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The abuse of illicit drug addiction is a worldwide public health and social problem. In this paper, we reported on a simple and rapid colorimetric biosensor for duplexed detection of methamphetamine (METH) and cocaine in a single assay. Gold nanoparticles (AuNPs) and Au@Ag NPs were synthesized and functionalized with DNA reporter probes (RPs) for METH and cocaine, respectively. The magnetic beads (MBs) were conjugated with two capture probes (CPs) respective to METH and cocaine. The respective RPs and CPs were designed to hybridize with each illicit drug-binding DNA aptamers through DNA-DNA hybridization, forming a sandwich structure. This MBs-based sandwich structure could be removed with an external magnetic field. However, due to the higher affinity of DNA aptamers with illicit drugs, the sandwich structure was disassembled when illicit drugs are introduced into the solution, leading to the colour changes of the supernatant. Utilizing a non-negative matrix factorization (NMF) algorithm to process the data, we demonstrated the ability of our biosensor for the simultaneous quantification of two illicit drugs. Under the optimal condition, our sensors were able to detect both METH and cocaine at the nM level with a wide dynamic range. This sensing platform provides a huge potential on drug consumption evaluation at the community level for wastewater-based epidemiology.

In this work, an electrochemical paper-based aptasensor was fabricated for label-free and ultrasensitive detection of epidermal growth factor receptor (EGFR) by employing anti-EGFR aptamers as the bio-recognition element. The device used the concept of paper-folding, or origami, to serve as a valve between sample introduction and detection, so reducing sampling volumes and improving operation convenience. Amino-functionalized graphene (NH2-GO)/thionine (THI)/gold particle (AuNP) nanocomposites were used to modify the working electrode not only to generate the electrochemical signals, but also to provide an environment conducive to aptamer immobilization. Electrochemical characterization revealed that the formation of an insulating aptamer–antigen immunocomplex would hinder electron transfer from the sample medium to the working electrode, thus resulting in a lower signal. The experimental results showed that the proposed aptasensor exhibited a linear range from 0.05 to 200 ngmL−1 (R2 = 0.989) and a detection limit of 5 pgmL−1 for EGFR. The analytical reliability of the proposed paper-based aptasensor was further investigated by analyzing serum samples, showing good agreement with the gold-standard enzyme-linked immunosorbent assay. A low-cost electrochemical paper-based sensor has been developed for the highly sensitive detection of epidermal growth factor receptor (EGFR). EGFR normally activates relevant genes, resulting in cell division and proliferation, although its overexpression has been observed in some forms of cancer. There is thus a growing interest in determining EGFR levels as a biomarker for early-stage disease diagnosis. A team headed by Xinxia Cai at the Chinese Academy of Sciences, Beijing succeeded in developing a biosensor for EGFR by combining the screen printing of a graphene-modified nanocomposite electrode onto an origami paper-folding for enabling microfluidic reagent and sample processing. The device gave a low detection limit and linear responses across a wide range of EGFR concentrations in human serum (electronic input values). The authors believe that their device can be easily adapted to other soluble biomarkers and that it has potential for use as a handheld instrument as point-of-care testing in early diagnosis and efficacy evaluation of cancer.

Auxetic materials with negative Poisson’s ratios unusually exhibit intuitive mechanical behaviors, such as cross-section expansion instead of contraction during tension. Such behaviors are interesting because they may enhance unusual mechanical properties. However, controllable preparation of materials with negative Poisson’s ratio is still a major challenge. In this study, we report the synthesis of a flexible auxetic graphene assembled macrofilm (GAMF) from graphene oxide nanosheets by a thermal annealing and press assistant method. The obtained materials exhibit good flexibility and significantly wide tunable negative Poisson’s ratios ranging from −0.11 to −0.53. We also develop a reconstruction model for characterization the uniaxial tension of GAMF based on X-ray tomographic images. The tensile simulation result predicts the function relationship between Poisson’s ratio and critical thickness of pore channels, which is in good agreement with the experimental data. As a result, an effective tunable way is proposed for customizable fabrication of GAMF with tunable negative Poisson’s ratios, and the GAMF materials with good flexibility, high electrical conductivity and superior auxetic behavior looks promising for future development of wearable electronics.

Wastewater-based epidemiology (WBE) was applied for the first time in seven cities across Europe with the aim of estimating quinolones consumption via the analysis of human urinary metabolites in wastewater. This report is also the first pan-European study focussed on the enantiomeric profiling of chiral quinolones in wastewater. By considering loads of (fluoro)quinolones in wastewater within the context of human stereoselective metabolism, we identified cities in Southern Europe characterised by both high usage and direct disposal of unused ofloxacin. In Northern European cities, S-(-)-ofloxacin loads were predominant with respect to R-(+)-ofloxacin. Much more potent, enantiomerically pure S-(-)-ofloxacin was detected in wastewaters from Southern European cities, reflecting consumption of the enantiomerically pure antibiotic. Nalidixic acid, norfloxacin and lomefloxacin were detected in wastewater even though they were not prescribed according to official prescription data. S,S-(-)-moxifloxacin and S,S-(-)-moxifloxacin-N-sulphate were detected in wastewater due to metabolism of moxifloxacin. For the first time, average population-normalised ulifloxacin loads of 22.3 and 1.5 mg day−1 1000 people−1 were reported for Milan and Castellón as a result of prulifloxacin metabolism. Enrichment of flumequine with first-eluting enantiomer in all the samples indicated animal metabolism rather than its direct disposal. Fluoroquinolone loads were compared with qnrS gene encoding quinolone resistance to correlate usage of fluoroquinolone and prevalence of resistance. The highest daily loads of the qnrS gene in Milan corresponded with the highest total quinolone load in Milan proving the hypothesis that higher usage of quinolones is linked with higher prevalence of quinolone resistance genes. Utrecht, with the lowest quinolones usage (low daily loads) had also one of the lowest daily loads of the qnrS gene. However, a similar trend was not observed in Oslo nor Bristol where higher qnrS gene loads were observed despite low quinolone usage.

We report a novel colorimetric biosensor based on non-aggregation Au@Ag core-shell nanoparticles to detect methamphetamine and cocaine. The biosensor consisted of a reporter probe (RP) that is a specific single-stranded DNA (ssDNA) sequence coated on Au@Ag nanoparticles, a capture probe (CP) conjugated with magnetic beads, and an illicit drug-binding DNA aptamer (Apt). Au@Ag nanoparticles were synthesized by seed growth and characterized by scanning electron microscope (SEM), high-resolution transmission electron microscopy (HR-TEM), and UV–vis spectra. Methamphetamine (METH) was used as an example to evaluate the feasibility of the biosensor and to optimize the detection conditions. We demonstrated that this sensing platform was able to detect as low as 0.1 nM (14.9 ng L−1) METH with a negligible interference from other common illicit drugs. Various concentrations of METH were spiked into urines, and the biosensor yielded recoveries more than 83.1%. In addition, the biosensor also showed a high sensitivity to detect cocaine. These results demonstrated that our colorimetric sensor holds promise to be implemented as a visual sensing platform to detect multiple illicit drugs in biological samples and environmental matrices.

Human biomonitoring, i.e. the determination of chemicals and/or their metabolites in human specimens, is the most common and potent tool for assessing human exposure to pesticides, but it suffers from limitations such as high costs and biases in sampling. Wastewater-based epidemiology (WBE) is an innovative approach based on the chemical analysis of specific human metabolic excretion products (biomarkers) in wastewater, and provides objective and real-time information on xenobiotics directly or indirectly ingested by a population. This study applied the WBE approach for the first time to evaluate human exposure to pesticides in eight cities across Europe. 24 h-composite wastewater samples were collected from the main wastewater treatment plants and analyzed for urinary metabolites of three classes of pesticides, namely triazines, organophosphates and pyrethroids, by liquid chromatography-tandem mass spectrometry. The mass loads (mg/day/1000 inhabitants) were highest for organophosphates and lowest for triazines. Different patterns were observed among the cities and for the various classes of pesticides. Population weighted loads of specific biomarkers indicated higher exposure in Castellon, Milan, Copenhagen and Bristol for pyrethroids, and in Castellon, Bristol and Zurich for organophosphates. The lowest mass loads (mg/day/1000 inhabitants) were found in Utrecht and Oslo. These results were in agreement with several national statistics related to pesticides exposure such as pesticides sales. The daily intake of pyrethroids was estimated in each city and it was found to exceed the acceptable daily intake (ADI) only in one city (Castellon, Spain). This was the first large-scale application of WBE to monitor population exposure to pesticides. The results indicated that WBE can give new information about the "average exposure" of the population to pesticides, and is a useful complementary biomonitoring tool to study population-wide exposure to pesticides. (C) 2017 Elsevier Ltd. All rights reserved.

In this work, a simple, cost-effective, and label-free biosensor was constructed for methamphetamine (METH) detection. The biosensor consists of a G-quadruplex–hemin DNAzyme molecular beacon (DNAzyme MB), a METH aptamer, and a colorimetric substrate. The DNAzyme MB loses peroxidase activity when it hybridizes with the METH aptamer. In the presence of METH, DNAzyme MB dissociates from the inactive hybrid due to preferable hybridization of METH with the aptamer. This process recovers the activity of DNAzyme MB, which catalyzes a reaction with the colorimetric substrate to yield measurable signals. Under optimized conditions, a detection limit as low as 0.5 nM (74.6 ng L−1) was achieved. Common illicit drugs were found to have little interference on detection of METH. Recoveries of METH spiked in urines of addicts were greater than 85%. Good agreement was observed between METH concentrations in urines determined by the sensor and by liquid chromatography-tandem mass spectrometer. These results indicate that the G-quadruplex–hemin DNAzyme MB probe holds promise to detect METH not only in biological samples, but also in environmental matrices.

Caffeine metabolites in wastewater were investigated as potential biomarkers for assessing caffeine intake in a population. The main human urinary metabolites of caffeine were measured in the urban wastewater of ten European cities and the metabolic profiles in wastewater were compared with the human urinary excretion profile. A good match was found for 1,7-dimethyluric acid, an exclusive caffeine metabolite, suggesting that might be a suitable biomarker in wastewater for assessing population-level caffeine consumption. A correction factor was developed considering the percentage of excretion of this metabolite in humans, according to published pharmacokinetic studies. Daily caffeine intake estimated from wastewater analysis was compared with the average daily intake calculated from the average amount of coffee consumed by country per capita. Good agreement was found in some cities but further information is needed to standardize this approach. Wastewater analysis proved useful to providing additional local information on caffeine use. (C) 2017 Elsevier B.V. All rights reserved.

β-Nucleated isotactic polypropylene (β-iPP) blend with maleic anhydride grafted polyethylene-vinyl acetate (EVA-g-MA) and β-iPP/polyamide (PA) 6 blend, as well as its compatibilized version with EVA-g-MA as a compatibilizer were prepared with an internal mixer. Analysis from differential scanning calorimeter (DSC) and wide angle X-ray diffraction (WAXD) indicates that the addition of EVA-g-MA into β-nucleated iPP decreases the crystallization temperature (Tcp) of PP, but it has no pronounced influence on the β-crystal content for β-nucleated iPP. For β-nucleated iPP/PA6 blends, PA6 obviously decreases the β-crystal content. However, the addition of EVA-g-MA is quite benefit for the formation of β-crystal in β-nucleated iPP/PA6 blends and the β-crystal content increases with increasing EVA-g-MA content. It is suggested that the nucleating agent mainly disperses in the PA6 phase and/or the interface between iPP and PA6 in iPP/PA6 blend, which was proved by etching the blends with sulfuric acid and experimental facts from SEM.

A highly novel nano-CaCO3 supported β-nucleating agent was employed to prepare β-nucleated isotactic polypropylene (iPP) blend with polyamide (PA) 66, β-nucleated iPP/PA66 blend, as well as its compatibilized version with maleic anhydride grafted PP (PP-g-MA), maleic anhydride grafted polyethylene-octene (POE-g-MA), and polyethylene-vinyl acetate (EVA-g-MA), respectively. Nonisothermal crystallization behavior and melting characteristics of β-nucleated iPP and its blends were investigated by differential scanning calorimeter and wide angle X-ray diffraction. Experimental results indicated that the crystallization temperature (T) of PP shifts to high temperature in the non-nucleated PP/PA66 blends because of the α-nucleating effect of PA66. T of PP and the β-crystal content (Kβ) in β-nucleated iPP/PA66 blends not only depended on the PA66 content, but also on the compatibilizer type. Addition of PP-g-MA and POE-g-MA into β-nucleated iPP/PA66 blends increased the β-crystal content; however, EVA-g-MA is not benefit for the formation of β-crystal in the compatibilized β-nucleated iPP/PA66 blend. It can be relative to the different interfacial interactions between PP and compatibilizers. The nonisothermal crystallization kinetics of PP in the blends was evaluated by Mo's method. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

BACKGROUND: The distribution of nucleating agents in different phases is still an open question in general, and how to control conditions to prepare alloys rich in β-crystals of polypropylene (PP) is hardly reported. The main goal of this study was to find out the factors influencing the β-crystal content in β-nucleated PP/polyamide 6 (PA6) alloys and determine the best preparation conditions to obtain β-nucleated PP/PA6 alloys rich in β-crystals. RESULTS: The compounding methods had little influence on the crystallization temperature of both PP and PA6. However, the melting characteristic and β-crystal content in β-nucleated PP/PA6 alloys not only depended upon the compounding methods, but also on the temperature at which the nucleating agent was added. A higher β-crystal content can be obtained by adding the nucleating agent at a temperature below 190 °C, which is also dependent on the mixing time. CONCLUSION: It is proved by etching the alloys with sulfuric acid that the nucleating agent mainly disperses in the PA6 phase and/or the interface between PP and PA6 when blended at high temperature. Copyright © 2009 Society of Chemical Industry

β-Nucleated isotactic polypropylene (iPP) blends with polyamide 6 (PA6) were prepared with a novel and highly efficient nano-CaCO3-supported β-nucleating agent. Maleic anhydride grafted polypropylene (PP-g-MA), glycidyl methacrylate grafted polypropylene (PP-g-GMA), maleic anhydride grafted poly(ethylene octene) (POE-g-MA), and maleic anhydride grafted poly(ethylene vinyl acetate) (EVA-g-MA) elastomers were added to the blends as compatibilizers. The nonisothermal crystallization behavior and melting characteristics of β-nucleated iPP and its blends were investigated with differential scanning calorimetry and wide-angle X-ray diffraction. The results indicated that the β-iPP content in the β-nucleated iPP blends depended not only on the preparation conditions but also on the compatibilizer type. A high β-iPP content (>95%) in the β-nucleated iPP/PA6 blends was obtained. The addition of PP-g-MA, POE-g-MA, and EVA-g-MA to the β-nucleated iPP/PA6 blends increased the content of β-iPP but decreased the crystallization temperature of iPP in the β-nucleated iPP/PA6 blends. However, the addition of PP-g-GMA decreased the content of β-iPP in the β-nucleated iPP/PA6 blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Non-nucleated polypropylene alloy with polyamide 6 (PP/PA6) and β-nucleated polypropylene (β-PP)/PA6 alloy, as well as its compatibilized version with maleic anhydride grafted PP (PP-g-MA) were prepared with an internal mixer. In the all alloys, PP formed a continuous phase with a dispersive PA6. Effects of PA6 on the non-isothermal crystallization behavior, melting characteristics and the β-PP content of alloys were investigated by differential scanning calorimeter (DSC) and wide angle X-ray diffraction (WAXD). The results indicated that the crystallization temperature ( T c p ) of PP shifts to high temperature in the non-nucleated PP/PA6 alloys due to the α-nucleating effect of PA6. However, in the β-nucleated PP/PA6 alloys, PA6 hardly has an effect on the T c p of PP. The β-PP content in the alloys not only depends on the content of the PA6, but also on the melting temperatures. It is proved by etching the alloys with sulfuric acid that the nucleating agent mainly disperses in the PA6 phase and/or the interface between PP and PA6 when blended at high temperature. Addition of PP-g-MA promotes the formation of β-PP in the β-nucleated PP/PA6 alloys. The increase in the PA6 content has a little influence on the T c p of PP and the β-PP content in the compatibilized β-nucleated PP/PA6 alloys. The non-isothermal crystallization kinetics of PP in the alloys was evaluated by Mo’s method.

The β-nucleated PP with high β-PP content was prepared by a novel supported β-nucleating agent, which was prepared with pimelic acid supported on nano-CaCO3 as support. The influences of the content of the support and supported β-nucleating agent, pre-melting temperature (Tmelt) and scan rates on crystallization behavior and melting characteristics, and the β-PP content of β-nucleated PP were determined by Differential Scanning Calorimeter (DSC) and Wide-Angle X-ray Diffraction (WAXD). The results indicated that the addition of supported β-nucleating agent markedly increased the crystallization temperature (Tc) of PP. Increasing the content of supported β-nucleating agent slightly increased the Tc, but had no influence on the melting temperatures (Tm) of β-nucleated PP. The Tc and Tm of β-nucleated PP decreased slightly with increasing the content of the support nano-CaCO3. The effects of scan rates and multiple scans with different Tmelt on the crystallization and melting behavior of PP nucleated by supported β-nucleating agent are similar to that of PP nucleated by calcium pimelate (CaHA). The β-PP content above 90 percent was obtained in PP nucleated by supported β-nucleating agent and was not influenced by the content of nano-CaCO3. The supported β-nucleating agent prepared by supporting pimelic acid on nano-CaCO3 is a β-nucleating agent with high efficiency and selectivity, and low cost.

In this paper, nano-CaCO3 supported β-nucleating agent for polypropylene (PP) was prepared by supporting pimelic acid on nano-CaCO3 with two methods. The thermal properties of pimelic acid and nano-CaCO3 supported β-nucleating agent were investigated by differential scanning calorimetry and thermogravimetry coupled with Fourier transform infrared spectrometry. The results indicated that the formation of β-nucleating agent supported on nano-CaCO3 was attributed to the chemical reaction between nano-CaCO3 and pimelic acid. The β-nucleating agent was added to PP to examine its β-nucleating ability for PP, the polymorphism of the PP was characterized by wide-angle X-ray diffractometer. The results of investigation showed that the nano-CaCO3 supported β-nucleating agent exhibited higher nucleation ability and lower price compared to calcium pimelate β-nucleating agent.

We report on a novel strategy for DNA aptamer immobilization to develop sensitive electrochemical detection of a protein biomarker, with prostate specific antigen (PSA) as a case biomarker. Thiolated single-stranded DNA (ssDNA) was co-immobilized with 3-mercapto-1-propanol on gold electrodes, and used as a scaffold for DNA aptamer attachment through hybridization of the aptamer overhang (so-called “DNA-directed immobilization aptamer sensors”, DDIAS). In the approach, the complementary DNA aptamer against PSA was assembled by the probe ssDNA onto the electrode to detect PSA; or the probe ssDNA directly hybridized with a complementary DNA aptamer/PSA complex following their pre-incubation in solution, so-called ‘on-chip’ and ‘in-solution’ methods, respectively. A double stranded DNA intercalator with a ferrocenyl (Fc) redox marker was synthesized to evaluate the feasibility of the strategy. The results demonstrate that the ‘in-solution’ method offers a favourable medium (in a homogeneous solution) for the binding between the aptamer and PSA, which shows to be more efficient than the ‘on-chip’ approach. DDIAS shows promising analytical performance under optimized conditions, with a limit of detection in the range of fM and low non-specific adsorption.

International audience; Antibody microarrays are powerful and high-throughput tools for screening and identifying tumor markers from small sample volumes of only a few microliters. Optimization of surface chemistry and spotting conditions are crucial parameters to enhance antibodies' immobilization efficiency and to maintain their biological activity. Here, we report the implementation of an antibody microarray for the detection of tumor markers involved in colorectal cancer. Three-dimensional microstructured glass slides were functionalized with three different aminated molecules ((3-aminopropyl)dimethylethoxysilane (APDMES), Jeffamine, and chitosan) varying in their chain length, their amine density, and their hydrophilic/hydrophobic balance. The physicochemical properties of the resulting surfaces were characterized. Antibody immobilization efficiency through physical interaction was studied as a function of surface properties as well as a function of the immobilization conditions. The results show that surface energy, steric hindrance, and pH of spotting buffer have great effects on protein immobilization. Under optimal conditions, biological activities of four immobilized antitumor marker antibodies were evaluated in multiplex immunoassay for the detection of the corresponding tumor markers. Results indicated that the chitosan functionalized surface displayed the highest binding capacity and allowed to retain maximal biological activity of the four tested antibody/antigen systems. Thus, we successfully demonstrated the application of amino-based surface modification for antibody microarrays to efficiently detect tumor markers.

Core shell Ag@SiO2 -Streptavidin- Cy3 nanoparticles were prepared. Ag@SiO2 nanoparticles were synthesized via a sol–gel method. Then, Streptavidin- Cy3 was covalently bonded to the Ag@SiO2 surface. These core-shell nanoparticles were characterized by steady-state fluorescence spectroscopy and fluorescence scanning. In presence of the silver core, a 2.5-time enhancement of Cy3 fluorescence intensity was obtained. This result shows that these nanoparticles can be potentially helpful in surface analysis based on biochip.