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.

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.

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.

Enhancement of copper availability and microbial community changes in rice rhizospheres affected by sulfur.

The role of sulfur on the availability of Cu and the bacterial community in rice rhizospheres was investigated by pot experiments. With sulfur addition, pH in rhizosphere soil decreased and Mg(NO3)2 extractable Cu increased significantly. The bacterial community composition also changed with sulfur addition. Some specific clones having high similarity to Thiobacillus, which indicated that sulfur oxidation in the rice rhizosphere could increase the availability of Cu. These results suggested that sulfur source which could provide substrate to sulfur oxidizing bacteria and enhance the availability of Cu was not a suitable sulfur fertilizer for Cu polluted soil.

The pathway of in-situ ammonium removal from aerated municipal solid waste bioreactor: nitrification/denitrification or air stripping?

In-situ ammonium removal from municipal solid waste (MSW) landfill is an attractive method due to its economic advantages. In this study, two simulated MSW bioreactors with different degrees of initial bio-stabilization were utilized to investigate the effects of intermittent aeration mode and the addition of activated sludge on the removal of ammonium. The results showed that up to 90% of ammonium could be removed and the amount of NO(x)-N produced was less than 1% of NH4 (+)-N removed in both reactors. The pH values increased rapidly and finally arrived at a high level of 8.5-8.8. The efficiency of ammonium removal was improved by increasing the continuous aeration time, but it was not affected by the addition of activated sludge. A portion of liquid escaped from the reactors in the form of vapour, and as high as 195-258 mg L(-1) of NH(4) ( +)-N was detected in the vapour collector. According to calculation, nitrification was inhibited by the high level of free ammonia in the bioreactors. As a result, air stripping was enhanced and became the primary pathway of ammonium removal. Therefore, controlling free ammonia concentration was essential in ammonium removal from the aerated MSW bioreactor.

Use of 13C labeling to assess carbon partitioning in transgenic and nontransgenic (parental) rice and their rhizosphere soil microbial communities.

Photosynthetic assimilation of CO2 is a primary source of carbon in soil and root exudates and can influence the community dynamics of rhizosphere organisms. Thus, if carbon partitioning is affected in transgenic crops, rhizosphere microbial communities may also be affected. In this study, the temporal effects of gene transformation on carbon partitioning in rice and rhizosphere microbial communities were investigated under greenhouse conditions using the 13C pulse-chase labeling method and phospholipid fatty acid (PLFA) analysis. The 13C contents in leaves of transgenic (Bt) and nontransgenic (Ck) rice were significantly different at the seedling, booting and heading stages. There were no detectable differences in 13C distribution in rice roots and rhizosphere microorganisms at any point during rice development. Although a significantly lower amount of Gram-positive bacterial PLFAs and a higher amount of Gram-negative bacterial PLFAs were observed in Bt rice rhizosphere as compared with Ck at all plant development stages, there were no significant differences in the amount of individual 13C-PLFA between Bt and Ck rhizospheres at any growing stage. These findings indicate that the insertion of cry1Ab and marker genes into rice had no persistent or adverse effect on the photosynthate distribution in rice or the microbial community composition in its rhizosphere.

Struvite recovery from swine waste biogas digester effluent through a stainless steel device under constant pH conditions.

OBJECTIVE: To investigate the struvite precipitation under constant and non-constant pH conditions and to test a stainless steel device under different operating regimes to maximize the recovery of struvite. METHODS: The molar ratio of NH4+: Mg2+: PO4(3-) was adjusted to 1: 1.2: 1.2 and pH was elevated to 9.0. The absorbance measurement was used to trace the process of struvite crystallization. Wastewater and precipitate analysis was done by standard analytical methods. RESULTS: The pH constant experiment reported a significantly higher struvite precipitation (24.6 +/- 0.86 g) than the non-constant pH experiment (19.8 +/- 1.86 g). The SAR ranged from 5.6 to 8.2 g m(-2) h(-1) to 3.6-4.8 g m(-2) h(-1) in pH constant and non-constant experiments, respectively. The highest struvite deposit on the device was found in regime 3 followed by in regimes 2 and 4. The highest PO4(3-) (97.2%) and NH4+ (71%) removal was reported in the R1 regime. None of the influent Cu2+ or Zn2+ was precipitated on the device. CONCLUSION: A higher struvite yield is evident in pH constant experiments. Moreover, the stainless steel device facilitates the isolation of heavy metal free pure (around 96%) struvite from swine waste biogas digester effluent contaminated with cu2+ and Zn2+ and the highest yield is attainable with the device operating at 50 rpm with agitation by a magnetic stirrer.

Nitrogen loss through lateral seepage in near-trench paddy fields.

A near-trench paddy field experiment with five urea application rates (0-360 kg N ha(-1) in 90-kg increments) was conducted on a paddy soil in the Taihu Lake Region of China to elucidate N losses through lateral seepage during three rice (Oryza sativa L.) growing seasons. The total N (Nt), NH4(+) -N, and NO3(-) -N concentrations in the lateral seepage water increased with increasing N rates. The seasonal Nt fluxes by lateral seepage varied from 6.8 to 25.6 kg N ha(-1) for urea application rates of 90 to 360 kg N ha(-1). Lateral seepage accounted for 4.7 to 6.6% of the Nt applied, implying that lateral seepage was an important pathway of N loss from near-trench paddy fields. The cumulative N loss via lateral seepage was significantly related to N fertilization rate (P = 0.05). Floodwater level was also identified as a main factor affecting N losses via lateral seepage from paddy fields, as indicated by a positive linear relationship (R2 = 0.43) between floodwater level and daily lateral flow during the flooded period (P = 0.05). Under the conditions of these experiments, a shallow floodwater depth of 50 mm, urea application rates of 90 kg N ha(-1) or less, and no rainfall within 1 wk after N application reduced N losses by lateral seepage from paddy fields.

Effect of MSW source-classified collection on the emission of PCDDs/Fs and heavy metals from incineration in China.

Municipal solid waste (MSW) source-classified collection represents a change in MSW management in China and other developing countries. Comparative experiments were performed to evaluate the effect of a newly established MSW source-classified collection system on the emission of PCDDs/Fs (polychlorinated dibenzo-p-dioxins and dibenzofurans) and heavy metals (HMs) from a full-scale incinerator in China. As a result of presorting and dewatering, the chlorine level, heavy metal and water content were lower, but heat value was higher in the source-classified MSW (classified MSW) as compared with the conventionally mixed collected MSW (mixed MSW). The generation of PCDDs/Fs in flue gas from the classified MSW incineration was 9.28 ng I-TEQ/Nm(3), only 69.4% of that from the mixed MSW incineration, and the final emission of PCDDs/Fs was only 0.12 ng I-TEQ/Nm(3), although activated carbon injection was reduced by 20%. The level of PCDDs/Fs in fly ash from the bag filter was 0.27 ng I-TEQ/g. These results indicated that the source-classified collection with pretreatment could improve the characteristics of MSW for incineration, and significantly decrease formation of PCDDs/Fs in MSW incineration. Furthermore, distributions of HMs such as Cd, Pb, Cu, Zn, Cr, As, Ni, Hg in bottom ash and fly ash were investigated to assess the need for treatment of residual ash.

Heavy metals and PAHs in sewage sludge from twelve wastewater treatment plants in Zhejiang province.

OBJECTIVE: To investigate the heavy metals (HMs) and polycyclic aromatic hydrocarbons (PAHs) in sludge of twelve wastewater treatment plants (WWTPs) in Zhejiang province of China, and to assess their potential for land application. METHODS: Sludge was collected from 12 WWTPs within the province. GC-MS and AAS were used to measure PAHs and HMs contents in sludge. RESULTS: Concentrations of HMs in most of the sludge samples were below the regulatory limits for the sludge to be used in agriculture in China with the exception of Zn in 2 sludge samples and Cd in 1 sample. All 16 PAHs, targeted by the USEPA agency, were found in the sludge from the twelve plants with a total concentration ranging from 33.73 mg kg(-1) to 82.58 mg kg(-1) (dry weight, d.w.). The levels of Sigma9 PAHs varied from 13.87 mg kg(-1) to 61.86 mg kg(-1) (d.w.) in the sludge, far exceeding the limitation value recommended by the Europe Union. The concentration and composition of PAHs in sewage sludge varied and depended mainly on the quantity and type of industrial wastewater accepted by the WWTPs. A significant relationship between the proportion of industrial wastewater received by WWTPs and the total content of 16 PAHs in the sludge was observed. CONCLUSION: PAHs have become one of the primary pollutants in sludge of Zhejiang WWTPs instead of HMs. It is, therefore, essential to reduce the contents of PAHs before the sludge can be used in agriculture through proper treatment.

Source separation of household waste: a case study in China.

A pilot program concerning source separation of household waste was launched in Hangzhou, capital city of Zhejiang province, China. Detailed investigations on the composition and properties of household waste in the experimental communities revealed that high water content and high percentage of food waste are the main limiting factors in the recovery of recyclables, especially paper from household waste, and the main contributors to the high cost and low efficiency of waste disposal. On the basis of the investigation, a novel source separation method, according to which household waste was classified as food waste, dry waste and harmful waste, was proposed and performed in four selected communities. In addition, a corresponding household waste management system that involves all stakeholders, a recovery system and a mechanical dehydration system for food waste were constituted to promote source separation activity. Performances and the questionnaire survey results showed that the active support and investment of a real estate company and a community residential committee play important roles in enhancing public participation and awareness of the importance of waste source separation. In comparison with the conventional mixed collection and transportation system of household waste, the established source separation and management system is cost-effective. It could be extended to the entire city and used by other cities in China as a source of reference.

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.

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.

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.

Influence of the DMPP (3,4-dimethyl pyrazole phosphate) on nitrogen transformation and leaching in multi-layer soil columns.

The application of nitrogen fertilizers leads to various ecological problems such as nitrate leaching. The use of nitrification inhibitors as nitrate leaching retardants is a proposal that has been suggested for inclusion in regulations in many countries. In this study, using a multi-layer soil column device, the influence of new nitrification inhibitor DMPP (3,4-dimethyl pyrazole phosphate) was studied for understanding the nitrogen vertical transformation and lowering the nitrate leaching at different soil profile depths. The results indicated that, within 60 d of experiment, the regular urea added 1.0% DMPP can effectively inhibit the ammonium oxidation in the soil, and improve the ammonium concentration in soil solution over the 20cm depths of soil profile, while decline the concentrations of nitrate and nitrite. No obvious difference was found on ammonium concentrations in soil solution collected from deep profile under 20cm depths between regular urea and the urea added 1.0% DMPP. There was also no significant difference for the nitrate, ammonium and nitrite concentrations in the soil solution under 40cm depths of soil profile with the increasing nitrogen application level, among the treatments of urea added 1.0% DMPP within 60 d. It is proposed that DMPP could be used as an effective nitrification inhibitor in some region to control ammonium oxidation and decline the ion-nitrogen leaching, minimizing the shallow groundwater pollution risk and being beneficial for the ecological environment.

Trimethylamine (TMA) biofiltration and transformation in biofilters.

Bioremoval of trimethylamine (TMA) in two three-stage biofilters packed with compost (A) and sludge (B), respectively, was investigated. Both biofilters were operated with an influent TMA concentration of 19.2-57.2mgm(-3) for 67 days. Results showed that all of the inlet TMA could be removed by both biofilters. However, removal efficiency and transformation of TMA in each section of both biofilters was different. In the Introduction section, TMA removal efficiency and maximum elimination capacity of the compost medium were greater than those of sludge medium under higher inlet TMA concentration. In comparison with biofilter A, considerably higher NH(3) concentrations in effluent of all three sections in biofilter B were observed after day 19. Although, NO(2)(-)-N concentration in each section of biofilter A was relatively lower, NO(3)(-)-N content in each section of biofilter A increased after day 26, especially in the Materials and method section which increased remarkably due to a lesser amount of TMA and higher ammonia oxidation and nitrification in compost medium. In contrast, neither NO(2)(-)-N nor NO(3)(-)-N were detected in either section of biofilter B at any time throughout the course of the experiment. The cumulative results indicated that compost is more favorable for the growth of TMA-degrading and nitrifying bacteria as compared to the sludge and could be a highly suitable packing material for biodegradation and transformation of TMA.

Recovery of nitrogen and phosphorous as struvite from swine waste biogas digester effluent.

OBJECTIVE: To investigate the feasibility of nitrogen and phosphorus recovery from swine waste biogas digester effluent and the effects of pH and NH4+: Mg2+: PO4(3-) molar ratio on its precipitation. METHODS: Precipitation experiments with swine waste biogas digester effluent were conducted at pH 7.5, 8.0, 8.5, and 9.0 together with NH4+: Mg2+: PO4(3-) molar ratios 1: 0.2: 0.08, 1: 1: 1, and 1: 1.5: 1.5. Chemical and X-ray diffraction (XRD) analysis were done to determine the composition of the precipitate. RESULTS: The highest removal and recovery of NH4+ and PO4(3-) were achieved at pH 9.0 in each experiment. The elevation of pH to 9.0 alone could decrease the initial PO4(3-) concentration from 42 mg L(-1) to 4.7 mg L(-1) and 89.2% PO4(3-) recovery was achieved. The pH-molar ratio combination 9.0-1: 1.5: 1.5 effected 76.5% NH4+ and 68.5% PO4(3-) recovery. The molar ratio of 1: 1: 1 together with pH elevation to 9.0 was determined to be the optimum combination for both NH4+ and PO4(3-) removal as it recovered over 70% and 97% of the initial NH4+ and PO4(3-), respectively. CONCLUSIONS: Nitrogen and phosphorus can be recovered from biogas digester effluent as struvite.

Evaluation of organ distribution of microcystins in the freshwater phytoplanktivorous fish Hypophthalmichthys molitrix.

To evaluate the public health risk of exposure to microcystins in fish food in China, the distribution pattern of microcystin-LR and microcystin-RR in various organs (liver, intestine, kidney, muscle and lipid) of the dominant freshwater phytoplanktivorous fish Hypophthalmichthys molitrix in Hangzhou, China's Tiesha River was investigated with the method of HPLC-ESI-MS analysis. The distribution of microcystins was different in the fish organs and the major total microcystins (microcystin-LR and microcystin-RR) were present in the intestines (6.49 micro g/g fresh weight), followed by the livers (4.52 micro g/g fresh weight) and the muscles (2.86 micro g/g fresh weight). Microcystins were detected in kidneys (1.35 micro g/g fresh weight), but not detected in lipid. The results suggested that the mean daily intake from fish was 0.03 micro g/kg body weight which was very close to the recommended WHO tolerable daily intake (TDI) level of 0.04 micro g/kg body weight per day, and local people were warned they may have health risk if they consumed fish from the river.

Heavy metal availability and impact on activity of soil microorganisms along a Cu/Zn contamination gradient.

All the regulations that define a maximum concentration of metals in the receiving soil are based on total soil metal concentration. However, the potential toxicity of a heavy metal in the soil depends on its speciation and availability. We studied the effects of heavy metal speciation and availability on soil microorganism activities along a Cu/Zn contamination gradient. Microbial biomass and enzyme activity of soil contaminated with both Cu and Zn were investigated. The results showed that microbial biomass was negatively affected by the elevated metal levels. The microbial biomass-C (C(mic))/organic C (C(org)) ratio was closely correlated to heavy metal stress. There were negative correlations between soil microbial biomass, phosphatase activity and NH4NO3 extractable heavy metals. The soil microorganism activity could be predicted using empirical models with the availability of Cu and Zn. We observed that 72% of the variation in phosphatase activity could be explained by the NH4NO3-extractable and total heavy metal concentration. By considering different monitoring approaches and different viewpoints, this set of methods applied in this study seemed sensitive to site differences and contributed to a better understanding of the effects of heavy metals on the size and activity of microorganisms in soils. The data presented demonstrate the relationship between heavy metals availability and heavy metal toxicity to soil microorganism along a contamination gradient.

Nitrogen interception in floodwater of rice field in Taihu region of China.

A field experiment located in Taihu Lake Basin of China was conducted, by application of urea or a mixture of urea with manure, to elucidate the interception of nitrogen (N) export in a typical rice field through "zero-drainage water management" combined with sound irrigation, rainfall forecasting and field drying. N concentrations in floodwater rapidly declined before the first event of field drying after three split fertilizations, and subsequently tended to return to the background level. Before the first field drying, total particulate nitrogen (TPN) was the predominant N form in floodwater of plots with no N input, dissolved inorganic nitrogen (DIN) on plots that received urea only, and dissolved organic nitrogen (DON) on plots treated with the mixture of urea and manure. Thereafter TPN became the major form. No N export was found from the rice field, but total nitrogen (TN) of 15.8 kg/hm2 was remained, mainly due to soil N sorption. The results recommended the zero-drainage water management for full-scale areas for minimizing N export.