Interlaced CNT Electrodes for Bacterial Fouling Reduction of Microfiltration Membranes.

Interlaced carbon nanotube electrodes (ICE) were prepared by vacuum filtering a well-dispersed carbon nanotube-Nafion solution through a laser-cut acrylic stencil onto a commercial polyvinylidene fluoride (PVDF) microfiltration (MF) membrane. Dead-end filtration was carried out using 107 and 108 CFU mL-1 Pseudomonas fluorescens to study the effects of the electrochemically active ICE on bacterial density and morphology, as well as to evaluate the bacterial fouling trend and backwash (BW) efficacy, respectively. Finally, a simplified COMSOL model of the ICE electric field was used to help elucidate the antifouling mechanism in solution. At 2 V DC and AC (total cell potential), the average bacterial log removal of the ICE-PVDF increased by ∼1 log compared to the control PVDF (3.5-4 log). Bacterial surface density was affected by the presence and polarity of DC electric potential, being 87-90% lower on the ICE cathode and 59-93% lower on the ICE anode than that on the PVDF after filtration, and BW further reduced the density on the cathode significantly. The optimal operating conditions (2 V AC) reduced the fouling rate by 75% versus the control and achieved up to 96% fouling resistance recovery (FRR) during BW at 8 V AC using 155 mM NaCl. The antifouling performance should mainly be due to electrokinetic effects, and the electric field simulation by COMSOL model suggested electrophoresis and dielectrophoresis as likely mechanisms.

Wettability, polarity, and water absorption of holm oak leaves: effect of leaf side and age.

Plant trichomes play important protective functions and may have a major influence on leaf surface wettability. With the aim of gaining insight into trichome structure, composition, and function in relation to water-plant surface interactions, we analyzed the adaxial and abaxial leaf surface of holm oak (Quercus ilex) as a model. By measuring the leaf water potential 24 h after the deposition of water drops onto abaxial and adaxial surfaces, evidence for water penetration through the upper leaf side was gained in young and mature leaves. The structure and chemical composition of the abaxial (always present) and adaxial (occurring only in young leaves) trichomes were analyzed by various microscopic and analytical procedures. The adaxial surfaces were wettable and had a high degree of water drop adhesion in contrast to the highly unwettable and water-repellent abaxial holm oak leaf sides. The surface free energy and solubility parameter decreased with leaf age, with higher values determined for the adaxial sides. All holm oak leaf trichomes were covered with a cuticle. The abaxial trichomes were composed of 8% soluble waxes, 49% cutin, and 43% polysaccharides. For the adaxial side, it is concluded that trichomes and the scars after trichome shedding contribute to water uptake, while the abaxial leaf side is highly hydrophobic due to its high degree of pubescence and different trichome structure, composition, and density. Results are interpreted in terms of water-plant surface interactions, plant surface physical chemistry, and plant ecophysiology.

Ultrastructure of plant leaf cuticles in relation to sample preparation as observed by transmission electron microscopy.

The leaf cuticular ultrastructure of some plant species has been examined by transmission electron microscopy (TEM) in only few studies. Attending to the different cuticle layers and inner structure, plant cuticles have been grouped into six general morphological types. With the aim of critically examining the effect of cuticle isolation and preparation for TEM analysis on cuticular ultrastructure, adaxial leaf cuticles of blue-gum eucalypt, grey poplar, and European pear were assessed, following a membrane science approach. The embedding and staining protocols affected the ultrastructure of the cuticles analysed. The solubility parameter, surface tension, and contact angles with water of pure Spurr's and LR-White resins were within a similar range. Differences were however estimated for resin : solvent mixtures, since Spurr's resin is combined with acetone and LR-White resin is mixed with ethanol. Given the composite hydrophilic and lipophilic nature of plant cuticles, the particular TEM tissue embedding and staining procedures employed may affect sample ultrastructure and the interpretation of the results in physicochemical and biological terms. It is concluded that tissue preparation procedures may be optimised to facilitate the observation of the micro- and nanostructure of cuticular layers and components with different degrees of polarity and hydrophobicity.

Chitosan-Based Composite Membranes with Different Biocompatible Metal Oxide Nanoparticles: Physicochemical Properties and Drug-Release Study.

Chitosan (CS) composite membranes were prepared using different biocompatible metal oxide nanoparticles (NPs): titanium dioxide (TiO2); iron oxide (Fe3O4); and aluminum oxide (Al2O3). For each nanoparticle, the CS-based composite membranes were prepared with two NPs contents in the CS solution, high (H) and low (L) NPs concentrations. To establish both concentrations, the NPs saturation point in the CS polymeric matrix was determined. The influence of NP concentrations on the physicochemical properties of the CS films was assessed. The prepared CS membranes were characterized with different techniques, such as X-ray diffraction (XRD), scanning electron microscopy (SEM), and zeta potential. It was found that the addition of NPs in the CS matrix improved both swelling and mechanical properties. Nanocomposite CS membranes could be prepared using Al2O3 NPs. Swelling experiments revealed different pH-sensitive mechanisms, which might be beneficial in biomedical applications since solute permeation through CS-based composite membranes could be controlled by adjusting environmental conditions. When aspirin transport (ASA) through the prepared membranes was carried out in different release media, SGF (simulating gastric fluid) and SIF (simulating intestinal fluid without enzymes), it was observed that the Fickian diffusion coefficient (D) was conditioned by the pH of the release solution. In SGIT (simulating gastrointestinal transit) medium, a transition time (ttrans) was detected due to the shrinkage of the CS polymeric chains, and the drug release depended not only on the Fickian's diffusion but also on the shrinkage of the biopolymer, obeying Peppas and Sahlin equation.

Applications of electrically conductive membranes in water treatment via membrane distillation: Joule heating, membrane fouling/scaling/wetting mitigation and monitoring.

Membrane distillation (MD) is a thermally driven separation process that is driven by phase change. The core of this technology is the hydrophobic microporous membrane that prevents mass transfer of the liquid while allowing the vapor phase to pass through the membrane's pores. Currently, MD is challenged by its high energy consumption and membrane degradation due to fouling, scaling and wetting. The use of electrically conductive membranes (ECMs) is a promising alternative method to overcome these challenges by inducing localized Joule heating, as well as mitigating and monitoring membrane fouling/scaling/wetting. The objective of this review is to consolidate recent advances in ECMs from the standpoint of conductive materials, membrane fabrication methodologies, and applications in MD processes. First, the mechanisms of ECMs-based MD processes are reviewed. Then the current trends in conductive materials and membrane fabrication methods are discussed. Thereafter, a comprehensive review of ECMs in MD applications is presented in terms of the different processes using Joule heating and various works related to membrane fouling, scaling, and wetting control and monitoring. Key insights in terms of energy consumption, economic viability and scalability are furnished to provide readers with a holistic perspective of the ECMs potential to achieve better performances and higher efficiencies in MD. Finally, we illustrate our perspectives on the innovative methods to address current challenges and provide insights for advancing new ECMs designs. Overall, this review sums up the current status of ECMs, looking at the wide range of conductive materials and array of fabrication methods used thus far, and putting into perspective strategies to deliver a more competitive ECMs-based MD process in water treatment.

Development of Novel Electrospun Fibers Based on Cyclic Olefin Polymer.

For the first time, a systematic study to investigate the electrospinnability of cyclic olefin polymer (COP) was performed. Different solvents and mixtures were tested together with different electrospinning parameters and post-treatment types to prepare bead-free fibers without defects. These were successfully obtained using a chloroform/chlorobenzene (40/60 wt.%) solvent mixture with a 15 wt.% COP polymer, a 1 mL/h polymer solution flow rate, a 15 cm distance between the needle and collector, and a 12 kV electric voltage. COP fibers were in the micron range and the hot-press post-treatment (5 MPa, 5 min and 120 °C) induced an integrated fibrous structure along with more junctions between fibers, reducing the mean and maximum inter-fiber space. When the temperature of the press post-treatment was increased (from 25 °C to 120 °C), better strength and less elongation at break of COP fibers were achieved. However, when applying a temperature above the COP glass temperature (Tg = 138 °C) the fibers coalesced, showing a mechanical behavior similar to a plastic film and a low elongation at break with a high strength. The addition of a high dielectric constant non-solvent, N,N-dimethylacetamide (DMAc), resulted in a considerable reduction in the COP fiber diameter. Based on the cloud point approach, it was found that the use of DMAc and the solvent chloroform or chlorobenzene improved the electrospinnability of COP polymer solution.

New insights into the properties of pubescent surfaces: peach fruit as a model.

The surface of peach (Prunus persica 'Calrico') is covered by a dense indumentum, which may serve various protective purposes. With the aim of relating structure to function, the chemical composition, morphology, and hydrophobicity of the peach skin was assessed as a model for a pubescent plant surface. Distinct physicochemical features were observed for trichomes versus isolated cuticles. Peach cuticles were composed of 53% cutan, 27% waxes, 23% cutin, and 1% hydroxycinnamic acid derivatives (mainly ferulic and p-coumaric acids). Trichomes were covered by a thin cuticular layer containing 15% waxes and 19% cutin and were filled by polysaccharide material (63%) containing hydroxycinnamic acid derivatives and flavonoids. The surface free energy, polarity, and work of adhesion of intact and shaved peach surfaces were calculated from contact angle measurements of water, glycerol, and diiodomethane. The removal of the trichomes from the surface increased polarity from 3.8% (intact surface) to 23.6% and decreased the total surface free energy chiefly due to a decrease on its nonpolar component. The extraction of waxes and the removal of trichomes led to higher fruit dehydration rates. However, trichomes were found to have a higher water sorption capacity as compared with isolated cuticles. The results show that the peach surface is composed of two different materials that establish a polarity gradient: the trichome network, which has a higher surface free energy and a higher dispersive component, and the cuticle underneath, which has a lower surface free energy and higher surface polarity. The significance of the data concerning water-plant surface interactions is discussed within a physiological context.

Estimation of the solubility parameters of model plant surfaces and agrochemicals: a valuable tool for understanding plant surface interactions.

BACKGROUND: Most aerial plant parts are covered with a hydrophobic lipid-rich cuticle, which is the interface between the plant organs and the surrounding environment. Plant surfaces may have a high degree of hydrophobicity because of the combined effects of surface chemistry and roughness. The physical and chemical complexity of the plant cuticle limits the development of models that explain its internal structure and interactions with surface-applied agrochemicals. In this article we introduce a thermodynamic method for estimating the solubilities of model plant surface constituents and relating them to the effects of agrochemicals. RESULTS: Following the van Krevelen and Hoftyzer method, we calculated the solubility parameters of three model plant species and eight compounds that differ in hydrophobicity and polarity. In addition, intact tissues were examined by scanning electron microscopy and the surface free energy, polarity, solubility parameter and work of adhesion of each were calculated from contact angle measurements of three liquids with different polarities. By comparing the affinities between plant surface constituents and agrochemicals derived from (a) theoretical calculations and (b) contact angle measurements we were able to distinguish the physical effect of surface roughness from the effect of the chemical nature of the epicuticular waxes. A solubility parameter model for plant surfaces is proposed on the basis of an increasing gradient from the cuticular surface towards the underlying cell wall. CONCLUSIONS: The procedure enabled us to predict the interactions among agrochemicals, plant surfaces, and cuticular and cell wall components, and promises to be a useful tool for improving our understanding of biological surface interactions.

Thermal conductivity and thermal diffusivity of fullerene-based nanofluids.

Owing to their outstanding characteristics, carbon based nanofluids (CbNFs) have been applied to various advanced heat transfer and cooling technologies. It was claimed that these CbNFs can considerably improve the properties of the base working fluids. Among all the thermal characteristics, the thermal conductivity (λ) is regarded as the primary parameter to be considered for the application of nanofluids (NFs). In the present research study we measured for the first time both λ and thermal diffusivity (aT) of very stable fullerene (C60)-based NFs in liquid phase (1,2,3,4-tetrahydronaphthalene and 1,2-dicholorobenzene) by the transient multi-current hot wire technique at atmospheric pressure in a wide range of temperature (254-323 K). Similar to the base liquids (BLs), we observed a slight decrease in λ with an increase in temperature. Additionally, compared to the BLs λ was reduced upon the addition of C60. The results were compared with the predicted ones using different theoretical models. Not much variation in aT was observed between the C60 NFs and the corresponding BLs due partly to the small variation of λ with the addition of C60.

A complementary approach of response surface methodology and an artificial neural network for the optimization and prediction of low salinity reverse osmosis performance.

The treatment of saline water sources by reverse osmosis (RO) is being utilized increasingly to address water shortages around the world. The application of RO is energy-intensive; therefore, plant and process optimization are crucial. The desalination of low salinity water sources with total dissolved solids (TDS) of <5000 mg/L is less energy intensive than the desalination of highly saline seawater and brackish water. A gap exists in optimization studies on lower salinity water (TDS = 500-5000 mg/L). The novelty of the study is the development of a complementary approach using response surface methodology (RSM) and an artificial neural network (ANN) for performance modelling, optimization, and prediction of RO desalination of low salinity water. Feed water salinity, pressure, and temperature were controlled variables to model the performance of the RO system. A performance index incorporating salt rejection efficiency and permeate flux was used as the response target of the system. The optimal parameter combination within their modelled range for the best performance index occurred near the highest pressure input of 150.57 psi, at the temperature of 38.8 °C, and at the lowest feed salt concentration of 577 mg/L. Both the RSM and ANN models demonstrated high validity. The RSM and ANN showed R2 values of 0.99 each and with a root mean square error of 2.41 and 5.85 respectively. The RSM showed a small benefit in model accuracy over the ANN, but the ANN has the benefit of not requiring the central composite design before experimentation and being a continuously improving prediction method as more data becomes available. Further applications of the optimization and modelling approach can be applied to RO system optimization considering membrane types and additional feedwater characteristics.

Electrospun Nanostructured Membrane Engineering Using Reverse Osmosis Recycled Modules: Membrane Distillation Application.

As a consequence of the increase in reverse osmosis (RO) desalination plants, the number of discarded RO modules for 2020 was estimated to be 14.8 million annually. Currently, these discarded modules are disposed of in nearby landfills generating high volumes of waste. In order to extend their useful life, in this research study, we propose recycling and reusing the internal components of the discarded RO modules, membranes and spacers, in membrane engineering for membrane distillation (MD) technology. After passive cleaning with a sodium hypochlorite aqueous solution, these recycled components were reused as support for polyvinylidene fluoride nanofibrous membranes prepared by electrospinning technique. The prepared membranes were characterized by different techniques and, finally, tested in desalination of high saline solutions (brines) by direct contact membrane distillation (DCMD). The effect of the electrospinning time, which is the same as the thickness of the nanofibrous layer, was studied in order to optimize the permeate flux together with the salt rejection factor and to obtain robust membranes with stable DCMD desalination performance. When the recycled RO membrane or the permeate spacer were used as supports with 60 min electrospinning time, good permeate fluxes were achieved, 43.2 and 18.1 kg m-2 h-1, respectively; with very high salt rejection factors, greater than 99.99%. These results are reasonably competitive compared to other supported and unsupported MD nanofibrous membranes. In contrast, when using the feed spacer as support, inhomogeneous structures were observed on the electrospun nanofibrous layer due to the special characteristics of this spacer resulting in low salt rejection factors and mechanical properties of the electrospun nanofibrous membrane.

High-Flux Thin Film Composite PIM-1 Membranes for Butanol Recovery: Experimental Study and Process Simulations.

Thin film composite (TFC) membranes of the prototypical polymer of intrinsic microporosity (PIM-1) have been prepared by dip-coating on a highly porous electrospun polyvinylidene fluoride (PVDF) nanofibrous support. Prior to coating, the support was impregnated in a non-solvent to avoid the penetration of PIM-1 inside the PVDF network. Different non-solvents were considered and the results were compared with those of the dry support. When applied for the separation of n-butanol/water mixtures by pervaporation (PV), the developed membranes exhibited very high permeate fluxes, in the range of 16.1-35.4 kg m-2 h-1, with an acceptable n-butanol/water separation factor of about 8. The PV separation index (PSI) of the prepared membranes is around 115, which is among the highest PSI values that have been reported so far. Hybrid PV-distillation systems have been designed and modeled in Aspen HYSYS using Aspen Custom Modeler for setting up the PIM-1 TFC and commercial PDMS membranes as a benchmark. The butanol recovery cost for the hybrid systems is compared with a conventional stand-alone distillation process used for n-butanol/water separation, and a 10% reduction in recovery cost was obtained.

Mixed Matrix Polytetrafluoroethylene/Polysulfone Electrospun Nanofibrous Membranes for Water Desalination by Membrane Distillation.

The electrospinning technique was used successfully to fabricate nanofibers of polysulfone (PSF) in which polytetrafuoroethylene nanoparticles (PTFE NPs) were embedded. The size of the PTFE NPs is only 1.7 to 3.6 times smaller than the nanofiber diameter. The transition from hydrophobic to superhydrophobic character of the bead-free PSF electrospun nanofiber mats occurred with a PTFE NPs loading in the range 12-18% of the PSF weight. Transmission electron microscopy images revealed protruding nanosized asperities on the fiber surface due to the embedded PTFE NPs in the PSF matrix. For low PTFE NPs content in PSF matrix (<6% of the polymer weight), the PTFE NPs were arranged one by one in a single file along the PSF nanofiber axis. The structural characteristics of the nanofibers and electrospun nanofibrous membranes (ENMs) were studied by means of different techniques and their relationship with the PTFE NPs loading in PSF were discussed. The PSF/PTFE ENMs were tested in desalination by direct contact membrane distillation (DCMD) and the obtained performance was discussed in terms of the ENMs structural characteristics. Competitive permeate fluxes, as high as 39.5 kg/m2h, with stable low permeate electrical conductivities (<7.145 µS/cm) for 30 g/L NaCl aqueous solution and transmembrane temperature of 60 °C were achieved without detecting any interfiber space wetting.

Structural, Mechanical, and Transport Properties of Electron Beam-Irradiated Chitosan Membranes at Different Doses.

Chitosan powder irradiated by electron beam at different doses, up to 250 kGy, was used to prepare membranes for drug release applications. The irradiation effect on the molecular weight of powder chitosan, the characteristics of the prepared membranes, and their transport of sulfamerazine sodium salt (SULF) were investigated. The effect of the addition of glutaraldehyde (GLA) as a crosslinking agent in the chitosan solution used for the preparation of the membranes was also studied. A decrease in the chitosan molecular weight with the increase in the irradiation dose was observed, while the membranes prepared with the irradiated chitosan at higher dose exhibited lower swelling. However, an opposite behavior was detected when the membranes were prepared with GLA-crosslinked chitosan. A GLA crosslinking agent reduced the crystallinity of the chitosan membranes and the swelling, whereas the water contact angle and SULF transport increased with the increase in the irradiation dose.

Evaluation of the surface free energy of plant surfaces: toward standardizing the procedure.

Plant surfaces have been found to have a major chemical and physical heterogeneity and play a key protecting role against multiple stress factors. During the last decade, there is a raising interest in examining plant surface properties for the development of biomimetic materials. Contact angle measurement of different liquids is a common tool for characterizing synthetic materials, which is just beginning to be applied to plant surfaces. However, some studies performed with polymers and other materials showed that for the same surface, different surface free energy values may be obtained depending on the number and nature of the test liquids analyzed, materials' properties, and surface free energy calculation methods employed. For 3 rough and 3 rather smooth plant materials, we calculated their surface free energy using 2 or 3 test liquids and 3 different calculation methods. Regardless of the degree of surface roughness, the methods based on 2 test liquids often led to the under- or over-estimation of surface free energies as compared to the results derived from the 3-Liquids method. Given the major chemical and structural diversity of plant surfaces, it is concluded that 3 different liquids must be considered for characterizing materials of unknown physico-chemical properties, which may significantly differ in terms of polar and dispersive interactions. Since there are just few surface free energy data of plant surfaces with the aim of standardizing the calculation procedure and interpretation of the results among for instance, different species, organs, or phenological states, we suggest the use of 3 liquids and the mean surface tension values provided in this study.

Chemical and structural analysis of Eucalyptus globulus and E. camaldulensis leaf cuticles: a lipidized cell wall region.

The plant cuticle has traditionally been conceived as an independent hydrophobic layer that covers the external epidermal cell wall. Due to its complexity, the existing relationship between cuticle chemical composition and ultra-structure remains unclear to date. This study aimed to examine the link between chemical composition and structure of isolated, adaxial leaf cuticles of Eucalyptus camaldulensis and E. globulus by the gradual extraction and identification of lipid constituents (cutin and soluble lipids), coupled to spectroscopic and microscopic analyses. The soluble compounds and cutin monomers identified could not be assigned to a concrete internal cuticle ultra-structure. After cutin depolymerization, a cellulose network resembling the cell wall was observed, with different structural patterns in the regions ascribed to the cuticle proper and cuticular layer, respectively. Our results suggest that the current cuticle model should be revised, stressing the presence and major role of cell wall polysaccharides. It is concluded that the cuticle may be interpreted as a modified cell wall region which contains additional lipids. The major heterogeneity of the plant cuticle makes it difficult to establish a direct link between cuticle chemistry and structure with the existing methodologies.

Localization of polysaccharides in isolated and intact cuticles of eucalypt, poplar and pear leaves by enzyme-gold labelling.

The presence and characteristics of cuticle polysaccharides have been demonstrated by staining and spectroscopic methods, but their location in the cuticle remains unclear. Furthermore, according to the prevailing model, polysaccharides are believed to be restricted to the cuticular layer and absent in the cuticle proper. With the aim of gaining insight into cuticular ultra-structure focussing on polysaccharides, cellulose and pectins have been identified and located in the transversal sections of isolated and intact adaxial leaf cuticles of Eucalyptus globulus, Populus × canescens and Pyrus communis by means of enzyme gold-labelling (Au-cellulase, EC 3.2.1.4, and -pectinase, EC 3.2.1.15) and transmission electron microscopy (TEM). The structure of the interface between the cuticle and the cell wall underneath was observed to influence the process of enzymatic isolation of leaf cuticles. Cellulose and pectins were detected for the first time in enzymatically isolated cuticles, sometimes appearing closely underneath the epicuticular wax layer. The location and presence of polysaccharides in intact and isolated leaf cuticles may have multiple implications, such as when estimating the bi-directional transport of substances between plant organs and the surrounding environment, or when interpreting organ ontogeny. The results are discussed within a plant ontological and ecophysiological context.

Membranes and theoretical modeling of membrane distillation: a review.

Membrane distillation (MD) is one of the non-isothermal membrane separation processes used in various applications such desalination, environmental/waste cleanup, food, etc. It is known since 1963 and is still being developed at laboratory stage for different purposes and not fully implemented in industry. An abrupt increase in the number of papers on MD membrane engineering (i.e. design, fabrication and testing in MD) is seen since only 6 years ago. The present paper offers a comprehensive MD state-of-the-art review covering a wide range of commercial membranes, MD membrane engineering, their MD performance, transport mechanisms, experimental and theoretical modeling of different MD configurations as well as recent developments in MD. Improved MD membranes with specific morphology, micro- and nano-structures are highly demanded. Membranes with different pore sizes, porosities, thicknesses and materials as well as novel structures are required in order to carry out systematic MD studies for better understanding mass transport in different MD configurations, thereby improving the MD performance and looking for MD industrialization.

Micellar enhanced ultrafiltration process for the treatment of olive mill wastewater.

Olive mill wastewater (OMW) is an important environmental pollution problem, especially in the Mediterranean, which is the main olive oil production region worldwide. Environmental impact of OMW is related to its high organic load and particularly to the phytotoxic and antibacterial action of its phenolic content. In fact, polyphenols are known as powerful antioxidants with interesting nutritional and pharmaceutical properties. In the present work, the efficiency of OMW Micellar Enhanced Ultrafiltration (MEUF) treatment for removal and concentration of polyphenols was investigated, using an anionic surfactant (Sodium Dodecyl Sulfate salt, SDS) and a hydrophobic poly(vinyldene fluoride) (PVDF) membrane. The effects of the process experimental conditions on the permeate flux were investigated, and the secondary membrane resistance created by SDS molecules was evaluated. The initial fluxes of OMW processing by MEUF using SDS were 25.7 and 44.5 l/m2 h under transmembrane pressures of 3.5 and 4.5 bar, respectively. The rejection rate of polyphenols without using any surfactant ranged from 5 to 28%, whereas, it reached 74% when SDS was used under optimum pH (pH 2). The MEUF provides a slightly colored permeate (about 88% less dark), which requires clearly less chemical oxygen demand (COD) for its oxidation (4.33% of the initial COD). These results showed that MEUF process can efficiently be applied to the treatment of OMW and for the concentration and recovery of polyphenols.