Microalgae to biodiesel: A novel green conversion method for high-quality lipids recovery and in-situ transesterification to fatty acid methyl esters.

Greenhouse gases (GHGs) emissions due to increasing energy demand have raised the need to identify effective solutions to produce clean and renewable energy. Biotechnologies are an effective platform to attain green transition objectives, especially when synergically integrated to promote health and environmental protection. In this context, microalgae-based biotechnologies are considered among the most effective tools for treating gaseous effluents and simultaneously capturing carbon sources for further biomass valorisation. The production of biodiesel is regarded as a promising avenue for harnessing value from residual algal biomass. Nonetheless, the existing techniques for extracting lipids still face certain limitations, primarily centred around the cost-effectiveness of the process.This study is dedicated to developing and optimising an innovative and cost-efficient technique for extracting lipids from algal biomass produced during gaseous emissions treatment based on algal-bacterial biotechnology. This integrated treatment technology combines a bio-scrubber for degrading gaseous contaminants and a photobioreactor for capturing the produced CO2 within valuable algal biomass. The cultivated biomass is then processed with the process newly designed to extract lipids simultaneously transesterificated in fatty acid methyl esters (FAME) via In Situ Transesterification (IST) with a Kumagawa-type extractor. The results of this study demonstrated the potential application of the optimised method to overcome the gap to green transition. Energy production was obtained from residuals produced during the necessary treatment of gaseous emissions. Using hexane-methanol (v/v = 19:1) mixture in the presence KOH in Kumagawa extractor lipids were extracted with extraction yield higher than 12% and converted in fatty acid methyl esters. The process showed the enhanced extraction of lipids converted in bio-sourced fuels with circular economy approach, broadening the applicability of biotechnologies as sustainable tools for energy source diversification.

Carbon neutrality in wastewater treatment plants: An integrated biotechnological-based solution for nutrients recovery, odour abatement and CO2 conversion in alternative energy drivers.

Wastewater treatment plants play a crucial role in water security and sanitation, ensuring ecosystems balance and avoiding significant negative effects on humans and environment. However, they determine also negative pressures, including greenhouse gas and odourous emissions, which should be minimized to mitigate climate changes besides avoiding complaints. The research has been focused on the validation of an innovative integrated biological system for the sustainable treatment of complex gaseous emissions from wastewater treatment plants. The proposed system consists of a moving bed biofilm reactor coupled with an algal photobioreactor, with the dual objective of: i) reducing the inlet concentration of the odourous contaminants (in this case, hydrogen sulphide, toluene and p-xylene); ii) capturing and converting the carbon dioxide emissions produced by the degradation process into exploitable algal biomass. The first reactor promoted the degradation of chemical compounds up to 99.57% for an inlet load (IL) of 22.97 g m-3 d-1 while the second allowed the capture of the CO2 resulting from the degradation of gaseous compounds, with biofixation rate up to 81.55%. The absorbed CO2 was converted in valuable feedstocks, with a maximum algal biomass productivity in aPBR of 0.22 g L-1 d-1. Dairy wastewater has been used as alternative nutrient source for both reactors, with a view of reusing wastewater while cultivating biomass, framing the proposed technology in a context of a biorefinery within a circular economy perspective. The biomass produced in the algal photobioreactor was indeed characterized by a high lipid content, with a maximum percentage of lipids per dry weight biomass of 35%. The biomass can therefore be exploited for the production of alternative and clean energy carrier. The proposed biotechnology represents an effective tool for shifiting the conventional plants in carbon neutral platform for implementing principles of ecological transition while achieving high levels of environmental protection.

Tuning the surface functionality of polyethylene glycol-modified graphene oxide/chitosan composite for efficient removal of dye.

There has been a lot of attention on water pollution by dyes in recent years because of their serious toxicological implications on human health and the environment. Therefore, the current study presented a novel polyethylene glycol-functionalized graphene oxide/chitosan composite (PEG-GO/CS) to remove dyes from aqueous solutions. Several characterization techniques, such as SEM, TEM, FTIR, TGA/DTG, XRD, and XPS, were employed to correlate the structure-property relationship between the adsorption performance and PEG-GO/CS composites. Taguchi's (L25) approach was used to optimize the batch adsorption process variables [pH, contact time, adsorbent dose, and initial concentration of methyl orange (MO)] for maximal adsorption capacity. pH = 2, contact time = 90 min, adsorbent dose = 10 mg/10 mL, and MO initial concentration = 200 mg/L were found to be optimal. The material has a maximum adsorption capacity of 271 mg/g for MO at room temperature. With the greatest R2 = 0.8930 values, the Langmuir isotherm model was shown to be the most appropriate. Compared to the pseudo-first-order model (R2 = 0.9685), the pseudo-second-order model (R2 = 0.9707) better fits the kinetic data. Electrostatic interactions were the dominant mechanism underlying MO sorption onto the PEG/GO-CS composite. The as-synthesized composite was reusable for up to three adsorption cycles. Thus, the PEG/GO-CS composite fabricated through a simple procedure may remove MO and other similar organic dyes in real contaminated water.

Unraveling microbial community by next-generation sequencing in living membrane bioreactors for wastewater treatment.

This study delves into the microbial community complexity and its role in self-forming dynamic membrane (SFDM) systems, designed to remove nutrients and pollutants from wastewater, by means of the analysis of Next-Generation Sequencing (NGS) data. In these systems, microorganisms are naturally incorporated into the SFDM layer, which acts as a biological and physical filter. The microorganisms present in an innovative and highly efficient aerobic, electrochemically enhanced, encapsulated SFDM bioreactor were studied to elucidate the nature of the dominant microbial communities present in sludge and in encapsulated SFDM, patented as living membrane® (LM) of the experimental setup. The results were compared to those obtained from the microbial communities found in similar experimental reactors without an applied electric field. The data gathered from the NGS microbiome profiling showed that the microbial consortia found in the experimental systems are comprised of archaeal, bacterial, and fungal communities. However, the distribution of the microbial communities found in e-LMBR and LMBR had significant differences. The results showed that the presence of an intermittently applied electric field in e-LMBR promotes the growth of some types of microorganisms (mainly electroactive microorganisms) responsible for the highly efficient treatment of the wastewater and for the mitigation of the membrane fouling found for those bioreactors.

Advanced treatment of toluene emissions with a cutting-edge algal bacterial photo-bioreactor: Performance assessment in a circular economy perspective.

A novel approach for the treatment of VOCs (by using toluene used as a model compound) and the simultaneous conversion of carbon dioxide into valuable biomass has been investigated by using a combination of an activated sludge moving bed bioreactor (MBBR) and an algal photo-bioreactor (PBR). The first unit (MBBR, R1) promoted toluene removal up to 99.9 % for inlet load (IL) of 119.91 g m-3 d-1. The CO2 resulting from the degradation of toluene was then fixed in PBR (R2), with a fixation rate up to 95.8 %. The CO2 uptake was promoted by algae, with average production of algal biomass in Stage VI of 1.3 g L-1 d-1. In the contest of the circular economy, alternative sources of nutrients have been assessed, using synthetic urban wastewater (UWW) and dairy wastewater (DWW) for liquid renewal. The produced biomass with DWW showed a high lipid content, with a maximum productivity of 450.25 mg of lipids L-1 d-1. The solution proposed may be thus regarded as a sustainable and profitable strategy for VOCs treatment in a circular economy perspective.

Living membrane bioreactor for highly effective and eco-friendly treatment of textile wastewater.

The treatability of synthetic textile wastewater containing model dyes, such as reactive black and direct black dye (25.0 ± 2.6 mgdye/L), with chemical oxygen demand (COD, 1000 ± 113 mg/L), ammonia­nitrogen (NH3-N, 140 ± 97 mg/L) and sulphate ions (SO42-, 1357 ± 10.86 mg/L) was investigated in this study using an innovative living membrane bioreactor (LMBR) using an encapsulated self-forming dynamic membrane (ESFDM). The key advantage of ESFDMBR is the self-forming of the biological filtering layer protected between two meshes of inert robust and inexpensive material. A laboratory scale bioreactor (BR) equipped with a filtering unit mounting polyester meshes with a pore size of 30 µm, operated at an influent flux of 30 LMH was thus used. After the formation of the biological living membrane (LM), the treatment significantly reduced COD and DOC concentrations to the average values of 34 ± 10 mg/L and 32 ± 7 mg/L, corresponding to reduction efficiencies of 96.0 ± 1.1 % and 94 ± 1.05 %, respectively. Throughout the LMBR operation, the colours were successfully removed from synthetic textile wastewater with an overall removal efficiency of about 85.0 ± 1.8 and 86.0 ± 1.9 % for direct and reactive dyes, respectively. In addition, the proposed system was also found effective in affording removal efficiency of ammonia (NH3) of 97 ± 0.5 %. Finally, this treatment afforded circa 40.7 ± 5.8 % sulphate removal, with a final concentration value of 805 ± 78.61 mg/L. The innovative living membrane, based on an encapsulated self-forming dynamic membrane allows a prolonged containment of the membrane fouling, confirmed by investigating the concentration of membrane fouling precursors and the time-course variations of turbidity and transmembrane pressure (TMP). Those final concentrations of wastewater pollutants were found to be below the limits for admission of the effluents in public sanitation networks in Italy and Tunisia, as representative countries for the regulation in force in Europe and North Africa. In conclusion, due to the low costs of plant and maintenance, the simple applicability, the rapid online implementation, the application of LMBR results in a promising method for the treatment of textile wastewater.

One-Step Fabrication of Novel Polyethersulfone-Based Composite Electrospun Nanofiber Membranes for Food Industry Wastewater Treatment.

Using an environmentally friendly approach for eliminating methylene blue from an aqueous solution, the authors developed a unique electrospun nanofiber membrane made of a combination of polyethersulfone and hydroxypropyl cellulose (PES/HPC). SEM results confirmed the formation of a uniformly sized nanofiber membrane with an ultrathin diameter of 168.5 nm (for PES/HPC) and 261.5 nm (for pristine PES), which can be correlated by observing the absorption peaks in FTIR spectra and their amorphous/crystalline phases in the XRD pattern. Additionally, TGA analysis indicated that the addition of HPC plays a role in modulating their thermal stability. Moreover, the blended nanofiber membrane exhibited better mechanical strength and good hydrophilicity (measured by the contact angle). The highest adsorption capacity was achieved at a neutral pH under room temperature (259.74 mg/g), and the pseudo-second-order model was found to be accurate. In accordance with the Langmuir fitted model and MB adsorption data, it was revealed that the adsorption process occurred in a monolayer form on the membrane surface. The adsorption capacity of the MB was affected by the presence of various concentrations of NaCl (0.1-0.5 M). The satisfactory reusability of the PES/HPC nanofiber membrane was revealed for up to five cycles. According to the mechanism given for the adsorption process, the electrostatic attraction was shown to be the most dominant in increasing the adsorption capacity. Based on these findings, it can be concluded that this unique membrane may be used for wastewater treatment operations with high efficiency and performance.

Advances in virus detection methods for wastewater-based epidemiological applications.

Wastewater-based epidemiology (WBE) is a powerful tool that has the potential to reveal the extent of an ongoing disease outbreak or to predict an emerging one. Recent studies have shown that SARS-CoV-2 concentration in wastewater may be correlated with the number of COVID-19 cases in the corresponding population. Most of the recent studies and applications of wastewater-based surveillance of SARS-CoV-2 applied the "gold standard" real-time quantitative reverse transcription-polymerase chain reaction (RT-qPCR) detection method. However, this method also has its limitations. The paper aimed to present recent improvements and applications of the PCR-based methods for SARS-CoV-2 monitoring in wastewater. Furthermore, it aimed to review alternative methods utilized and/or proposed for the detection of the virus in wastewater matrices. From the review, it was found that several studies have investigated the use of reverse-transcription digital polymerase reaction (RT-dPCR), which was generally shown to have a lower limit of detection (LOD) over the RT-qPCR. Aside from this, non-PCR-based and non-RNA based methods have also been explored for the detection of SARS-CoV-2 in wastewater, with detailed attention given to the detection of SARS-CoV-2 proteins. The potential methods for protein detection include mass spectrometry, the use of immunosensors, and nanotechnological applications. In addition, the review of recent studies also revealed two types of emerging methods related to the detection of SARS-CoV-2 in wastewater: i) capsid-integrity assays to infer about the infectivity of SARS-CoV-2 present in wastewater, and ii) alternative methods for detection of SARS-CoV-2 variants of concern (VOCs) in wastewater. The recent studies on proposed methods of SARS-CoV-2 detection in wastewater have considered improving this approach in one or more of the following aspects: rapidity, simplicity, cost, sensitivity, and specificity. However, further studies are needed in order to realize the full application of these methods for WBE in the field.

Innovative encapsulated self-forming dynamic bio-membrane bioreactor (ESFDMBR) for efficient wastewater treatment and fouling control.

The concept of a novel living encapsulated self-forming dynamic bio-membranes (ESFDM) for an innovative wastewater treatment in membrane bioreactor (MBR) is presented in the current study. The active filtering membrane is encapsulated, and thus stabilized, between two support meshes with pore in micrometer size. The combination of activated sludge, the ESFDM and the cake layer formed external to the filtering module contributed to the treatment of municipal wastewater. COD concentration reductions (average value of 95.55 ± 1.44%) by ESFDM bioreactor (ESFDMBR) were comparable to those obtained with a previously reported membrane bioreactor (MBR), where a conventional membrane was studied under the same operating conditions. The ESFDMBR, compared to the conventional MBR, obtained higher reductions of NH3-N, NO3-N and PO43-P concentrations. Increased removals of nitrogen-containing nutrients were ascribed to anoxic conditions reached in the ESFDM layer protected from the aeration by the external cake layer. Rate of increase of transmembrane pressure (TMP) per day in the ESFDMBR (0.03 kPa/day) was lower than the value obtained in the previously reported conventional MBR (8.08 kPa/day). Lower concentrations of fouling precursors in combination with the effective filtration capacity of the porous living ESFDM resulted in the reduction of the fouling rate. Analysis of microbiological community revealed that the microbial community structures in the mixed liquor and ESFDM were different. The ESFDM layer promoted growth of bacteria as indicated by the higher total cell count and higher microbial diversity compared to those observed in the mixed liquor.

Advances in technological control of greenhouse gas emissions from wastewater in the context of circular economy.

This review paper aims to identify the main sources of carbon dioxide (CO2) emissions from wastewater treatment plants (WWTPs) and highlights the technologies developed for CO2 capture in this milieu. CO2 is emitted in all the operational units of conventional WWTPs and even after the disposal of treated effluents and sludges. CO2 emissions from wastewater can be captured or mitigated by several technologies such as the production of biochar from sludge, the application of constructed wetlands (CWs), the treatment of wastewater in microbial electrochemical processes (microbial electrosynthesis, MES; microbial electrolytic carbon capture, MECC; in microbial carbon capture, MCC), and via microalgal cultivation. Sludge-to-biochar and CW systems showed a high cost-effectiveness in the capture of CO2, while MES, MECC, MCC technologies, and microalgal cultivation offered efficient capture of CO2 with associate production of value-added by-products. At the state-of-the-art, these technologies, utilized for carbon capture and utilization from wastewater, require more research for further configuration, development and cost-effectiveness. Moreover, the integration of these technologies has a potential internal rate of return (IRR) that could equate the operation or provide additional revenue to wastewater management. In the context of circular economy, these carbon capture technologies will pave the way for new sustainable concepts of WWTPs, as an essential element for the mitigation of climate change fostering the transition to a decarbonised economy.

Wastewater treatment and fouling control in an electro algae-activated sludge membrane bioreactor.

The effect of addition of algae to activated sludge as active biomass in membrane bioreactors (MBRs) and electro-MBRs (e-MBRs) for wastewater remediation was examined in this study. The performances of Algae-Activated Sludge Membrane Bioreactor (AAS-MBR) and electro Algae-Activated Sludge Membrane Bioreactor (e-AAS-MBR) were compared to those observed in conventional MBR and e-MBR, which were previously reported and utilized activated sludge as biomass. The effect of application of electric field was also examined by the comparison of performances of e-AAS-MBR and AAS-MBR. Similar chemical oxygen demand (COD) reduction efficiencies of AAS-MBR, e-AAS-MBR, MBR, and e-MBR (98.35 ± 0.35%, 99.12 ± 0.08%, 97.70 ± 1.10%, and 98.10 ± 1.70%, respectively) were observed. The effect of the algae-activated sludge system was significantly higher in the nutrient removals. Ammoniacal nitrogen (NH3-N) removal efficiencies of AAS-MBR and e-AAS-MBR were higher by 43.89% and 26.61% than in the conventional MBR and e-MBR, respectively. Phosphate phosphorous (PO43--P) removals were also higher in AAS-MBR and e-AAS-MBR by 6.43% and 2.66% than those in conventional MBR and e-MBR. Membrane fouling rates in AAS-MBR and e-AAS-MBR were lower by 57.30% and 61.95% than in MBR and e-MBR, respectively. Lower concentrations of fouling substances were also observed in the reactors containing algae-activated sludge biomass. Results revealed that addition of algae improved nutrient removal and membrane fouling mitigation. The study also highlighted that the application of electric field in the e-AAS-MBR enhanced organic contaminants and nutrients removal, and fouling rate reduction.

Coronavirus in water media: Analysis, fate, disinfection and epidemiological applications.

Considerable attention has been recently given to possible transmission of SARS-CoV-2 via water media. This review addresses this issue and examines the fate of coronaviruses (CoVs) in water systems, with particular attention to the recently available information on the novel SARS-CoV-2. The methods for the determination of viable virus particles and quantification of CoVs and, in particular, of SARS-CoV-2 in water and wastewater are discussed with particular regard to the methods of concentration and to the emerging methods of detection. The analysis of the environmental stability of CoVs, with particular regard of SARS-CoV-2, and the efficacy of the disinfection methods are extensively reviewed as well. This information provides a broad view of the state-of-the-art for researchers involved in the investigation of CoVs in aquatic systems, and poses the basis for further analyses and discussions on the risk associated to the presence of SARS-CoV-2 in water media. The examined data indicates that detection of the virus in wastewater and natural water bodies provides a potentially powerful tool for quantitative microbiological risk assessment (QMRA) and for wastewater-based epidemiology (WBE) for the evaluation of the level of circulation of the virus in a population. Assays of the viable virions in water media provide information on the integrity, capability of replication (in suitable host species) and on the potential infectivity. Challenges and critical issues relevant to the detection of coronaviruses in different water matrixes with both direct and surrogate methods as well as in the implementation of epidemiological tools are presented and critically discussed.

Indoor versus outdoor transmission of SARS-COV-2: environmental factors in virus spread and underestimated sources of risk.

The first case of Coronavirus Disease 2019 (COVID-19), which is caused by Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2), in Europe was officially confirmed in February 2020. On 11 March 2020, after thousands of deaths from this disease had been reported worldwide, the WHO changed their classification of COVID-19 from a public health emergency of international concern to a pandemic. The SARS-CoV-2 virus has been shown to be much more resistant to environmental degradation than other coated viruses. Several studies have shown that environmental conditions can influence its viability and infectivity. This review summarizes current knowledge on the transmission pathways of the novel coronavirus, and directs attention towards potentially underestimated factors that affect its propagation, notably indoor spread and outdoor risk sources. The contributions of significant indoor factors such as ventilation systems to the spread of this virus need to be carefully ascertained. Outdoor risk sources such as aerosolized particles emitted during wastewater treatment and particulate matter (PM), both of which may act as virus carriers, should be examined as well. This study shows the influence of certain underestimated factors on the environmental behavior and survival of the SARS-CoV-2 virus. These aspects of coronavirus propagation need to be accounted for when devising actions to limit not only the current pandemic but also future outbreaks.

Innovative membrane photobioreactor for sustainable CO2 capture and utilization.

The rising of greenhouse-gas emissions (GHG), during the last 200 years, is associated to the well known global warming phenomena. One of the main sources of CO2-equivalent GHGs emissions are the environmental protection plants accounting for 1.57% of the global emissions and thus sustainable and effective technologies for their mitigation are strongly needed. The current paper presents and discusses the assessment of an innovative membrane photo-bioreactor (MPBR) whose aim was the promotion of CO2 capture from conveyed flows, such as those from wastewater treatment plants (WWTPs), landfill and composting plants, for production and energy valorisation of algal biomass. Chlorella vulgaris microalgae strain was selected as photosynthetic platform for the abovementioned purposes. The influence of various operating parameters has been explored, including the photosynthetic photon flux densities (PPFD) (60 and 120 µmol m-2 s-1), liquid/gas ratio (L/G = 5, 10 or 15) and CO2 concentration (5, 10 and 15%) in order to investigated their effects on carbon capture effectiveness and biomass production. The results demonstrated that the increasing of PPFD significantly enhanced the biomass production in terms of biomass productivity (P) and total dry weight (DW). The highest biomass concentration of 1.01 g L-1 was achieved at PPFD of 120 µmol m-2 s-1 with a L/G of 15. Under the aforementioned conditions, carbon dioxide removal efficiency (RE) reached values up to 80%. In addition, the novel MPBR equipped with an innovative self-forming dynamic membrane (SFDM) showed a simultaneous biomass harvesting rate of 41 g m-2 h-1.

Viruses in wastewater: occurrence, abundance and detection methods.

This paper presents an updated and comprehensive review on the different methods used for detection and quantification of viruses in wastewater treatment systems. The analysis of viability of viruses in wastewater and sludge is another thrust of this review. Recent studies have mostly focused on determining the abundance and diversity of viruses in wastewater influents, in samples from primary, secondary, and tertiary treatment stages, and in final effluents. A few studies have also examined the occurrence and diversity of viruses in raw and digested sludge samples. Recent efforts to improve efficiency of virus detection and quantification methods in the complex wastewater and sludge matrices are highlighted in this review. A summary and a detailed comparison of the pre-treatment methods that have been utilized for wastewater and sludge samples are also presented. The role of metagenomics or sequencing analysis in monitoring wastewater systems to predict disease outbreaks, to conduct public health surveillance, to assess the efficiency of existing treatment systems in virus removal, and to re-evaluate current regulations regarding pathogenic viruses in wastewater is discussed in this paper. Challenges and future perspectives in the detection of viruses, including emerging and newly emerged viruses such as the Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2), in wastewater systems are discussed in this review.

NIR multiphoton ablation of cancer cells, fluorescence quenching and cellular uptake of dansyl-glutathione-coated gold nanoparticles.

Theranostics based on two-photon excitation of therapeutics in the NIR region is an emerging and powerful tool in cancer therapy since this radiation deeply penetrates healthy biological tissues and produces selective cell death. Aggregates of gold nanoparticles coated with glutathione corona functionalized with the dansyl chromophore (a-DG-AuNPs) were synthesized and found efficient nanodevice for applications in photothermal therapy (PTT). Actually the nanoparticle aggregation enhances the quenching of radiative excitation and the consequent conversion into heat. The a-DG-AuNPs are readily internalized in Hep G2 where the chromophore acts as both antenna and transducer of the NIR radiation under two-photons excitation, determining efficient cell ablation via photothermal effect.

Structure and dynamics of catalytically competent but labile paramagnetic metal-hydrides: the Ti(iii)-H in homogeneous olefin polymerization.

Metal hydride complexes find widespread application in catalysis and their properties are often understood on the basis of the available crystal structures. However, some catalytically relevant metal hydrides are only spontaneously formed in situ, cannot be isolated in large quantities or crystallised and their structure is therefore ill defined. One such example is the paramagnetic Ti(iii)-hydride involved in homogeneous Ziegler-Natta catalysis, formed upon activation of CpTi(iv)Cl3 with modified methylalumoxane (MMAO). In this contribution, through a combined use of electron paramagnetic resonance (EPR), electron-nuclear double resonance (ENDOR) and hyperfine sublevel correlation (HYSCORE) spectroscopies we identify the nature of the ligands, their bonding interaction and the extent of the spin distribution. From the data, an atomistic and electronic model is proposed, which supports the presence of a self-assembled ion pair between a cationic terminal Ti-hydride and an aluminate anion, with a hydrodynamic radius of ca. 16 Å.

Synthesis and Characterization of Syndiotactic Polystyrene-Polyethylene Block Copolymer.

The direct synthesis of syndiotactic polystyrene-block-polyethylene copolymer (sPS-b-PE) with a diblock structure has been achieved. The synthetic strategy consists of the sequential stereocontrolled polymerization of styrene and ethylene in the presence of a single catalytic system: cyclopentadienyltitanium(IV) trichloride activated by modified methylaluminoxane (CpTiCl3/MMAO). The reaction conditions suitable for affording the partially living polymerization of these monomers were identified, and the resulting copolymer, purified from contaminant homopolymers, was fully characterized. Gel permeation chromatography coupled with two-dimensional NMR spectroscopy COSY, HSQC, and DOSY confirmed the block nature of the obtained polymer, whose thermal behaviour and thin film morphology were also investigated by differential scanning calorimetry, powder wide angle x-ray diffraction, and atomic force microscopy.

Green, Mild, and Efficient Friedel-Crafts Benzylation of Scarcely Reactive Arenes and Heteroarenes under On-Water Conditions.

Metal-free Friedel-Crafts benzylation (FCB) of scarcely reactive arenes and heteroarenes was performed under on-water conditions by an environmentally sustainable procedure. The catalytic strategy exploits the hydrophobicity of the resorcinarene macrocycle 1 a. The proposed mechanism is based on the activation of benzyl chloride by H-bonding interactions with catalyst 1 a. In fact, under on-water conditions the hydrophobic amplification of the strength of the H-bonding interactions between the OH groups of the resorcinarene catalyst and the chlorine atom of benzyl chloride leads to polarization of the C-Cl bond, which consequently promotes electrophilic attack of the π nucleophile. Thus, many arenes and heteroarenes were efficiently benzylated under mild on-water conditions by using resorcinarene 1 a as catalyst. The FCB of benzene is industrially relevant for the synthesis of diphenylmethane, and hence the on-water procedure was extended to the gram-scale synthesis of diphenylmethane, starting from benzene and benzyl chloride in the presence of resorcinarene catalyst 1 a.

Aerobic Oxidation and Oxidative Esterification of 5-Hydroxymethylfurfural by Gold Nanoparticles Supported on Nanoporous Polymer Host Matrix.

The aerobic oxidation and oxidative esterification of 5-hydroxymethylfurfural (HMF) catalyzed by gold nanoparticles (AuNPs) supported on a semicrystalline nanoporous multiblock copolymer matrix consisting of syndiotactic poly(styrene)-cis-1,4-poly(butadiene) (sPSB) have been investigated. Depending on the reaction parameters (support nanoporosity, presence of water, solvent, temperature, cocatalyst, oxygen pressure), the conversion of HMF can be finely addressed to the formation of the desired oxidation product, such as 2,5-diformylfuran (DFF), 5-formylfuran-2-carboxylic acid (FFCA), methyl 5-(hydroxymethyl)furan-2-carboxylate (MHMFC), dimethyl furan-2,5-dicarboxylate (DMFC), and furan-2,5-dicarboxylic acid (FDCA), under optimized reaction conditions. The AuNP-sPSB catalyst is highly effective and selective because the polymer support acts as a conveyor and concentrator of the reactants toward the catalytic sites.