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.

Massive foreign body reaction and osteolysis following primary anterior cruciate ligament reconstruction with the ligament augmentation and reconstruction system (LARS): a case report with histopathological and physicochemical analysis.

BACKGROUND: Autologous hamstrings and patellar tendon have historically been considered the gold standard grafts for anterior cruciate ligament reconstruction (ACLR). In the last decades, the utilization of synthetic grafts has re-emerged due to advantageous lack of donor site morbidity and more rapid return to sport. The Ligament Augmentation and Reconstruction System (LARS) has demonstrated to be a valid and safe option for ACLR in the short term. However, recent studies have pointed out the notable frequency of associated complications, including synovitis, mechanical failure, and even chondrolysis requiring joint replacement. CASE PRESENTATION: We report the case of a 23-year-old male who developed a serious foreign body reaction with wide osteolysis of both femoral and tibial tunnels following ACLR with LARS. During first-stage arthroscopy, we performed a debridement of the pseudocystic mass incorporating the anterior cruciate ligament (ACL) and extending towards the tunnels, which were filled with autologous anterior iliac crest bone graft chips. Histological analysis revealed the presence of chronic inflammation, fibrosis, and foreign body giant cells with synthetic fiber inclusions. Furthermore, physicochemical analysis showed signs of fiber depolymerization, increased crystallinity and formation of lipid peroxidation-derived aldehydes, which indicate mechanical aging and instability of the graft. After 8 months, revision surgery was performed and ACL revision surgery with autologous hamstrings was successfully carried out. CONCLUSIONS: The use of the LARS grafts for ACLR should be cautiously contemplated considering the high risk of complications and early failure.

High Surface Area Mesoporous Silica Nanoparticles with Tunable Size in the Sub-Micrometer Regime: Insights on the Size and Porosity Control Mechanisms.

Mesoporous silica nanostructures (MSNs) attract high interest due to their unique and tunable physical chemical features, including high specific surface area and large pore volume, that hold a great potential in a variety of fields, i.e., adsorption, catalysis, and biomedicine. An essential feature for biomedical application of MSNs is limiting MSN size in the sub-micrometer regime to control uptake and cell viability. However, careful size tuning in such a regime remains still challenging. We aim to tackling this issue by developing two synthetic procedures for MSN size modulation, performed in homogenous aqueous/ethanol solution or two-phase aqueous/ethyl acetate system. Both approaches make use of tetraethyl orthosilicate as precursor, in the presence of cetyltrimethylammonium bromide, as structure-directing agent, and NaOH, as base-catalyst. NaOH catalyzed syntheses usually require high temperature (>80 °C) and large reaction medium volume to trigger MSN formation and limit aggregation. Here, a successful modulation of MSNs size from 40 up to 150 nm is demonstrated to be achieved by purposely balancing synthesis conditions, being able, in addition, to keep reaction temperature not higher than 50 °C (30 °C and 50 °C, respectively) and reaction mixture volume low. Through a comprehensive and in-depth systematic morphological and structural investigation, the mechanism and kinetics that sustain the control of MSNs size in such low dimensional regime are defined, highlighting that modulation of size and pores of the structures are mainly mediated by base concentration, reaction time and temperature and ageing, for the homogenous phase approach, and by temperature for the two-phase synthesis. Finally, an in vitro study is performed on bEnd.3 cells to investigate on the cytotoxicity of the MNSs.

Curing Behavior and Properties of Sustainable Furan-Based Epoxy/Anhydride Resins.

The last two decades have witnessed a significant growth in using bioderived materials, driven by the necessity of replacing fossil-derived precursors, reducing the fossil fuel consumption, and lowering the global environmental impact. This is possible thanks to the availability of abundant resources from biomasses and the development of optimized technologies based on the principles of sustainability and circular economy. Herein, we report on the synthesis and characterization of new carbohydrate-derived epoxy resins. In particular, 2,5-bis[(oxiran-2-ylmethoxy)methyl]furan has been synthesized and cured with methyl nadic anhydride. The effect of different initiators was studied, in order to identify the most efficient curable formulations. A series of resins was then prepared varying the epoxide-anhydride ratios. The results gathered from physicochemical, mechanical, morphological analyses have demonstrated that the produced furan-based thermosets have the potential to be proposed as sustainable alternatives to the traditional, bisphenol A-containing epoxy resins.

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.

Artificial biomelanin: highly light-absorbing nano-sized eumelanin by biomimetic synthesis in chicken egg white.

The spontaneous oxidative polymerization of 0.01-1% w/w 5,6-dihydroxyindole (DHI) in chicken egg white (CEW) in the absence of added solvents leads to a black, water-soluble, and processable artificial biomelanin (ABM) with robust and 1 order of magnitude stronger broadband light absorption compared to natural and synthetic eumelanin suspensions. Small angle neutron scattering (SANS) and transmission electron microscopy (TEM) analysis indicated the presence in the ABM matrix of isolated eumelanin nanoparticles (≤100 nm) differing in shape from pure DHI melanin nanoparticles (SANS evidence). Electron paramagnetic resonance (EPR) spectra showed a slightly asymmetric signal (g ∼ 2.0035) similar to that of solid DHI melanin but with a smaller amplitude (ΔB), suggesting hindered spin delocalization in biomatrix. Enhanced light absorption, altered nanoparticle morphology and decreased free radical delocalization in ABM would reflect CEW-induced inhibition of eumelanin aggregation during polymerization accompanied in part by covalent binding of growing polymer to the proteins (SDS-PAGE evidence). The technological potential of eumelanin nanosizing by biomimetic synthesis within a CEW biomatrix is demonstrated by the preparation of an ABM-based black flexible film with characteristics comparable to those of commercially available polymers typically used in electronics and biomedical applications.

Bio-based epoxy resin/carbon nanotube coatings applied on cotton fabrics for smart wearable systems.

Electroactive coatings for smart wearable textiles based on a furan bio-epoxy monomer (BOMF) crosslinked with isophorone diamine (IPD) and additivated with carbon nanotubes (CNTs) are reported herein. The effect of BOMF/IPD molar ratio on the curing reaction, as well as on the properties of the crosslinked resins was first assessed, and it was found that 1.5:1 BOMF/IPD molar ratio provided higher heat of reaction, glass transition temperature, and mechanical performance. The resin was then modified with CNT to prepare electrically conductive nanocomposite films, which exhibited conductivity values increased by eight orders of magnitude upon addition of 5 phr of CNTs. The epoxy/CNT nanocomposites were finally applied as coatings onto a cotton fabric to develop electrically conductive, hydrophobic and breathable textiles. Notably, the integration of CNTs imparted efficient and reversible electrothermal behavior to the cotton fabric, showcasing its potential application in smart and comfortable wearable electronic devices.

Characterization of polyethylene terephthalate (PET) and polyamide (PA) true-to-life nanoplastics and their biological interactions.

Plastic and microplastics, including polyethylene (PE), polypropylene (PP), and polystyrene (PS), are major contributors to environmental pollution. However, there is a growing recognition of the need to investigate a wider range of plastic polymers to fully understand the extent and impacts of plastic pollution. This study focuses on the comprehensive characterization of true-to-life nanoplastics (T2LNPs) derived from polyethylene terephthalate (PET) and polyamide (PA) to enhance our understanding of environmental nanoplastics pollution. T2LNPs were produced through cryogenic mechanical fragmentation of everyday items made from these polymers. A solid methodological framework incorporating various characterization techniques was established. Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and thermogravimetric analysis (TGA) were employed to study the chemical composition and confirm the absence of chemical modifications possibly occurring during fragmentation. Atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were used to analyze the morphology of the T2LNPs. Additionally, AFM image analysis compared to dynamic light scattering (DLS) measurements provided insights into the size distribution and the stability of the T2LNP suspensions. The results revealed the heterogeneity of T2LNPs derived from PET and PA, emphasizing the importance of studying different plastic compositions to comprehensively understand nanoplastics pollution. Lastly, the distinctive characteristics and morphology of T2LNPs were translated into the realm of biological interactions, offering initial insights into the influence of these disparities on the formation of the protein corona on the surface of T2LNPs. By proposing T2LNPs as test materials and establishing a comprehensive characterization approach, this study aims to bridge the knowledge gap regarding the behavior and toxicity of nanoplastics. Furthermore, it highlights the need for a reliable and transferable analytical package for nanoplastic characterization to facilitate future studies on the environmental impact of nanoplastics.

Non-invasive NMR stratigraphy of a multi-layered artefact: an ancient detached mural painting.

NMR stratigraphy was used to investigate in situ, non-destructively and non-invasively, the stratigraphy of hydrogen-rich layers of an ancient Nubian detached mural painting. Because of the detachment procedure, a complex multi-layered artefact was obtained, where, besides layers of the original mural painting, also the materials used during the procedure all became constitutive parts of the artefact. NMR measurements in situ enabled monitoring of the state of conservation of the artefact and planning of minimum representative sampling to validate results obtained in situ by solid-state NMR analysis of the samples. This analysis enabled chemical characterization of all organic materials. Use of reference compounds and prepared specimens assisted data interpretation.

Monitoring Water Absorption and Desorption in Untreated and Consolidated Tuff by a Non-Invasive Graphene-Based Humidity Sensor.

A hybrid montmorillonite (MMT)/reduced graphene oxide (rGO) film was realised and used as a non-invasive sensor for the monitoring of water absorption and desorption in pristine and consolidated tuff stones. This film was obtained by casting from a water dispersion containing graphene oxide (GO), montmorillonite and ascorbic acid; then the GO component was thermo-chemically reduced and the ascorbic acid phase was removed by washing. The hybrid film showed electrical surface conductivity that varied linearly with the relative humidity, ranging from 2.3 × 10-3 S in dry conditions to 5.0 × 10-3 S at 100% RH. The sensor was applied onto tuff stone samples through the use of a high amorphous polyvinyl alcohol layer (HAVOH) adhesive, which guaranteed good water diffusion from the stone to the film and was tested during water capillary absorption and drying tests. Results show that the sensor is able to monitor water content changes in the stone, being potentially useful to evaluate the water absorption and desorption behaviour of porous samples both in laboratory environments and in situ.

Cellulose Isolation from Tomato Pomace: Part II-Integrating High-Pressure Homogenization in a Cascade Hydrolysis Process for the Recovery of Nanostructured Cellulose and Bioactive Molecules.

This work proposes a biorefinery approach for utilizing tomato pomace (TP) through a top-down deconstructing strategy, combining mild chemical hydrolysis with high-pressure homogenization (HPH). The objective of the study is to isolate cellulose pulp using different combinations of chemical and physical processes: (i) direct HPH treatment of the raw material, (ii) HPH treatment following acid hydrolysis, and (iii) HPH treatment following alkaline hydrolysis. The results demonstrate that these isolation routes enable the production of cellulose with tailored morphological properties from TP with higher yields (up to +21% when HPH was applied before hydrolysis and approximately +6% when applied after acid or after alkaline hydrolysis). Additionally, the side streams generated by this cascade process show a four-fold increase in phenolic compounds when HPH is integrated after acid hydrolysis compared to untreated sample, and they also contain nanoparticles composed of hemicellulose and lignin, as shown by FT-IR and SEM. Notably, the further application of HPH treatment enables the production of nanostructured cellulose from cellulose pulp derived from TP, offering tunable properties. This approach presents a sustainable pathway for the extraction of cellulose and nanocellulose, as well as the valorization of value-added compounds found in residual biomass in the form of side streams.

Effectiveness of Mesoporous Silica Nanoparticles Functionalized with Benzoyl Chloride in pH-Responsive Anticorrosion Polymer Coatings.

Smart polymer coatings embedding stimuli-responsive corrosion inhibitor nanocarriers are commonly exploited, in the literature, for the development of high-performance active coatings. In this work, high-surface-area amino-functionalized mesoporous silica nanoparticles (MSN-NH2) were developed with a one-step synthesis process and then functionalized with benzoyl chloride (MSN-BC) through a reaction with amino groups. MSN-BC are able to release benzoic acid (BA) in acid and alkaline conditions as a result of the hydrolysis of the pH-sensitive amide bond. MSN-BC were embedded in polymer coatings to exploit the pH-dependent release of corrosion-inhibiting BA. After an in-depth characterization of the developed functional nanoparticles and of their pH-dependent release kinetics of BA, MSN-BC were embedded in an acrylic matrix, realizing coatings for the corrosion protection of aluminum AA2024 alloys. Results demonstrate the effectiveness of the nanoparticles' porous structure for a high loading of the anticorrosive active agent BA and the long-lasting efficiency of the coating for the corrosion protection of aluminum alloys, as validated by morphological and electrochemical impedance spectroscopy (EIS) measurements. EIS experiments were carried out with up to 21 days of exposure to a corrosive environment, revealing the potentialities of the acrylic coatings embedding MSN-BC for the protection of aluminum alloys.

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 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.

Direct Laser Writing of Chitosan-Borax Composites: Toward Sustainable Electrochemical Sensors.

In this study, the laser-induced graphitization process of sustainable chitosan-based formulations was investigated. In particular, optimal lasing conditions were investigated alongside the effect of borax concentration in the chitosan matrix. In all cases, it was found that the obtained formulations were graphitizable with a CO2 laser. This process gave rise to the formation of high surface area, porous, and electrically conductive laser-induced graphene (LIG) structures. It was found that borax, as a cross-linker of chitosan, enabled the graphitization process when its content was ≥30 wt % in the chitosan matrix, allowing the formation of an LIG phase with a significant content of graphite-like structures. The graphitization process was investigated by thermogravimetric analysis (TGA), Raman, X-ray photoemission (XPS), and Fourier transform infrared (FTIR) spectroscopies. LIG electrodes obtained from CS/40B formulations displayed a sheet resistance as low as 110 Ω/sq. Electrochemical characterization was performed after a 10 min electrode activation by cycling in 1 M KCl. A heterogeneous electron transfer rate, k0, of 4 × 10-3 cm s-1 was determined, indicating rapid electron transfer rates at the electrode surface. These results show promise for the introduction of a new class of sustainable composites for LIG electrochemical sensing platforms.

Preparation and properties of novel binary and ternary highly amorphous poly(vinyl alcohol)-based composites with hybrid nanofillers.

Smart protective coatings and devices are currently of great interest. In particular, they can absorb or reflect harmful waves of electromagnetic interference (EMI). In this work, novel binary and ternary composites with highly amorphous poly(vinyl alcohol) (HAVOH) as a matrix and single-walled carbon nanotubes (SWCNTs) and MXenes as nanofillers were prepared. HAVOH is a recently patented kind of poly(vinyl alcohol) (PVOH) that was modified with diol monomers. MXenes are a new type of inorganic two-dimensional (2D) nanoparticle consisting of carbides, nitrides and carbonitrides. Three series of composites, HAVOH/SWCNTs, HAVOH/MXenes and HAVOH/SWCNTs/MXenes, were prepared using the solvent casting method. Samples were tested with various methods to study their structure, electrical properties, thermal behavior and EMI-shielding properties. HAVOH/3.0 wt.% SWCNTs/3.0 wt.% MXene specimens revealed a shielding effectiveness of 55 dB, which is 122 times better than that of the neat matrix. These results are promising for the fabrication of films with protective effects against EMI.

All natural mussel-inspired bioadhesives from soy proteins and plant derived polyphenols with marked water-resistance and favourable antibacterial profile for wound treatment applications.

HYPOTHESIS: Implementation of tissue adhesives from natural sources endowed with good mechanical properties and underwater resistance still represents a challenging research goal. Inspired by the extraordinary wet adhesion properties of mussel byssus proteins resulting from interaction of catechol and amino residues, hydrogels from soy protein isolate (SPI) and selected polyphenols i.e. caffeic acid (CA), chlorogenic acid (CGA) and gallic acid (GA) under mild aerial oxidative conditions were prepared. EXPERIMENTS: The hydrogels were subjected to chemical assays, ATR FT-IR and EPR spectroscopy, rheological and morphological SEM analysis. Mechanical tests were carried out on hydrogels prepared by inclusion of agarose. Biological tests included evaluation of the antibacterial and wound healing activity, and hemocompatibility. FINDINGS: The decrease of free NH2 and SH groups of SPI, the EPR features, the good cohesive strength and excellent underwater resistance (15 days for SPI/GA) under conditions relevant to their use as surgical glues indicated an efficient interaction of the polyphenols with the protein in the hydrogels. The polyphenols greatly also improved the mechanical properties of the SPI/ agarose/polyphenols hydrogels. These latter proved biocompatible, hemocompatible, not harmful to skin, displayed durable adhesiveness and good water-vapour permeability. Excellent antibacterial properties and in some cases (SPI/CGA) a favourable wound healing activity on dermal fibroblasts was obtained.

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.

Instant in situ formation of a polymer film at the water-oil interface.

The water-oil interface is an environment that is often found in many contexts of the natural sciences and technological arenas. This interface has always been considered a special environment as it is rich in different phenomena, thus stimulating numerous studies aimed at understanding the abundance of physico-chemical problems that occur there. The intense research activity and the intriguing results that emerged from these investigations have inspired scientists to consider the water-oil interface even as a suitable setting for bottom-up nanofabrication processes, such as molecular self-assembly, or fabrication of nanofilms or nano-devices. On the other hand, biphasic liquid separation is a key enabling technology in many applications, including water treatment for environmental problems. Here we show for the first time an instant nanofabrication strategy of a thin film of biopolymer at the water-oil interface. The polymer film is fabricated in situ, simply by injecting a drop of polymer solution at the interface. Furthermore, we demonstrate that with an appropriate multiple drop delivery it is also possible to quickly produce a large area film (up to 150 cm2). The film inherently separates the two liquids, thus forming a separation layer between them and remains stable at the interface for a long time. Furthermore, we demonstrate the fabrication with different oils, thus suggesting potential exploitation in different fields (e.g. food, pollution, biotechnology). We believe that the new strategy fabrication could inspire different uses and promote applications among the many scenarios already explored or to be studied in the future at this special interface environment.