Analysis of brominide disinfection by-products (DBPs) in aquaculture water using ultra-high performance liquid chromatography-quadrupole-time of flight mass spectrometry (UPLC-Q-tof/MS).

BACKGROUND: halogenic disinfectants have been shown to produce toxic and carcinogenic disinfection by-products in the water disinfection process. Dibromohydantoin (DBDMH) is a commonly used water disinfectant in aquaculture. Aquaculture water has more complex matrix, and the analytical method for disinfection by-products (DBPs) have not been reported. Since the content of DBPs is related to the external conditions such as ultraviolet irradiation, temperatures, pH and humic acid. The semi-target screening method for mainly DBPs based on tracing mass spectrometry fragments of bromide and accurate mass of high resolution mass spectrometry was established by ultra performance liquid chromatography-quadrupole-time of flight-mass spectrometry (UPLC-Q-tof/MS). Br-DBPs as a important class of DBPs from DBDMH, which quantification analysis methods were developed based on accurate mass of high resolution mass spectrometry. METHODS: through screening method to identify unknown Br-DBPs and quantitative analysis of the typical 4-bromophenol by-product of accurate mass was established. The conditions of the instrument parameters of mass spectrometry and SPE sample preparation procedure in complex real sample were optimized. The high efficiency method was demonstrated for the determination of Br-DBPs with a good linear correlation (R2 = 0.999) in the range of 0.500-200 µg L-1 and limit of detections (LODs) and limit of quantifications (LOQs) were 0.0250 ng L-1 and 0.0834 ng L-1, respectively. CONCLUSION: the developed screening and quantification analytical strategy for Br-DBPs is rapid, accurate and sensitivity applicable for environmental in aquaculture water monitoring.

Screening and identification of lipase inhibitors extracted from Dioscorea nipponica Makino by UV-vis and HPLC coupled to UPLC-Q-TOF-MS/MS.

Dioscoreae nipponica Makino (D. nipponica) as the rhizome of dioscoreaceae rich in steroidal saponins, has been reported to have the hypolipidemic effects etc. However, it is still unclear which exact active components are primary responsible for the beneficial effects. This study was conducted to fish out the lipase inhibitors from D. nipponica, and evaluate the inhibitory activity on porcine pancreatic lipase (PPL) through in vitro kinetic assay using p-nitrophenyl palmitate as substrate. Accordingly, the ethanolic extract was subjected to D101 macroporous resin purification for spectrophotometric screening, high performance liquid chromatography (HPLC) separation and structural characterization by ultra-performance liquid chromatography-quadrupole time-of-flight mass spectrometry. Through orlistat validation, the PPL inhibitory activity and IC50 value of the extract were respectively 68.34 ± 1.47 % and 107.05 µg/mL under the optimized inhibition conditions. From 6 steroidal saponins identified, the inhibitory components named the protodioscin, protogracillin, dioscin and gracillin were fished out by grouping separation and HPLC analysis. Furthermore, dioscin and gracillin with the parent structure of diogenin were confirmed as the major inhibitors by virtue of stability tests based on transformation of protodioscin and protogracillin. Finally, the inhibitory mechanism of the major inhibitors toward PPL was further clarified by kinetic analysis and molecular docking analysis. The proposed method not only revealed the PPL inhibitory components in D. nipponica, but also provided an effective approach to hierarchical screening of PPL inhibitors from natural plants.

Ultrasonic Enhancement of Aqueous Two-Phase Extraction and Acid Hydrolysis of Flavonoids from Malvaviscus arboreus Cav. Flower for Evaluation of Antioxidant Activity.

The ultrasonic-assisted aqueous two-phase extraction (UAATPE) of flavonoid glycosides from Malvaviscus arboreous Cav. flower (MACF) was developed using ethanol/ammonia sulfate systems, followed by the ultrasonic-assisted acid hydrolysis (UAAH) of the top extract with HCl solution. The optimization of UAATPE and UAAH processes was accomplished by single-factor experiments and response surface methodology. As a result, the flavonoid glycosides enriched in the top phase could achieve a maximum yield of 35.9 ± 1.1 mg/g by UAATPE and were completely hydrolyzed by UAAH deglycosylation. The flavonoid glycosides and their hydrolyzates were separated and characterized by high-performance liquid chromatography and ultra-high-performance liquid chromatography-quadrupole-time-of-flight mass spectrometry. Ultrasonic enhancement of the extraction and hydrolysis was explored by comparative study. Furthermore, the in vitro activity of the flavonoid glycosides and the aglycones were comprehensively evaluated by antioxidant activity assays, including ferric-reducing antioxidant power and scavenging DPPH, hydroxyl, and superoxide radicals. All of the IC50 values suggest that the antioxidant activity of flavonoid aglycones was stronger than that of their glucosides and even vitamin C, revealing that the deglycosylated flavonoids from MACF were the more powerful antioxidants. This study provided an effective and eco-friendly strategy for the extraction, separation, and purification of flavonoids from MACF, as well as for the development of the potential flavonoid antioxidants.

Processing High-Performance Thermoelectric Materials in a Green Way: A Proof of Concept in Cold Sintered PbTe0.94Se0.06.

For years, most of the advanced polycrystalline thermoelectric (TE) materials are fabricated by spark plasma sintering (SPS) in the research field, mainly because of its high processing efficiency. However, issues like high energy consumption and an expensive apparatus have prevented the application of this strategy in industry. Herein, taking PbTe0.94Se0.06 (PTS) as a typical n-type mid-temperature material, we demonstrate that the cold sintering process (CSP) can serve as a green and cost-effective technology for preparing advanced TE materials. By selecting the solvothermal precursors as liquid sintering aids, the CSP-densified PTS shows a maximum figure of merit of 0.96 at 700 K, which is on par with, if not better than, the reported similar materials prepared by SPS. This remarkable performance is ascribed to the distinct densification procedure in the CSP: (1) the ultralow temperature alleviates the precipitation of Pb, which preserves the high carrier concentration of PTS; (2) the transient liquid phase forms intimate grain boundaries comparable to the high-temperature sintered one, leading to a high carrier mobility; (3) the dissolution-precipitation process greatly restrains the coarsening of precipitates, which effectively suppresses the bipolar effect and lattice thermal conductivity due to enhanced scattering. We believe that these results can greatly encourage the application of CSP in the future development of TE materials.

A Robust Hierarchical MXene/Ni/Aluminosilicate Glass Composite for High-Performance Microwave Absorption.

The 2D titanium carbide MXene with both extraordinary electromagnetic attenuation and elastic properties has shown great potential as the building block for constructing mechanically robust microwave absorbing composites (MACs). However, the weak thermal stability has inhibited the successful incorporation of MXene into the inorganic MACs matrix so far. Herein, an ultralow temperature sintering strategy to fabricate a hierarchical aluminosilicate glass composite is demonstrated by using EMT zeolite as starting powder, which can not only endow the composites with high sinterability, but also facilitate the alignment of MXene in the glass matrix. Accordingly, the highly oriented MXene and mesoporous structure can effectively reduce the conduction loss in the out-of-plane direction while maintaining its large polarization loss. Meanwhile, the in situ formed Ni nanoparticles via ion exchange serve as a synergistic modulator to further improve the attenuation capability and impedance matching of composite, resulting in a low reflection loss of -59.5 dB in X band and general values below -20 dB with a low fitting thickness from 4 to 18 GHz. More attractively, such a delicate structure also gives the composite a remarkable fracture strength and contact-damage-resistance, which qualifies the mesoporous glass composite as a structural MACs with a superior comprehensive performance.

Simultaneously Breaking the Double Schottky Barrier and Phonon Transport in SrTiO3-Based Thermoelectric Ceramics via Two-Step Reduction.

The low powder factor (PF) of polycrystalline oxide perovskites induced by the resistive grain boundaries or known as double Schottky barrier (DSB) greatly restricts their thermoelectric performance in application. Here, a general protocol including (i) powder and (ii) bulk reduction in H2/Ar forming gas is demonstrated to break the DSB in La and Nb codoped SrTiO3. While the powder reduction guarantees a high carrier concentration by fully stimulating the donor doping effect, the bulk reduction effectively lowers the DSB by influencing the point defects at grain boundaries, which is proved by the combination of cathode luminescence spectra and energy-dispersive X-ray spectroscopy in transmission electron microscopy. The Hall mobility can approach 10 cm2 V-1 s-1 after two-step reduction, which is similar to the level of single crystals. However, the Seebeck coefficient is not compromised, giving rise to high PF values up to 1.70 mW m-1 K-1 under proper reduction strength. Meanwhile, the reduction process also promotes mild precipitation of Nb nanoparticles, thus effectively lowering the lattice thermal conductivity by scattering phonons. As a result, a remarkable figure of merit reaching 0.4 at 700 K is obtained, which validates the two-step reduction as a reliable strategy toward "electron crystal-phonon glass" behavior in SrTiO3-based perovskites.

Electrochemical Synthesis and Electro-Optical Properties of Dibenzothiophene/Thiophene Conjugated Polymers With Stepwise Enhanced Conjugation Lengths.

A total of six conjugated polymers, namely PDBT-Th, PDBT-Th:Th, PDBT-2Th, PDBT-Th:2Th, PDBT-2Th:Th, and PDBT-2Th:2Th, consisting of dibenzothiophene, thiophene, and bithiophene were electrochemically synthesized. Their electrochemical and electrochromic properties were investigated in relation to the conjugation chain lengths of the thiophene units in the conjugated backbones. Density functional theory (DFT) calculations showed that longer conjugation lengths resulted in decreased HOMO-LUMO gaps in the polymers. The optical band gaps (E g,opt) and electrochemical band gaps (E g,cv) were decreased from PDBT-Th to PDBT-Th:Th, however, PDBT-Th:2Th, PDBT-2Th, PDBT-2Th:Th and PDBT-2Th:2Th displayed the similar band gaps. The conjugation length increments significantly improved the electrochemical stability of the conjugated polymers and exhibited reversible color changes due to the formation of polarons and bipolarons. The results suggest that the conjugated polymers prepared herein are promising candidates for fabricating flexible organic electrochromic devices.

Protective effect of luteolin on skin ischemia-reperfusion injury through an AKT-dependent mechanism.

Cutaneous ischemia­reperfusion (I/R) injury is one of the most crucial problems in flap surgery, which affects the survival of the skin flap and patient prognosis, luteolin, a plant derived flavonoid, has previously been shown to exert a variety of beneficial effects for reducing I/R injury in several organs. The aim of the present study was to evaluate the anti­inflammatory and anti­oxidative stress effects of luteolin on cutaneous I/R injury. The in vitro study were performed using a permanent human immortalized epidermal keratinocyte cell line (HaCaT), cells were cultured in the presence of luteolin and were then treated with hydrogen peroxide, the cell viability, mitochondrial membrane potential and the cell survival/apoptosis related signaling pathway activation were assessed to investigate the cytoprotective effects of luteolin. For in vivo experiments, skin flap I/R injury animal model was established in Sprague­Dawley rats, by measuring the area of flap survival, analyzing the expression of pro­inflammatory cytokine and evaluation of the histological changes in the skin tissue, the protective effects of luteolin on skin I/R injury were investigated. The function of protein kinase B (AKT) and heme oxygenase­1 (HO­1) activation on luteolin mediated I/R injury protection was assessed by administration of phosphoinositide­3­kinase/AKT inhibitor LY294002 and HO­1 inhibitor ZNPP. The results showed that luteolin treatment significantly increased the viability of HaCaT cells upon exposure to hydrogen peroxide, and the administration of luteolin in vivo significantly improved skin flap survival in the I/R injury rat model. The mechanisms underlying these beneficial effects included increased phosphoinositide­3­kinase/protein kinase B activation, improved expression of antioxidant enzyme, and scavenging the cytotoxic effects of reactive oxygen species (ROS). Taken together, the results suggested that luteolin preconditioning yielded significant protection against cutaneous I/R injury by protecting skin keratinocytes from ROS­induced damage.

Adsorption behavior of epirubicin hydrochloride on carboxylated carbon nanotubes.

The aim of this study was to understand the interaction between carboxylated carbon nanotubes (c-CNTs) and anticancer agents and evaluate the drug-loading ability of c-CNTs. We prepared carboxylated multi-walled carbon nanotubes (c-MWNTs) with nitric acid treatment, then evaluated the adsorption ability of c-MWNTs as adsorbents for loading of the anticancer drug, epirubicin hydrochloride (EPI), and investigated the adsorption behavior of EPI on c-MWNTs. Unmodified multi-walled carbon nanotubes (MWNTs) and single-walled carbon nanotubes (SWNTs) were included as comparative adsorbents. The results showed that carbon nanotubes were able to form supramolecular complexes with EPI via π-π stacking and possessed favorable loading properties as drug carriers. The Freundilich adsorption model was successfully employed to describe the adsorption process. Because of the high surface area and hydrogen bonding, c-MWNTs' adsorption efficiency was the highest and the most stable and their drug-loading capacity was superior to that of MWNTs. With the increase of pH, the adsorption capacity of EPI on the c-MWNTs increased. Low-temperature facilitated the adsorption. More rapid EPI adsorption rate and higher drug-loading ability were observed from c-MWNTs with smaller diameter. Moreover, the adsorption kinetics of EPI on c-MWNTs could be well depicted by using the pseudo-second-order kinetic model.