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A diphenyl prolinol TMS ether-catalyzed stereoselective reaction of 1-bromo-2-naphthols with enals has been developed. The organocatalyzed cross coupling-like reaction servers an efficient approach to sterically congested (E)-α-naphthyl enals. The formal C(sp2)-C(sp2) cross-coupling products are obtained in good yields and with excellent stereoselectivities in favor of E-isomers. A broad range of aromatic enals and 1-bromo-2-naphthols are tolerated. The synthetic strategy significantly expands the scope of the organocatalytic cross-coupling-like reactions by enabling sterically demanding 1-bromo-2-naphthols as viable substrates.

Oral squamous cell carcinoma (OSCC), the eighth most prevalent cancer in the world, arises from the interaction of multiple factors including tobacco, alcohol consumption, and betel quid. Chemotherapeutic agents such as cisplatin, 5‐fluorouracil, and paclitaxel have now become the first‐line options for OSCC patients. Nevertheless, most OSCC patients eventually acquire drug resistance, leading to poor prognosis. With the discovery and identification of non‐coding RNAs (ncRNAs), the functions of dysregulated ncRNAs in OSCC development and drug resistance are gradually being widely recognized. The mechanisms of drug resistance of OSCC are intricate and involve drug efflux, epithelial‐mesenchymal transition, DNA damage repair, and autophagy. At present, strategies to explore the reversal of drug resistance of OSCC need to be urgently developed. Nano‐delivery and self‐cellular drug delivery platforms are considered as effective strategies to overcome drug resistance due to their tumor targeting, controlled release, and consistent pharmacokinetic profiles. In particular, the combined application of new technologies (including CRISPR systems) opened up new horizons for the treatment of drug resistance of OSCC. Hence, this review explored emerging regulatory functions of ncRNAs in drug resistance of OSCC, elucidated multiple ncRNA‐meditated mechanisms of drug resistance of OSCC, and discussed the potential value of drug delivery platforms using nanoparticles and self‐cells as carriers in drug resistance of OSCC., The mechanisms of drug resistance are intricate and involve drug efflux, epithelial mesenchymal transition, DNA damage repair, and autophagy. Nano‐delivery and self‐cellular drug delivery platforms have a broad prospective for alleviating OSCC drug resistance. In particular, the combined application of new technologies (including CRISPR systems) opens up new horizons for treatment of OSCC drug resistance.

Polyolefins with high molecular weight and broad molecular weight distribution have attracted great attention due to their ease of processing and wide applications. In this paper, methylene-bridged asymmetric disalicylaldimine ligands bearing phenylthio and alkylthio sidearms (4a–4c) were synthesized from methylene-bridged disalicylaldehyde that reacted successively with 2-phenylthio and 2-alkylthio anilines, which then directly coordinated with TiCl4 to afford asymmetric bis-salicylaldiminato binuclear titanium complexes 5a–5c in one step. The asymmetric complexes were detailedly characterized by FTIR, 1H NMR, 13C NMR, and elemental analysis. Under the activation of modified methylaluminoxane (MMAO), these asymmetric complexes displayed high activity over 106 g mol(Ti)−1 h−1 atm−1 for ethylene polymerization and copolymerization with 1-hexene or norbornene. Compared with the corresponding mononuclear complexes, the asymmetric binuclear catalysts showed higher catalytic activity (up to 2.29 × 106 g mol(Ti)−1 h−1 atm−1) for ethylene polymerization to produce higher molecular weight polyethylenes with much wider molecular weight distribution due to the presence of two different active centers. For ethylene polymerization and copolymerization with 1-hexene, the catalytic activity of binuclear 5a which carries phenylthio and methylthio sidearms and the properties of the obtained polyolefins were more similar to those of mononuclear 6b which bears a phenylthio sidearm, indicating that the phenylthio group exerted major influences. However, for ethylene/norbornene copolymerization, 5a showed an activity significantly higher than that of 6b, yet similar to that of mononuclear 6a which bears a methylthio sidearm, indicating that the methylthio sidearm in 5a played a major role in this case. A smaller sidearm in the ligand was more conducive to the polymerization reaction when large comonomers were involved, and a balance of the steric hindrance between the ligand and the comonomer might be needed for achieving high catalytic performance.

A mild, organophotoredox synthetic protocol for forming C(sp3) -S/Se bond by reacting widespread redox-active esters with thio/selenosulfonates has been developed. The power of the synthetic manifold is fueled by an unprecedented broad substrate scope and wide functional group tolerance.

In this work, 8mol% yttria-stabilized zirconia (8YSZ) ripple-shaped electrolytes have been prepared by digital light processing (DLP) 3D printing and their electrochemical performances have been investigated. The total conductivities of flat samples printed at different angles were tested firstly to confirm that there is no huge influence on the electrochemical performance from the printing itself. Then, by using ripple-shaped electrolytes, primary cells were assembled and their electrochemical performance were investigated. Compared with the reference flat cell, an improvement of ~32% was achieved in the power density for the same thickness of the electrolyte (~200 µm) at 800 °C.

Sulfomycins are sulfur-rich, ribosomally synthesized, and post-translationally modified peptides (RiPPs) that are characterized by a 35-membered macrocyclic ring system with a pyridine domain central to five azoles and additional dehydroamino acids. The pathway through which these large thiopeptide antibiotics are formed in

In this work, a superhydrophobic material was successfully prepared with a water contact angle of about 155.5° and a rolling-off angle of about 6.8°, which showed superior UV resistance (365 nm, 5.0 ± 0.6 mW cm-2) for an illumination period of 30 h. The degradation of organic dyes, such as Nile red, methyl blue and orange, could be also achieved with our prepared surface. Anti-UV water-repellency was combined with photocatalysis to realize a self-cleaning surface for both dirt removal and organic degradation. Moreover, the reversible changes with superhydrophobicity and superhydrophilicity were induced by the self-healing property on such a surface, contributing to heavy and light oils/water separation. Because of ultra-long UV-resistance, photocatalysis, self-cleaning, self-healing and oil/water separation functions, our reported surface has potential for application in a variety of fields.

Purpose: Periodontitis is a progressive and inflammatory oral disease and results in the damage of the supporting tissues of teeth. Peroxiredoxin 6 (PRDX6) is an antioxidant enzyme identified as a redox balance regulator. This study aimed to investigate whether PRDX6 could protect human gingival fibroblasts (HGFs) from lipopolysaccharide (LPS) induced inflammation and its mechanisms.Methods: Both inflamed and non-inflamed human gingival tissues were collected to assess the expression of PRDX6 and NRF2 by Immunohistochemistry and Western blotting. Furthermore, HGFs were stimulated with LPS, MJ33 (PRDX6 phospholipase A2 inhibitor), or ML385 (NRF2 inhibitor). The expression levels of inflammatory cytokines were measured by RT-qPCR and ELISA, and reactive oxygen species (ROS) were detected using DCFH-DA.Results: PRDX6 was downregulated in inflamed gingival tissues. In HGFs, LPS induced inflammatory cytokines and ROS was upregulated in PRDX6 knockdown cells. Furthermore, co-treatment with MJ33 alleviated LPS-induced inflammatory cytokines and ROS while inhibiting NRF2 upregulated those in HGFs.Conclusion: Therefore, this study provided a new mechanistic insight that PRDX6, regulated by the NRF2 signaling, alleviates LPS-induced periodontitis in human gingival fibroblasts.

By using coarse-grained molecular dynamics simulations, we have investigated the structure and dynamics of supercooled single-chain cross-linked nanoparticle (SCNP) melts having a range of cross-linking degrees ϕ. We find a nearly linear increase in glass-transition temperature (Tg) with increasing ϕ. Correspondingly, we have also experimentally synthesized a series of polystyrene-based SCNPs and have found that the measured Tg estimated from differential scanning calorimetry is qualitatively consistent with the trend predicted by our simulation estimates. Experimentally, an increase in Tg as large as ΔTg = 61 K for ϕ = 0.36 is found compared with their linear chain counterparts, indicating that the changes in dynamics with cross-links are quite appreciable. We attribute the increase in Tg to the enlarged effective hard-core volume and the corresponding reduction in the free volume of the polymer segments. Topological constraints evidently frustrate the local packing. In addition, the introduction of intra-molecular cross-linking bonds slows down the structural relaxation and simultaneously enhances the local coupling motion on the length scales within SCNPs. Consequently, a more pronounced dynamical heterogeneity (DH) is observed for larger ϕ, as quantified by measuring the dynamical correlation length through the four-point susceptibility parameter, χ4. The increase in DH is directly related to the enhanced local cooperative motion derived from intra-molecular cross-linking bonds and structural heterogeneity derived from the cross-linking process. These results shed new light on the influence of intra-molecular topological constraints on the segmental dynamics of polymer melts.

Benefited from hierarchical porous structure of Loofah sponge (LS) fibers, a 3D electrically and thermally conductive network structure termed conductive cellulose skeleton (Cellulose-RGO-TDI) was fabricated. In addition, PA6 molecular chains were covalently bonded with conductive cellulose skeleton by reaction between imino groups of PA6 and isocyanate groups of Cellulose-RGO-TDI. As a result, PA6/Cellulose-RGO-TDI nano-composite with high electrical and thermal conductivity was fabricated via reactive melt processing. Both RGO outside the fiber and RGO inside the 3D-bundled micro-channel work together to assemble omnibearing trans-scale conductive networks in the whole hierarchical porous structure of the cellulose skeleton. Finally, more integral conductive pathways are established by RGO along the cellulose fiber, which is more beneficial to transmission of charge carrier and phonons in the whole cellulose skeleton. Exfoliated RGO nano-sheets homogeneously dispersed between matrix and cellulose skeleton and a good interface forms, which promoted formation of electrically and thermally conductive network, resulting in the remarkably improved electrically conductivity of 5.8 × 10−1 S/m and thermally conductivity of 0.419 W m−1 K−1 of the composite with 1.2 vol% RGO loading.

A simple arylamine-catalyzed Mannich-cyclization cascade reaction was developed for facile synthesis of substituted 2H-benzo[h]chromenes. The notable feature of the process included the efficient generation of ortho-quinone methides (o-QMs) catalyzed by a simple aniline. The mild reaction conditions allowed for a broad spectrum of 1- and 2-naphthols and trans-cinnamaldehydes to engage in the cascade sequence with high efficiency.

At present, emerging evidences shows that non-coding RNAs (ncRNAs) play crucial roles for development of multiple tumors. Amongst these ncRNAs, long non-coding RNAs (lncRNAs) play prominent roles in physiological and pathological processes. LncRNAs are a type of transcript of more than 200 nucleotides, which are a significant obsession in various types of tumors and have extremely complex regulatory networks with DNA, RNA, and proteins in tumor cells, so that lncRNAs have attracted wide attention from researchers. LncRNAs are RNA transcripts larger than 200 nucleotides and have been shown to serve important regulatory roles in different types of cancer via interactions with DNA, RNA and proteins. Head and neck squamous cell carcinoma (HNSCC) are is one of the most malignant tumors with low survival rates in advanced stages. Recently, lncRNAs have been demonstrated to be involved in a wide range of biological processes, including proliferation, metastasis, and prognosis of HNSCC. Therefore, this review describes molecular mechanisms of up- or down-regulation of lncRNAs and expounds their functions in pathology and clinical practices in HNSCC. It also highlights their potential clinical applications as biomarkers for the diagnosis, prognosis, and treatment of HNSCC. However, studies on lncRNAs are still not comprehensive, and more investigations are needed in the future.

This chapter presents one related modulator-like functionality; i.e., switching of a propagating light wave. This functionality is important for many applications, including signal multiplexing in time and wavelength, signal routing, and signal encoding. An effective photonic switch requires a high extinction ratio, low loss, and a short response time. Switches are shown to be based on mechanical movement, thermo-optic, electro-optic, or electron-plasma optical to change the refractive index. Our discussion focuses on electro-optical switches since they were the most important type for integrated switches particularly those for ultrafast lithium niobate crystals. In addition, the chapter includes a short section on thermo-optical-based switches as well. Finally, methods of improving switch performance are also presented in the chapter.

Electro-optic modulators are based on the control of guided waves using electro-optic variation of the phase or amplitude using an applied electric field. Different theoretical approaches can be used to describe electro-optic control including coupled-mode theory. Phase retardation of the guided light enables polarization splitting, optical switching, and wavelength-selective coupling. Two model–material systems, which are extensively used for E/O devices: GaAs (or other III–V semiconductor material) and lithium niobate. In addition, secondary material systems are mentioned throughout.

The materials technology for integrated optics is complex and thus this chapter examines the optical properties, the electronic properties, the fabrication, and pattering of a set of the most common materials. These include polymers, crystalline silicon, epitaxial three-five thin films, and doped titanium dioxide. In the discussion, the relative importance of each material is described.

We study the interfacial structure and dynamics of a polymer nanocomposite (PNC) composed of octaaminophenyl polyhedral oligomeric silsesquioxane (OAPS) and poly(2-vinylpyridine) (P2VP) by performing full atomistic molecular dynamics simulations. There are eight aminophenyl groups grafted on the surface of the OAPS particle and the particle has a size comparable to the Kuhn segment of P2VP. These aminophenyl groups can form hydrogen bonds (HBs) with pyridine rings from surrounding P2VP chains. We found that OAPS can form ∼2 HBs on average with surrounding polymer chains. The effect of the HBs is investigated in detail by either switching on or off these HBs in our simulation. By analyzing the interfacial static packing structure and dynamic properties, we demonstrate that the system has an ∼1 nm interface width, similar to the OAPS particle size. We also found that HBs can prevent the further penetration of polymers into the inner zone (grafting layer) of the OAPS, and therefore keep the P2VP chains in the outer layer (>1 nm), remaining bulk-like, which is well consistent with experimental results. In addition, we found that NP diffusion is coupled to the absorbed polymer chains, which also dramatically slows down the diffusion of polymer segments in return. The core–shell model in which the NP and absorbed polymers diffuse as a single object is validated here at the full atomistic level. These results provide atomistic insights into the unique structure and dynamics in the small attractive NP–polymer interfacial region. We hope these results will be helpful for the understanding of peculiar phenomena in attractive polymer nanocomposites containing small NPs.

Ample evidence suggests that early life stress (ELS) is a high-risk factor for the development of visceral pain disorders, whereas the mechanism underlying neuronal circuit remains elusive. Herein, we employed neonatal colorectal distension (CRD) to induce visceral hypersensitivity in rats. A combination of electrophysiology, pharmacology, behavioral test, molecular biology, chemogenetics and optogenetics confirmed that CRD in neonatal rats could predispose the elevated firing frequency of the parvocellular corticotropin-releasing hormone (CRH) neurons in the paraventricular nucleus of hypothalamus (PVN) in adulthood, with the CRH neurons activated and the frequency of spontaneous inhibitory postsynaptic currents (sIPSC) diminished, both contributing to chronic visceral hypersensitivity. Moreover, following administration of exogenous GABA (300 mM/0.5 μL) and GABAA receptor agonist muscimol (3 mM/0.5 μL) in PVN, visceral hyperalgesia was abrogated. In addition, the PVN-projecting GABAergic neurons were mainly distributed in the anterior ventral (AV) region in the bed nucleus of stria terminalis (BNST), and the excitability of these GABAergic neurons was weakened in visceral hypersensitivity. Specific depletion of the GABAergic neurons in AV region precipitated visceral hyperalgesia. Moreover, chemogenetic activation of the PVN-projecting neurons alleviated the visceral hypersensitivity. Photoactivation of PVN-projecting GABAergic neurons abated the visceral hypersensitivity in neonatal-CRD rats, whereas photoinhibition evoked visceral hyperalgesia in naive rats. Our findings demonstrated that disinhibition of the PVN-projecting GABAergic neurons in AV region contributed to the excitation of CRH neurons, thereby mediating visceral hypersensitivity. Our study might provide a novel insight into the neuronal circuits involved in the ELS-induced visceral hypersensitivity.

Ion gating is strategic to the development of low-voltage, printable, and flexible transistors. Tin dioxide (SnO2) is an attractive material for ion-gated transistors due to its good conductivity and low processing temperature. Solution-processed SnO2 ion-gated transistors were demonstrated on rigid and flexible substrates. The mode of transistor operation of the charge carriers can be controlled by the rational processing and patterning of the metal oxide.

Although the hard template method is often employed to prepare N-doped mesoporous carbon(N-MC), the removal of the silica template commonly involves the use of highly toxic HF or repeated treatment with NaOH solution. Herein, we report a polyvinylidene fluoride-assisted one-step method for synthesis of N-MC, namely the silica-free N-MC can be prepared via temperature-programmed thermal treatment of a slurry obtained by dispersing nano-silica into a solution containing sucrose, urea, oxalic acid, polyvinylidene fluoride and dimethylacetamide. The resulting N-MC, which owns 3.47%(mass fraction) nitrogen and a surface area of 929 m2/g, is a highly suitable support of Pd catalyst used in hydrodechlorination of 2,4-dichlorophenol, with its performance being much better than those of MC and activated carbon. The excellent catalytic hydrodechlorination activity of the Pd/N-MC catalyst can be attributed to its strong metal-support interaction which results in a good Pd dispersion and high resistance to the growth of nanosized Pd under reaction conditions.

Adding small nanoparticles (NPs) into polymer melt can lead to a non-Einstein-like decrease in viscosity. However, the underlying mechanism remains a long-standing unsolved puzzle. Here, for an all-polymer nanocomposite formed by linear polystyrene (PS) chains and PS single-chain nanoparticles (SCNPs), we perform large-scale molecular dynamics simulations and experimental rheology measurements. We show that with a fixed (small) loading of the SCNP, viscosity reduction (VR) effect can be largely amplified with an increase in matrix chain length \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$N$$\end{document}N, and that the system with longer polymer chains will have a larger VR. We demonstrate that such \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$N$$\end{document}N-dependent VR can be attributed to the friction reduction experienced by polymer segment blobs which have similar size and interact directly with these SCNPs. A theoretical model is proposed based on the tube model. We demonstrate that it can well describe the friction reduction experienced by melt polymers and the VR effect in these composite systems., Addition of small nanoparticles into polymer melt can lead to decrease in viscosity but the underlying mechanism for such viscosity reduction remains unclear. Here, the authors investigate the reduction in viscosity by large-scale molecular dynamics simulation and experimental rheology measurements for an all-polymer nanocomposite formed by linear polystyrene chains and PS single-chain nanoparticle.

Background Diabetic kidney disease (DKD) is the main cause of end-stage kidney disease and has become a heavy economic and social burden due to its high prevalence and morbidity. The most effective strategy is that patients with DKD should be diagnosed and treated early. Preliminary studies showed that the Chinese herbal Tangshen Formula (TSF) may delay the progression of DKD, reducing microalbuminuria and macroalbuminuria and improving renal function. We designed a randomized, double-blind, placebo-controlled trial to evaluate the efficacy of TSF in patients with DKD. Methods/design This trial is a 13-center, randomized, double-blind, placebo-controlled study. A total of 632 participants will be randomized in a 1:1 ratio to an experiment group (TSF plus losartan) and a control group (placebo plus losartan). The trial cycle will last 24 weeks. The primary outcome will be the change in the urine microalbumin–creatinine ratio from baseline to week 24. The secondary outcome will be the change in the rate of progression to the clinical proteinuria period after intervention, the rate of urine microalbumin negative conversion, the rate of normal urinary microalbumin, the doubling rate of the baseline creatinine value and the glomerular filtration rate between the two groups. Safety in medication will also be evaluated. Discussion We hypothesize that patients with type 2 diabetes in the early stage of DKD will benefit from TSF. If successful, this study will provide evidence-based recommendations for clinicians. Trial registration ClinicalTrials.gov, NCT03009864. Registered January 2017.

The Chinese citrus fly, Bactrocera minax (Enderlein) (Diptera: Tephritidae), is the most destructive pest in many citrus orchards of south central China. Methyl eugenol and cuelure, 2 potent male lures that are effective for capturing related species, are believed not to attract this species. Limited knowledge is available about the effectiveness of attractant traps for this pest. A field trial was carried out to determine the efficacy of 8 attractant traps to B. minax. The study was conducted during the adult occurrence season in an orchard of navel orange, Citrus sinensis (L.) Osbeck (Rutaceae), in Zhijiang County, Hunan Province, China, in 2016. To link the efficacy of these attractant traps with the pest population, fruit infestations in the orchard also were investigated. As expected, this study confirmed that methyl eugenol and cuelure were not attractive to B. minax. Green-colored sticky spheres trapped significantly more flies and males than methyl eugenol and cuelure-baited traps. On average, ammonium acetate putrescine trapped more females than males, but it was not statistically better than any of the other tested attractant traps. Fruit infestation rates by B. minax ranged from 0.7 to 11.1% in the replicates. Judging by the results of trapping and actual field infestation, it appears that trap effectiveness of the 8 attractant traps was low. A more potent attractant trap is needed, especially for early detection of the pest.

Gene expression noise influences organism evolution and fitness. The mechanisms determining the relationship between stochasticity and the functional role of translation machinery components are critical to viability. eIF4G is an essential translation factor that exerts strong control over protein synthesis. We observe an asymmetric, approximately bell-shaped, relationship between the average intracellular abundance of eIF4G and rates of cell population growth and global mRNA translation, with peak rates occurring at normal physiological abundance. This relationship fits a computational model in which eIF4G is at the core of a multi-component– complex assembly pathway. This model also correctly predicts a plateau-like response of translation to super-physiological increases in abundance of the other cap-complex factors, eIF4E and eIF4A. Engineered changes in eIF4G abundance amplify noise, demonstrating that minimum stochasticity coincides with physiological abundance of this factor. Noise is not increased when eIF4E is overproduced. Plasmid-mediated synthesis of eIF4G imposes increased global gene expression stochasticity and reduced viability because the intrinsic noise for this factor influences total cellular gene noise. The naturally evolved eIF4G gene expression noise minimum maps within the optimal activity zone dictated by eIF4G’s mechanistic role. Rate control and noise are therefore interdependent and have co-evolved to share an optimal physiological abundance point.

Background Total glucosides of paeony (TGP), an active compound extracted from the roots of Paeonia lactiflora Pallas, has been increasingly used as the adjunctive therapy for rheumatoid arthritis (RA) patients. Though TGP could mitigate the unanticipated adverse effects during the conventional treatment of RA, high-quality evidence-based meta-analysis data on this subject are still insufficient. The objective of this study is to evaluate the clinical safety of TGP adjuvant therapy in the RA treatment. Methods PubMed, EMBASE, Web of Science, China Network Knowledge Infrastructure (CNKI), SinoMed and WanFang Data were retrieved for randomized controlled trials (RCTs) and cohort study about TGP adjuvant therapy in patients with RA up to 28 January 2021. Literatures with eligibility criteria and information were screened and extracted by two researchers independently. The RevMan5.3 software was used for data analysis with effect estimates as risk ratio (RR) with 95% confidence interval (CI). Results A total of 39 studies involving 3680 RA participants were included. There were 8 comparisons: TGP plus methotrexate (MTX) therapy versus MTX therapy, TGP plus leflunomide (LEF) therapy versus LEF therapy, TGP plus MTX and LEF therapy versus MTX plus LEF therapy, TGP plus tripterygium glycosides (TG) therapy versus TG therapy, TGP plus meloxicam (MLX) therapy versus MLX therapy and TGP plus sulfasalazine (SSZ) therapy versus SSZ therapy, TGP plus iguratimod (IGU) therapy versus IGU therapy, TGP plus prednisone acetate tablets (PAT) therapy versus PAT therapy. The meta-analysis results showed that the occurrence of hepatic adverse effect (RR = 0.31, 95% CI = 0.23–0.41, P P = 0.0002) in TGP adjuvant therapy was significant decreased compared with non-TGP therapy. However, only TGP plus LEF therapy (RR = 0.22, 95% CI = 0.08–0.60, P = 0.003) and TGP plus MTX and LEF therapy (RR = 0.31, 95% CI = 0.22–0.42, P P = 0.02) had statistical difference. Conclusions This meta-analysis indicated that TGP adjuvant therapy might alleviate the incidence of hepatic adverse effect and leukopenia for the RA treatment compared to non-TGP therapy. The clinical safety of TGP adjuvant therapy warrant further investigation in experimental studies.

Nanoscale zero-valent iron (nZVI) was prepared and used as a heterogeneous Fenton-like catalyst for the degradation of nuclear-grade cationic exchange resin. The properties of nZVI before and after reaction were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and Brunauer–Emmett–Teller (BET) surface area analysis. The results showed that nZVI–H2O2 system exhibited the enhanced degradation of cationic resins, compared with Fe2+–H2O2, Cu0–H2O2, and Fe0/Cu0–H2O2 systems. The effects of initial temperature, nZVI dose, and H2O2 concentration were studied, and the higher temperature and nZVI dose with relatively low H2O2 concentration brought faster degradation rate. The degradation of cationic resins followed the pseudo-first-order kinetics with the apparent activation energy of 53.29 kJ/mol. According to the experimental and calculated infrared and UV-visible spectra, the carbon skeleton of cationic resins was broken with the detachment of benzene ring and the desulfonation of resin polymer by hydroxyl radicals (•OH), generating long-chain alkenes. These intermediates were further oxidized through the hydroxyl substitution, hydrogen abstraction, ring cleavage, or carbonylation reactions, finally forming carboxylic acids remained in solution.

Made available in DSpace on 2019-10-04T12:38:12Z (GMT). No. of bitstreams: 0 Previous issue date: 2019-07-24 NSERC DG MESI PSIIRI 936 China Scholarship Council Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Trottier Energy Institute FRQNT-RQMP Ion-gated transistors employ ionic gating media (e.g. ionic liquids, polymer electrolytes, aqueous saline solutions) to modulate the density of the charge carriers in the transistor channel. Not only they operate at low voltages (ca 0.5-1 V) but they can also feature printability, flexibility and easy integration with chemo- and bio-sensing platforms. Metal oxides are transistor channel materials interesting for their processability in air, at low temperature. Among metal oxides, tungsten oxide (band gap ca 2.5-2.7 eV) stands out for its electrochromic, gas sensing and photocatalytic properties. Here we demonstrate ion-gated tungsten oxide transistors and phototransistors working in different ion gating media, such as one hydrophobic ionic liquid and an aqueous electrolyte, fabricated both on rigid and flexible substrates. Ion-gated tungsten oxide phototransistors operating in aqueous media could be used as photocatalytic sensors in portable applications. Polytech Montreal, Dept Genie Phys, CP 6079,Succ Ctr Ville, Montreal, PQ H3C 3A7, Canada Univ Fed Minas Gerais, Dept Fis, BR-30123970 Belo Horizonte, MG, Brazil Polytech Montreal, Dept Genie Chim, CP 6079,Succ Ctr Ville, Montreal, PQ H3C 3A7, Canada Univ Estadual Paulista, Dept Fis Quim, Rua Prof Degni 55, BR-14800060 Araraquara, Brazil Univ Montreal, Dept Chim, CP 6128,Succ Ctr Ville, Montreal, PQ H3C 3J7, Canada Univ Bologna, Dipartimento Chim Giacomo Ciamician, Via Selmi 2, I-40126 Bologna, Italy Univ Estadual Paulista, Dept Fis Quim, Rua Prof Degni 55, BR-14800060 Araraquara, Brazil FAPESP: 2014/27079-9 FAPESP: 2015/50526-4 FAPESP: 2016/09033-7

The rational design of high-performance flexible pressure sensors with both high sensitivity and wide linear range attracts great attention because of their potential applications in wearable electronics and human-machine interfaces. Here, polyaniline nanofiber wrapped nonwoven fabric was used as the active material to construct high performance, flexible, all fabric pressure sensors with a bottom interdigitated textile electrode. Due to the unique hierarchical structures, large surface roughness of the polyaniline coated fabric and high conductivity of the interdigitated textile electrodes, the obtained pressure sensor shows superior performance, including ultrahigh sensitivity of 46.48 kPa&minus, 1 in a wide linear range (&lt, 4.5 kPa), rapid response/relaxation time (7/16 ms) and low detection limit (0.46 Pa). Based on these merits, the practical applications in monitoring human physiological signals and detecting spatial distribution of subtle pressure are demonstrated, showing its potential for health monitoring as wearable electronics.

Creating vertically aligned 2D nanostructures is a promising approach to achieving advanced electronic and optoelectronic materials. In this study, Mg2Si nanosheet bundles were synthesized by Ca atom extraction from CaSi2 microwalls grown on Si substrates via thermal annealing in a MgCl2/Mg mixed vapor. The nanosheet bundle structure was modified to compound nanosheet bundles from previously reported Si nanosheet bundles. The observed Mg2Si nanosheets consist of thin Mg2Si layers, and well-defined fine-scale Mg2Si superlattice-like structures were achieved in the nanosheet bundles. In addition, the Raman scattering and photoluminescence properties were examined, and structural and electronic modifications of the nanosheet bundle compared with the bulk crystals were suggested. To obtain tailored properties and functionalities of the nanosheet bundles, structural modification of layered crystals is a useful technique.

Si nanosheets connected to Si nanowires were synthesized using a MnCl 2 /Si powder source with an Au catalyst. The synthesis method has benefits in terms of avoiding conventionally used air-sensitive SiH 4 or SiCl 4 . The existence of the Si nanosheets connected to the Si nanowires, like sprouts or leaves with petioles, was observed, and the surface of the nanosheets was Si{111}. The nanosheets were grown in the growth direction of perpendicular to that of the Si nanowires. It was evident from these structural features of the nanosheets that the nanosheets were formed by the twin-plane reentrant-edge mechanism. The feature of the observed lattice fringes, which do not appear for Si bulk crystals, of the Si(111) nanosheets obtained by high resolution transmission electron microscopy was clearly explained due to the extra diffraction spots that arose by the reciprocal lattice streaking effect.

Structural control and morphological modification of a series of Si-based nanostructures were studied from the viewpoint of modifying the catalyst’s characteristics. The catalyst was modified from a liquid to a solid during its growth. The growth evolution of the faceted Si nanowires occurred via a vapor–liquid–solid mechanism followed by a silicide vapor–solid–solid mechanism. The shapes of the catalysts defined the shapes of the nanowires during the vapor–solid–solid growth. The catalyst was further modified by the deposition of MnCl2. Only irregularly shaped Si particles or MnCl2 particles were observed on top of the Si nanowires. The characteristic modification of catalysts by liquid-phase crystal nucleation and deposition of liquid-phase droplets was discussed. In addition, the synthesis of a CrSi2 nanowire bundle by the formation of dense nanoparticles was studied.

Sulfomycins are sulfur-rich, ribosomally synthesized, and post-translationally modified peptides (RiPPs) that are characterized by a 35-membered macrocyclic ring system with a pyridine domain centr...

The role of microorganism in human diseases cannot be ignored. These microorganisms have evolved together with humans and worked together with body's mechanism to maintain immune and metabolic function. Emerging evidence shows that gut microbe and their metabolites open up new doors for the study of human response mechanism. The complexity and interdependence of these microbe-metabolite-host interactions are rapidly being elucidated. There are various changes of microbial levels in models or in patients of various autoimmune diseases (AIDs). In addition, the relevant metabolites involved in mechanism mainly include short-chain fatty acids (SCFAs), bile acids (BAs), and polysaccharide A (PSA). Meanwhile, the interaction between microbes and host genes is also a factor that must be considered. It has been demonstrated that human microbes are involved in the development of a variety of AIDs, including organ-specific AIDs and systemic AIDs. At the same time, microbes or related products can be used to remodel body's response to alleviate or cure diseases. This review summarizes the latest research of microbes and their related metabolites in AIDs. More importantly, it highlights novel and potential therapeutics, including fecal microbial transplantation, probiotics, prebiotics, and synbiotics. Nonetheless, exact mechanisms still remain elusive, and future research will focus on finding a specific strain that can act as a biomarker of an autoimmune disease.

The diffusion dynamics of fullerene (C 60 ) in unentangled linear atactic polystyrene (PS) and polypropylene (PP) melts and the structure and dynamic properties of polymers in interface area are investigated by performing all-atom molecular dynamics simulations. The comparison of the results in two systems emphasises the influence of local interactions exerted by polymer side group on the diffusion dynamics of the nanoparticle. In the normal diffusive regime at long time scales, the displacement distribution function (DDF) follows a Gaussian distribution in PP system, indicating a normal diffusion of C 60 . However, we observe multiple peaks in the DDF curve for C 60 diffusing in PS melt, which indicates a diffusion mechanism of hopping of C 60 . The attractive interaction between C 60 and phenyl ring side groups are found to be responsible for the observed hopping diffusion. In addition, we find that the C 60 is dynamically coupled with a subsection of a tetramer on PS chain, which has a similar size with C 60 . The phenyl ring on PS chain backbone tends to have a parallel configuration in the vicinity of C 60 surface, therefore neighbouring phenyl rings can form chelation effect on the C 60 surface. Consequently, the rotational dynamics of phenyl ring and the translational diffusion of styrene monomers are found to be slowed down in this interface area. We hope our results can be helpful for understanding of the influence of the local interactions on the nanoparticle diffusion dynamics and interfacial properties in polymer/nanoparticle composites.

A copper-catalyzed asymmetric radical oxytrifluoromethylation of alkenyl oxime and Togni's reagent has been successfully developed, thereby providing straightforward access to CF3 -containing isoxazolines bearing α-tertiary stereocenters with excellent yield and enantioselectivity. The key to success is the rational design of cinchona-alkaloid-based sulfonamides as neutral/anionic hybrid ligands to effectively control the stereochemistry in copper-catalyzed reactions involving free alkyl radical species. The utility of this method is illustrated by efficient transformation of the products into useful chiral CF3 -containing 1,3-aminoalcohols.

Electrolyte-gated transistors hold promise for applications in printable and flexible electronics. Metal oxide semiconductors are particularly interesting as electrolyte-gated channel materials for their abundance, thermodynamic stability and ease of processing under ambient conditions. In this work, we synthesized by sol–gel and hydrothermal methods different types of tungsten oxide to be used as channel materials in ion gel-gated transistors. X-ray diffraction and scanning and transmission electron microscopy revealed that the differently processed oxides show a different structure (hexagonal and monoclinic) and morphology (granular, nanofiber and nanoplate). We studied the electrochemical and transistor properties of the oxides using, as the gating media, two different ion gels prepared from the same ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM]TFSI), and two different block copolymers. We tentatively propose that for sufficiently high values of the gate–source bias, the doping results from chemical and electrochemical contributions.

Made available in DSpace on 2022-04-28T19:01:35Z (GMT). No. of bitstreams: 0 Previous issue date: 2015-09-17 Electrolyte-gated (EG) transistors, based on electrolyte gating media, are powerful device structures to modulate the charge carrier density of materials by orders of magnitude, at relatively low operating voltages (sub-2 V). Tungsten trioxide (WO3) is a metal oxide semiconductor well investigated for applications in electrochromism, sensing, photocatalysis, and photoelectrochemistry. In this work, we report on EG transistors making use of mesoporous nanostructured WO3 thin films easily permeated by the electrolyte as the transistor channel and bis(trifluoromethylsulfonyl)imide ([TFSI])-based ionic liquids as the gating media. The WO3 EG transistors operate at ca. 1 V. Using a combination of cyclic voltammetry, X-ray diffraction, and transistor performance characterizations, complemented by spectroscopic (Raman and infrared) investigations, we correlate the metal oxidation state and the charge transport properties of the metal oxide, shedding light on the doping process in electrically biased WO3 nanostructured thin films exposed to electrolytes. Département de Génie Physique Polytechnique Montréal, C.P. 6079, Succ. Centre Ville Departamento de Físico-Química Universidade Estadual Paulista, Rua Professor Degni, 55 CNR-IENI Dipartimento di Scienze Chimiche Università di Padova, Via F. Marzolo 1 Département de Chimie Université de Montréal, C.P. 6128, Succ. Centre Ville Dipartimento di Chimica giacomo Ciamician Università di Bologna, Via Selmi, 2 Departamento de Físico-Química Universidade Estadual Paulista, Rua Professor Degni, 55

The coassembly of block copolymers (BCPs) with nanoscale inorganic objects is an important route to fabricate nanostructured polymer composites. However, the immiscibility of inorganic/polymeric interface is a recurring challenge to overcome, particularly for inorganic clusters, such as the polyoxometalates (POMs)/BCPs system. In this paper, we present a general method to incorporate POMs into BCP matrices, in which a POM cluster is embedded as a core in a supramolecular star polymer (SSP) whose arms possess the same chemical composition as a BCP segment. Because of the enthalpic interaction between SSP arms and BCP segments, the SSP can carry POM into BCP matrices to realize their coassembly. By this way, we successfully localize a Keggin-type POM cluster [CoW12O40]6– modified with polystyrene (PS) arms into the PS domain of poly(styrene-b-ethylene oxide) micelles, which induces the formation of a series of hybrid micelles with spherical, toroidal, and bicontinuous structures. The morphological transitio...

The adsorption of methane on intrinsic, vacancy and N-doped graphene are investigated using the first-principles method of density functional theory. We build models by placing methane on three different adsorption sites, including the A, B and C sites above the perfect, vacancy and N-doped graphene. The results indicate that the different adsorption sites of methane on the perfect, vacancy and N-doped graphene have little impact on the band structures. The introduction of N atom can possibly make the adsorption of methane on graphene much easier in the case of A adsorption site. The interactions between methane and N-doped graphenes with a vacancy are much stronger than other systems in the case of B and C adsorption sites.

Background: Alzheimer’s disease (AD) is a neurodegenerative disease featured by memory loss, neuroinflammation and oxidative stress. Overproduction or insufficient clearance of Aβ leads to its pathological aggregation and deposition, which is considered the predominant neuropathological hallmark of AD. Therefore, reducing Aβ levels and inhibiting Aβ-induced neurotoxicity are feasible therapeutic strategies for AD treatment. Wolfberry has been traditionally used as a natural antioxidant and anti-aging product. However, whether wolfberry species has therapeutic potential on AD remains unknown. Method: The effects of fruitless wolfberry-sprout extract (FWE) on Aβ fibrillation and fibril disaggregation was measured by thioflavin T fluorescence and transmission electron microscope imaging; Aβ oligomer level was determined by dot-blot; Cell viability and apoptosis was assessed by MTT and TUNEL assay. The levels of Aβ40/42, oxidative stress biomarkers and inflammatory cytokines were detected by corresponding kits. 8-month-old male APP/PS1 mice and their age-matched WT littermates were treated with FWE or vehicle by oral administration (gavage) once a day for 4 weeks. Then the cognitive performance was determined using object recognition test and Y-maze test. The Aβ burden and gliosis was evaluated by immunostaining and immunoblotting, respectively. Results: FWE significantly inhibited Aβ fibrillation and disaggregated the formed Aβ fibrils, lowered Aβ oligomer level and Aβ-induced neuro-cytotoxicity, and attenuated oxidative stress in vitro. Oral administration of FWE remarkably improved cognitive function, reduced Aβ burden, decreased gliosis and inflammatory cytokines release, and ameliorated oxidative stress in the brains of APP/PS1 mice. Conclusion: These findings indicate that FWE is a promising natural agent for AD treatment.

Cardiovascular Disease (CVD) and related disorders remain a leading cause of health disparities and premature death for African Americans. Hypovitaminosis D is disproportionately prevalent in African Americans and has been linked to CVD and CVD risk factors including hypertension, diabetes and obesity. Thus, hypovitaminosis D may represent a common pathway influencing CV risk factors in a select subgroup of persons. The purpose of this paper is to report the study design of a prospective eight week prospective double-blind randomized, placebo-controlled trial (n = 330 allocated 2:1 to intervention vs. control) to assess the effect of placebo vs. high-dose oral cholecalciferol (100,000 IU vitamin D3 at baseline and week 2) on 6-week change of select biologic cardiometabolic risk factors (including parathyroid hormone to assess biologic activity, pro-inflammatory/pro-thrombotic/fibrotic markers, insulin sensitivity and vitamin D metabolites) and their relationship to vitamin D administration and modification by vitamin D receptor polymorphisms in overweight, hypertensive African Americans with hypovitaminosis D. Findings from this trial will present insights into potential causal links between vitamin D repletion and mechanistic pathways of CV disease, including established and novel genomic markers.

Penaeidin-2 (Pen-2) is an important antimicrobial peptide derived from the Pacific white shrimp, Penaeus vannamei, and possesses both antibacterial and antifungal activities. Recent studies suggest that recombinant penaeidins show similar activities to the native Pen-2 protein. Previous researches have shown that some antimicrobial peptides (AMPs) exhibit cytotoxic activity against cancer cells. To date, there have been no studies on the antitumor effects of Pen-2. This study evaluated the potential of recombinant pen-2 (rPen-2) in the selective killing of kidney cancer cell lines ACHN and A498, and its action mechanism. MTT assays found the maximal growth inhibition of HK-2, ACHN and A498 cells treated with 100 μg/mL rPen-2 at 48 h was 13.2%, 62.4%, and 70.4%, respectively. DNA-specific fluorescent dye staining showed a high percentage of apoptosis on cancer cells. Flow cytometry revealed that the apoptosis rate of HK-2, ACHN and A498 cells was 15.2%, 55.2%, and 61.5% at 48 h respectively, suggesting that rPen-2 induced higher apoptosis rate in cancer cells than in HK-2 cells. Laser confocal scanning microscopy demonstrated that the plasma membrane was the key site where rPen-2 interacted with and destroyed tumor cells. Scanning electron microscopy showed the morphologic changes of the cell membranes of kidney cancer cells treated with rPen-2. These results suggest that rPen-2 is a novel potential therapeutic agent that may be useful in treating kidney cancers.

Phenanthrene (PHE), a major component of crude oil, is one of the most abundant polycyclic aromatic hydrocarbons (PAHs) in aquatic ecosystems, and is readily bioavailable to marine organisms. Understanding the toxicity of PAHs in animals requires knowledge of the systems for xenobiotic biotransformation and antioxidant defence and these are poorly understood in bivalves. We report, for the first time, new transcripts and tissue-specific transcription in gill and digestive gland from the oyster Crassostrea brasiliana following 24 h exposure to 100 and 1000 μg L−1 PHE, a model PAH. Six new cytochrome P450 (CYP) and four new glutathione S-transferase (GST) genes were analysed by means of quantitative reverse transcription PCR (qRT-PCR). Different antioxidant endpoints, including both enzymatic and non-enzymatic parameters, were assessed as potential biomarkers of oxidative stress. GST activity was measured as an indicator of phase II biotransformation. Rapid clearance of PHE was associated with upregulation of both phase I and II genes, with more pronounced effects in the gill at 1000 μg L−1 PHE. After 24 h of exposure, PHE also caused impairment of the antioxidant system, decreasing non-protein thiols and glutathione levels. On the other hand, no change in antioxidant enzymes was observed. PHE treatment (100 μg L−1) significantly decreased GST activity in the gill of exposed oysters. Both CYP and GST were transcribed in a tissue-specific manner, reflecting the importance of the gill in the detoxification of PAHs. Likewise, the antioxidant parameters followed a similar pattern. The data provide strong evidence that these genes play key roles in C. brasiliana biotransformation of PHE and highlight the importance of gill in xenobiotic metabolism.

Background Vitamin D deficiency has been implicated as a potential risk factor for cardiovascular disease. The high rate of vitamin D deficiency ( 25) African Americans with elevated blood pressure (130 - 150/85 - 100 mmHg) and low serum vitamin D level (10 - 25 ng/ml). Results There was a significant increase in the serum 25(OH)D levels to a mean level of 34.5 ng/ml (SD = 7.1) with the intervention (p < 0.001). The increase in 25(OH)D levels was associated with a significant decrease in the serum level of intact PTH (p = 0.02), mean urinary isoprostane (p = 0.02) and adipocyte cytokine expression. Although the increase in the 25(OH)D levels was not associated with any significant change in the Pulse Wave Velocity (PWV) in the overall study sample, it was associated with a significant decrease in the augmentation index among the participants with the highest tertile of urinary isoprostane (p = 0.007). Conclusion We concluded that vitamin D supplementation increased serum 25(OH)D levels, decreased intact PTH level and the levels of select inflammatory and oxidative stress mediators of arterial stiffness. Longer term prospective studies are warranted to evaluate the effect of high dose vitamin D supplementation on arterial stiffness.

Working memory impairment is a common cognitive dysfunction after traumatic brain injury (TBI), which severely affects the quality of life of patients. Acetylcholine is a neurotransmitter which is closely related to cognitive functions. In addition, epigenetic modifications are also related to cognitive functions. A neurorehabilitation strategy, enriched environment (EE) intervention, has been widely used to improve cognitive impairment. However, studies of the mechanism of EE on cholinergic system and epigenetic modifications in mouse with TBI have not been reported yet. In this paper, a mouse model with traumatic frontal lobe injury was established, and the mechanism on EE for the mice with TBI was explored. It was found that EE could improve Y-maze performance of mice with TBI, the function of cholinergic system, and the imbalance of acetylation homeostasis in the prefrontal cortex of contralateral side of TBI. In addition, EE also could increase the level of CREB binding protein and histones H3 acetylation at ChAT gene promoter region in the prefrontal cortex of contralateral side of TBI. These indicate that EE has an important effect on the improvement of working memory impairment and the underlying mechanism may involve in histones H3 acetylation at ChAT gene promoter regions in the prefrontal cortex.

The areal capacity of lithium-ion microbatteies (LIMBs) can be potentially increased by adopting a three-dimensional (3D) architectured electrode. Herein, we report the novel 3D Ni/SnOx/C hybrid nanostructured arrays that were built directly on current collectors via a facile hydrothermal method followed by a calcination-reduction process. Branched SnO2 nanorods grew uniformly on Ni2(OH)2CO3 nanowall arrays, resulting in the formation of precursors with a 3D interconnected architecture. By using ethylene glycol as the reducing agent, the glucose-coated SnO2/Ni2(OH)2CO3 precursors were evolved into an interesting 3D Ni/SnOx/C hybrid nanostructured arrays within the calcination treatment. Compared to conventional 2D SnOx/C nanorod arrays, the electrode of 3D Ni/SnOx/C hybrid nanostructured arrays exhibited enhanced lithium storage capacity per unit area, preferable rate capability and improved cycling performance when tested for LIMBs. The superior performance might be attributed to the open-up Ni frameworks that can not only serve as effective channels for electrons transport and Li+ diffusion but also help to accommodate the large volume changes upon lithiation/delithiation.

The aim of the present study was to investigate the changes in mitotic reorientation and relative differential gene expression in rat prostate epithelial cells following long-term exposure to testosterone propionate (TP). Sprague-Dawley rats were randomly divided into two groups as follows: TP group, which received 3.7 mg/kg/day TP for 30 days (n=10); and control group, in which rats were injected with olive oil (n=10). Microscopic analysis of the prostate tissue was performed by immunohistochemical analysis and hematoxylin and eosin staining. Differential gene expression analysis was performed via gene microarray, and a total of five genes (Dkk3, Ran, Fas, Tgm4 and Wnt2) were selected and their expression levels were verified using reverse transcription-polymerase chain reaction. For rats treated with TP, mitosis was significantly reoriented, becoming parallel to the basement membrane. By contrast, in the control group cells mitotic orientation remained perpendicular to the basement membrane. Genes such as Ran and Tgm4 in the androgen receptor (AR) signaling pathway and Wnt2 in the Wnt signaling pathway, were upregulated following treatment with TP. Conversely, the Dkk3 and Fas genes were downregulated following treatment with TP. In conclusion, mitotic orientation of prostate epithelial cells was altered following long-term administration of TP. Wnt and AR signaling pathways influenced cell proliferation and may have participated in the mitotic orientation change.

The gas-phase oxidation of ethanol over unsupported nanoporous gold was studied using catalyst with Ag content of 26.56% and 0.72%. Influence of Ag content in the catalyst, partial pressure of oxygen and temperature are analyzed. Under optimal conditions, selectivity toward acetaldehyde, ethyl acetate and acetic acid achieved 90%, 85% and 48% respectively.