt1 expression was inhibited, the reduction of hepatocyte gluconeogenesis and the regulation of the insulin signaling pathway by MNAM were reversed. CONCLUSION: MNAM activates SIRT1 and inhibits acetylation of FOXO1, which in turn regulates insulin sensitivity in type 2 diabetic mice, leading to a reduction of hepatic glucose output and improvement of insulin resistance.

Specific metabolism related to sulfonamide tolerance and uptake in wetland plants.

Wetland plants are proven to perform well in water treatment. However, the phytoremediation capability of wetland plants for antibiotics, especially the uptake and metabolism involved in vivo, is poorly understood. In this study, we investigated the removal, uptake, and specific metabolism by Canna indica and Iris pseudacorus of five sulfonamides (SAs) using hydroponic experiments for seven days. The removal of SAs ranged from 15.2% to 98.4% in the planted groups, whereas that in the unplanted control group was much lower (12.6%-39.9%). The accumulation of SAs in plants was in a concentration-dependent manner via an active process and is not a major removal mechanism (constituted 0.31%-3.62% of the total removal load in plant system). The results also showed differences in the removal and accumulation by plant species of SAs. The acetyl conjugates (N-acetyl SA) were formed, which significantly enhanced the uptake of SAs (P < 0.001) except sulfapyridine. The concentrations of N-acetyl SA accounted for only 0.4%-23.8% of the total SAs distribution in plants, suggesting the involvement of other metabolism pathways. Methylation and oxidation metabolites were identified in plant tissues and no SA-induced growth stress occurred, revealing that antibiotic metabolism in vivo should be associated with the ability of wetland plants to accumulate antibiotic and tolerate antibiotic stress.

Biodegradability and biodegradation pathway of di-(2-ethylhexyl) phthalate by Burkholderia pyrrocinia B1213.

This study was conducted to investigate the biodegradation of di-(2-ethylhexyl) phthalate (DEHP) by Burkholderia pyrrocinia B1213. The results showed that DEHP at concentration of 500 mg/L in a mineral salt medium containing 1.0% yeast extract can be almost completely degraded (98.05%) by strain B1213. The optimal condition for DEHP degradation was pH 7.0, temperature 30 °C. Moreover, B1213 shows better degradation effect on long-chain PAEs, such as DEHP, which provides a great potential for its use in bioremediation of soils contaminated with PAEs. The kinetic studies showed that DEHP depletion curves fit well to the modified Gompertz model. The mono(2-ethylhexyl) phthalate (MEHP), mono-dibutyl phthalate (MBP), phthalic acid (PA) and 4-oxo-hexanoic acid were identified as the metabolites of DEHP by HPLC-ESI-QTOFMS. The detection of MBP and 4-oxo-hexanoic acid as intermediates prompted us to propose a novel and more complete DEHP biodegradation pathway compared to the classic pathway: DEHP is first degraded to MEHP by esterases, which is then converted to MBP through ß-oxidation. Then MBP is degraded to PA by esterases, which is then converted to protocatechuate (PCA) under aerobic conditions rapidly. PCA is ultimately cleaved to generate CO2 and H2O via 4-oxo-hexanoic acid.

CALB Immobilized onto Magnetic Nanoparticles for Efficient Kinetic Resolution of Racemic Secondary Alcohols: Long-Term Stability and Reusability.

In this study, an immobilization strategy for magnetic cross-linking enzyme aggregates of lipase B from Candida antarctica (CALB) was developed and investigated. Magnetic particles were prepared by conventional co-precipitation. The magnetic nanoparticles were modified with 3-aminopropyltriethoxysilane (APTES) to obtain surface amino-functionalized magnetic nanoparticles (APTES⁻Fe3O4) as immobilization materials. Glutaraldehyde was used as a crosslinker to covalently bind CALB to APTES⁻Fe3O4. The optimal conditions of immobilization of lipase and resolution of racemic 1-phenylethanol were investigated. Under optimal conditions, esters could be obtained with conversion of 50%, enantiomeric excess of product (eep) > 99%, enantiomeric excess of substrate (ees) > 99%, and enantiomeric ratio (E) > 1000. The magnetic CALB CLEAs were successfully used for enzymatic kinetic resolution of fifteen secondary alcohols. Compared with Novozym 435, the magnetic CALB CLEAs exhibited a better enantioselectivity for most substrates. The conversion was still greater than 49% after the magnetic CALB CLEAs had been reused 10 times in a 48 h reaction cycle; both ees and eep were close to 99%. Furthermore, there was little decrease in catalytic activity and enantioselectivity after being stored at -20 °C for 90 days.

Synthesis of o-Alkenylated 2-Arylbenzoxazoles via Rh-Catalyzed Oxidative Olefination of 2-Arylbenzoxazoles: Scope Investigation, Structural Features, and Mechanism Studies.

2-Arylbenzazoles are promising molecules for potential applications in medicine and material areas. Efficient protocols for direct regioselective functionalization of 2-arylbenzoxazoles are in high demand. Herein, we disclose a general method for selective ortho-olefination of 2-arylbenzo[d]oxazoles with alkenes enabled by versatile Cp*Rh(III) in high yields. This protocol features broad functional group tolerance and high regioselectivity. Intermolecular competition studies and kinetic isotope effect experiments imply that the oxidative olefination process occurs via an electrophilic C-H activation pathway. The molecular structure of the m-fluoro-substituted olefination product confirms regioselective C-H activation/olefination at the more hindered site in cases where the meta F atom or heteroatom substituent existed. Apparent torsion angles were observed in the structures of mono- and bis-olefination products, which resulted in distinct different chemical shifts of olefinic protons. Additionally, two gram-scale reactions and further transformation experiments demonstrate that this method is practical for synthesis of ortho-alkenylated 2-arylbenzoxazole derivatives.