Immobilized enzymatic membrane surfaces for biocatalytic organics removal and fouling resistance.

This research reported on the immobilization of environmentally friendly enzymes, such as horseradish peroxidase (HRP) and laccase (L), along with the hydrophilic zwitterionic compound l-DOPA on nano-filtration (NF) membranes. This approach introduced biocatalytic membranes, leveraging combined effects between membranes and enzymes. The aim was to systematically assess the efficacy of the enzymatic modified membrane (HRP-NF) in degrading colors in the wastewater, as well as enhancing the membrane resistance toward organic fouling. The enzymatic immobilized membrane demonstrated 96.3 ± 1.8% to 96.6 ± 1.9% removal of colors, and 65.2 ± 1.3% to 67.2 ± 1.3% removal of TOC. This result was underpinned by the insights obtained from the radical scavenger coumarin, which was employed to trap and confirm the formation of PRs through the reaction of enzymes and H2O2. Furthermore, membranes modified with enzymes exhibited significantly improved antifouling properties. The HRP-NF membrane experienced an 8% decline in flux, while the co-immobilized HRP-L-NF membrane demonstrated as low as 6% flux decline, contributed by the synergistic effect of increased hydrophilicity and biocatalytic effects. These findings confirmed that the immobilized enzymatic surface has added function of degrading contaminants in addition to separation function of nanofiltration membrane. These l-DOPA-immobilized enzymatic membranes offered a promising hybrid biocatalytic membrane to eliminate dyes and mitigate membrane fouling, which can be applied in many industrial and domestic water and wastewater treatment.

Phosphorus-modified copper ferrite (P-CuFe2O4) nanoparticles for photocatalytic ozonation of lomefloxacin.

Phosphorus-modified copper ferrite (P-CuFe2O4) nanoparticles were prepared by a simple sol-gel auto-combustion process and used for the photocatalytic ozonation of lomefloxacin (LOM). The morphology, crystallinity, and structure of the synthesized CuFe2O4 and P-CuFe2O4 nanoparticles were investigated using various techniques. The high-performance liquid chromatography (HPLC) analysis revealed that the degradation of LOM achieved a 99% reduction after a duration of 90 min in the photocatalytic ozonation system. In accordance with the charge-to-mass ratio, four intermediates were proposed with the help of their fragments obtained in LC-MS/MS. The degradation kinetics of lomefloxacin followed a pseudo-first order reaction, and the degradation mechanism was proposed based on the results. P0.035Cu0.965Fe2O4 showed the highest total organic carbon (TOC) removal with 20.15% in 90 min, highest specific surface area and the highest fluoride and ammonium production using the ion chromatography (IC). The experimental results obtained from the electron paramagnetic resonance (EPR) analysis indicated that the modified P-CuFe2O4 samples exhibited significantly elevated levels of superoxide (.O2-) production compared to the CuFe2O4 samples. The findings of this study demonstrate that the introduction of phosphorus modification into the copper ferrite photocatalyst led to an augmentation of both the specific surface area and the total pore volume. Furthermore, the incorporation of phosphorus served to promote the efficient separation of electron-hole pairs by effectively trapping electrons in the conduction band, hence enhancing the degradation efficiency.

Environmental fate of sulfonated-PCBs: Soil partitioning properties, bioaccumulation, persistence, and mobility.

Two new classes of PCB metabolites were recently discovered: sulfonated-polychlorinated biphenyls (sulfonated-PCBs) and hydroxy-sulfonated-polychlorinated biphenyls (OH-sulfonated-PCBs). These metabolites, originating from PCB degradation, seem to possess more polar characteristics than their parent compounds. However, no other information, such as their chemical identity (CAS number) or their ecotoxicity or toxicity, is available so far, although more than about one hundred different chemicals were observed in soil samples. In addition, their physico-chemical properties are still uncertain since only estimations are available. Here we show the first evidence on the fate of these new classes of contaminants in the environment, producing results from several experiments, to evaluate sulfonated-PCBs and OH-sulfonated-PCBs soil partition coefficients, degradation in soil after 18 months of rhizoremediation, uptake into plant roots and earthworms, as well as a preliminary analytical method to extract and concentrate these chemicals from water. The results give an overview of the expected environmental fate of these chemicals and open questions for further studies.

Functional Foods Acceptability: A Consumers' Survey on Bread Enriched with Oenological By-Products.

In recent years, consumers have shown considerable attention to functional foods that can provide various benefits. At the same time, the awareness of the problem of waste generation from the agri-food supply chains has increased; thus, scholars and practitioners are devoting great attention to sustainable food waste management. Within the wine processing, the production phase generates by-products such as marc, grape seeds, stems, and wine lees. In most cases, these by-products are treated as waste rather than as a resource, creating environmental, economic, and social impacts related to their disposal. By contrast, the reuse of oenological by-products in food production can have several health benefits, since they are rich in functional molecules such as fibres, polyphenols, and vitamin E, and can also trigger a circular economy model. The aim of this research is to investigate the acceptance of consumers towards bread enriched with oenological by-products through the application of k-means clustering, providing insights on the characterisation of groups of consumers based on their specific features and declared attitudes. The results showed three different consumers' clusters, highlighting that the acceptance of this enriched bread is not influenced by the consumers' socio-economic features, but it is related to consumers' sensitivity. Therefore, target strategies should be put in place to inform consumers about the benefits associated with the consumption of bread enriched with oenological by-products.

From Batch to the Semi-Continuous Flow Hydrogenation of pNB, pNZ-Protected Meropenem.

Meropenem is currently the most common carbapenem in clinical applications. Industrially, the final synthetic step is characterized by a heterogeneous catalytic hydrogenation in batch mode with hydrogen and Pd/C. The required high-quality standard is very difficult to meet and specific conditions are required to remove both protecting groups [i.e., p-nitrobenzyl (pNB) and p-nitrobenzyloxycarbonyl (pNZ)] simultaneously. The three-phase gas-liquid-solid system makes this step difficult and unsafe. The introduction of new technologies for small-molecule synthesis in recent years has opened up new landscapes in process chemistry. In this context, we have investigated meropenem hydrogenolysis using microwave (MW)-assisted flow chemistry for use as a new technology with industrial prospects. The reaction parameters (catalyst amount, T, P, residence time, flow rate) in the move from the batch process to semi-continuous flow were investigated under mild conditions to determine their influence on the reaction rate. The optimization of the residence time (840 s) and the number of cycles (4) allowed us to develop a novel protocol that halves the reaction time compared to batch production (14 min vs. 30 min) while maintaining the same product quality. The increase in productivity using this semi-continuous flow technique compensates for the slightly lower yield (70% vs. 74%) obtained in batch mode.

Synthesis of a new sulfonated-hexachlorobiphenyl standard for environmental analysis, ecotoxicological, and toxicological studies.

Sulfonated-polychlorinated biphenyls (sulfonated-PCBs) are a newly discovered class of PCB metabolites. They were observed for the first time in polar bear serum and lately, in soil, together with hydroxy-sulfonated-PCBs. Their presence is ubiquitous in soils, and their estimated physical chemical properties show high mobility in water, compared to the parent compounds. However, no single pure standards exist so far and therefore their quantification in the environmental matrices is not accurate. Additionally, pure standards are needed to experimentally determine their physical chemical properties, as well as the ecotoxicological and toxicological characteristics. In the present work, the challenging goal of preparing a polychlorinated biphenyl monosulfonic acid was achieved exploring different synthetic approaches, along which the selection of the starting material resulted in a crucial point. Using PCB-153 (2,2'-4,4'-5,5'-hexachloro-1,1'-biphenyl) the synthesis afforded, as the major species, a side compound. On the contrary, the use of PCB-155 (2,2'-4,4'-6,6'-hexachloro-1,1'-biphenyl), a symmetric hexachlorobiphenyl derivative showing chlorine atoms at all the ortho positions, gave the target sulfonated-PCB compound. In this case, sulfonation was successfully carried out through a two-step procedure, involving chlorosulfonylation and the subsequent hydrolysis of the chlorosulfonyl intermediate.

Towards Antibiotic Synthesis in Continuous-Flow Processes.

Continuous-flow chemistry has become a mainstream process and a notable trend among emerging technologies for drug synthesis. It is routinely used in academic and industrial laboratories to generate a wide variety of molecules and building blocks. The advantages it provides, in terms of safety, speed, cost efficiency and small-equipment footprint compared to analog batch processes, have been known for some time. What has become even more important in recent years is its compliance with the quality objectives that are required by drug-development protocols that integrate inline analysis and purification tools. There can be no doubt that worldwide government agencies have strongly encouraged the study and implementation of this innovative, sustainable and environmentally friendly technology. In this brief review, we list and evaluate the development and applications of continuous-flow processes for antibiotic synthesis. This work spans the period of 2012-2022 and highlights the main cases in which either active ingredients or their intermediates were produced under continuous flow. We hope that this manuscript will provide an overview of the field and a starting point for a deeper understanding of the impact of flow chemistry on the broad panorama of antibiotic synthesis.

Acrylamide adsorption by Enterococcus durans and Enterococcus faecalis: In vitro optimization, simulated digestive system and binding mechanism.

Acrylamide is an unsaturated amide that forms in heated, starchy food products. This study was conducted to (1) examine the ability of 38 LAB to remove acrylamide; (2) optimize acrylamide removal of selected LAB under various conditions (pH, temperature, time and salt) using the Box-Behnken design (BBD); (3) the behavior of the selected LAB under the simulated gastrointestinal conditions; and (4) investigate the mechanism of adsorption. Out of the 38 LAB, Enterococcus durans and Enterococcus faecalis had the highest results in removing acrylamide, with 33 and 30% removal, respectively. Those two LAB were further examined for their binding abilities under optimized conditions of pH (4.5-6.5), temperature (32°C - 42°C), time (14-22 h), and NaCl (0-3% w/v) using BBD. pH was the main factor influenced the acrylamide removal compared to other factors. E. durans and E. faecalis exhibited acrylamide removal of 44 and 53%, respectively, after the in vitro digestion. Zeta potential results indicated that the changes in the charges were not the main cause of acrylamide removal. Transmission electron microscopes (TEM) results indicated that the cell walls of the bacteria increased when cultured in media supplemented with acrylamide.

Cefonicid Benzathine Salt: A Convenient, Lean, and High-Performance Protocol to Make an Old Cephalosporin Shine.

Cefonicid is a second-generation cephalosporin sold under the brand name Sintocef™. It is an injectable drug obtained via a freeze-drying process and is also available for oral preparations. The high-quality standard required is very challenging to satisfy, and current production protocols are characterized by steps that are lengthy and cumbersome, making the product unattractive for the international market. Industrial R&D is constantly working on the process optimization for API synthesis, with the aim of increasing productivity and decreasing production costs and waste. We herein report a new and efficient method for the synthesis of the cefonicid benzathine salt that provides a good yield and high product stability. The double-nucleophilic and lipophilic nature of N',N″-dibenzylethylene diacetate enables the deformylation of the OH-protected group on the mandelic moiety and also enables product crystallization to occur. We demonstrate that the formyl group in the peculiar position has high reactivity, promoting an amidation reaction that deprotects a hydroxy group and generates a new C-N bond in the reaction by-product. Several amines and OH-protected groups have been studied, but none were able to replicate the excellent results of benzathine diacetate.

Coupling Long-Range Facet Junction and Interfacial Heterojunction via Edge-Selective Deposition for High-Performance Z-Scheme Photocatalyst.

The construction of photocatalytic systems that have strong redox capability, effective charge separation, and large reactive surfaces is of great scientific and practical interest. Herein, an edge-connected 2D/2D Z-scheme system that combines the facet junction and the interfacial heterojunction to achieve effective long-range charge separation and large reactive surface exposure is designed and fabricated. The heterostructure is realized by the selective growth of 2D-layered MoS2 nanoflakes on the edge-sites of thin TiO2 nanosheets via an Au-promoted photodeposition method. Attributed to the synergetic coupling of the facet junction and the interfacial heterojunction that assures the effective charge separation, and the tremendous but physically separated reactive sites offered by layered MoS2 and highly-exposed (001) facets of TiO2 , respectively, the artificial Z-scheme exhibits excellent photocatalytic performance in photodegradation tests. Moreover, the junctional plasmonic Au nanoclusters not only act as electron traps to promote the edge-selective synthesis but also generate "hot electrons" to further boost photocatalytic performance. The Z-scheme charge-flow direction in the heterostructure and the roles of electrons and holes are comprehensively studied using in situ irradiated X-ray photoelectron spectroscopy and photodegradation tests. This work offers a new insight into designing high-performance Z-scheme photocatalytic systems.

Design of a Microfluidic Photocatalytic Reactor for Removal of Volatile Organic Components: Process Simulation and Techno-Economic Assessment.

This study reports on a gas-phase photocatalytic microreactor (MR) employed for the degradation of 2-propanol in indoor air. A process flow diagram was developed and simulated in Aspen Hysys V10, and a techno-economic assessment was carried out based on the simulated results. An economic evaluation was carried out using a fixed and demand-dependent variable cost model. Decreasing the mass flow rate or the initial concentration of the 2-propanol in indoor air and increasing the diameter or length of the MR resulted in a better air remediation efficacy. Sensitivity analysis for the economics of the manufactured MR showed that the optimal plant production volume is 10,000 units per year. At this volume, the total manufacturing cost was 2.8 M$/y with a production cost of $ 127 per unit and a levelized cost of a MR (LCOM) of about $ 280 per unit. These findings herein can help bolster research into both technical and economic aspects of MR production for the photocatalytic remediation of air. The resulting design could be applied in air conditioner units and other home ventilation units for the removal of harmful volatile organic compounds in the air.

Motivations of Human Helping Behavior towards Dogs.

Human-dog interactions have a positive effect on human sociality and health. The relationship with dogs helps humans to cope with stress during an emotionally challenging period, such as the COVID-19 pandemic. During this period, a growing global interest in pets has been registered, including the volunteering for shelter/stray dog protection. However, a considerable increase of human dysfunctional interventions toward dogs has been observed in Southern Italy. In this study, we investigated the psychological characteristics of humans volunteering at animal shelter or engaged in stray dog protection. The effect of psychological training and education about dog ethological needs on volunteers' helping behavior was also analyzed. We report that the intervention can improve volunteers' physiological features and, consequently, may enhance human management and dog welfare.

Acrylamide Elimination by Lactic Acid Bacteria: Screening, Optimization, In Vitro Digestion, and Mechanism.

Acrylamide is a toxic compound that is formed in cooked carbohydrate-rich food. Baking, roasting, frying, and grilling are cooking methods that cause its formation in the presence of reducing sugar and asparagine. To prevent acrylamide formation or to remove it after its formation, scientists have been trying to understand acrylamide formation pathways, and methods of prevention and removal. Therefore, this study aimed to: (1) screen newly isolated LAB for acrylamide removal, (2) optimize conditions (pH, temperature, time, salt) of the acrylamide removal for selected LAB isolates using Box-Behnken design (BBD), (3) investigate the acrylamide removal abilities of selected LAB isolates under the in vitro digestion conditions using INFO-GEST2.0 model, and (4) explore the mechanism of the acrylamide removal using scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDS), zeta potential, transmission electron microscopy (TEM) measurement, and Fourier transform infrared spectroscopy (FTIR). Forty strains were tested in MRS broth, where Streptococcus lutetiensis and Lactiplantibacillus plantarum had the highest capability of acrylamide removal by 39% and 26%, respectively. To enhance the binding ability, both strains were tested under controlled conditions of pH (4.5, 5.5 and 6.5), temperature (32 °C, 37 °C and 42 °C), time (14, 18 and 22 h), and NaCl (0%, 1.5% and 3% w/v) using Box-Behnken design (BBD). Both strains removed more acrylamide in the range of 35-46% for S. lutetiensis and 45-55% for L. plantarum. After testing the bacterial binding ability, both strains were exposed to a simulated gastrointestinal tract environment, removing more than 30% of acrylamide at the gastric stage and around 40% at the intestinal stage. To understand the mechanism of removal, LAB cells were characterized via scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDS) and transmission electron microscopy (TEM) techniques. Cell charges were characterized by zeta potential and functional groups analyzed by Fourier transform infrared spectroscopy (FTIR). Results indicated that increasing cell wall thickness improved acrylamide adsorption capacity. Both FTIR and EDS indicated that functional groups C=O, C-O, and N-H were associated with acrylamide adsorption.

Micronized cellulose from citrus processing waste using water and electricity only.

Along with a water-soluble fraction rich in pectin, the hydrodynamic cavitation of citrus processing waste carried out in water demonstrated directly on semi-industrial scale affords an insoluble fraction consisting of micronized cellulose of low crystallinity ("CytroCell"). Lemon and grapefruit CytroCell respectively consist of 100-500 nm wide cellulose nanorods, and of 500-1000 nm wide ramified microfibrils extending for several µm. These findings establish a technically viable route to low crystallinity micronized cellulose laying in between nano- and microcellulose, using water and electricity only.

Current and future perspectives on catalytic-based integrated carbon capture and utilization.

There exist several well-known methods with varying maturity for capturing carbon dioxide from emission sources of different concentrations, including absorption, adsorption, cryogenics and membrane separation, among others. The capture and separation steps can produce almost pure CO2, but at substantial cost for being conditioned for transport and final utilization, with high economical risks to be considered. A possible way for the elimination of this conditioning and cost is direct CO2 utilization, whether on-site in a further process but within the same plant, or in-situ, coupling both capture and conversion in the same unit. This approach is usually called integrated carbon capture and utilization (ICCU) or integrated carbon capture and conversion (ICCC), and has lately started receiving considerable attention in many circles. As CO2 is already industrially employed in other sectors, such as food preservation, water treatment and conversion to high added-value chemicals and fuels such as methanol, methane, etc., among others, it is of great interest to explore the global ICCC approach. Catalytic-based processes play a key role in CO2 conversion, and different technologies are gaining great attention from both academia and industry. However, the 'big picture of ICCU' and in which technology the efforts should focus on at large scale is still unclear. This review analyzes some promising concepts of ICCU specifically on CO2 catalytic conversion, highlighting their current commercial relevance as well as challenges that have to be faced today and in the next future.

A review of recent and emerging antimicrobial nanomaterials in wastewater treatment applications.

In this paper, we present a critical review on antimicrobial nanomaterials with demonstrated potential for application as a disinfection technology in wastewater treatment. Studies involving fabrication and testing of antimicrobial nanomaterials for wastewater treatment were gathered, critically reviewed, and analyzed. Our review shows that there are only a few eligible candidate nanoparticles (NPs) (metal and metal oxide) that can adequately serve as an antimicrobial agent. Nanosilver (nAg) was the most studied and moderately understood metal NPs with proven antimicrobial activity followed by ZnO (among antimicrobial metal oxide NPs) which outperformed titania (in the absence of light) in efficacy due to its better solubility in aqueous condition. The direction of future work was found to be in the development of antimicrobial nanocomposites, since they provide more stability for antimicrobial metal and metal oxides NPs in water, thereby increasing their activity. This review will serve as an updated survey, yet touching also the fundamentals of the antimicrobial activity, with vital information for researchers planning to embark on the development of superior antimicrobial nanomaterials for wastewater treatment applications.

Antiscaling 3D printed feed spacers via facile nanoparticle coating for membrane distillation.

Surface modification of feed spacers rather than membranes may hold more merit as an antiscaling strategy in membrane distillation (MD), as it avoids compromising the functionality of MD membrane. In this work, an antiscaling polyamide 3D printed spacer was developed for MD. The surface of the printed spacer was coated with fluorinated silica (FS) nanoparticles synthesized via a sol-gel process. The sol-gel approach used to synthesize the FS nanoparticles is considered a convenient and easy approach for engineering the spacer's surface structure and roughness. The performance of the FS coated printed surface was evaluated against other coating materials of different chemical properties. The coated surfaces were characterized using water contact angle measurements, ATR-FTIR, Raman, FESEM-EDX, atomic force and 3D microscopes. The 3D printed surface's microscale roughness and hydrophobicity increased, while its surface-free energy decreased with FS nanoparticles coating. The antiscaling performance of uncoated and FS coated spacers was then assessed in a direct contact MD process, using a scale-inducing aqueous solution of calcium sulfate as its feed. The scalant (Ca2+) attachment on the FS coated spacer was 0.24 mg cm-2, 74% lower than on the uncoated 3D spacer (0.95 mg cm-2). Also, by using the antiscaling FS coated spacer, scaling on the membrane surface dropped by 60%. The predominant factors that helped minimize scaling with FS coating were microscale roughness-induced hydrophobicity and reduced surface-free energy that weakened the scalant 's interaction with the spacer surface.

Highlights on Recent Developments of Heterogeneous and Homogeneous Photocatalysis.

Photocatalysis emerged in the last decades as a versatile technology, whose applications range from environmental remediation to hydrogen production, energy harvesting, and organic synthesis, with exciting examples also in medicine, electronics, and advanced functional materials [...].

Insects as Novel Food: A Consumer Attitude Analysis through the Dominance-Based Rough Set Approach.

In Western societies, the unfamiliarity with insect-based food is a hindrance for consumption and market development. This may depend on neophobia and reactions of disgust, individual characteristics and socio-cultural background, and risk-perceptions for health and production technologies. In addition, in many European countries, the sale of insects for human consumption is still illegal, although European Union (EU) and the European Food Safety Authority (EFSA) are developing regulatory frameworks and environmental and quality standards. This research aims to advance the knowledge on entomophagy, providing insights to improve consumer acceptance in Italy. This is done by carrying out the characterization of a sample of consumers according to their willingness to taste several types of insect-based food and taking into account the connections among the consumers' features. Thus, the dominance-based rough set approach is applied using the data collected from 310 Italian consumers. This approach provided 206 certain decision rules characterizing the consumers into five groups, showing the consumers' features determining their specific classification. Although many Italian consumers are willing to accept only insects in the form of feed stuffs or supplements, this choice is a first step towards entomophagy. Conversely, young Italian people are a niche market, but they can play a role in changing trends.

A Direct, Regioselective and Atom-Economical Synthesis of 3-Aroyl-N-hydroxy-5-nitroindoles by Cycloaddition of 4-Nitronitrosobenzene with Alkynones.

We introduced a regioselective and atom-economical procedure for the synthesis of 3-substituted indoles by annulation of nitrosoarenes with ethynyl ketones. The reactions were carried out achieving indoles without any catalyst and with excellent regioselectivity. No traces of 2-aroylindole products were detected. Working with 4-nitronitrosobenzene as starting material, the 3-aroyl-N-hydroxy-5-nitroindole products precipitated from the reaction mixtures and were isolated by filtration without any further purification technique. Differently from the corresponding N-hydroxy-3-aryl indoles that, spontaneously in solution, give dehydrodimerization products, the N-hydroxy-3-aroyl indoles are stable and no dimerization compounds were observed.