Chitosan as a Bio-Based Ligand for the Production of Hydrogenation Catalysts.

Bio-based polymers are attracting increasing interest as alternatives to harmful and environmentally concerning non-biodegradable fossil-based products. In particular, bio-based polymers may be employed as ligands for the preparation of metal nanoparticles (M(0)NPs). In this study, chitosan (CS) was used for the stabilization of Ru(0) and Rh(0) metal nanoparticles (MNPs), prepared by simply mixing RhCl3 × 3H2O or RuCl3 with an aqueous solution of CS, followed by NaBH4 reduction. The formation of M(0)NPs-CS was confirmed by Fourier Transform Infrared Spectroscopy (FT-IR), Differential Scanning Calorimetry (DSC), Thermal Gravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), Energy-Dispersive X-ray Analysis (EDX), Transmission Electron Microscopy (TEM) and X-ray Diffraction (XRD). Their size was estimated to be below 40 nm for Rh(0)-CS and 10nm for Ru(0)-CS by SEM analysis. M(0)NPs-CS were employed for the hydrogenation of (E)-cinnamic aldehyde and levulinic acid. Easy recovery by liquid-liquid extraction made it possible to separate the catalyst from the reaction products. Recycling experiments demonstrated that M(0)NPs-CS were highly efficient up to four times in the best hydrogenation conditions. The data found in this study show that CS is an excellent ligand for the stabilization of Rh(0) and Ru(0) nanoparticles, allowing the production of some of the most efficient, selective and recyclable hydrogenation catalysts known in the literature.

Mechanical and Physical Changes in Bio-Polybutylene-Succinate Induced by UVC Ray Photodegradation.

Bio-polybutylene succinate (PBS) is a biodegradable polymer obtained from renewable feedstock having physical-mechanical properties like traditional low-density polyethylene (LDPE). PBS is employed by many manufacturing sectors, from biomedical to agri-food and cosmetics. Although some studies have already evaluated the resistance of PBS to photodegradation caused by natural outdoor solar exposure (UVA-UVB), a systematic study on the resistance to degradation caused by exposure to UVC rays, which is the subject of this study, has not yet been carried out. PBS was exposed to UVC either neat or filled with 2% carbon black (CB). Mechanical and physical characterization (tensile, hardness, calorimetry, contact angle, morphology, and surface roughness analyses) indicates that the bulk and surface properties of the polymer matrix changes after exposure to UVC radiations, due to a severe degradation. However, the presence of carbon black compensates for the degradation phenomenon. Because UVC rays are used for the sterilization process, necessary in applications such as biomedical, cosmetic, pharmaceutical, food, and other products, a comparison of the protocol used in this paper with the literature's data has been reported and discussed.

Use of carboxymethyl cellulose as binder for the production of water-soluble catalysts.

Bio-based polymers are materials of high interest given the harmful environmental impact that involves the use of non-biodegradable fossil products for industrial applications. These materials are also particularly interesting as bio-based ligands for the preparation of metal nanoparticles (MNPs), employed as catalysts for the synthesis of high value chemicals. In the present study, Ru (0) and Rh(0) Metal Nanoparticles supported on Sodium Carboxymethyl cellulose (MNP(0)s-CMCNa) were prepared by simply mixing RhCl3x3H2O or RuCl3 with an aqueous solution of CMCNa, followed by NaBH4 reduction. The formation of MNP(0)s-CMCNa was confirmed by FT-IR and XRD, and their size estimated to be around 1.5 and 2.2 nm by TEM analysis. MNP(0)s-CMCNa were employed for the hydrogenation of (E)-cinnamic aldehyde, furfural and levulinic acid. Hydrogenation experiments revealed that CMCNa is an excellent ligand for the stabilization of Rh(0) and Ru(0) nanoparticles allowing to obtain high conversions (>90 %) and selectivities (>98 %) with all substrates tested. Easy recovery by liquid/liquid extraction allowed to separate the catalyst from the reaction products, and recycling experiments demonstrated that MNPs-CS were highly efficiency up to three times in best hydrogenation conditions.

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.

May 1,3,5-Triazine derivatives be the future of leather tanning? A critical review.

Leather is produced by a multi-step process among which the tanning phase is the most relevant, transforming animal skin collagen into a stable, non-putrescible material used to produce a variety of different goods, for the footwear, automotive, garments, and sports industry. Most of the leather produced today is tanned with chromium (III) salts or alternatively with aldehydes or synthetic tannins, generating high environmental concern. Over the years, high exhaustion tanning systems have been developed to reduce the environmental impact of chromium salts, which nevertheless do not avoid the use of metals. Chrome-free alternatives such as aldehydes and phenol based synthetic tannins, are suffering from Reach restrictions due to their toxicity. Thus, the need for environmentally benign and economically sustainable tanning agents is increasingly urgent. In this review, the synthesis, use and tanning mechanism of a new class of tanning agents, 1,3,5-triazines derivatives, have been reported together with organoleptic, physical mechanical characteristics of tanned leather produced. Additionally environmental performance and economic data available for 1,3,5-triazines have been compared with those of a standard basic chromium sulphate tanning process, evidencing the high potentiality for sustainable, metal, aldehyde, and phenol free leather manufacturing.

Plastics today: Key challenges and EU strategies towards carbon neutrality: A review.

Never as today the need for collaborative interactions between industry, the scientific community, NGOs, policy makers and citizens has become crucial for the development of shared political choices and protection of the environment, for the safeguard of future generations. The complex socio-economic and environmental interconnections that underlie the EU strategy of the last years, within the framework of the Agenda 2030 and the green deal, often create perplexity and confusion that make difficult to outline the definition of a common path to achieve carbon neutrality and "net zero emissions" by 2050. Scope of this work is to give a general overview of EU policies, directives, regulations, and laws concerning polymers and plastic manufacturing, aiming to reduce plastic pollution, allowing for a better understanding of the implications that environmental concern and protection may generate from a social-economical point of view.

Agri-Food Wastes for Bioplastics: European Prospective on Possible Applications in Their Second Life for a Circular Economy.

Agri-food wastes (such as brewer's spent grain, olive pomace, residual pulp from fruit juice production, etc.) are produced annually in very high quantities posing a serious problem, both environmentally and economically. These wastes can be used as secondary starting materials to produce value-added goods within the principles of the circular economy. In this context, this review focuses on the use of agri-food wastes either to produce building blocks for bioplastics manufacturing or biofillers to be mixed with other bioplastics. The pros and cons of the literature analysis have been highlighted, together with the main aspects related to the production of bioplastics, their use and recycling. The high number of European Union (EU)-funded projects for the valorisation of agri-food waste with the best European practices for this industrial sector confirm a growing interest in safeguarding our planet from environmental pollution. However, problems such as the correct labelling and separation of bioplastics from fossil ones remain open and to be optimised, with the possibility of reuse before final composting and selective recovery of biomass.

Boosting physical-mechanical properties of adipic acid/chitosan films by DMTMM cross-linking.

In this paper we present a novel strategy to easily prepare biodegradable chitosan derived films as new packaging systems. Combination of chitosan, adipic acid and 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methyl-morpholinium chloride (DMTMM) allowed to obtain high-performing cross-linked films. Biobased glycerol was employed as plasticizer. An in-depth study was performed on ten different samples in order to evaluate the role of DMTMM as cross-linking agent. Experimental data showed that 15 wt% of DMTMM enhanced moisture content and moisture uptake (10.42% and 11.11%), water vapor permeability (0.13 10-7 g m-1 h-1 Pa-1) and good UV barrier properties. Additionally, 30 wt% of DMTMM significantly increased the tensile strength of films up to 83 MPa and elongation at break values reached 39.7%. Thermogravimetric, IR, XRD and SEM analysis confirmed that physical-mechanical properties of the obtained films were considerably improved, due to cross-linking by DMTMM, demonstrating promising properties for packaging applications.

Recent Advancements in Plastic Packaging Recycling: A Mini-Review.

Today, the scientific community is facing crucial challenges in delivering a healthier world for future generations. Among these, the quest for circular and sustainable approaches for plastic recycling is one of the most demanding for several reasons. Indeed, the massive use of plastic materials over the last century has generated large amounts of long-lasting waste, which, for much time, has not been object of adequate recovery and disposal politics. Most of this waste is generated by packaging materials. Nevertheless, in the last decade, a new trend imposed by environmental concerns brought this topic under the magnifying glass, as testified by the increasing number of related publications. Several methods have been proposed for the recycling of polymeric plastic materials based on chemical or mechanical methods. A panorama of the most promising studies related to the recycling of polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), and polystyrene (PS) is given within this review.

Synthesis and Antimicrobial Evaluation of Bis-morpholine Triazine Quaternary Ammonium Salts.

Efficient, environmentally and economically sustainable, and nontoxic antibacterial products are of global relevance in the fight against microorganism contamination. In this work, an easy and straightforward method for the synthesis of bis-morpholino triazine quaternary ammonium salts (bis-mTQAS) is reported, starting from 2,4,6-trichloro-1,3,5-triazine or 2,4-dichloro-6-methoxy-1,3,5-triazine and various N-alkylmorpholines. Bis-mTQAS were tested as antimicrobials against Gram-negative and Gram-positive bacterial strains. The best-performing bis-mTQAS were found to achieve total disinfection against Staphylococcus aureus ATCC 25923 and Escherichia coli ATCC 25922 at 50 and 400 µg/mL, respectively. Distinctively, bis-mTQAS with the highest antimicrobial efficiency had lowest cytotoxicity.

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.

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.

Sustainable triazine-derived quaternary ammonium salts as antimicrobial agents.

The first examples of highly efficient antimicrobial triazine-derived bis imidazolium quaternary ammonium salts (TQAS) are reported. TQAS have been prepared with an easy, atom efficient, economically sustainable strategy and tested as antimicrobial agents, reaching MIC values below 10 mg L-1. Distinctively, TQAS have low MIC and low cytotoxicity.

Development of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methyl-morpholinium 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 cross-link CMC to produce films for food packaging.

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.

Synthesis, characterization and catalytic activity of novel ruthenium complexes bearing NNN click based ligands.

Novel air stable ruthenium(ii) complexes bearing tridentate ligands bis((1-benzyl-1H-1,2,3-triazol-4-yl)methyl)amine (L1), 1-(1-benzyl-1H-1,2,3-triazol-4-yl)-N-(pyridin-2-ylmethyl)methanamine (L2) or 2-(4-phenyl-1H-1,2,3-triazol-1-yl)-N-(pyridin-2-ylmethyl)ethan-1-amine (L3) were synthesised. The nitrogen based ligands were easily prepared by virtue of click chemistry using cheap and commercially available reagents. The ruthenium complexes were obtained by heating the Ru(PPh3)3Cl2 precursor and the tridentate NNN ligand in toluene under reflux for 2 hours, achieving yields of 82-87%. These complexes were fully characterized by means of NMR, FT-IR and high resolution ESI spectroscopy. The crystal structure of one of the complexes was determined. These complexes showed excellent activity and selectivity in the hydrogenation of ketones and aldehydes. DFT calculations show that complex 3 may react through an outer-sphere catalytic cycle rather than via an inner-sphere mechanism.

Efficient Chemo-Enzymatic Transformation of Animal Biomass Waste for Eco-Friendly Leather Production.

Enzymatically processed animal biomass derived from treated bovine hides (wet blue scraps) is herein used as building block for the synthesis of a novel biopolymer. An enzymatic hydrolysis process allows to produce water-soluble lower molecular weight proteins (Bio-A), which are then reacted with glycerol and maleic anhydride (MA) in order to obtain a new intermediate (Bio-IA). With Bio-IA in hand, co-polymerization in the presence of acrylic acid is then carried out. Hydrolysed biomass, intermediates and the final biopolymer (Bio-Ac) have been characterized by means of NMR, FTIR and GPC analysis. Bio-Ac shows good performance when used as retanning agent to produce leather. Physical and mechanical properties of the leather treated with Bio-Ac have been compared with acrylic resin retanned leather, showing similar performance. The reported protocol represents an environmental-friendly interesting alternative to traditional petrochemical based retanning agents, commonly used by the leather industry.

An alternative stereoselective synthesis of (R)- and (S)-Rosaphen® via asymmetric catalytic hydrogenation.

We report an alternative synthesis of the two enantiomers of the floral fragrance Rosaphen®. The key intermediate 2-methyl-5-phenylpentanoic acid 3 is synthesized via asymmetric hydrogenation (ee up to 99%) in the presence of an in situ prepared ruthenium catalyst containing the chiral ferrocenyl phosphine Mandyphos-4.