Anti-Cancer Activity of Porphyran and Carrageenan from Red Seaweeds.

Seaweeds are some of the largest producers of biomass in the marine environment and are rich in bioactive compounds that are often used for human and animal health. Porphyran and carrageenan are natural compounds derived from red seaweeds. The former is a characteristic polysaccharide of Porphyra, while the latter is well known from Chondrus, Gigartina, and various Eucheuma species, all in Rhodophyceae. The two polysaccharides have been found to have anti-cancer activity by improving immunity and targeting key apoptotic molecules and therefore deemed as potential chemotherapeutic or chemopreventive agents. This review attempts to review the current study of anti-cancer activity and the possible mechanisms of porphyran and carrageenan derived from red seaweeds to various cancers, and their cooperative actions with other anti-cancer chemotherapeutic agents is also discussed.

Low-Temperature Synthesis of Cuboid Silver Tetrathiotungstate (Ag2WS4) as Electrocatalyst for Hydrogen Evolution Reaction.

Ternary bimetallic sulfide silver tetrathiotungstate (Ag2WS4) was prepared by a simple low-temperature precipitation method. The structure of Ag2WS4 was determined using the data from powder X-ray diffraction, which is in space group I4̅2 m (I-phase) with a tetragonal unit cell of a = b = 5.950 71 Å and c = 9.562 65 Å, containing layers of edge-sharing AgS4 and WS4 tetrahedra. The Ag2WS4 was also used as an electrocatalyst for the hydrogen evolution reaction (HER) in acid electrolyte. The results demonstrated that, attributed to its unique composition, large electrochemical active surface area, and high electric conductivity, the Ag2WS4 exhibited superior electrocatalytic activity for HER, in comparison with the ternary counterparts of WS2 and Ag2S with a low onset potential and small Tafel slope. The Ag2WS4 also presented superior stability and maintained the electrocatalytic activity of HER for at least 24 h in 0.5 M H2SO4.

Dual signal-based electrochemical aptasensor for simultaneous detection of Lead(II) and Mercury(II) in environmental water samples.

The Pb2+-binding aptamer (PBA) and Hg2+-binding aptamer (HBA) have been widely adopted as biosensing elements for lead(II) (Pb2+) and mercury (II) (Hg2+), due to the formation of stable and specific Pb2+-G-quadruplex and T-Hg2+-T structures. However, the currently developed electrochemical sensors are only applicable for single-element analysis of Pb2+ or Hg2+. Herein, a dual signal interface was realized by in-situ grafting the signal tags (Melamine-Cu2+ complex and Nile blue) bearing different redox potentials on the terminal of PBA and HBA that were co-immobilized on gold electrode. The results show that the interface has two pairs of independent redox peaks, ascribing to the melamine-Cu2+ complex and Nile blue, respectively. The sensor is not only applicable for single-element detection of Pb2+ or Hg2+, but also for simultaneous detection of them. The surface density of PBA and HBA on the gold electrode and the grafting efficiency of the electroactive tags on the aptamers have been determined. The detection limits for Pb2+ and Hg2+ were estimated to be 0.98 pM and 19 pM, respectively. The dual signal sensor is successfully applied for Pb2+ and Hg2+ determination in real water samples, showing its potential in the environmental monitoring of Pb2+ and Hg2+.

Bioaccumulation of legacy organic contaminants in pregnant Indo-Pacific humpback dolphins (Sousa chinensis): Unique features on the transplacental transfer.

The placental transfer and congener composition of organic contaminants (OCs) in Indo-Pacific humpback dolphins have been little studied. In the present study, 16 polycyclic aromatic hydrocarbons (PAHs), 18 organochlorine pesticides (OCPs), and 28 polychlorinated biphenyl (PCB) congeners were analyzed in muscle, lung, liver, kidney, and blubber tissues from three mother-fetus pairs of this species stranded along the Pearl River Estuary, China. For PCBs, tetra-, penta-, hexa-, and hepta-chlorobenzene congeners were dominant in all the analyzed samples. Among them, hexachlorobenzene congeners showed the highest level in most dolphin mother-fetus tissue samples. The concentrations of PCBs and OCPs in adult females were higher in the detoxification organs (liver and kidneys) than in the muscles and lungs, whereas muscle tissues in fetuses generally exhibited higher PCBs and OCPs levels than the livers and kidneys. The most abundant PAHs in the four tissues were those with lower molecular weights, which were also the most water-soluble and bioavailable. Negative correlations between the octanol/water partition coefficients (log KOW) and the fetus/mother ratios for PCB congeners revealed that the transfer of PCBs may be determined by their lipid solubility. OCPs and PCBs with low molecular weights and low log KOW values would be more likely to accumulate in the dolphin liver, lung, kidney and muscle tissues. Furthermore, OCs with low molecular weights and low log KOW values were more concentrated in the fetal blubber, lung, and liver tissues than in their respective mothers. The ubiquitous existence of OCs in the mother-fetus pairs strongly suggested that these contaminants could pass through the placenta and partition in fetal tissue. The high transfer efficiency of PAHs and PCBs indicated that the placenta might not be an efficient barrier for these pollutants. PCBs levels in both mother and fetus dolphins could cause immunosuppression.

Factors that influence parents' intentions of using autonomous vehicles to transport children to and from school.

High-level autonomous vehicles (AVs) are likely to improve the quality of children's travel to and from school (such as improve travel safety and increase travel mobility). These expected benefits will not be presented if parents are not willing to use AVs. Therefore, it is necessary to explore parents' intentions of using AVs to transport children to and from school (parents' intentions). This study has two primary aims: 1) Exploring parents' intentions and their potential determinants. 2) Making recommendations for manufacturers to develop and market AVs suitable for school travel based on the research results. Research results show that face consciousness with Chinese characteristics can significantly affect parents' intentions. Knowledge of AVs is the most significant factor in influencing parents' intentions. Perceived usefulness, attitude towards school travel in AVs, and perceived risk can significantly affect parents' intentions. The direct impact of perceived ease of use and public engagement on parents' intentions is not significant. Finally, this research could provide decision-making support for governments and manufacturers to formulate relevant policies and marketing strategies, promoting parents' acceptance of AVs.

Bio-accumulation of organic contaminants in Indo-Pacific humpback dolphins: Preliminary unique features of the brain and testes.

There is little information about the residue levels and congener composition of organic contaminants (OCs) in cetaceans. In the present study, we investigated the polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) in the blubber, blood, brain and testes of Indo-Pacific humpback dolphins (Sousa chinensis) stranded in the Pearl River Estuary (PRE), China. The lowest blubber/tissue partition coefficients were found for sum hexachlorocyclohexanes (ΣHCHs) and ΣPAHs, while the highest were in ΣPCBs and sum dichlorodiphenyltrichloroethanes (ΣDDTs), likely attributing to the octanol-water partition features. The low levels of OCs in brain and testes theoretically resulted from the blood-brain barrier, blood-testes barrier, contaminant molecule dimensions and unique lipid compositions in the brain and testes. Compared with other contaminants, the higher mean brain/blood and testes/blood partition coefficients found for mirex, heptachlor, dieldrin and endrin would increase the risks associated with exposure-related toxicity and the bioavailability of contaminants within these tissues. Observations also suggest that as lipid mobilizes from blubber, contaminants may redistribute, leading to elevated tissue (such as brain) concentrations. Therefore, dolphins with less blubber may be more susceptible to health risks. The Indo-Pacific humpback dolphins living in PRE are at great risk due to variety of OCs in indirect contact with non-target organisms, affecting the health of animals (toxic effects and accumulation). Our findings contribute to the knowledge of the potential effects of OCs exposure on developmental neurotoxicity and reproductive damage in marine mammals.

DDT exposure induces cell cycle arrest and apoptosis of skin fibroblasts from Indo-Pacific humpback dolphin via mitochondria dysfunction.

Although the global use of the 1,1,1-trichloro-2,2-bis (4-chlorophenyl) ethane (p,p'-DDT) has been prohibited, its persistence in the environment has caused long-lasting exposure on marine mammals. Our previous studies revealed exceedingly high residue levels of DDTs in Indo-Pacific humpback dolphins (Sousa chinensis) from the Pearl River Estuary region, China. However, the molecular mechanisms of p,p'-DDT toxicity on the dolphin are largely unknown. This study conducted the first cytotoxicity effect exploration of p,p'-DDT on the dolphin skin fibroblasts (ScSFs) to enhance the understanding of the cellular and molecular regulation impacts. ScSF cells were exposed to p,p'-DDT (28∼168 µM) for 24, 48 and 72 h. The exposure remarkably decreased viability of ScSF cells, possibly due to the synergetic effects of cell cycle arrest and apoptosis via DNA damage and mitochondria dysfunction. The DNA damage and mitochondria dysfunction were likely triggered by an increase of cellular reactive oxygen species (ROS), alteration in mitochondrial membrane potential, reduction in the cellular ATP levels, decreased expression of the genes CDK1, CDK4, cyclin B1, cyclin D1 and apoptosis regulator Bcl-2, release of cytochrome c, and activation of caspase-3, caspase-8 and caspase-9. Moreover, caspase inhibitor displayed protective activity against p,p'-DDT-induced apoptosis, indicating that caspases played a central role in p,p'-DDT-triggered apoptosis in the ScSF cells. We hypothesize apoptosis likely plays a minor role in cytocidal effects induced by p,p'-DDT exposure, but the mechanisms remain unclear. Overall, this research provides new evidence of the cytotoxic mechanisms underlying p,p'-DDT exposure on humpback dolphin skin cells, and suggests that p,p'-DDT contamination is one of key health concern issues for the protection of this marine mammal.

Tissue distribution of organic contaminants in stranded pregnant sperm whale (Physeter microcephalus) from the Huizhou coast of the South China Sea.

Twelve persistent organic pollutants (POPs) were measured in 11 tissue samples from a pregnant sperm whale stranded on the Huizhou coast of the South China Sea, China, in March 2017. POPs were found to be more concentrated in the irrigated tissues such as placenta, ovary, mammary gland, and liver than the less irrigated tissues such as epidermis. High POP levels detected in the placenta might result in abnormal hormone secretion in the placenta, which would affect the unborn offspring. We hypothesized that ovary is potentially vulnerable to the exposure of higher contaminant levels. The PAH concentrations were higher in the lung than in other tissues, which suggest that PAH levels in the lung were breath-dependent in the sperm whale. The concentrations of POPs except PAHs in the sperm whale blubber were lower than those in the same species in the Northern Hemisphere and were comparable to or lower than those in the same species in the Southern Hemisphere.

Chromatographic enantioseparations of binaphthyl compounds on an immobilized polysaccharide-based chiral stationary phase.

Seven binaphthyl compounds were enantioseparated by HPLC with an immobilized polysaccharide-based chiral stationary phase, Chiralpak IA. The experiments were performed under normal-phase conditions. Effects of polar modifier and column temperature on the retention time and separation factor were evaluated. All examined compounds obtained complete resolutions. This was the unique one ever reported that 1,1'-bi-2-naphthol and its monoether, diether and diester derivatives could all be enantioseparated on a given CSP. Apparent thermodynamic parameters were also deduced from Van't Hoff plots, and some aspects of chiral recognition mechanism were discussed further.

Levels and trends of polycyclic aromatic hydrocarbons in the Indo-Pacific humpback dolphins from the Pearl River Estuary (2012-2017).

We investigated the levels and trends of the 16 USEPA priority PAHs in the blubber of 37 Indo-Pacific humpback dolphins sampled during the period 2012-2017 from the Pearl River Estuary (PRE), China. Σ16PAHs concentrations (17.6-6080 ng g-1 wet weight) were at median level compared to dolphin species worldwide. Humpback dolphins affiliated with the hotspots of PAHs, had significantly higher levels of Σ16PAHs than individuals from the other areas in the PRE. Moreover, dolphins stranded on the coast of Lingdingyang are significantly more contaminated by Σ16PAHs than those in the West-four region of the PRE, which appears to reflect the heterogeneous distribution of PAHs in the environment. A marked decline in blubber Σ16PAHs levels is observed over the studied period, with the control of a range of confounding factors. The trend is strongly and statistically significant (p < 0.0001), indicating that the loading of PAHs are gradually being reduced.

Electroactive crown ester-Cu2+ complex with in-situ modification at molecular beacon probe serving as a facile electrochemical DNA biosensor for the detection of CaMV 35s.

A novel electrochemical DNA biosensor has been facilely constructed by in-situ assembly of electroactive 4'-aminobenzo-18-crown-6-copper(II) complex (AbC-Cu2+) on the free terminal of the hairpin-structured molecule beacon. The 3'-SH modified molecule beacon probe was first immobilized on the gold electrode (AuE) surface through self-assembly chemistry of Au-S bond. Then the crow ester of AbC was covalently coupled with 5'-COOH on the molecule beacon, and served as a platform to attach the Cu2+ by coordination with ether bond (-O-) of the crown cycle. Thus, an electroactive molecule beacon-based biosensing interface was constructed. In comparison with conventional methods for preparation of electroactive molecule beacon, the approach presented in this work is much simpler, reagent- and labor-saving. Selectivity study shows that the in-situ fabricated electroactive molecule beacon remains excellent recognition ability of pristine molecule beacon probe to well differentiate various DNA fragments. The target DNA can be quantatively determined over the range from 0.10pM to 0.50nM. The detection limit of 0.060pM was estimated based on signal-to-noise ratio of 3. When the biosensor was applied for the detection cauliflower mosaic virus 35s (CaMV 35s) in soybean extraction samples, satisfactory results are achieved. This work opens a new strategy for facilely fabricating electrochemical sensing interface, which also shows great potential in aptasensor and immurosensor fabrication.

Selective binding of Pb2+ with manganese-terephthalic acid MOF/SWCNTs: Theoretical modeling, experimental study and electroanalytical application.

A nanocomposite of flake-shaped manganese-terephthalic acid MOF/single-walled carbon nanotubes (Mn(TPA)-SWCNTs) was synthesized using manganese chloride, terephthalic acid and SWCNTs as raw materials. Theoretical modeling study shows that the Mn(TPA) component has stronger adsorption ability to lead ion (Pb2+) than the other common heavy metal ions, which is in good agreement with the result of electrochemical assay. Then, the Mn(TPA)-SWCNTs were used as a sensing matrix for the voltammetric determination of Pb2+. The results displayed that the sensor shows high analytical performance for Pb2+ due to the synergy of Mn(TPA) with highly selective binding to Pb2+ and SWCNTs with high electronic conductivity. Under the optimal conditions, the Mn(TPA)-SWCNTs-based electrochemical sensor presented a wide linear response over the concentration range from 0.10 to 14.0µM. The limit of detection was achieved to be 38nM. Satisfactory results were also achieved when the Mn(TPA)-SWCNTs-based sensor was utilized for the determination of Pb2+ in the practical samples of industrial wastewater and human serum, suggesting great promising of the sensor for practical application.

An electrochemical sensor for gallic acid based on Fe2O3/electro-reduced graphene oxide composite: Estimation for the antioxidant capacity index of wines.

A highly sensitive electrochemical sensor for gallic acid (GA), an important polyphenolic compound, was fabricated using the hybrid material of chitosan (CS), fishbone-shaped Fe2O3 (fFe2O3), and electrochemically reduced graphene oxide (ERGO) as the sensing matrix. The electrochemical characterization experiments showed that the CS-fFe2O3-ERGO modified glassy carbon electrode (CS-fFe2O3-ERGO/GCE) had large surface area, excellent electronic conductivity and high stability. The GA presented a superior electrochemical response on CS-fFe2O3-ERGO/GCE in comparison with the single-component modified electrode. The electrochemical mechanism and optimal test conditions of GA on the electrode surface were carefully investigated. Under the optimal conditions, the oxidation peak currents in differential pulse voltammetry (DPV) experiments exhibited a good linear relationship with the logarithmic values of GA concentration over the range from 1.0×10(-6)M to 1.0×10(-4)M. Based on signal-to-noise (S/N) characteristic of 3, the detection limit was estimated to be 1.5×10(-7)M. The proposed sensor has also been applied for estimating the antioxidant capacity index of real samples of red and white wines.

Solvent effect in the chromatographic enantioseparation of 1,1'-bi-2-naphthol on a polysaccharide-based chiral stationary phase.

Enantioseparation of 1,1'-bi-2-naphthol (BINOL) was performed on a polysaccharide-based chiral stationary phase, Chiralcel OD-H, under normal-phase mode. The effects of polar modifier in the mobile phase on the retention, enantioseparation and elution order were investigated in detail. Solvent-induced reversal of elution order for BINOL was observed. When linear alcohols were adopted, R-BINOL was always eluted first. S-BINOL was eluted first when 2-propanol was used as a polar modifier. Enantioseparation could not be obtained when sec-butyl alcohol or tert-butyl alcohol was used as a polar modifier. When isoamyl alcohol or cyclohexanol was used as a polar modifier, favorable enantioseparation was obtained as with 1-pentanol or 1-hexanol; also, R-BINOL was the first-eluted enantiomer. It is worth emphasizing that significantly better enantioseparation was obtained when higher alcohols were used as polar modifier of the mobile phase. A nonlinear characteristic for the lnalpha against 1/T plots was universally observed in this study though the lnk against 1/T plots exhibited a linear feature. Associated with the obtained thermodynamic parameters, some interesting inferences about chiral recognition mechanism were proposed.

Temperature-induced inversion of elution order in the chromatographic enantioseparation of 1,1'-bi-2-naphthol on an immobilized polysaccharide-based chiral stationary phase.

In this work, the enantioseparations of 1,1'-bi-2-naphthol (BINOL) and its three derivatives were performed on an immobilized polysaccharide-based chiral stationary phase, Chiralpak IA, under normal-phase mode. The effects of the content of polar modifier in the mobile phase and the column temperature on the retention and enantioseparation were investigated in detail. Temperature-induced inversion of elution order for BINOL was observed directly when n-hexane/2-propanol (92/8, v/v) was used as mobile phase. The isoenantioselective temperature (T(iso)) was calculated to be 31.4 degrees C. When n-hexane/2-propanol/THF (93/2/5, v/v/v) was used as mobile phase, the T(iso) value decreased to -8.2 degrees C. Entropically driven enantioseparation which had practical application was obtained successfully (separation factor being 1.189 and 1.332 at 25 degrees C and 50 degrees C, respectively). The corresponding thermodynamic parameters for other three binaphthyl compounds were compared with that for BINOL. Some inferences about chiral recognition mechanism were stressed.

Determination of traces of bismuth by quenching of solid-substrate room-temperature phosphorescence from morin-labeled silicon dioxide nano-particles.

Silicon dioxide nano-particles, diameter 50 nm, containing morin (morin-SiO2) have been synthesized by the sol-gel method. They emit strong and stable room-temperature phosphorescence (SS-RTP) on filter paper as substrate, and bismuth can quench the intensity of the SS-RTP. On this basis a new morin-SiO2 solid-substrate room-temperature phosphorescence-quenching method has been established for determination of traces of bismuth. Reduction of phosphorescence intensity (DeltaI(p)) is directly proportional to the concentration of bismuth in the working range 0.16-14.4 ag spot(-1) (sample volume 0.40 muL spot(-1), corresponding to the concentration range 0.40-36.0 fg mL(-1)). The regression equation of the working curve is DeltaI(p)=14.86+5.279x[Bi3+] (ag spot(-1)) (n=6, r=0.9982). The detection limit of this method is 0.026 ag spot(-1) (corresponding to a concentration of 6.5 x 10(-17) g mL(-1)).This sensitive, reproducible and accurate method has been used for successful analysis of real samples.