Efficient Triazine Derivatives for Collagenous Materials Stabilization

Nowadays, the need to reduce plastic waste and scantly biodegradable fossil-based products is of great importance. The use of leather as an alternative to synthetic materials is gaining renewed interest, but it is fundamental that any alternative to plastic-based materials should not generate an additional environmental burden. In the present work, a simple protocol for collagen stabilization mediated by 2-chloro-4,6-diethoxy-1,3,5-triazine (CDET) and a tert-amine has been described. Different tert-amines were tested in combination with CDET in a standard amidation reaction between 2-phenylethylamine and benzoic acid. Best performing condensation systems have been further tested for the cross-linking of both collagen powder and calf hides. The best results were achieved with CDET/NMM giving high-quality leather with improved environmental performances.Nowadays, the need to reduce plastic waste and scantly biodegradable fossil-based products is of great importance. The use of leather as an alternative to synthetic materials is gaining renewed interest, but it is fundamental that any alternative to plastic-based materials should not generate an additional environmental burden. In the present work, a simple protocol for collagen stabilization mediated by 2-chloro-4,6-diethoxy-1,3,5-triazine (CDET) and a tert-amine has been described. Different tert-amines were tested in combination with CDET in a standard amidation reaction between 2-phenylethylamine and benzoic acid. Best performing condensation systems have been further tested for the cross-linking of both collagen powder and calf hides. The best results were achieved with CDET/NMM giving high-quality leather with improved environmental performances

Polyamidoamide Dendrimers and Cross-Linking Agents for Stabilized Bioenzymatic Resistant Metal-Free Bovine Collagen

The work reports the use of polyamidoamine dendrimers (PAMAM) and a cross-linking agent, 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide/N-hydroxysuccinimide (EDC/NHS) or 4-(4,6-dimethoxy[1,3,5]triazin-2-yl)-4-methyl-morpholinium chloride (DMTMM), for the thermal stabilization of dermal bovine collagen. The efficiency of EDC/NHS/PAMAM and DMTMM/PAMAM in the cross-linking of collagen is correlated to the increase of the collagen shrinkage temperature (Ts), measured by differential scanning calorimetry (DSC). An alternative enzymatic protocol was adopted to measure the degradability of EDC/NHS/PAMAM tanned hides; these data are correlated to the thermal stability values measured by DSC. In the presence of PAMAMs, EDC/NHS provides very high stabilization of bovine dermal collagen, giving Ts of up to 95 °C, while DMTMM achieves lower stabilization. Preliminary tanning tests carried out in best reaction conditions show that EDC/NHS/PAMAM could be an interesting, environmentally-sustainable tanning system which is completely free of metals, formaldehyde, and phenols. Two new unreported dendrimeric species were synthesized and employed

Waste Cooking Oil as Eco-Friendly Rejuvenator for Reclaimed Asphalt Pavement

Over 50 MioT of Waste Cooking Oil (WCO) was collected worldwide in 2020 from domestic and industrial activities, constituting a potential hazard for both water and land environments, and requiring appropriate disposal management strategies. In line with the principles of circular economy and eco-design, in this paper an innovative methodology for the valorisation of WCO as a rejuvenating agent for bitumen 50/70 coming from Reclaimed Asphalt Pavement (RAP) is reported. In particular, WCO or hydrolysed WCO (HWCO) was modified by transesterification or amidation reactions to achieve various WCO esters and amides. All samples were characterised by nuclear magnetic resonance, melting, and boiling point. Since rejuvenating agents for RAP Cold Mix Asphalt require a melting point ≤0 °C, only WCO esters could further be tested. Efficiency of WCO esters was assessed by means of the Asphaltenes Dispersant Test and the Heithaus Parameter. In particular, bitumen blends containing 25 wt% of WCO modified with 2-phenylethyl alcohol, showed high dispersing capacity in n-heptane even after a week, compared to bitumen alone (1 h). Additionally, the Heithaus Parameter of this bitumen blend was almost three times higher than bitumen alone, further demonstrating beneficial effects deriving from the use of WCO esters as rejuvenating agents

Sustainable Triazine-Based Dehydro-Condensation Agents for Amide Synthesis

Conventional methods employed today for the synthesis of amides often lack of economic and environmental sustainability. Triazine-derived quaternary ammonium salts, e.g., 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM(Cl)), emerged as promising dehydro-condensation agents for amide synthesis, although suffering of limited stability and high costs. In the present work, a simple protocol for the synthesis of amides mediated by 2-chloro-4,6-dimethoxy-1,3,5-triazine (CDMT) and a tert-amine has been described and data are compared to DMTMM(Cl) and other CDMT-derived quaternary ammonium salts (DMT-Ams(X), X: Cl− or ClO4−). Different tert-amines (Ams) were tested for the synthesis of various DMT-Ams(Cl), but only DMTMM(Cl) could be isolated and employed for dehydro-condensation reactions, while all CDMT/tert-amine systems tested were efficient as dehydro-condensation agents. Interestingly, in best reaction conditions, CDMT and 1,4-dimethylpiperazine gave N-phenethyl benzamide in 93% yield in 15 min, with up to half the amount of tert-amine consumption. The efficiency of CDMT/tert-amine was further compared to more stable triazine quaternary ammonium salts having a perchlorate counter anion (DMT-Ams(ClO4)). Overall CDMT/tert-amine systems appear to be a viable and more economical alternative to most dehydro-condensation agents employed today

Recyclable Ir Nanoparticles for the Catalytic Hydrogenation of Biomass-Derived Carbonyl Compounds

The valorisation of biomass-derived platform chemicals via catalytic hydrogenation is an eco-friendly tool which allows us to recover bio-based building blocks and produce fine chemicals with high industrial appeal. In the present study, a novel surfactant-type triazolyl-thioether ligand was prepared, showing excellent catalytic activity in the presence of bis(1,5-cyclooctadiene)diiridium(I) dichloride [Ir(COD)Cl]2 for the hydrogenation of furfural, cinnamaldehyde, levulinic acid, 5-hydroxymethylfurfural, vanillin, and citral. Easy recovery by liquid/liquid extraction allowed us to recover the catalyst, which could then be efficiently recycled up to 11 times for the hydrogenation of furfural. In-depth analysis revealed the formation of spherical structures with metal nanoparticles as big as 2–6 nm surrounded by the anionic ligand, preventing iridium nanoparticle degradation

Development of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride cross-linked carboxymethyl cellulose films

First example of the use of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methyl-morpholinium chloride (DMTMM) as cross-linking agent for the development of carboxymethyl cellulose (CMC) films for food packaging is reported. Influence of different wt % of DMTMM and glycerol on the physical-mechanical properties of CMC films was investigated. The presence of DMTMM effectively improved moisture uptake, moisture content, water vapour permeability, water solubility of the films, oil resistance together with good biodegradability. Best compromise between high water resistance, vapour permeability and mechanical properties was accomplished with 5 wt % DMTMM and 50 wt % glycerol giving tensile strength and elongation at break of 52.25 ± 4.33 and 37.32 ± 2.04 respectively. DSC, TGA and SEM analysis further confirmed CMC cross-linking by DMTMM. All films prepared showed low opacity and high transparencies. Therefore, data reported show that DMTMM can efficiently crosslink CMC to produce films for food packaging.First example of the use of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methyl-morpholinium chloride (DMTMM) as cross-linking agent for the development of carboxymethyl cellulose (CMC) films for food packaging is reported. Influence of different wt % of DMTMM and glycerol on the physical-mechanical properties of CMC films was investigated. The presence of DMTMM effectively improved moisture uptake, moisture content, water vapour permeability, water solubility of the films, oil resistance together with good biodegradability. Best compromise between high water resistance, vapour permeability and mechanical properties was accomplished with 5 wt % DMTMM and 50 wt % glycerol giving tensile strength and elongation at break of 52.25 ± 4.33 and 37.32 ± 2.04 respectively. DSC, TGA and SEM analysis further confirmed CMC cross-linking by DMTMM. All films prepared showed low opacity and high transparencies. Therefore, data reported show that DMTMM can efficiently cross-link CMC to produce films for food packaging

Synthesis of Amidation Agents and Their Reactivity in Condensation Reactions

Nowadays, the development of new approaches which smartly bypass the use of harsh reaction conditions and hazardous chemicals covers a pivotal role. In this research paper the synthesis, characterization, and application of novel libraries of triazine bis-quaternary ammonium salts, employed as coupling agents to produce amides is reported. Full characterization of the novel compounds by 1H and 13C NMR, FT-IR spectroscopy, ESI-HRMS, and elemental analysis is provided. Furthermore, a comparison in terms of activity of the preformed triazine compounds versus in situ formulations has been evaluated for the formation of amides in the presence of phenylethylamine and different aliphatic or aromatic acids. A possible correlation between the chemical structure of the triazine and their reactivity for the formation of the triazine bis-quaternary ammonium salts is also reported. Moreover, best performing condensation agents have been further tested for the cross-linking of collagen powder as possible wet white tanning systems, for sustainable and environmentally friendly leather tanning

By-products from mechanical recycling of polyolefins improve hot mix asphalt performance

Waste of polyolefin (WOPO), the sinking fraction of polyolefin recycling, is today a production waste sent to incineration. This work reports a method for the recycling of WOPO as efficient additives to produce hot mix asphalt (HMA). Physical-mechanical characteristics of HMA containing bitumen 50/70 and WOPO were compared to PE/PP mixed polyolefin (MPO) and standard HMA control specimen. Modified HMA mixtures were characterized by density, air voids, indirect tensile strength, indirect traction coefficient, Marshall stability and quotation. Atmospheric emissions for HMA containing WOPO were proven to comply within Italian legal requirements. Data acquired demonstrate that HMA containing 4 wt% of grinded WOPO by weight of asphalt binder may be efficiently employed as flexible and resistant mixture for road pavement. Environmental and economic data reported further highlight the impact of this technology, not only for asphalt producers, but also for recycling facilities, improving plastic recycling, reducing plastic incineration, waste management costs and greenhouse emissions