ß-Cyclodextrin network crosslinked by novel phosphonium-based tetrakiscarboxylic acid derived from PH3 tail gas: Synthesis and application for rapid removal of organic dyes from wastewater.

Organic dyes, such as methyl orange (MO), Congo red (CR), crystal violet (CV) and methylene blue (MB), are common organic pollutants existing in wastewater. Therefore, the exploration of bio-based adsorbents for the efficient removal of organic dyes from wastewater has gained many attentions. Here, we report a PCl3-free synthetic method for the synthesis of phosphonium-containing polymers, in which the prepared tetrakis(2-carboxyethyl) phosphonium chloride-crosslinked ß-cyclodextrin (TCPC-ß-CD) polymers were applied to the removal of dyes from water. The effects of contact time, pH (1-11), and dye concentration were investigated. The selected dye molecules could be captured by the host-gest inclusion of ß-CD cavities, and the phosphonium and carboxyl groups in the polymer structure would respectively facilitate the removal of cationic dyes (MB and CV) and anionic dyes (MO and CR) via electrostatic interactions. In a mono-component system, over 99 % of MB could be removed from water within the first 10 min. Based on the Langmuir model, the calculated maximum adsorption capacities of MO, CR, MB, and CV were 180.43, 426.34, 306.57, and 470.11 mg/g (or 0.55, 0.61, 0.96 and 1.15 mmol/g), respectively. Additionally, TCPC-ß-CD was easily regenerated using 1 % HCl in ethanol, and the regenerative adsorbent still showed high removal capacities for MO, CR, and MB even after seven treatment cycles.

Comparative Investigation on the Phytochemicals and Biological Activities of Jackfruit (Artocarpus heterophyllus Lam.) pulp from Five Cultivars.

Jackfruit is one of the major tropical fruits, but information on the phytochemicals and biological benefits of its pulp is limited. In this study, the phytochemicals and biological activities including antioxidant, antitumor and anti-inflammatory activities of five jackfruit pulp cultivars (M1, M2, M3, M7 and T5) were comparatively investigated. A total of 11 compounds were identified in all cultivars of jackfruit pulp, among which 4-hydroxybenzoic acid, caffeic acid, ferulic acid and tryptophan N-glucoside were reported for the first time in jackfruit. T5 exhibited the highest total phenolic content (7.69 ± 0.73 mg GAE/g DW), antioxidant capacity (109.8, 96.7 and 207 mg VCE/g DW for DPPH, ABTS and FRAP, respectively), antitumor activity (80.31%) and anti-inflammatory activity (78.44%) among five cultivars. These results can provide a reference for growers to choose jackfruit cultivar and offer an insight into the industrial application of jackfruit pulp derived-products.

Isoquinoline Alkaloids as Protein Tyrosine Phosphatase Inhibitors from a Deep-Sea-Derived Fungus Aspergillus puniceus.

Puniceusines A-N (1-14), 14 new isoquinoline alkaloids, were isolated from the extracts of a deep-sea-derived fungus, Aspergillus puniceus SCSIO z021. Their structures were elucidated by spectroscopic analyses. The absolute configuration of 9 was determined by ECD calculations, and the structures of 6 and 12 were further confirmed by a single-crystal X-ray diffraction analysis. Compounds 3-5 and 8-13 unprecedentedly contained an isoquinolinyl, a polysubstituted benzyl or a pyronyl at position C-7 of isoquinoline nucleus. Compounds 3 and 4 showed selective inhibitory activity against protein tyrosine phosphatase CD45 with IC50 values of 8.4 and 5.6 µM, respectively, 4 also had a moderate cytotoxicity towards human lung adenocarcinoma cell line H1975 with an IC50 value of 11.0 µM, and 14, which contained an active center, -C=N+, exhibited antibacterial activity. An analysis of the relationship between the structures, enzyme inhibitory activity and cytotoxicity of 1-14 revealed that the substituents at C-7 of the isoquinoline nucleus could greatly affect their bioactivity.

Catgut implantation at acupoints increases the expression of glutamate aspartate transporter and glial glutamate transporter-1 in the brain of rats with spasticity after stroke.

Catgut implantation at acupoints has been shown to alleviate spasticity after stroke in rats. However, the underlying mechanisms are poorly understood. In this study, we used the rat middle cerebral artery occlusion model of stroke. Three days after surgery, absorbable surgical catgut sutures were implanted at Dazhui (GV14), Jizhong (GV6), Houhui, Guanyuan (CV4) and Zhongwan (CV12). The Zea Longa score was used to assess neurological function. The Modified Ashworth Scale was used to evaluate muscle tension. The 2,3,5-triphenyl-tetrazolium chloride assay was used to measure infarct volume. Immunohistochemical staining was performed for glutamate aspartate transporter (GLAST) and glial glutamate transporter-1 (GLT-1) expression. Western blot assay was used to analyze the expression of GLAST and GLT-1. Reverse transcription and polymerase chain reaction were carried out to assess the expression of GLAST and GLT-1 mRNAs. After catgut implantation at the acupoints, neurological function was substantially improved, muscle tension was decreased, and infarct volume was reduced in rats with spasticity after stroke. Furthermore, the expression of GLAST and GLT-1 mRNAs was increased on the injured (left) side. Our findings demonstrate that catgut implantation at acupoints alleviates spasticity after stroke, likely by increasing the expression of GLAST and GLT-1.

Molecular and Functional Properties of Protein Fractions and Isolate from Cashew Nut (Anacardium occidentale L.).

Some molecular and functional properties of albumin (83.6% protein), globulin (95.5% protein), glutelin (81.3% protein) as well as protein isolate (80.7% protein) from cashew nut were investigated. These proteins were subjected to molecular (circular dichroism, gel electrophoresis, scanning electron microscopy) and functional (solubility, emulsification, foaming, water/oil holding capacity) tests. Cashew nut proteins represent an abundant nutrient with well-balanced amino acid composition and could meet the requirements recommended by FAO/WHO. SDS-PAGE pattern indicated cashew nut proteins were mainly composed of a polypeptide with molecular weight (MW) of 53 kDa, which presented two bands with MW of 32 and 21 kDa under reducing conditions. The far-UV CD spectra indicated that cashew proteins were rich in ß-sheets. The surface hydrophobicity of the protein isolate was higher than that of the protein fractions. In pH 7.0, the solubility of protein fractions was above 70%, which was higher than protein isolate at any pH. Glutelin had the highest water/oil holding capacity and foaming properties. Protein isolate displayed better emulsifying properties than protein fractions. In summary, cashew nut kernel proteins have potential as valuable nutrition sources and could be used effectively in the food industry.

Phytochemical profiles and antioxidant activity of brown rice varieties.

The phytochemical content and antioxidant activity of eight varieties of brown rice (BR) are reported. The total phenolic contents of BR ranged from 72.45 to 120.13mg of gallic acid equiv./100g. The phenolics from bound fraction contributed 40.6-50.2% of the total phenolic content. The total flavonoid contents of BR ranged from 75.90 to 112.03mg catechin equiv./100g. The flavonoids from the bound fraction contributed 26.9-48.2% of total flavonoids. Trans-ferulic acid was the predominant phenolic acid in BR. Total trans-ferulic acid content ranged from 161.42 to 374.81µg/100g. The percentage of trans-ferulic acid in bound fraction ranged from 96.4% to 99.2%. Only α- and γ-tocopherols and -tocotrienols were detected in BR with α-tocopherol and γ-tocotrienol being the predominant. The total peroxyl radical scavenging capacity (PSC) of BR ranged from 18.29 to 40.33mg vitamin C equiv./100g. The bound fraction contributed 67.2-77.2% of total PSC.

Enhanced conductivity of rGO/Ag NPs composites for electrochemical immunoassay of prostate-specific antigen.

Electrode materials play a vital role in the development of electrochemical immunosensors (EIs), particularly of label-free EIs. In this study, composites containing reduced graphene oxide with silver nanoparticles (rGO/Ag NPs) were synthesized using binary reductants, i.e. hydrazine hydrate and sodium citrate. Due to the fact that graphene oxide (GO) was fully restored to rGO, and rGO stacking was effectively inhibited by insertion of small Ag NPs between the graphene sheets, the electrical conductivity of rGO/Ag NPs composites was significantly improved compared to rGO alone, with an enhancement factor of 346% at 40wt% of rGO. Moreover, the conducting path between rGO and Ag NPs formed because the structural defects in rGO were effectively repaired by decoration with Ag NPs. Subsequently, based on a screen-printed three-electrode system, a label-free EI for detecting prostate-specific antigen (PSA) was constructed using rGO/Ag NPs composites as a support material. The fabricated EIs demonstrated a wide linear response range (1.0-1000ng/ml), low detection limit (0.01ng/ml) and excellent specificity, reproducibility and stability. Thus, the proposed EIs based on rGO/Ag NPs composites can be easily extended for the ultrasensitive detection of different protein biomarkers.

Phosphorus-containing polymers from THPS. IV: Synthesis and properties of phosphorus-containing polybenzoxazines as a green route for recycling toxic phosphine (PH3) tail gas.

A convenient route to convert the highly toxic phosphine (PH3) tail gas into high-performance polybenzoxazines was first described in this paper. Two aliphatic polyamines, namely tris(aminomethyl)phosphine oxide and bis(aminomethyl)phenylphosphine oxide, were synthesized from tetrakis(hydroxymethyl)phosphonium sulfate (THPS), a green derivative of PH3 tail gas. And then two novel phosphorus-containing benzoxazine monomers, tris(3,4-dihydro-2H-1,3-benzoxazin-3-yl-methyl)phosphine oxide (TBOz) and benzylbis(3,4-dihydro-2H-1,3-benzoxazin-3-yl-methyl) phosphine oxide (BBOz) were prepared by three-steps procedure. FT-IR and DSC technologies were adopted to study the thermal-initiated polymerization behaviors of two benzoxazine monomers. Thermal properties of these crosslinked polymers were studied by TGA and DMA. The results display that the polybenzoxazines (PTBOz and PBBOz) exhibite good thermal stabilities and high glass transition temperatures. The char yield of polybanzoxazine is high as 47% and indiactes that phosphorus-containing polybenzoxazines show high fire-retardancy. The surface free energies of the PTBOz and PBBOz are 37.1 and 40.4mJm-2 by Owens two-liquid method. The dielectric properties of the PTBOz and PBBOz remaine near constant in the experimental frequency range.

Inhibitory Effects of Enterolactone on Growth and Metastasis in Human Breast Cancer.

A lignan-rich diet is associated with a lower risk of human breast cancer. Enterolactone, an active polyphenol metabolites of lignan, was reported to have an antitumor effect. We investigated the mechanism for the effect of enterolactone against human breast cancer. Cellular changes, and associated genes induced by enterolactone, were investigated in MDA-MB-231 cells. Enterolactone showed an antiproliferative effect, and its IC50 was 261.9 ± 10.5 µM for a treatment period of 48 hr. The mRNA levels of the genes related to cell proliferation, Ki67, PCNA, and FoxM1, were reduced. Enterolactone induced accumulation of cells in the S phase, and a lower expression of Cyclin E1, Cyclin A2, Cyclin B1, and Cyclin B2 genes. There were almost no changes in the transcription levels of the genes that participate in G0/G1 phase regulation, CDK4, CDK6, and Cyclin D1. Furthermore, enterolactone interfered with the cytoskeleton by downregulating phosphorylation of the FAK/paxillin pathway, inhibiting migration and invasion of cells. The results suggest that enterolactone exerts an antitumor effect by regulating the expression of genes associated with cell proliferation and the cell cycle and by blocking the FAK/paxillin signaling pathway. These findings provide new insights into the molecular mechanisms behind the antitumor effect of enterolactone.

The Stability, Sustained Release and Cellular Antioxidant Activity of Curcumin Nanoliposomes.

Curcumin is a multifunctional and natural agent considered to be pharmacologically safe. However, its application in the food and medical industry is greatly limited by its poor water solubility, physicochemical instability and inadequate bioavailability. Nanoliposome encapsulation could significantly enhance the solubility and stability of curcumin. Curcumin nanoliposomes exhibited good physicochemical properties (entrapment efficiency = 57.1, particle size = 68.1 nm, polydispersity index = 0.246, and zeta potential = -3.16 mV). Compared with free curcumin, curcumin nanoliposomes exhibited good stability against alkaline pH and metal ions as well as good storage stability at 4 °C. Curcumin nanoliposomes also showed good sustained release properties. Compared with free curcumin, curcumin nanoliposomes presented an equal cellular antioxidant activity, which is mainly attributed to its lower cellular uptake as detected by fluorescence microscopy and flow cytometry. This study provide theoretical and practical guides for the further application of curcumin nanoliposomes.

Characterization and bioavailability of tea polyphenol nanoliposome prepared by combining an ethanol injection method with dynamic high-pressure microfluidization.

Tea polyphenols are major polyphenolic substances found in green tea with various biological activities. To overcome their instability toward oxygen and alkaline environments, tea polyphenol nanoliposome (TPN) was prepared by combining an ethanol injection method with dynamic high-pressure microfluidization. Good physicochemical characterizations (entrapment efficiency = 78.5%, particle size = 66.8 nm, polydispersity index = 0.213, and zeta potential = -6.16 mv) of TPN were observed. Compared with tea polyphenol solution, TPN showed equivalent antioxidant activities, indicated by equal DPPH free radical scavenging and slightly lower ferric reducing activities and lower inhibitions against Staphylococcus aureus , Escerhichia coli , Salmonella typhimurium , and Listeria monocytogenes . In addition, a relatively good sustained release property was observed in TPN, with only 29.8% tea polyphenols released from nanoliposome after 24 h of incubation. Moreover, TPN improved the stability of tea polyphenol in alkaline solution. This study expects to provide theories and practice guides for further applications of TPN.

Comparison of glycation in conventionally and microwave-heated ovalbumin by high resolution mass spectrometry.

The glycation extent of ovalbumin under two heating conditions, conventional and microwave heating was monitored by high resolution mass spectrometry, following pepsin digestion. The sequence coverage of the unglycated and glycated ovalbumin was 100% and 95%, respectively. About 35.2% of the lysines after microwave heating and 40.8% of the lysines after conventional heating were modified by d-glucose. The glycation content increased quickly when ovalbumin-glucose mixture was incubated for 15min, under both processing conditions. These modifications were slowed down after 30min of heating and no obvious advanced stage products were observed. The glycated peptides exhibited varying degrees of glycation, under both conventional and microwave heating, suggesting that glycation is strongly relevant to the protein structure. The fact that some peptides showed a lower level of glycation when heated by microwave indicated that microwave radiation might be a non-thermal process. In addition, the lack of browning after microwave heating emphasised the difference between microwave and conventional heating.

The effect of citric acid on the activity, thermodynamics and conformation of mushroom polyphenoloxidase.

Few reports have focused on the effect of citric acid on thermodynamics and conformation of polyphenoloxidase (PPO). In this study, variations on activity, thermodynamics and conformation of mushroom PPO induced by citric acid (1-60mM) and relationships among these were investigated. It showed that with the increasing concentration of citric acid, the activity of PPO decreased gradually to an inactivity condition; inactivation rate constant (k) of PPO increased and the activation energy (Ea) as well as thermodynamic parameters (ΔG, ΔH, ΔS) decreased, which indicated that the thermosensitivity, stability and number of non-covalent bonds of PPO decreased. The conformation was gradually unfolded, which was reflected in the decrease of α-helix contents, increase of ß-sheet and exposure of aromatic amino acid residuals. Moreover, two linear relationships of relative activities, enthalpies (ΔH) against α-helix contents were obtained. It indicated that changes of activity and thermodynamics might correlate to the unfolding of conformation.

Synthesis of 1,3,4-thiadiazole derivatives as aminopeptidase N inhibitors.

Aminopeptidase N (APN) is a zinc-dependent ectopeptidase which plays an important role in the invasion of metastatic tumors. In this study, we report the synthesis and in vitro enzyme inhibition assay of 1,3,4-thiadiazole scaffold compounds. These new compounds have potent inhibitory activities toward APN with IC50 values in the micromolar range.

Crosslinking property of an oligomeric unsaturated phosphoester used as a potential injectable biomaterial.

An unsaturated polyphosphoester (UPPE) that has double bonds in repeatable units could crosslink with a vinyl monomer. A study of how the crosslinking temperature, setting time and mechanical properties are affected by the UPPE molecular weight, N-vinyl pyrrolidinone (NVP)/UPPE ratio and benzoyl peroxide (BPO)/UPPE ratio was conducted. The results of the study indicated that the maximum crosslinking temperature is between 41.1 degrees C and 82.3 degrees C, which is lower than the 97 degrees C of poly(methyl methacrylate) bone cement. The BPO concentration strongly affected the maximum temperature and setting time. High concentration of BPO gives a rapid polymerization rate, causing reaction heat to be released immediately. The compressive strength and compressive modulus will be enhanced with an increase in the NVP/UPPE ratio, the UPPE molecular weight and the BPO concentration. For all formulations, the compressive strength values are between 3.3 MPa and 11.0 MPa and the compressive modulus values are between 4.9 MPa and 101.9 MPa. These initial studies suggest that UPPE is one kind of potential injectable bone tissue engineering scaffold material.

The synthesis and preliminary activity assay in vitro of peptide-like derivatives as APN inhibitors.

Both the aminopeptidase N (APN) and matrix metalloproteinase (MMP) are essential metallopeptidases in the development of tumor invasion and angiogenesis. A series of novel peptide-like derivatives were designed and synthesized as antitumor agents. Their structures were confirmed by IR, MS, and (1)H-NMR. These compounds exhibited potent inhibitory activities against APN and low activity against MMP in vitro. The derivatives with methoxy group show better activities than those with other substituted group and could be used as lead compounds for exploring new APN inhibitors in the future.