Development of an aptasensor for dibutyl phthalate detection and the elucidation of assay inhibition factors.

We developed a fluorescence aptasensor (hereafter 'SG-aptasensor') using SYBR Green I, a newly truncated 20-mer aptamer, and probe DNA to detect dibutyl phthalate (DBP). The detection range of DBP was 0.1-100 ng L-1 with 0.08 ng L-1 as the limit of detection. To adapt the assay to environmental samples in the near future, possible inhibition factors (experimental and environmental) have been tested and reported. The experimental inhibitors included the incubation time, temperature, pH, and ionic strength. Consequently, temperature (2-25 °C) and pH (7.0-9.0) ranges did not significantly inhibit the assay. The incubation time required for sufficient reaction was at least 4 h, and a relative humidity <20% may have induced fluorescence quenching. Tris-HCl-based incubation buffer with excess ionic strength (more than 0.2 M NaCl) demonstrated an abnormal increase in fluorescence. Environmental inhibitors including cations (Mg2+, Ca2+, and Cu2+) and humic acids were tested. The fluorescence signal was significantly reduced (∼99%) by 100 mM Cu2+ compared to that by 0 mM Cu2+. In contrast, the reduction in fluorescence signal was marginal (<15%) when Mg2+ or Ca2+ ions were present. Inhibition of the assay was observed (∼28%) in the presence of 100 mg L-1 humic acids.

Multi-target aptamer assay for endocrine-disrupting phthalic acid ester panel screening in plastic leachates.

A multi-target aptamer assay was developed as a phthalic acid ester (PAE) panel to screen selected PAEs in plastic leachate samples. The panel comprises 13 PAEs (PAE-13), namely dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, di-n-hexyl phthalate, diisobutyl phthalate, diisononyl phthalate, diisodecyl phthalate, mono-2-ethylhexyl phthalate, di-2-ethylhexyl phthalate, diphenyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, and phthalic acid. Herein, we proposed an aptamer assay using a newly truncated aptamer (20-mer) and the 7-aminoactinomycin D fluorophore, which selectively binds to guanine in single-stranded DNA, resulting in increased fluorescence intensity. The assay is highly selective for PAE-13 clusters. The selectivity of the assay was evaluated using 13 different PAEs and mixtures depending on the side chain structure. The quantitative detection of PAEs was demonstrated by adopting mixed PAE-13 simulants and achieved a limit of detection of ∼1.4 pg/mL. The repeatability and reproducibility of the assay were also evaluated by presenting acceptable coefficients of variation (%CV less than 10% and 15%, respectively). The performance of the assay was demonstrated by analyzing the plastic leachate samples, and the positive correlation (correlation coefficient, r = 0.985) was confirmed by comparing them with the total sum of individual PAE peak areas obtained by gas chromatography mass spectrometry analysis.

Photocatalytic and electrocatalytic degradation of bisphenol A in the presence of graphene/graphene oxide-based nanocatalysts: A review.

Bisphenol A (BPA), a widely recognized endocrine disrupting compound, has been discovered in drinking water sources/finished water and domestic wastewater influent/effluent. Numerous studies have shown photocatalytic and electrocatalytic oxidation to be very effective for the removal of BPA, particularly in the addition of graphene/graphene oxide (GO)-based nanocatalysts. Nevertheless, the photocatalytic and electrocatalytic degradation of BPA in aqueous solutions has not been reviewed. Therefore, this review gives a comprehensive understanding of BPA degradation during photo-/electro-catalytic activity in the presence of graphene/GO-based nanocatalysts. Herein, this review evaluated the main photo-/electro-catalytic degradation mechanisms and pathways for BPA removal under various water quality/chemistry conditions (pH, background ions, natural organic matter, promotors, and scavengers), the physicochemical characteristics of various graphene/GO-based nanocatalysts, and various operating conditions (voltage and current). Additionally, the reusability/stability of graphene/GO-based nanocatalysts, hybrid systems combined with ozone/ultrasonic/Fenton oxidation, and prospective research areas are briefly described.

Ultrasonic treatment of dye chemicals in wastewater: A review.

The existence of pollutants, such as toxic organic dye chemicals, in water and wastewater raises concerns as they are inadequately eliminated through conventional water and wastewater treatment methods, including physicochemical and biological processes. Ultrasonic treatment has emerged as an advanced treatment process that has been widely applied to the decomposition of recalcitrant organic contaminants. Ultrasonic treatment has several advantages, including easy operation, sustainability, non-secondary pollutant production, and saving energy. This review examines the elimination of dye chemicals and categorizes them into cationic and anionic dyes based on the existing literature. The objectives include (i) analyzing the primary factors (water quality and ultrasonic conditions) that influence the sonodegradation of dye chemicals and their byproducts during ultrasonication, (ii) assessing the impact of the different sonocatalysts and combined systems (with ozone and ultraviolet) on sonodegradation, and (iii) exploring the characteristics-based removal mechanisms of dyes. In addition, this review proposes areas for future research on ultrasonic treatment of dye chemicals in water and wastewater.

Photocatalytic boron nitride-based nanomaterials for the removal of selected organic and inorganic contaminants in aqueous solution: A review.

Boron nitride (BN) coupled with various conventional and advanced photocatalysts has been demonstrated to exhibit extraordinary activity for photocatalytic degradation because of its unique properties, including a high surface area, constant wide-bandgap semiconducting property, high thermal-oxidation resistance, good hydrogen-adsorption performance, and high chemical/mechanical stability. However, only limited reviews have discussed the application of BN or BN-based nanomaterials as innovative photocatalysts, and it does not cover the recent results and the developments on the application of BN-based nanomaterials for water purification. Herein, we present a complete review of the present findings on the photocatalytic degradation of different contaminants by various BN-based nanomaterials. This review includes the following: (i) the degradation behavior of different BN-based photocatalysts for various contaminants, such as selected dye compounds, pharmaceuticals, personal care products, pesticides, and inorganics; (ii) the stability/reusability of BN-based photocatalysts; and (iii) brief discussion for research areas/future studies on BN-based photocatalysts.

A multi-functional reagent suitable for 1-step rapid DNA intercalation fluorescence-based screening of total bacteria in drinking water.

The prerequisites for rapid screening of total bacteria in drinking water are low detection limit and convenience. Inspired by commercial adenosine 5'-triphosphate (ATP) based total bacterial detection kits, we pursued likewise convenience but with much lower detection limit. Existing intercalation fluorescence-based techniques employ multiple reagents to permeate the cell membrane and intercalate dye into the DNA in discrete sequential steps. A simple multi-functional reagent is proposed to do the same within one step. Surfactants (TritonX and SDS), and intercalating dyes (SYBR green, SYBR gold) were examined for their mutual compatibility and augmented with EDTA. Evaluation was performed with Gram negative Escherichia coli K12 (E. coli K12) and Gram positive Bacillus subtilis (B. subtilis) at serial dilution ratios from 10-6 to 10-2. Comparison was made with absorbance (600 nm) measurements and a commercial ATP kit. Using charge integrated photodetection, the proposed 1-step reagent achieved an LOD (1.00 × 10-6, B. subtilis) that is two orders of magnitude lower than that of ATP kit (LOD = 1.06× 10-4). This means it could detect minute quantity of total bacteria that is otherwise undetected by the ATP kit.

Switchable inhibitory behavior of divalent magnesium ion in DNA hybridization-based gene quantification.

Contrary to the understanding that divalent cations only result in under-estimation of gene quantification via DNA hybridization-based assays, we have discovered that Mg2+ could cause either under or over-estimation at different concentrations. Its switchable inhibitory behavior is likely due to its rigid first solvation (hydrated) shell and hence it is inclined to form non-direct binding with DNA. At low concentrations, it caused under-estimation by occupying the hybridization sites. At high concentrations, it caused probe, signaling and target DNA to aggregate non-specifically via Coulomb forces. By quantifying target DNAs at a range of Mg2+ concentrations using a gene quantification assay (NanoGene assay), a Mg2+ inflection concentration of ∼10-3 M was observed for both target ssDNA and dsDNA. Field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDS), and Fourier transform infrared spectroscopy (FT-IR) were employed to observe Mg2+-induced non-specific binding in the complexes that mimicked the presence of target DNA. Together with two other divalent cations Ca2+ and Cu2+, they were further examined via zeta potential measurements as well as NanoGene assay. This study revealed the importance of Mg2+ in achieving accurate gene quantification. Through a better mechanistic understanding of this phenomenon, it will be possible to develop strategies to mitigate the impact of Mg2+ on DNA hybridization-based gene quantification.

Clustered Detection of Eleven Phthalic Acid Esters by Fluorescence of Graphene Quantum Dots Displaced from Gold Nanoparticles.

A gold nanoparticle-quenched graphene quantum dot-based aptasensor was developed to perform clustered detection of 11 phthalic acid esters (PAEs). The binding of the target PAEs to the aptasensor frees the graphene quantum dots that are otherwise quenched by the carrier gold nanoparticle. The resultant fluorescence upon excitation is proportional to the number of freed graphene quantum dots and hence the target PAE concentration. The synthesis of the proposed aptasensor was first verified step-by-step via FT-IR measurement, scanning electron microscopy, and fluorescence measurement. Selectivity was evaluated for individual and combined target PAEs and compared against seven non-PAE endocrine disrupting compounds. The proposed aptasensor successfully quantified 11 PAEs in test samples with varying concentrations of 0.001-50 ng PAEs/mL and demonstrated a limit of detection of ∼4 pg./mL. Finally, the AuNP-gQD aptasensor was employed to detect multiple combinations of commonly regulated PAEs (DBP, DIBP, DEHP, and BBP). The recovery (%) for all four PAEs combination in environmentally relevant concentrations of 0.5, 1, 5, and 10 ng/mL were ∼100%.

Review of adsorption-membrane hybrid systems for water and wastewater treatment.

Adsorption is an effective method for the removal of inorganic and organic contaminants and has been commonly used as a pretreatment method to improve contaminant removal and control flux during membrane filtration. Over the last two decades, many researchers have reported the use of hybrid systems comprising various adsorbents and different types of membranes, such as nanofiltration (NF), ultrafiltration (UF), and microfiltration (MF) membranes, to remove contaminants from water. However, a comprehensive evaluation of the removal mechanisms and effects of the operating conditions on the transport of contaminants through hybrid systems comprising various adsorbents and NF, UF, or MF membranes has not been performed to date. Therefore, a systematic review of contaminant removal using adsorption-membrane hybrid systems is critical, because the transport of inorganic and organic contaminants via the hybrid systems is considerably affected by the contaminant properties, water quality parameters, and adsorbent/membrane physicochemical properties. Herein, we provide a comprehensive summary of the most recent studies on adsorption-NF/UF/MF membrane systems using various adsorbents and membranes for contaminant removal from water and wastewater and highlight the future research directions to address the current knowledge gap.

Chia seed-assisted separation and detection of polyvinyl chloride microplastics in water via gas chromatography mass spectrometry.

Chia seeds were used to significantly improve the separation efficiency of polyvinyl chloride (PVC) microplastics from water samples via centrifugation. Upon hydration, the mucilage of chia seeds were able to capture PVC microplastics with sizes ranging from tens to hundreds of micrometers. Since PVC microplastics contained di-2-etylhexyl phthalate (DEHP) as a plasticizer (verified via Fourier transform infrared spectrometry), DEHP was used as an indicator in the subsequent quantification via gas chromatography - mass spectrometry (GC-MS) analysis. Specifically after verifying the DEHP peak in the GC spectrum using DEHP reference standard as a positive control, the GC spectral area of that peak was used to quantify the amount of DEHP in the sample. Using nominal operation settings at 10 min and 1000 rpm with 100 mg of chia seeds, the separation efficiency could be improved by 5 times (500%) as compared to the absence of chia seeds. Furthermore, chia seeds were also compatible with simulated synthetic wastewater samples. Most importantly, the use of chia seeds did not interfere with GC-MS quantification protocol and accuracy. The result suggested the proposed method can be used as a simple screening tool of microplastics entering wastewater treatment plant, even though a series of follow-up studies are needed in future.

Review of MXene-based nanocomposites for photocatalysis.

Since multilayered MXenes (Ti3C2Tx, a new family of two-dimensional materials) were initially introduced by researchers at Drexel University in 2011, various MXene-based nanocomposites have received increased attention as photocatalysts owing to their exceptional properties (e.g., rich surface chemistry, adjustable bandgap structures, high electrical conductivity, hydrophilicity, thermal stability, and large specific surface area). Therefore, we present a comprehensive review of recent studies on fabrication methods for MXene-based photocatalysts and photocatalytic performance for contaminant degradation, CO2 reduction, H2 evolution, and N2 fixation with various MXene-based nanocomposites. In addition, this review briefly discusses the stability of MXene-based nanophotocatalysts, current limitations, and future research needs, along with the various corresponding challenges, in an effort to reveal the unique properties of MXene-based nanocomposites.

Ozonation enhancement of low cost double-stranded DNA binding dye based fluorescence measurement of total bacterial load in water.

We demonstrated the feasibility of using ozonation to enhance the performance of dsDNA binding dye SYBR Green I in the fluorescence measurement of total bacterial load in water. Unlike its membrane permeable but expensive equivalent such as SYTO82 dye, SYBR Green I is many times cheaper but membrane impermeable. Ozonation allowed SYBR Green I dye to permeate the membrane and bind with the dsDNA within by first breaching it. Using E. coli K12 bacteria at serial dilution ratios from 1/1 (980 CFU mL-1) to 1/200, we achieved corresponding quantification from 618.7 ± 9.4 to 68.0 ± 1.9 RFU (100 to 11.00% normalized RFU). In comparison, plate counting and optical density measurement were only able to quantify up till a serial dilution ratio of 1/50 (40 CFU mL-1 and 0.0421, respectively). Most importantly with ozonation, the sensitivity of SYBR Green I dye based fluorescence measurement was improved by ∼140 to 210% as compared to that without ozonation. Given its low electrical power consumption, lab-on-chip compatibility and reagent-less nature, ozonation is highly compatible with portable fluorimeters to realize low-cost monitoring of total bacterial load in water.

Single-stranded DNA probe paired aptasensor with extra dye binding sites to enhance its fluorescence response in the presence of a target compound.

The purpose of this study is to investigate the possibility of improving the performance of a DNA binding dye water quenching based aptasensor without changing or truncating the aptamer. To demonstrate the possibility of increasing the change in fluorescence of the aptasensor by pairing it with a suitable ssDNA probe, three ssDNA probes (probe 1, 2, and 3) were employed and the fluorescence from the bound dyes was measured. This showed that ssDNA probe 2 created the most additional binding sites. By varying the target compound concentration (0, 0.05, 0.5, 5, 50, and 500 mg L-1 4-n-nonylphenol), the corresponding change in the fluorescence signal of the unpaired and ssDNA probe paired aptasensors were measured and compared over a range of emission wavelengths. The response of all three ssDNA probe paired aptasensors showed good fit (R 2 = 0.88-0.92) to a logarithmic response. The sensitivity of the aptasensor paired with ssDNA probe 2 was improved by ∼60%, whereas that of the aptasensor paired with ssDNA probe 3 was only improved by a marginal ∼3%. This study is a demonstration of using an appropriate ssDNA probe to increase the number of binding sites and hence the performance of a DNA binding dye and water quenched aptasensor. It is a possibility that can be extended to similar aptasensors without having to change or truncate the aptamer.

A simple reagent-less approach using electrical discharge as a substitution for chelating agent in addressing genomic assay inhibition by divalent cations.

Electrical discharge treatment was shown to be a viable substitution for chelating agent in genomic assays. Divalent cation Mg2+ inhibits the performance of DNA hybridization based genomic assays by binding to the DNA and disrupting DNA hybridization. Until now, chelating agents such as ethylenediaminetetraacetic acid (EDTA) was the only option to address the presence of Mg2+ in samples. However, EDTA is a well-known environmental contaminant. In this work, we successfully employed electrical discharge instead of EDTA to render Mg2+ insipid. Its preliminary efficacy was first observed via circular dichroism (CD) and zeta potential analyses. After electrical discharge treatment, the reduction in CD shift at 280 nm was significant for samples with 10-3 and 10-8 M Mg2+. The zeta potential of Mg2+ laden samples were also restored from -4.71 ± 1.38 to -20.59 ± 6.37 mV after electrical discharge treatment. Both CD shift and change in zeta potential suggested that 2 min of electrical discharge treatment could prevent Mg2+ from binding to DNA. The complete efficacy of electrical discharge treatment was demonstrated with the performance recovery (within ∼15% of the control) of a genomic assay variant (NanoGene assay) while analyzing Mg2+ laden samples (10-5-10-3 M). Assuming 10 million samples are analyzed annually, the proposed electrical discharge treatment (∼50 mW per sample) would allow us to trade environmental contamination by ∼50 kg of hazardous EDTA with a single 250 W STC (standard test conditions) solar panel.

Development of non-equilibrium rapid replacement aptamer assay for ultra-fast detection of phthalic acid esters.

In this paper, we developed a non-equilibrium rapid replacement aptamer (NERRA) assay that performed ultra-fast (in 30 s) quantitative detection of phthalic acid esters (PAEs) without waiting for the reaction to reach equilibrium. NERRA assay employed fluorescence PoPo3 dye intercalated in an ssDNA aptamer to selectively detect and quantify the PAEs in water. As the intercalated dye was replaced by the PAEs and quenched in the water, the rate of fluorescence change became proportional to PAEs concentration. The sensitivity of NERRA assay was first evaluated with a commercial spectrofluorometer. The selectivity for PAE mixture, individual PAEs, and non-phthalate compounds were also investigated. NERRA assay was also able to quantitatively detect the PAEs in a common plastic product (picnic mat), and the results were compared with those of gas chromatography mass spectrometry. Finally, a custom analyzer (8.5 cm × 8.5 cm × 16.5 cm) was built to demonstrate the portability of the NERRA assay. Using a commercial spectrofluorometer, NERRA assay was able to quantitatively detect a PAE mixture in 30 min with an LOQ of 0.1 µg/L. Using the portable custom analyzer, the detection time was shortened to 30 s with a tradeoff in the LOQ (1 µg/L). In both cases, the LOQs remain within the environmentally relevant PAE concentrations of 0.1-1472 µg/L.

A self-powered insulin patch pump with a superabsorbent polymer as a biodegradable battery substitute.

Highly popular insulin patch pumps have in-built non-removable batteries. These batteries are routinely disposed of together with the used pumps as medical waste and end up in landfills. This is an environmental contamination conundrum by design. To address this issue, we proposed a self-powered patch pump that uses a biodegradable superabsorbent polymer (SAP) instead of a battery as a power source to drive the infusion. Continuous infusion rates from 6.1 µL min-1 to 49.1 µL min-1 were achieved. Together with valve throttling, basal and bolus infusion rates of ∼10 µL h-1 (1 U h-1) and 100 µL (10 U) in ∼11 min could also be implemented for glycemic control. The generated pressure at ∼0.7 psi is also adequate for infusion as it exceeded an adult's maximum peripheral venous pressure of 0.6 psi. Given the current number of patch pump users, the proposed design could prevent ∼100 000 used batteries from entering the medical waste stream and landfill daily. Most importantly, this work highlights the possibility of addressing environmental contamination without compromising on healthcare standards by using SAP as an alternative means of energy storage.

Detection of Nonylphenol with a Gold-Nanoparticle-Based Small-Molecule Sensing System Using an ssDNA Aptamer.

Endocrine-disrupting chemicals (EDCs) threaten many kinds of life throughout the world. These compounds function the same as sexual hormones, inducing precocious puberty, gynecomastia, etc., in the human body. To prevent excess exposure to nonylphenol (NP), a simple and rapid detection system is needed. In this study, we develop a nonylphenol-specific aptamer from a random single-stranded DNA library and test a rapid sensor system based on the aptamer and gold nanoparticles (AuNPs). The aptamer was screened by a methodology involving reduced graphene oxide (rGO). As a result of screening and sequencing, a DNA aptamer was developed that recognizes the target with high binding affinity (Kd = 194.2 ± 65.9 nM) and specificity. The sensor system developed using the aptamer and gold nanoparticles is sensitive (LOD = 2.239 nM). Circular dichroism (CD) spectrometry results show that the free aptamer binds to the target molecule. The aptamer was characterized using gold nanoparticles to measure UV absorbance. Our results suggest that the sensor system developed using this aptamer is useful for field diagnosis of small molecules.

Aqueous removal of inorganic and organic contaminants by graphene-based nanoadsorbents: A review.

Various graphene-based nanoadsorbents, including graphenes, graphene oxides, reduced graphene oxides, and their nanocomposites, have been widely studied as potential adsorbents due to their unique physicochemical properties, such as structural variability, chemical strength, low density, and the possibility of large scale fabrication. Adsorption mechanisms are governed largely by the physicochemical properties of contaminants, the characteristics of nanoadsorbents, and background water quality conditions. This review summarizes recent comprehensive studies on the removal of various inorganic (mainly heavy metals) and organic contaminants by graphene-based nanoadsorbents, and also discusses valuable information for applications of these nanoadsorbents in water and wastewater treatment. In particular, the aqueous removal of various contaminants was reviewed to (i) summarize the general adsorption capacities of various graphene-based nanoadsorbents for the removal of different inorganic and organic contaminants, (ii) evaluate the effects of key water quality parameters such as pH, temperature, background major ions/ionic strength, and natural organic matter on adsorption, (iii) provide a comprehensive discussion of the mechanisms that influence adsorption on these nanoadsorbents, and (iv) discuss the potential regeneration and reusability of nanoadsorbents. In addition, current challenges and future research needs for the removal of contaminants by graphene-based nanoadsorbents in water treatment processes are discussed briefly.

Monocycloplatinated Solvento Complex Displays Turn-on Ratiometric Phosphorescence Responses to Histamine.

The study of biological histamine (HA) requires probes capable of ratiometric photoluminescence detection of HA. We discovered that a monocycloplatinated complex having two solvento ligands ([Pt(2-(2-naphthyl)quinolinate)(NCCH3)2]ClO4) could produce ratiometric phosphorescence responses to HA in aerated aqueous solutions buffered to pH 7.4. The HA response was characterized with a hypsochromic shift of an emission peak wavelength from 635 to 567 nm. The corresponding phosphorescence intensity ratio (i.e., I567 nm/ I635 nm) increased from 0.26 to 1.90. Spectroscopic and spectrometric investigations indicated an occurrence of spontaneous displacement of the labile CH3CN ligands with HA. An independently prepared HA adduct supported this notion. The ratiometric phosphorescence responses to HA were highly tolerant to other biological stimuli, including changes in pH and the presence of biometals and biological Lewis bases such as amino acids, nucleosides, biothiols, neurotransmitters, and small molecular metabolites. Of note was the high selectivity toward HA over common biological ligands, including histidine, cysteine, and homocysteine, which was ascribed to tighter HA binding. Our phosphorescence measurements employing Boc-protected derivatives of HA suggested that the bis-chelate motif involving imidazolyl and terminal amino groups was crucial for eliciting the ratiometric phosphorescence signaling. Finally, the bioimaging utility of the HA probe was validated using RAW 264.7 macrophages that were exogenously supplemented with HA or stimulated with thapsigargin to enrich intracellular HA. Ratiometric phosphorescence imaging microscopy experiments demonstrated the ability of the probe for monitoring intracellular HA uptake. In addition, photoluminescence lifetime imaging microscopy techniques could be applied for visualization of HA within the RAW 264.7 cells, because the HA binding elongated the photoluminescence lifetime. Our study demonstrated the promising utility of inner-sphere interactions of phosphorescent Pt(II) complexes for detection of biological HA.

Development of quantum dot aptasensor and its portable analyzer for the detection of di-2-ethylhexyl phthalate.

We have developed a quantum dot aptasensor (QD-aptasensor) and its accompanying portable analyzer for the detection of di-2-ethylhexyl phthalate (DEHP). This sensor is based on a newly screened aptamer (60-mer) via SELEX and shows a binding affinity of 213 nmol/L with DEHP. The 60-mer aptamer together with its three shorter truncated aptamers (45, 28, and 22-mer) as well as three different DNA probes (12, 9, and 13-mer) were further investigated to form the best combination for the QD-aptasensor. Using a 22-mer-truncated aptamer and a 12-mer DNA probe combination, the QD-aptasensor demonstrated excellent DEHP sensitivity with an LOQ = 0.5 pg/mL as well as good selectivity in the presence of other phthalate analogs. The binding between the truncated aptamers and DEHP was also characterized. Finally, a QD-aptasensor-based portable analyzer was also developed, and its equivalence to the laboratory protocol was established with a correlation coefficient r = 0.86 for DEHP concentrations ranging from 0.0005 to 100 ng/mL.