Kaisong Zhang

A newly-discovered Cd-hyperaccumulator Solanum nigrum L.

A systematic investigation was conducted to screen for cadmium-hyperaccumulator from 54 species in 20 weed families using outdoor pot-culture experiment and small-scale field experiment. The results from the outdoor pot-culture experiment showed that Cd concentrations in the stems and leaves of Solatium nigrum L. growing in a soil spiked with 25 mg/kg Cd were up to 103.8 and 124.6 mg/kg (DW), respectively, which was greater than 100 mg/kg, minimum Cd concentration for a Cd-hyperaccumulator. The Cd enrichment factor (EF, concentration ratio in plant to soil) in shoots was as high as 2.68. Moreover, Cd accumulation in shoots was greater than that in roots (TF, concentration ratio in shoots to roots) and the plant biomass growth was not inhibited at the Cd concentrations tested compared with the control. The results of the small-scale field experiment also showed that the characteristics of Cd accumulation in S. nigrum were all consistent with the characteristics of Cd-hyperaccumulators. Thus S. nigrum can be classified as a Cd-hyperaccumulator. This work is important for further research in the areas of hyperaccumulators screening, and plant-tolerance physiology and evolution. It provides a patentable new plant species for phytoremediation of Cd-contaminated soils.

Biogenic silver nanoparticles (bio-Ag0) decrease biofouling of bio-Ag0/PES nanocomposite membranes

Biofouling is a major problem for the application of membrane technology in water and wastewater treatment. One of the practical strategies to decrease biofouling is the use of advanced anti-biofouling membrane material. In this study, different amounts of biogenic silver nanoparticles (bio-Ag(0)) were embedded in polyethersulfone (PES) membranes, using the phase-inversion method. The effects of the bio-Ag(0) content on the structure of the membrane and its filtration performance were systematically investigated. The results demonstrated that silver-containing nanostructures were uniformly distributed on membrane surface. Bio-Ag(0) incorporation slightly increased the hydrophilicity of the PES membrane and increased the permeate flux. The anti-bacterial and anti-biofouling properties of the bio-Ag(0)/PES nanocomposites membrane were tested with pure cultures (Escherichia coli and Pseudomonas aeruginosa) and a mixed culture (an activated sludge bioreactor), respectively. The bio-Ag(0)/PES composite membranes, even with the lowest content of biogenic silver (140 mg bio-Ag(0)m(-2)), not only exhibited excellent anti-bacterial activity, but also prevented bacterial attachment to the membrane surface and decreased the biofilm formation during a 9 weeks test.

In Situ Study of the Antibacterial Activity and Mechanism of Action of Silver Nanoparticles by Surface-Enhanced Raman Spectroscopy

Silver nanoparticles (Ag NPs) are extensively used as an antibacterial additive in commercial products and their release has caused environmental risk. However, conventional methods for the toxicity detection of Ag NPs are very time consuming and the mechanisms of action are not clear. We developed a new, in situ, rapid, and sensitive fingerprinting approach, using surface-enhanced Raman spectroscopy (SERS), to study the antibacterial activity and mechanism of Ag NPs of 80 and 18 nm (Ag80 and Ag18, respectively), by using the strong electromagnetic enhancement generated by Ag NPs. Sensitive spectra changes representing various biomolecules in bacteria were observed with increasing concentrations of Ag NPs. They not only allowed SERS to monitor the antibacterial activity of Ag NPs of different sizes in different water media but also to study the antibacterial mechanism at the molecular level. Ag18 were found to be more toxic than Ag80 in water, but their toxicity declined to a similar level in the PBS medium. The antibacterial mechanism was proposed on the basis of a careful identification of the chemical origins by comparing the SERS spectra with model compounds. The dramatic change in protein, hypoxanthine, adenosine, and guanosine bands suggested that Ag NPs have a significant impact on the protein and metabolic processes of purine. Finally, by adding nontoxic and SERS active Au NPs, SERS was successfully utilized to study the action mode of the NPs unable to produce an observable SERS signal. This work opens a window for the future extensive SERS studies of the antibacterial mechanism of a great variety of non-SERS-active NPs.

The antibacterial and anti-biofouling performance of biogenic silver nanoparticles by Lactobacillus fermentum

Biofouling is a major challenge in the water industry and public health. Silver nanoparticles (AgNPs) have excellent antimicrobial properties and are considered to be a promising anti-biofouling agent. A modified method was used to produce small sized and well-dispersed biogenic silver nanoparticles with a mean size of ~6 nm (Bio-Ag0-6) using Lactobacillus fermentum. The morphology, size distribution, zeta potential and oxidation state of the silver were systematically characterized. Determination of minimal inhibitory and bactericidal concentration results revealed that biogenic silver Bio-Ag0-6 can effectively suppress the growth of the test bacteria. Additionally, the inhibition effects of Bio-Ag0-6 on biofilm formation and on established biofilms were evaluated using P. aeruginosa (ATCC 27853) as the model bacterium. The results from microtiter plates and confocal laser scanning microscopy demonstrated that Bio-Ag0-6 not only exhibited excellent antibacterial performance but also could control biofilm formation and induce detachment of the bulk of P. aeruginosa biofilms leaving a small residual matrix.

The Effects of Sulfonated Poly(ether ether ketone) Ion Exchange Preparation Conditions on Membrane Properties.

A low cost cation exchange membrane to be used in a specific bioelectrochemical system has been developed using poly(ether ether ketone) (PEEK). This material is presented as an alternative to current commercial ion exchange membranes that have been primarily designed for fuel cell applications. To increase the hydrophilicity and ion transport of the PEEK material, charged groups are introduced through sulfonation. The effect of sulfonation and casting conditions on membrane performance has been systematically determined by producing a series of membranes synthesized over an array of reaction and casting conditions. Optimal reaction and casting conditions for producing SPEEK ion exchange membranes with appropriate performance characteristics have been established by this uniquely systematic experimental series. Membrane materials were characterized by ion exchange capacity, water uptake, swelling, potential difference and NMR analysis. Testing this extensive membranes series established that the most appropriate sulfonation conditions were 60 °C for 6 h. For mechanical stability and ease of handling, SPEEK membranes cast from solvent casting concentrations of 15%–25% with a resulting thickness of 30–50 µm were also found to be most suitable from the series of tested casting conditions. Drying conditions did not have any apparent impact on the measured parameters in this study. The conductivity of SPEEK membranes was found to be in the range of 10−3 S cm−1, which is suitable for use as a low cost membrane in the intended bioelectrochemical systems.

Sensitive and Versatile Detection of the Fouling Process and Fouling Propensity of Proteins on Polyvinylidene Fluoride Membranes via Surface-Enhanced Raman Spectroscopy

Membrane fouling is the major drawback of membrane-based technologies because it will lead to severe flux declines and the need to clean or replace the fouled membrane. A technique capable of early diagnosis, process monitoring, and evaluation of the role of different foulants playing in the fouling process is crucial for the fouling control. We develop surface-enhanced Raman spectroscopy (SERS) as a new and versatile tool to investigate the fouling process of protein on PVDF (polyvinylidene fluoride) membranes as well as the fouling propensity of three different proteins. We optimized the aggregation level and volume of SERS-active Ag sol and the spectra acquisition method combined with a statistical analysis method to ensure a high detection sensitivity, signal uniformity, and stability. We then used SERS for the early diagnosis of the fouling process and determining when the membrane pores would be blocked. The fouled area was visualized by a combination of the silver staining and Raman mapping. The fouling propensity of different proteins was studied by comparing the relative SERS band intensities of different proteins on a glass slide and after membrane filtration. Compared with fluorescence-based techniques, the narrow, well-resolved Raman band, especially the use of the same excitation line and laser power, endows SERS the ability to compare the fouling propensity in a very simple way.

Distributions of typical contaminant species in urban short-term storm runoff and their fates during rain events： A case of Xiamen City

The pollutants in urban storm runoff, which lead to an non-point source contamination of water environment around cities, are of great concerns. The distributions of typical contaminants and the variations of their species in short term storm runoff from different land surfaces in Xiamen City were investigated. The concentrations of various contaminants, including organic matter, nutrients (i.e., N and P) and heavy metals, were significantly higher in parking lot and road runoff than those in roof and lawn runoff. The early runoff samples from traffic road and parking lot contained much high total nitrogen (TN 6-19 mg/L) and total phosphorus (TP 1-3 mg/L). A large proportion (around 60%) of TN existed as total dissolved nitrogen (TDN) species in most runoff. The percentage of TDN and the percentage of total dissolved phosphorus remained relatively stable during the rain events and did not decrease as dramatically as TN and TP. In addition, only parking lot and road runoff were contaminated by heavy metals, and both Pb (25-120 microg/L) and Zn (0.1-1.2 mg/L) were major heavy metals contaminating both runoff. Soluble Pb and Zn were predominantly existed as labile complex species (50%-99%), which may be adsorbed onto the surfaces of suspended particles and could be easily released out when pH decreased. This would have the great impact to the environment.

Interrogating chemical variation via layer-by-layer SERS during biofouling and cleaning of nanofiltration membranes with further investigations into cleaning efficiency

Periodic chemical cleaning is an essential step to maintain nanofiltration (NF) membrane performance and mitigate biofouling, a major impediment in high-quality water reclamation from wastewater effluent. To target the important issue of how to clean and control biofouling more efficiently, this study developed surface-enhanced Raman spectroscopy (SERS) as a layer-by-layer tool to interrogate the chemical variations during both biofouling and cleaning processes. The fact that SERS only reveals information on the surface composition of biofouling directly exposed to cleaning reagents makes it ideal for evaluating cleaning processes and efficiency. SERS features were highly distinct and consistent with different biofouling stages (bacterial adhesion, rapid growth, mature and aged biofilm). Cleaning was performed on two levels of biofouling after 18 h (rapid growth of biofilm) and 48 h (aged biofilm) development. An opposing profile of SERS bands between biofouling and cleaning was observed and this suggests a layer-by-layer cleaning mode. In addition, further dynamic biochemical and infrastructural changes were demonstrated to occur in the more severe 48-h biofouling, resulting in the easier removal of sessile cells from the NF membrane. Biofouling substance-dependent cleaning efficiency was also evaluated using the surfactant sodium dodecyl sulfate (SDS). SDS appeared more efficient in cleaning lipid than polysaccharide and DNA. Protein and DNA were the predominant residual substances (irreversible fouling) on NF membrane leading to permanent flux loss. The chemical information revealed by layer-by-layer SERS will lend new insights into the optimization of cleaning reagents and protocols for practical membrane processes.

Surface-Enhanced Raman Spectroscopy for Identification of Heavy Metal Arsenic(V)-Mediated Enhancing Effect on Antibiotic Resistance

Bacterial antibiotic resistance poses a threat to global public health. Restricted usage of antibiotics does not necessarily prevent its continued emergence. Rapid and sensitive screening of triggers, in addition to antibiotic, and exploring the underlying mechanism are still major challenges. Herein, by developing a homogeneous vacuum filtration-based bacterial sample fabrication enabling high surface-enhanced Raman scattering (SERS) reproducibility across multiple bacterial samples and negating interfering spectral variations from inhomogeneous sample geometry and SERS enhancement, SERS was employed to study heavy metal arsenic [As(V)]-mediated antibiotic resistance in a robust, sensitive, and rapid fashion. Independent and robust spectral changes representing phenotypic bacterial responses, combined with multivariate analysis, clearly identified that As(V) enhanced antibiotic resistance to tetracycline (Tet). Similar spectral alteration profile to As(V) and Tet indicated that cross-resistance, whereby As(V)-induced bacterial resistance simultaneously blocked Tet action, could account for the enhanced resistance. The sensitive, robust, and rich phenotypic profile provided by SERS, combined with additional advantages in imposing no need to cultivate bacteria and single-cell sensitivity, can be further exploited to evaluate resistance-intervening factors in real microbiota.

Effect of toxicity of Ag nanoparticles on SERS spectral variance of bacteria.

Ag nanoparticles (NPs) have been extensively utilized in surface-enhanced Raman scattering (SERS) spectroscopy for bacterial identification. However, Ag NPs are toxic to bacteria. Whether such toxicity can affect SERS features of bacteria and interfere with bacterial identification is still unknown and needed to explore. Here, by carrying out a comparative study on non-toxic Au NPs with that on toxic Ag NPs, we investigated the influence of nanoparticle concentration and incubation time on bacterial SERS spectral variance, both of which were demonstrated to be closely related to the toxicity of Ag NPs. Sensitive spectral alterations were observed on Ag NPs with increase of NPs concentration or incubation time, accompanied with an obvious decrease in number of viable bacteria. In contrast, SERS spectra and viable bacterial number on Au NPs were rather constant under the same conditions. A further analysis on spectral changes demonstrated that it was cell response (i.e. metabolic activity or death) to the toxicity of Ag NPs causing spectral variance. However, biochemical responses to the toxicity of Ag were very different in different bacteria, indicating the complex toxic mechanism of Ag NPs. Ag NPs are toxic to a great variety of organisms, including bacteria, fungi, algae, protozoa etc., therefore, this work will be helpful in guiding the future application of SERS technique in various complex biological systems.