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.

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.

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.

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.

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.

Carbon Dots from Sugars and Ascorbic Acid: Role of the Precursors on Morphology, Properties, Toxicity, and Drug Uptake.

There is the need for reproducible, simple, high-yielding synthetic protocols aimed at obtaining carbon dots (CDs) with controlled fluorescence, photothermal and photochemical behavior, surface properties, biocompatibility, tumor targeting ability, drug absorption biodistribution, and tumor uptake. This Letter describes a systematic study on the effect of glucose, fructose, and ascorbic acid as starting materials for the preparation of highly luminescent CDs, characterized by a blue emission. Their composition and morphology are investigated by titration of OH surface groups, spectroscopic techniques, and high-resolution transmission electron microscopy (HR-TEM), and their toxicity was tested toward HeLa cells. CDs made using fructose were toxic, while those made from glucose and ascorbic acid showed good biocompatibility. The reproducible and simple synthetic procedure yields luminescent biomass-derived CDs for combined cancer therapy and diagnostics. Their doxorubicin (DOX) drug uptake was measured by spectrofluorimetry, indicating a crucial role of the morphologies of the CDs in controlling DOX loading. The glucose derived CDs showed up to 28% w/w of DOX loading.