Removal of lead in water by coagulation flocculation process using Cactus-based natural coagulant: optimization and modeling by response surface methodology (RSM).

The aim of this research is to study the ability of Cactus leaves to act as a biocoagulants for the removal of lead in water. Different solvents, such as distilled water, NaCl, NaOH, and HCl, were used as chemical activators to extract the active components from the Cactus. The Cactus was utilized as an organic coagulant in five different forms: (i) Cactus juice (CJ); Cactus extract using (ii) distilled water (C-H2O); (iii) NaCl at 0.5 M concentration (C-NaCl); (iv) NaOH at 0.05 M concentration (C-NaOH); and (v) HCl at 0.05 M concentration (C-HCl). In order to establish the optimal conditions for the coagulation, this study employed the jar test as an experimental technique and the Box-Behnken design (BBD) as an experimental approach. According to BBD, there are three factors (k = 3), namely pH, biocoagulant dosage, and settling time. The R2 and R2 adjusted for all coagulants were close to 100%, confirming the validity of all the mathematical models. The results were significant; the highest lead removal efficiencies were 98.11%, 98.34%, 95.65, 96.19%, and 97.49%, utilizing CJ, C-H2O, C-NaCl, C-HCl, and C-NaOH as natural coagulants. The Cactus has been characterized using FTIR, XRD, and SEM to identify the active components that remove lead.

Determination of phenolic compounds by MALDI-TOF and essential oil composition by GC-MS during three development stages of Origanum majorana L.

This study aimed to investigate the effect of the maturation process of sweet marjoram (Origanum majorana L.) on essential oil composition, the phenolic profile of ethanolic extract and their antioxidant capacities. The essential oil composition was studied at three stages of maturity by GC-MS. Thirty compounds were detected representing 100% of the total essential oil. p-Menth-1-en-4-ol was the major compound (37.15-76.94%) followed by cyclohexanol-3,3,5 trimethyl (5.41-15.99%) and α-terpineol (0.94-11.34%). During the maturation process, an accumulation of oxygenated monoterpenes was observed. The phenolic composition was studied using matrix-assisted laser desorption/ionization time of flight. The analysis showed the presence of short flavonoid monomers at all stages of maturation. The antioxidant capacity of ethanolic extracts and essential oils was evaluated using the DPPH assay, iron chelating power and reducing power assay. The highest phenolic content and antioxidant capacity were found at flowering stage. These findings on essential oil composition, phenolic profile and antioxidant capacity of O. majorana at three different stages of development provide more information on how these secondary metabolites are accumulated.

In Vitro and In Vivo Anti-Melanoma Effects of Pituranthos tortuosus Essential Oil Via Inhibition of FAK and Src Activities.

A large number of plants used in traditional medicines have been shown to possess antitumor activities. The aims of this study were to evaluate any anticancer effect of the essential oil (EO) extracted from P. tortuosus against B16F10 melanoma cancer cells in vitro as well as in vivo. In vitro, EO was shown to induce apoptosis and to inhibit migration and invasion processes. Further investigation revealed that EO decreased focal adhesion and invadopodia formation which was accompanied by a drastic downregulation of FAK, Src, ERK, p130Cas and paxillin. Moreover, EO treatment decreased the expression level of p190RhoGAP, and Grb2, which impair cell migration and actin assembly. Mice bearing the melanoma cells were used to confirm any in vivo effectiveness of the EO as an anti-tumor promoting agent. In mice dosed with 100 mg EO/kg/d (for 27 days), tumor weight was inhibited by 98% compared to that in mice that did not receive the product. In conclusion, these data suggested to us that an EO of P. tortuosus could evolve to be a potential medicinal resource for use in the treatment of cancers.

Immunomodulatory and anticancer effects of Pituranthos tortuosus essential oil.

Many studies have been performed to assess potential utility of natural products as immunomodulants to enhance antitumor activity in situ. In this study, an essential oil (EO) from the aerial parts of Pituranthos tortuosus was prepared using hydrodistillation, its composition was characterized, and its immunomodulatory potential was assessed. The results indicated that the EO contained sabinene, α-pinene, limonene, and terpinen-4-ol as major constituents. EO was also found to be able to significantly promote lipopolysaccharide (LPS)-stimulated splenocyte proliferation, suggestive of a potential for activation of B cells and enhanced humoral immune responses in hosts given this product. Effects of EO on cell proliferation and apoptosis were also investigated in B16F10 melanoma cells. EO-induced tumor cell growth inhibition was associated with characteristic apoptotic changes in the cells, including nuclear condensation. In conclusion, these data suggested to us that an EO of P. tortuosus could evolve to be a potential medicinal resource for use in the treatment of cancers.

Limoniastrum guyonianum methanol extract induces immunomodulatory and anti-inflammatory effects by activating cellular anti-oxidant activity.

Evaluation of the immunomodulatory activity of plant extracts is an interesting and growing area of research. In this study, effects of a methanolic extract of Limoniastrum guyonianum stems (M extract) on mice immune cell function in vitro were investigated. These studies showed that mitogen-induced lymphocyte proliferation was dose-dependently inhibited by the extract. Further, the lectin-induced response appeared to be more sensitive to the suppressive effects of the extract than were LPS-stimulated responses. In studies to assess any potential effects of extract on innate immunity, the results showed that the extract significantly enhanced the killing activity of isolated NK cells. In addition, studies here demonstrated that the extract could enhance lysosomal enzyme activity and inhibit nitrite oxide (NO) production by murine peritoneal macrophages ex vivo, suggesting a potential anti-inflammatory effect in situ. The anti-inflammatory activity was concomitant with the cellular anti-oxidant effect in macrophages and splenocytes.

Limoniastrum guyonianum aqueous gall extract induces apoptosis in colorectal cancer cells by inhibiting calpain activity.

Several studies have reported that plant-derived natural products have cancer chemopreventive and chemotherapeutic properties. The aim of the present study was to determine the antiproliferative and pro-apoptotic potential of Limoniastrum guyonianum aqueous gall extract (G extract) on human colorectal cancer BE cell line and, if so, to characterize the mechanism involved. The G extract-induced growth inhibitory effect was associated with an arrest of cell cycle progression in G2/M phase as shown by the cell phase distribution. In addition, G extract promoted in a concentration-dependent manner these cells towards apoptosis as indicated by the presence of cleaved poly(ADP-ribose) polymerase (PARP). In order to characterize the mechanism involved in the antiproliferative and pro-apoptotic signaling pathway activated by G extract, calpain activity and the expression of the cell cycle inhibitor p16(INK4A) were determined. The present findings indicated that G extract exhibited significant inhibitory activity against calpain and caused a marked and concentration-dependent upregulation of p16(INK4A). These effects could be ascribed to the presence of condensed tannins and polyphenols such as epicatechin and epigallocatechin gallate in G extract.

Effect of Technological Factors on the Extraction of Polymeric Condensed Tannins from Acacia Species.

The aim of this research work was to investigate the influence of parameters such as particle size, mass/solvent ratio, temperature and spray drying on the tannin extraction process in order to develop cost-effective methods with better environmental and structural performance. The pods of Acacia nilotica ssp. tomentosa (ANT) were fractionated into three fractions, coarse fraction (C) (>2 mm), medium fraction (M) (1-2 mm), and fine fraction (F) < 1 mµ), and extracted with different water-to-pod ratios (2:1, 4:1 and 6:1) at different temperatures (30, 50 and 70 °C). The best results were scaled up using the three fractions of ANT, its bark and the bark of Acacia seyal var. seyal (ASS). Part of their extract was spray dried. The tannin content and total polyphenolic materials were evaluated using standard methods. Their adhesives were tested for their tensile strength. Tannins of ASS were characterized by 13C NMR and MALDI-TOF. The results revealed that the fine fraction (F) gave the highest percentage of tannins in both small and scaled-up experiments. The results of the tensile strength conformed to the European standard. The 13C NMR spectra of ANT and ASS showed that the bark contained condensed tannins mainly consisting of procyanidins/prodelphinidin of 70%/30% and 60%/40%, respectively. MALDI-TOF spectra confirmed the results obtained by 13C NMR and detailed the presence of flavonoid monomers and oligomers, some of which were linked to short carbohydrate monomers or dimers.

Preparation and fire resistance modification on tannin-based non-isocyanate polyurethane (NIPU) rigid foams.

Non-isocyanate polyurethane (NIPU) as a new type of polyurethane material has become a hot research topic in the polyurethane industry due to its no utilization of toxic isocyanates during the synthesis process. And the developing on recyclable biomass materials has also much attention in the industrial sector, hence the preparation and application of bio-based NIPU has also become a very meaningful study work. So, in this paper, tannin as a biomass material was used to synthesize tannin based non-isocyanate polyurethanes (TNIPU) resin, and then successfully prepared a self-blowing TNIPU foam at room temperature by using formic acid as initiator and glutaraldehyde as cross-linking agent. The compressive strength of this foam as high as 0.8 MPa, which is an excellent compressive performance. Meanwhile it will return to the state before compression when removing the pressure. This indicating that the foam has good toughness. In addition, formic acid can react with the amino groups in TNIPU to form amide substances, and generated enough heat to initiate the foaming process. Glutaraldehyde, as a crosslinking agent, reacts with the amino group in TNIPU to form a network structure system. By scanning electron microscope (SEM) observation of the cell shapes, it can be seen that the foam cells were uniform in size and shape, and the cell pores showed open and closed cells. The limiting oxygen index (LOI) tested value of this TNIPU foam is 24.45 % without any flame retardant added, but compared to the LOI value of polyurethane foam (17 %-19 %), TNIPU foam reveal a better fire resistance. It has a wider application prospect.

Preparation and characterization on the eco-friendly corn starch based adhesive of with salient water resistance, mildew resistance.

Starch adhesive is a commonly used bonding glue that is sustainable, formaldehyde-free and biodegradable. However, there are obviously some problems related to its high viscosity, poor water and mildew resistance. Hence, exploring a starch-based adhesive with good properties that satisfies the requirements of wood processing presents the context of the current research. Thus, corn starch was used as raw material to form oxidized starch (OCS) via oxidation using sodium periodate, it was reacted with a synthesis polyurea compound that prepared from hexanediamine-urea (HU) obtained by deamination to yield a oxidized starch-hexanediamine-urea adhesive (denoted hereafter as OCSHU). The oxidation process was optimized in terms of oxidant concentration, reaction time and temperature. Furthermore, the impact of HU addition on the mechanical properties of the adhesive was explored. Results indicate adhesive exhibited outstanding shear strength, when 13 % of NaIO4 was used as an oxidant to treat starch at 55 °C for 24 h, and involved in a subsequent reaction with 40 % of HU. The dry shear strength, 24 h cold water strength, 3 h hot water strength and 3 h boiling water strength are 1.84, 1.50, 1.32, and 1.31 MPa. Meantime, OCSHU adhesive solution revealed good storage stability whereas cured resin exhibited mildew resistance. The developed adhesive is a simple and green biomass wood adhesive.

Characterization of a composite based on Cissus dinklagei tannin resin.

The tannin extract of Cissus dinklagei was used in the preparation of a 3 % paraformaldehyde resin for the manufacture of particleboard. This tannin is of the procyanidin type associated with furan residues. The modulus of elasticity of the resin obtained after the thermomechanical analysis is 3825 MPa. The TGA performed on the panels obtained shows three degradation zones with a thermal stability zone between 74 and 210 °C. These panels have good thermomechanical properties. The values of the best density, internal bond, modulus of elasticity in flexion (MOE) and resistance to flexion (MOR) are respectively 658 kg/m3; 0.52 MPa; 2035.4 MPa; 16.3 MPa. These results classify this panel for generalinterior construction and furniture uses according to the NF EN 312 standard.

Systematic studies of tannin-formaldehyde aerogels: preparation and properties.

Gelation of tannin-formaldehyde (TF) solutions was systematically investigated by changing pH and concentration of TF resin in water. In this way we constructed the TF phase diagram, from which chemical hydrogels could be described, and also synthesized thermoreversible tannin-based hydrogels. Conditions of non-gelation were also determined. Hydrogels were dried in supercritical CO2, leading to a broad range of TF aerogels. The latter were investigated for volume shrinkage, total porosity, micro-, meso- and macropore volumes, Brunauer-Emmett-Teller (BET) surface area, microscopic texture, mechanical and thermal properties. All these properties are discussed in relation to each other, leading to an accurate and self-consistent description of these bioresource-based highly porous materials. The conditions for obtaining the highest BET surface area or mesopore volume were determined and explained in relation to the preparation conditions. The highest BET surface area, 880 m2 g-1, is remarkably high for organic aerogels derived from a natural resource.

Structural Variations in Biobased Polyfurfuryl Alcohol Induced by Polymerization in Water.

Poly(furfuryl alcohol) is a thermostable biobased thermoset. The polymerization of furfuryl alcohol (FA) is sensitive to a number of side reactions, mainly the opening of the furan ring into carbonyl species. Such carbonyls can be used to introduce new properties into the PFA materials through derivatization. Hence, better understanding of the furan ring opening is required to develop new applications for PFA. This article studies the structural discrepancies between a PFA prepared in neat conditions versus a PFA prepared in aqueous conditions, i.e., with more carbonyls, through NMR and MALDI ToF. Overall, the PFA prepared in water exhibited a structure more heterogeneous than the PFA prepared in neat conditions. The presence of ketonic derivatives such as enols and ketals were highlighted in the case of the aqueous PFA. In this line, the addition of water at the beginning of the polymerization stimulated the production of aldehydes by a factor two. Finally, the PFA prepared in neat conditions showed terminal lactones instead of aldehydes.

Preparation and characterization of the bonding performance of a starch-based water resistance adhesive by Schiff base reaction.

Starch is one of the important raw materials for the preparation of biomass adhesives for its good viscosity and low-cost properties. However, the drawbacks of poor water resistance and bonding performance seriously restrict its application in the wood industry. To resolve those problems, an environment-friendly renewable, and high water resistance starch-based adhesive (OSTH) was prepared with oxidized starch and hexanediamine by Schiff base reaction. In order to optimize the adhesive preparation process, the effect of different oxidation times and oxidant addition on the mechanical performance of plywood were investigated. In addition, the curing behavior characteristics, thermomechanical properties, and thermal stability of the OSTH adhesives were analyzed by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermogravimetric analysis (TG). Fourier-transform infrared (FTIR) spectrometry and Liquid Chromatography-Mass Spectrometry (LC-MS) were used to explain the reaction mechanisms involved. The results show this adhesive has an excellent bonding performance at the oxidation time of 12 h with 11 % (w/w, dry starch basis) NaIO4 as an oxidant. The dry shear strength, 24-hour cold water, and 3-hour hot water (63 °C) soaking shear strength of the plywood bonded with this resin were respectively 1.87 MPa, 0.96 MPa, and 0.91 MPa, which satisfied the standard requirement of GB/T 9846-2015 (≥0.7 MPa). Thus, this study provided a potential strategy to prepare starch-based wood adhesives with good bonding performance and water resistance.

Highly Branched Tannin-Tris(2-aminoethyl)amine-Urea Wood Adhesives.

Condensed tannin copolymerized with hyperbranched tris(2-aminoethyl)amine-urea formed by amine-amido deamination yields a particleboard thermosetting adhesive without any aldehydes satisfying the requirements of relevant standards for the particleboard internal bond strength. The tannin-triamine-urea cures well at 180 °C, a relatively low temperature for today's particleboard hot pressing. As aldehydes were not used, the formaldehyde emission was found to be zero, not even in traces due to the heating of wood. The effect is ascribed to the presence of many reactive sites, such as amide, amino, and phenolic groups belonging to the three reagents used. The tannin appears to function as an additional cross-linking agent, almost a nucleating agent, for the triamine-urea hyperbranched oligomers. Chemical analysis by MALDI ToF and 13C NMR has shown that the predominant cross-linking reaction is that of the substitution of the tannin phenolic hydroxyls by the amino groups of the triamine. The reaction of tannin with the still-free amide groups of urea is rather rare, but it may occur with the rarer tannin flavonoid units in which the heterocyclic ring is opened. Due to the temperature gradient between the surfaces and the board core in the particleboard during hot pressing, the type and the relative balance of covalent and ionic bonds in the resin structure may differ in the surfaces and the board core.

A Study of Concept to Prepare Totally Biosourced Wood Adhesives from Only Soy Protein and Tannin.

This is a study of concept on the initial application for wood adhesives totally biosourced from the covalent reaction between soy protein isolate (SPI) and a commercial flavonoid tannin, namely quebracho tannin. The adhesive is composed exclusively of the two vegetable biomaterials mentioned and thus is totally biosourced and non-toxic, as tannin has been classified as being not at all toxic by the European Commission REACH program. The pre-reaction between the two yielded the best plywood bonding results when limited to a temperature of 40 °C, final cross-linking being achieved during the plywood higher temperature hot pressing procedure, as for any other thermosetting adhesive. Pre-reaction at higher temperatures, namely 60 °C and 80 °C, achieved extensive premature cross-linking that lost any activity to cross-link further when hot pressed for preparing plywood. The reaction was followed by thermomechanical analysis, by matrix assisted laser desorption ionization time of flight (MALDI ToF) mass spectrometry, and by plywood shear strength tested dry, after a 24 h cold water soak and 1 h in boiling water. The adhesive of this approach lends itself to be further reinforced by the multitude of approaches on soy resins already developed by several other research groups.

Furanic Polymerization Causes the Change, Conservation and Recovery of Thermally-Treated Wood Hydrophobicity before and after Moist Conditions Exposure.

The Whilhelmy method of contact angle, wood thermal properties (TG/DTG), infrared spectroscopy, etc. was used to define the hydrophobicity of heat-treated beech and fir wood at increasing temperatures between 120 °C and 300 °C. By exposure to wet conditions during 1 week, the hydrophobic character obtained by the heat treatment remains constant heat-treated. Heat induced wood hydrophobation, was shown by CP MAS 13C NMR and MALDI ToF mass spectrometry to be mainly caused by furanic moieties produced from heat-induced hemicelluloses degradation. This is caused by the acid environment generated by the hydrolysis of the hemicelluloses acetyl groups. Furfural polymerizes to linear and branched oligomers and finally to water repellent, insoluble furanic resins. The water repellent, black colored, cross-linked polymerized furanic network is present throughout the heat-treated wood. Wood darkening as well as its water repellency due to increasing proportions of black colored furanic resins increase as a function of the increase with treating temperature, becoming particularly evident in the 200 to 300 °C treating temperature range.

Fully Biobased Adhesive from Glucose and Citric Acid for Plywood with High Performance.

Biomass-based adhesives have attracted much attention due to their eco-friendly, sustainable characteristics compared to formaldehyde-based adhesives; however, their low bonding strength and water resistance restrict their application. Thus, developing a high-performance biomass-based adhesive with excellent bonding strength and water resistance is necessary. In this work, a fully biomass-based citric acid-glucose (CAG) adhesive was produced by the esterification reaction of glucose and citric acid, which was validated by Fourier transform infrared (FT-IR), 13C nuclear magnetic resonance (13C NMR), and liquid chromatography-mass spectrometry (LC-MS). Furthermore, the properties of the CAG adhesive were tuned considering the effects of reaction time and molar ratio of citric acid/glucose (CA/G). It was revealed that increasing the molar ratio of CA/G is more advantageous to improve the shear strength and water resistance of plywood than the reaction time. The dry and wet strengths of plywood bonded by the CAG adhesive can reach the standard requirement (≥0.7 MPa) when the molar ratios of CA/G were more than 0.6 and the reaction time was 1 h. These results were better than those bonded by the urea-formaldehyde (UF) resin. Therefore, this green adhesive shows great potential to replace the existing industrial UF resin adhesives.

A Comparative Study of Several Properties of Plywood Bonded with Virgin and Recycled LDPE Films.

In this work, to better understand the bonding process of plastic plywood panels, the effects of recycled low-density polyethylene (rLDPE) film of three thicknesses (50, 100, and 150 µm) and veneers of four various wood species (beech, birch, hornbeam, and poplar) on the properties of panels were studied. The obtained properties were also compared with the properties of plywood panels bonded by virgin low-density polyethylene (LDPE) film. The results showed that properties of plywood samples bonded with rLDPE and virgin LDPE films differ insignificantly. Samples bonded with rLDPE film demonstrated satisfactory physical and mechanical properties. It was also established that the best mechanical properties of plywood are provided by beech veneer and the lowest by poplar veneer. However, poplar plywood had the best water absorption and swelling thickness, and the bonding strength at the level of birch and hornbeam plywood. The properties of rLDPE-bonded plywood improved with increasing the thickness of the film. The panels bonded with rLDPE film had a close-to-zero formaldehyde content (0.01-0.10 mg/m2·h) and reached the super E0 emission class that allows for defining the laboratory-manufactured plastic-bonded plywood as an eco-friendly composite.

A Green Resin Wood Adhesive from Synthetic Polyamide Crosslinking with Glyoxal.

Glyoxal is considered to be the most likely substitute for formaldehyde to synthesize resin adhesives for wood bonding due to its reactivity, structural characteristics, being non-toxic, low volatility, and acceptable cost. Regrettably, the performance of the resin synthesized using glyoxal to directly replace all formaldehyde is not totally satisfactory, especially as it has almost no water resistance. This makes such a simple alternative fail to be suitable for industrial production. To prepare an environment-friendly glyoxal-based adhesive with good bonding performance, the work presented here relies first on reacting citric acid and hexamethylene diamine, producing a polyamide, with glyoxal, and then crosslinking it, thus synthesizing a thermosetting resin (namely CHG) adhesive and applying it for plywood bonding. The plywood prepared exhibits excellent dry and wet shear strength, which are better than GB/T9846-2015 standard requirements (≥0.7 MPa), and even after being soaked in hot water at 63 °C for 3 h, its strength is still as high as 1.35 MPa. The CHG resin is then potentially an adhesive for industrial application for replacing UF (urea-formaldehyde) and MUF (melamine-urea-formaldehyde) adhesives for wood composites.

Modification of Ramie Fiber via Impregnation with Low Viscosity Bio-Polyurethane Resins Derived from Lignin.

The purpose of this study was to prepare low-viscosity lignin-based polyurethane (LPU) resins for the modification of ramie (Boehmeria nivea (L.) Gaudich) fiber via impregnation to improve the fiber's thermal and mechanical properties. Low-viscosity LPU resins were prepared by dissolving lignin in 20% NaOH and then adding polymeric 4,4-methane diphenyl diisocyanate (pMDI, 31% NCO) with a mole ratio of 0.3 NCO/OH. Ramie fiber was impregnated with LPU in a vacuum chamber equipped with a two-stage vacuum pump. Several techniques such as Fourier-transform infrared (FTIR) spectroscopy, differential scanning calorimetry, thermogravimetric analysis, pyrolysis-gas chromatography-mass spectroscopy, field emission-scanning electron microscopy coupled with energy dispersive X-ray (EDX), and a universal testing machine were used to characterize lignin, LPU, and ramie fiber. The LPU resins had low viscosity ranging from 77 to 317 mPa·s-1. According to FTIR and EDX analysis, urethane bonds were formed during the synthesis of LPU resins and after impregnation into ramie fibers. After impregnation, the reaction between the LPU's urethane group and the hydroxy group of ramie fiber increased thermal stability by an average of 6% and mechanical properties by an average of 100% compared to the untreated ramie fiber. The highest thermal stability and tensile strength were obtained at ramie impregnated with LPU-ethyl acetate for 30 min, with a residual weight of 22% and tensile strength of 648.7 MPa. This study showed that impregnation with LPU resins can enhance the thermal and mechanical properties of fibers and increase their wider industrial utilization in value-added applications.