Study on UF PES Membranes Spray-Coated with Polymerizable Bicontinuous Microemulsion Materials for Low-Fouling Behavior.

The low-fouling propensity of commercially available polyethersulfone (PES) membranes was studied after modification of the membrane surface via coating with polymerizable bicontinuous microemulsion (PBM) materials. The PBM coating was polymerized within 1 min using ultraviolet (UV) light exposure. It was detected on the PES membrane surface via attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. The PBM coating led to an average 10% increase in the hydrophilicity of the PES membrane surface and an increase in total organic content (TOC) removal by more than 15%. Flux-step tests were conducted with model foulant comprising 100 mg L-1 humic acid (HA) solution to detect the onset of critical fouling, characterized by a rapid and substantial increase in TMP, and to compare the fouling propensity of commercially available PES membranes with PBM-coated membranes. The critical flux was found to be about 40% higher for PBM spray-coated membrane and 20% lower for PBM casting-coated membrane than the commercial PES membrane. This demonstrates the performance advantages of the thin PBM layer spray-coated on PES membrane compared to the thick casting-coated PBM layer. The study showcases the potential of PBM spray-coated membranes over commercial PES membranes for use in membrane bioreactors (MBR) for wastewater treatment systems with reduced maintenance over longer operation periods.

Palladium Iodide Catalyzed Multicomponent Carbonylative Synthesis of 2-(4-Acylfuran-2-yl)acetamides.

2-Propargyl-1,3-dicarbonyl compounds have been carbonylated under oxidative conditions and with the catalysis of the PdI2/KI catalytic system to selectively afford previously unreported 2-(4-acylfuran-2-yl)acetamides in fair to good yields (54-81%) over 19 examples. The process takes place under relatively mild conditions and occurs via a mechanistic pathway involving Csp-H activation by oxidative monoamincarbonylation of the terminal triple bond of the substrates with formation of 2-ynamide intermediates, followed by 5-exo-dig O-cyclization (via intramolecular conjugate addition of the in situ formed enolate to the 2-ynamide moiety) and aromative isomerization.

Synthesis of Benzothiophene-3-carboxylic Esters by Palladium Iodide-Catalyzed Oxidative Cyclization-Deprotection-Alkoxycarbonylation Sequence under Aerobic Conditions.

A palladium-catalyzed carbonylative approach to benzothiophene-3-carboxylic esters, starting from simple and readily available building blocks [2-(methylthio)phenylacetylenes, CO, an alcohol, and O2 (from air)], is reported. The process is catalyzed by the simple PdI2/KI catalytic system to give the desired products in fair to high yields (57-83%). Interestingly, the reaction also works nicely in the ionic liquid BmimBF4 as the solvent, with the possibility to recycle the catalytic system several times without appreciable loss of activity.

Modular desalination concept with low-pressure reverse osmosis and capacitive deionization: Performance study of a pilot plant in Vietnam in comparison to seawater reverse osmosis.

Membrane capacitive deionization (MCDI) has shown many advances, however, its performance in combination with other treatment technologies has not been widely reported. In this study, a pilot-scale low-pressure reverse osmosis (LPRO) (FilmTec™ XLE-2540) with MCDI (CapDI© C17, Voltea) was developed and tested as a promising modular desalination system. The systems were evaluated individually at different salinities and tested together as a modular system. The study focused in the comparison to conventional seawater reverse osmosis (SWRO) (FilmTec™ SW30-2540) at pilot-scale and in theory using the software Water Application Value Engine (WAVE, DuPont™), including a cost evaluation of the systems. Pilot tests were carried out in Can Gio, a riverine estuary region in South Vietnam, which is affected by progressive salinization (TDS ≈ 1-25 g/L). Drinking water quality (TDS < 600 mg/L) was achieved with a specific energy consumption (SEC) of 5.2 kWh/m³. Additionally, fouling mitigation was investigated for the ultrafiltration (UF) pre-treatment by periodic hydraulic and chemical enhanced backwashing. While the SWRO had a slightly lower SEC of 5.0 kWh/m³, WAVE calculations showed that lowering the SEC to 3.6 kWh/m³ is possible by improving the LPRO pump design and an optimization of the MCDI operation.

The Rainbow Arching over the Fluorescent Thienoviologen Mesophases.

Thermofluorochromic materials exhibit tunable fluorescence emission on heating or cooling. They are highly desirable for applications ranging from temperature sensing to high-security anti-counterfeiting. Luminescent matrices based on liquid crystals are very promising, particularly those based on liquid crystals with intrinsic fluorescence. However, only a few examples have been reported, suggesting ample margins for development in the field, due to the wide range of fluorophores and supramolecular organizations to be explored. Moreover, thermofluorochromic liquid crystals can be tailored with further functionalities to afford multi-stimuli responsive materials. For the first time, herein we report the thermofluorochromism of thienoviologen liquid crystals, already known to show bulk electrochromism and electrofluorochromism. In particular, we studied their photophysics in the 25 °C-220 °C range and as a function of the length of the N-linear alkyl chains, m (9 ≤ m ≤ 12 C atoms), and the type of anion, X (X = OTs-, OTf-, BF4-, NTf2-). Interestingly, by changing the parameters m, X and T, their fluorescence can be finely tuned in the whole visible spectral range up to the NIR, by switching among different mesophases. Importantly, by fixing the structural parameters m and X, an interesting thermofluorochromism can be achieved for each thienoviologen in a homologous series, leading to a switch of the emitted light from red to green and from white to blue as a consequence of the temperature-induced variation in the supramolecular interactions in the self-assembled phases.

Orange-Peel-Derived Nanobiochar for Targeted Cancer Therapy.

Cancer-targeted drug delivery systems (DDS) based on carbon nanostructures have shown great promise in cancer therapy due to their ability to selectively recognize specific receptors overexpressed in cancer cells. In this paper, we have explored a green route to synthesize nanobiochar (NBC) endowed with graphene structure from the hydrothermal carbonization (HTC) of orange peels and evaluated the suitability of this nanomaterial as a nanoplatform for cancer therapy. In order to compare the cancer-targeting ability of different widely used targeting ligands (TL), we have conjugated NBC with biotin, riboflavin, folic acid and hyaluronic acid and have tested, in vitro, their biocompatibility and uptake ability towards a human alveolar cancer cell line (A549 cells). The nanosystems which showed the best biological performances-namely, the biotin- and riboflavin- conjugated systems-have been loaded with the poorly water-soluble drug DHF (5,5-dimethyl-6a-phenyl-3-(trimethylsilyl)-6,6a-dihydrofuro[3,2-b]furan-2(5H)-one) and tested for their anticancer activity. The in vitro biological tests demonstrated the ability of both systems to internalize the drug in A549 cells. In particular, the biotin-functionalized NBC caused cell death percentages to more than double with respect to the drug alone. The reported results also highlight the positive effect of the presence of oxygen-containing functional groups, present on the NBC surface, to improve the water dispersion stability of the DDS and thus make the approach of using this nanomaterial as nanocarrier for poorly water-soluble drugs effective.

In Situ Application of Anti-Fouling Solutions on a Mosaic of the Archaeological Park of Ostia Antica.

Biodegradation is among the most common issues affecting Cultural Heritage stone materials in outdoor environments. In recent years, the application of chemical agents with biocidal activity has been the most usual practice when dealing with biofilm removal. In outdoor environments, the use of these biocides is not effective enough, since the materials are constantly exposed to environmental agents and atmospheric pollutants. Thus, it becomes necessary to protect the surface of Cultural Heritage works with antimicrobial coatings to either prevent or at least limit future colonization. In this study, innovative biocides-both natural and synthetic-were applied on a Roman mosaic located in the Archaeological Park of Ostia Antica to compare their effectiveness in removing the biological degradation affecting it. In addition, an antimicrobial coating called "SI-QUAT" was applied and analyzed in situ. SI-QUAT has recently entered the market for its prevention activity against biocolonization. The biocidal activity of these products was tested and monitored using different analytical portable instruments, such as the multispectral system, the spectrocolorimeter, and the bioluminometer. The analyses showed that promising results can be obtained using the combination of the biocide and the protective effect of Preventol® RI50 and SI-QUAT.

Deep Eutectic Solvents (DESs): Preliminary Results for Their Use Such as Biocides in the Building Cultural Heritage.

Biodeterioration is an increasingly widespread process of degradation in the context of the conservation of cultural heritage, which involves a combination of physical and chemical damages together with an aesthetic alteration of materials. For biological damage on monuments caused by pathogens, macro- and microorganisms, chemical treatments are generally used, most of the time dangerous for the environment and for the operator. In this context, new eco-friendly products represent necessary tools for the treatment of biologically deteriorated stone surfaces and represent a new challenge in the field of restoration and conservation of materials of cultural interest. A relatively new class of unconventional green solvents are deep eutectic solvents (DESs), which have peculiar chemical-physical characteristics such as being non-toxic, ecological, biodegradable, non-flammable, and stable in the presence of water. Furthermore, many DESs known in the literature have also been shown to have a biocidal action. All these characteristics make DESs very advantageous and safe, and they could be used as biocidal agents for the treatment of biodegraded surfaces of cultural heritage, being non-toxic for the environment and for the operator. So far, they are used in various fields, but they still represent a novel frontier in the cultural heritage sector. The present research aims at testing five different DESs for the first time in cultural heritage. In particular, DESs are applied to a mosaic located in the Ostia Antica Archaeological Park (Rome), and their efficiency is compared with a biocide product currently used in the restoration field, namely, Preventol RI50, through luminescence, bio-luminometry, and spectrocolorimetry analysis. The preliminary results achieved show the different behaviors of each DESs, highlighting the possibility of employing them in the field of cultural heritage. Further studies have been planned, some of which are already underway, to investigate the properties of DESs and indicate any improvements to make them more effective, both as solvents and as biocides, and easy to apply to various types of materials. The results obtained from this first study are very promising for the use of DES as a new green strategy for cleaning and conservation treatments of materials in the field of cultural heritage.

Titanium Surface Modification for Implantable Medical Devices with Anti-Bacterial Adhesion Properties.

Pure titanium and titanium alloys are widely used in dentistry and orthopedics. However, despite their outstanding mechanical and biological properties, implant failure mainly due to post-operative infection still remains a significant concern. The possibility to develop inherent antibacterial medical devices was here investigated by covalently inserting bioactive ammonium salts onto the surface of titanium metal substrates. Titanium discs have been functionalized with quaternary ammonium salts (QASs) and with oleic acid (OA), affording the Ti-AEMAC Ti-GTMAC, Ti-AUTEAB, and Ti-OA samples, which were characterized by ATR-FTIR and SEM-EDX analyses and investigated for the roughness and hydrophilic behavior. The chemical modifications were shown to deeply affect the surface properties of the metal substrates and, as a consequence, their bio-interaction. The bacterial adhesion tests against the Gram-negative Escherichia Coli and Gram-positive Staphylococcus aureus, at 1.5 and 24 h of bacterial contact, showed good anti-adhesion activity for Ti-AUTEAB and Ti-OA samples, containing a long alkyl chain between the silicon atom and the ammonium functionality. In particular, the Ti-AUTEAB sample showed inhibition of bacteria adhesion against Escherichia Coli of about one log with respect to the other samples, after 1.5 h. The results of this study highlight the importance of chemical functionalization in addressing the antimicrobial activity of metal surfaces and could open new perspectives in the development of inherent antibacterial medical devices.

Organic Synthesis via Transition Metal-Catalysis.

In recent years, the development of transition-metal-catalyzed reactions has acquired an increasing importance [...].

Advances in Palladium-Catalyzed Carboxylation Reactions.

In this short review, we highlight the advancements in the field of palladium-catalyzed carbon dioxide utilization for the synthesis of high value added organic molecules. The review is structured on the basis of the kind of substrate undergoing the Pd-catalyzed carboxylation process. Accordingly, after the introductory section, the main sections of the review will illustrate Pd-catalyzed carboxylation of olefinic substrates, acetylenic substrates, and other substrates (aryl halides and triflates).

Pd-Catalysed oxidative carbonylation of α-amino amides to hydantoins under mild conditions.

The first example of palladium-catalysed oxidative carbonylation of unprotected α-amino amides to hydantoins is described here. The selective synthesis of the target compounds was achieved under mild conditions (1 atm of CO), without ligands and bases. The catalytic system overrode the common reaction pathway that usually leads instead to the formation of symmetrical ureas.

Anticancer potential of novel α,ß-unsaturated γ-lactam derivatives targeting the PI3K/AKT signaling pathway.

Six recently synthesized alkyl (Z)-2-(2-oxopyrrolidin-3-ylidene)acetates were evaluated for their potential as cytotoxic and anticancer agents. All compounds were tested in the ERα positive MCF-7, triple negative MDA-MB-231, and Her2+ SKBR-3 breast cancer cell lines. The most lipophilic derivatives, bearing the 4-isopropylphenyl (2) or 4-tert-butylphenyl (3) group at the γ-lactam nitrogen, proved to be cytotoxic against all the cancer cell lines tested (IC50 values ranging from 18 to 63 µM), exerting their greatest activity in SKBR-3 cells, with IC50 values of 33 and 18 µM, respectively. Biological studies showed that the cytotoxic effects of 2 and 3 are accompanied by apoptotic death in breast cancer cells, and both compounds showed no significant toxicity on healthy cells (e.g., MCF-10A) and red blood cells. An in-depth mechanistic study based on molecular biology, immunoblotting analysis and in silico docking calculations suggested that α,ß-unsaturated γ-lactam derivatives could interfere with the functioning of PI3K and PDK-1, two key enzymes in the PI3K/AKT signaling pathway, whose overactivation is related to the regulation of cell growth and survival in several malignancies.

A Zinc-Mediated Deprotective Annulation Approach to New Polycyclic Heterocycles.

A straightforward approach to new polycyclic heterocycles, 1H-benzo[4,5]imidazo[1,2-c][1,3]oxazin-1-ones, is presented. It is based on the ZnCl2-promoted deprotective 6-endo-dig heterocyclization of N-Boc-2-alkynylbenzimidazoles under mild conditions (CH2Cl2, 40 °C for 3 h). The zinc center plays a dual role, as it promotes Boc deprotection (with formation of the tert-butyl carbocation, which can be trapped by substrates bearing a nucleophilic group) and activates the triple bond toward intramolecular nucleophilic attack by the carbamate group. The structure of representative products has been confirmed by X-ray diffraction analysis.

Small-scale membrane-based arsenic removal for decentralized applications-Developing a conceptual approach for future utilization.

Various technologies are used for the treatment of arsenic (As) contaminated water, but only a few seem to be suitable for small-scale applications; these are mostly used in rural communities where the access to potable water is the most vulnerable. In this review paper, the salient advantages and most notable challenges of membrane-based technologies for the removal of arsenate As(V) and arsenite As(III) are evaluated and systematically compared to alternative technologies such as e.g. adsorption. A comparison of different scientific papers, case studies and pilot trials is used to discuss the most important aspects when evaluating As mitigation technologies, including the ability to comply with the stringent WHO drinking water guideline limit value of 10 µg/L As and the safe disposal of produced As-laden waste. The use of renewable energies such as solar power in small-scale (<10 m³/day) membrane applications is evaluated. Finally, a conceptual approach for holistic As mitigation is proposed as an important approach to prevent exposure to As by providing a safe water supply.

Viscosity Modification of Polymerizable Bicontinuous Microemulsion by Controlled Radical Polymerization for Membrane Coating Applications.

Membrane modification is becoming ever more relevant for mitigating fouling phenomena within wastewater treatment applications. Past research included a novel low-fouling coating using polymerizable bicontinuous microemulsion (PBM) induced by UV-LED polymerization. This additional cover layer deteriorated the filtration capacity significantly, potentially due to the observed high pore intrusion of the liquid PBM prior to the casting process. Therefore, this work addressed an innovative experimental protocol for controlling the viscosity of polymerizable bicontinuous microemulsions (PBM) before casting on commercial ultrafiltration (UF) membranes. Prior to the coating procedure, the PBM viscosity modulation was carried out by controlled radical polymerization (CRP). The regulation was conducted by introducing the radical inhibitor 2,2,6,6-tetramethylpiperidine 1-oxyl after a certain time (CRP time). The ensuing controlled radical polymerized PBM (CRP-PBM) showed a higher viscosity than the original unpolymerized PBM, as confirmed by rheological measurements. Nevertheless, the resulting CRP-PBM-cast membranes had a lower permeability in water filtration experiments despite a higher viscosity and potentially lower pore intrusion. This result is due to different polymeric structures of the differently polymerized PBM, as confirmed by solid-state nuclear magnetic resonance (NMR) investigations. The findings can be useful for future developments in the membrane science field for production of specific membrane-coating layers for diverse applications.

Membrane Bioreactor-Treated Domestic Wastewater for Sustainable Reuse in the Lake Victoria Region.

Lake Victoria is a shared water resource between Kenya, Uganda, and Tanzania, which is the second largest freshwater lake in the world. It has long since suffered from the consequences of overexploitation of its resources, mainly fish stocks, and increasingly high pollution. The closure of 58% of the fish processing plants (FPPs) is attributed to the declining fish stocks due to overfishing and pollution in particular. The installation and operation of a pilot membrane bioreactor (MBR) in Kisumu, Kenya, adopts an integrated approach by providing an integral, sustainable, cost-effective, and robust solution for water sanitation, which also meets the demand for clean water in the fish processing industry, aquaculture, and irrigation. The innovative system comprises a pilot MBR coupled with a recirculation aquaculture system (RAS). The RAS is able to recirculate 90% to 95% of its water volume; only the water loss through evaporation and drum filter back flushing has to be replaced. To compensate for this water deficit, the MBR treats domestic wastewater for further reuse. Additionally, excess purified water is used for irrigating a variety of local vegetables and could also be used in FPPs. The pilot-scale MBR plant with around 6 m2 submerged commercial polyethersulfone (PES) membranes provides treated water in basic agreement with Food and Agriculture Organization (FAO) standards for irrigation and aquaculture, showing no adverse effects on tilapia fingerlings production. A novel membrane module with a low-fouling coating is operating stably but has not yet shown improved performance compared to the commercial one. Integr Environ Assess Manag 2020;16:942-954. © 2020 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

5-(Carbamoylmethylene)-oxazolidin-2-ones as a Promising Class of Heterocycles Inducing Apoptosis Triggered by Increased ROS Levels and Mitochondrial Dysfunction in Breast and Cervical Cancer.

Oxazolidinones are antibiotics that inhibit protein synthesis by binding the 50S ribosomal subunit. Recently, numerous worldwide researches focused on their properties and possible involvement in cancer therapy have been conducted. Here, we evaluated in vitro the antiproliferative activity of some 5-(carbamoylmethylene)-oxazolidin-2-ones on MCF-7 and HeLa cells. The tested compounds displayed a wide range of cytotoxicity on these cancer cell lines, measured by MTT assay, exhibiting no cytotoxicity on non-tumorigenic MCF-10A cells. Among the nine tested derivatives, four displayed a good anticancer potential. Remarkably, OI compound showed IC50 values of 17.66 and 31.10 µM for MCF-7 and HeLa cancer cells, respectively. Furthermore, we assessed OI effect on the cell cycle by FACS analysis, highlighting a G1 phase arrest after 72 h, supported by a low expression level of Cyclin D1 protein. Moreover, mitochondrial membrane potential was reduced after OI treatment driven by high levels of ROS. These findings demonstrate that OI treatment can inhibit MCF-7 and HeLa cell proliferation and induce apoptosis by caspase-9 activation and cytochrome c release in the cytosol. Hence, 5-(carbamoylmethylene)-oxazolidin-2-ones have a promising anticancer activity, in particular, OI derivative could represent a good candidate for in vivo further studies and potential clinical use.

Site-Selective Double and Tetracyclization Routes to Fused Polyheterocyclic Structures by Pd-Catalyzed Carbonylation Reactions.

In this contribution, we report novel palladium-catalyzed carbonylative cascade approaches to highly functionalized polyheterocyclic structures. The Pd-catalyzed carbonylative process involves the regioselective insertion of one to three CO molecules and the sequential ordered formation of up to eight new bonds (one C-O, two C-C, five C-N). The exclusive formation of six-membered heterocycles is elucidated by detailed modeling studies.

Cyclometalated Ruthenium Pincer Complexes as Catalysts for the α-Alkylation of Ketones with Alcohols.

Ruthenium PNP pincer complexes bearing supplementary cyclometalated C,N-bound ligands have been prepared and fully characterized for the first time. By replacing CO and H- as ancillary ligands in such complexes, additional electronic and steric modifications of this topical class of catalysts are possible. The advantages of the new catalysts are demonstrated in the general α-alkylation of ketones with alcohols following a hydrogen autotransfer protocol. Herein, various aliphatic and benzylic alcohols were applied as green alkylating agents for ketones bearing aromatic, heteroaromatic or aliphatic substituents as well as cyclic ones. Mechanistic investigations revealed that during catalysis, Ru carboxylate complexes are predominantly formed whereas neither the PNP nor the CN ligand are released from the catalyst in significant amounts.