Unique fluorophilic pores engineering within porous aromatic frameworks for trace perfluorooctanoic acid removal.

Perfluorooctanoic acid (PFOA), a representative of per/polyfluorinated alkyl substances, has become a persistent water pollutant of widespread concern due to its biological toxicity and refractory property. In this work, we design and synthesize two porous aromatic frameworks (PAF) of PAF-CF3 and PAF-C2F5 using fluorine-containing alkyl based monomers in tetrahedral geometry. Both PAFs exhibit nanosized pores (∼1.0 nm) of high surface areas (over 800 m2 g-1) and good fluorophilicity. Remarkable adsorption capacity (˃740 mg g-1) and superior efficiency (˃24 g mg-1 h-1) are achieved toward the removal of PFOA with 1 µg L-1 concentration owing to unique C-F···F-C interactions. In particular, PAF-CF3 and PAF-C2F5 are able to reduce the PFOA concentration in water to 37.9 ng L-1 and 43.3 ng L-1, below EPA regulations (70 ng L-1). The reusability and high efficiency give both PAFs a great potential for sewage treatment.

Construction of a ratiometric fluorescent probe for visual detection of urea in human urine based on carbon dots prepared from Toona sinensis leaves and 5-carboxyfluorescein.

In this work, pH-sensitive blue fluorescent carbon dots (CDs) with high fluorescence quantum yield (17.24%) were synthesized by hydrothermal method using Toona sinensis leaves and ethylenediamine (EDA) as raw materials. The CDs can detect urea with a limit of detection (LOD) of 6.700 mmol L-1. For more sensitive detection of urea, we constructed a ratiometric fluorescent probe (CDs@5-FAM) using CDs and 5-carboxyfluorescein (5-FAM). The CDs@5-FAM probe can rapidly and sensitively detect urea according to the changes of I514/I405, with LOD as low as 0.014 mmol L-1. Furthermore, with the help of a smartphone and RGB analysis software, urea's visual intelligent detection was realized using a CDs@5-FAM probe. The method proposed in this paper is consistent with the standard method, which indicates that the pH-sensitive ratiometric fluorescent probe CDs@5-FAM is accurate and reliable for practical application. It provides a new way for rapid and visual detection of urea.

H2O2-assisted detection of melamine using fluorescent probe based on corn cob carbon dots-Ionic Liquid-Silver nanoparticles.

In this work, a new sustainable melamine detection method was developed. Biomass-derived carbon dots (CDs) were successfully prepared by ionic liquid (1-Allyl-3-methylimidazolium chloride, IL) hydrothermal method using agricultural waste corn cob as the carbon source, and combined with silver nanoparticles (AgNPs) to construct fluorescent probe CDs@IL-AgNPs. The probe was characterized and the formation mechanism of the probe was discussed. The direct detection of H2O2 and the indirect sensitive detection of melamine were realized. The detection limit of melamine was 0.94 µmol/L, which is far lower than the minimum allowable amount of melamine in milk powder (7.95 µmol/L). The high sensitivity and selectivity probe was used to detect melamine in commercial dairy products, and the recovery rate of standard addition was between 94 % and 110 %. This study provides valuable new application ideas for the detection of melamine in dairy products and the low-carbon and environmentally friendly treatment of agricultural waste.

Photocatalytic performance of heterojunction S-Tyr-NDI-Tyr/TiO2 formed by self-assembled naphthalimide derivatives and titanium dioxide.

In this paper, a type of heterojunction photocatalyst S-Tyr-NDI-Tyr/TiO2 was prepared by self-assembly of tyrosine-substituted naphthamide (NDA) and bonding with titanium dioxide. The self-assembly process and driving force of monomer M-Tyr-NDI-Tyr were simulated by theoretical calculation. Taking atenolol as the target pollutant, the photocatalytic performance of the heterojunction photocatalyst under visible light was studied, and the degradation products were analyzed by mass spectrometry. The environmental toxicity of photocatalytic process was evaluated by luminescent bacteria. The principle of high photocatalytic activity of S-Tyr-NDI-Tyr/TiO2 heterojunction photocatalyst was proposed by analyzing the fluorescence spectrum, photocurrent density and resistance, electron paramagnetic resonance spectrum, free radical capture experiment and energy band position of S-Tyr-NDI-Tyr/TiO2 heterojunction photocatalyst. In addition, the photocatalytic degradation of different pollutants by S-Tyr-NDI-Tyr/TiO2 heterojunction photocatalyst was also studied. This work will provide a useful example for the further development of new and efficient organic supramolecular/inorganic semiconductor composite photocatalysts.

Foamer-Derived Bulk Nitrogen Defects and Oxygen-Doped Porous Carbon Nitride with Greatly Extended Visible-Light Response and Efficient Photocatalytic Activity.

Constructing bulk defects and doping are feasible ways to essentially narrow the band gap and improve the light absorption of photocatalysts. Herein, inspired by bread foaming, the foaming agent azoformamide or azodicarbonamide (AC) was introduced during the thermal polymerization of urea. In the polymerization process, a large number of bubbles produced by AC decomposition seriously interfered with the polymerization of urea, resulting in the breaking of the hydrogen bonds and van der Waals interaction in carbon nitride, distortion of its structure, and partial oxidation, thus forming a series of porous carbon nitrides U/ACx (x is the ratio of AC to urea; where x = 0.25, 0.5, and 1) with bulk N defects and O doping. Its band gap was reduced to 1.91 eV and the absorption band edge was greatly extended to 650 nm. The optimal U/AC0.5 exhibits the highest visible light photocatalytic hydrogen production rate of about 44.7 µmol·h-1 (10 mg catalysts) and shows superior photocatalytic performance for the oxidation of diphenylhydrazine to azobenzene, with conversion and selectivity of almost 100%, and is one of the most active defective carbon nitrides, especially under long-wavelength (λ ≥ 550 nm) light irradiation. It paves the way for the design of highly efficient and wide-spectral-response photocatalysts.

Photocatalytic kinetics and cyclic stability of photocatalysts Fe-complex/TiO2 in the synergistic degradation of phenolic pollutants and reduction of Cr(VI).

In this paper, the kinetic characteristics and cycle stability of Fe-complex/TiO2 in the process of degradation of phenolic pollutants and reduction of heavy metal Cr(VI) were studied systematically. First, the structural characteristics and photocatalytic activities of Fe(III)-(8-hydroxyquinoline-5-carboxylic acid)-TiO2 (Fe-HQC-TiO2) nanoparticle to degrade phenolic pollutants and reduce Cr(VI) simultaneously had been investigated. Compared with the single degradation, the efficiency of synergistic degradation/reduction had been improved and the degradation/reduction rate had been obviously accelerated. In particular, the cyclic stability of Fe-HQC-TiO2 photocatalyst decreased obviously when it was used to reduce Cr(VI) alone, but it could still keep above 90% after three cycles when it was used for reduction of Cr(VI) and degradation of phenol synergistically. Second, to Fe-HQS/TiO2 nanoparticle or Fe-HQS/TiO2 nanotube (HQS (8-hydroxyquinoline-5-sulfonic acid)), the synergistic degradation/reduction (2,4-dichlorophenol/Cr(VI)) efficiencies were always greater than those of a single degradation/reduction and the time was greatly reduced. All the results indicated that there were interactions between Cr(VI) and phenol or 2,4-dichlorophenol in the photocatalytic process. The possible mechanism of synergistic accelerated degradation of phenolic compounds and reduction of Cr(VI) was proposed by analyzing and testing the surface characteristics of photocatalyst and the properties of photocatalytic system during the synergistic degradation/reduction.

Copper doping and organic sensitization enhance photocatalytic activity of titanium dioxide: Efficient degradation of phenol and tetrabromobisphenol A.

A novel photocatalyst (Cu-TiO2@HQ) had been synthesized by combining Cu-doped TiO2 nanoparticles with 8-Hydroxyquinoline (HQ) via hydrothermal method. The photocatalytic activities of Cu-TiO2@HQ were investigated by using phenol and tetrabromobisphenol A (TBBPA) as target pollutants, respectively. The results indicated that the degradation efficiencies of phenol and TBBPA by Cu-TiO2@HQ were 99.2% (in 30 min) and 99.4% (in 10 min) under visible light irradiation. Both of them were much better than that of pure TiO2 (8.63% in 30 min) and Cu-TiO2 (14.74% in 30 min). When phenol or TBBPA were degraded together with the reduction of Cr (VI), the reaction rate of each pollutant was significantly increased, and the cyclic stability of photocatalyst Cu-TiO2@HQ was greatly improved. Based on the spectroscopic and photoelectric characteristic analysis we found that in the mixture of phenol-Cr (VI) or TBBPA-Cr (VI) both photo-generated electrons and holes can be consumed simultaneously, thus preventing their recombination. The possible degradation products of phenol and TBBPA including its degradation path way were also analyzed by high resolution liquid chromatography-mass spectrometry-mass spectrometry.

Two-dimensional polyimide heterojunctions for the efficient removal of environmental pollutants under visible-light irradiation.

Two-dimensional (2D) heteromaterials with large interface contact and intimate interfacial charge transition have been considered to be an ideal model for constructing highly efficient photocatalysts. However, few studies have reported on these 2D heterojunctions. Herein, we report a series of new 2D heterojunctions comprising polyimide (PI) and perylene-3,4,9,10-tetracarboxylic dianhydride (TD). These heterojunctions, denoted as PI-TDx (where x represents the amount of TD added, i.e., x = 0.13, 0.18, 0.27, 0.54, and 1.08 g), were prepared by the solid thermal copolymerization of melamine (MA), pyromellitic dianhydride (PD), and different amounts of TD. FT-IR spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy analyses were used to verify the 2D heterojunction structure. Photocatalytic experiments reveal that PI-TDx exhibit excellent and stable photocatalytic performance for the degradation of the organic dyes rhodamine B (RhB) and methyl violet (MV), as well as for the photoreduction of Cr(vi), under visible-light irradiation. Among the samples, PI-TD0.18 exhibits the best photocatalytic performance. Its activity is about 2.7 times and 7.5 times higher than that of individual PIMP (formed by MA and PD) and PIMT (formed by MA and TD) for RhB degradation, respectively. Notably, PI-TD0.18 retains a certain photocatalytic activity under light irradiation at 600 nm. The photocatalytic-mechanism study demonstrates that PI-TD0.18 has a classic type-II heterojunction. Its 2D heterojunction greatly enhances the visible-light absorption of the composites and effectively suppresses the radiation recombination of photogenerated carriers, thereby improving its charge transfer and separation abilities and providing excellent photocatalytic performance. This work may serve as an important reference for the design and construction of new highly efficient 2D organic conjugated-polymer photocatalysts.

Imaging of water soluble CdTe/CdS core-shell quantum dots in inhibiting multidrug resistance of cancer cells.

Two different colors of water-soluble core-shell quantum dots CdTe/CdS (green and orange red) have been synthesized and characterized in this paper. The formation of core-shell quantum dots not only improves the fluorescence quantum yield, but also reduces the biological toxicity of quantum dots, and improves the fluorescence lifetime. Two novel fluorescent bioprobes, CdTe/CdS (λem = 545 nm)-5-Fu and Bio-CdTe/CdS (λem = 600 nm)-TAM, have been synthesized via the interaction of these two core-shell quantum dots with anticancer drugs (5-Fu) and P-gp inhibitors (TAM), respectively. These two fluorescent probes have been simultaneously used in fluorescence imaging of human breast cancer cells MDA-MB-231/MDR. It can be observed that under the action of P-gp inhibitors distributed on the cell membrane, anticancer drugs can be retained in cancer cells. According to the color of quantum dots on the probe, the visualization results of the action of anticancer drugs and P-gp inhibitors can be obtained. This study shows that to prepare functional bioprobes using core-shell quantum dots CdTe/CdS has great potential in the field of biomedical research such as anticancer drugs.

Novel photocatalytic system Fe-complex/TiO2 for efficient degradation of phenol and norfloxacin in water.

Photocatalysis is one of the effective strategies to eliminate various organic pollutants in water body. In this paper we have prepared a series of new composite photocatalysts to degrade phenol and norfloxacin under visible light irradiation. They were [FeII(dpbpy)2(H2O)2]/TiO2, [FeII(dpbpy)(phen)2]/TiO2 and [FeII(dpbpy)(bpy)2]/TiO2 (dpbpy: 2,2'-bipyridine-4,4'-diphosphoric acid, phen: 1,10-phenanthroline, bpy: 2,2-bipyridyl). The results show that their photocatalytic performance and cyclic stability are much better than that of pure TiO2 or P25. Phenol can be degraded almost completely and the active groups or substituents of norfloxacin (NOR) can be destroyed also, which greatly reduced the biological toxicity of phenol and norfloxacin in water. The possible mechanisms of improving the photocatalytic activity and stability of TiO2 by using Fe-complex are proposed based on free radical capture test and density functional theory calculation. It is clearly that the interfacial interaction between Fe-complex and titanium dioxide directly affects the photocatalytic activity and stability of the composite photocatalyst. The conjugated structure of the complexes plays a crucial role.

SSeCKS/AKAP12 induces repulsion between human prostate cancer and microvessel endothelial cells through the activation of Semaphorin 3F.

Metastasis remains the primary cause of prostate cancer related death. Cancer cells need to contact endothelial cells and disrupt endothelial junctions to cross the endothelium for invasion and metastasis. The suppression of heterotypic repulsion between cancer and endothelial cells allows cancer cells to invade into the surrounding tissue. Here, we demonstrate that SSeCKS/AKAP12 induced repulsion between human prostate cancer and microvessel endothelial cells, which was mediated by an angiogenesis inhibitor Semaphorin 3F. Moreover, we examined AKAP12 and Semaphorin 3F mRNA expression in 42 prostate cancer and 30 benign prostatic hyperplasia tissue samples, and found that the expression of AKAP12 and Semaphorin 3F mRNA was inversely associated with the degree of aggressiveness of prostate cancer cells and tissues. An ordinal logistic regression analysis indicates that there is a positive association between the expression of AKAP12 and Semaphorin 3F in prostate cancer, suggesting that the activation of Semaphorin 3F by SSeCKS/AKAP12 may be involved in prostate cancer progression and metastasis.

The Long Noncoding RNA MEG3 Is Downregulated and Inversely Associated with VEGF Levels in Osteoarthritis.

Osteoarthritis (OA) is becoming a major public health problem in China, especially considering the increase in average life expectancy of the population. Thus, enhanced understanding of the molecular changes associated with OA is urgently needed to develop more effective strategies for the diagnosis and treatment of this debilitating disease. LncRNAs play an important role in the processes of bone and cartilage development. Maternally expressed gene 3 (MEG3) is a maternally expressed lncRNA and may function as a tumor suppressor by inhibiting angiogenesis. OA is closely associated with angiogenesis and the inhibition of angiogenesis presents a novel therapeutic approach to reduce inflammation and pain in OA. In this study, we detected the mRNA expression of MEG3 and VEGF in articular cartilage samples from 20 OA patients and 10 healthy volunteers by real-time RT-PCR. VEGF protein is detected by ELISA in cartilage samples. The results show that human MEG3 is significantly downregulated in OA patients compared to normal cartilage samples. However, higher levels of VEGF mRNA and protein are found in OA compared to the control. Moreover, MEG3 levels are inversely associated with VEGF levels, suggesting that MEG3 may be involved in OA development through the regulation of angiogenesis.

Circulating miR-126 is a potential biomarker to predict the onset of type 2 diabetes mellitus in susceptible individuals.

Type 2 diabetes mellitus (T2DM) is a major public health problem in China. Diagnostic markers are urgently needed to identify individuals at risk of developing T2DM and thus encouraging healthier life styles. Circulating miRNAs are valuable sources for non-invasive biomarkers of various diseases. The aim of this study was to examine whether reduced miR-126 expression could predict the onset of T2DM in susceptible individuals. Two groups of study subjects were involved, one group was diagnosed T2DM in 2013 and the other group was healthy control. To this end, our results showed that miR-126 expression were already decreased before the manifestation of T2DM. Univariable logistic regression confirmed that the plasma miR-126 level was inversely associated with the onset of DM (P = 0.0158 Ë‚ 0.05), suggesting reduced miR-126 is a predictor for the onset of T2DM. According to the logistic regression model and ROC curve, a cut-off points of miR-126 plasma level as 35 is recommended for clinical study to predict whether an individual is more likely to develop T2DM. If miR-126 expression is lower than 35, the individual is more likely to T2DM in the next 2 years. In conclusion, our results support the notion that the circulating miR-126 can be developed into a non-invasive and rapid diagnostic tool for the prediction of susceptible individuals to developing T2DM.

Electrochemical behavior of L-cysteine and its detection at ordered mesoporous carbon-modified glassy carbon electrode.

In this paper, the electrochemical behavior of L-cysteine (CySH) was investigated thoroughly at an ordered mesoporous carbon-modified glassy carbon (OMC/GC) electrode. The voltammetric studies showed there were three anodic peaks for the electrooxidation of CySH in the pH range of 2.00-5.00; however, one peak disappeared above pH 5.00. This behavior has never been reported before. Through the studies of the effect of pH on the distribution fractions (delta) of the four chemical species of CySH, we conclude only CySH2+ (H3A+) and CyS- (HA-) are the electroactive substances and should be responsible for the electrooxidation of CySH. And for the first time, we successfully established the exact and systemic mechanisms based on the electroactive species to explain CySH oxidation at different pH values. On the other hand, a sensitive CySH sensor was developed based on an OMC/GC electrode, which shows a large determination range (18-2500 micromol L(-1)), a high sensitivity (23.6 microA mmol L(-1)), and a remarkably low detection limit (2.0 nmol L(-1), which is the lowest value ever reported for direct CySH determination on the electrodes) at pH 2.00. At pH 7.00, the modified electrode can be still used to readily detect CySH in the range of the physiological levels. These make OMC/GC electrode a promising candidate for efficient electrochemical sensors for the detection of CySH.

Three-phase extraction study of cyanex 923-n-heptane/H(2)SO(4) system.

Phase behavior of the extraction system, Cyanex 923-heptane/H(2)SO(4)-H(2)O has been studied. The third phase appeared at different aqueous H(2)SO(4) concentration with varying initial Cyanex 923 concentration and temperature affects its appearance. Almost all of H(2)SO(4) and H(2)O are extracted into the middle phase. The H(2)SO(4) concentration in the third phase increases with the increasing aqueous acid concentration (C(H(2)SO(4),b)) while the water content first increases and then reaches a constant value at C(H(2)SO(4),b)=11.3 mol l(-1). In the region of C(H(2)SO(4),b) higher than 5.2 mol l(-1), the composition of the middle phase is only related to the equilibrium concentration of H(2)SO(4) in the bottom phase. H(2)SO(4) and H(2)O are transferred into the middle phase mainly by their coordination with Cyanex 923 when C(H(2)SO(4),b) is less than 11.3 mol l(-1). When C(H(2)SO(4),b) is higher than 11.3 mol l(-1), excess H(2)SO(4) is solubilized into the polar layer of the aggregates. In the region considered, the extracted complex changes from C923 . H(2)SO(4) to C923 . H(2)SO(4) . H(2)O and then to C923 . (H(2)SO(4))(2) . H(2)O.