Intramolecular Cyclopropanation of Active Methylene Derivatives Based on FeCl2 or FeCl3-Promoted Radical-Polar Crossover Reactions.

Radical-polar crossover reactions were studied for the intramolecular cyclopropanation of active methylene derivatives. In the presence of FeCl3 as a stoichiometric oxidant and K2HPO4 as a base, the dehydrogenative cyclopropanation of active methylenes proceeded through the FeCl3-promoted oxidative radical cyclization followed by the ionic cyclization to give the bicyclic cyclopropanes. The use of α-chloro-active methylenes leads the subcatalytic cyclopropanation involving two redox pathways. In the presence of K2HPO4, the redox cyclopropanation proceeded by using FeCl2 (20 mol%) in combination with ligand (20 mol%).

Mild Iron-Catalyzed Oxidative Cross-Coupling of Quinoxalinones with Indoles.

Utilizing iron chloride as a Lewis acid catalyst, we developed a straightforward and mild oxidative cross-coupling reaction between quinoxalinones and indoles, yielding a series of versatile 3-(indol-3-yl)quinoxalin-2-one derivatives. This approach allows for the incorporation of a wide array of functional groups into the final products, demonstrating its synthetic versatility. Notably, the method was successfully scaled up to gram-scale reactions while maintaining high yields. Our mechanistic investigation indicates that iron chloride serves as a catalyst to facilitate the formation of key intermediates which subsequently undergo oxidation to afford the desired products. The merits of this protocol include its cost effectiveness, operational simplicity, and the ease of product isolation via filtration.

Evaluation of combined thermo-chemical processes for the treatment of landfill leachate using virgin and recovered FeCl3 coagulants.

Sludge resulting from treatment of municipal waste landfill leachate contains suitable cationic substances such as Fe-based recovered coagulants which, if not recovered, can cause environmental problems. The present study aimed to maximise coagulant recoverability and investigate its potential reuse for the treatment of municipal waste landfill leachate. The study focused on establishing (i) the effect of mineral acids on leaching of Fe, (ii) the % of maximum recovery of Fe coagulant, (iii) the impact of ultrasound on recovery, and (iv) effectiveness of recovered coagulant when reused in coagulation-flocculation treatment of landfill leachate. Sulfuric acid outran hydrochloric acid in performance, with the acid leaching process leading to the recovery of 70.12% of Fe (acid concentration = 3.80 M, solid-to-liquid ratio = 8%, and heating time = 5 h). Subsequently, a developed acid leaching process was tested, which results showed that the highest rate of Fe recovery occurred without ultrasound treatment, meaning the use of it could reduce the recovery rate due to the increase in the iron (III) oxide-hydroxide [Fe(OH)3] sedimentation. Comparative experiments were undertaken with the recovered and virgin coagulants. These revealed that Fe-based recovered coagulant led to the 60.21% and 91.40% removal of COD and total suspended solid respectively, while the values of the COD and total suspended solid removal with the virgin FeCl3 were 7.66% and 6.42% lower than that of Fe under optimal conditions (dosage = 9.38 g/L, pH = 8.94, settling time = 52.9 min). The present study established that Fe recovered could be exploited as an eco-friendly coagulant to replace FeCl3 in the landfill leachate treatment.

Life cycle assessment of zinc and iron recovery from spent pickling acids by membrane-based solvent extraction and electrowinning.

In this paper we conducted a life cycle assessment to evaluate the environmental performance of the valorization of spent pickling acid (SPA) generated in the hot-dip galvanizing (HDG) process. We analyzed the environmental impacts of treating one m3 of SPA, comparing the reference treatment consisting of neutralization, precipitation, stabilization, and landfilling of the metallic sludge (scenario #1), with the innovative LIFE2ACID technology (scenario #2) that produces secondary zinc and iron chloride in solution through non-dispersive solvent extraction (NDSX) and electrowinning (EW). The results showed that the materials credits achieved by the implementation of LIFE2ACID technology turned most of the impact categories evaluated (toxicity, acidification, eutrophication, ozone depletion, etc.) into environmental benefits. Scenario #2 was adapted to achieve either zinc-only recovery (#2.1) or simultaneous iron and zinc recovery (#2.2). The abiotic depletion potential (ADP) of fossil fuels increased slightly from scenario #1 to scenario #2.1 because of the higher energy demand and NaOH consumption of EW, and because only zinc was recovered. However, the valorization of both zinc and iron chloride in scenario #2.2 reduced the ADP-fossil by 27%, compared to the reference treatment. Furthermore, the global warming impact was reduced by 20% and 97% in scenarios #2.1 and #2.2, respectively. With the focus on promoting the circular economy concept, we conclude that the LIFE2ACID technology significantly improves the environmental performance of SPA management. Next steps should consider the life-cycle costs analysis in specific scenarios to find out the trade-off between environmental and economic objectives.

Removal efficiency of dissolved organic matter from secondary effluent by coagulation-flocculation processes.

Wastewater reuse has been widely discussed as an essential strategy to minimize the consumption of drinking water for less noble purposes. During biological wastewater treatment, organic matter is converted into a complex matrix containing a variety of soluble organic compounds. The objective of the present study was to evaluate the removal efficiency of the residual organic load in the final effluent from wastewater treatment plant with a conventional activated sludge process by different coagulants and parameters of coagulation-flocculation process, using dissolved organic carbon (DOC) concentration, molecular weight (MW) size distribution by size exclusion chromatography (SEC) coupled to mass spectrometry (MS), and zeta potential (ZP) analyses. The results showed a DOC removal efficiency up to 45% with iron chloride, and of 38% for aluminum sulfate and 31% for PAC coagulants. ZP was also measured during the procedures and authors conclude that the ZP also does not have a determining role in these removals. SEC and MS assessment was able to detect changes on secondary effluent molecular weight distribution profile after effluent coagulation-flocculation, this technique might be a promising tool to understand the composition of effluent organic matter and be helpful to estimate and optimize the performance of wastewater effluents treatment processes.

The effect of salt and temperature on the conformational changes of P1LEA-22, a repeat unit of plant Late Embryogenesis Abundant proteins.

The effect of choline chloride on the conformational dynamics of the 11-mer repeat unit P1LEA-22 of group 3 Late Embryogenesis Abundant (G3LEA) proteins was studied. Circular dichroism data of aqueous solutions of P1LEA-22 revealed that the peptide favors a polyproline II (PPII) helix structure at low temperature, with increasing temperature promoting a gain of unstructured conformations. Furthermore, increases in sample FeCl3 or choline chloride concentrations causes a gain in PPII helical structure at low temperature. The potential role of PPII structure in intrinsically disordered and G3LEA proteins is discussed, including its ability to easily access other secondary structural conformations such as α-helix and ß-sheet, which have been observed for dehydrated G3LEA proteins. The observed effect of FeCl3 and choline chloride salts on P1LEA-22 suggests favorable cation interactions with the PPII helix, supporting ion sequestration as a G3LEA protein function. As choline chloride is suggested to improve salt tolerance and protect cell membrane in plants at low temperature, our results support adoption of the PPII structure as a possible damage-preventing measure of Late Embryogenesis Abundant proteins.

Optimization with Response Surface Methodology of Microwave-Assisted Conversion of Xylose to Furfural.

The production of furfural from renewable sources, such as lignocellulosic biomass, has gained great interest within the concept of biorefineries. In lignocellulosic materials, xylose is the most abundant pentose, which forms the hemicellulosic part. One of the key steps in the production of furfural from biomass is the dehydration reaction of the pentoses. The objective of this work was to assess the conditions under which the concentration of furfural is maximized from a synthetic, monophasic, and homogeneous xylose medium. The experiments were carried out in a microwave reactor. FeCl3 in different proportions and sulfuric acid were used as catalysts. A two-level, three-factor experimental design was developed for this purpose. The results were further analyzed through a second experimental design and optimization was performed by response surface methodology. The best operational conditions for the highest furfural yield (57%) turned out to be 210 °C, 0.5 min, and 0.05 M FeCl3.

Hg0 removal from flue gas over different zeolites modified by FeCl3.

The elemental mercury removal abilities of three different zeolites (NaA, NaX, HZSM-5) impregnated with iron(III) chloride were studied on a lab-scale fixed-bed reactor. X-ray diffraction, nitrogen adsorption porosimetry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption (TPD) analyses were used to investigate the physicochemical properties. Results indicated that the pore structure and active chloride species on the surface of the samples are the key factors for physisorption and oxidation of Hg0, respectively. Relatively high surface area and micropore volume are beneficial to efficient mercury adsorption. The active Cl species generated on the surface of the samples were effective oxidants able to convert elemental mercury (Hg0) into oxidized mercury (Hg2+). The crystallization of NaCl due to the ion exchange effect during the impregnation of NaA and NaX reduced the number of active Cl species on the surface, and restricted the physisorption of Hg0. Therefore, the Hg0 removal efficiencies of the samples were inhibited. The TPD analysis revealed that the species of mercury on the surface of FeCl3-HZSM-5 was mainly in the form of mercuric chloride (HgCl2), while on FeCl3-NaX and FeCl3-NaA it was mainly mercuric oxide (HgO).

A Facile Approach to Produce Activated Carbon from Waste Textiles via Self-Purging Microwave Pyrolysis and FeCl3 Activation for Electromagnetic Shielding Applications.

This study aims to convert composite textile structures composed of nonwoven and woven fabrics produced from cotton-jute wastes into activated carbon textile structures and investigate the possibilities of using them for electromagnetic shielding applications. To this end, the novel contribution of this study is that it shows that directly carbonized nonwoven textile via self-purging microwave pyrolysis can provide Electromagnetic Interference (EMI) shielding without any processing, including cleaning. Textile carbonization is generally achieved with conventional heating methods, using inert gas and long processing times. In the present study, nonwoven fabric from cotton-jute waste was converted into an activated carbon textile structure in a shorter time via microwaves without inert gas. Due to its polar structure, FeCl3 has been used as a microwave absorbent, providing homogeneous heating in the microwave and acting as an activating agent to serve dual purposes in the carbonization process. The maximum surface area (789.9 m2/g) was obtained for 5% FeCl3. The carbonized composite textile structure has a maximum of 39.4 dB at 1 GHz of EMI shielding effectiveness for 10% FeCl3, which corresponds to an excellent grade for general use and a moderate grade for professional use, exceeding the acceptable range for industrial and commercial applications of 20 dB, according to FTTS-FA-003.

Advancement of biochar-aided with iron chloride for contaminants removal from wastewater and biogas production: A review.

The use of fossil fuels, emission of greenhouse gases (GHG) into the atmosphere, and waste pose a problem to the environment and public health that urgently needs to be dealt with. Among numerous chemical activating agents that can be added to anaerobic digestion (AD) to enhance nutrient removal and increase the quality and quantity of biomethane, iron chloride (FeCl3) is the one that has the lowest cost and is the most environmentally friendly. This state-of-the-art review aims to revise the influence of FeCl3 on the Brunauer-Emmett-Teller (BET) surface area of biochar and its ability to increase methane (CH4) yield and remove contaminants from biogas and wastewater. The novelty of the study is that FeCl3, an activating agent, can increase the BET surface area of biochar, and its efficacy increases when combined with zinc chloride or phosphoric acid. Regarding the removal of contaminants from wastewater and biogas, FeCl3 has proven to be an effective coagulant, reducing the chemical oxygen demand (COD) of wastewater and hydrogen sulfide in biogas. The performance of FeCl3 depends on the dosage, pH, and feedstock used. Therefore, FeCl3 can increase the BET surface area of biochar and CH4 yield and remove contaminants from wastewater and biogas. More research is needed to investigate the ability of FeCl3 to remove water vapor and carbon dioxide during biogas production while accounting for a set of other parameters, including FeCl3 size.

Comparing Ultralong Carbon Nanotube Growth from Methane over Mono- and Bi-Metallic Iron Chloride Catalysts.

This research endeavours to study the growth of ultralong carbon nanotubes (UL-CNTs) from methane using diverse catalysts, namely FeCl3, bi-metallic Fe-Cu, Fe-Ni, and Fe-Co chlorides. Aqueous catalyst solutions were evenly dispersed on silica substrates and grown at 950 °C in the presence of hydrogen via a horizontal chemical vapour deposition (CVD) furnace. The samples underwent characterisation by Raman spectroscopy, scanning electron microscopy (SEM), and optical microscopy to identify the quality of CNTs and enumerate individual UL-CNTs. Our findings revealed that FeCl3, as a mono-metallic catalyst, generated the longest UL-CNTs, which measured 1.32 cm, followed by Fe-Cu (0.85 cm), Fe-Co (0.7 cm), and Fe-Ni (0.6 cm), respectively. The G/D ratio (graphene to defects) from the Raman spectroscopy was the highest with the FeCl3 catalyst (3.09), followed by Fe-Cu (2.79), Fe-Co catalyst (2.13), and Fe-Ni (2.52). It indicates that the mono-iron-based catalyst also produces the highest purity CNTs. Moreover, this study scrutinises the vapour-liquid-solid (VLS) model for CNT growth and the impact of carbide formation as a precursor to CNT growth. Our research findings indicate that forming iron carbide (Fe3C) is a crucial transition phase for amorphous carbon transformation to CNTs. Notably, the iron catalyst generated the longest and densest CNTs relative to other iron-based bi-metallic catalysts, which is consistent with the temperature of carbide formation in the mono-metallic system. From correlations made using the phase diagram with carbon, we conclude that CNT growth is favoured because of increased carbon solubility within the mono-metallic catalyst compared to the bi-metallic catalysts.

Biosynthesis and characterization of iron oxide nanoparticles from Mentha spicata and screening its combating potential against Phytophthora infestans.

Plant pathogens cause serious diseases to agricultural crops which lead to food insecurity in the world. To combat plant pathogens, various strategies have been developed including the use of agrochemicals. The overuse of these chemicals is now leading to the pesticide-resistant capability of pathogens. To overcome this problem, modern nanobiotechnology offers the production of alternative nano drugs. In this study, we used Mentha spicata for the synthesis of iron oxide nanoparticles using the green synthesis method. The synthesis of Fe2O3 NPs was confirmed through various characterizations. UV-Vis analysis detected a characteristic absorbance at the spectral range of 272 nm. The SEM micrographic analysis at various magnifications displayed circular or rod-shaped nanoparticles with a size ranging from 21 to 82 nm. The elemental EDX characterization showed intense peaks with a weight percent of 57, 34.93, and 8.07 for Fe, O, and, Cl respectively. TGA analysis showed that weight loss at 44-182, 500, and 660°C with no further modification indicates the thermal stability of iron oxide nanoparticles. FTIR spectrum of uncalined detects various bands at 3331, 1625, and 1,437 cm-1 for the hydroxyl group. After calcination two bands at 527 and 434 cm-1 were observed for Fe-O. The antimicrobial in vitro study showed maximum growth inhibition of Phytophthora infestans by the concentration of 100 µg ml-1 of Fe2O3-PE and Fe2O3 NPs. Therefore, this study resulted that bio-stable iron oxide nanoparticles can be used as alternative antimicrobial agents.

Comparison of ultrafiltration and iron chloride flocculation in the preparation of aquatic viromes from contrasting sample types.

Viral metagenomes (viromes) are a valuable untargeted tool for studying viral diversity and the central roles viruses play in host disease, ecology, and evolution. Establishing effective methods to concentrate and purify viral genomes prior to sequencing is essential for high quality viromes. Using virus spike-and-recovery experiments, we stepwise compared two common approaches for virus concentration, ultrafiltration and iron chloride flocculation, across diverse matrices: wastewater influent, wastewater secondary effluent, river water, and seawater. Viral DNA was purified by removing cellular DNA via chloroform cell lysis, filtration, and enzymatic degradation of extra-viral DNA. We found that viral genomes were concentrated 1-2 orders of magnitude more with ultrafiltration than iron chloride flocculation for all matrices and resulted in higher quality DNA suitable for amplification-free and long-read sequencing. Given its widespread use and utility as an inexpensive field method for virome sampling, we nonetheless sought to optimize iron flocculation. We found viruses were best concentrated in seawater with five-fold higher iron concentrations than the standard used, inhibition of DNase activity reduced purification effectiveness, and five-fold more iron was needed to flocculate viruses from freshwater than seawater-critical knowledge for those seeking to apply this broadly used method to freshwater virome samples. Overall, our results demonstrated that ultrafiltration and purification performed better than iron chloride flocculation and purification in the tested matrices. Given that the method performance depended on the solids content and salinity of the samples, we suggest spike-and-recovery experiments be applied when concentrating and purifying sample types that diverge from those tested here.

Coagulation of TiO2 , CeO2 nanoparticles, and polystyrene nanoplastics in bottled mineral and surface waters. Effect of water properties, coagulant type, and dosage.

Intensive use of engineered nanoparticles (NPs) results in their release into aquatic systems and consequently into drinking water resources. Therefore, it is important to evaluate how NPs can be effectively removed through water treatment processes, such as coagulation, to control environmental and health risks associated with NP exposure. This work investigates the effect of two conventional coagulants, polyaluminum chloride (PACl) and iron chloride (FeCl3 ), on NPs. Three bottled mineral and Lake Geneva waters, currently used as drinking water resources, were considered to get an insight into coagulation efficiency. TiO2 , CeO2 NPs, and polystyrene (PS) nanoplastics were selected, owing to their large number of applications and contrasting surface charge and aggregation behavior at environmental pH. Our findings indicate that PACl is more efficient compared with FeCl3 since lower dosages are required to coagulate all nanoparticles. On the other hand, nanoplastic coagulation is found less efficient compared with TiO2 and CeO2 NPs. This is an important outcome indicating that nanoplastic stability and dispersion state will be more pronounced and therefore more challenging to eliminate. Results highlight the key role of NP and PS nanoplastic surface charge, as well as water properties, coagulant type, and dosage on nanoparticle elimination from aquatic systems. PRACTITIONER POINTS: pH, water hardness, and NOM are playing roles in final coagulant dosage concentration. PACl is more efficient than FeCl3 in most conditions. Positively charged nanoplastics are more difficult to eliminate by coagulation. NP surface properties in bottled mineral and surface waters are controlled by pH, divalent cations, and NOM. NP surface charge and coagulation efficiency depend on water properties.

Iron Chloride Flocculation of Bacteriophages from Seawater.

Viruses influence ecosystem dynamics by modulating microbial host population dynamics, evolutionary trajectories and metabolic outputs. While they are ecologically important across diverse ecosystems, viruses are challenging to study due to minimal biomass often obtained when sampling natural communities. Here we describe a technique using chemical flocculation, filtration and resuspension to recover bacteriophages from seawater and other natural waters. The method uses iron to precipitate viruses which are recovered by filtration onto large-pore size membranes and then resuspended using a buffer containing magnesium and a reductant (ascorbic acid or oxalic acid) at slightly acid pH (6-6.5). The recovery of bacteriophages using iron flocculation is efficient (>90%), inexpensive and reliable, resulting in preparations that are amenable to downstream analysis by next generation DNA sequencing, proteomics and, in some cases, can be used to study virus-host interactions.

Study of the presence of PCDDs/PCDFs on zero-valent iron nanoparticles.

Studies show that nanoscale zero-valent iron (nZVI) particles enhance the formation of chlorinated compounds such as polychlorinated dioxins and furans (PCDD/Fs) during thermal processes. However, it is unclear whether nZVI acts as a catalyst for the formation of these compounds or contains impurities, such as PCDD/Fs, within its structure. We analyzed the presence of PCDD/Fs in nZVI particles synthesized through various production methods to elucidate this uncertainty. None of the 2,3,7,8-substituted congeners were found in the commercially-produced nZVI, but they were present in the laboratory-synthesized nZVI produced through the borohydride method, particularly in particles synthesized from iron (III) chloride rather than from iron sulfate. Total PCDD/F WHO-TEQ concentrations of up to 35 pg/g were observed in nZVI particles, with hepta- and octa-chlorinated congeners being the most abundant. The reagents used in the borohydride method were also analyzed, and our findings suggest that FeCl3 effectively contains PCDD/Fs at concentrations that could explain the concentrations observed in the nZVI product. Both FeCl3 and nZVI showed a similar PCDD/F patterns with slight differences. These results suggest that PCDD/Fs might transfer from FeCl3 to nZVI during the production method, and thus, care should be taken when employing certain nZVI for environmental remediation.

Antimicrobial and antioxidant activities of Flammulina velutipes polysaccharides and polysaccharide-iron(III) complex [corrected].

FVP is polysacchrides obtained from Flammulina velutipes. A polysacchride named FVP2 was isolated from FVP by DEAE cellulose-52 chromatography and Sephadex G-100 size-exclusion chromatography. FVP-Fe and FVP2-Fe were synthesized by neutralization of FeCl3 carbohydrate solution. The antibacterial and antifungal activities of FVP, FVP2, FVP-Fe, FVP2-Fe were investigated and their antioxidant effects on hydroxyl, 2,2-diphenyl-1-picrylhydrazyl (DPPH), superoxide anion, 2,2'-azobis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radicals, reducing power, inhibition of malondialdehyde (MDA) were assessed in vitro. The results suggested that FVP-Fe and FVP2-Fe significantly suppressed the growth of bacteria Staphylococcus aureus, Escherichia coli, and Bacillus subtilis, and have relatively strong antioxidant activity to scavenge superoxide anion radical. In addition, FVP exhibited strong antioxidant activity to eliminate hydroxyl, DPPH, ABTS radicals, had high reducing power and inhibited the MDA production of health mice liver homogenate induced by auto-oxidation and Fe2+-H2O2 system.

Management of eutrophication in Lake De Kuil (The Netherlands) using combined flocculant - Lanthanum modified bentonite treatment.

Eutrophication of Lake De Kuil (The Netherlands, 6.7 ha, maximum depth 9 m) has frequently caused cyanobacterial blooms resulting in swimming bans or the issue of water quality warnings during summer. The eutrophication was mainly driven by sediment phosphorus (P)-release. The external P-loading was in the range of the critical loading for phytoplankton blooms. Hence, the reduction of the internal P-loading provided a promising way to reduce cyanobacterial blooms. To mitigate the cyanobacterial blooms, the combination of a low dose flocculant (iron(III)chloride; Flock) and a solid phase phosphate fixative (lanthanum modified bentonite; Lock) was applied in May 2009. This combined approach both removed cyanobacterial biomass from the water column and also intercepted P released from the bottom sediments. Immediately after treatment, the Secchi depth increased from 1.5 m up to 5 m. Sediment P-release decreased from 5.2 mg P m(-2) d(-1) (2009) to 0.4 mg P m(-2) d(-1) (2010) but increased in later years. Mean summer concentrations of total P decreased from 0.05 mg L(-1) (1992-2008) to 0.02 mg L(-1) (2009-2014) and chlorophyll-a from 16 µg L(-1) (1992-2008) to 6 µg L(-1) (2009-2014). Mean summer Secchi depth increased from 2.31 m (1992-2008) to 3.12 m (2009-2014). The coverage of macrophytes tripled from 2009 to 2011. In the winter of 2010/2011 Planktothrix rubescens bloomed, but cyanobacterial biomass decreased during the summers after the Flock and Lock treatment in comparison to prior years. After the Flock & Lock the bathing water requirements have been fulfilled for six consecutive summers. As the sediment P-release has gradually increased in recent years, there is a risk of a reversion from the present mesotrophic state to a eutrophic state.