A novel scalable polycationic melamine sponge-based filtration matrix for continuous ultrafast adsorption of anionic pollutants.

Effective capturing of anionic pollutants from wastewater under industrial operating conditions, which requires high processing flux and fast adsorption rate remains a challenge. Here, a commercially available melamine sponge (MS) with reticulated 3D macroporous structures was covalently modified with positively charged moieties using a single step functionalization under mild conditions. The developed novel polycationic melamine sponge (MS+) was formed by a nucleophilic addition reaction between glycidyltrimethylammonium chloride (GMTA) and MS, followed by a self-propagation of GMTA. The produced MS+ possessed strong electrostatic interactions with different anions such as Rose Bengal (RB) and phosphates (P) under a wide pH range (3-11). The MS+ exhibited promoted static adsorption efficiencies of 400 mg g-1 (P) and 600 mg g-1 (RB), within 5 min and 60 s, respectively. Furthermore, the MS+ showed high stability and recyclability for up to 15 cycles of uses, and the recycling process was environmentally friendly by using 1 M NaCl as a releasing solution. Benefiting from fast flow through the macroporous MS+ and highly positive charged skeleton, the MS+ was applied for rapid dynamic enrichment process of P from real manure wastewater with an enrichment factor of 4.4. Utilization of the MS+ as the substrate brings additional advantages such as low cost, availability, and flexibility to fit into existing filtration devices. The developed MS+ could be expanded for enrichments of other anionic species from various polluted water sources.

A label-free electrochemical immunosensor based on decorated cellulose nanofibrous membrane for point-of-care diagnosis of amanitin poisoning via human urine.

α-Amanitin (AMN) is one of the deadliest toxins from mushrooms, present in the deadly mushroom species Amanita phalloides. It is a bicyclic octapeptide and represents up to 40% of the amatoxins in mushrooms, damaging the liver and kidneys. Current methods of detecting amatoxins are time-consuming and require the use of expensive equipment. A novel label-free electrochemical immunosensor was successfully developed for rapid detection of α-amanitin, which was fabricated by immobilization of anti-α-amanitin antibodies onto a functionalized cellulose nanofibrous membrane-modified carbon screen-printed electrode. An oxidation peak of the captured amanitin on the tethered antibodies was observed at 0.45 V. The performance of the nanofibrous membrane on the electrode and necessary fabrication steps were investigated by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). Due to its unique structural features and properties such as high specific surface area and microporous structure, the nanofibrous membrane as an immunosensor matrix for antibody tethering improved the electrochemical performance of the immunosensor by more than 3 times compared with cast membranes. Under the optimal conditions, the assembled immunosensor exhibited high sensitivity toward α-amanitin detection in the range of 0.009-2 ng mL-1 with a limit of detection of 8.3 pg mL-1. The results clearly indicate that the fabricated nanofiber-based-immunosensor is suitable for point-of-care detection of lethal α-amanitin in human urine without any pretreatment within 30 min.

Cationic microcrystalline cellulose - Montmorillonite composite aerogel for preconcentration of inorganic anions from dairy wastewater.

Development of efficient adsorbents to inorganic anions as a solid phase extraction (SPE) material is highly desirable for chromatographic analysis and pollution control. In this work we developed a new hybrid cationic microcrystalline cellulose aerogel composite. Cationic cetylpyridinium imbedded montmorillonite (CPC-MT) was uniformly entrapped in microcrystalline cellulose (MCC) to enhance anionic adsorption efficiency and mechanical stability. The developed CPC-MT@MCC aerogel was used as an SPE adsorbent for anions from dairy wastewater by coupling with ion-column chromatography. Further quaternized CPC-MT@MCC aerogel (CPC-MT@QMCC) showed unique low density (10.6 mg cm-3), large specific surface area (320 m2 g-1), porosity 70%, 800 mg g-1 nitrate adsorption capacity within 60 min and ease of elution in alkaline solutions. The CPC-MT@QMCC aerogel showed efficient regeneration and reuse performances for up to 10 cycles. More importantly, a dynamic binding efficiency of 710 mg g-1 highlights its excellent performance for practical applications. 96% of nitrate anion from environmental manure wastewater samples were adsorbed with 98.7% recovery. A good linear relationship was obtained in the range of 0.01-10 mg L-1 and the limits of detection was 0.5 mg L-1 using CPC-MT@QMCC aerogel as a preconcentration column. The successful synthesis of such intriguing and economic CPC-MT@QMCC aerogel may provide a promising matrix for high-performance and high efficiency chromatographic media.

Predicting Escherichia coli levels in manure using machine learning in weeping wall and mechanical liquid solid separation systems.

An increased understanding of the interaction between manure management and public and environmental health has led to the development of Alternative Dairy Effluent Management Strategies (ADEMS). The efficiency of such ADEMS can be increased using mechanical solid-liquid-separator (SLS) or gravitational Weeping-Wall (WW) solid separation systems. In this research, using pilot study data from 96 samples, the chemical, physical, biological, seasonal, and structural parameters between SLS and WW of ADEM systems were compared. Parameters including sodium, potassium, total salts, volatile solids, pH, and E. coli levels were significantly different between the SLS and WW of ADEMS. The separated solid fraction of the dairy effluents had the lowest E. coli levels, which could have beneficial downstream implications in terms of microbial pollution control. To predict effluent quality and microbial pollution risk, we used Escherichia coli as the indicator organism, and a versatile machine learning, ensemble, stacked, super-learner model called E-C-MAN (Escherichia coli-Manure) was developed. Using pilot data, the E-C-MAN model was trained, and the trained model was validated with the test dataset. These results demonstrate that the heuristic E-C-MAN ensemble model can provide a pilot framework toward predicting Escherichia coli levels in manure treated by SLS or WW systems.

Fabrication of polydopamine-based NIR-light responsive imprinted nanofibrous membrane for effective lysozyme extraction and controlled release from chicken egg white.

The development of highly efficient performance matrix for protein adsorption and scalable throughput adsorbent is highly desired, especially in pharmaceuticals and food industries. In this work, we present a simple methodology to prepare a nanofibrous membrane based surface molecular imprinted matrix (MIP) for selective separation of lysozyme. The MIP was developed by coating carboxylated poly (vinyl alcohol-co-ethylene) nanofibrous mat (EVOH-CCA NFM) with a near infrared (NIR)-light responsive polydopamine (PDA) layer. The open porous nanofibrous structure and a thin PDA layer endowed the MIPs with adsorption capacity (500 mg.g-1) within 150 min. The developed surface MIPs not only showed imprinting factor (IF = 4) with reusability upon 5 cycles, but also capability of extracting lysozyme from egg-white directly. The MIPs showed controlled release of extracted lysozyme triggered by the NIR-light responsive property of the PDA layer. Moreover, the released lysozyme possesses good bioactivity, evidenced by efficient decomposition of micrococcus bacterial cell wall.

Effective tetracycline removal from liquid streams of dairy manure via hierarchical poly (vinyl alcohol-co-ethylene)/polyaniline metal complex nanofibrous membranes.

Antibiotic residues from animal wastes enter underground and surface water streams, posing high risks to public health. Novel technologies capable of removing the residues from the matrix of concern such as animal waste should be developed. This research investigates the development of nanofiber absorbent for removing tetracycline (TC) antibiotic residues from liquid streams of dairy manure produced in a typical dairy farm. Hierarchically structured nanofibrous adsorbent was developed through growing a uniform polyaniline (PAni) nanodots on poly (vinyl alcohol-co-ethylene) (EVOH) nanofiber membrane (NFM). Moreover, Cu2+ ions were chelated on the developed EVOH/PAni-Cl NFM to improve TC adsorption efficiency and selectivity. The TC adsorption capacities of EVOH/PAni-Cl-Cu2+ and EVOH/PAni-Cl) NFM were 1100 mg g-1 and 600 mg g-1 within 120 min., respectively. The NFMs adsorption efficiency was investigated using dairy wastewater. Initial TC concentrations in dairy wastewater sample varied between 20 and 50 ppm. The EVOH/PAni-Cl-Cu2+ NFM showed TC removal of 86% from dairy manure samples at 25 ppm initial TC concentration within 60 min. during batch mode treatment. Results showed that the dynamic binding efficiency of 450 mg g-1 can be achieved at an initial TC concentration of 50 ppm. Furthermore, the NFM displayed efficient chemical and physical stability even after 8 cycles of reusing without significant changes in its performance or hazardous Cu2+ leaching.

Rapid removal of nitrate from liquid dairy manure by cationic poly (vinyl alcohol-co-ethylene) nanofiber membrane.

Elevated levels of nitrate in surface water is a leading concern, which impacts human and animal health, and controlling it requires improved and sustainable methods capable of removing nitrate anions from source waste water to reduce nitrate anions transport to environment. In liquid dairy manure, nitrogen content can vary from 200 to 600 ppm and the transport of manure nitrogen into ambient water through hydrologic processes has a potential to exceed the maximum contaminant level limit (10 ppm) of nitrate nitrogen for regulated public water systems. Dairy manure is considered as a reservoir of nitrate. This research investigates on the determination of optimal designing of nanofiber membrane to remove nitrate anions from liquid dairy manure. A cationic poly (vinyl alcohol-co-ethylene) nanofiber membrane (EVOH) NFM was grafted via UV with 2-(methacryloyloxy) ethyl trimethylammonium chloride (DMAC) monomers. The adsorption efficiency of nitrate by the membrane was determined on liquid manure of dairy lagoons located in Central Valley of California. Initial nitrate concentrations in dairy manure varied from 75 to 100 ppm. Results showed that nitrate in dairy water was removed by 70% in 40 min. Tortuous structure and chemical stability of membrane resulted in nitrate dynamic binding capacity of 40 mg g-1. Furthermore, it exhibits efficient reusability without significant changes in its performance using 0.5 M sodium hydroxide solution for nitrate desorption. Results showed that change in pH, and multi-anion conditions had limited effects on nitrate removal efficiency, and EVOH NFM can be a viable option to remove nitrate of liquid manure. This could be used for mitigating transport of excess nitrate from manure to environment. Overall, the results suggest that EVOH-g-DMAC NFM is efficient, low-cost (13 USD/m3) and recyclable material for sustainable removal of nitrate from dairy manure wastewater without requiring any ionic strength or pH adjustment.

Dipteran Carboxymethyl Chitosan as an Inexhaustible Derivative with a Potential Antiproliferative Activity in Hepatocellular Carcinoma Cells.

Traditional folk therapies indicate that insects have diverse medicinal potentials. However, the therapeutic application of insect chitosan and its derivatives has not been explored. To investigate the application of chitosan and its derivatives, the carboxymethyl derivative of chitosan (CM-Ch) was extracted from two dipteran larvae species, Chrysomya albiceps and Sarcophaga aegyptiaca. The degree of deacetylation (DD) and CM-Ch functional groups were validated using Fourier-transform infrared (FTIR) spectroscopy analysis and proton nuclear magnetic resonance spectroscopy (1H NMR), respectively. The molecular weight was estimated using MALDI-TOF MS analysis. The effect of CM-Ch on the morphology and proliferation of human liver HepG2 cancer cells was assessed. IC50 of CM-Ch induced significant growth-inhibitory effects in HepG2 cells. CM-Ch treatment altered the morphology of HepG2 in a dose-dependent manner and induced apoptosis in a caspase-dependent manner. CM-Ch treatment showed no signs of toxicity, and no alterations in liver and kidney biochemical markers were observed in albino rats. A CM-Ch derivative from commercial crustacean chitosan was used to assess the efficacy of the insect-derived CM-Ch. The data presented here introduce insect CM-Ch as a promising, inexhaustible, safe derivative of chitosan with antitumor potential in liver cancer. This is the first report highlighting the anticancer activity of insect CM-Ch in hepatocellular carcinoma cells.

A signal-on electrochemical aptasensor based on silanized cellulose nanofibers for rapid point-of-use detection of ochratoxin A.

An innovative ultrasensitive electrochemical aptamer-based sensor was developed for ochratoxin A (OTA) detection in cold brew coffee through revolutionary combination of nanofibers, electrochemical method, and aptamer technologies. The assembly of the aptasensor was based on the activation of silanized cellulose nanofibrous membranes as a supporting matrix for methylene blue (MB) redox probe-labeled aptamer tethering. Cellulose nanofibrous membranes were regenerated by deacetylating electrospun cellulose acetate nanofibrous membranes with deacetylation efficacy of 97%, followed by silanization of the nanofiber surfaces by using (3-aminopropyl)triethoxysilane (APTES). A replacement of conventionally casted membranes by the nanofibrous membranes increased the active surface area on the working electrode of a screen-printed three-electrode sensor by more than two times, consequently enhancing the fabricated aptasensor performance. The developed aptasensor demonstrated high sensitivity and specificity toward OTA in a range 0.002-2 ng mL-1, with a detection limit of 0.81 pg mL-1. Moreover, the assembled aptamer-based sensor successfully detected OTA in cold brew coffee samples without any pretreatment. The aptasensor exhibited good reusability and stability over long storage time. Graphical abstract.

Functionalized nanofibrous nylon 6 membranes for efficient reusable and selective separation of laccase enzyme.

The development of biomolecules adsorbent with superb efficiency and large processing throughput is of great importance for separation and reusing of enzymes in its free form in various vital industries. Herein, laccase enzyme adsorbent was prepared by carboxylation of nanofibrous nylon 6 membranes (Ny NFM) to form complex with copper metal ions [Ny-CCA-Cu(II)] with high selectivity for laccase adsorption with adsorption capacity 220 mg.g-1 within 4 h. The prepared nylon NFM provides a promising candidate for separation and use of laccase enzyme in its free form for several times without significant change in its activity. Moreover, [Ny-CCA-Cu(II)] showed dynamic binding efficiency of 160 mg g-1 which was achieved solely by a gravity filtration, as well as good reusability of [Ny-CCA-Cu(II)] at least for 5 cycles. The results were due to stable physical and chemical structures, highly tortuous open-porous structure of the nanofibrous membranes, and incorporated Cu+2 complex in [Ny-CCA-Cu(II)]. This simple approach may introduce a way for the design and development of a cost-effective, environmentally friendly and selective adsorptive membranes to recover the valuable enzymes in industrial applications.

An Innovative Nanobody-Based Electrochemical Immunosensor Using Decorated Nylon Nanofibers for Point-of-Care Monitoring of Human Exposure to Pyrethroid Insecticides.

A novel ultrasensitive nanobody-based electrochemical immunoassay was prepared for assessing human exposure to pyrethroid insecticides. 3-Phenoxybenzoic acid (3-PBA) is a common human urinary metabolite for numerous pyrethroids, which broadly served as a biomarker for following the human exposure to this pesticide group. The 3-PBA detection was via a direct competition for binding to alkaline phosphatase-embedded nanobodies between free 3-PBA and a 3-PBA-bovine serum albumin conjugate covalently immobilized onto citric acid-decorated nylon nanofibers, which were incorporated on a screen-printed electrode (SPE). Electrochemical impedance spectroscopy (EIS) was utilized to support the advantage of the employment of nanofibrous membranes and the success of the immunosensor assembly. The coupling between the nanofiber and nanobody technologies provided an ultrasensitive and selective immunosensor for 3-PBA detection in the range of 0.8 to 1000 pg mL-1 with a detection limit of 0.64 pg mL-1. Moreover, when the test for 3-PBA was applied to real samples, the established immunosensor proved to be a viable alternative to the conventional methods for 3-PBA detection in human urine even without sample cleanup. It showed excellent properties and stability over time.

Ultrasensitive label-free electrochemical immunosensor based on PVA-co-PE nanofibrous membrane for the detection of chloramphenicol residues in milk.

An ultrasensitive label-free amperometric immunosensor for the detection of chloramphenicol (CAP) residues in milk has been developed by using a screen-printed carbon electrode laminated with a layer of poly (vinyl alcohol-co-ethylene) (PVA-co-PE) nanofibrous membrane that is covalently immobilized with a CAP antibody (anti-CAP). The performance of the PVA-co-PE nanofiber membrane (PVA-co-PE NFM) on the electrode was compared with a PVA-co-PE casted membrane (PVA-co-PE CM), necessary fabrication steps and performance of the sensors were investigated by electrochemical impedance spectroscopy (EIS). The application of the PVA-co-PE NFM decreased the electron-transfer-resistance by about 4 times compared with a conventional PVA-co-PE casted membrane. Under the optimal conditions, the established immunosensor exhibited high sensitivity for determination of CAP in a range 0.01-10 ng mL-1, with a limit of detection of 0.0047 ng mL-1. In addition to the good selectivity, reusability and stability over time, the prepared immunosensor was successfully used in the detection of CAP in milk samples without any pretreatment.

Reusable anionic sulfonate functionalized nanofibrous membranes for cellulase enzyme adsorption and separation.

Poly (vinyl alcohol-co-ethylene) nanofibrous membranes (PVA-co-PE NFM) were successfully modified by sodium-3-sulfobenzoate to become negatively charged with sulfonate groups, and the sulfonated (PVA-co-PE) nanofiber membrane SS (PVA-co-PE NFM) was used in non-covalent adsorption of cellulases via electrostatic attraction. The modified NFM showed excellent adsorption to the enzyme molecules due to the incorporated static charge interaction with the fibers, high open-porosity and ultrahigh surface areas of the nanofibers. Such unique morphology and chemical structures lead to the adsorption capacity of 130 mg g-1 and reusability for 5 cycles without significant change in catalytic functions. The morphology changes of the nanofibrous membranes were observed by using a scanning electron microscopy, and chemical structures of the membranes were characterized by using FTIR and water contact angle measurements. SS (PVA-co-PE NFM) is a promising solid support media for enzyme immobilization, and the immobilized enzymes can be applied in industrial applications.