Advancements in Nanoenabled Membrane Distillation for a Sustainable Water-Energy-Environment Nexus.

The emergence of nano innovations in membrane distillation (MD) has garnered increasing scientific interest. This enables the exploration of state-of-the-art nano-enabled MD membranes with desirable properties, which significantly improve the efficiency and reliability of the MD process and open up opportunities for achieving a sustainable water-energy-environment (WEE) nexus. This comprehensive review provides broad coverage and in-depth analysis of recent innovations in nano-enabled MD membranes, focusing on their role in achieving desirable properties, such as strong liquid-repellence, high resistance to scaling, fouling, and wetting, as well as efficient self-heating and self-cleaning functionalities. The recent developments in nano-enhanced photothermal-catalytic applications for water-energy co-generation within a single MD system are also discussed. Furthermore, the bottlenecks are identified that impede the scale-up of nanoenhanced MD membranes and a future roadmap is proposed for their sustainable commercialiation. This holistic overview is expected to inspire future research and development efforts to fully harness the potential of nano-enabled MD membranes to achieve sustainable integration of water, energy, and the environment.

EI/IOT of PFCs: Environmental impacts/interactions, occurrences, and toxicities of perfluorochemicals.

Various studies have been conducted on the perfluorochemicals (PFCs) family over the years. These compounds have been sought in various industrial aspects involving the synthesis of everyday utilities due to their broad range of applications. As a result, PFCs have built up in the environment, causing concern. The presence of PFCs in various environmental media, such as terrestrial and marine settings, as well as the mechanisms of transport, bioaccumulation, and physio-chemical interactions of PFCs within plants, aquatic organisms, microplastics, and, ultimately, the human body, are discussed in this review, which draws on a variety of research publications. The interaction of PFCs with proteins, translocation, and adsorption by hydrophobic interactions were observed, and this had an impact on the natural functioning of biological processes, resulting in events such as phylogenic clustering, competitive inhibition, and many others, posing potential hazards to human health and other relevant organisms in the ecosystem. However, further research is needed to have a better knowledge of PFCs and their interactions so that low-cost treatments can be developed to eliminate them. It is therefore, future research should focus on the role of soil matrix as a defensive mechanism for PFCs, as well as the impact of PFC chain length rejection.

Rational Design of PDA/P-PVDF@PP Janus Membrane with Asymmetric Wettability for Switchable Emulsion Separation.

Water pollution caused by oil spills or sewage discharges has become a serious ecological environmental issue. Despite the membrane separation technique having a promising application in wastewater purification, the membrane fabrication method and separation robustness have remained unsatisfactory until now. Herein, we developed a novel strategy, spacer-assisted sequential phase conversion, to create a patterned polyvinylidene fluoride@polypropylene (P-PVDF@PP) substrate membrane with a multiscale roughened surface. Based on that surface structure, the underwater oil resistance behavior of the P-PVDF@PP membrane was improved. Moreover, owing to the abundant active sites on the P-PVDF@PP surface, the polydopamine/P-PVDF@PP (PDA/P-PVDF@PP) Janus membrane could be readily fabricated via wet chemical modification, which exhibited excellent switchable oil-water separation performance. Regarding surfactant-stabilized oil-water emulsion, the as-prepared PDA/P-PVDF@PP Janus membrane also had robust separation efficiency (as high as 99% in the n-hexane/water, chloroform/water, and toluene/water emulsion separation cases) and desirable reusability. Finally, the underlying mechanism of emulsion separation in the PDA/P-PVDF@PP Janus membrane was specified. The as-designed PDA/P-PVDF@PP Janus membrane with high-efficiency oil-water separation shows potential application in oily wastewater treatment, and the developed fabrication method has implications for the fabrication of advanced separation membranes.

Noninvasive Real-Time Monitoring of Wetting Progression in Membrane Distillation Using Impedance Spectroscopy.

Membrane distillation (MD) is a promising technology for the treatment of high salinity wastewater using a hydrophobic membrane; however, the occurrence of wetting due to surfactants in polluted or low surface tension liquid impedes MD application. Common monitoring approaches, such as conductivity and flux measurement, cannot explain the wetting phenomenon that occurs during the wetting process in detail. Recently, impedance spectroscopy has been proposed for early wetting detection, as it depends on the change of water/air composition in the membrane pores. An earlier and larger variation was observed with precise signal detection. In this study, we proposed an analytical approach to estimate the wetting front, which is the average feed intrusion distance, by the impedance value recorded in real-time operation. With this proposed approach, the wetting mechanism in the presence of a surfactant and the effect of pore size on a commercial polyvinylidene fluoride membrane could be quantified, which cannot be explained in detail using conductivity and flux measurements.

Ten Years of Glory in the α-Functionalizations of Acetophenones: Progress Through Kornblum Oxidation and C-H Functionalization.

This review article focuses on the α-functionalization of acetophenones involving Kornblum oxidation and C-H functionalizations. Although various other strategies, such as classical approaches, enamine approaches and umpolung strategy are also known for this functionalization, here we discuss mainly the Kornblum oxidation approach and C-H functionalization strategy as they have advantages over the others. In Kornblum oxidation, the reaction uses iodine and dimethylsulfoxide and proceeds through the formation of arylglyoxal as the key intermediate. In C-H functionalization, the reaction requires metal, or metal-free catalyst, and generates radical intermediate in most cases. α-Functionalization of acetophenones is very important because of their huge applications in the synthesis of various natural products and pharmaceuticals and, therefore, a number of research articles have been published in this area. However, no review articles are available so far. In this article, we present a succinct discussion of various important and novel reactions, along with their mechanisms, published since 2012 to date. We believe that this first review article in this field will give readers one-stop information on this topic and encourage further intriguing work in this area.

L-Proline-catalyzed regioselective C1 arylation of tetrahydroisoquinolines through a multicomponent reaction under solvent-free conditions.

Here we disclose the C1 arylation of tetrahydroisoquinolines (THIQ) through regioselective C(sp3)-H functionalization using a multicomponent reaction. The reaction was performed by reacting THIQ, aldehydes and aminopyrazoles or indoles under neat conditions with l-proline as a catalyst. The regioselectivity of the products was confirmed by X-ray analysis and spectroscopic data. The formation of an azomethine ylide intermediate is crucial for obtaining the regioselectivity.

Recent Advances on the C2-Functionalization of Indole via Umpolung.

Heterocyclic compounds having a nitrogen atom in the ring exhibit very interesting biological activities. Indole is the core structure of many bioactive compounds owing to its high affinity to bind with most biological targets. Indole is an electron-rich compound and generally prefers electrophilic rather than nucleophilic substitution. Hence, many important indole derivatives are difficult to synthesize through the conventional reactivity of indole. This limitation can be avoided by using the umpolung, from the German word meaning polarity inversion. In umpolung, the indole molecule, especially the C2 and C3 positions, behave as an electrophile. As C2-functionalized indoles have substantial importance in synthetic and pharmaceutical chemistry, this review focuses on the C2 umpolung of indoles via the indirect approach which is less explored. Unlike direct approaches of indole umpolung, indirect methods have several advantages and therefore a number of research articles have been published in this field. But no review is available up till now. This is the first review on this topic and we believe that it will surely motivate the readers to work in this area further.

Macro-corrugated and nano-patterned hierarchically structured superomniphobic membrane for treatment of low surface tension oily wastewater by membrane distillation.

A hierarchically assembled superomniphobic membrane with three levels of reentrant structure was designed and fabricated to enable effective treatment of low surface tension, hypersaline oily wastewaters using direct contact membrane distillation (DCMD). The overall structure is a combination of macro corrugations obtained by surface imprinting, with the micro spherulites morphology achieved through the applied phase inversion method and nano patterns obtained by fluorinated Silica nanoparticles (SiNPs) coating. This resulted in a superomniphobic membrane surface with remarkable anti-wetting properties repelling both high surface tension water and low surface tension oils. Measurements of contact angle (CA) with DI water, an anionic surfactant, oil, and ethanol demonstrated a robust wetting resistance against low surface tension liquids showing both superhydrophobicity and superoleophobicity. CA values of 160.8 ± 2.3° and 154.3 ± 1.9° for water and oil were obtained, respectively. Calculations revealed a high liquid-vapor interface for the fabricated membrane with more than 89% of the water droplet contact area being with air pockets entrapped between adjacent SiNPs and only 11% come into contact with the solid membrane surface. Moreover, the high liquid-vapor interface imparts the membrane with high liquid repellency, self-cleaning and slippery effects, characterized by a minimum droplet-membrane interaction and complete water droplet bouncing on the surface within only 18 ms. When tested in DCMD with synthetic hypersaline oily wastewaters, the fabricated superomniphobic membrane demonstrated stable, non-wetting MD operation over 24 h, even at high concentrations of low surface tension 1.0 mM Sodium dodecyl sulfate and 400 ppm oil, potentially offering a sustainable option for treatment of low surface tension oily industrial wastewater.

Omniphobic re-entrant PVDF membrane with ZnO nanoparticles composite for desalination of low surface tension oily seawater.

In this study, an omniphobic membrane was fabricated by electrospraying fluorinated zinc oxide (ZnO) nanoparticles (NPs) mixed with polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) on the surface of an organosilane functionalized polyvinylidene difluoride (PVDF) membrane. Our results revealed that the functionalized ZnO NPs membrane exhibited a rough hierarchical re-entrant morphology with low surface energy which allowed it to achieve high omniphobic characteristics. It was observed that the addition of 30% ZnO (w/w of PVDF-HFP) was found to be optimal and imparted a high repulsive characteristic. The optimized PVDF/ZnO(30)/FAS/PVDF-HFP referred as cPFP-30Z membrane exhibited a high contact angle values of 159.0 ±â€¯3.1°, 129.6 ±â€¯2.2°, 130.4 ±â€¯4.1° and 126.1 ±â€¯1.2° for water, sodium dodecyl sulfate (SDS) saline solution (0.3 mM SDS in 3.5% NaCl), ethanol, and vegetable oil, respectively. The low surface energy and high surface roughness (Ra) of optimised membrane was assessed as 0.78 ±â€¯0.14 mN m-1 and 1.37 µm, respectively. Additionally, in contrast with the commercial PVDF membrane, the cPFP-30Z membrane exhibited superior anti-wetting/anti-fouling characteristics and high salt rejection performance (>99%) when operated with a saline oil solution (0.015 v/v) and SDS (0.4 mM) feed solutions.

Electrospun Nanofiber Membranes Incorporating PDMS-Aerogel Superhydrophobic Coating with Enhanced Flux and Improved Antiwettability in Membrane Distillation.

Electrospun nanofiber membranes (ENMs) have garnered increasing interest due to their controllable nanofiber structure and high void volume fraction properties in membrane distillation (MD). However, MD technology still faces limitations mainly due to low permeate flux and membrane wetting for feeds containing low surface tension compounds. Perfluorinated superhydrophobic membranes could be an alternative, but it has negative environmental impacts. Therefore, other low surface energy materials such as silica aerogel and polydimethylsiloxane (PDMS) have great relevancy in ENMs fabrication. Herein, we have reported the high flux and nonwettability of ENMs fabricated by electrospraying aerogel/polydimethylsiloxane (PDMS)/polyvinylidene fluoride (PVDF) over electrospinning polyvinylidene fluoride- co-hexafluoropropylene (PVDF-HFP) membrane (E-PH). Among various concentrations of aerogel, the 30% aerogel (E-M3-A30) dual layer membrane achieved highest superhydrophobicity (∼170° water contact angle), liquid entry pressure (LEP) of 129.5 ± 3.4 kPa, short water droplet bouncing performance (11.6 ms), low surface energy (4.18 ± 0.27 mN m-1) and high surface roughness ( Ra: 5.04 µm) with re-entrant structure. It also demonstrated nonwetting MD performance over a continuous 7 days operation of saline water (3.5% of NaCl), high antiwetting with harsh saline water containing 0.5 mM sodium dodecyl sulfate (SDS, 28.9 mN m-1), synthetic algal organic matter (AOM).

Multi-component synthesis of 3-substituted indoles and their cyclisation to α-carbolines via I2-promoted intramolecular C2 oxidative amination/aromatisation at room temperature.

Condensation of indoles, aldehydes and pyrazol-5-amine in the presence of ceric ammonium nitrate gives 3-substituted indoles. These then cyclise to α-carbolines at room temperature through I2-promoted intramolecular C2 amination and aromatisation in open air. A plausible mechanism is proposed based on some controlled experiments.

Mitigation of algal organic matter released from Chaetoceros affinis and Hymenomonas by in situ generated ferrate.

This study demonstrates the application of in situ ferrate (Fe(VI)) for the efficient removal of dissolved algal organic matter (AOM) from seawater. Sodium hypochlorite (NaOCl) and ferric (Fe(III)) were used to produce in situ Fe(VI) by wet chemical oxidation. First, the removal efficiencies of two model AOM compounds, humic acid (HA) and sodium alginate (SA), were evaluated in the presence of sodium chloride with an initial influent dissolved organic carbon (DOC) concentration of 5.0 mg C L-1 at different pH levels to establish the optimal doses for in situ Fe(VI) generation. The concentration of Fe(VI) was determined by the 2,2-Azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) ultraviolet-visible spectrophotometry method. In the case of HA, 72% DOC removal was recorded when applied with 1.5 mg L-1 of Fe(III) and 1.5 mg L-1 of NaOCl (in situ Fe(VI) concentration of 1.46 mg L-1) while 42% DOC removal was observed for SA. Subsequently, the removal of AOM extracted from two bloom-forming algal species, Chaetoceros affinis (CA) and Hymenomonas (Hym), cultivated in seawater from the Red Sea, were tested with in situ generated Fe(VI) at the established optimum condition. In situ Fe(VI) recorded superior performance in removing AOM extracted from CA and Hym, showing 83% and 92% DOC removal when the influent DOC concentrations were 2.48 and 2.63 mg L-1, respectively. A detailed AOM characterization was conducted using liquid chromatography-organic carbon detection.

Engineering the Re-Entrant Hierarchy and Surface Energy of PDMS-PVDF Membrane for Membrane Distillation Using a Facile and Benign Microsphere Coating.

To consolidate the position of membrane distillation (MD) as an emerging membrane technology that meets global water challenges, it is crucial to develop membranes with ideal material properties. This study reports a facile approach for a polyvinylidene fluoride (PVDF) membrane surface modification that is achieved through the coating of the surface with poly(dimethylsiloxane) (PDMS) polymeric microspheres to lower the membrane surface energy. The hierarchical surface of the microspheres was built without any assistance of a nano/microcomposite by combining the rapid evaporation of tetrahydrofuran (THF) and the phase separation from condensed water vapor. The fabricated membrane exhibited superhydrophobicity-a high contact angle of 156.9° and a low contact-angle hysteresis of 11.3°-and a high wetting resistance to seawater containing sodium dodecyl sulfate (SDS). Compared with the control PVDF-hexafluoropropylene (HFP) single-layer nanofiber membrane, the proposed fabricated membrane with the polymeric microsphere layer showed a smaller pore size and higher liquid entry pressure (LEP). When it was tested for the direct-contact MD (DCMD) in terms of the desalination of seawater (3.5% of NaCl) containing SDS of a progressively increased concentration, the fabricated membrane showed stable desalination and partial wetting for the 0.1 and 0.2 mM SDS, respectively.