Thermophilic biocatalysts for one-step conversion of citrus waste into lactic acid.

Agri-food residues offer significant potential as a raw material for the production of L-lactic acid through microbial fermentation. Weizmannia coagulans, previously known as Bacillus coagulans, is a spore-forming, lactic acid-producing, gram-positive, with known probiotic and prebiotic properties. This study aimed to evaluate the feasibility of utilizing untreated citrus waste as a sustainable feedstock for the production of L-lactic acid in a one-step process, by using the strain W. coagulans MA-13. By employing a thermophilic enzymatic cocktail (Cellic CTec2) in conjunction with the hydrolytic capabilities of MA-13, biomass degradation was enhanced by up to 62%. Moreover, batch and fed-batch fermentation experiments demonstrated the complete fermentation of glucose into L-lactic acid, achieving a concentration of up to 44.8 g/L. These results point to MA-13 as a microbial cell factory for one-step production of L-lactic acid, by combining cost-effective saccharification with MA-13 fermentative performance, on agri-food wastes. Moreover, the potential of this approach for sustainable valorization of agricultural waste streams is successfully proven. KEY POINTS: • Valorization of citrus waste, an abundant residue in Mediterranean countries. • Sustainable production of the L-( +)-lactic acid in one-step process. • Enzymatic pretreatment is a valuable alternative to the use of chemical.

Green and Facile Esterification Procedure Leading to Crystalline-Functionalized Graphite Oxide.

A simple and eco-friendly procedure of esterification of graphite oxide (GO), which uses acetic anhydride as a model reagent and ethyl acetate as a green solvent, is reported. The procedure leads to high functionalization degrees (at least up to 4.5 mol % of acetyl groups, referred to as graphitic C atoms) and it is much more effective than the literature method based on pure acetic anhydride. Surprisingly, our acetylation procedure does not destroy or reduce GO crystallinity but, irrespective of a substantial increase of distance between GO layers (from 0.84 nm up to 0.95 nm), leads to an increased order in the direction perpendicular to the graphitic planes. This phenomenon indicates that acetyl groups of acetylated GO (AcGO) are easily accommodated between graphitic layers, even improving interlayer order. The esterification procedure is generally applicable with various anhydrides providing differently functionalized graphite oxide. Dispersion of crystalline functionalized GO in volatile organic solvents followed by solvent fast removal, can easily lead to complete exfoliation.

Multifunctional Thin Films and Coatings from Caffeic Acid and a Cross-Linking Diamine.

The exploitation of easily accessible and nontoxic natural catechol compounds for surface functionalization and coating is attracting growing interest for biomedical applications. We report herein the deposition on different substrates of chemically stable thin films by autoxidation of 1 mM caffeic acid (CA) solutions at pH 9 in the presence of equimolar amounts of hexamethylenediamine (HMDA). UV-visible, mass spectrometric, and solid state 13C and 15N NMR analysis indicated covalent incorporation of the amine during CA polymerization to produce insoluble trioxybenzacridinium scaffolds decorated with carboxyl and amine functionalities. Similar coatings are obtained by replacing CA with 4-methylcatechol (MC) in the presence of HMDA. No significant film deposition was detected in the absence of HMDA nor by replacing it with shorter chain ethylenediamine, or with monoamines. The CA/HMDA-based films resisted oxidative and reductive treatments, displayed efficient Fe(II) and Cu(II) binding capacity and organic dyes adsorption, and provided an excellent cytocompatible platform for growing embryonic stem cells. These results pointed to HMDA as an efficient cross-linking mediator of film deposition from natural catechols for surface functionalization and coatings.

Pure titanium particle loaded nanocomposites: study on the polymer/filler interface and hMSC biocompatibility.

The integration of inorganic nanoparticles into polymer matrices allows for the modification of physical properties as well as the implementation of new features for unexplored application fields. Here, we propose the study of a new metal/polymer nanocomposite fabricated by dispersing pure Ti nanoparticles into a poly(methylmetacrilate) matrix via solvent casting process, to investigate its potential use as new biomaterial for biomedical applications. We demonstrated that Ti nanoparticles embedded in the poly(methylmetacrilate) matrix can act as reinforcing agent, not negatively influencing the biological response of human mesenchymal stem cell in terms of cytotoxicity and cell viability. As a function of relative amount and surface treatment, Ti nanoparticles may enhance mechanical strength of the composite-ranging from 31.1 ± 2.5 to 43.7 ± 0.7 MPa-also contributing to biological response in terms of adhesion and proliferation mechanisms. In particular, for 1 wt% Ti, treated Ti nanoparticles improve cell materials recognition, as confirmed by higher cell spreading-quantified in terms of cell area via image analysis-locally promoting stronger interactions at cell matrix interface. At this stage, these preliminary results suggest a promising use of pure Ti nanoparticles as filler in polymer composites for biomedical applications.

Unilateral NMR investigation of multifunctional treatments on stones based on colloidal inorganic and organic nanoparticles.

Consolidation and protection are among the most important treatments usually carried out in conservation of stone artifacts and monuments. In this paper, portable unilateral NMR and conventional techniques were used for investigating new multifunctional treatments based on tetraethoxysilane, silica, and polytetrafluoroethylene nanoparticles. The study was carried out on a very complex and heterogeneous porous stone such as tuff. NMR study allowed to obtain detailed information on the penetration depth of treatments, the hydrophobic effect, and changes in the open porosity caused by treatments. Physical and chemical inhomogeneities between the impregnated layers of tuff and the layers underneath were also detected. The average pores radius and pores interconnection obtained from NMR diffusion measurements were used for the first time to compare effects of different consolidating and/or protective treatments on stone. Because unilateral NMR technique is neither destructive nor invasive, investigation of treatments can be also carried out and optimized directly on buildings and monuments of interest for Cultural Heritage.

Supramolecular halogen bond passivation of organic-inorganic halide perovskite solar cells.

Organic-inorganic halide perovskites, such as CH3NH3PbX3 (X = I(-), Br(-), Cl(-)), are attracting growing interest to prepare low-cost solar cells that are capable of converting sunlight to electricity at the highest efficiencies. Despite negligible effort on enhancing materials' purity or passivation of surfaces, high efficiencies have already been achieved. Here, we show that trap states at the perovskite surface generate charge accumulation and consequent recombination losses in working solar cells. We identify that undercoordinated iodine ions within the perovskite structure are responsible and make use of supramolecular halogen bond complexation to successfully passivate these sites. Following this strategy, we demonstrate solar cells with maximum power conversion efficiency of 15.7% and stable power output over 15% under constant 0.81 V forward bias in simulated full sunlight. The surface passivation introduces an important direction for future progress in perovskite solar cells.

Exploring the Untapped Potential of Pine Nut Skin By-Products: A Holistic Characterization and Recycling Approach.

The increasing population, food demand, waste management concerns, and the search for sustainable alternatives to plastic polymers have led researchers to explore the potential of waste materials. This study focused on a waste of pine nut processing referred to in this paper as pine nut skin. For the first time, its nutritional profile, potential bioactive peptide, contaminants, and morphological structure were assessed. Pine nut skin was composed mainly of carbohydrates (56.2%) and fiber (27.5%). The fat (9.8%) was about 45%, 35%, and 20% saturated, monounsaturated, and polyunsaturated fatty acid, respectively, and Omega-9,-6, and -3 were detected. Notably, oleic acid, known for its health benefits, was found in significant quantities, resembling its presence in pine nut oil. The presence of bioactive compounds such as eicosapentaenoic acid (EPA) and phytosterols further adds to its nutritional value. Some essential elements were reported, whereas most of the contaminants such as heavy metals, polycyclic aromatic hydrocarbons, rare earth elements, and pesticides were below the limit of quantification. Furthermore, the in silico analysis showed the occurrence of potential precursor peptides of bioactive compounds, indicating health-promoting attributes. Lastly, the morphological structural characterization of the pine nut skin was followed by Fourier Transform Infrared and solid-state NMR spectroscopy to identify the major components, such as lignin, cellulose, and hemicellulose. The thermostability of the pine nut skin was monitored via thermogravimetric analysis, and the surface of the integument was analyzed via scanning electron microscopy and volumetric nitrogen adsorption. This information provides a more comprehensive view of the potential uses of pine nut skin as a filler material for biocomposite materials. A full characterization of the by-products of the food chain is essential for their more appropriate reuse.

Protic ionic liquids as p-dopant for organic hole transporting materials and their application in high efficiency hybrid solar cells.

Chemical doping is a powerful method to improve the charge transport and to control the conductivity in organic semiconductors (OSs) for a wide range of electronic devices. We demonstrate protic ionic liquids (PILs) as effective p-dopant in both polymeric and small molecule OSs. In particular, we show that PILs promote single electron oxidation, which increases the hole concentration in the semiconducting film. The illustrated PIL-doping mechanism is compatible with materials processed by solution and is stable in air. We report the use of PIL-doping in hybrid solar cells based on triarylamine hole transporting materials, such as 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9'-spirobifluorene (spiro-OMeTAD). We show improved power conversion efficiency by replacing lithium salts, typical p-dopants for spiro-OMeTAD, with PILs. We use photovoltage-photocurrent decay and photoinduced absorption spectroscopy to establish that significantly improved device performance is mainly due to reduced charge transport resistance in the hole-transporting layer, as potentiated by PIL-doping.

Lithium salts as "redox active" p-type dopants for organic semiconductors and their impact in solid-state dye-sensitized solar cells.

Lithium salts have been shown to dramatically increase the conductivity in a broad range of polymeric and small molecule organic semiconductors (OSs). Here we demonstrate and identify the mechanism by which Li(+) p-dopes OSs in the presence of oxygen. After we established the lithium doping mechanism, we re-evaluate the role of lithium bis(trifluoromethylsulfonyl)-imide (Li-TFSI) in 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9'-Spirobifluorene (Spiro-OMeTAD) based solid-state dye-sensitized solar cells (ss-DSSCs). The doping mechanism consumes Li(+) during the device operation, which poses a problem, since the lithium salt is required at the dye-sensitized heterojunction to enhance charge generation. This compromise highlights that new additives are required to maximize the performance and the long-term stability of ss-DSSCs.

Sustainable and Green Production of Nanostructured Cellulose by a 2-Step Mechano-Enzymatic Process.

Nanostructured cellulose (NC) represents an emerging sustainable biomaterial for diverse biotechnological applications; however, its production requires hazardous chemicals that render the process ecologically unfriendly. Using commercial plant-derived cellulose, an innovative strategy for NC production based on the combination of mechanical and enzymatic approaches was proposed as a sustainable alternative to conventional chemical procedures. After ball milling, the average length of the fibers was reduced by one order of magnitude (down to 10-20 µm) and the crystallinity index decreased from 0.54 to 0.07-0.18. Moreover, a 60 min ball milling pre-treatment followed by 3 h Cellic Ctec2 enzymatic hydrolysis led to NC production (15% yield). Analysis of the structural features of NC obtained by the mechano-enzymatic process revealed that the diameters of the obtained cellulose fibrils and particles were in the range of 200-500 nm and approximately 50 nm, respectively. Interestingly, the film-forming property on polyethylene (coating ≅ 2 µm thickness) was successfully demonstrated and a significant reduction (18%) of the oxygen transmission rate was obtained. Altogether, these findings demonstrated that nanostructured cellulose could be successfully produced using a novel, cheap, and rapid 2-step physico-enzymatic process that provides a potential green and sustainable route that could be exploitable in future biorefineries.

Layer-by-Layer-Coated Cellulose Fibers Enable the Production of Porous, Flame-Retardant, and Lightweight Materials.

New sustainable materials produced by green processing routes are required in order to meet the concepts of circular economy. The replacement of insulating materials comprising flammable synthetic polymers by bio-based materials represents a potential opportunity to achieve this task. In this paper, low-density and flame-retardant (FR) porous fiber networks are prepared by assembling Layer-by-Layer (LbL)-functionalized cellulose fibers by means of freeze-drying. The LbL coating, encompassing chitosan and sodium hexametaphosphate, enables the formation of a self-sustained porous structure by enhancing fiber-fiber interactions during the freeze-drying process. Fiber networks prepared from 3 Bi-Layer (BL)-coated fibers contain 80% wt of cellulose and can easily self-extinguish the flame during flammability tests in vertical configuration while displaying extremely low combustion rates in forced combustion tests. Smoke release is 1 order of magnitude lower than that of commercially available polyurethane foams. Such high FR efficiency is ascribed to the homogeneity of the deposited assembly, which produces a protective exoskeleton at the air/cellulose interface. The results reported in this paper represent an excellent opportunity for the development of fire-safe materials, encompassing natural components where sustainability and performance are maximized.

Poly(lactic acid)/Plasticizer/Nano-Silica Ternary Systems: Properties Evolution and Effects on Degradation Rate.

Plasticized nanocomposites based on poly(lactic acid) have been prepared by melt mixing following a two-step approach, adding two different oligomeric esters of lactic acid (OLAs) as plasticizers and fumed silica nanoparticles. The nanocomposites maintained a remarkable elongation at break in the presence of the nanoparticles, with no strong effects on modulus and strength. Measuring thermo-mechanical properties as a function of aging time revealed a progressive deterioration of properties, with the buildup of phase separation, related to the nature of the plasticizer. Materials containing hydroxyl-terminated OLA showed a higher stability of properties upon aging. On the contrary, a synergistic effect of the acid-terminated plasticizer and silica nanoparticles was pointed out, inducing an accelerated hydrolytic degradation of PLA: materials at high silica content exhibited a marked brittleness and a dramatic decrease of molecular weight after 16 weeks of aging.

Sustainable Cellulose-Aluminum-Plastic Composites from Beverage Cartons Scraps and Recycled Polyethylene.

The sustainable management of multilayer paper/plastic waste is a technological challenge due to its composite nature. In this paper, a mechanical recycling approach for multilayer cartons (MC) is reported, illustrating the realization of thermoplastic composites based on recycled polyethylene and an amount of milled MC ranging from 20 to 90 wt%. The effect of composition of the composites on the morphology and on thermal, mechanical, and water absorption behavior was investigated and rationalized, demonstrating that above 80 wt% of MC, the fibrous nature of the filler dominates the overall properties of the materials. A maleated polyethylene was also used as a coupling agent and its effectiveness in improving mechanical parameters of composites up to 60 wt% of MC was highlighted.

A versatile approach to evaluate the occurrence of microfibers in mussels Mytilus galloprovincialis.

Microplastics of fibrous shape are esteemed to be the most abundant micro-debris form present in the environment. Despite the occurrence of microfibers in fish may pose a risk to human health, the literature is scarce regarding studies on the contamination in commercial marine fish mostly due to methodological issues. In this study, a versatile approach, able to discriminate among natural and synthetic microfibers according to the evaluation of specific morphological features, is proposed in farmed mussels (Mytilus galloprovincialis). The approach was useful to determine that microfibers were present in 74% of mussel samples, with a mean number of 14.57 microfibers/individual, corresponding to 3.13 microfibers/g w.w. A negative correlation between the size of analysed mussels and the amount of microfibers/g w.w. was detected, showing that smaller specimens contained more microfibers than the larger ones. This work paves the way to further studies aimed to adequately assess the risk that microfibers may pose to marine biota, also considering the commercial value as seafood items of many species of the Mytilus genus and the potential implication for human exposure.

O/W Pickering Emulsions Stabilized with Cellulose Nanofibrils Produced through Different Mechanical Treatments.

This work aimed at studying the stabilization of O/W Pickering emulsions using nanosized cellulosic material, produced from raw cellulose or tomato pomace through different mechanical treatments, such as ball milling (BM) and high-pressure homogenization (HPH). The cellulose nanofibrils obtained via HPH, which exhibited longer fibers with higher flexibility than those obtained via ball milling, are characterized by lower interfacial tension values and higher viscosity, as well as better emulsion stabilization capability. Emulsion stability tests, carried out at 4 °C for 28 d or under centrifugation at different pH values (2.0, 7.0, and 12.0), revealed that HPH-treated cellulose limited the occurrence of coalescence phenomena and significantly slowed down gravitational separation in comparison with BM-treated cellulose. HPH-treated cellulose was responsible for the formation of a 3D network structure in the continuous phase, entrapping the oil droplets also due to the affinity with the cellulose nanofibrils, whereas BM-treated cellulose produced fibers with a more compact structure, which did adequately cover the oil droplets. HPH-treated tomato pomace gave similar results in terms of particle morphology and interfacial tension, and slightly lower emulsion stabilization capability than HPH-treated cellulose, suggesting that the used mechanical disruption process does not require cellulose isolation for its efficient defibrillation.

Valorization and Mechanical Recycling of Heterogeneous Post-Consumer Polymer Waste through a Mechano-Chemical Process.

In this paper, a sustainable strategy to valorize and recycle heterogeneous polymer-based post-consumer waste is proposed. This strategy is based on a high-energy mechano-chemical treatment and has been applied to a polyolefin-rich fraction, coded as FIL/S, deriving from household plastic waste collection. This processing, performed in a planetary ball mill, allowed us to obtain fine grinding and, consequently, to induce an intimate mixing of the different polymer fractions and contaminants composing the FIL/S, as demonstrated by SEM analysis. As a result, an improvement in the deformability of the treated material was obtained, recording values for elongation at the break which were two and half times higher than the neat FIL/S. Finally, the addition of small amounts of organic peroxide during mechano-chemical treatment was tested, determining a more homogeneous morphology and a further improvement in mechanical parameters.

Comparison of biodegradable polyesters degradation behavior in sand.

Sandy beaches represent environmental compartments particularly vulnerable to litter pollution, and they reflect the magnitude of pollution of adjacent compartments: water and coastal areas. The substitution of conventional polymers by biodegradable materials is generally considered as an alternative for reducing environmental accumulation of plastic debris. The present study is aimed to investigate the degradation of poly(lactic acid), poly(ε-caprolactone), poly(butylenesuccinate adipate) and poly(3-hydroxybutyrate) buried in sand for 267 days, simulating them as beach litter. The analysed polyesters showed different degradation mechanisms and kinetics. PLA is mainly subjected to weathering by physical aging; after an initial faster degradation of the amorphous phase, PCL showed a decrease of its degradation rate; similarly to PCL, the degradation of PBSA started from the amorphous phase; PHB is clearly subjected to biological degradation. The degradation trend of the investigated materials in sand decreased in the order PHB > PBSA > PCL > PLA. PLA, PCL and PBSA did not undergo complete degradation in sand during the testing time.

Washing load influences the microplastic release from polyester fabrics by affecting wettability and mechanical stress.

Microplastics released from textiles during the washing process represent the most prevalent type of microparticles found in different environmental compartments and ecosystems around the world. Release of microfibres during the washing process of synthetic textiles is due to the mechanical and chemical stresses that clothes undergo in washing machines. Several washing process parameters, conditions, formulations of laundering additives have been correlated to microfibre release and some of them have been identified to affect microfibre release during washing process, while no correlation has been evaluated between microfibre release and washing load. In the present study, microfibre release was evaluated as function of the washing load in a real washing process, indicating a progressive decrease of microfibre release with increasing washing load. The quantity of released microfibres increased by around 5 times by decreasing the washing load due to a synergistic effect between water-volume to fabric ratio and mechanical stress during washing. Moreover, the higher mechanical stress to which the fabric is subjected in the case of a low washing load, hinders the discrimination of the effect on the release of other washing parameters like the type of detergent and laundry additives used.

Hyper-Crosslinked Polymer Nanocomposites Containing Mesoporous Silica Nanoparticles with Enhanced Adsorption Towards Polar Dyes.

The development of new styrene-based hyper-crosslinked nanocomposites (HCLN) containing mesoporous silica nanoparticles (MSN) is reported here as a new strategy to obtain functional high surface area materials with an enhanced hydrophilic character. The HCLN composition, morphology and porous structure were analyzed using a multi-technique approach. The HCLN displayed a high surface area (above 1600 m2/g) and higher microporosity than the corresponding hyper-crosslinked neat resin. The enhanced adsorption properties of the HCLN towards polar organic dyes was demonstrated through the adsorption of a reactive dye, Remazol Brilliant Blue R (RB). In particular, the HCLN containing 5phr MSN showed the highest adsorption capacity of RB.

Environmental life cycle assessment of the recycling processes of waste plastics recovered by landfill mining.

Enhanced Landfill Mining (ELFM) is a powerful tool for the sustainable management of landfill sites, aiming at both land reclamation and material recovery/reuse. To enhance the recovery and recycling rate of excavated plastic fractions, in most cases destined to energy recovery, new convenient, effective and sustainable strategies are needed. In this study, a recovery and valorization process of ELFM excavated plastics has been validated through an integrated experimental and Life Cycle Assessment (LCA) approach, demonstrating the environmental sustainability of the secondary raw material generated, in terms of use of resources and emissions generated. In particular, the secondary granulate from ELFM was compared with a virgin product and the last one resulted to have a higher impact (more than 4.46 times greater than the first one), in particular for the use of the resource crude oil as raw material in the production of primary LDPE. The valorization process of the excavated plastic made the mechanical properties of the secondary raw material comparable to that of a primary material.