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Polystyrene microplastics (PS MPs) and carbamazepine (CBZ) are frequently detected in freshwater ecosystems. However, the transgenerational effects of PS MPs and CBZ on the reproduction of aquatic organisms and the corresponding mechanisms are still unclear. In the present study, D. magna was used to evaluate the reproductive toxicity in two consecutive generations (F0, F1). Molting and reproduction parameters, the expression of reproduction, and toxic metabolism genes were examined after 21 d exposure. A significantly enhanced toxicity was observed in the presence of 5 μm PS MPs and CBZ. Chronic exposure results showed that the 5 μm PS MPs alone, CBZ alone, and their mixtures exerted significant reproductive toxicity of D. magna. The results of RT-qPCR showed transcripts of genes related to reproduction (cyp314, ecr-b, cut, vtg1, vtg2, dmrt93b) and toxic metabolism (cyp4, gst) were altered in both the F0 and F1. In addition, for the F0, gene transcriptional changes of reproduction were not fully translated into physiological performance, probably due to the compensatory responses caused by the low dose of PS MPs alone, CBZ alone, and their mixtures. Whereas for the F1, the trade-off between reproduction and toxic metabolism at gene levels was observed, which translated into a significant reduction in the total neonate number of F1. These findings suggest that long-term exposure to MPs and CBZ can cause serious reproduction damage to aquatic animals, which needs to be given sufficient attention.

Driving macrophages M2 polarization has attracted growing attention for improving osteogenesis. Here, the in situ growth of tunable gold nanoparticles (AuNPs) on titania nanotubes (TiNTs) array was realized by electrodeposition, with the guidance of TiNTs. The fabricated Au layer showed excellent biocompatibility with different osteoimmune effects. Briefly, the Au deposition on 5 and 10 V anodized TiNTs surface could induce RAW264.7 cells to M2 polarization, whereas the Au deposition on 20 V anodized TiNTs surface showed M1 polarization, as indicated by various markers determination through immunofluorescence staining, qPCR, Western blot, and ELISA. Furthermore, the osteogenic differentiation of MC3T3-E1 was significantly enhanced by the macrophages conditioned medium from the Au@10VNTs surface. The in vivo tests also confirmed denser and thicker new trabecula bone formation and more M2 macrophages infiltration both on and adjacent to the Au@10VNTs implant surface. In mechanism, the cytokine array analysis of macrophages conditioned medium from the Au@10VNTs surface revealed the upregulation of pro-healing cytokines such as IL-10 and VEGF and downregulation of pro-inflammatory cytokines such as IL-1β and MCSF. In addition, the NF-κB pathway was significantly inhibited. In conclusion, the electrodeposition of a Au layer guided by TiNTs is a promising strategy for reducing postoperative inflammatory reactions and improving osseointegration through modulating macrophages polarization.

Macrophages and osteoclasts are both derived from monocyte/macrophage lineage, which plays as the osteoclastic part of bone metabolism. Although they are regulated by bone implant surface nanoarchitecture and involved in osseointegration, the beneath mechanism has not been simultaneously analyzed in a given surface model and their communication with osteoblasts is also blurring. Here, the effect of implant surface topography on monocyte/macrophage lineage osteoclastogenesis and the subsequent effect on osteogenesis are systematically investigated. The nanoporous surface is fabricated on titanium implant by etching and anodizing to get the nanotubes structure. The early bone formation around implant is significantly accelerated by the nanoporous surface in vivo. Meanwhile, the macrophage recruitment and osteoclast formation are increased and decreased respectively. Mechanistically, the integrin mediated FAK phosphorylation and its downstream MAPK pathway (p-p38) are significantly downregulated by the nanoporous surface, which account for the inhibition of osteoclastogenesis. In addition, the nanoporous surface can alleviate the inhibition of osteoclasts on osteogenesis by changing the secretion of clastokines, and accelerate bone regeneration by macrophage cytokine profiles. In conclusion, these data indicate that physical topography of implant surface is a critical factor modulating monocyte/macrophage lineage commitment, which provides theoretical guidance and mechanism basis for promoting osseointegration by coupling the osteogenesis and osteoclastogenesis., Graphical abstract This paper investigates the modulation of osteogenesis by monocyte/macrophage lineage on titanium surface nanoarchitecture. The nanoporous surface promotes bone regeneration by changing the secretion profiles of macrophage (Mϕ) cytokines and clastokines. Mechanistically, the nanoporous surface inhibit the differentiation of macrophages into osteoclasts by blocking integrin mediated FAK phosphorylation and downstream MAPK pathway.Image 1, Highlights • Nanoporous implant inhibits osteoclastogenesis via integrin β1/FAKpY397/MAPK. • Nanoporous implant with larger diameter inhibits osteoclastogenesis more strongly. • Nanoporous implant increases osteogenic cytokines of macrophages/osteoclasts.

The comprehensive recognition of communications between bone marrow mesenchymal stem cells (bm-MSCs) and macrophages in the peri-implant microenvironment is crucial for implantation prognosis. Our previous studies have clarified the indirect influence of Ti surface topography in the osteogenic differentiation of bm-MSCs through modulating macrophage polarization. However, cell communication is commutative and multi-directional. As the immune regulatory properties of MSCs have become increasingly prominent, whether bm-MSCs could also play an immunomodulatory role on macrophages under the influence of Ti surface topography is unclear. To further illuminate the communications between bm-MSCs and macrophages, the bm-MSCs inoculated on Ti with nanoporous topography were indirectly co-cultured with macrophages, and by blocking exosome secretion or extracting the purified exosomes to induce independently, we bidirectionally confirmed that under the influence of TiO2 nanoporous topography with 80–100 nm tube diameters, bm-MSCs can exert immunomodulatory effects through exosome-mediated paracrine actions and induce M1 polarization of macrophages, adversely affecting the osteogenic microenvironment around the implant. This finding provides a reference for the optimal design of the implant surface topography for inducing better bone regeneration.

Mesoporous silica thin film has been widely used in various fields, particularly the medical implant coating for drug delivery. However, some drawbacks remain with the films produced by traditional method (evaporation-induced self-assembly, EISA), such as the poor permeability caused by their horizontal aligned mesochannels. In this study, the vertical aligned mesoporous silica thin film (VMSTF) is uniformly grown alongside the walls of titania nanotubes array via a biphase stratification growth method, resulting in a hierarchical two-layered nanotubular structure. Due to the exposure of opened mesopores, VMSTF exhibits more appealing performances, including rapid degradation, efficient small-molecular drug (dexamethasone) loading and release, enhanced early adhesion and osteogenic differentiation of MC3T3-E1 cells. This is the first time successfully depositing VMSTF on nanoporous substrate and our findings suggest that the VMSTF may be a promising candidate for bone implant surface coating to obtain bioactive performances., Graphical abstract Image 1, Highlights • The film is successfully fabricated alongside the titania nanotubes array via a biphase stratification growth method. • The film appears a hydrophilic property, rapid degradation (

Wide usage of plastic products leads to the global occurrence of microplastics (MPs) in the aquatic environment. Due to the small size, they can be bio-ingested, which may cause certain health effects. The present review starts with summarizing the main sources of various types of MPs and their occurrences in the aquatic environment, as well as their transportation and degradation pathways. The analysis of migration of MPs in water environments shows that the ultimate fate of most MPs in water environments is cracked into small fragments and sinking into the bottom of the ocean. The advantages and disadvantages of existing methods for detection and analysis of MPs are summarized. In addition, based on recent researches, the present review discusses MPs as carriers of organic pollutants and microorganisms, and explores the specific effects of MPs on aquatic organisms in the case of single and combined pollutants. Finally, by analysing the causes and influencing factors of their trophic transfer, the impact of MPs on high-level trophic organisms is explored.

The biological treatment efficiency of dye wastewater using activated sludge (AS) is largely limited to the chromaticity and ecotoxicity of dyestuff. To alleviate this limitation, eleven industrial-grade disperse dyes were obtained from a fiber-dyeing factory, and for the first time, we studied the decolorization and detoxification effects of using the

Ozonation is often applied to eliminate the recalcitrant contaminants in water. During the process, toxic transformation products (TPs) can be generated mainly via the reactions with ozone and hydroxyl radicals (

Background The proper topography of implant surface can induce macrophages polarization, whereas the regulation mechanism has not been fully deciphered. The study aimed to examine the regulation mechanism of macrophages M2 polarization by titanium (Ti) implant surface micro/nano topography. Results Firstly, the titanium implant micropits-nanotubular surface with ~30 nm diameters (MNT) can induce the M2 polarization of RAW264.7 spontaneously, as indicated by the spindle-like cell morphological alteration and specific molecular marker arginase-1 (Arg1) expression. Next, the autophagic vacuoles (AVs) number is significantly increased on MNT surface, as confirmed by the monodansylcadaverine (MDC) and CYTO-ID staining as well as the transmission electron microscope (TEM) observation. In addition, increasing or decreasing the autophagosomes number by rapamycin or 3-methyladenine (3-MA) will result in augmentation or attenuation of Arg1. Furthermore, blocking the fusion between autophagosomes and lysosomes by bafilomycin also significantly reduces Arg1, even in the presence of rapamycin. Finally, the ERK phosphorylation is selectively upregulated on MNT surface and the AVs number and Arg1 expression are significantly suppressed by U0126 treatment. Conclusion Our findings suggest that the ERK-Beclin-1-autophagy axis may play a pivotal role in the regulation of M2 polarization induced by nanotopography.

Developing a greener, sustainable catalyst is a very important but challenging task in organic synthesis. Herein, for the first time, we choose more economical and greener surface modified sewage sludge-derived carbonaceous materials (SW) treated by perchloric acid as a new catalyst for carbene insertion of α-aryl α-diazoacetates into O–H bonds of phenols with good yields and high functional group tolerance. Significantly, we explored the scope of natural phenols with compelling biological activity, and successfully afforded the O–H insertion and meta C–H functionalization products. Their structures have been confirmed by single-crystal X-ray crystallography. Furthermore, the bioactivities (anti-tumor and anti-inflammatory) of the majority of O–H insertion products are better than those of the natural phenols themselves. The IC50 values indicated that the remarkable compounds 7a (IC50 = 16.80 μM) and 7c (IC50 = 16.48 μM) had better inhibition for tumor cell A-549 than positive control DDP (IC50 = 20.62 μM). It should be noted that these transformations may provide a new strategy to derive natural products and discover new drugs.

Polybrominated diphenyl ethers (PBDEs), commonly used as flame retardants in a wide variety of consumer products, are emerging persistent pollutants and ubiquitously distributed in the environment. The lack of proper bacterial populations to detoxify these recalcitrant pollutants, in particular of higher brominated congeners, has confounded the attempts to bioremediate PBDE-contaminated sites. In this study, we report a

Nebivolol (NEB), a β-blocker frequently used to treat cardiovascular diseases, has been widely detected in aquatic environments, and can be degraded under exposure to UV radiation, leading to the formation of certain transformation products (UV-TPs). Thus, the toxic effects of NEB and its UV-TPs on aquatic organisms are of great importance for aquatic ecosystems. In the present study, the degradation pathway of NEB under UV radiation was investigated. Subsequently, zebrafish embryos/larvae were used to assess the median lethal concentration (LC

Despite extensive investigation on the toxicity of microplastics (MPs), an emerging global concern, little is known about the combined toxicity of MPs and co-occurring pollutants in aquatic environments. In this study, the combined toxicity of polystyrene MPs and sulfamethoxazole (SMZ) antibiotics was explored in zebrafish embryos in terms of the developmental, physiological, and endocrine toxicities. Exposure to PS and SMZ induced mortality (rate: 25.0 ± 7.5%) and malformation (rate: 20~35%) at multiple regions and stages of zebrafish development. Physiological toxicity was also induced as shown by the significant decrease in fetal movement (by 31.1~37.0%) and swimming frequency (by 26.9~36.8%) and the increase in heartbeat rate (by 19.0~20.9%). Finally, PS and SMZ exposure also induced extensive endocrine toxicities in zebrafish as confirmed by increases in various biomarkers including vitellogenin, 17β-estradiol, testosterone, and triiodothyronine. The combination index showed that antagonistic effects were present between PS and SMZ toxicity, which slightly decreased their combined toxicity. This study aims to further understand the combined toxicity of MPs and co-occurring pollutants in aquatic environments.

A p-type TiO2 with Ti vacancies (D-TiO2 ) was synthesized by a facile solvothermal treatment, and Ag/TiO2 with different Ag loading amount was prepared through a photo-reduction deposition method. The samples were characterized through scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The adsorption and photocatalytic characteristics of tetrabromobisphenol A (TBBPA) on D-TiO2 and Ag/TiO2 were investigated. The adsorption of TBBPA on Ag/TiO2 was significantly enhanced and was five times greater than that of pure TiO2 . The increase in pH significantly inhibited the adsorption of TBBPA. The 2%-Ag/TiO2 nearly completely degraded TBBPA in 10 min under UV-Vis light (λ > 360 nm), and the apparent reaction rate constant (kapp ) reached 0.63 min-1 . The significantly enhanced UV-Vis light catalytic properties of the Ag/TiO2 in comparison with that of TiO2 were attributed to the increased adsorption capacity and electron transfer ability of the Ag/TiO2 . Free radical trap experiments results showed that holes and superoxide radicals play a major role in the catalytic degradation of TBBPA by Ag/TiO2 . Moreover, the Ag/TiO2 catalyst exhibits high stability during TBBPA degradation even after three cycles. PRACTITIONER POINTS: Ti-defected TiO2 and Ag/TiO2 were synthesized using a solvothermal and photo-reduction deposition, respectively. Ag/TiO2 exhibited outstanding adsorption and photocatalytic activity for TBBPA removal under UV-Vis light. Holes and superoxide radicals play a major role in the photocatalytic degradation of TBBPA.

In this study, the degradation of ofloxacin (OFX) over Cu–Ce tyre carbon catalysts by the microwave assisted persulfate process was examined for the first time. The results showed that the Cu–Ce tyre carbon catalysts dramatically improved OFX decay efficiency. The optimal reaction conditions were the Cu–Ce tyre carbon catalysts of 2.0 g/L and the persulfate dosage of 12.0 g/L under microwave power of 400 W at 60 °C. The OFX conversion and total organic carbon (TOC) removal reached 95.8% and 87.6%, respectively, after 60 min catalytic oxidation under optimal conditions. To identify the properties of Cu–Ce tyre carbon catalyst, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), the Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and the ultraviolet–visible (UV–vis) diffuse reflectance spectra studies have been carried out. Eleven kinds of degradation products and five pathways during degradation process of OFX and degradation products were identified by GC–MS and HRMS.

Gabapentin-lactam (GBP-L) is a transformation product (TP) of gabapentin (GBP), a widely used anti-epileptic pharmaceutical. Due to its high persistence, GBP-L has been frequently detected in the surface water. However, the effects of GBP-L on aquatic organisms have not been thoroughly investigated. In the present study, zebrafish (Danio rerio) embryos as a model organism were used to study the impacts of GBP-L in terms of embryos LC50, spontaneous movement at 24 hpf (hours post fertilization), heartbeat rates at 48 hpf, and body length at 72 hpf, with the concentrations of GBP-L down to 0.01 μg/L, covering its environmental concentrations. Various biomarkers from nervous, antioxidant and immune systems of zebrafish larvae were analyzed, including acetylcholinesterase, acetylcholine, dopamine, gamma-aminobutyric acid, superoxide dismutase, catalase, glutathione S-transferase, C reactive protein, and lysozyme, to assess its toxicity on these systems. RT-qPCR was then used to further verify the results and explain the toxicological mechanism at the gene level. The results demonstrated that GBP-L is much more toxic than its parent compound, and could lead to adverse impacts on the aquatic organisms even at every low concentrations.

Background The proper topography of implant surface can induce macrophages polarization, whereas the regulation mechanism has not been fully deciphered. The study aimed to examine the regulation mechanism of macrophages M2 polarization by titanium (Ti) implant surface micro/nano topography. Results Firstly, the titanium implant micropits-nanotubular surface with ~30 nm diameters (MNT) can induce the M2 polarization of RAW264.7 spontaneously, as indicated by the spindle-like cell morphological alteration and specific molecular marker arginase-1 (Arg1) expression. Next, the autophagic vacuoles (AVs) number is significantly increased on MNT surface, as confirmed by the monodansylcadaverine (MDC) and CYTO-ID staining as well as the transmission electron microscope (TEM) observation. In addition, increasing or decreasing the autophagosomes number by rapamycin or 3-methyladenine (3-MA) will result in augmentation or attenuation of Arg1. Furthermore, blocking the fusion between autophagosomes and lysosomes by bafilomycin also significantly reduces Arg1, even in the presence of rapamycin. Finally, the ERK phosphorylation is selectively upregulated on MNT surface and the AVs number and Arg1 expression are significantly suppressed by U0126 treatment. Conclusion Our findings suggest that the ERK-Beclin-1-autophagy axis may play a pivotal role in the regulation of M2 polarization induced by nanotopography.

Various pollutants co-exist in the aquatic environment such as carbamazepine (CBZ) and copper (Cu), which can cause complex effects on inhabiting organisms. The toxic impacts of the single substance have been studied extensively. However, the studies about their combined adverse impacts are not enough. In the present study, zebrafish were exposed to environmental relevant concentrations of CBZ (1, 10, and 100 μg/L), Cu (0.5, 5, and 10 μg/L) and the mixtures (1 μg/L CBZ + 0.5 μg/L Cu, 10 μg/L CBZ + 5 μg/L Cu, 100 μg/L CBZ + 10 μg/L Cu) for 45 days, the effects on nervous and antioxidant systems of zebrafish were investigated. The results demonstrated that, in comparison with single exposure group, the combined presence of CBZ and Cu exacerbated the effect of antioxidant system (the ability of inhibition of hydroxyl radicals (IHR), superoxide dismutase (SOD), catalase (CAT) and glutathione S-transferase (GST)) but not nervous system (Acetylcholinesterase [AChE]). The qPCR results supported the changes of corresponding enzymes activities. Hepatic histopathological analysis verified the results of biomarkers. Our work illustrated that the toxicity of mixed pollutants is very complicated, which cannot simply be inferred from the toxicity of single pollutant, and calls for more co-exposure experiments to better understanding of the co-effects of pollutants on aquatic organisms.

The titanium implant surface topography optimization for improving osseointegration has been performed for many years, whereas understanding the mechanisms of topography-induced osteogenic differentiation is still insufficient. In this study, the micro/nano-textured topography was created on titanium implant surface by acid etching and anodization. The MC3T3-E1 cells were incubated with different surfaces and the RNA sequencing technique was performed to obtain the transcriptomic information, which suggested the enrichment at "membrane" and "organelle" (GO) as well as "Calcium signal pathway" (KEGG). Consequently, a special attention was paid to the store-operated calcium entry (SOCE) mediated by Orai1 at ER-PM contact site. By fluorescence staining and western blot, it was confirmed that the Orai1 was upregulated on the micro/nano-textured titanium surface, which was correlated to the enhanced osteogenic differentiation induced by topography. Further experiments indicated that the CaMKII/ERK1/2 pathway was involved in. This research is the first time giving a comprehensive transcriptomic information of osteoblasts on micro/nano-textured topography and may provide deeper insight into the interaction between biomaterials and host.

Cadmium (Cd) and lead (Pb) contaminations are disturbing environmental issues, which causes serious harm to aqueous systems and human health. Therefore, removing them from aqueous solution is essential to prevent its damage to the environment. Environmental adsorption research as one solution has seen a boom over the past decade. Using modified biochar has proved to be more suitable for the adsorption of cadmium and lead. Most of the studies apply a routine method such as kinetic and isotherm modelling to demonstrate the macroscopic trend of adsorption, often without elaborative evaluation of the effectiveness and characteristics of the models. This review compiles different adsorption kinetics and isotherms models and also presents their origins, modified versions, and their applicability in the liquid adsorption situation. The effect of experimental parameters and adsorption mechanisms are discussed to study the adsorption performances of modified biochar. The adsorption mechanism was majorly by surface precipitation, ion exchange, electrostatic attraction, complexation and physical adsorption. The adsorption was majorly endothermic and spontaneous. Additionally, preparation and regeneration of modified biochar are also presented to provide a direction for sustainable improvement. This paper summarizes with a note on challenges, prospects and future perspectives of adsorption of cadmium and lead pollutions.

Sulfamethoxazole (SMX) is a commonly used antibiotic for both human and animals. The frequent detection of SMX in natural water bodies and sediment has become an issue of great environmental concern due to its potential risk to induce antibiotic resistance in pathogenic bacteria. In the present work, the catalytic wet peroxide oxidation (CWPO) was investigated to remove SMX with sludge-derived carbon (SC) as a cheap alternative catalyst. Different acids were used to modify SC. It was found that SC modified with sulphuric acid (SC-H2SO4) demonstrated the best catalytic activity. The removal efficiency of SMX and TOC was 97.7% and 65.7%, respectively, after 260 min, at pH 5 with a dosage of 220 mg/L H2O2. The effects of temperature, initial pH and H2O2 dosage were also investigated. The study demonstrated that the increase of temperature could significantly improve the degradation of SMX from 10.0% at 20°C to 94.7% at 60°C.

Gabapentin (GAB) is an emerging contaminant that is frequently detected in water bodies across the globe. The present study used zebrafish as a model organism to investigate the effects of GAB on the early development of zebrafish and on its antioxidant system. Acute toxicity tests indicated that the 96 h LC50 value of GAB for zebrafish embryos was 59.9 g L−1. Further, it was observed that GAB causes malformation of embryos such as hemagglutination and pericardial edema. Compared to the control group, a significant enhancement (p < 0.05) of heartbeat rates was found at GAB concentrations exceeding 50 mg L−1, while the swimming frequency was clearly increased upon exposure to GAB at a concentration of 100 mg L−1 (p < 0.05). Additionally, the development of the zebrafish embryo was also negatively impacted after exposure to GAB as demonstrated by significantly decreased body lengths. Exposure to GAB at concentrations exceeding 50 mg L−1 significantly influenced the development of zebrafish, leading to malformation of organs and abnormal movements. Although no significant developmental effects of GAB were observed at environmentally relevant concentrations (0.1 and 10 μg L−1), further research about the antioxidant system confirmed that severe oxidant injury happened inside the organisms. catalase (CAT), lactate dehydrogenase (LDH), glutathione S-transferase (GST), glutathione (GSH) and the ability of inhibition of hydroxyl radicals (IHR) were used as biomarkers in the present study to illustrate GAB toxicity at environmentally relevant concentrations. The results showed that activities of CAT, LDH and GST as well as IHR were all elevated after GAB exposure, which proved that ROS were formed in the body as derived from GAB exposure. Among all of these biomarkers, CAT was the most sensitive one to evaluate the influence of GAB, and showed a significant increase even at a very low exposure concentration (0.1 μg L−1).

The injectable hydrogel is an ideal reservoir for drug delivery. In this study, a new injectable DNA hydrogel was fabricated. Firstly, the DNA pre-gel was obtained by heat-cool treatments to induce cross-linkage through base-paring. Then, the pre-gel was cross-linked with chitosan (CS) through electrostatic interaction, which was confirmed by ATR-FTIR and XPS analysis. The DNA-CS hybrid gel showed finely tunable various properties such as porosity and viscosity. To simulate the biomedical application, the dexamethasone (Dex) was loaded into the gel and coated onto titanium implant surface to induce macrophages M2 polarization. Due to the excellent biocompatibility and Dex delivery, the decorated implant surface was favorable for RAW264.7 cells growth and showed powerful effects of inducing M2 polarization both in vitro and in vivo. In conclusion, it is the first report of DNA hydrogel synthesis via CS cross-linkage and the injectable DNA-CS hybrid gel was superb for therapeutic delivery.

1,4,7,10-Tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) derivatives are applied in quantitative proteomics owing to their ability to react with different functional groups, to harbor lanthanoides and hence their compatibility with molecular and elemental mass spectrometry. The new DOTA derivatives, namely Ln-MeCAT-Click and Ln-DOTA-Dimedone, allow efficient thiol labeling and targeting sulfenation as an important post-translational modification, respectively. Quantitative applications require the investigation of fragmentation behavior of these reagents. Therefore, the fragmentation behavior of Ln-MeCAT-Click and Ln-DOTA-Dimedone was studied using collision-induced dissociation (CID), infrared multiphoton dissociation (IRMPD) and higher-energy collision dissociation (HCD) using different energy levels, and the efficiency of reporter ion production was estimated. The efficiency of characteristic fragment formation was in the order IRMPD > HCD (normal energy level) > CID. On the other hand, the application of HCD at high energy levels (HCD@HE; NCE > 250%) resulted in a significant increase in reporter ion production (33-54%). This new strategy was successfully applied to generate label-specific reporter ions for DOTA amino labeling at the N-termini and in a quantitative fashion for the estimation of amino:thiol ratio in peptides. Copyright © 2017 John Wiley & Sons, Ltd.

A p-type TiO

In this paper, the relationship with reliability, maintainability, testability, safety and risk related to parts failure have been analyzed. The process of determining and collecting important parts bring catastrophic consequences has been established. The risk assessment process has been formed considering the man-machine-environment factors, which will decrease the loss of human and aircraft resources.

Gabapentin (GPT) has become an emerging contaminant in aquatic environments due to its wide application in medical treatment all over the world. In this study, embryos of zebrafish were exposed to gabapentin at realistically environmental concentrations, 0.1 μg/L and 10 μg/L, so as to evaluate the ecotoxicity of this emergent contaminant. The transcriptomics profiling of deep sequencing was employed to illustrate the mechanisms. The zebrafish (Danio rerio) embryo were exposed to GPT from 12 hpf to 96 hpf resulting in 136 and 750 genes differentially expressed, respectively. The results of gene ontology (GO) analysis and the Kyoto encyclopedia of genes and genomes (KEGG) pathway analysis illustrated that a large amount of differentially expressed genes (DEGs) were involved in the antioxidant system, the immune system and the nervous system. RT-qPCR was applied to validate the results of RNA-seq, which provided direct evidence that the selected genes involved in those systems mentioned above were all down-regulated. Acetylcholinesterase (AChE), lysozyme (LZM) and the content of C-reactive protein (CRP) were decreased at the end of exposure, which is consistent with the transcriptomics results. The overall results of this study demonstrate that GPT simultaneously affects various vital functionalities of zebrafish at early developmental stage, even at environmentally relevant concentrations.

In this study, natural manganese oxides (MnO x ), an environmental material with high redox potential, were used as a promising low-cost oxidant to degrade the widely used dyestuff methylene blue (MB) in aqueous solution. Although the surface area of MnO x was only 7.17 m 2 g −1 , it performed well in the degradation of MB with a removal percentage of 85.6% at pH 4. It was found that MB was chemically degraded in a low-pH reaction system and the degradation efficiency correlated negatively with the pH value (4–8) and initial concentration of MB (10–50 mg l −1 ), but positively with the dosage of MnO x (1–5 g l −1 ). The degradation of MB fitted well with the second-order kinetics. Mathematical models were also built for the correlation of the kinetic constants with the pH value, the initial concentration of MB and the dosage of MnO x . Furthermore, several transformation products of MB were identified with HPLC-MS, which was linked with the bond energy theory to reveal that the degradation was initiated with demethylation.

Sulfamethazine (SMZ), a kind of sulfonamide antibiotics, can exist for a long periods of time and has been widely detected in the environment, which could pose a potential health threat to human beings. In this study, sludge-derived carbon (SC) catalyst was modified and applied to degrade SMZ during catalytic oxidation process. Degradation products and possible transformation pathways were investigated based on data of GC–MS. The toxicity evolution of SMZ degradation after catalytic oxidation process was tested with zebrafish and microbial degradation respirometer. As a consequence, SC modified with nitric acid (SC HNO3) exhibited highly catalytic efficiency reached 92.2% SMZ conversion and 75.2% total organic carbon (TOC) removal rate after 480 min. Ten kinds of possible products were identified by GC–MS during degradation process of SMZ, indicating two possible pathways. No pronounced malformation was observed in the toxicity experiments with zebrafish until 120 h post fertilization (hpf). However, further analysis showed that zebrafish incubated with SMZ solution had higher mortality, lower hatching rate, slower spontaneous movement and shorter body length, compared with the group used normal nutrient solution, while the water after treatment had lower toxicity effects on zebrafish. The toxicity experiments with microbial degradation respirometer showed that SMZ solution had lower value of oxygen uptake, which indicated that SMZ solution had higher values of toxicity and inhibition of pharmaceutical compounds. This study provides a catalyst with low cost and high catalytic efficiency for degradation process of SMZ and gives a deeper insight into the ecotoxicity of treated water.

Figures S1 - S2 and Table S1

The inflammatory response is the first and inevitable event after implant surgery in vivo, in which the macrophages M1 polarization is mediated. Numerous publications indicate that the physical properties of implant surface nanostructure can influence macrophages M1 polarization status, whereas the regulation mechanisms have not been elucidated yet. Unlike the conventional biochemical factors that can directly bind to the cellular surface receptors or be transported into cytoplasm, the physical information of implant surface nanostructure can only be sensed by direct contact with cells. Therefore, we infer that the implant surface nanostructure may have unique regulation mechanisms. In this study, we compared the influences of the titanium implant surface coated with titania nanotubes on the surface (∼100 nm diameter, NT-100) and the standard IFN-γ/LPS stimulation on the macrophages M1 polarization. Both the NT-100 surface and IFN-γ/LPS stimulation could induce macrophages M1 polarization, indicated by significant upregulation of M1-specific molecules including CD86, iNOS, CCR7 and IL-1β, without affecting the M2-specific molecules including CD206, Arg1 and IL-10. However, we found that the IFN-γ/LPS induced macrophages M1 polarization was mediated by RBP-J-IRF8 pathway, whereas the NT-100 surface was more related to FAK-MAPKs pathway, particularly the JNK and ERK1/2 signaling. Our study demonstrated that the implant surface nanostructure has great potential to trigger the host inflammatory response through distinct pathways from conventional biochemical factors, which may remind us to re-consider the unique regulation mechanisms of nano surface on cell functions. Our finding offers a theoretical basis for titanium implant modification to benefit tissue integration.

Ofloxacin (OFL), a typical fluoroquinolone antibiotic, has been frequently detected in the aquatic environment and may cause potential ecological risks. In this work, biogenic Fe-Mn oxides (bio-FeMnOx) were produced by Pseudomonas sp. F2. The harvested bio-FeMnOx mainly consisted of γ-Fe2O3 and a mix valence of Mn2+, Mn3+ and Mn4+ and was applied for the first time to catalyze the heterogeneous photo-Fenton for the degradation of OFL as a model organic contaminant. It was found that bio-FeMnOx exhibited a 2-fold higher catalytic activity than chemically synthesized Fe-Mn oxides: pseudo-first-order kinetic constant 3.41 × 10−2 min−1 vs 1.53 × 10−2 min−1, respectively. The scavenger study indicated the substantial participation of hydroxyl radical (OH ), electron (e−) and hole (h+) in the degradation of OFL but a negligible involvement of superoxide radical anion (O2 −). Possible intermediates were identified with HPLC-MS, revealing that the degradation may involve the reactions of hydrolysis, dehydration, dealkylation, and C C breakage. In addition, nearly 50% of the biological respiration inhibition of OFL was removed after the heterogeneous photo-Fenton over bio-FeMnOx.

In this study, heterogeneous Fenton-like degradation of ofloxacin (OFX) was investigated by sludge derived carbon (SC). The effects of SC catalyst, temperature and pH on the efficiency of ofloxacin degradation were investigated. SC treated with sulfuric acid (SC-H2SO4) performed high catalytic activity, indicating that sulfate group produced low pH of the surface and was beneficial for heterogeneous Fenton-like degradation. The removal of ofloxacin and TOC was 91.5% and 62.3%, respectively, after 180 min adsorption and 540 min oxidation, at pH 6 and a dosage of 138 mg L−1 H2O2. It was found that OFX conversion increased with the decrease of pH and OFX was degraded under the wide range of pH (3–6) by SC-H2SO4. These promising results clearly demonstrate the potential of the heterogeneous Fenton-like process for the effective degradation of ofloxacin by SC-H2SO4. Based on intermediated products identified by gas chromatography–mass spectrometry, a possible OFX oxidation pathway in Fenton-like reaction was proposed.

In this work, we present a two-step labeling approach for the efficient tagging with lanthanide-containing complexes. For this purpose, derivatization of the cysteine residues with an alkyne group acting as linker was done before the DOTA complex was introduced using in situ click chemistry. The characterization of this new methodology is presented including the optimization of the labeling process, demonstration of the quantitative capabilities using both electrospray ionization mass spectrometry (ESI-MS) and inductively coupled plasma mass spectrometry (ICP-MS) detection, and study of the fragmentation behavior of the labeled peptides by collision-induced dissociation (CID) for identification purposes. The results show that, in terms of labeling efficiency, this new methodology improves previously developed DOTA-based label strategies, such as MeCAT-maleimide (metal-coded affinity tag, MeCAT-Mal) and MeCAT-iodoacetamide (MeCAT-IA) reagents. The goal of reducing the steric hindrance caused by the voluminous DOTA complex was fulfilled allowing both, quantification and identification of labeled biopolymers.

In aquatic environments, organisms are exposed to mixtures of pollutants which may change the toxicity profile of each contaminant, compared to its toxicity alone. Carbamazepine (CBZ) and cadmium (Cd) are among the pollutants that co-occur in aquatic environments. To date, most research about their toxicity towards aquatic vertebrates is based on single exposure experiments. The present study aims to evaluate single and combined effects of CBZ and Cd on biomarkers in female Danio rerio (zebrafish) by exposing them to environmentally relevant concentrations of these two pollutants for ten days. Four kinds of biomarkers involved in antioxidant systems, energy metabolism, nervous system, and endocrine disruption, respectively, were studied. Our research results coincided with those of former studies in single exposure experiments. However, the combined exposure of CBZ and Cd exerted different responses from other studies in which these two contaminants were examined alone in zebrafish. The present study evidenced the need to conduct more coexposure studies to enhance the environmental relevance of these experimental results.

The degradation behavior of oxytetracycline (OTC) in aqueous solution using sludge derived carbon (SC) was investigated in this paper. SC treated with different kinds of acids were characterized by BET and thermogravimetric analysis. The results showed that SC-H2SO4 exhibited higher catalytic activity than SC-HCl and SC. The maximum removal of OTC and total organic carbon (TOC) after catalytic oxidation process at 60 °C was 92.6% and 70.2%, respectively. The safety of antibiotics after advanced oxidation processes (AOPs) has attracted much attention due to the possibility of toxicity increasing. Seven intermediate products were identified by GC–MS and four pathways were proposed. Furthermore, the toxicity of OTC degradation was investigated by zebrafish embryos for the first time. Zebrafish incubated with OTC solution (TE2) had haemagglutination, pericardial edema and showed significant changes in heartbeat, body length, and roaming frequency compared with the normal nutrient solution (TE1). Moreover, all zebrafish embryos had condensation phenomenon and did not hatch out in the treated OTC solution (TE3). In contrast, the zebrafish could hatch out without abnormality cultured with the treated OTC solution adjusted to the neutral pH (TE4). Results indicated that the treated OTC solution after catalytic oxidation process should be adjusted to the neutral pH to reduce the toxicity to the ecology.

Weikun Tang,1 Junpeng Fan,1 Yide He,1 Bihai Huang,2 Huihui Liu,1 Daiwen Pang,2 Zhixiong Xie11College of Life Sciences, 2College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, People's Republic of ChinaAbstract: Quantum dots (QDs) have many potential clinical and biological applications because of their advantages over traditional fluorescent dyes. However, the genotoxicity potential of QDs still remains unclear. In this paper, a plasmid-based system was designed to explore the genotoxic mechanism of QDs by detecting changes in DNA configuration and biological activities. The direct chemicobiological interactions between DNA and mercaptoacetic acid-coated CdSe-core QDs (MAA–QDs) were investigated. After incubation with different concentrations of MAA–QDs (0.043, 0.13, 0.4, 1.2, and 3.6 µmol/L) in the dark, the DNA conversion of the covalently closed circular (CCC) DNA to the open circular (OC) DNA was significantly enhanced (from 13.9% ± 2.2% to 59.9% ± 12.8%) while the residual transformation activity of plasmid DNA was greatly decreased (from 80.7% ± 12.8% to 13.6% ± 0.8%), which indicated that the damages to the DNA structure and biological activities induced by MAA–QDs were concentration-dependent. The electrospray ionization mass spectrometry data suggested that the observed genotoxicity might be correlated with the cadmium–mercaptoacetic acid complex (Cd–MAA) that is formed in the solution of MAA–QDs. Circular dichroism spectroscopy and transformation assay results indicated that the Cd–MAA complex might interact with DNA through the groove-binding mode and prefer binding to DNA fragments with high adenine and thymine content. Furthermore, the plasmid transformation assay could be used as an effective method to evaluate the genotoxicities of nanoparticles.Keywords: genotoxicity, MAA CdSe quantum dots, cadmium–MAA complex, transformation assay, DNA&nbsp