Growth and Primary Metabolism of Lettuce Seedlings (Lactuca sativa L.) Are Promoted by an Innovative Iron-Based Fenton-Composted Amendment.

Information regarding the physiological and molecular plant responses to the treatment with new biofertilizers is limited. In this study, a fast-composting soil amendment obtained from solid waste by means of a Fenton reaction was assessed to evaluate the effects on the growth of Lactuca sativa L. var. longifolia seedlings. Growth rate, root biomass, chlorophyll concentration, and total soluble proteins of seedlings treated with the 2% fast-composting soil amendment showed significant increases in comparison with the control seedlings. Proteomic analysis revealed that the soil amendment induced the up-regulation of proteins belonging to photosynthesis machinery, carbohydrate metabolism, and promoted energy metabolism. Root proteomics indicated that the fast-composting soil amendment strongly induced the organs morphogenesis and development; root cap development, lateral root formation, and post-embryonic root morphogenesis were the main biological processes enriched by the treatment. Overall, our data suggest that the addition of the fast-composting soil amendment formulation to the base soils might ameliorate plant growth by inducing carbohydrate primary metabolism and the differentiation of a robust root system.

Evaluation of the Ecotoxicity of New Polyurethane Composites on Target Organisms for Aquatic and Atmospheric Environments.

The present study investigated if new biocomposite materials, polyurethanes (PURs) added with functionalized cellulose fibers, produce potential toxic effects on two target organisms currently used in biomonitoring the quality of two different environmental compartments. Natural fibers were extracted from the species Spartium junceum L., a shrub commonly found in the southern region of the Mediterranean having a high cellulose content. All PURs produced were characterized by Fourier-transform infrared spectroscopy, and their structure was analyzed by scanning electron microscopy. We measured the effects of exposure to aromatic and aliphatic PUR composites (containing or not cellulose fibers) on the aquatic model organism Daphnia magna Straus, a freshwater crustacean (Cladocera), and a biomonitor of air quality, the fruticose epiphytic lichen Pseudevernia furfuracea (L.) Zopf. Leachates from aliphatic PUR composite not containing cellulose are more toxic to D. magna than all others, showing a slight acute toxicity in the case of the shortest exposure (24 h) and a moderate acute toxicity in the longer one (48 h). This effect is most likely due to the presence of free organic ammines and amides, which, in their turn, are immobilized in composites containing cellulosic fibers because of the considerable amount of chemical functional groups. Regarding lichens, both types of aliphatic PURs resulted in a toxic effect. Formulate not added with cellulose strongly promoted fungal peroxidation, whereas that which was functionalized affected the pigment concentration of the algal partner. Our results suggest that the use of cellulose in PUR production, in general, can limit the ecotoxicological effects on both test organisms and reduce the potential environmental impact due to this type of polymer. Environ Toxicol Chem 2023;42:421-436. © 2022 SETAC.

Water-Based Aerosol for Book Deacidification: Experimental Apparatus and Theoretical Interpretation of Results.

One of the major problems in book conservation is the long-term deconstructive effect of acidity introduced into the paper by several additives, which, in the presence of humidity, generates a hydrogen cation with a strong catalytic role in cellulose depolymerization. Many types of treatment have been used in the past, but up to now, research for less-invasive, fast and cheap methods is still vividly ongoing. In this study, an approach to book deacidification is presented, where alkaline water solutions are administered to bound books in the form of micrometer-sized aerosol droplets, without using vacuum apparatus accessories. Alkaline clouds treatments were alternated with gentle air fluxes of drying steps. Few cycles are required to achieve uniform deacidification of books. The treatment could be conducted with proper apparatus on large volumes, resulting in rapid treatment time and low cost. The titration curve reporting the variation of book pH, with respect to the amount of absorbed alkaline aerosol, was built and interpreted in terms of a chemical model for the neutralization process. FTIR, PXRD and XRF spectroscopies were used to characterize the book chemistry. The effects of the treatment on the book were evaluated by measuring the degree of polymerization (DP) of the paper and the colorimetric coordinates of the paper and ink. Artificial aging tests revealed a general increase in the aging stability of the deacidified paper samples with respect to the untreated samples. Finally, the alkaline reserve data are discussed.

Chemical-physical and dynamical-mechanical characterization on Spartium junceum L. cellulosic fiber treated with softener agents: a preliminary investigation.

Long cellulose fiber (10-30 cm), extracted from Spartium junceum, was chemically treated with different softening agents with the aim to improve its textile applicability. A preliminary sensory evaluation of the treated fibers revealed an evident, though qualitative, improvement of the fiber softness. The effects of the softening agents on the fiber was evaluated quantitatively, by means of macroscopic measurements of the wettability, viscoelasticity, and thermal (thermal gravimetry) properties. Moreover, the effects of the softening treatments on the microscopic structure of the fiber and on its properties at a molecular level, were studied by optical and scanning electron microscope and X-ray diffraction (XRD), respectively. The macroscopic analysis showed that the softeners used increases the hydrophilicity and water wettability of the cellulose fiber with respect to the raw one. Moreover, the dynamical mechanical analysis on sample yarns showed that the softeners increase the interfiber frictional forces. A linear correlation between the interfiber friction and the increase of hydrophilicity and fiber wettability was shown. The treated fiber exhibits a more homogeneous thermal behaviour, due to more homogeneous structural features, since the thermal-induced cellulose fibrils depolimerization undergoes a marked temperature range contraction. These data can be well related with those obtained by microscopy analysis, showing that the fiber surface, after the treatment, appears thinner and less rough, as well as with the XRD analysis, which shows that softeners induce a significant decrease of the fiber crystallinity.

Organic Matter Characterization and Phytotoxic Potential Assessment of a Solid Anaerobic Digestate Following Chemical Stabilization by an Iron-Based Fenton Reaction.

Digestates, a byproduct of the anaerobic bioconversion of organic wastes for the production of biogas, are highly variable in chemical and biological properties, thus limiting their potential use in agriculture as soil amendment. Using a lab-scale glass reactor, we aimed to assess the feasibility to chemically stabilize the solid fraction of an anaerobic digestate by applying a Fenton reaction under constant pH (3.0), temperature (70 °C), reaction time (8 h), and various combinations of H2O2 and Fe2+. In Fenton-treated samples, the phytotoxic potential (determined on a test plant), total phenols, and the bad smell odor index markedly declined, whereas total C and N remained unaltered. Thermogravimetric (TG) analysis and Fourier transform infrared (FT-IR) spectroscopy revealed contrasting changes in extracted humic and fulvic fractions being increased or depleted, respectively, in aromatic substances. Process feasibility and optimum conditions for an effective biomass stabilization were achieved with a H2O2/Fe2+ ratio between 0.02 and 0.03.

Totally green cellulose conversion into bio-oil and cellulose citrate using molten citric acid in an open system: synthesis, characterization and computational investigation of reaction mechanisms.

The simultaneous transformation of crystalline or amorphous cellulose into a furan-based bio-oil and cellulose citrate was realized avoiding the use of strong inorganic acids, drastic conditions, enzymatic treatments or microorganism fermentation. This innovative method is very eco-friendly and involves the use of molten citric acid under solvent free conditions at atmospheric pressure. An accurate discussion on chemical composition of the bio-oil enriched in bioprivileged molecules as well as structural and morphological characterization of cellulose citrate was reported. Moreover, mechanistic hypotheses were formulated on the basis of experimental findings and detailed DFT quantum-mechanical simulations were carried out to confirm, step by step, the proposed reaction paths.

Photocatalytic inactivation of Escherichia coli bacteria in water using low pressure plasma deposited TiO2 cellulose fabric.

Fabrics obtained from cellulose spinning, extracted from Spanish broom, were coated with TiO2 film, through the low pressure plasma sputtering technique, in order to get antibacterial activity. The obtained fabrics were used for the photocatalytic degradation of Escherichia coli, by irradiation with UV-light emitting diodes (UV-LED), in a batch photocatalytic reactor. Before and after functionalization treatments, cellulosic substrates were chemically characterized by X-ray photoelectron spectroscopy (XPS) analyses. Water Contact Angle (WCA) measurements allowed obtaining information about the hydrophilicity of the materials, while their antibacterial efficiency was determined at several initial concentrations (from 103 up to 108 CFU mL-1) of bacteria in distilled water, bottled water and synthetic wastewater. It was found that photocatalytic reactions were capable of achieving up to 100% bacterial inactivation in 1 h of treatment, following a pseudo-first order kinetic model. No bacterial regrowth was observed after photocatalytic treatments in almost all experimental conditions. In contrast, during photolytic treatment (i.e. in the absence of the TiO2 coated fabrics) bacteria recovered their initial concentration after 3 h in the dark. Finally, the reusability of the plasma modified fibers to inactivate bacteria was studied.

High-Performance Electrofluorochromic Switching Devices Using a Novel Arylamine-Fluorene Redox-Active Fluorophore.

Fluorescent light modulation by small electric potentials has gained huge interest in the past few years. This phenomenon, called electrofluorochromism, is of the utmost importance for applications in optoelectronic devices. Huge efforts are being addressed to developing electrofluorochromic systems with improved performances. One of the most critical issue is their low cyclability, which hampers their widespread use. It mostly depends on the intrinsic reversibility of the electroactive/fluorophore molecular system and on device architecture. Here we show a novel fluorene-based mixed-valence electrofluorochromic system that allows direct electrofluorochromic switching and exhibits incomparable electrochemical reversibility and device cyclability of more than 10 000 cycles.

Removal of Endocrine Disrupting Chemicals from Water: Adsorption of Bisphenol-A by Biobased Hydrophobic Functionalized Cellulose.

The aim of this study is to examine the efficiency of biobased Spanish broom (SB) surface modified cellulose fibers to remove bisphenol A (BPA), a well-known endocrine disruptor, from water. Spanish brooms are flowering plants, which are native and abundant to Mediterranean regions. The functionalized fibers (FF) were found to have the best adsorption efficiency at pH 5, due to the optimal hydrophobic interaction between the FF fiber and BPA. Adsorption kinetics of BPA was found to fit well a pseudo-second order reaction. Equilibrium isotherm data were fitted by Langmuir and Freundlich models. A very fast and simple regeneration method was developed and it was observed that adsorption capacity of the fibers was kept almost unchanged after 3 consecutive uses. Bottled water and synthetic wastewater were also tested to assess the efficiency of the process under more realistic water and wastewater treatment conditions. It was found that BPA removal was slightly decreased from 77% in ultrapure water to 64% in synthetic wastewater matrix, indicating that FF has a high selectivity toward BPA, even in the presence of other organic compounds. Overall, it was observed that SB-modified fibers can be a new promising green biotechnology for water purification.

Remediation of hydrocarbons polluted water by hydrophobic functionalized cellulose.

Remediation of water bodies from petroleum hydrocarbons is of the utmost importance due to health risks related to the high toxicity, mutagenicity and carcinogenicity of the hydrocarbons components that may enter into the food chain. Though several methods were proposed to face up this challenge, they are generally not easily feasible at a contaminated site and quite costly. Here we propose a green, cost-effective technology based on hydrophobized Spanish Broom (SB) cellulose fiber. The natural cellulose fiber was extracted by alkaline digestion of the raw vegetable. The hydrophilic cellulose surface was transformed into a hydrophobic one by the reaction with 4,4'-diphenylmethane diisocyanate (MDI) forming a very stable urethane linkage with the hydroxyl groups of cellulose emerging from the fibers surface. Chemical functionalization was performed with a novel solvent-free technology based on a home-made still reactor were the fiber was kept under vortex stirring and the MDI reactant then spread onto the fiber surface by nebulizing it in form of micrometer-sized droplets. The functionalized fiber, characterized by means of WCA measurements, XPS and ATR-FTIR spectroscopy, shows fast adsorption kinetics adsorption capacity as high as 220 mg/g, among the highest ever reported so far in the literature for cellulosic materials.

Spanish Broom (Spartium junceum L.) fibers impregnated with vancomycin-loaded chitosan nanoparticles as new antibacterial wound dressing: Preparation, characterization and antibacterial activity.

In this work, we propose as new wound dressing, the Spanish Broom fibers impregnated with vancomycin (VM) loaded chitosan nanoparticles. Spanish Broom fibers were extracted by patented method DiCoDe and the morphological, physical and mechanical properties were investigated. Chitosan nanoparticles were prepared by ionic gelation using different weight ratios between chitosan (CH) and tripolyphosphate (TPP). Nanoparticles were characterized in terms of size, zeta potential, yield, encapsulation efficiency, stability and drug release. Finally, the antibacterial activity against Staphylococcus aureus as well as in vitro cytotoxicity on HaCaT cells were evaluated. The best formulation CH/TPP 4:1 was selected based on the encapsulation efficiency and yield. Spanish Broom fibers impregnated with loaded nanoparticles showed an increased antibacterial activity against S. aureus compared to the same fibers containing VM without nanoparticles. Moreover, these fibers were not toxic to HaCaT keratinocytes cells. In conclusion, Spanish Broom fibers impregnated with VM loaded CH/TPP nanoparticles would appear to be a promising candidate for wound dressing application.

Electro-optical Properties of Neutral and Radical Ion Thienosquaraines.

Thienosquaraines are an interesting class of electroactive dyes that are useful for applications in organic electronics. Herein, the redox chemistry and electrochromic response of a few newly synthesized thienosquaraines are presented. These properties are compared to those of the commercial 2,4-bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl]squaraine. The stability of the radical ions formed in electrochemical processes strongly affects these properties, as shown by cyclic voltammetry, in situ spectroelectrochemistry, and quantum chemical calculations. Furthermore, all of the dyes show aggregation tendency resulting in panchromatic absorption covering the whole UV/Vis spectral range.

Antiproliferative effect of linalool on RPMI 7932 human melanoma cell line: ultrastructural studies.

Linalool, a small monoterpene molecule, is used widely for its flavoring and fragrant properties in many cosmetic products. In this work, we investigated the antiproliferative effect of two different linalool solutions on RPMI 7932 human melanoma and NCTC 2544 normal keratinocites cell lines using the trypan blue method. Morphological changes in cells were investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). In addition, apoptosis was evaluated using caspase 3-antibody. Linalool showed a selective inhibitory effect on the growth of melanoma cells in a concentrationdependent manner, inducing several morphological changes, as revealed by SEM and TEM analysis. Moreover, the labelling for caspase-3 is abundant in the melanoma cells and almost absent in the normal keratinocites cells. The results suggest that linalool could be used as drug and/or as model drug for developing potential therapeutic agents for melanoma.

Effect of millimetre waves on phosphatidylcholine membrane models: a non-thermal mechanism of interaction.

The nonthermal biological effects of millimeter waves have been mainly attributed to the interaction with biological membranes. Several data on biomimetic membrane systems seem to support this conclusion. In this paper a mechanistic hypothesis is evaluated to explain such an interaction taking into account experimental NMR data on deuterium-labeled phospholipid vesicles. These data showed that millimeter waves induce a time and a hydration-dependent reduction of the water ordering around the phosphocholine headgroups. This effect is here interpreted as a change in membrane water partitioning, due to the coupling of the radiation with the fast rotational dynamics of bound water molecules, that results in a measurable relocation of water molecules from the inner to the outer binding regions of the membrane interface. When millimeter wave exposure is performed in the vicinity of the transition point, this effect can lead to an upward shift of the membrane phase transition temperature from the fluid to the gel phase. At a macroscopic level, this unique sensitivity may be explained by the universal dynamic behaviour of the membranes in the vicinity of the transition point, where a pretransitional increase of membrane area fluctuations, i.e., of the mean area per phospholipid headgroup, is observed. Exposure to millimeter waves increases the above fluctuations and enhances the second order character of the transition.

Electrofluorochromism in π-conjugated ionic liquid crystals.

Materials in which photoluminescence is modulated by redox processes are known as electrofluorochromic. Intrinsically switchable fluorophores, incorporating both redox and fluorescent moieties, could be ideal electrofluorochromic materials if they possess high fluorescence quantum yields in at least one of their redox states. Fluorescent liquid crystals with redox active centres could combine the above requirements with the advantage to work in bulk anisotropic phases. However, electrofluorochromic liquid crystals have not been reported yet because their synthesis is challenging due to aggregation-caused fluorescent quenching. Here we show the first examples of electrofluorochromic π-conjugated ionic liquid crystals based on thienoviologens. These ordered materials, combining ionic and electronic functions, are highly fluorescence in the bulk state (quantum yield>60%). Their direct electrochemical reduction leads to fast and reversible bulk electrofluorochromic response in both columnar and smectic phases allowing for fluorescence intensity modulation and colour tuning.

The influence of millimeter waves on the physical properties of large and giant unilamellar vesicles.

Exposure of cell membranes to an electromagnetic field (EMF) in the millimeter wave band (30-300 GHz) can produce a variety of responses. Further, many of the vibrational modes in complex biomolecules fall in the 1-100 GHz range. In addition to fundamental scientific interest, this may have applications in the development of diagnostic and therapeutic medical applications. In the present work, lipid vesicles of different size were used to study the effects of exposure to radiation at 52-72 GHz, with incident power densities (IPD) of 0.0035-0.010 mW/cm(2), on the chemical-physical properties of cell membranes. Large unilamellar vesicles (LUVs) were used to study the effect of the radiation on the physical stability of vesicles by dynamic light scattering. An inhibition of the aging processes (Ostwald ripening), which usually occur in these vesicles because of their thermodynamic instability, resulted. Giant unilamellar vesicles (GUVs) were used to study the effect of the radiation on membrane water permeability under osmotic stress by phase contrast microscopy. In this case, a decrease in the water membrane permeability of the irradiated samples was observed. We advance the hypothesis that both the above effects may be explained in terms of a change of the polarization states of water induced by the radiation, which causes a partial dehydration of the membrane and consequently a greater packing density (increased membrane rigidity).

Millimeter Wave Radiations Affect Membrane Hydration in Phosphatidylcholine Vesicles.

A clear understanding of the response of biological systems to millimeter waves exposure is of increasing interest for the scientific community due to the recent convincing use of these radiations in the ultrafast wireless communications. Here we report a deuterium nuclear magnetic resonance spectroscopy (²H-NMR) investigation on the effects of millimeter waves in the 53-78 GHz range on phosphocholine bio-mimetic membranes. Millimeter waves significantly affect the polar interface of the membrane causing a decrease of the heavy water quadrupole splitting. This effect is as important as inducing the transition from the fluid to the gel phase when the membrane exposure occurs in the neighborhood of the transition point. On the molecular level, the above effect can be well explained by membrane dehydration induced by the radiation.

Spartium junceum aromatic water: chemical composition and antitumor activity.

The purpose of this study was to analyse the chemical composition of Spartium junceum L. (also known as Spanish Broom) aromatic water and to evaluate its cytotoxic activity against a series of human cancer cell lines (melanoma: RPMI 7932; leukemia: K562; breast cancer cell: MCF7-Bart and MCF7-ICLC, colon adenocarcinoma: SW480). The results show that the aromatic water was cytotoxic toward the tumor cell lines analyzed (RPMI 7932, K562, MCF7-Bart, MCF7-ICLC, SW480), while it did not appreciably alter the viability of normal keratinocytes (NCTC 2544) suggesting its potential use as an antitumor agent for cancer treatment and/or prevention.

Microwave induced shift of the main phase transition in phosphatidylcholine membranes.

Numerous experimental evidence show that exposure of biological systems to extremely high frequency microwaves may induce significant effects even at low powers. These effects are thought to occur via nonthermal mechanisms involving primarily the interaction of microwaves with phospholipid membrane structures. However, no conclusive experimental evidence that biomembranes exhibit remarkable sensitivity to this radiation has been provided up to now. Here, deuterium nuclear magnetic resonance spectroscopy is used to study the effects of microwaves on 1,2-Dimyristoyl-sn-glycero-3-phosphatidylcholine/(2)H(2)O multilamellar vesicles that serve as biomimetic membranes. Here we show that, if the membrane is brought into close proximity to the transition point, microwaves induce a reduction of water ordering at the membrane interface, an upward shift of the main phase transition temperature and a broadening of the transition region. A deep dosimetric analysis shows that the above effects are nonthermal, indicating the need for a nonthermal hypothesis to explain them. This study suggests that exposure to high-frequency microwaves can have far reaching consequences on active biological systems.

Highly routinely reproducible alignment of 1H NMR spectral peaks of metabolites in huge sets of urines.

A method to obtain high reproducibility of (1)H NMR chemical shift of peaks of biofluid metabolites, by simple acidification with HCl is evaluated. Biofluid (1)H NMR analysis is indeed spoiled by a strong chemical shift dependence of metabolite peaks on parameters such as ionic strength, concentration of some earth alkali cations and, mostly, on pH of samples. The resulting chemical shift variations, as large as 0.1 ppm, generate misalignments of homogeneous peaks, artifacts and misinterpretations. Reproducible alignment is essential in (1)H NMR based metabonomics, where peak misalignments prevent even very wide bins (i.e., 0.04 ppm, as elsewhere proposed) from being used to integrate spectral data for multivariate statistical analysis. Here is demonstrated that routine acidification with HCl to 1.2≤pH≤2.0 ensures highly reproducible peak alignment of urine (1)H NMR spectra. In this respect, simple inspection of citrate peaks in the urine can be used to measure pH, as it will be extensively discussed, in that at such low pH they show no dependency on other urine components as reported at higher pH. Under these conditions, in as many as 493 urine samples, in which concentrations of Ca(2+), Mg(2+), K(+), Na(+), Cl(-), phosphate, and creatinine and ionic strength measured by means of well standardized conventional procedures, showed very wide ranges, peaks align within a SD always lower than 0.002 ppm, thus allowing the use of integration bins at least five times narrower than 0.04 ppm.