Facile On-Site Aqueous Pollutant Monitoring Using a Flexible, Ultralight, and Robust Surface-Enhanced Raman Spectroscopy Substrate: Interface Self-Assembly of Au@Ag Nanocubes on a Polyvinyl Chloride Template.

Aquatic ecosystems and human health have been seriously threatened by illegal discharge of wastewater, while simple and effective monitoring methods are still sparse. Here, we propose a facile method for on-site pollutant monitoring by surface-enhanced Raman spectroscopy with a novel substrate. This substrate is fabricated by interface self-assembly of Au@Ag nanocubes (NCs) on a simultaneously formed polyvinyl chloride (PVC) template, followed by coating with a thin Au film. The Au@Ag@Au-NCs/PVC film is flexible, ultralight, and robust and could float on the surface of water and firmly contact with water even under harsh environmental conditions. Moreover, the Au@Ag@Au-NCs/PVC film is translucent, allowing penetration of laser beams and enhancement of Raman signals. When thiram was used as a model contaminant in aqueous solution, a good linear relationship ( R2 = 0.972) was obtained over the range of 0.1-50 ppb with a detection limit of 0.1 ppb. Raman signals of thiram can be instantly and consecutively detected with the enhancement of the film in the simulated experiments, suggesting its possible use in the long run. Furthermore, the film can be easily regenerated by NaBH4 solution washing, which could reduce the operating cost. In summary, the Au@Ag@Au-NCs/PVC film has great potential in on-site pollutant monitoring in aqueous environments with a portable Raman spectrometer.

Self-assembly of Au nanoparticles on PMMA template as flexible, transparent, and highly active SERS substrates.

We report a simple and rapid method for fabricating a surface-enhanced Raman scattering (SERS) substrate, which offers good flexibility, excellent optical transparency, and high SERS activity. Specifically, the SERS substrate (AuNPs/PMMA film) was obtained through self-assembly of gold nanoparticles (AuNPs) on newborn poly(methyl methacrylate) (PMMA) template. The UV-vis spectroscopy analysis and scanning electron microscopy observation revealed that the gold nanoparticles were closely assembled on the flexible and transparent PMMA template. The fabricated AuNPs/PMMA film SERS substrate allowed detection of model molecule, malachite green isothiocyanate, at a concentration as low as 0.1 nM, and exhibited good reproducibility in the SERS measurement. The Raman enhancement factor (EF) of the AuNPs/PMMA film was found to be as high as (2.4 ± 0.3) × 10(7). In addition, measure of residual malachite green on fish surface was carried out, and the result indicated that the AuNPs/PMMA film had great potential in the in situ ultrasensitive detection of analyte on irregular objects.

Adsorption of typical natural organic matter on microplastics in aqueous solution: Kinetics, isotherm, influence factors and mechanism.

With rapid urbanization, microplastics and natural organic matters (NOMs) are ubiquitous in aquatic environment, and microplastics could act as carriers for organic matters in the aqueous solution and may pose a potential risk. In this study, the adsorption behaviors and mechanism of typical NOM, humic acid (HA), on polyvinyl chloride (PVC) and polystyrene (PS) microplastics were investigated. Various influence factors such as solution pH, ions species and concentrations, particle size, and coexisting surfactants were studied. The results suggested that HA adsorption onto PVC and PS was low pH-dependent, and ion species and concentrations have a significant impact on the adsorption capacity. In addition, the particle size of PVC and PS microplastics exhibited a significant correlation with HA adsorption, and the adsorption process was influenced by the surfactant species and concentrations. Moreover, the adsorption behaviors of HA in different real water environments were tested, and UV aging exhibited the opposite effects on adsorption capacity of PVC and PS. Furthermore, the adsorption mechanisms of HA onto PVC and PS were explored, indicating halogen bonding, hydrogen bonding, and π-π interaction play important roles in the adsorption process.

Functionalization of regenerated cellulose membrane via surface initiated atom transfer radical polymerization for boron removal from aqueous solution.

In this study, an adsorptive membrane was prepared for efficient boron removal. Poly(glycidyl methacrylate) was grafted on the surfaces of the regenerated cellulose (RC) membrane via surface-initiated atom transfer radical polymerization, and N-methylglucamine was used to further react with epoxide rings to introduce polyhydroxyl functional groups, which served as the major binding sites for boron. The pristine and modified membranes were characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), dynamic water contact angle measurement, and scanning electron microscopy. It was shown that the designed functional groups were successfully grafted onto the RC membrane, and surface modification contributed to higher boron binding capability. The optimal pH range for boron adsorption was 4-8. Under a neutral pH condition, the maximum adsorption capacity of the modified membrane was determined to be 0.75 mmol/g, which was comparable with those of commercial resins. Studies of electrolyte influence indicated the formation of inner-sphere surface complexes on the membrane surface. The ATR-FTIR and XPS analyses showed that secondary alcohol and tertiary amine groups were mainly involved in boron adsorption, and tetrahedral boron complexes were found on the membrane surface.

Determination of the pore size distribution and porosity of aerobic granules using size-exclusion chromatography.

The pore size distribution and porosity of aerobic granules with different diameters were evaluated using size-exclusion chromatography, in which polyethylene glycols and distilled water were, respectively, used as solute and mobile phase. The porosity of the aerobic granules varied from 68% to 93% and the exclusion limit, expressed as molecular mass, showed a significant difference. For the small-size granules with a diameter of 0.2-0.6mm, molecules greater than 137,000Da could not penetrate the pores, while the exclusion limits of the middle-size granules with a diameter of 0.6-0.9mm and large-size ones with a diameter of 0.9-1.5mm were 76,000 and 29,000Da, respectively. The extracellular polymeric substances of the granules might clog the pores and might be responsible for the reduced porosity. A correlation between the bioactivity and available porosity of the aerobic granules was found. The experimental results show that the size-exclusion chromatography was appropriate for elucidating the pore size distribution and porosity of the aerobic granules.

Synthesis of Fe3O4/Polyacrylonitrile Composite Electrospun Nanofiber Mat for Effective Adsorption of Tetracycline.

Novel Fe3O4/polyacrylonitrile (PAN) composite nanofibers (NFs) were prepared by a simple two-step process, an electrospinning and solvothermal method. Characterization by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) demonstrated formation of a uniform nanoparticles coating (about 20 nm in thickness) on the PAN nanofiber backbone. The coating was constructed by well-crystallized cubic phase Fe3O4 nanoparticles as examined by X-ray diffraction spectroscopy (XRD). The coating doubled the specific surface area of NFs, from 8.4 to 17.8 m2 g(-1), as confirmed by nitrogen sorption isotherm analysis. To evaluate the feasibility of Fe3O4/PAN composite NFs as a potential adsorbent for antibiotic removal, batch adsorption experiments were conducted using tetracycline (TC) as the model antibiotic molecule. The results showed that Fe3O4/PAN composite NFs were effective in removing TC with no impactful loss of Fe in the pH regime of environmental interest (5-8). The adsorption of TC onto Fe3O4/PAN composite NFs better fitted the pseudo-second-order kinetics model, and the maximum adsorption capacity calculated from Langmuir isotherm model was 257.07 mg g(-1) at pH 6. The composite NFs also exhibited good regenerability over repeated adsorption/desorption cycles. Surface complexation between TC and the composite NFs contributed most to the adsorption as elucidated by X-ray photoelectron spectroscopy (XPS). This highly effective and novel adsorbent can be easily modularized and separated, promising its huge potential in drinking and wastewater treatment for antibiotic removal.