Controllable construction of ZIF-derived Co9S8 hollow polyporous polyhedrons with Ru-doping for enhanced hydrogen evolution reaction.

Ru-doped Co9S8 hollow porous polyhedrons (Ru-Co9S8 HPPs) derived from zeolitic-imidazolate-frameworks were synthesized through hydrothermal coprecipitation and thermal decomposition methods. The results indicate that Ru-Co9S8-500 HPPs possess a strong Ru-Co synergistic effect, large electrochemical surface area, and sufficient active sites, endowing them with excellent hydrogen evolution reaction performance.

Recent advances in nanomaterial-based electrochemical and optical sensing platforms for microRNA assays.

MicroRNA (MiRNA) plays a crucial role in biological cells to enable assessment of a cancer's development stage. Increasing evidence has shown that the accurate and sensitive detection of miRNA holds the key toward correct disease diagnosis. However, some characteristics of miRNAs, such as their short chains, low concentration, and similar sequences, make it difficult to detect miRNA in biological samples. Nanomaterials usually have good optical, electronic, and mechanical properties and therefore provide new possibilities for improving the performance of miRNA assays. Many different sorts of nanomaterials, including metal nanomaterials, carbon nanomaterials, quantum dots, and transition-metal dichalcogenides, have been used to construct optical and electrochemical assays for miRNA and have shown attractive results. This review describes recent efforts in the application of nanomaterials as sensing elements in electrochemical and optical miRNA assays. The analytical figures of merit of various methods for the detection of miRNA are compared in the present article. The current capabilities, limitations, and future challenges in miRNA detection and analysis based on nanomaterials are also addressed.

Electrochemical biosensor based on Se-doped MWCNTs-graphene and Y-shaped DNA-aided target-triggered amplification strategy.

A highly sensitive electrochemical biosensor for detection of platelet-derived growth factor-BB (PDGF-BB) is developed by using Se-doped multi-walled carbon nanotubes (MWCNTs)-graphene hybrids as electrode supporting substrate, hemin/G-quadruplex as trace labels and Y-shaped DNA-aided target recycling as signal magnifier. The aptamer-containing hairpin probes were first immobilized on the electrode. When target PDGF-BB was added, the aptamer binded PDGF-BB to trigger catalytic assembly of two other hairpins to form many G-quadruplex Y-junction DNA structures, which released PDGF-BB to again bind the intact aptamer to initiate another assembly cycle. G-quadruplex/hemin complexes were produced when hemin was added to generate substantially amplified current output. The developed assay showed a linear range toward PDGF-BB from 0.1 pM to 10 nM with a detection limit of 27 fM (S/N = 3). The method showed excellent specificity and repeatability, and could be expediently applied for sensitive detection of other molecules by simply changing the aptamers.

Recent advances in signal amplification strategy based on oligonucleotide and nanomaterials for microRNA detection-a review.

MicroRNAs (MiRNAs) play multiple crucial regulating roles in cell which can regulate one third of protein-coding genes. MiRNAs participate in the developmental and physiological processes of human body, while their aberrant adjustment will be more likely to trigger diseases such as cancers, kidney disease, central nervous system diseases, cardiovascular diseases, diabetes, viral infections and so on. What's worse, for the detection of miRNAs, their small size, high sequence similarity, low abundance and difficult extraction from cells impose great challenges in the analysis. Hence, it's necessary to fabricate accurate and sensitive biosensing platform for miRNAs detection. Up to now, researchers have developed many signal-amplification strategies for miRNAs detection, including hybridization chain reaction, nuclease amplification, rolling circle amplification, catalyzed hairpin assembly amplification and nanomaterials based amplification. These methods are typical, feasible and frequently used. In this review, we retrospect recent advances in signal amplification strategies for detecting miRNAs and point out the pros and cons of them. Furthermore, further prospects and promising developments of the signal-amplification strategies for detecting miRNAs are proposed.

Tetrahedral DNA probe coupling with hybridization chain reaction for competitive thrombin aptasensor.

A novel competitive aptasensor for thrombin detection is developed by using a tetrahedral DNA (T-DNA) probe and hybridization chain reaction (HCR) signal amplification. Sulfur and nitrogen co-doped reduced graphene oxide (SN-rGO) is firstly prepared by a simple reflux method and used for supporting substrate of biosensor. Then, T-DNA probe is modified on the electrode by Au-S bond and a competition is happened between target thrombin and the complementary DNA (cDNA) of aptamer. The aptamer binding to thrombin forms an aptamer-target conjugate and make the cDNA remained, and subsequently hybridizes with the vertical domain of T-DNA. Finally, the cDNAs trigger HCR, which results in a great current response by the catalysis of horseradish peroxidase to the hydrogen peroxide + hydroquinone system. For thrombin detection, the proposed biosensor shows a wide linearity range of 10-13-10-8M and a low detection limit of 11.6fM (S/N = 3), which is hopeful to apply in biotechnology and clinical diagnosis.

An electrochemical microRNA sensing platform based on tungsten diselenide nanosheets and competitive RNA-RNA hybridization.

In this work, we report an ultrasensitive electrochemical biosensor for microRNA-21 (miRNA-21) detection by using a competitive RNA-RNA hybridization configuration. A biotinylated miRNA of the self-same sequence with the target miRNA is mixed with the samples, and allowed competition with the target miRNA for a thiolated RNA probe immobilized onto a tungsten diselenide (WSe2) nanosheet modified electrode. Thereafter the current response is obtained by forming the hybridized biotinylated miRNA with streptavidin-horseradish peroxidase (HRP) conjugates to catalyze the H2O2 + hydroquinone (HQ) system. Benefiting from the high specific surface area of WSe2 nanosheets, the competitive hybridization configuration and the signal amplification of the H2O2 + HQ detection system, the proposed assay exhibits a wide linear range of 0.0001-100 pM towards target miRNA with a detection limit of 0.06 fM (S/N = 3), and shows excellent discrimination ability for base-mismatched miRNA sequences. Therefore, the designed platform has promising prospects for the detection of miRNA in biomedical research and early clinical diagnosis.

Ultrasensitive electrochemical sensing platform based on graphene wrapping SnO2 nanocorals and autonomous cascade DNA duplication strategy.

In this work, a sensitive, universal and reusable electrochemical biosensor based on stannic oxide nanocorals-graphene hybrids (SnO2 NCs-Gr) is developed for target DNA detection by using two kinds of DNA enzymes for signal amplification through an autonomous cascade DNA duplication strategy. A hairpin probe is designed composing of a projecting part at the 3'-end as identification sequence for target, a recognition site for nicking endonuclease, and an 18-carbon shim to stop polymerization process. The designed DNA duplication-incision-replacement process is handled by KF polymerase and endonuclease, then combining with gold nanoparticles as signal carrier for further signal amplification. In the detection system, the electrochemical-chemical-chemical procedure, which uses ferrocene methanol, tris(2-carboxyethyl)phosphine and l-ascorbic acid 2-phosphate as oxidoreduction neurogen, deoxidizer and zymolyte, separately, is applied to amplify detection signal. Benefiting from the multiple signal amplification mechanism, the proposed sensor reveals a good linear connection between the peak current and logarithm of analyte concentration in range of 0.0001-1 × 10-11molL-1 with a detection limit of 1.25 × 10-17molL-1 (S/N=3). This assay also opens one promising strategy for ultrasensitive determination of other biological molecules for bioanalysis and biomedicine diagnostics.

Au nanoparticles/hollow molybdenum disulfide microcubes based biosensor for microRNA-21 detection coupled with duplex-specific nuclease and enzyme signal amplification.

An ultrasensitive electrochemical biosensor for detecting microRNAs is fabricated based on hollow molybdenum disulfide (MoS2) microcubes. Duplex-specific nuclease, enzyme and electrochemical-chemical-chemical redox cycling are used for signal amplification. Hollow MoS2 microcubes constructed by ultrathin nanosheets are synthesized by a facile template-assisted strategy and used as supporting substrate. For biosensor assembling, biotinylated ssDNA capture probes are first immobilized on Au nanoparticles (AuNPs)/MoS2 modified electrode in order to combine with streptavidin-conjugated alkaline phosphatase (SA-ALP). When capture probes hybridize with miRNAs, duplex-specific nuclease cleaves the formative duplexes. At the moment, the biotin group strips from the electrode surface and SA-ALP is incapacitated to attach onto electrode. Then, ascorbic acids induce the electrochemical-chemical-chemical redox cycling to produce electrochemical response in the presence of ferrocene methanol and tris (2-carboxyethyl) phosphine. Under optimum conditions, the proposed biosensor shows a good linear relationship between the current variation and logarithm of the microRNAs concentration ranging from 0.1fM to 0.1pM with a detection limit of 0.086fM (S/N=3). Furthermore, the biosensor is successfully applied to detect target miRNA-21 in human serum samples.

Ultrasensitive electrochemical sensing platform for microRNA based on tungsten oxide-graphene composites coupling with catalyzed hairpin assembly target recycling and enzyme signal amplification.

An ultrasensitive electrochemical biosensor for microRNA (miRNA) is developed based on tungsten oxide-graphene composites coupling with catalyzed hairpin assembly target recycling and enzyme signal amplification. WO3-Gr is prepared by a simple hydrothermal method and then coupled with gold nanoparticles to act as a sensing platform. The thiol-terminated capture probe H1 is immobilized on electrode through Au-S interaction. In the presence of target miRNA, H1 opens its hairpin structure by hybridization with target miRNA. This hybridization can be displaced from the structure by another stable biotinylated hairpin DNA (H2), and target miRNA is released back to the sample solution for next cycle. Thus, a large amount of H1-H2 duplex is produced after the cyclic process. At this point, a lot of signal indicators streptavidin-conjugated alkaline phosphatase (SA-ALP) are immobilized on the electrode by the specific binding of avidin-biotin. Then, thousands of ascorbic acid, which is the enzymatic product of ALP, induces the electrochemical-chemical-chemical redox cycling to produce a strongly electrochemical response in the presence of ferrocene methanol and tris (2-carboxyethyl) phosphine. Under the optimal experimental conditions, the established biosensor can detect target miRNA down to 0.05fM (S/N=3) with a linear range from 0.1fM to 100pM, and discriminate target miRNA from mismatched miRNA with a high selectivity.

A layered tungsten disulfide/acetylene black composite based DNA biosensing platform coupled with hybridization chain reaction for signal amplification.

A 2-dimensional tungsten disulfide-acetylene black (WS2-AB) composite is synthesized by a simple hydrothermal method to achieve excellent electrochemical properties for applications as a DNA biosensor. The biosensor is fabricated based on the Au nanoparticles (AuNPs) and WS2-AB composite modified electrode, which subsequently is used to couple with a capture probe by an Au-S bond, then modified with target DNA, auxiliary DNA and bio-H1-bio-H2 (H1-H2) to perform hybridization chain reaction for signal amplification. Herein, two DNA hairpins H1 and H2 are opened by the recognition probe. The nicked double helices from hybridization chain reaction are used to immobilize horseradish peroxidase enzymes via biotin-avidin reaction, which produces signal-amplification detection of target DNA through the catalytic reaction of the hydrogenperoxide + hydroquinone system. Under optimum conditions, the as-prepared biosensor shows a good linear relationship between the current value and logarithm of the target DNA concentration ranging from 0.001 pM to 100 pM and a detection limit as low as 0.12 fM. Moreover, the fabricated biosensor exhibits good selectivity to differentiate the one-base mismatched DNA sequence. This work will open a pathway for ultrasensitive detection of other biorecognition events and gene-related diseases based on layered WS2-AB and hybridization chain reaction.

[Lead adsorption by the root cell wall of tea plant].

A research was done to study the Pb adsorption by the root cell wall of tea plant extracted from Longjing 43. It was indicated that the amount of Pb adsorbed by the root cell wall increased with augment of the initial pH of the solution under acidic condition, dramatically as the pH ranged from 2.0 to 4.5. The amount of Pb increased with the Pb concentration in the solution at pH 4.5, which could be well fitted by the Freundlich adsorption model. The adsorbed Pb reached 9.7 mg x g(-1) under equilibrium condition, 90% of which was adsorbed in 320 minutes, while 50% was desorbed in 60 minutes based on the desorption dynamic curve. The kinetics of both adsorption and desorption could be well described by a second-order rate equation. The amount of absorbed Pb by the root cell wall varied after modified treatments, reducing by 51.1% after esterifing, 41.3% with pectinase, and 10.8% via aminomethylation, suggesting that carboxyl, galacturonic acid, pectin and amino, to some extent, all took part in the Pb adsorption by the root cell wall.

[Effect of pilot UASB-SFSBR-MAP process for the large scale swine wastewater treatment].

In this paper, a treatment process consisted of UASB, step-fed sequencing batch reactor (SFSBR) and magnesium ammonium phosphate precipitation reactor (MAP) was built to treat the large scale swine wastewater, which aimed at overcoming drawbacks of conventional anaerobic-aerobic treatment process and SBR treatment process, such as the low denitrification efficiency, high operating costs and high nutrient losses and so on. Based on the treatment process, a pilot engineering was constructed. It was concluded from the experiment results that the removal efficiency of COD, NH4(+) -N and TP reached 95.1%, 92.7% and 88.8%, the recovery rate of NH4(+) -N and TP by MAP process reached 23.9% and 83.8%, the effluent quality was superior to the discharge standard of pollutants for livestock and poultry breeding (GB 18596-2001), mass concentration of COD, TN, NH4(+) -N, TP and SS were not higher than 135, 116, 43, 7.3 and 50 mg x L(-1) respectively. The process developed was reliable, kept self-balance of carbon source and alkalinity, reached high nutrient recovery efficiency. And the operating cost was equal to that of the traditional anaerobic-aerobic treatment process. So the treatment process could provide a high value of application and dissemination and be fit for the treatment pf the large scale swine wastewater in China.

[Thermophiles and their working mechanisms in degrading excess sludge: a review].

Activated sludge process is widely used in treating a wide variety of wastewater, but the by-product is the large amount of excess sludge. To treat the excess sludge properly could spend 25%-60% of the total cost of wastewater treatment, while improperly treating the sludge could cause serious secondary pollution. Therefore, the reduction of excess sludge is becoming a rising challenge. Using thermophiles to degrade excess sludge is a way easy in operation and inexpensive in maintenance, being a promising method in application. This paper reviewed the recent progress in the researches of sludge-degrading thermophiles, their working mechanisms, and the enzymes from thermophiles, such as thermophilic proteolytic enzymes and thermophilic lipases which play an important role in the degradation of sludge. The factors affecting the degradation of sludge by thermophiles were summarized, and the perspectives for the further research on the application of thermophiles in digesting sludge were discussed.

Improving Anammox start-up with bamboo charcoal.

Three Upflow Anaerobic Sludge Blanket (UASB) reactors were compared for Anammox enrichment using synthetic wastewater with Spherical Plastic (SP) and Bamboo Charcoal (BC) addition, and without carrier (CK). After four months of operation, the Anammox activity occurred in all reactors allowing continuous removal of ammonium and nitrite. Ammonium and nitrite removal efficiencies were all higher than 98% in steady phase with the effluent concentrations below 1 mg L(-1). The start-up time could be shortened from 117 to 97 d in CK and SP reactor to 85 d in BC amendment reactor. Quantitative PCR (q-PCR) analyses indicated a significant increase in the number of Anammox bacteria in BC amended reactor as compared with CK and SP during the entire start-up periods. The copy numbers of Anammox of 16S rRNA gene in the reactor with BC amendment could reach up to 6×10(9)copies g(-1) Volatile Suspended Solids, around 22.5 times and 12.3 times greater than that in CK and SP reactor, respectively. BC addition could accelerate the start-up of Anammox and significantly increase the Anammox bacteria number.

[Research progress in anammox-denitrification coupling process].

Anammox (anaerobic ammonium oxidation) is an important process of nitrogen cycle, with great potential for the practical use in removing nitrogen from the wastewater containing high concentration ammonium. However, the presence of high concentration organic carbon source is considered unfavorable to anammox. Coupling anammox and denitrification under the presence of organic carbon source could be a useful technique for removing both nitrogen and carbon. This paper reviewed the mechanisms of anammox-denitrification coupling process, functional microbial groups, initiation of the coupling process and its control, and related environmental affecting factors. The future research prospects and potential applications of anammox-denitrification coupling process in wastewater treatment were discussed.

Optimization of struvite crystallization protocol for pretreating the swine wastewater and its impact on subsequent anaerobic biodegradation of pollutants.

Higher contents of NH(4)(+) and SS in wastewater hamper the anaerobic digestion; necessitating its pretreatment to reduce them. This study reveals optimization of struvite/MAP precipitation protocol followed by anaerobic digestion of pretreated swine wastewater for pollutants removal. Levels of different treatments: stirring speeds, 400 and 160 rpm; pH values, 9.0, 9.5, 10.0, 10.5, 11.0 and 11.5; and P:Mg:N ratios, 1:1:1.2, 1:1:1.7, 1:1:2.2, 1:1:2.7, 1:1:4.0 and 1:1:5.0 were evaluated for MAP crystallization. Among various combinations, protocol comprising of initial 10 min stirring at 400 rpm followed by 160 rpm for 30 min, pH 10.0, and P:Mg:N ratio 1:1:1.2 rendered the best removal efficiency for NH(4)(+), PO(4)(3-), COD, TC and TOC. Subsequent anaerobic biodegradation revealed superiority of MAP supernatant over raw swine wastewater for methane yield and NH(4)(+)-N, PO(4)(3-)-P, COD, TC and TOC removals. It suggests that struvite precipitation as pretreatment to anaerobic digestion is highly effective and advantageous in wastewater treatment.

Fertilization increases paddy soil organic carbon density.

Field experiments provide an opportunity to study the effects of fertilization on soil organic carbon (SOC) sequestration. We sampled soils from a long-term (25 years) paddy experiment in subtropical China. The experiment included eight treatments: (1) check, (2) PK, (3) NP, (4) NK, (5) NPK, (6) 7F:3M (N, P, K inorganic fertilizers+30% organic N), (7) 5F:5M (N, P, K inorganic fertilizers+50% organic N), (8) 3F:7M (N, P, K inorganic fertilizers+70% organic N). Fertilization increased SOC content in the plow layers compared to the non-fertilized check treatment. The SOC density in the top 100 cm of soil ranged from 73.12 to 91.36 Mg/ha. The SOC densities of all fertilizer treatments were greater than that of the check. Those treatments that combined inorganic fertilizers and organic amendments had greater SOC densities than those receiving only inorganic fertilizers. The SOC density was closely correlated to the sum of the soil carbon converted from organic amendments and rice residues. Carbon sequestration in paddy soils could be achieved by balanced and combined fertilization. Fertilization combining both inorganic fertilizers and organic amendments is an effective sustainable practice to sequestrate SOC.

[Biodegradation of organic pollutants by thermophiles and their applications: a review].

Persistent organic pollutants have increasingly become a critical environmental concern, while thermophiles have the high potential of degrading various kinds of environmental organic pollutants. At high temperatures, thermophiles have higher metabolic activity, and the competition by mesophiles is reduced, meanwhile, the solubility and bioavailability of some persistent organic pollutants are greatly increased, and thus, the degradation of the pollutants by thermophiles is more rapid and complete. Therefore, thermophils are of great significance for the bio-treatment of organic wastewater and the bioremediation of organic pollutants-contaminated sites. This paper introduced the research progress on the degradation of organic pollutants by thermophiles in terms of the characteristics of thermophiles in degrading organic pollutants, the effects of temperature on the degradation, the degradation pathways, the degradation enzymes, their coding genes, and practical engineering applications. The future research directions including the degradation mechanisms of thermophiles, their resources reserve, related technology strategies and their applications were also prospected.

[Research advances in microbial dechlorination of polychlorinated biphenyls].

Polychlorinated biphenyls (PCBs) are the typical persistent organic pollutants (POPs) in the environment. As a ubiquitous attenuation course of chlorinated organic compounds in anoxic environment, the microorganism-mediated reductive dechlorination process plays an important role in PCBs transformation, especially the transformation of higher chlorinated PCBs. The higher chlorinated PCBs can be dechlorinated in anaerobic condition, and thus, their persistence and toxicity can be decreased. The resultant lower chlorinated PCBs from the dechlorination can be further degraded and completely mineralized in aerobic condition. This paper summarized the research advances of PCBs microbial reductive dechlorination, introduced the mechanisms and characteristics of the dechlorination and the related specific microorganisms, and approached the affecting factors of PCBs bio-dechlorination, as well as the significances of anaerobic dechlorination coupling with aerobic degradation. The future research directions, including the complex metabolic networks of dechlorinating microbial populations, the screening of novel specific dechlorinators and their practical applications in the remediation of PCBs contaminated sites were also prospected.

[Applications of soil metaproteomics in soil pollution assessment: a review].

Soil microbial indicator is one of the important biological indicators in evaluating the extent of soil contamination. In recent years, with the development of molecular biology, many studies have focused on the ecological functions of soil microorganisms by using metagenomics, metatranscriptome and metaproteomics. Relative to metagenomics and metatranscriptome, soil metaproteomics aims to investigate the spatial and temporal changes of the proteins extracted from soil as well as the functional components of soil microbial genomic expression products, which is more conclusive to explore the ecological functions of soil microbes and their roles in soil pollutants transportation and transformation. Therefore, soil metaproteomics has great potential in soil pollution assessment. Currently, soil metaproteomics is still at its infancy stage, while soil protein extraction method is one of the key factors restraining the potential application of soil metaproteomics. In this paper, the advantages and disadvantage of soil metaproteomics in soil pollution assessment were reviewed, with the focus on the comparison of different soil protein extraction methods. In combining with case studies, the feasibility and limits of soil proteins as an indicator for soil pollution assessment were analyzed. In addition, the future research perspectives on the development of soil metaproteomics were discussed.