N-doped molybdenum oxide quantum dots as fluorescent probes for the quantitative detection of copper ions in environmental samples.

A novel, sensitive, and selective fluorescence sensor based on N-doped Mo oxide quantum dots (N-MoOx QDs) was fabricated for the detection of Cu2+ ions in water. The presence of Cu2+ induced dynamic fluorescence quenching of the N-MoOx QDs. The sensing conditions were optimized to enhance selectivity and sensitivity. Under optimal conditions, the linear relationship between fluorescence response at 408 nm and Cu2+ concentration was determined. The linear range of this relationship was 1-100 µM. The limits of detection (LOD) and quantitation (LOQ) for Cu2+ were 0.78 µM and 2.34 µM, respectively. The method was successfully applied to detect Cu2+ in water samples with satisfactory sample recovery rates from 91.7 to 116.4%. The sensor exhibits high selectivity toward Cu2+, making it useful for environmental sample monitoring.

Bifunctional Al-Doped Cobalt Ferrocyanide Nanocube Array for Energy-Saving Hydrogen Production via Urea Electrolysis.

The very slow anodic oxygen evolution reaction (OER) greatly limits the development of large-scale hydrogen production via water electrolysis. By replacing OER with an easier urea oxidation reaction (UOR), developing an HER/UOR coupling electrolysis system for hydrogen production could save a significant amount of energy and money. An Al-doped cobalt ferrocyanide (Al-Co2Fe(CN)6) nanocube array was in situ grown on nickel foam (Al-Co2Fe(CN)6/NF). Due to the unique nanocube array structure and regulated electronic structure of Al-Co2Fe(CN)6, the as-prepared Al-Co2Fe(CN)6/NF electrode exhibited outstanding catalytic activities and long-term stability to both UOR and HER. The Al-Co2Fe(CN)6/NF electrode needed potentials of 0.169 V and 1.118 V (vs. a reversible hydrogen electrode) to drive 10 mA cm-2 for HER and UOR, respectively, in alkaline conditions. Applying the Al-Co2Fe(CN)6/NF to a whole-urea electrolysis system, 10 mA cm-2 was achieved at a cell voltage of 1.357 V, which saved 11.2% electricity energy compared to that of traditional water splitting. Density functional theory calculations demonstrated that the boosted UOR activity comes from Co sites with Al-doped electronic environments. This promoted and balanced the adsorption/desorption of the main intermediates in the UOR process. This work indicates that Co-based materials as efficient catalysts have great prospects for application in urea electrolysis systems and are expected to achieve low-cost and energy-saving H2 production.

Direct Z-scheme heterojunction Bi/Bi2S3/α-MoO3 photoelectrocatalytic degradation of tetracycline under visible light.

A hot research topic in visible-light-driven photoelectrocatalytic (PEC) oxidation technology is the development of superior photoanode materials. The design of the photoanode system with a direct Z-scheme charge transfer mechanism is crucial to achieving effective charge separation for sustainable photoelectrocatalysis. Here, a novel Bi/Bi2S3/α-MoO3 heterostructure was successfully assembled by a simple and feasible strategy. The direct Z-scheme heterogeneous formed between Bi2S3 and α-MoO3 has the advantages of low resistance, high optical response current and the surface plasmon resonance (SPR) effect of Bi nanoparticles (Bi NPs). Thus, the efficiency of photogenerated carrier separation and transfer is further enhanced, and the catalytic activity is significantly improved. It is impressive that the unique photoanode has achieved a maximum removal efficiency of 85.8% of tetracycline (TC) pollutants under visible light irradiation within 60 min and has excellent stability, which is expected to degrade antibiotics efficiently and environmentally in harsh environments. These characteristics give Bi/Bi2S3/α-MoO3 promising candidates for practical applications in antibiotic degradation.

A series of lanthanide(III) metal-organic frameworks derived from a pyridyl-dicarboxylate ligand: single-molecule magnet behaviour and luminescence properties.

The reactions of LnIII ions with a versatile pyridyl-decorated dicarboxylic acid ligand lead to the formation of a series of novel three-dimensional (3D) Ln-MOFs, [Ln3(pta)4(Hpta)(H2O)]·xH2O (Ln = Dy (1), Eu (2), Gd (3), Tb (4), H2pta = 2-(4-pyridyl)-terephthalic acid, x = 6 for 1, 2.5 for 2, 1.5 for 3 and 2 for 4). The Ln3+ ions act as nine-coordinated muffin spheres, linking to each other to generate trinuclear {Ln3(OOC)6N2} SBUs, which are further extended to be interesting 3D topological architectures. To the best of our knowledge, the Dy-MOF exhibits zero-field single-molecule magnet (SMM) behaviour with the largest effective energy barrier among the previously reported 3D MOF-based Dy-SMMs. The combined analyses of a diluted sample (1@Y) and ab initio calculations demonstrate that the thermally assisted slow relaxation is mainly attributed to the single-ion magnetism. Furthermore, fluorescence measurements reveal that H2pta can sensitize EuIII and TbIII characteristic luminescence.

One-step synthesis of Ni(OH)2/MWCNT nanocomposites for constructing a nonenzymatic hydroquinone/O2 fuel cell.

In this work, a H-type hydroquinone/O2 fuel cell was assembled and shows high energy density in neutral phosphate buffer solution at moderate temperature. The anodic material, Ni(OH)2/MWCNTs, was synthesized by a one-step hydrothermal synthesis method to oxidize hydroquinone. The cathode material, Pt/MWCNTs, was obtained by an electrodeposition method, and shows great oxygen reduction reaction (ORR) activity. The properties and the morphology of Ni(OH)2/MWCNT nanocomposites were characterized by TEM, XPS, EDS-mapping and electrochemical methods, like cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results show that Ni(OH)2/MWCNTs can effectively oxidize hydroquinone and play a dominant role in enhancing the fuel cell performance. The nonenzymatic fuel cell possesses a high power density of 0.24 mW cm-2 at a cell potential of 0.49 V.

Magnesium and nitrogen co-doped carbon dots as fluorescent probes for quenchometric determination of paraoxon using pralidoxime as a linker.

Carbon dots codoped with magnesium and nitrogen (Mg,N-CDs) were synthesized via a one-step microwave-assisted method. They display blue fluorescence (with excitation/emission peaks at 380/460 nm and a 33% quantum yield) and possess high dispersity in aqueous solution. The fluorescence of the Mg,N-CDs is highly sensitive to paraoxon in the presence of pralidoxime (PAM) acting as the linking agent. Electron transfer from Mg,N-CDs to paraoxon in the presence of PAM leads to the fluorescence quenching of Mg,N-CDs. The concentration of paraoxon is determined by measuring the quenching efficiency of the Mg,N-CD-PAM assay system. Fluorescence drops with increasing concentrations of paraoxon in the 0.005-3.0 µM range, and the limit of detection is 0.87 nM. The method is highly selective for paraoxon even in the presence of possible interferences. Real sample study of tap and river water showed the assay to have good repeatability and accuracy. Graphical abstract Schematic diagram of magnesium and nitrogen co-doped carbon dots (Mg,N-CDs) as a fluorescent probe for paraoxon detection by using pralidoxime as a linker.

Synthesis and biological evaluation of memantine nitrates as a potential treatment for neurodegenerative diseases.

A series of memantine nitrate derivatives, as dual functional compounds with neuroprotective and vasodilatory activity for neurodegenerative diseases, was designed and synthesized. These compounds combined the memantine skeleton and a nitrate moiety, and thus inhibited the N-methyl-d-aspartic acid receptor and released NO in the central nervous system. The biological evaluation results revealed that the new memantine nitrates were effective in protecting neurons against glutamate-induced injury in vitro. Moreover, memantine nitrates dilated aortic rings against phenylephrine-induced contraction. The structure-activity relationships of neuroprotection and vasodilation were both analyzed. In further studies, compound MN-05 significantly protected cortical neurons by inhibiting Ca2+ influx, reducing free radical production and maintaining the mitochondrial membrane potential. Further research on MN-05 is warranted.

Preparation, Characterization and Intracellular Imaging of 2,4-Dichlorophenoxyacetic Acid Conjugated Gold Nanorods.

Visualizing the biodistribution of pesticides inside living cells is great importance for enhancing targeting of pesticides. Here we reported for the first time that gold nanorods (Au NRs) with size of 39.4 nm x 11.3 nm could be used as a fluorescent tracer to examine the distribution of a typical herbicide, 2,4-dichlorophenoxyacetic acid (2,4-D), in tobacco bright yellow 2 (BY-2) cells. The nanostructures of hybrid materials were analyzed by using Raman spectra and X-ray photoelectron spectroscopy (XPS), including spectra assignments and electronic property. These data revealed 2,4-D has successfully conjugated MP-Au NRs according to Raman and XPS. The biodistribution of the conjugates inside BY-2 cells was directly examined at 12 and 24 h by the two-photon microscopy. The intensity of two-photon luminescence (TPL) inside cells demonstrated that the conjugates could be localized and excluded by BY-2 cells. Thus, this labeling approach opens up new avenues to the facile and efficient labeling of pesticides.

Magnetic colorimetric immunoassay for human interleukin-6 based on the oxidase activity of ceria spheres.

A novel magnetic colorimetric immunoassay strategy was designed for sensitive detection of human interleukin-6 (IL-6) using ceria spheres as labels. Ceria spheres showed excellent oxidase activity, which can directly catalyze the oxidation of substrate o-phenylenediamine (OPD) to a stable yellow product, 2,3-diaminophenazine (oxOPD). The absorbance of oxOPD was recorded to reflect the level of IL-6. The relatively mild conditions made the immunoassay strategy more robust, reliable, and easy. A linear relationship between absorbance intensity and the logarithm of IL-6 concentrations was obtained in the range of 0.0001-10 ng mL(-1) with a detection limit of 0.04 pg mL(-1) (S/N = 3). The colorimetric immunoassay exhibited high sensitivity and specificity for the detection of IL-6. This immunoassay has been successfully applied in the detection of IL-6 in serum samples and can be readily extended toward the on-site monitoring of cancer biomarkers in serum samples.

Single-ion-magnet behavior in a two-dimensional coordination polymer constructed from Co(II) nodes and a pyridylhydrazone derivative.

A novel two-dimensional (2D) coordination polymer, [Co(ppad)2]n (1), resulted from the assembly of Co(II) ions based on a versatile ligand termed N(3)-(3-pyridoyl)-3-pyridinecarboxamidrazone. Alternating/direct-current magnetic studies of compound 1 indicate that the spatially separated high-spin Co(II) ions act as single-ion magnets (SIMs). The present work represents the first case of a 2D Co(II)-based SIM composed of a monocomponent organic spacer.

Gene expression profile change and growth inhibition in Drosophila larvae treated with azadirachtin.

Azadirachtin is a botanical insecticide that affects various biological processes. The effects of azadirachtin on the digital gene expression profile and growth inhibition in Drosophila larvae have not been investigated. In this study, we applied high-throughput sequencing technology to detect the differentially expressed genes of Drosophila larvae regulated by azadirachtin. A total of 15,322 genes were detected, and 28 genes were found to be significantly regulated by azadirachtin. Biological process and pathway analysis showed that azadirachtin affected starch and sucrose metabolism, defense response, signal transduction, instar larval or pupal development, and chemosensory behavior processes. The genes regulated by azadirachtin were mainly enriched in starch and sucrose metabolism. This study provided a general digital gene expression profile of dysregulated genes in response to azadirachtin and showed that azadirachtin provoked potent growth inhibitory effects in Drosophila larvae by regulating the genes of cuticular protein, amylase, and odorant-binding protein. Finally, we propose a potential mechanism underlying the dysregulation of the insulin/insulin-like growth factor signaling pathway by azadirachtin.

2,4-Dichlorophenoxyacetic acid functionalized gold nanoparticles: synthesis, characterization and biological effects.

Understanding and visualizing the biodistribution of agricultural chemicals inside cells and living plants is very important for enhancing targeting and changing the application approaches of chemicals. Here, a novel material was synthesized through 2,4-dichlorophenoxyacetic acid functionalized small gold nanoparticles (2,4-D-MP-Au NPs). The successful modification of Au NPs (4.46 ± 0.70 nm) was ascertained by UV-vis, TEM, FTIR and XPS. TGA data revealed about 1197 molecules of 2,4-D were coupled to the surface of one Au nanoparticle, which was sufficient for bioapplications. The optical imaging of 2,4-D-MP-Au NPs inside BY-2 cells was directly examined, revealing that 2,4-D-MP-Au NPs could be internalized in BY-2 cells by the two-photo microscopy and endocytosis, as the internalization mechanism was energy dependent for 2,4-D-MP-Au NPs. Furthermore, the biodistribution of 2,4-D-MP-Au NPs in Ricinus cotyledons was measured, revealing that 2,4-D-MP-Au NPs could enter into mesophyll cells of Ricinus cotyledons; the cell recognition was enhanced after 2,4-D conjugated Au NPs. These results indicate that the conjugates have great potential for applications on bioimaging and biolabeling for agricultural chemicals in plant physiology.

Ionic liquid-assisted preparation of laccase-based biocathodes with improved biocompatibility.

Laccase enzyme has been widely used as the catalyst of the biocathodes in enzymatic biofuel cells (BFCs); the poor biocompatibility of this enzyme (e.g., poor catalytic activity in neutral media and low tolerance against chloride ion) and the lack of selectivity for oxygen reduction at the laccase-based biocathode against ascorbic acid, unfortunately, offer a great limitation to future biological applications of laccase-based BFCs. This study demonstrates a facial yet effective solution to these limitations with the assistance of hydrophobic room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (Bmim(+)PF(6)(-)). With the Bmim(+)PF(6)(-) overcoating, the laccase-based biocathodes possess a good bioelectrocatalytic activity toward O(2) reduction in neutral media and a high tolerance against Cl(-). Moreover, the Bmim(+)PF(6)(-) overcoating applied to the laccase-based biocathodes also well suppresses the oxidation of ascorbic acid (AA) at the biocathodes and thereby avoids the AA-induced decrease in the power output of the laccase-based BFCs. The mechanisms underlying the excellent properties of the Bmim(+)PF(6)(-) overcoating are proposed based on the intrinsic features of ionic liquid Bmim(+)PF(6)(-). To demonstrate the applications of the BFCs with the as-prepared biocathodes in biologically relevant systems, an AA/O(2) BFC is assembled with single-walled carbon nanotubes (SWNTs) as electrode materials both for accelerating AA oxidation at the bioanode and for promoting direct electron transfer of laccase at the biocathode. With the presence of 0.50 mM AA in 0.10 M quiescent phosphate buffer (pH 7.2), the assembled BFC has an open circuit voltage of 0.73 V and a maximum power output of 24 µW cm(-2) at 0.40 V under ambient air and room temperature. This study essentially offers a new strategy for the development of enzymatic BFCs with a high biocompatibility.

[Study on molecular spectrum of fried linseed oil].

In order to ensure security of fried food and find out regularity of frying oil, the change of linseed oil fried in different time was investigated by three dimensional fluorescence and UV. The experiment results showed that the property of fried oil has not changed obviously in first two hours, but with the prolongation of frying time, the fluorescence spectra and UV spectra of fried linseed oil changed immensely after frying for six hours, which indicates that more harmful substances were produced after linseed oil was fried more than six hours.

Sensitive and selective DNA detection based on the combination of hairpin-type probe with endonuclease/GNP signal amplification using quartz-crystal-microbalance transduction.

In order to develop a highly sensitive and selective piezoelectric transducer for the detection of DNA, the bio-recognizing probe is for the first time designed by introducing a hairpin structure and a recognition site for EcoRI into an oligonucleotide sequence and signal amplifiers are prepared by modifying gold nanoparticles (GNPs) with biomolecules, deepening the application and understanding of biomaterials. The piezoelectric transducer is prepared by immobilizing designed hairpin recognition probe onto the quartz-crystal-microbalance (QCM). In the absence of target DNA, the hairpin probe is removed from the QCM surface after exposure to endonuclease, inhibiting the subsequent signaling reaction. In contrast, introduction of target DNA can open the hairpin probe due to the probe/target hybridization, dissociating the cleavable double-stranded portion. In this case, even if being treated with endonuclease, the integrated hairpin probe is maintained. Subsequent introduction of GNPs modified with detection probes that can hybridize to the terminal sequence of hairpin probe results in a many-folds increase of the frequency response. Utilizing the proposed transduction scheme, the reliable target DNA detection can be accomplished. The detection limit of 2 pM and dynamic response range for target DNA from 2 to 300 pM are obtained. Furthermore, single-base mismatched DNAs can be easily identified. The developed proof-of-principle of a novel piezoelectric transduction scheme is expected to establish a potential platform for the disease-associated mutation analysis and DNA hybridization detection in biotechnology and medical diagnostics.

[Quality research on Epimedium cut crude drug processed with oil].

OBJECTIVE: To study internal quality of 14 batches Epimedium cut crude drug processed with oil, and to provide informations for quality specification in Chinese Pharmacopeia of 2010 edition. METHODS: 14 batches Epimedium cut crude drug processed with oil were investigated impurity, moisture content, total ash, acid-insoluble ash, extractum and assaying to analyze and evaluate their quality condition. RESULTS: It is suggested that, in Epimedium cut crude drug processed with oil, the moisture content should not pass 8.0%, total ash should not pass 8.0%, acid-insoluble ash should not pass 2.0%, extractum content should not lower than 12.0%, total flavonoids content should not lower than 5.0%, icariin content should not lower than 0.6%, and Baohuoside I content should not lower than 0.1%. CONCLUSION: Quality evaluation system of Epimedium cut crude drug processed with oil has been constructed initially, it will offer scientific basis for instituting quality specification in Chinese Pharmacopeia of 2010 edition.

An electrochemical molecular switch for one-step, reusable detection of a single-base mutation of DNA.

A new strategy for one-step, reusable and sensitive detection of a single-base mutation based on an electrochemical molecular switch is developed in the present work. When the hybridization reaction takes place in the presence of target DNA, the Fc-labeled terminal of the open switch molecule can be captured by the probe through the predesigned complementary bases of both sequences. By this method, a signal-on sensor featuring both generalizability and simplicity towards reagentless detection of DNA with sensitivity and selectivity electrochemical system is built on. The approach had been demonstrated with the identification of a single-base mutation of alpha-thalassemia point mutation in Hb Constant Spring codon 142 (TAA --> CAA). The wild-type and mutant-type of the synthetic 16 mer DNA sequences as the model targets were successfully discriminated. The results showed that the response signal was linear to the logarithm of the target concentration in the range from 0.01 to 100 pM with a detection limit of 0.01 pM. The regeneration experiment demonstrated that the sensor interface can be easily and successfully regenerated. All these revealed that the present system is a promising candidate for single-base mutation discrimination.

An ultrasensitive electrochemical "turn-on" label-free biosensor for Hg2+with AuNP-functionalized reporter DNA as a signal amplifier.

A highly selective electrochemical biosensor for the ultrasensitive detection of Hg2+ in aqueous solution has been developed based on the strong and specific binding of Hg2+ by two DNA thymine bases (T-Hg2+-T) and the use of AuNP-functionalized reporter DNA to achieve signal amplification.

Biocatalyzed deposition amplification for detection of aflatoxin B1 based on quartz crystal microbalance.

An ultrasensitive piezoelectric method for the detection of the aflatoxin B1 (AFB1) based on the indirect competitive immunoassay and the biocatalyzed deposition amplification has been developed. In this method, the quartz crystal surface was coated with a self-assembled monolayer of 3-mercaptopropionic acid (MPA) for covalently immobilization of the BSA-AFB1 conjugate, which could compete with the free AFB1 for binding to the anti-AFB1 antibody (MsIgG). After the competitive immunoreaction, the horseradish peroxidase (HRP) labeled goat anti-mouse IgG (G-Anti-MsIgG) was introduced into the detection cell to combine with the anti-AFB1 antibody on the crystal surface. The enzyme labeled G-Anti-MsIgG as a biocatalyst could accelerate the oxidation of 4-chloro-1-naphthol by H2O2 to yield the insoluble product benzo-4-chlorohexadienone on the surface of quartz crystal microbalance (QCM), resulting in a mass increase that was reflected by a decrease in the resonance frequency of the QCM. The proposed approach could allow for the determination of AFB(1) in the concentration range of 0.01-10.0 ng mL(-1). Furthermore, several artificially contaminated milk samples were analyzed with good recoveries obtained, which demonstrated the suitability of the proposed method for detecting AFB1.

Ultrasensitive electrochemical immunosensor for ochratoxin A using gold colloid-mediated hapten immobilization.

A convenient, specific, and highly sensitive electrochemical immunosensor based on an indirect competitive assay format was developed for the determination of ochratoxin A (OTA), a common toxic contaminant in various kinds of agricultural products. The sensing substrate was prepared using a gold electrode modified with a self-assembled monolayer of 1,6-hexanedithiol that mediated the assembly of a gold colloid layer, which could enhance the surface loading of OTA-ovalbumin conjugate and improve the sensitivity in electrochemical readouts. After competition of the limited anti-OTA mouse monoclonal antibody between immobilized hapten and OTA analyte in sample solution, alkaline phosphatase (ALP)-labeled horse anti-mouse immunoglobulin G (IgG) antibody was selectively bound onto the surface of the electrode, affording an indicator for OTA concentration in the sample. Electrochemical response arising from the oxidation of enzymatic product of 1-naphthyl phosphate was observed to be inversely proportional to OTA concentration in the range from 10 pg/ml to 100 ng/ml with a detection limit as low as 8.2 pg/ml. Furthermore, a negligible matrix effect and good recoveries were obtained in the determination of corn samples, evidencing the feasibility of the proposed method for accurate determination of OTA in corn samples.