Stable Graphene-Based Membrane with pH-Responsive Gates for Advanced Molecular Separation.

Graphene-based stable pH-responsive membranes (GPMs) were developed by alternative deposition of graphene oxide (GO) with polyethylenimine (PEI) in a layer-by-layer manner. Different from the conventional pore-blocking pH-responsive membranes, the size of the gaps among the GO sheets were first designed to respond to the surrounding pH. Atomic force microscopy was used to dynamically explore the internal structure alteration of GPM in the pH range from 3 to 11. It was found that the PEI molecules not only cross-linked the GO sheets through amide bonds to ensure the membrane stability but also reversibly altered the gate size of GPM in a certain extent according to the surrounding pH. In filtration, the gates of GPM were widened with the decreasing pH of the feed and vice versa. As a result, the permeate flux of GPM increased with the decreasing feed pH. More importantly, the molecular weight cutoff of GPM could be continuously regulated by the feed pH in a certain range; during the filtration of the polyvinylpyrrolidone (PVP) and polyethylene oxide (PEO) mixed solution, only PVP (58 kDa) could penetrate GPM at pH 11, while the left PEO (600 kDa) would penetrate GPM at pH 3. The controlled penetration through GPM led to a complete separation and recovery of the molecules in different sizes, which is highly desirable for advanced molecular separation in environmental applications.

Porous PVdF/GO Nanofibrous Membranes for Selective Separation and Recycling of Charged Organic Dyes from Water.

Graphene oxide (GO) membranes are robust and continue to attract great attention due to their fascinating properties, despite their potential issues regarding stability and selectivity in aqueous-phase processing. That being said, however, the functional moieties of GO could be used for membrane surface modification, while ensuring simultaneous removal and recycling of industrial organic dyes. Herein, we present a versatile porous structured polyvinylidene fluoride-graphene oxide (PVdF-GO) nanofibrous membranes (NFMs), prepared by using simple and straightforward electrospinning approach for selective separation and filtration. The GO nanosheets were distributed homogeneously throughout the PVdF nanofiber, regulating the surface morphology and performance of PVdF-GO NFM. The PVdF-GO NFMs possesses high mechanical strength and surface free energy (SFE), consequently resulting high permeation and filtration efficiency as compared to PVdF NFM. The selectivity (99%) toward positively charged dyes based on electrostatic attraction, while maintaining rejection (100%) for negatively charged dye from mixed solutions highlight the role of GO in PVdF-GO NFM, owing to uniform pores and negatively charged surface. In addition, the actual efficiency of NFMs could be recovered easily up to three consecutive filtration cycles by regeneration, thereby assuring high stability. The high permeation, purification and filtration efficiency, good stability and recycling of PVdF-GO NFMs are promising for use in practical water purification and applications, particularly for selective filtration and recycling of dyes.

Nanocomposite Membrane with Polyethylenimine-Grafted Graphene Oxide as a Novel Additive to Enhance Pollutant Filtration Performance.

Synthetic membranes often suffer ubiquitous fouling as well as a trade-off between permeability and selectivity. However, emerging materials which are able to mitigate membrane fouling and break the permeability and selectivity trade-off are urgently needed. A novel additive, GO-PEI, bearing a positive charge and hydrophilic nature was prepared by the covalent grafting of polyethylenimine (PEI) molecules with graphene oxide (GO) nanosheets, which later was blended with bulk poly(ether sulfone) (PES) to fabricate the graphene containing nanocomposite membranes (NCMs). Strong π-π interactions contributed to the uniform dispersion of GO-PEI nanosheets in bulk PES to form the asymmetric structure of NCM without leaching. The ratio of the GO-PEI additive regulated the surface charge and hydrophilicity of NCMs. To filter charged proteins, the designed NCM exhibited a high permeability (flux) and high selectivity (retention) while showing resistance to fouling by the charged proteins, which could be attributed to the asymmetric structure and composition of the NCM that the porous internal and surface composited with the GO-PEI additive was responsible for the NCM's high flux; thereafter, the electrostatic attraction of the NCM surface to the charged pollutant enhanced the solute/water selectivity; finally, the synergistic effect of the hydrophilic and charged functional groups of the GO-PEI contributed to the formation of a dense hydration layer on the membrane surface thereby reducing membrane fouling. The NCM functionalized with the GO-PEI additive demonstrated potential for high-performance pollutant removal in water and wastewater treatments.

Controlling the kinetic chain length of the crosslinks in photo-polymerized biodegradable networks.

Biodegradable polymer networks were prepared by photo-initiated radical polymerization of methacrylate functionalized poly(D,L-lactide) oligomers. The kinetic chains formed in this radical polymerization are the multifunctional crosslinks of the networks. These chains are carbon-carbon chains that remain after degradation. If their molecular weight is too high these poly(methacrylic acid) chains can not be excreted by the kidneys. The effect of the photo-initiator concentration and the addition of 2-mercaptoethanol as a chain transfer agent on the molecular weight of the kinetic chains was investigated. It was found that both increasing the initiator concentration and adding 2-mercaptoethanol decrease the kinetic chain length. However, the effect of adding 2-mercaptoethanol was much larger. Some network properties such as the glass transition temperature and the swelling ratio in acetone are affected when the kinetic chain length is decreased.

Metal pollution and ecological risk assessment in marine sediments of Karachi Coast, Pakistan.

Concentrations of 12 metals (Fe, Mn, Cr, Mo, Ni, Pb, Se, Sr, U, V, Zn, and Zr) in surface sediments of Karachi Coast, Pakistan were determined to evaluate their distribution and pollution assessment. The measured metals in the sediments were found to be in the range of Fe, 0.84-6.96 %; Mn, 300-1,300 µg/g; Cr, 12.0-319.84 µg/g; Mo, 0.49-2.03 µg/g; Ni, 1.53-58.86 µg/g; Pb, 9.0-49.46 µg/g; Se, 0.25-.86 µg/g; Sr, 192-1185 µg/g; U, 0.19-1.66 µg/g; V, 15.80-118.20 µg/g; Zn, 15.60-666.28 µg/g; and Zr, 44.02-175.26 µg/g. The mean contents of the metal studied were: Fe, 3.07 %, Mn, 0.05 %; Cr, 96.75 µg/g; Mo, 1.34 µg/g; Ni, 31.39 µg/g; Pb, 23.24 µg/g; Se, 0.61 µg/g; Sr, 374.83 µg/g; U, 0.64 µg/g; V, 61.75 µg/g; Zn, 204.75 µg/g; and Zr:76.27 µg/g, and arrangement of the metals from higher to lower mean content in this area is: Fe > Zn > Mn > Sr > Zn > Cr > Zr > V > Ni > Pb > Mo > U > Se. There is no significant correlation among most of these metals, indicating different anthropogenic and natural sources. To assess ecotoxic potential of marine sediments, Numerical Sediment Quality Guidelines were also applied. The concentration of Pb in all the sediments except one was lower than the threshold effect concentration (TECs) showing that there are no harmful effects to marine life from Pb. On the other hand, the concentrations of Cr, Ni, and Zn exceeded TEC in three stations, indicating their potential risk. The degree of pollution in sediments for metals was assessed by calculating enrichment factor (EF) and pollution load index (PLI). The results indicated that sediments of Layari River Mouth Area, Fish Harbour, and KPT Boat Building Area are highly enriched with Cr and Zn (EF > 5). Sediments of Layari River Outfall Zone were moderately enriched with Ni and Pb (EF > 2). The pollution load index was found in the range of 0.98 to 1.34. Lower values of PLI (≤ 1) at most of sampling locations imply no appreciable input from anthropogenic sources. However, relatively higher PLI values (>1) at Layari River Mouth Area, Fish Harbour, and KPT Boat Building Area are attributed to increased human activity in the area.

Copolymerization of Carbonyl Sulfide and Propylene Oxide via a Heterogeneous Prussian Blue Analogue Catalyst with High Productivity and Selectivity.

This study demonstrates the superiority of a stable and well-defined heterogeneous cobalt hexacyanocobaltate (Co3 [Co(CN)6 ]2 ), a typical cobalt Prussian Blue Analogue (CoCo-PBA) that catalyzes the copolymerization of carbonyl sulfide (COS) and propylene oxide (PO) to produce poly(propylene monothiocarbonate)s (PPMTC). The number-average molecular weights of the PPMTC were 66.4 to 139.4 kg/mol, with a polydispersity of 2.0-3.9. The catalyst productivity reached 1040 g polymer/g catalyst (12.0 h). The oxygen-sulfur exchange reaction (O/S ER), which would generate random thiocarbonate and carbonate units, was effectively suppressed, and thus the selectivity of the monothiocarbonate over carbonate linkages was up to >99%. It was shown that no cyclic thiocarbonate byproduct was produced during the heterogeneous catalysis of COS/PO copolymerization using CoCo-PBA as the catalyst. The content of monothiocarbonate and ether units in the copolymer chain could be regulated by tuning the feeding amount of COS.

Development and characterization of chitosan and acrylic acid-based novel biodegradable polymeric films for soil conditioning.

In this study, biodegradable polymeric films (BPFs) based on chitosan and acrylic acid cross-linked with 3-aminopropyl triethoxysilane (APTES) were developed for water retention and soil-conditioning applications in areas sufferings from water scarcity. A series of BPFs were prepared by varying the amount of silica nanoparticles (SiNPs) (0.67% to 2.6%) and a correlation of the optimum amount of SiNPs with thermal stability, morphology, swellability (at various pH), degradability, and anti-microbial activity were deduced. The obtained results showed that the NP 8 (containing 2.51% of SiNPs) exhibited the maximum absorption capacity (1815%) in distilled water, whereas NP6 (including 1.88% of SiNPs) expressed the maximum thermal stability (T50% at 375.61 °C). The microscopic images further strengthen this observation because the maximum number of micro-porous cavities was shown on the surface of NP8. The time-dependent swelling response in distilled water accomplished that hydrophilicity (percentage swelling) of films was enhanced with an increase in the concentration of SiNPs. All BPFs samples exhibited inhibitory response against both gram-positive (for Staphylococcus aureus was 2.9 cm for NP6) and gram-negative (for Escherichia coli was 0.9 cm for NP8) bacteria. The biodegradation test inferred that the degradation of BPFs in soil did not affect the soil fertility as nano-silica is proven as growth-promoting miniatures. It can be concluded that these BPFs may be efficiently employed in the agriculture sector for water retention and as a soil conditioner.

Role of brain macrophages on IL-1beta and fatigue following eccentric exercise-induced muscle damage.

Fatigue associated with recovery from muscle damage has recently been linked to increases in brain and muscle proinflammatory cytokines. However, little is known regarding the origin of these cytokines. Since macrophage-like cells in the brain are a primary source of cytokines, we used a brain specific macrophage depletion technique involving liposome encapsulated clodronate (CLD) to examine the role of macrophages on brain IL-1beta and fatigue following eccentric exercise-induced muscle damage. Mice were assigned to six groups: Downhill saline (DWNSAL), downhill clodronate (DWNCLD), uphill saline (UPSAL), uphill clodronate (UPCLD), non-running saline (CONSAL) or non-running clodronate (CONCLD). Mice were given intracerebroventricular (ICV) (10 microL) injections of clodronate-filled liposomes (CLD) to deplete macrophages, or saline-filled liposomes (SAL) and run on a treadmill at 22m/min and -14% (DWN) or 14% (UP) grade for 150 min. A subset of uphill and downhill running mice (n=40) was then run to fatigue on a treadmill at 36m/min, 8% grade at 24h after the uphill and downhill runs. A second subset of uphill, downhill, and control mice (n=30) was sacrificed 24h after the run for analysis of brain IL-1beta concentration. Histological examination confirmed previous reports that CLD administration reduced perivascular and meningeal macrophage subsets in the brain. CLD reduced IL-1beta concentration in the cortex of DWN mice (P<0.05), which was associated with enhanced treadmill performance 24h after both uphill and downhill runs (P<0.05) although the magnitude was greater following the downhill run. These results suggest that brain macrophages can contribute to the increase in brain IL-1beta and fatigue that are associated with recovery from exercise-induced muscle damage.

Controlled-release behavior of ciprofloxacin from a biocompatible polymeric system based on sodium alginate/poly(ethylene glycol) mono methyl ether.

In this study, a facile drug release system was developed through a solution casting technique using a combination of sodium alginate (SA), poly(ethylene glycol)monomethyl ether (mPEG) and ciprofloxacin hydrochloride (CPX). The structure of the membranes was characterized using ATR-FTIR, AFM and the static contact angle (SCA) was determined to find surface nature of membranes. ATR-FTIR confirmed the existence of intermolecular hydrogen bonding between SA/mPEG in bio-polymeric membranes. AFM micrographs exhibited the extent of roughness which decreased as the contents of mPEG in the membranes were increased up to 40% (w/w). The SCA values ranged between 24° to 84° (at 0 s) and 14° to 80° (at 60 s) and showed an increase in hydrophilicity due to the incorporation of mPEG. In vitro drug release profile of CPX loaded on a membrane comprising of SA/mPEG (80/20) was evaluated in SGF (pH 1.2) and PBS (pH 7.4) solutions till 3 h. At pH 1.2, the maximum amount of CPX (~80%) was released in 70-120 min while ~75% drug was released in 90-120 min at pH 7.4. The present study demonstrated a facile and cost-effective approach to prepare SA/mPEG membranes that may be potentially employed as a drug delivery system in various biomedical applications.

Co-concentration effect of silane with natural extract on biodegradable polymeric films for food packaging.

Novel biodegradable films were prepared by blending guar gum, chitosan and poly (vinyl alcohol) having mint (ME) and grapefruit peel (GE) extracts and crosslinked with nontoxic tetraethoxysilane (TEOS). The co-concentration effect of TEOS with natural extracts on the films was studied. FTIR analysis confirmed the presence of incorporated components and the developed interactions among the polymer chains. The surface morphology of the films by SEM showed the hydrophilic character due to porous network structure. The films having both ME and GE with maximum amount of crosslinker (100µL), showed maximum swelling (58g/g) and stability while the optical properties showed increased protection against UV light. This film sample showed compact network structure which enhanced the ultimate tensile strength (40.03MPa) and elongation at break (104.8%). ME/GE conferred the antioxidant properties determined by radical scavenging activity and total phenolic contents (TPC) as ME films have greater TPC compared to GE films. The soil burial test exhibited the degradation of films rapidly (6days) confirming their strong microbial activity in soil. The lower water vapour transmission rate and water vapour permeability showed better shelf life; hence, these biodegradable films are environmental friendly and have potential for food and other packaging.

Organic matter source and degradation as revealed by molecular biomarkers in agricultural soils of Yuanyang terrace.

Three soils with different tillage activities were collected and compared for their organic matter sources and degradation. Two soils (TD and TP) with human activities showed more diverse of chemicals in both free lipids and CuO oxidation products than the one (NS) without human activities. Branched alkanoic acids only accounted for less than 5% of lipids, indicating limited microbial inputs in all three investigated soils. The degradation of lignin in NS and TD was relatively higher than TP, probably because of the chemical degradation, most likely UV light-involved photodegradation. Lignin parameters obtained from CuO oxidation products confirmed that woody gymnosperm tissue (such as pine trees) may be the main source for NS, while angiosperm tissues from vascular plant may be the predominant source for the lignins in TD and TP. Analysis of BPCAs illustrated that BC in NS may be mainly originated from soot or other fossil carbon sources, whereas BC in TD and TP may be produced during corn stalk and straw burning. BC was involved in mineral interactions for TD and TP. The dynamics of organic matter needs to be extensively examined for their nonideal interactions with contaminants.

Injectable biopolymer based hydrogels for drug delivery applications.

Biopolymer based pH-sensitive hydrogels were prepared using chitosan (CS) with polyethylene glycol (PEG) of different molecular weights in the presence of silane crosslinker. The incorporated components remain undissolved in different swelling media as they are connected by siloxane linkage which was confirmed by Fourier transform infrared spectroscopy. The swelling in water was enhanced by the addition of higher molecular weight PEG. The swelling behaviour of the hydrogels against pH showed high swelling in acidic and basic pH, whereas, low swelling was examined at pH 6 and 7. This characteristic pH responsive behaviour at neutral pH made them suitable for injectable controlled drug delivery. The controlled release analysis of Cefixime (CFX) (model drug) loaded CS/PEG hydrogel exhibited that the entire drug was released in 30 min in simulated gastric fluid (SGF) while in simulated intestinal fluid (SIF), 85% of drug was released in controlled manner within 80 min. This inferred that the developed hydrogels can be an attractive biomaterial for injectable drug delivery with physiological pH and other biomedical applications.

Design of polymer-brush-grafted magnetic nanoparticles for highly efficient water remediation.

Highly efficient removal of mercury(II) ions (Hg(II)) from water has been reported by employing polymer-brush-functionalized magnetic nanoparticles (MNPs). Surface-initiated conventional radical polymerization (SI-cRP) was used to grow poly(2-aminoethyl methacrylate hydrochloride) (poly-AEMA·HCl) polymer chains on magnetite nanoparticles (Fe3O4), followed by the transformation of pendant amino groups into dithiocarbamate (DTC) groups, which showed high chelating affinity toward Hg(II) ions. This polymer-brush-based DTC-functionalized MNP (MNPs-polyAEMA·DTC) platform showed the complete removal of Hg(II) from aqueous solutions. The Hg(II) ion removal capacity and efficiency of MNPs-polyAEMA·DTC were compared with its monolayer analogue, which was derived from the direct transformation of amino groups of (3-aminopropyl) triethoxysilane (APTES)-functionalized MNPs (MNPs-APTES) to DTC functional groups (MNPs-DTC). The surface chemical modifications and higher chelating functional group density, in the case of MNPs-polyAEMA·DTC, were ascertained by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), physical property measurement system (PPMS), attenuated total reflectance infrared (ATR-IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The Hg(II) ion removal capacity and efficiency of monolayer and polymer-brush-based DTC-functionalized MNPs (MNPs-DTC and MNPs-polyAEMA·DTC, respectively) were evaluated and compared by studying the effect of various factors on the percentage removal of Hg(II) such as adsorbent amount, temperature, and contact time. Furthermore, the adsorption behavior of MNPs-DTC and MNPs-polyAEMA·DTC was analyzed by applying Langmuir and Freundlich adsorption isotherm models. In addition, the adsorption thermodynamics, as well as the adsorption kinetics, were also evaluated in detail. The higher surface functional group density of MNPs-polyAEMA·DTC led to superior remediation characteristics toward Hg(II) ions than its monolayer analogue.