Effects of different factors on fly ash-based functional soil and its oat grass cultivation.

Using fly ash as the main matrix for plant ecological restoration is effective for constructing a sustainable and ecological environment. The relevant properties of functional soil change due to different factors. Based on the orthogonal experiment of functional soil and the pot experiment of oat grass, fly ash was used as the matrix material for functional soil. Afterward, MX (large granules dispensing certain nutrients), SJJXWS (a water-retaining agent), and AF (a nutrient conditioner) additives were added to study the physical, chemical, and agronomic properties of functional soil, such as the emergence rate and weight of plants. The results showed the high pH and conductivity of functional soil, implying alkaline soils with high salinity. The contents of organic matter and available phosphorus and potassium were relatively high, indicating its high nutrient content. Further analysis revealed that the MX was the key factor affecting functional soil's electrical conductivity and evaporation, and thus, the corresponding plant emergence rate, plant weight, and other related indicators. The influence of each factor on the corresponding plant emergence rate, plant weight, and other indicators of functional soil was arranged in the order of MX (large granules dispensing certain nutrients), SJJXWS (a water-retaining agent), and AF (a nutrient conditioner). The optimum additive ratio in functional soil was 0.45 t·hm-2 of MX, 0.12 t·hm-2 of SJJXWS, and 1.65 t·hm-2 of AF. The results of this study provide a theoretical basis for further development of functional soil for ecological cycle restoration purposes.

Copper-thiosemicarbazone complexes conjugated-cellulose fibers: Biodegradable materials with antibacterial capacity.

Personal protective equipment (PPE) is vital in battling bacteria crisis, but conventional PPE materials lack antimicrobial activities and environmental friendliness. Our work focused on developing biodegradable and antibacterial fibers as promising bioprotective materials. Here, we grafted highly effective antibacterial copper-thiosemicarbazone complexes (CT1-4) on cellulose fibers via covalent linkages. Multiple methods were used to characterize the chemical composition or morphology of CT1-4 conjugated-fibers. Conjugation of CT1-4 maintains the mechanical properties (Breaking strength: 2.35-2.45 cN/dtex, Breaking elongation: 7.19 %-7.42 %) and thermal stability of fibers. CT1 can endow cellulose fibers with the excellent growth inhibition towards Escherichia coli (E. coli) (GIR: 61.5 % ± 1.28 %), Staphylococcus aureus (S. aureus) (GIR: 85.7 % ± 1.93 %), and Bacillus subtilis (B. subtilis) (GIR: 87.6 % ± 1.44 %). We believe that the application of CT1 conjugated-cellulose fibers is not limited to the high-performance PPE, and also can be extended to various types of protective equipment for food and medicine safety.

Metal Complexes or Chelators with ROS Regulation Capacity: Promising Candidates for Cancer Treatment.

Reactive oxygen species (ROS) are rapidly eliminated and reproduced in organisms, and they always play important roles in various biological functions and abnormal pathological processes. Evaluated ROS have frequently been observed in various cancers to activate multiple pro-tumorigenic signaling pathways and induce the survival and proliferation of cancer cells. Hydrogen peroxide (H2O2) and superoxide anion (O2•-) are the most important redox signaling agents in cancer cells, the homeostasis of which is maintained by dozens of growth factors, cytokines, and antioxidant enzymes. Therefore, antioxidant enzymes tend to have higher activity levels to maintain the homeostasis of ROS in cancer cells. Effective intervention in the ROS homeostasis of cancer cells by chelating agents or metal complexes has already developed into an important anti-cancer strategy. We can inhibit the activity of antioxidant enzymes using chelators or metal complexes; on the other hand, we can also use metal complexes to directly regulate the level of ROS in cancer cells via mitochondria. In this review, metal complexes or chelators with ROS regulation capacity and with anti-cancer applications are collectively and comprehensively analyzed, which is beneficial for the development of the next generation of inorganic anti-cancer drugs based on ROS regulation. We expect that this review will provide a new perspective to develop novel inorganic reagents for killing cancer cells and, further, as candidates or clinical drugs.

3-Hydroxyflavone derivatives: promising scaffolds for fluorescent imaging in cells.

As a typical class of excited-state intramolecular proton transfer (ESIPT) molecules, 3-hydroxyflavone derivatives (3HF, also known as flavonols) have received much attention recently. Thereinto, the role of hydrophobic microenvironment is significant importance in promoting the process and effects of ESIPT, which can be regulated by the solvents, the existence of metal ions and proteins rich with α-helix structures or the advanced DNA structures. Considering that plenty of biological macromolecules offer cellular hydrophobic microenvironment, enhancing the ESIPT effects and resulting in dual emission, 3HF could be a promising scaffold for the development of fluorescent imaging in cells. Furthermore, as the widespread occurance of compounds with biological activity in plants, 3HF derivatives are much more secure to be cellular diagnosis and treatment integrated fluorescent probes. In this review, multiple regulatory strategies for the fluorescence emission of 3HF derivatives have been collectively and comprehensively analyzed, including the solvent effects, metal chelation, interaction with proteins or DNAs, which would be beneficial for ESIPT-promoting or ESIPT-blocking processes and then enhance or control the fluorescence emission of 3HF effectively. We expect that this review would provide a new perspective to develop novel 3HF-based fluorescent sensors for imaging in cells and plants.

Modification of Polyacrylonitrile Fibers by Coupling to Thiosemicarbazones.

This work reports the modification of Polyacrylonitrile (PAN) fibers by coupling to thiosemicarbazones to achieve the biological activity for the applications in the food product packaging. After modification, seven thiosemicarbazone compounds were synthesized. The as-synthesized thiosemicarbazone compounds were bonded to PAN fibers via covalent coupling, which was confirmed using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy. The mean graft efficiency of the compounds was about 1.92%, and the antibacterial efficiency was 88.6% and 45.1% against Staphylococcus aureus (S-aureus) bacteria. All the seven thiosemicarbazone compounds exerted excellent tyrosinase activity, low cytotoxicity, excellent metal ion chelation ability, and anti-bacterial behavior against both gram-positive and negative bacteria. The mechanical properties of the fibers have been maintained without significant damage after the chemical modification. The break strength test and elongation at the break test were done to measure the fracture strength of the modified fibers. Overall, the promising properties of the modified PAN fibers show potential applications in food packaging materials for fruits and vegetables, which require long-term anti-browning effects during their transportation and storage.

Environmentally Friendly Flexible Strain Sensor from Waste Cotton Fabrics and Natural Rubber Latex.

A green approach was successfully developed to fabricate flexible sensors by utilizing carbonized waste cotton fabrics in combination with natural rubber latex. Waste cotton fabrics were firstly carbonized by heat treatment in the nitrogen atmosphere before they were combined with natural rubber latex using three methods, i.e., vacuum bagging, negative pressure adsorption and drop coating. After impregnation with natural rubber, the carbonized cotton maintained the fabric structure and showed good conductivity. More importantly, the electric resistance of the textile composites changed with the tensile strain. The cyclic stretching-releasing tests indicated that the prepared wearable flexible strain sensors were sensitive to strain and stable under cyclic loading. The flexible strain sensor also demonstrated the capability of monitoring human finger and arm motion.

Activation of peroxymonosulfate by magnetic carbon supported Prussian blue nanocomposite for the degradation of organic contaminants with singlet oxygen and superoxide radicals.

In order to develop efficient and green catalyst for organic pollutants removal, magnetic carbon supported Prussian blue nanocomposite Fe3O4@C/PB was prepared for the first time. The performance of Fe3O4@C/PB in activating peroxymonosulfate (PMS) for the degradation of 2,4-dichlorophenol (2,4-DCP) was investigated. 2,4-DCP could be effectively degraded under the "Fe3O4@C/PB + PMS" system within a broad pH range of 2-9. Without pH adjustment (pH 3), 2,4-DCP (20 mg/L) was completely degraded in 50 min along with a 70% removal of TOC; while the required time for complete degradation of 2,4-DCP was shortened to 40 min under initial solution pH at 7. Fe3O4@C/PB could also activate PMS for the degradation of phenol, Acid Orange II, Reactive brilliant red X-3B, Rhodamine B and Methylene blue. The degradation rates higher than 95% could be achieved for all these contaminants within the time scale of 15-60 min. The studies of radical-quenching and electron paramagnetic resonance demonstrated that singlet oxygen (1O2) and superoxide radicals (O2-), rather than sulfate (SO4-) and hydroxyl (OH) radicals, were the dominant species responsible for the oxidation of organic pollutants. The plausible mechanism of the catalytic degradation was proposed and the enhanced activity of Fe3O4@C/PB was assumed to be related to the increased electron transfer owing to the synergic effect between the magnetic carbon and the mixed-valence units in PB. Fe3O4@C/PB is promising in wastewater treatment owing to its high efficiency, excellent stability and reusability, environmental friendliness and magnetic separability.

The rational design of specific SOD1 inhibitors via copper coordination and their application in ROS signaling research.

Efficient methods for the regulation of intracellular O2˙- and H2O2 levels, without altering intracellular processes, are urgently required for the rapidly growing interest in ROS signaling, as ROS signaling has been confirmed to be involved in a series of basic cellular processes including proliferation, differentiation, growth and migration. Intracellular H2O2 is formed mainly via the catalytic dismutation of O2˙- by SODs including SOD1, SOD2 and SOD3. Thus, the intracellular levels of O2˙- and H2O2 can directly be controlled through regulating SOD1 activity. Here, based on the active site structure and catalytic mechanism of SOD1, we developed a new type of efficient and specific SOD1 inhibitors which can directly change the intracellular levels of H2O2 and O2˙-. These inhibitors inactivate intracellular SOD1 via localization into the SOD1 active site, thereby coordinating to the Cu2+ in the active site of SOD1, blocking the access of O2˙- to Cu2+, and breaking the Cu2+/Cu+ catalytic cycle essential for O2˙- dismutation. The reduced ERK1/2 phosphorylation induced by the specific SOD1 inactivation-mediated decrease of intracellular H2O2 levels reveals the potential of these specific SOD1 inhibitors in understanding and regulating ROS signaling. Furthermore, these specific SOD1 inhibitors also lead to selectively elevated cancer cell apoptosis, indicating that these kinds of SOD1 inhibitors might be candidates for lead compounds for cancer treatment.

Ultraviolet light triggers the conversion of Cu2+-bound Aß42 aggregates into cytotoxic species in a copper chelation-independent manner.

Increasing evidence indicates that abnormal Cu2+ binding to Aß peptides are responsible for the formation of soluble Aß oligomers and ROS that play essential roles in AD pathogenesis. During studying the Cu2+-chelating treatment of Cu2+-bound Aß42 aggregates, we found that UV light exposure pronouncedly enhances cytotoxicity of the chelator-treated and -untreated Cu2+-bound Aß42 aggregates. This stimulated us to thoroughly investigate (1) either the chelation treatment or UV light exposure leads to the increased cytotoxicity of the aggregates, and (2) why the chelator-treated and -untreated Cu2+-bound Aß42 aggregates exhibit the increased cytotoxicity following UV light exposure if the latter is the case. The data indicated that the controlled UV exposure induced the dissociation of Cu2+-free and -bound Aß42 aggregates into SDS-stable soluble oligomers and the production of ROS including H2O2 in an UV light intensity- and time-dependent, but Cu2+ chelation-independent manner. Although we can't fully understand the meaning of this finding at the current stage, the fact that the UV illuminated Aß42 aggregates can efficiently kill HeLa cells implies that the aggregates after UV light exposure could be used to decrease the viability of skin cancer cells through skin administration.

Selective recognition of parallel and anti-parallel thrombin-binding aptamer G-quadruplexes by different fluorescent dyes.

G-quadruplexes (G4) have been found increasing potential in applications, such as molecular therapeutics, diagnostics and sensing. Both Thioflavin T (ThT) and N-Methyl mesoporphyrin IX (NMM) become fluorescent in the presence of most G4, but thrombin-binding aptamer (TBA) has been reported as the only exception of the known G4-forming oligonucleotides when ThT is used as a high-throughput assay to identify G4 formation. Here, we investigate the interactions between ThT/NMM and TBA through fluorescence spectroscopy, circular dichroism and molecular docking simulation experiments in the absence or presence of cations. The results display that a large ThT fluorescence enhancement can be observed only when ThT bind to the parallel TBA quadruplex, which is induced to form by ThT in the absence of cations. On the other hand, great promotion in NMM fluorescence can be obtained only in the presence of anti-parallel TBA quadruplex, which is induced to fold by K+ or thrombin. The highly selective recognition of TBA quadruplex with different topologies by the two probes may be useful to investigate the interactions between conformation-specific G4 and the associated proteins, and could also be applied in label-free fluorescent sensing of other biomolecules.

An ESIPT fluorescent probe sensitive to protein α-helix structures.

A large majority of membrane proteins have one or more transmembrane regions consisting of α-helices. Membrane protein levels differ from one type of cell to another, and the expression of membrane proteins also changes from normal to diseased cells. For example, prostate cancer cells have been reported to have downregulated expression of membrane proteins, including zinc transporters, compared with normal prostate cells. These reports inspired us to design a fluorescence probe sensitive to protein α-helical structures to discriminate individual prostate cancer cells from normal ones. A benzazole derivative ( in this study) was observed to emit strong fluorescence resulting from an excited-state intramolecular proton transfer (ESIPT) in protein α-helical environments. The intensity of ESIPT fluorescence of was observed to be positively correlated with the α-helix content of proteins. The molecular docking simulation suggested that it had low energy for the binding of to proteins when the binding sites were localized within the α-helical regions of protein via H-bonds. Furthermore, was found to be localized in cell membranes through binding to transmembrane α-helical regions of membrane proteins, and was capable of probing differences in the α-helix contents of membrane proteins between normal and cancerous prostate cells through changes in the ESIPT emission intensity. These results indicated that could distinguish individual prostate cancer cells from normal ones, as the changes in the ESIPT fluorescence intensity of could reflect the regulation in expression of the membrane proteins including zinc transporters. This recognition strategy of individual prostate cancer cells might contribute to early diagnosis techniques for prostate cancer.

Metal-polybenzimidazole complexes as a nonviral gene carrier: effects of the DNA affinity on gene delivery.

The metal complex-based carriers are emerging likely as a new type of gene-delivery systems prone to systematic structural alteration and chemical tailoring. In our work, the DNA affinity of metal complexes with polybenzimidazoles was found to be one of the determinants that can regulate expression of the transgenes. Here, the correlations between the DNA affinity and transfection efficacy were explored by characterizing gene-delivering properties of a series of Co(2+)- and Ca(2+)-polybenzimidazole complexes. The binding equilibrium constants (Kobs) of the divalent metal complexes to DNA, which is considered as a measure of the DNA affinity of metal complexes, were evaluated by isothermal titration calorimetry (ITC) and UV-visible absorption titration. The properties of DNA condensates formed with the metal complexes including sizes, ζ potential and morphology were observed to be altered with Kobs values. The monodispersed spherical condensates were found only for the Ca(2+) complexes whose DNA affinity is weaker than that of the Co(2+) complexes. However, the cell internalization examination indicated that cell uptake of the DNA condensates is independent of homogeneity in their sizes and morphology. The comparison of transgene expression showed that that the Ca(2+) complex-mediated transfection has higher efficiency than the Co(2+) complexes under the conditions tested, and the transfection efficacy cannot be correlated with the cell uptake of DNA condensates. Moreover, the Ca(2+) complexes and their DNA condensates had lower cytotoxicity than the Co(2+) complexes. Thus, the DNA affinity should be one of the factors to be capable of regulating the gene-delivering property of metal complexes.

Synthesis, structure and urease inhibition studies of Schiff base copper(II) complexes with planar four-coordinate copper(II) centers.

Seven new Schiff base copper(II) complexes with planar four-coordinate copper(II) centers have been synthesized and structurally characterized. The solid state structures of complexes 1, 3, 4, 5, 6 and 7 present a square-planar coordination geometry at the metal centers while complex 2 shows a slightly distorted square-planar geometry. Density functional theory calculations have been performed to evaluate the electronic structure of copper(II) complex 7. Inhibition of jack bean urease by copper(II) complexes 1-7 have also been investigated, and potent inhibitory activities with IC50 range of 2.60-17.00µM have been observed for these mononuclear copper(II) complexes. A docking analysis using a DOCK program was conducted to explain the urease inhibitory activity of the copper(II) complexes and the structure-activity relationships were further discussed.

Synthesis, structures and urease inhibition studies of Schiff base metal complexes derived from 3,5-dibromosalicylaldehyde.

Eleven mononuclear copper(II), nickel(II), zinc(II) and cobalt(II) complexes of Schiff base ligands derived from 3,5-dibromosalicylaldehyde/3,5-dichlorosalicylaldehyde were synthesized and determined by single crystal X-ray analysis. The crystal structures of complexes 1, 2, 4, 5, 6, 8 and 11 present the square-planar coordination geometry at the metal center and complexes 7, 9 and 10 show the distorted tetrahedral geometry. While one copper center in 3 has a square-planar geometry, the other copper is slightly distorted square-planar. The inhibitory activities of all the obtained complexes were tested in vitro against jack bean urease. It was found that Schiff base copper(II) complexes 1, 3, 5, 8 and 11 showed strong urease inhibitory activities (IC(50) = 1.51-3.52 µM) compared with acetohydroxamic acid (IC(50) = 62.52 µM), which was a positive reference. Their structure-activity relationships were further discussed.

Synthesis, inhibitory activity and molecular docking studies of two Cu(II) complexes against Helicobacter pylori urease.

Two mononuclear copper(II) complexes, [Cu(C(15)H(16)NO(2))(2)] (1) and [Cu(C(6)H(9)N(2)O(4))(2)·3H(2)O] (2·3H(2)O), were synthesised and structurally characterised by single-crystal X-ray analysis. The copper(II) atom adopts a square-planar environment in complex 1, while the geometry in 2·3H(2)O could be described as the distorted square pyramidal. Complexes 1 and 2·3H(2)O were evaluated for their inhibitory activities against Helicobacter pylori (H. pylori) urease in vitro. They both were found to have strong inhibitory activities against H. pylori urease comparable to that of acetohydroxamic acid (AHA). A docking simulation was performed to position 2 into the H. pylori urease active site to determine the probable binding conformation.

Synthesis, structures and urease inhibition studies of copper(II) and nickel(II) complexes with bidentate N,O-donor Schiff base ligands.

Five mononuclear copper(II) and nickel(II) complexes of Schiff base ligands derived from 4-hydroxyphenethylamine and 2-phenylethylamine were synthesized and determined by single crystal X-ray analysis. The crystal structures of these complexes presented the square planar coordination geometry at the metal center. The inhibitory activity of all the obtained complexes was tested in vitro against jack bean urease. It was found that Schiff base copper(II) complexes, namely [Cu(C(15)H(13)BrNO(2))(2)]·2(C(6)H(7)N) (1), [Cu(C(15)H(12)Br(2)NO(2))(2)]·2(DMF) (2), Cu(C(19)H(16)NO(2))(2) (3) and Cu(C(19)H(16)NO)(2) (5), showed strong inhibitory activity against jack bean urease (IC(50)=1.45-3.59 µM), while Schiff base nickel(II) complex, [Ni(C(19)H(16)NO(2))(2)]·2(DMF) (4), exhibited weak inhibitory activity (IC(50)>50 µM). Their structure-activity relationships were further discussed.