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The membrane fouling layer in the combined aerobic granular membrane bioreactor (AGMBR) process and the conventional MBR process was probed in this study using the multiple staining and confocal laser scanning microscope (CLSM) technique. The fouling layer built up outside and inside the membrane was principally composed of live cells embedded in a matrix of proteins and polysaccharides. The fouling layer presented outside the membrane is noted denser in structure than that inside the membrane. [ABSTRACT FROM AUTHOR]

Aerobic sludge granules are compact, strong microbial aggregates that have excellent settling ability and capability to efficiently treat high-strength and toxic wastewaters. Aerobic granules disintegrate under high organic loading rates (OLR). This study cultivated aerobic granules using acetate as the sole carbon and energy source in three identical sequencing batch reactors operated under OLR of 9–21.3 kg chemical oxygen demand (COD) m−3 day−1. The cultivated granules removed 94–96% of fed COD at OLR up to 9–19.5 kg COD m−3 day−1, and disintegrated at OLR of 21.3 kg COD m−3 day−1. Most tested isolates did not grow in the medium at >3,000 mg COD l−1; additionally, these strains lost capability for auto-aggregation and protein or polysaccharide productivity. This critical COD regime correlates strongly with the OLR range in which granules started disintegrating. Reduced protein quantity secreted by isolates was associated with the noted poor granule integrity under high OLR. This work identified a potential cause of biological nature for aerobic granules breakdown. [ABSTRACT FROM AUTHOR]

Efficient nitrification and denitrification of wastewater containing 1,700 mgl−1 of ammonium-nitrogen was achieved using aerobic granular sludge cultivated at medium-to-high organic loading rates. The cultivated granules were tested in a sequencing batch reactor (SBR) fed with 6.4 or 10.2 kg NH-N m−3 day−1, a loading significantly higher than that reported in literature. With alternating 2 h oxic and 2 h anoxic operation (OA) modes, removal rate was 45.5 mg NH-N g−1 volatile suspended solids−1 h−1 at 6.4 kg NH-N m−3 day−1 loading and 41.3 ± 2.0 at 10.2 kg NH-N m−3 day−1 loading. Following the 60 days SBR test, granules were intact. The fluorescence in situ hybridization and confocal laser scanning microscopy results indicate that the SBR-OA granules have a distribution with nitrifers outside and heterotrophs outside that can effectively expose functional strains to surrounding substrates at high concentrations with minimal mass transfer limit. This microbial alignment combined with the smooth granule surface achieved nitrification–denitrification of wastewaters containing high-strength ammonium using aerobic granules. Conversely, the SBR continuous aeration mode yielded a distribution with nitrifers outside and heterotrophs inside with an unsatisfactory denitrification rate and floating granules as gas likely accumulated deep in the granules. [ABSTRACT FROM AUTHOR]

The article focuses on microporous polymers with cascaded cavities for controlled transport of small gas molecules. Topics icnlude the membrane-based separation, molecular size differences relative to membrane pore sizes govern mass flux and separation efficiency, and the applications requiring complex molecular differentiation, such as in natural gas processing, cascaded pore size distributions in membranes allow different permeate molecules to be separated without a reduction in throughput.

Environmental stimuli-responsive nucleobase-functionalized supramolecular polymers, a combination of oligomeric polypropylene glycol segments as a thermosensitive element and hydrogen-bonded uracil as a photosensitive moiety, were successfully developed and undergo spontaneous self-assembly to form uniform nanosized micelles via self-complementary double hydrogen bonding interactions between the uracil moieties in an aqueous environment. These micelles exhibit unique properties such as dual thermo- and photoresponsiveness, controllable lower critical concentration solution temperature (LCST), photoreactivity, and morphological transformation, making them highly attractive for various applications. More importantly, phase transitions and morphological studies confirmed the LCST behavior, size, and shape of the micelles can be easily tuned by adjusting the concentration and duration of ultraviolet irradiation of samples in aqueous solution, indicating introduction of uracil molecules into a water-soluble polymer matrix may represent a promising approach toward development of multiple stimuli-responsive polymeric micelles whose self-assembly behavior can be manipulated. In view of the ease of fabrication, high biocompatibility, multifunctionality, and tailorable micellar properties, this newly developed supramolecular micelle may be a promising candidate nanocarrier for controlled drug delivery and bioimaging systems. [ABSTRACT FROM AUTHOR]

Membrane support properties influence the performance of thin-film composite nanofiltration membranes. We fabricated several polysulfone (PSf) supports. The physicochemical properties of PSf were altered by adding polyethylene glycol (PEG) of varying molecular weights (200-35,000 g/mol). This alteration facilitated the formation of a thin polyamide layer on the PSf surface during the interfacial polymerization reaction involving an aqueous solution of piperazine containing 4-aminobenzoic acid and an organic solution of trimesoyl chloride. Attenuated total reflectance-Fourier transform infrared validated the presence of PEG in the membrane support. Scanning electron microscopy and atomic force microscopy illustrated that the thin-film polyamide layer morphology transformed from a rough to a smooth surface. A cross-flow filtration test indicated that a thin-film composite polyamide membrane comprising a PSf support (TFC-PEG20k) with a low surface porosity, small pore size, and suitable hydrophilicity delivered the highest water flux and separation efficiency (J = 81.1 ± 6.4 L⋅m-2·h-1, RNa2SO4 = 91.1% ± 1.8%, and RNaCl = 35.7% ± 3.1% at 0.60 MPa). This membrane had a molecular weight cutoff of 292 g/mol and also a high rejection for negatively charged dyes. Therefore, a PSf support exhibiting suitable physicochemical properties endowed a thin-film composite polyamide membrane with high performance [ABSTRACT FROM AUTHOR]

Reduced graphene oxide (rGO) has been prepared through hydrothermal reduction, an environmentally safe reduction of graphene oxide (GO). rGO is used to fabricate a highly compatible and orderly stacked lamellar structure of composite membranes with chitosan (CS). This method also facilitates a continuous large-scale fabrication of membranes. Conventionally, GO and CS are the preferred compounds for this type of fabrication because of their hydrophilic nature. Nevertheless, when they are mixed together, the occurrence of ionic complexation (-COO- H3+ N-R) between the negatively charged carboxylate ions of GO and the positively charged protonated amines of CS create extreme membrane aggregation. Hydrothermal reduction is useful for preventing undesired ionic complexation from mixing rGO and CS because it can remove most carboxylate ions from GO. Consequently, the hydrophilic CS molecular chain is inserted in between the rGO laminates, improving the dispersion and enabling the rGO/CS to stack-up and self-assemble into a lamellar structure. Furthermore, excellent methanol dehydration can be observed through pervaporation, which is attributed to the selective water channels formed in the rGO laminates. [ABSTRACT FROM AUTHOR]

A thermoresponsive chitosan derivative was synthesized by reacting chitosan (CS) with butyl glycidyl ether (BGE) to break the inter- and intramolecular hydrogen bonds of the polymer. An aqueous solution of the thermoresponsive CS derivative exhibits a lower critical solution temperature (LCST) than CS, and it undergoes a phase transition separation when the temperature changes. Successful incorporation of BGE into the CS was confirmed by FTIR and XPS analyses. Varying the BGE content and the concentration of the aqueous solution produced different LCST ranges, as shown by transmittance vs temperature curves. The particle size was observed by scanning electron microscopy, which revealed that the particles were smaller and well dispersed at 15 °C, whereas the particles became larger and tended to aggregate at 60 °C. A similar trend was observed with the mean particle size measured using dynamic light scattering. Positron annihilation lifetime spectroscopy data also revealed the reversibility of the particle properties as a function of temperature. Microstructure analysis showed that the particles had larger free-volume sizes at 15 °C than at 60 °C. The particles were also found to be nontoxic with 92% cell survival. A simple forward osmosis (FO) test for dye dehydration revealed the potential use of the thermoresponsive chitosan derivative as a draw solute with a flux of 8.6 L/m2 h and rejection of 99.8%. [ABSTRACT FROM AUTHOR]

Novel electrochromic polynorbornenes poly(NBPYTPAM) and poly(HNBPYTPAM), containing electroactive chromophores, were prepared via ring-opening metathesis polymerization (ROMP) from a new norbornene derivative (NBPYTPAM) using Grubbs’ catalyst and followed by hydrogen reduction. The glass transition temperatures (Tg) of poly(NBPYTPAM) and hydrogenated poly(HNBPYTPAM) were 190 and 175 °C, respectively. The cyclic voltammogram of the poly(HNBPYTPAM) film cast onto flexible graphene-coated polyethylene terephthalene (PET) substrates exhibited two reversible oxidation redox couples at 1.0 and 1.9 V. Flexible electrochromic devices were fabricated from the electroactive polymers and graphene-coated PET substrates. The electrochromic characteristics of poly(HNBPYTPAM) showed excellent stability and reversibility, with multistaged color changes from its yellow neutral form to green and then to dark-blue. [ABSTRACT FROM AUTHOR]

Aerobic granulation (AG) and membrane bioreactor (MBR) are two promising, novel environmental biotechnological processes that draw interest of researchers working in the area of biological wastewater treatment. Membrane fouling in the combined aerobic granular membrane bioreactor (AGMBR) process and the conventional MBR process was investigated in this work. The irreversible fouling on hollow-fibre membranes in both reactors were observed with the multiple staining and confocal laser scanning microscope technique. Following physical and chemical washing, the external fouling layers were mostly removed. However, the biofilms built up in the interior surface of membrane remained and contributed to the irreversible fouling resistance. AGMBR retained most cells with granules, thereby reducing their penetration through membrane and thus the chance to form internal fouling layer. The internal biofilm layer was principally composed of live cells embedded in a matrix of proteins and polysaccharides, with that on AGMBR denser and thicker than that on MBR. Prevention of development of internal biofilm is essential to reduce irreversible fouling of AGMBR and MBR membranes. [ABSTRACT FROM AUTHOR]

A variable monoenergy slow positron beam (VMSPB) operating at a high vacuum on insulating materials encounters a problem of significant surface charging effect with time. As a result, positronium formation is inhibited, and the positron annihilation radiation counting rate is reduced; these consequently distorted the experimental positron annihilation and results. To solve such problems, a technique of depositing an ultrathin layer of sputtering noble metals on insulators is developed. We report a successful method of sputtering a few atomic layers of platinum (∼1 nm) on a polyamide membrane to completely remove the charging effect for VMSPB applications in insulators. [ABSTRACT FROM AUTHOR]

This work studies the aggregation structures and free volumes of novel polyelectrolyte complex membranes (PECMs) and correlates the two with their ultrahigh permeability to water. Solution-processable PECs between poly(2-methacryloyloxy ethyl trimethylammonium chloride) (PDMC) and sodium carboxymethyl cellulose (CMCNa) were prepared in a two-step method, i.e., precipitation in HCl and redispersion in NaOH. PECMs were subsequently made in a solution casting method. Chemical and aggregation structures of PECs solids were characterized by FT-IR, element analysis (EA), ζ potential, transmission electron microscopy (TEM), and dynamic light scattering (DLS). Surface and cross-section structures of PECMs were characterized by a field emission scanning microscopy (FESEM) and an atomic force microscopy (AFM). Free volume of PECMs was characterized by positron annihilation lifetime spectroscopy (PALS). The free volume of PECMs is larger than that of component polyelectrolyte and is ascribed to the unique aggregation structures of PECMs. Moreover, PALS shows that a long lifetime component (τ4) exists with PECMs, indicating that there are water channels in PECMs. Due to these channels, PECMs showed ultrahigh permeability and selectivity. [ABSTRACT FROM AUTHOR]

The soluble microbial products (SMP) and extracellular polymeric substances (EPS) significantly affect fouling in membrane filtration. This work filtered SMP and fractionated EPS of activated sludge using a 0.45 mm filter membrane. The fluorescently labeled stains and confocol laser scanning microscopy (CLSM) images in situ visualized the distributions of proteins, α-polysaccharides, β-polysaccharides, lipids, total cells, and dead cells of different EPS fractions in the fouling layers. The role of individual SMP and fractionated EPS fractions on membrane fouling was discussed. [ABSTRACT FROM AUTHOR]

Coagulation is a commonly adopted process as a pretreatment step for minimizing membrane fouling. Three coagulants, polyaluminum chloride (PACl), alum, and FeCl3 were tested under four mixing-settling schemes for turbidity and natural organic matters (NOM) removal. The organic matters in the raw waters were fractionated by high performance size exclusion chromatography (HP-SEC) system and were characterized using the excitation-emission matrix (EEM) fluorescence spectra. Sufficient rapid mixing and slow mixing or applying two-stage coagulation benefit turbidity removal using PACl or FeCl3 under “electrostatic patch coagulation” (EPC) mechanism. The EPC mechanism is not efficient for alum coagulation. At higher coagulant doses, the NOM removal is not affected by mixing condition. Intensive rapid mixing alone benefits NOM removal using PACl or FeCl3. Alum is a poor coagulant for NOM removal under EPC mechanism. [ABSTRACT FROM AUTHOR]

Layer-by-layer deposition of polyelectrolyte multilayer (PEM) membranes has recently been applied successfully to a number of biomedical applications. This simple and versatile technique provides a broad surface modification platform, for example, for the display of biomolecules such as cell-adhesion peptides. In this work, we investigated the effects of PEM coatings on RGD-immobilization and osteoblast cell culture. RGD-containing peptides were conjugated to the amino groups of poly(allylamine hydrochloride) (PAH), and then adsorbed on top of 10-layer PAH/poly(acrylic acid) (PAA) multilayer membranes that were assembled at either pH 2.0 or pH 6.5. MG63 osteoblast-like cells were then seeded and cultured on the RGD-conjugated surfaces. We found that the cells adhered to and grew better on the RGD-conjugated PEM membranes. Furthermore, the cells grew better on the RGD-conjugated PEM coatings assembled at pH 6.5 than those assembled at pH 2.0. On the other hand, MG63 cells exhibited better differentiated phenotype on the pH 2.0 coatings compared to the pH 6.5 coatings with respect to alkaline phosphatase activity and calcium deposition, while cells did not express osteoblast phenotype on the PAH surfaces. These results clearly show that the base PEM membranes play an important role in RGD-immobilization and osteoblast functions. [ABSTRACT FROM AUTHOR]

Phenol degradation was carried out by using a modified three-stage airlift packing-bed bioreactor. A laboratory-scale airlift packing-bed reactor, with hydrodynamic flexible packing material in the three-stage bioreactor, was constructed and operated for phenol removal from synthetic wastewater. The airlift packing-bed reactor successfully degraded phenol and lowered the chemical oxygen demand (COD) of wastewater. High COD removal was observed, and much lower sludge effluent was obtained in this investigation. This airlift bioreactor showed a superior hydrodynamics performance and broad operating conditions for phenolic material removal. Different operating modes were discussed to obtain the optimal condition for phenol degradation (i.e., hydraulic retention time [HRT] and gas flowrate of airlift). The HRT and feed phenol concentration of wastewater dominated the removal efficiency of phenol and COD. In this bioreactor, surface loading up to 2.84 g phenoll m²·d, almost 100% phenol removal, and over 90% COD removal was achieved. The-lower operating cost combined with higher phenol-removal efficiency and a low sludge effluent concentration can be achieved by using this reactor for phenol wastewater treatment. [ABSTRACT FROM AUTHOR]

Membrane fouling results in flux decline or transmembrane pressure drop increase during membrane bioreactor (MBR) operation. Physical and chemical cleanings are essential to keep an MBR operating at an appropriate membrane flux. Considerable residual membrane permeability loss that cannot be removed by conventional cleaning requires membrane replacement. This study demonstrates that an internal biofilm can develop inside a hollow-fiber membrane and can probably account for up to 58.9 and 81.3% of total membrane resistance for aerobic granular MBR operated in sequencing batch reactor (SBR) mode or continuous-fed mode, respectively. The Arthrobacter sp. (accession no. AM900505 in GenBank) corresponded to internal biofilm development by polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) analysis and the agar-plating technique. This study also identifies a single strain, Arthrobacter sp., generates the internal biofilm. The Arthrobacter sp. is a rod-shaped bacterium with a size close to that of membrane pores, and can secrete excess bound proteins, hence can penetrate and attach itself inside the membrane and grow. Internal biofilm growth could contribute significantly to membrane resistance during long-term MBR operation. [ABSTRACT FROM AUTHOR]

To investigate the polyamide thin-film composite membranes structure in regard to the variation in the free volume in thin-film composite membrane polyamide active layers, positron annihilation spectroscopy (PAS) experiments using a slow positron beam were performed. The correlation between the pervaporation performance and polyamide active layer free volume explored using the slow positron beam technique was also investigated. The composite membranes were prepared via the interfacial polymerization reaction between ethylenediamine (EDA) and trimesoyl chloride (TMC) on the surface of a modified polyacrylonitrile (mPAN) membrane (EDA−TMC/mPAN). The variations in the Sparameter at positron incident energies of 0.5−2.5 keV indicate a decrease in the Sparameter when the concentration of EDA in aqueous solution increased from 0.5 to 10 wt %. The positron annihilation took place at the surface of the polyamide active layer for the variations at low Sparameters and high Wparameters (positron incident energy <0.5 keV). The positron annihilation occurred at the free volume in the polyamide active layer for the variations at high Sparameters and low Wparameters (positron incident energy: 0.5−2.5 keV). From the o-Ps lifetime results, the density of EDA−TMC polyamide active layer decreases along the thin-film growth direction from the aqueous phase toward the organic phase in the range of 1−2 keV positron incident energy. From the positron annihilation lifetime spectroscopy, the variation in the free volume in the EDA−TMC active layer showed a good correlation with the pervaporation performance. [ABSTRACT FROM AUTHOR]

The free-volume depth profile of asymmetric polymeric membrane systems prepared by interfacial polymerization is studied using positron annihilation spectroscopy coupled with a variable monoenergy slow positron beam. Significant variations of S, W, andRparameters from the Doppler broadened energy spectra vs positron incident energy up to 30 keV and orthopositronium lifetime and intensity are observed at different doping times of triethylenetetraamine (TETA) reacting with trimesoyl chloride (TMC) in an interfacial polymerization on modified porous polyacrylonitrile (PAN) asymmetric membrane. The positron annihilation data are analyzed in terms of free-volume parameters as a function of depth from the surface to nano- and micrometer regions of asymmetric membranes. A multilayer structure is obtained in polymerized polyamide (PA) on modified PAN membranes (m-PAN):  a nanometer scale skin polyamide layer, a nanometer to micrometer scale transition layer from dense to porous m-PAN, and the porous m-PAN support. The results of free-volume parameters and obtained layer thicknesses are compared with the flux (permeability) and water concentration in permeate (selectivity) through the pervaporation separation of 70 wt % 2-propanol aqueous solution. It is found that the water concentration in permeate is mainly controlled by the free-volume properties of skin polyamide and weakly related to the transition layer from the skin to porous m-PAN. The obtained layer structures of asymmetric polymeric membranes are supported by the data obtained by AFM, SEM, and ATR−FTIR. [ABSTRACT FROM AUTHOR]

Pure exo‐functional norbornene monomers containing various chromophores such as fluorene, pyrene, and carbazole were successfully prepared via the Diels–Alder reaction and condensation reaction. The living ring‐opening metathesis polymerization (ROMP) of a fluorene‐containing monomer, exo‐2‐(fluorene‐9‐ylcarboxymethyl)norborn‐5‐ene (exo‐1), was observed and confirmed by the formation of a diblock copolymer and a linear relationship between the number‐average molecular weight and [M]/[I] ratios ([M] = monomer concentration; [I] = initiator concentration). The synthesis and characteristics of novel fluorene‐containing polymers based on pure exo‐1 are reported with Grubbs catalyst I {RuCl2(CHPh)[P(C6H11)3]2} with a high molecular weight of 3.18 × 104 in 90 s ([M]/[I] = 100). However, the ROMP of pyrene‐ and carbazole‐containing monomers [exo‐5‐(pyrene methoxy carbonyl)bicyclo[2.2.1]hept‐2‐ene and exo‐5‐(carbazole ethoxy carbonyl)bicyclo[2.2.1]hept‐2‐ene, respectively] were carried out in a nonliving fashion. All the chromophore‐containing polymers showed excellent solubility in various organic solvents, particularly in chloroform, N‐methyl‐2‐pyrrolidinone, and 1,2‐dichlorobenzene. The glass transition temperatures of polynorbornenes containing various chromophores were determined to be 80–109 °C (by differential scanning calorimetry) higher than that of ring‐opened polynorbornene (glass transition temperature = 35 °C), indicating that the incorporation of the pendant aromatic moieties (e.g., fluorene, pyrene, and carbazole) could enhance the transition temperature for segmental motions of polymer chains. The photoluminescence spectra of all polymer solutions showed a strong emission in the blue region of the visible spectra. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3022–3031, 2007 [ABSTRACT FROM AUTHOR]

A new diamine containing a pyridine heterocyclic group and a naphthalene substituent, 4‐(2‐naphthyl)‐2,6‐bis(4‐aminophenyl) pyridine (NBAPP), was synthesized with the Chichibabin reaction and used in the preparation of poly(pyridine imide) by direct polycondensation with 4,4′‐hexafluoroisopropylidenediphathalic anhydride in N‐methyl‐2‐pyrrolidinone (NMP). The poly(pyridine imide) derived from diamine NBAPP with naphthalene substituents was highly organosoluble: it was soluble in tetrahydrofuran, NMP, N,N‐dimethylacetamide (DMAc), N,N‐dimethylformamide, and γ‐butyrolactone at room temperature and in pyridine, dimethyl sulfoxide, and cyclohexanone upon heating at 70 °C. The poly(pyridine imide) was converted into lightly colored, optically transparent, flexible, and tough polyimide films via casting onto glass from a DMAc solution. This polymer exhibited good thermal stability (temperature of 10% weight loss = 527 °C) in air and high dielectric constants (as high as 4.20 at 1 kHz). The polyimide films had a tensile strength of 102 MPa and a tensile modulus of 1.8 GPa. As for the optical properties, the polymer exhibited UV–vis absorption bands in the region of 223–450 nm and possessed strong green‐yellow fluorescence (500 nm) after being protonated with acid. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2367–2374, 2007 [ABSTRACT FROM AUTHOR]