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This study aims to improve the hydrophobic properties and corrosion resistance of fluorinated acrylate coatings. The surface of nano-SiO2 was modified by the silicone coupling reagent (KH-570), and the reactive functional groups were introduced to modify fluorinated acrylates. The functionalized SiO2-modified waterborne fluorinated acrylate emulsion was prepared by free polymerization with dual initiators. The structure of the polymer was analyzed by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectro-meter (1H-NMR), X-ray photoelectron spectroscopy (XPS) and Waters gel chromatography (GPC). The properties of the films and coatings were analyzed by contact angle, atomic force microscopy, scanning electron microscopy, and electrochemical analysis. The results showed that the contact angle reached 120° when the SiO2 content was 3%, the electrochemical impedance value reached 1.49 × 107 Ω·cm2, and the pencil hardness was 3H.

Solvent-free and highly branched water-soluble polyester (WPET) is prepared through self-emulsification methodology, using dimethyl terephthalate (DMT), sodium dimethyl isophthalate-5-sulfonate (SIPM), trimethylolpropane (TMP), and ethylene glycol (EG) by the transesterification and polycondensation. The WPET were first utilized as surface-sizing agents for cellulose fiber paper. The structure, average molecular weights, and physical properties of the water-soluble polyester were characterized by FTIR, 1H NMR, gel permeation chromatography (GPC), dynamic light scattering (DLS), X-ray diffraction (XRD), and dynamic rheometer. The effects of polymer structure and properties, as well as the surface sizing of the paper, were investigated. WPET displayed better surface sizing properties when it was prepared under the following conditions: –COO/–OH molar ratio of 1:2, the SIPM content of 17.98%, and TMP content of 11.10%. The relationships between the WPET structure and sized paper were clearly illustrated. The mechanical properties and water resistance of sized paper did not only depend on multi-branched hydroxyl groups of the WPET chains but also relied on the interactions among polymers and fibers, as well as the high toughness of surface sizing agent. The sizing paper possesses excellent mechanical properties as well as water resistance.

Epoxy resin is widely used in metal surface protection, because of corrosion resistance and adhesion. However, it’s water solubility, oxygen, and water impermeability are not enough. In this paper, linoleic acid (LOFA) and epoxy resin (E20) were used to synthesize epoxy ester (EL) and grafted with phosphonate esterified acrylic resin (AR-P) to prepare acrylic grafted epoxy ester (EL@AR-P). After modification, water solubility and film-forming property were improved, and the oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) decreased. At the addition of PM-2 at 2%, the OTR, WVTR, and water-uptake rate decreased by 12.9%, 25.0%, and 12.1%, respectively. Subsequently, the modified material was subjected to electrochemical impedance spectroscopy. The low-frequency impedance of EL@AR-P2 is three times higher than EL@AR-P0. After 16 days of immersion, the low-frequency impedance of EL@AR-P2 is 20 times higher than EL@AR-P. Energy dispersive spectrometer and X-ray photoelectron spectroscopy results showed that the P elements were concentrated on the substrate surface and found the presence of P–O–Fe bonds, demonstrating that the phosphonate groups were migrated to the substrate surface to form a chelate layer with the substrate and enhancing the coating adhesion and corrosion resistance. This paper modifies the molecular structure of epoxy resin, which is expected to be an excellent material for anti-corrosion coatings.

The MIL-53(Al)-NH2 was designed to remove fluoride with hierarchical hollow morphology. It was used as an adsorbent for fluoride removal at a wide pH range (1-12) due to the positive zeta potential of MIL-53(Al)-NH2. The pH did not significantly influence the fluoride adsorption into MIL-53(Al)-NH2. However, the adsorbent indicated good adsorption capacity with maximum adsorption of 1070.6 mg g-1. Different adsorption kinetic and thermodynamic models were investigated for MIL-53(Al)-NH2. The adsorption of fluoride into MIL-53(Al)-NH2 followed the pseudo-second-order model and a well-fitted Langmuir model indicating chemical and monolayer adsorption process. When mass transfer model was used at initial concentrations of 100 ppm and 1000 ppm, the rates of conversion were 8.4 × 10-8 and 4.7 × 10-8 m s-1. Moreover, anions such as [Formula: see text], [Formula: see text], [Formula: see text], Cl-, and Br- also had less effect on the adsorption of fluoride. Also, experimental and theoretical calculations on adsorption mechanism of MIL-53(Al)-NH2 revealed that the material had good stability and regenerative capacity using alum as regenerant. In a nutshell, the dominant crystal face (1 0 1) and adsorption sites Al, O, and N combined well with F-, HF, and HF2- through density functional theory. It opens a good way of designing hollow MOFs for adsorbing contaminants in wastewater.

In this paper, we present a 3D printed tumor spheroidal model suitable for drug discovery. This model is based on a hydroxyethyl cellulose/alginate/gelatin (HCSG) composite biomaterial that has three distinct properties: (1) the HCSG is similar to the commercial basement membrane extract in Ki67, MUC1, and PARP1 expressions of MCF-7 cells for embedding culture; (2) the HCSG is printable at room temperature; and (3) the HCSG can be large-scale manufactured at an ultralow cost. We printed a 3D MCF-7 spheroid model with HCSG and characterized it in terms of cell viability, spheroid size, key protein expression, and mitochondrial metabolic activity. We used the 3D MCF-7 spheroid model to evaluate the anti-breast cancer activity of 13 amino acid-based flavone phosphoramidates and found that the alanine structure induced a stronger drug resistance, whereas phenylalanine hardly caused drug resistance in the MCF-7 cells. This is the first time that 3D bioprinting technology has been used in a structure–activity relationship study.

Nutrient availability is a key regulator of soil respiration. Anthropogenic activities have dramatically accelerated the inputs of reactive nitrogen (N) and phosphorous (P) and increased the availability of N and P in soils. However, many previous studies of soil respiration have focused more on the effects of N, and less on the effects of P and its interaction with N. Therefore, the objective here was to examine the roles of N availability, P availability and their interaction in determining soil respiration. A manipulative N addition (100 kg N ha−1 year−1), P addition (50 kg P ha−1 year−1) and NP co-addition (100 kg N ha−1 year−1 + 50 kg P ha−1 year−1) experiment was conducted in a subtropical forest in Southwest China. N and P inputs were added monthly beginning in October 2017. The soil respiration rate was measured monthly from March 2018 to February 2019, and soil properties, microbial biomass carbon (MBC), and fine root biomass were measured in July 2018 and January 2019. The soil respiration rate in the control (without fertilizer added) treatment was 13.5% higher than that in the N treatment but 1.6% and 34.7% lower than those in the P treatment and NP treatment, respectively. Soil respiration was closely associated with soil temperature and soil moisture, and soil temperature played a more important role in regulating soil respiration than did soil moisture. The temperature sensitivity of respiration (Q10 values) in the CT, N, P and NP treatments did not differ significantly. Path analysis showed that nutrient additions changed soil respiration by regulating the MBC and fine root biomass. Our results highlight the divergent effects of N addition and NP co-addition on soil respiration. Ongoing N and P inputs may increase soil respiration by stimulating soil microbial and plant root activities in the subtropical evergreen broad-leaved forests of Southwest China.

We experimentally demonstrate an integrated strictly non-blocking silicon 4 × 4 optical switch chip that can be operated in both thermo-optic (TO) and electro-optic (EO) switching modes. It is based on the double-layer network (DLN) architecture and consists of twelve 2 × 2 Mach-Zehnder interferometer (MZI) switch elements. TO phase shifters based on TiN microheaters and EO phase shifters based on p-i-n diodes are embedded in both waveguide arms of the MZI elements. The power consumption for TO and EO switching is 34 mW/π and 7 mW/π, respectively. The on-chip insertion losses are 1.74 ± 0.59 dB and 3.79 dB ± 1.32 dB for TO and EO switching, respectively. Due to the merits of the DLN architecture and the optimized performance of the switch elements, the chip possesses low crosstalk of -29.1 dB and -19.4 dB for TO and EO switching, respectively. Quadrature phase-shift keying (QPSK) optical signals with a data rate of 64 Gb/s are transmitted through the switch with no observable deteriorations. Such an optical switch is a promising candidate for both optical circuit switching and optical packet switching for a variety of applications.

Aims: Dihydroartemisinin (DHA), a derivative of artemisinin, suppresses angiogenesis by regulating endothelial cell phenotypes. In this study, we investigated the effect of DHA on endothelial cell autophagy and the underlying mechanisms. Methods: Human umbilical vein endothelial cells (HUVECs) were treated with DHA. Formation of autophagosomes in HUVECs was observed by fluorescence microscope after pcDNA3.1-green fluorescent protein (GFP)-microtubule-associated protein 1 light chain 3 (LC3) plasmids transfection. Dichlorofluorescein diacetate (DCFH-DA) staining was used to detect intracellular reactive oxygen species (ROS). Western blot was performed to detect the protein levels of LC3, p62, beclin 1, autophagy-related protein (Atg) 5, p-Akt (protein kinase B), p-mTOR (mammalian target of rapamycin), p-4E-BP1 (eukaryotic translation initiation factor 4E-binding protein 1), and p-p70S6K (p70 ribosomal S6 kinase). Results: DHA increased LC3-II and the number of fluorescent GFP-LC3 puncta in HUVECs. Silencing ATG5 by siRNA interference attenuated DHA-induced LC3-II elevation. DHA enhanced ROS production, but pretreatment with antioxidant N-acety-l-cysteine (NAC) failed to reduce DHA-induced autophagy in HUVECs. Pretreatment with PD98059, SP600125 and SB203580, the inhibitors of ERK, JNK, and p38 MAPK, did not reverse autophagy in DHA-treated HUVECs. DHA significantly reduced phosphorylation of Akt, mTOR, p70S6K, 4E-BP1 in HUVECs. Rapamycin, an mTOR antagonist, compromised DHA-induced autophagy. Conclusion: DHA induces autophagy in HUVECs by inhibition of the Akt/mTOR pathway.

Herein, a novel modified polyvinyl alcohol(DA-IPVA) used as sizing agent was prepared by using diacetone acrylamide(DAAM) as graft monomer and N-(isobutoxymethyl)acrylamide(IBMA) as self-cross-linking monomer. The effect of the amount of DAAM on the properties of emulsion, film and sizing paper was discussed. The surface micro-structure of the sizing paper was characterized by SEM and AFM. The addition of DAAM/ADH and IBMA endowed DA-IPVA with cross-linked active group and increased cross-linking density and hydrophobicity after ADH was added into the emulsion and the cross-linking structure was formed. The enhancing mechanism of surface sizing agent for paper was revealed. The DA-IPVA can be cross-linked on the surface and inside of the paper to form a dense network structure, which improves the bonding force between the fibers. When the mole fraction of DAAM of the cross-linking monomer is 8%, the surface sizing performance of the paper is obviously improved compared with the base paper. The dry and wet strength is increased by 266.5% and 334.3% respectively, and the folding resistance is increased 2946.67%. This study can have a profound impact on the development of the technology of cross-linking surface sizing agent for paper.

Multiple myeloma (MM) is a tumor type characterized by the unregulated proliferation of clonal plasma cells in the bone marrow. Immunotherapy based on chimeric antigen receptor T cell (CAR-T) therapy has achieved exciting success in the treatment of hematological malignant tumors. CD38 is highly and evenly expressed in MM and is an attractive target for MM treatment. Here, we successfully constructed two novel second-generation CAR-T cells targeting CD38 by retroviral vector transduction. CD38 CAR-T cells could be activated effectively after stimulation with CD38-positive tumor cells and secrete cytokines such as IFN-γ and TNF-α to promote tumor cell apoptosis in in vitro experiments. Real-time fluorescence monitoring experiments, luciferase detection experiments and flow cytometry experiments revealed the efficient and specific killing abilities of CD38 CAR-T cells against CD38-positive tumor cells. The proliferation ability of CD38 CAR-T cells in vitro was higher than that of untransduced T cells. Further antitumor experiments in vivo showed that CD38 CAR-T cells could be quickly activated to secrete IFN-γ and eliminate tumors. Thus, novel CD38-targeted second-generation CAR-T cells have efficient and specific antitumor activity and may become a novel therapy for the clinical treatment of MM.

Bioink, a key element of three-dimensional (3D) bioprinting, is frequently engineered to achieve improved printing performance. Viscoelasticity related to rheological properties is correlative of the printability of bioink for extrusion bioprinting, which affects the complexity of printing 3D structures. This article shows the use of hydroxyethyl cellulose (HEC) as a rheological additive for engineering bioink to improve the printability without reducing the biocompatibility. Different concentrations of HEC were added to four types of bioink, namely, reagent-crosslinked, temperature-dependent phase change, ultraviolet-polymerized, and composite hydrogel bioinks, to investigate the effect on the viscoelasticity properties, print fidelity, and other printed scaffold properties. The results indicate that HEC is able to increase the rheological properties by 100 times to stabilize complex structures and improve the printing fidelity to narrow the gap between the design value and theoretical value, even converting nonviscous ink into directly printable ink, as well as tune the swelling ratio for better molecular permeability. The degradation of bioink can also be tuned by the addition of HEC. Moreover, this bioink is biocompatible for cell lines and primary cells. HEC is expected to be widely used in 3D extrusion-based bioprinting.

The natural DNA double helix consists of two strands of nucleotides that are held together by multiple hydrogen bonds. Here we propose to build an artificial double helix from fragments of two strands connected by covalent linkages therein, but with halogen bonding as the driving force for self-assembling the fragments to the double helix. We succeed in building such a double helix in both solution and solid state, by using a bilateral N-(p-iodobenzoyl)alanine based amidothiourea which in its folded cis-form allows double and crossed C−I···S halogen bonds that lead to right- or left-handed double helix when the two alanine residues are of the same L,L- or D,D-configuration. The double helix forms in dilute CH3CN solution of the micromolar concentration level, e.g., 5.6 μM from 2D NOESY experiments and exhibits a high thermal stability in solution up to 75 °C, suggesting cooperative and thereby strong intermolecular double crossed halogen bonding that makes the double helix stable. This is supported by the observed homochiral self-sorting in solution., Building an artificial double helix is a compelling challenge, and most strategies rely on the intertwining of two helical strands. Here, in a very different approach, the authors construct a supramolecular double helix from multiple synthetic small molecules chained together by double crossed halogen bonds.

The spike photosynthesis plays a curial role in wheat photosynthesis under drought stress. However, the mechanism of drought tolerance in the spike is still unclear. Our study compared the gas exchange parameters, antioxidant system, and phenylpropanoid pathway between the wheat flag leaf and spike in response to drought stress. Compared with the flag leaf, the spike organs exhibited lower reductions in the net photosynthetic rate (Pn), relative water content (RWC), and chlorophyll content (Chl) under drought stress. The activities of phenylalanine ammonia-lyase (PAL), cinnamate 4-hydroxylase (C4H), and 4-coumarate-coenzyme A ligase (4CL) enzymes, and the total contents of phenolics and flavonoids (TPC and TFC, respectively) were enhanced much more percentages in the spike organs than that in the flag leaf under drought stress. Drought also induced the expression of structural genes (TaPAL, TaC4H, Ta4CL, TaCHS, TaCHI, TaFNS, TaF3H, TaFLS, TaDFR, and TaANS) involved in the phenylpropanoid pathway of the spike organs during the middle and late grain filling periods. The spike organs also showed much smaller accumulations of O2.-, hydrogen peroxide (H2O2), and malondialdehyde (MDA) in treated wheat. Higher activities of antioxidant enzymes (superoxide dismutase, SOD; peroxidase, POD; and catalase, CAT) and more proline content were observed in the spike organs as compared to the flag leaf under drought stress. All these results indicated that the enhanced tolerance to drought stress in spike organs was related to the elevated phenylpropanoid pathway. It could make the spike maintain a better water status and further lead to the relatively higher photosynthesis and lower membrane damage.

Phosphorylated graphene oxide (PedGO) was synthesized through the in-situ phosphate esterification method with urea as catalyst and then embed into waterborne acrylate-epoxy resin emulsion (AE) coating to modify the coating. The TEM and AFM indicated that phosphate was uniformly decorated on GO sheets, forming a large phosphorylated graphene oxide sheets. The PedGO improved the water vapor permeability and the coating adhesion strength after 30 days of immersion in 3.5% NaCl of AE coatings, respectively. Electrochemical impedance spectroscopy measurements (EIS) revealed that the PedGO-modified AE (PedGO/AE) was an outstanding barrier against corrosive media compared with AE or GO-modified AE (GO/AE). Scratch tests also showed that the corrosion-promotion effect of PedGO in AE was inhibited. The enhanced corrosion protection performance was observed because on the one hand the PedGO can greatly prolonged the diffusion pathway of corrosive media in the coating matrix; on the other hand the organic p...

In vitro models for screening of drugs against type 2 diabetes are crucial for the pharmaceutical industry. This paper presents a new approach for integration of a three-dimensionally-cultured insulinoma cell line (INS-1 cell) incubated in a high concentration of glucose as a new model. In this model, INS-1 cells tended to aggregate in the 3D gel (basement membrane extractant, BME), in a similar way to 3D in vivo cell culture models. The proliferation of INS-1 cells in BME was initially promoted and then suppressed by the high concentration of glucose, and the function of insulin secretion also was initially enhanced and then inhibited by the high concentration of glucose. These phenomena were similar to hyperglycemia symptoms, proving the validity of the proposed model. This model can help find the drugs that stimulate insulin secretion. Then, we identified the difference between the new model and the traditional two-dimensional model in terms of cell morphology, inhibition rate of cell proliferation, and insulin secretion. Simultaneously, we developed a circular drug concentration gradient generator based on microfluidic technology. We integrated the high-glucose 3D INS-1 cell model and the circular concentration gradient generator in the same microdevice, tested the utility of this microdevice in the field of drug screening with glipizide as a model drug, and found that the microdevice was more sensitive than the traditional device to screen the anti-diabetic drugs.

Two imidazolium-based cationic polymeric nanotraps based on tetraphenylmethane building blocks (CPN-tpm) with different counterions were rationally designed and constructed for the efficient removal of Cr2O72- from wastewater. The influence of counterions on Cr2O72- adsorption performance was studied. With better wettability (contact angle as 28.61°), CPN-tpm-Cl exhibited a higher uptake capacity of 366 mg g−1 for Cr2O72- capture and a faster ion exchange kinetic process in 20 min. While CPN-tpm-Br with a contact angle of 83.16° showed a lower maximum capacity of 324 mg g−1. In addition, CPN-tpm-Cl can work in a wide pH range from 2 to 10 and possess excellent selectivity (such as Cl-, NO3- and SO42-) as well as good reusability for 5 times. Such excellent performances indicated that CPN-tpm-Cl is a promising candidate for the Cr2O72- capture application. Our work not only contributes cationic polymeric nanotraps as a promising candidate for Cr2O72- removal, but also suggests a new approach to develop new type of adsorbents for wastewater treatment.

Cross-linked polyvinyl alcohol (AZ-CIPVA) for effective paper sizing was prepared by using N-(isobutoxymethyl)acrylamide (IBMA) and aziridine cross-linker (AZ) as modifiers. The structure and the performances of the AZ-CIPVA with different dosage of AZ were characterized. The enhancing mechanism of paper sized by AZ-CIPVA was clarified. The results show that cross-linking structure is formed by the reaction between AZ and carboxyl groups in CIPVA molecules. With the increase of AZ content, the gel content, cross-linking density and thermal stability of the AZ-CIPVA film are increased. When the AZ dosage is 3.5%, both tensile strength and modulus of AZ-CIPVA film reach maximum, and the value are 68.34 MPa and 1037.02 MPa, respectively. The water absorption of the film reaches minimum and the folding endurance of the sizing paper reaches maximum when the content of AZ is 2.8%. When applied to the surface of the paper, the maximum dry and wet tensile indexes of the paper are increased by 223.77% and 432.56%, respectively. Roughness of the sizing paper increases slightly and the surface becomes uneven. The micro-structure shows that larger pores between the paper fibers are filled and cross-linked after sizing, which is beneficial to improve the mechanical strength of paper.

N dopping can enhance the electrochemical efficiency of carbon materials, but the effect of N on the electrochemical-mediated removal of Cr(VI) has been mostly ignored. Here, we report highly porous N-doped carbon spheres for electrochemical-mediated removal of Cr(VI), and the role of N on Cr(VI) removal has been systematically investigated using both experimental evaluations and theoretical validation. Experimental findings revealed that the removal capacity of Cr(VI) reached 186.5 mg·g−1 with a removal rate of 100%. In addition, the underlying processes for the role of N species have been investigated using density functional theory (DFT) calculations. The result agrees with the findings from the experimental evaluations thus suggesting that the removal process of Cr(VI) was mainly distributed by pyridinic-N and oxidized-N. This study has demonstrated that the removal of Cr(VI) by N species forms a crucial part in the removal of Cr(VI) using N-doped carbon materials and offers a possible alternative approach for enhancing the removal efficiency of carbon materials.

Increasing flavonoids have been reported to possess anti-angiogenic effects. Inhibition of angiogenesis plays a critical role in the treatment of cancer, especially in advanced metastatic cancer. In this study, we assessed the effect of Oroxylin A-7-glucuronide (Oroxyloside), a main metabolite of Oroxylin A, on angiogenesis in human endothelial cell-like EA.hy926 cells. Oroxyloside suppressed the migration and tube formation of EA.hy926 cells. Meanwhile, microvessels sprouting from aortic rings and new blood vessels on the chicken chorioallantoic membrane (CAM) were also inhibited. Mechanism studies showed that Oroxyloside reduced the autophosphorylation of vascular endothelial growth factor receptor 2 (VEGFR2/Flk-1) while it up-regulated the expression of R-Ras and VE-cadherin. In consequence, Oroxyloside inhibited the downstream Akt/MAPK/NF-κB pathways and then decreased the nuclear translocation and DNA binding ability of NF-κB. Furthermore, in vivo study showed that Oroxyloside exhibited a potential anti-angiogenic effect in Matrigel plug assay and inhibited growth of xenografted tumors with low systemic toxicity, which could be ascribed to the inhibition of VEGFR2 internalization. Taken together, these results suggested that Oroxyloside could inhibit angiogenesis in vitro and in vivo via suppressing the internalization of VEGFR2 and might serve as a potential antitumor agent.

In-situ surfactant-free emulsion polymerization was utilized to prepare polyacrylate/polyurethane (PUA) microemulsions in the absence of surfactant and organic solvent. For this purpose, PUA with higher acrylate content was successfully prepared, with the aim to reduce the coating cost. The dynamic light scattering results showed that the particle size of PUA microemulsion displayed a unimodal distribution and the particle size was ranged from 33 to 61 nm. In comparison with PUA prepared with conventional miniemulsion polymerization, the particle size distribution coefficient dropped by one order. Atomic force microscopy, together with thermogravimetric analyzer, demonstrated good compatibility and interaction between PU and acrylic components, and no phase separation was detected even at 58 wt% acrylic content. With the incorporation of acrylic component, the thermal stability and maximum stress were improved. The maximum stress greatly increased from 4.6 to 30.9 MPa, and the maximum stress of in-situ PUA was nearly three times larger than that of PUA prepared by miniemulsion polymerization. The effects of acrylic content on water resistance, pencil hardness, adhesion, and impact strength of wood coating were evaluated. With increasing the acrylic content, the water resistance and pencil hardness increased, though the impact strength of in-situ PUA films was slightly reduced.

Impurities may have a marked effect on crystal nucleation and growth. To further understand the role of impurities, the crystallization (solubility, nucleation, growth) of succinic acid in water in the presence of surfactants such as polyethylene glycol sorbitan monooleate (Tween 80), cetyltrimethylammonium bromide (CTAB) and sodium dodecylbenzenesulfonate (SDBS) was investigated experimentally. The presence of CTAB, SDBS or Tween 80 had little influence on succinic acid solubility but did slow crystallization kinetics. The surfactant monomer in solution, not micelles, proved to play the primary role affecting nucleation. The nucleation inhibition by surfactant was analyzed on the base of a two-step nucleation process: (1) the inhibition on the formation and growth of succinic acid nanodroplets and (2) the influence on succinic acid single nucleus (SASN) in secondary nucleation. SASN may play important role in secondary nucleation, although further work is necessary to conform this. The length of the surfactant hydrocarbon chain was found to affect crystal habit development.

We herein report on an examination of the compositions of copper relics unearthed from the Guangfentou site in Jiangchuan, Yunnan, China. Scanning electron microscopy combined with energy-dispersive X-ray spectroscopy (SED-EDS), metallographic microscopy, and lead isotope ratio analysis were used to analyze 20 metallurgical relics. The results indicated that the relics were either copper metal or copper slag. The copper metal was composed of either metallic copper or tin bronze, while the copper slags were either smelting slag or melting slag, with the melting slags being composed of refining or alloying slag. The Guangfentou site in the Jiangchuan county contains an extraordinarily complete set of bronze metallurgical relics from the Bronze Age of Yunnan. The processes involved in this site include smelting of sulfidic ores, refining of primary raw copper, bronze alloying, and bronze casting. This was an important metallurgical site in the ancient Dian Kingdom and has provided clues that will aid in efforts to reveal the origins of bronze smelting technologies and the sources of the copper ores used by the ancient Dian civilization.

We first prepared an unsaturated epoxy resin ester (EM) by addition–esterification reaction with acrylic acid and then synthesized a series of acrylic ester/epoxy hybrid latexes (AE) with core–shell structure by semicontinuous emulsion polymerization method. The resultant AE emulsions are utilized as anticorrosion coatings of metals. The influences of EM content and crosslinking agent (PEG(400)DA) content on the physicochemical properties of the resultant emulsions and anticorrosion coatings of metals are investigated in detail. The AE emulsion displays better anticorrosion properties when it is prepared under the following conditions: the EM content of 30 wt% and PEG(400)DA content of 2.0 wt%. The relationships between the AE structure and anticorrosion properties of AE coatings are clearly illustrated. The corrosion resistances of AE coatings are not only depend on the crosslinking density, hydrophilic, and polarity among the AE chains, but also rely on the stability of the emulsion and the integrality and homogeneity of the coatings.

Herein, we report a conformation switching-based fluorescence sensing scheme using dipeptide-based amidothioureas (azapeptides) that contain a folded β-turn structure. Amidothiourea is equipped at its two termini with an electron acceptor and an electron donor or two fluorophores, such that it exhibits enhanced exciplex or excimer emission because of the turn structure in which the two termini are brought into close proximity; on the other hand, it exhibits a dramatic ratiometric fluorescence response upon anion binding to the thiourea moiety because of the resultant extended conformation of the anion binding complex.

Muller cells are the major glial cells spanning the entire layer of the retina and maintaining retinal structure. Under pathological conditions, Muller cells are involved in retinal angiogenesis, a process of growing new blood vessels from pre-existing capillaries. In response to hypoxia, high glucose, and inflammation conditions, multiple signaling pathways are activated in Muller cells, followed by the increased production of proangiogenic factors including vascular endothelial growth factor, basic fibroblast growth factor, matrix metalloproteinases, Netrin-4, and angiopoietin-like 4. Expression of antiangiogenic factors is also downregulated in Muller cells. Besides, proliferation and dedifferentiation of Muller cells facilitates retinal angiogenesis. In this review, we summarized molecular mechanisms of Muller cells-related retinal angiogenesis. The potential of Muller cells as a therapeutic target for retinal angiogenesis was also discussed.

Rhenium is one of the most valuable elements found in nature, and its capture and recycle are highly desirable for resource recovery. However, the effective and efficient collection of this material from industrial waste remains quite challenging. Herein, a tetraphenylmethane-based cationic polymeric network (CPN-tpm) nanotrap is designed, synthesized, and evaluated for ReO4 - recovery. 3D building units are used to construct imidazolium salt-based polymers with positive charges, which yields a record maximum uptake capacity of 1133 mg g-1 for ReO4 - collection as well as fast kinetics ReO4 - uptake. The sorption equilibrium is reached within 20 min and a kd value of 8.5 × 105 mL g-1 is obtained. The sorption capacity of CPN-tpm remains stable over a wide range of pH values and the removal efficiency exceeds 60% for pH levels below 2. Moreover, CPN-tpm exhibits good recyclability for at least five cycles of the sorption-desorption process. This work provides a new route for constructing a kind of new high-performance polymeric material for rhenium recovery and rhenium-contained industrial wastewater treatment.

A directly coating method, controlled double-jet precipitation (CDJP), was developed for synthesizing magnetic Fe3O4@Cu(OH)2 composites in combination of advantages of magnetic rapid separation and satisfactory adsorption performance. The morphology and structure of the composites were analyzed by SEM, TEM, XRD, FTIR, XPS and VSM techniques. Through controlling the reaction on Fe3O4 particles, directly coating of Cu(OH)2 was successfully realized without the extra complicated procedures. The obtained Fe3O4@Cu(OH)2 consists of micro particles of size around 250 nm coated with special leaflike nanomorphologies, possessing high saturation magnetization (from 56.5 to 98.84 emu g−1). As the amount of loaded Cu increased, As(V) removal of the composites augmented from 11.11 to 35.71 mg g−1 far beyond that of reported traditional magnetic adsorbents. The adsorption isotherm was best fitted by Langmuir adsorption mode and the mechanism was mainly ascribed to the OH functionality of the Fe3O4@Cu(OH)2 composites and electrostatic attraction between As(V) species and Fe3O4@Cu(OH)2 composites. The Fe3O4@Cu(OH)2 composites is a promising candidate for treating arsenic contaminated water.

2‐Diazo‐1‐phenyl‐2‐((trifluoromethyl)sulfonyl)ethan‐1‐one (diazo‐triflone) (2) is not only a building block but also a reagent. In this study, diazo‐triflone, which was originally used for the synthesis of β‐lactam triflones as a trifluoromethanesulfonyl (SO2CF3) building block under catalyst‐free thermal conditions, is redisclosed as an effective electrophilic trifluoromethylthiolation reagent under copper catalysis. A broad set of enamines, indoles, β‐keto esters, pyrroles, and anilines were nicely transformed into corresponding trifluoromethylthio (SCF3) compounds in good to high yields by diazo‐triflone under copper catalysis via an electrophilic‐type reaction. A coupling‐type trifluoromethylthiolation reaction of aryl iodides was also realized by diazo‐triflone in acceptable yields.

Sulfur (S) application in pakchoi (Brassica chinensis L.) cultivation is vital for reducing cadmium (Cd) accumulation in the plants. However, the mechanism of S application on Cd uptake and translocation in pakchoi is unclear. In this study, a hydroponic experiment was performed to investigate the effects of S application on Cd accumulation in pakchoi at one Cd concentration (50 μM, in comparison to the control condition, 0 μM) and three S levels (0, 2, 4 mM). The results showed that excessive S application (4 mM) reduced Cd accumulation and alleviated pakchoi growth inhibition caused by Cd stress in shoots and roots. With increased S application, the proportion of Cd in the vacuolar fraction and the proportion of NaCl-extractable Cd increased in roots. Additionally, S application increased the content of glutathione (GSH) and phytochelatins (PCs). The reduced Cd uptake and accumulation in pakchoi shoots could have been due to increased Cd chelation and vacuolar sequestration in roots. In addition, sufficient S application (2 mM) increased the expression of γ-glutamylcysteine synthetase (GSH1) and nicotinamide synthase (NAS) in roots, and excessive S application upregulated the expression of ATP sulfurylase (ATPS) and phytochelatin synthase (PCs). This study provides evidence for the mechanism of mitigating Cd toxicity in pakchoi and will be helpful for developing strategies to reduce Cd accumulation in the edible parts of pakchoi through S fertilizer application.

Cu-N-C electrocatalyst was successfully prepared with Cu-BTC and polyacrylonitrile as templates by electrospinning and in-situ growth method. The effect of various [Formula: see text]-doped content on the electrochemical performance of the catalyst were investigated and the Cu-N-C-0.25 exhibited the best OER/ORR catalytic activities. When it was applied to the cathode of the zinc-air batteries, the power density of Cu-N-C-0.25 was 209.1[Formula: see text]mW[Formula: see text]cm[Formula: see text], which exceeded that of the commercial Pt/C[Formula: see text]IrO2 hybrid catalyst (157[Formula: see text]mW[Formula: see text]cm[Formula: see text]). The excellent electrochemical performance may be attributed to large number of active sites and high specific surface area on Cu-N-C electrocatalyst. It will be a promising alternative to precious metal catalysts containing Pt, Ir or Ru and their oxides.

Carcinoembryonic antigen (CEA) is a broad-spectrum tumor marker used in clinical applications. The primarily clinical method for measuring CEA is based on chemiluminescence in serum during enzyme-linked immunosorbent assays (ELISA) in 96-well plates. However, this multi-step process requires large and expensive instruments, and takes a long time. In this study, a high-throughput centrifugal microfluidic device was developed for detecting CEA in serum without the need for cumbersome washing steps normally used in immunoreactions. This centrifugal microdevice contains 14 identical pencil-like units, and the CEA molecules are separated from the bulk serum for subsequent immunofluorescence detection using density gradient centrifugation in each unit simultaneously. To determine the optimal conditions for CEA detection in serum, the effects of the density of the medium, rotation speed, and spin duration were investigated. The measured values from 34 clinical serum samples using this high-throughput centrifugal microfluidic device showed good agreement with the known values (average relative error = 9.22%). These results indicate that the high-throughput centrifugal microfluidic device could provide an alternative approach for replacing the classical method for CEA detection in clinical serum samples.

Cationic poly(urethane-acrylate) emulsifier-free microemulsions are prepared by seeded emulsion polymerization (SPUA) or in-situ emulsion polymerization (IPUA) with (a) or without (b) crosslinking agent hydroxyethyl acrylate (HEA). Furthermore, no surfactant is introduced into the reaction system. The effect of continuous phase and HEA on the rheological behavior and properties of microemulsions are studied. The results show that IPUA using vinylmonomers as the continuous phase and with HEA (IPUAMB-b) has the highest ζ value, lowest coagulation ratio, smallest particle size of 48 nm and apparent core–shell structures. Rheological research has concluded that the zero-shear viscosity of IPUAB-b and IPUAM-b emulsion is 6.03×102 and 7.89 Pa·s, respectively, and presents pseudoplastic behavior. However, IPUAMB-b and SPUA-b display Newtonian behavior with η0 of 0.136 Pa·s and 0.0823 Pa·s, respectively. PUA emulsions display similar rheological behavior when NMP is replaced by the mixture of MMA and BA.

Ascorbate-glutathione (ASA-GSH) cycle is a major pathway of H2O2 scavenging and an effective mechanism of detoxification in plants. The differences in photosynthesis, chlorophyll content (Chl), relative water content (RWC), antioxidants and antioxidative enzyme activities involved in ASA-GSH metabolism were measured between the flag leaves and spike bracts (glumes and lemmas) during grain filling under drought stress. The expression of APX1, GRC1, DHAR, MDHAR, GPX1, and GS3 in ASA-GSH cycle was also measured. Compared with the flag leaves, the spike bracts exhibited stable net photosynthetic rate (PN) and chlorophyll content (Chl), a lower accumulation of reactive oxygen species (ROS), and more enhanced percentages of antioxidant enzyme activities and key enzymes gene transcription levels involved in ASA-GSH metabolism during the grain-filling stage under drought conditions. This could be the reasonable explanation for the more stable photosynthetic capacity in spikes, and the glumes and lemmas senesced later than the flag leaves at the late grain-filling stage. Also, the function of ASA-GSH cycle could not be ignored in alleviating oxidative damage by scavenging more excess ROS in spikes under drought stress.

Polyelectrolyte hybrid hollow microspheres with sandwich structure of about 450 nm have been accomplished by layer-by-layer self-assembling of two modified ferroferric oxide nanoparticles, lysine modified ferroferric oxide nanoparticles (Fe3O4-LYs) and citrate modified ferroferric oxide nanoparticles (Fe3O4-CA), as the main assembling materials via electrostatic interaction for the first time. They are superparamagnetic with saturation magnetization of 45.69 emu/g, revealing their high magnetic content of 70%. As drug delivery system, they also exhibited pH-stimuli responsive controlled release of an anticancer drug doxorubicin, following the Fickian diffusion model. Their unique structure and high magnetic content make them good candidate for targeted delivery.

The unique reduction-triggered functional graphene oxide nanoparticles (GON) with well-defined size and uniform distribution were designed as an innovative drug delivery platform for cancer treatment for the first time, via the redox radical polymerization of methacrylic acid from the polyethylene glycol (PEG) modified GON (GON-PEG), following by cross-linking with cystamine. Thermogravimetric analysis demonstrates that the typical PMAA2-GON-PEG carriers contain about 16 wt % PEG segments and 33 wt % poly(methacrylic acid) (PMAA) brushes. PEG moieties are incorporated to make the drug delivery platforms stealthy during blood circulation. Notably, introducing the cross-linked PMAA brushes efficiently minimizes the premature release of doxorubicin (DOX) in the stimulated normal tissues, and accelerates DOX release in the stimulated tumor tissues through response to reduce agent. The carriers showed a 6-fold faster releasing rate at pH 5.0 in the presence of 10 mM glutathione (GSH) (stimulated tumor tissues) than at pH 7.4 with 10 μM GSH (stimulated normal tissues). In vitro cytotoxicity test also showed that the cross-linked PMAA2-GON-PEG (CPMAA2-GON-PEG) carriers had remarkable cytocompatibility, and that the DOX-loaded CPMAA2-GON-PEG had excellent killing capability to SiHa cells.

Background/Aims: Although early studies show that Mdm2 is the primary E3 ubiquitin ligase for the p53 tumor suppressor, an increasing amount of data suggests that p53 ubiquitination and degradation are more complex than once thought. Here, we investigated the role of RNF125, a non-Mdm2 ubiquitin-protein ligase, in the regulation of p53. Methods and Results: RNF125 physically interacted with p53 in exogenous/endogenous co-immunoprecipitation (IP) and GST-pull down assay, and a C72/75A mutation of RNF125 did not interfere with this interaction. Expression of RNF125 decreased the level of p53 in a dose-dependent manner, whereas knockdown of RNF125 by RNA interference increased the level of p53. As shown by Western blotting and ubiquitin assay, RNF125 ubiquitinated p53 and targeted it for proteasome degradation. Furthermore, RNF125 repressed p53 functions including p53-dependent transactivation and growth inhibition. Conclusion: Our data suggest that RNF125 negatively regulates p53 function through physical interaction and ubiquitin-mediated proteasome degradation.

Cu–m-phenylenediamine (Cu–mPD) complex was firstly exploited to efficiently synthesize poly(m-phenylenediamine)/reduced graphene oxide (PmPD/rGO) hydrogel. Cu–mPD complex shows high gelation and redox reaction activity with GO, which is ascribed to the joint and mediation effect of Cu2+. The green and efficient route realized high monomer polymerization (>99%) and decreased hydrothermal reaction time (1 h) without additional polymerization process. Scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transformed infrared spectroscopy, and Raman spectroscopy were conducted to characterize the morphology and structure of PmPD/rGO hydrogel. The macroscopic hydrogels exhibit high porosity, good mechanical strength, superior adsorption performance (with methylene blue adsorbance of 615 mg g−1), and readily recycle properties.

A uniform decoration of hyphae by polyaniline nanoparticles (PANI NPs) was achieved here. This novel hybrid structure can be effectively assembled into a film by filtration and disassembled in water by shaking. This reversible process is very fast, which promises applications in nanomaterials including adsorption.