Molecular level unveils anion exchange membrane fouling induced by natural organic matter via XDLVO and molecular simulation.

Membrane fouling, critically determined by the interplay of interfacial interaction between foulant and membrane, is a critical impediment that limits application extension of electrodialysis (ED) process. In this study, the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) model and molecular simulation were performed to quantify the interaction energy barrier for revealing anion exchange membranes (AEMs) fouling mechanisms of calcium ions coexisted with natural organic matter (NOM) (sodium alginate, humic acid, and bovine serum albumin). The insight gained from DMol3 module was also utilized to interpret the adhesion process of NOM at the molecular level. The interaction energy suggested that the presence of Ca-NOM complex magnify the adhesion on the surface cavities of AEMs structures. The molecular simulation and XDLVO presented a good agreement in predicting the fouling trajectory based on the experimental findings. The short-path acid-base interaction exerted a predominant influence on exploring the fouling formation process. In addition, the sodium alginate displayed more stable adhesion behavior through calcium ions bridges stimuli than humic acid and bovine serum albumin. In particular, the molecular simulation calculations exhibited a superior level of concurrence with colloid growth of membrane fouling. Combined XDLVO theory with DMol3 model proposed a new approach to understand membrane fouling mechanisms in ED process.

Long-Chain Modification of the Tips and Inner Walls of MWCNTs and Their Nanocomposite Reverse Osmosis Membranes.

Multi-walled carbon nanotubes (MWCNTs) were modified on the tips and inner walls by 12-chloro-12-oxododecanedioic acid-methyl ester groups and then added to the polyamide composite membranes to prepare MWCNT-CH2OCOC12H23O2 membranes for desalination. The characterization results of transmission electron microscopy, Fourier transform, infrared transform, and thermogravimetric analysis showed that the 12-chloro-12-oxododecanedioic acid-methyl ester group was successfully grafted to the entrances and inner walls of the MWCNTs. The performance of the MWCNTs' composite membranes was evaluated by scanning electron microscopy, contact angle, and filtration test. The modified membrane morphology is more uniform, and there is no structural damage. The grafting of carbon nanotubes with methyl 12-chloro-12-oxydodecyldicarboxylate could improve the hydrophilicity of the membrane. Under identical conditions, the water flux of MWCNT-CH2OCOC12H23O2 membranes was higher than that of the pristine carbon nanotube's membrane, and the desalination rate was also slightly improved.

Fabrication of a Cation-Exchange Membrane via the Blending of SPES/N-Phthaloyl Chitosan/MIL-101(Fe) Using Response Surface Methodology for Desalination.

In the present work, a novel mixed matrix cation exchange membrane composed of sulfonated polyether sulfone (SPES), N-phthaloyl chitosan (NPHCs) and MIL-101(Fe) was synthesized using response surface methodology (RSM). The electrochemical and physical properties of the membrane, such as ion exchange capacity, water content, morphology, contact angle, fixed ion concentration and thermal stability were investigated. The RSM based on the Box-Behnken design (BBD) model was employed to simulate and evaluate the influence of preparation conditions on the properties of CEMs. The regression model was validated via the analysis of variance (ANOVA) which exhibited a high reliability and accuracy of the results. Moreover, the experimental data have a good fit and high reproducibility with the predicted results according to the regression analysis. The embedding of MIL-101(Fe) nanoparticles contributed to the improvement of ion selective separation by forming hydrogen bonds with the polymer network in the membrane. The optimum synthesis parameters such as degree of sulfonation (DS), the content of SPES and NPHCs and the content of MIL-101(Fe) were acquired to be 30%, 85:15 and 2%, respectively, and the corresponding desalination rate of the CEMs improved to 136% while the energy consumption reduced to 90%. These results revealed that the RSM was a promising strategy for optimizing the preparation factors of CEMs and other similar multi-response optimization studies.

Influential Mechanism of Natural Organic Matters with Calcium Ion on the Anion Exchange Membrane Fouling Behavior via xDLVO Theory.

The fouling mechanism of the anion exchange membrane (AEM) induced by natural organic matter (NOM) in the absence and presence of calcium ions was systematically investigated via the extended Derjaguin-Landau-Verwey-Overbeek (xDLVO) approach. Sodium alginate (SA), humic acid (HA), and bovine serum albumin (BSA) were utilized as model NOM fractions. The results indicated that the presence of calcium ions tremendously aggravated the NOM fouling on the anion exchange membrane because of Ca-NOM complex formation. Furthermore, analysis of the interaction energy between the membrane surface and foulants via xDLVO revealed that short-range acid-base (AB) interaction energy played a significant role in the compositions of interaction energy during the electrodialysis (ED) process. The influence of NOM fractions in the presence of calcium ions on membrane fouling followed the order: SA > BSA > HA. This study demonstrated that the interaction energy was a dominating indicator for evaluating the tendency of anion exchange membranes fouling by natural organic matter.

Effect of black carbon on sorption and desorption of phosphorus onto sediments.

The sorption behavior of phosphorus onto sediment was investigated with the addition of BC derived from incomplete biomass combustion (PC). The sorption kinetic curves of phosphorus onto PC and sediment could be described by a two-compartment first order equation, and the sorption isotherms fit the Freundlich model well. With increasing amounts of PC added, the sorption capacity increased while the HI did not change much. The distribution of phosphorus forms showed that CaP (ACa-P plus DAP) constituted the highest fraction in the sediment samples. Throughout the sorption process, CaP and OP changed very little, but the Ex-P and FeP increased obviously, and the presence of PC made this increase more significantly. The high specific area and the presence of iron and aluminum, as well as the modification of the sediments surface properties, make the addition of PC be favorable for the sorption of phosphorus onto sediments.

Antibiofouling polysulfone ultrafiltration membranes via surface grafting of capsaicin derivatives.

Biofouling is a critical issue in the membrane separation process as it can increase the operational cost by lower down membrane permeability. Covalent binding of an antibacterial agent on the membrane surface to kill microorganisms to hinder biofouling formation process draws great attention. In this study, we used three kinds of capsaicin derivatives, MBHBA, HMBA, and HMOBA, to fabricate antibiofouling membrane via UV-assisted photo grafting method. The influence of these capsaicin derivatives on membrane properties was investigated and compared. The results suggest that HMBA showed the best UV activity, followed by HMOBA and MBHBA successively. Due to the difference of functional groups among capsaicin derivatives, there is an increase in membrane wettability of HMBA and HMOBA-modified membranes, while there is a decrease for MBHBA-modified membrane. MBHBA-modified membrane showed enhanced irreversible fouling, which is in contrast to that of HMBA- and HMOBA-modified membranes. The modified membranes showed similar antibacterial activity against Escherichia coli. The practicability of the modified membranes was examined by dipping them into tap water and seawater for 30 days, and the results displayed the modified surfaces have the potential to relieve biofouling for separation membranes.

Spatial distributions and sea-to-air fluxes of non-methane hydrocarbons in the atmosphere and seawater of the Western Pacific Ocean.

During an oceanographic campaign in the western Pacific Ocean from 12 August to 3 October 2014, the concentrations of five non-methane hydrocarbons (NMHCs) were measured in marine atmosphere and seawater. The average mixing ratios of ethane, ethylene, propane, propylene, and isoprene were 1.109 ±â€¯0.359, 0.658 ±â€¯0.137, 0.711 ±â€¯0.377, 0.429 ±â€¯0.139, and 0.255 ±â€¯0.201 ppbv, respectively. In general, atmospheric concentrations of ethane and propane showed significant decrease from the inshore area to the open ocean, while ethylene and propylene exhibited decreasing trends from low latitudes to high latitudes. The results suggested that atmospheric ethane and propane with long lifetimes were more likely influenced by the air mass transported from continent, while ethylene, propylene and isoprene with short lifetimes were mainly derived from the surface seawater. The average concentrations of ethane, ethylene, propane, propylene, and isoprene in the surface seawater were 6.6 ±â€¯5.8, 51.9 ±â€¯23.5, 15.4 ±â€¯4.3, 17.2 ±â€¯3.8, and 23.5 ±â€¯8.6 pmol L-1, respectively. A significant positive correlation was observed between ethane and propane (R2 = 0.45, n = 39, p < 0.001), implying that their production and removal pathways in the surface seawater were similar. High concentrations of isoprene were observed in the waters with high Chl-a values, suggesting that the biological process was a controlling factor. The estimated sea-to-air fluxes of ethane, propane, ethylene, propylene, and isoprene were in the range of 0.1-24.9, 4.2-235, 1.0-43.8, 1.5-90.2, and 2.1-149 nmol m-2 d-1, respectively. This study is of great importance to the contribution to the atmospheric NMHCs from the western Pacific Ocean and provides data supporting for global NMHCs emission estimates.

Preparation and Characterization of Novel Polyvinylidene Fluoride/2-Aminobenzothiazole Modified Ultrafiltration Membrane for the Removal of Cr(VI) in Wastewater.

Hexavalent chromium is one of the main heavy metal pollutants. As the environmental legislation becomes increasingly strict, seeking new technology to treat wastewater containing hexavalent chromium is becoming more and more important. In this research, a novel modified ultrafiltration membrane that could be applied to adsorb and purify water containing hexavalent chromium, was prepared by polyvinylidene fluoride (PVDF) blending with 2-aminobenzothiazole via phase inversion. The membrane performance was characterized by evaluation of the instrument of membrane performance, infrared spectroscopy (FTIR), scanning electron microscope (SEM), and water contact angle measurements. The results showed that the pure water flux of the PVDF/2-aminobenzothiazole modified ultrafiltration membrane was 231.27 L/m²·h, the contact angle was 76.1°, and the adsorption capacity of chromium ion was 157.75 µg/cm². The PVDF/2-aminobenzothiazole modified ultrafiltration membrane presented better adsorption abilities for chromium ion than that of the traditional PVDF membrane.

Effect of temperature variation on membrane fouling and microbial community structure in membrane bioreactor.

This study aimed to investigate the effect of temperature variation on membrane fouling and microbial community in a membrane bioreactor (MBRs). The results indicated that extracellular polymer substances (EPS) and soluble microbial products (SMPs) increased due to decreasing temperature, which triggered membrane fouling as evidenced by the trans-membrane pressure (TMP) increase rate. Moreover, fluorescent intensity variations in the excitation-emission matrix (EEM) fluorescence spectroscopy of SMPs were closely related to rapid increase in TMP, suggesting that they might be used to monitor SMPs variations and indicate membrane performance. In addition, 16S rRNA clone library and sequence analyses results demonstrated the predominant phyla were always Proteobacteria, Nitrospira and Bacteroidetes. However, at lower temperature, α-proteobacteria and some filamentous bacteria such as Actinobacteria, Haliscomenobacteria and Thiothrix were relatively rich. At higher temperature, Zoogloea showed its presence. Detrended correspondence analysis (DCA) and Mantel test results also demonstrated that temperature had strongly influence on microbial community.

Separation of fingerprint constituents using magnetic silica nanoparticles and direct on-particle SALDI-TOF-mass spectrometry.

Two types of amorphous, silica nanoparticles have been produced and used as surface assisting agents during laser desorption/ionisation time-of flight-mass spectrometry (SALDI-TOF-MS). The first is hydrophilic possessing surface aminopropyl groups and the second hydrophobic containing surface phenyl groups. Each particle type acts as a solid phase adsorbent, adsorbing analytes according to their charge and hydrophobicity. The adsorbed analytes can be directly analysed on the particles using SALDI-TOF-MS. Intrinsically magnetisable versions of the hydrophobic particles act as magnetic solid phase extraction (MSPE) materials which are used to selectively adsorb analytes within a mixture deposited onto a surface, transfer the adsorbed components using a magnetic wand and to deposit the particles at a site adjacent to that of the original mixture. Non-adsorbed components remain at the original site. The extracted and residual analytes are then directly analysed on the surface by SALDI-TOF-MS. Using fingerprints as an example of a complex biological matrix, this new approach has been used to separate polar (amino acids) and non-polar constituents (squalene and fatty acids) within latent fingerprints deposited on a surface and for their subsequent direct analysis on the surface by SALDI-TOF-MS. Alanine, ornithine, lysine and aspartic acid which were undetected or poorly detected prior to separation showed improved signal detection after separation.

Templated assembling of phthalocyanine arrays along a polymer chain.

Copper phthalocyanine can assemble along PPE backbones into molecular arrays and 2D assemblies with structural parameters different from its intrinsic 2D crystal. The template effect depends on the match between the size of phthalocyanine and the repeating period of the PPE backbone.

Doped amorphous silica nanoparticles as enhancing agents for surface-assisted time-of-flight mass spectrometry.

This article examines the use of doped amorphous silica nanoparticles for surface-assisted laser desorption/ionisation-time of flight-mass spectrometry (SALDI-TOF-MS) of hydrophilic and hydrophobic compounds. A range of particles with surface aliphatic carboxylic, aminophenyl, phenyl or aminopropyl groups have been produced and these have been doped with carbon black, polyaniline or graphite. The effects of surface groups and dopants on the laser desorption/ionisation process were studied. The key factor in effective LDI was the presence of carbon black dopant carrying carboxyphenyl or phenyl residues for positive and negative ion formation. The second key factor was the presence of hydrophilic surface functional groups for hydrophilic amino acid analytes for their detection in positive or negative mode as protonated or de-protonated species respectively whereas hydrophobic surfaces were need for ionisation via cationisation for the hydrophobic analyte squalene. The mechanism for LDI of these particles appears to involve initial adsorption of the analyte onto the surface of the particle, formation of primary ions via adsorption of laser UV irradiation by carboxyphenyl residues attached to the carbon black network which act in an equivalent way to the matrix in matrix-assisted LDI. This is followed by reaction of the primary ions with neighbouring adsorbed analyte molecules. The latter are then released possibly via thermal desorption following proton donation or acceptance from/to via surface residues such carboxylate groups associated with the carbon black within the dopant. Alternatively in the absence of such proton donor/acceptor residues as with hydrophobic particles, the primary ions are released from the particles during desorption and form cation adducts as sodiated and potassiated species in the gas phase above the surface.

Thermodynamic controlled hierarchical assembly of ternary supramolecular networks at the liquid-solid interface.

Building and networking: Ternary supramolecular networks have been formed by coadsorption of dissimilar ternary building units at the liquid-solid interface. The structural characteristics of the networks undergo distinctive transformations as the building units change from binary to ternary components (see graphic).

Self-assembly of a novel alternant amphiphilic poly(OPE-alt-TEO) copolymer: from nanowires to twist fibrillar architectures with molecular dimensions.

A novel alternant amphiphilic polymer poly[1,4-bis(phenylethynyl)-2,5-bis(hexyloxy)benzene-alt-tetra(ethylene oxide)] was prepared. Atom force microscope (AFM) images showed that the molecular self-assembly morphologies changed from molecular nanowires to twist fibrillar architectures with the increase of the solution concentrations. Short and thin wires formed in dilute solution, while large bundles developed in relatively concentrated ones, shown by fluorescence microscope images. The photoluminescence (PL) spectra of the corresponding films indicate a self-assembly process of the polymers under slow solvents evaporation. Coplanar aggregation was confirmed through PL and photoluminescence excitation (PLE) spectra. Furthermore, the self-assembly process in polymer bulk was studied by wide-angle X-ray diffraction. To the best of our knowledge, it is the first time to reveal the change of the molecular morphologies with the altering concentration for the alternant amphiphilic conjugated polymers.

Star-shaped oligofluorenes end-capped with carboxylic groups: syntheses and self-assembly at the liquid-solid interface.

A series of star-shaped oligofluorenes end-capped with carboxylic acid groups were synthesized. Different numbers of carboxyl groups that can form hydrogen bonds, and long alkane chains that have stabilizing effects, were intentionally introduced. The resulting molecular architectures of the so-prepared star-shaped oligofluorenes at the liquid-solid interface were investigated by scanning tunneling microscopy. It is found that the number of hydrogen-bonding groups and the symmetry of the target molecules have crucial influences on the structures of the ordered assemblies.

Direct laser desorption/ionization time-of-flight mass spectrometry of conjugated polymers.

Two conjugated polymers (CPs), poly(9,9-dioctylfluorene) (PF) and poly(3-octylthiophene) (PT) were analyzed by direct laser desorption/ionization time-of-flight mass spectrometry (LDI-ToF MS). Because of their strong absorption near the wavelength of the laser (337 nm), easy and transient energy transfer properties and sufficient thermal stability, CPs can be desorbed and ionized directly without a matrix. For comparison, these two polymers were also analyzed using matrix-assisted laser desorption/ionization (MALDI)-ToF MS in the positive reflectron mode. The results revealed that they are very similar in terms of quality and resolution. All results demonstrate that LDI-ToF MS is an alternative method for the mass characterization of some conjugated systems, thereby simplifying the process of sample preparation and result analysis.