Designing a circular carbon and plastics economy for a sustainable future.

The linear production and consumption of plastics today is unsustainable. It creates large amounts of unnecessary and mismanaged waste, pollution and carbon dioxide emissions, undermining global climate targets and the Sustainable Development Goals. This Perspective provides an integrated technological, economic and legal view on how to deliver a circular carbon and plastics economy that minimizes carbon dioxide emissions. Different pathways that maximize recirculation of carbon (dioxide) between plastics waste and feedstocks are outlined, including mechanical, chemical and biological recycling, and those involving the use of biomass and carbon dioxide. Four future scenarios are described, only one of which achieves sufficient greenhouse gas savings in line with global climate targets. Such a bold system change requires 50% reduction in future plastic demand, complete phase-out of fossil-derived plastics, 95% recycling rates of retrievable plastics and use of renewable energy. It is hard to overstate the challenge of achieving this goal. We therefore present a roadmap outlining the scale and timing of the economic and legal interventions that could possibly support this. Assessing the service lifespan and recoverability of plastic products, along with considerations of sufficiency and smart design, can moreover provide design principles to guide future manufacturing, use and disposal of plastics.

Cascade degradation and upcycling of polystyrene waste to high-value chemicals.

Plastic waste represents one of the most urgent environmental challenges facing humankind. Upcycling has been proposed to solve the low profitability and high market sensitivity of known recycling methods. Existing upcycling methods operate under energy-intense conditions and use precious-metal catalysts, but produce low-value oligomers, monomers, and common aromatics. Herein, we report a tandem degradation-upcycling strategy to exploit high-value chemicals from polystyrene (PS) waste with high selectivity. We first degrade PS waste to aromatics using ultraviolet (UV) light and then valorize the intermediate to diphenylmethane. Low-cost AlCl3 catalyzes both the reactions of degradation and upcycling at ambient temperatures under atmospheric pressure. The degraded intermediates can advantageously serve as solvents for processing the solid plastic wastes, forming a self-sustainable circuitry. The low-value-input and high-value-output approach is thus substantially more sustainable and economically viable than conventional thermal processes, which operate at high-temperature, high-pressure conditions and use precious-metal catalysts, but produce low-value oligomers, monomers, and common aromatics. The cascade strategy is resilient to impurities from plastic waste streams and is generalizable to other high-value chemicals (e.g., benzophenone, 1,2-diphenylethane, and 4-phenyl-4-oxo butyric acid). The upcycling to diphenylmethane was tested at 1-kg laboratory scale and attested by industrial-scale techno-economic analysis, demonstrating sustainability and economic viability without government subsidies or tax credits.

Red Light-Emitting Water-Soluble Luminescent Iridium-Containing Polynorbornenes: Synthesis, Characterization and Oxygen Sensing Properties in Biological Tissues In Vivo.

New water-soluble polynorbornenes P1-P4 containing oligoether, amino acid groups and luminophoric complexes of iridium(III) were synthesized by ring-opening metathesis polymerization. The polymeric products in organic solvents and in water demonstrate intense photoluminescence in the red spectral region. The polymers P1 and P3 with 1-phenylisoquinoline cyclometalating ligands in iridium fragments reveal 4-6 fold higher emission quantum yields in solutions than those of P2 and P4 that contain iridium complexes with 1-(thien-2-yl)isoquinoline cyclometalating ligands. The emission parameters of P1-P4 in degassed solutions essentially differ from those in the aerated solutions showing oxygen-dependent quenching of phosphorescence. Biological testing of P1 and P3 demonstrates that the polymers do not penetrate into live cultured cancer cells and normal skin fibroblasts and do not possess cytotoxicity within the concentrations and time ranges reasonable for biological studies. In vivo, the polymers display longer phosphorescence lifetimes in mouse tumors than in muscle, as measured using phosphorescence lifetime imaging (PLIM), which correlates with tumor hypoxia. Therefore, preliminary evaluation of the synthesized polymers shows their suitability for noninvasive in vivo assessments of oxygen levels in biological tissues.

Hydrophobization of arabinoxylan with n-butyl glycidyl ether yields stretchable thermoplastic materials.

Hemicelluloses are regarded as one of the first candidates for the development of value-added materials due to their renewability, abundance, and functionality. However, because most hemicelluloses are brittle, they can only be processed as a solution and cannot be processed using industrial melt-based polymer processing techniques. In this study, arabinoxylan (AX) was hydrophobized by incorporating butyl glycidyl ether (BuGE) into the hydroxyl groups through the opening of the BuGE epoxide ring, yielding alkoxy alcohols with terminal ethers. The formed BuGE derivatives were melt processable and can be manufactured into stretchable thermoplastic films through compression molding, which has never been done before with hemicellulose modified in a single step. The structural and thermomechanical properties of the one-step synthesis approach were compared to those of a two-step synthesis with a pre-activation step to demonstrate its robustness. The strain at break for the one-step synthesized AX thermoplastic with 3 mol of BuGE is ≈200%. These findings suggest that thermoplastic polymers can be composited with hemicelluloses or that thermoplastic polymers made entirely of hemicelluloses can be designed as packaging and stretchable electronics supports.

Efficient Design to Monitor the Site-specific Sustained Release of a Non-Emissive Anticancer Drug.

A pH-responsive smart nanocarrier with significant components was synthesized by conjugating the non-emissive anticancer drug methyl orange and polyethylene glycol derived folate moiety to the backbone of polynorbornene. Complete synthesis procedure and characterization methods of three monomers included in the work: norbornene-derived Chlorambucil (Monomer 1), norbornene grafted with polyethylene glycol, and folic acid (Monomer 2) and norbornene attached methyl orange (Monomer 3) connected to the norbornene backbone through ester linkage were clearly discussed. Finally, the random copolymer CHO PEG FOL METH was synthesized by ring-opening metathesis polymerization (ROMP) using Grubbs' second-generation catalyst. Advanced polymer chromatography (APC) was used to find the final polymer's molecular weight and polydispersity index (PDI). Dynamic light scattering, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were utilized to explore the prodrug's size and morphology. Release experiments of the anticancer drug, Chlorambucil and the coloring agent, methyl orange, were performed at different pH and time. Cell viability assay was carried out for determining the rate of survived cells, followed by the treatment of our final polymer named CHO PEG FOL METH.

Brominated flame retardants (BFRs) in contaminated food contact articles: identification using DART-HRMS and GC-MS.

Any food contact material (FCM) must be approved by the US FDA as being compliant with Title 21 of the Code of Federal regulations Parts 170-199, and/or obtain a non-objection letter through the Food Contact Notification Process, before being placed into the United States market. In the past years, several scientific articles identified FCM or more specifically, food contact articles (FCAs), which were contaminated with brominated flame retardants (BFRs) in the European Union. Prior research has suggested the source of BFR contamination was likely poorly recycled plastics containing waste electrical and electronic equipment (WEEE). We conducted a retail survey to evaluate the presence of BFR-contaminated reusable FCA in the US market. Using a Direct Analysis in Real Time ionisation High-Resolution Mass Spectrometry (DART-HRMS) screening technique and extraction gas chromatography-mass spectrometry (GC-MS) confirmation we were able to identify BFRs present in retail FCAs. Among non-targeted retail samples, 4 of 49 reusable FCAs contained 1-4 BFRs each. The identified BFRs, found in greatest estimated concentrations, were 2,4,6-tribromophenol (TBP), 3,3',5,5'-tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD), decabromodiphenylethane (DBDPE) and decabromodiphenylether (BDE-209). A second targeted FCA sampling (n = 28) confirmed these BFRs persisted in similar articles. Combined sample sets (n = 77) estimated DART false-positive/negative incidences of 5% & 4%, respectively, for BFR screening of FCAs. Because the presence of BFRs in some contaminated FCAs has been demonstrated and since these compounds are possible migrants into food, further studies are warranted. In order to estimate the potential exposure of the identified BFRs and conduct corresponding risk assessments, the next and logical step will be to study the mass transfer of BFRs from the contaminated FCM into food simulants and food.

Tethered Tungsten-Alkylidenes for the Synthesis of Cyclic Polynorbornene via Ring Expansion Metathesis: Unprecedented Stereoselectivity and Trapping of Key Catalytic Intermediates.

This report describes an approach for preparing tethered tungsten-imido alkylidene complexes featuring a tetra-anionic pincer ligand. Treating the tungsten alkylidyne [tBuOCO]W≡CtBu(THF)2 (1) with isocyanates (RNCO; R = tBu, Cy, and Ph) leads to cycloaddition occurring exclusively at the C═N bond to generate the tethered tungsten-imido alkylidenes (6-NR). Unanticipated intermediates reveal themselves, including the discovery of [(O2CtBuC═)W(η2-(N,C)-RNCO)(THF)] (11-R) and an unprecedented decarbonylation product [(tBuOCO)W(≡NR)(tBuCCO)] (14-R), on the pathway to the formation of 6-NR. Complex 11-R is kinetically stable for sterically bulky isocyanate R = tBu (11-tBu) and is isolated and characterized by single-crystal X-ray diffraction. Finally, adding to the short list of catalysts capable of ring expansion metathesis polymerization (REMP), complexes 6-NR and 11-tBu are active for the stereoselective synthesis of cyclic polynorbornene.

Preparation and characterization of solvent-free fluids reinforced and plasticized polylactic acid fibrous membrane.

In this paper, the electronspun Polylactic acid (PLA)/TiO2 nanofluids (nfs) fibrous membrane with good toughness, hydrophilicity and antibacterial activities are fabricated by taking full advantages of solvent-free TiO2 nfs with amphiphilicity and ionic conductivity. The resulting PLA/TiO2 nfs fibrous membrane exhibits excellent mechanical performance with a tensile strength and elongation at break of 3.68 MPa and 97.32 MPa at 5 wt% loading, respectively, which is 4 and 8 times higher than that of pure PLA, respectively. Additionally, TiO2 nfs can migrate onto the surface of PLA fibers during electrospun process, which significantly enhanced hydrophilicity, antistatic property, moisture sorption capacity and wicking properties of PLA fabrics. Meanwhile, the membrane also showed ultrafast water filtration of 3500 L m-2 h-1 driven by gravity force, which is 10-12 times higher than that of commercial ultrafiltration membrane. After ion-exchange reaction with salt solution, excellent antibacterial activity (against E. coli and S. aureus was 95% and 99.9%, respectively) and separation efficiency (above 90% on E. coli) of the obtained fabrics are also achieved. Overall, organic nfs are an idea candidate for fabricating hydrophilic PLA based biodegradable fabric that can be applied in contaminated water treatment, antibacterial textiles and biodegradable absorption materials.

Preparation of bioplastic using soy protein.

Soybean, one of the most abundant plants, has been cultivated around the world as a familiar crop. Especially, most of the soybean is globally used as a crop to obtain the oil. The degreased soybean contains a lot of protein in it. The part of the degreased soybean is used for the food of human consumption and livestock feed, however most of this are discarded as industrial waste throughout the world. Therefore, we demonstrated the preparation of bioplastics consisting of soy protein. Although the soy protein without the cross-linking reaction by formaldehyde (HCHO) was collapsed in water, bioplastics were stable in water. Additionally, the bending strength of the bioplastic increased with the HCHO concentration and showed the maximum value of approximately 35 MPa at a 1% HCHO concentration. Surprisingly, this bending strength value was the same as that of polyethylene. In contrast, the infrared spectra indicated the formation of methylene cross-linking between the basic amino acids, such as lysine and arginine. Finally, we estimated the biodegradable property of the bioplastic by pronase, one of the proteolytic enzymes. As a result, this bioplastic showed the weight loss of approximately 30% after the incubation time of 6 days. These results suggested that the bioplastic consisting of soy protein possesses a biodegradable property. Therefore, the bioplastic consisting of soybean may have the potential to be used as a biodegradable material, such as agricultural materials, industrial parts, and disposable items.

An Efficient Ring-Closure Method for Preparing Well-Defined Cyclic Polynorbornenes.

An efficient bimolecular ring-closure method is developed to prepare the well-defined cyclic polynorbornenes by combining the living ring-opening metathesis polymerization (ROMP) with the self-accelerating double strain-promoted azide-alkyne cycloaddition (DSPAAC) reaction. In this method, ROMP is used to synthesize the well-defined linear polynorbornenes with both azide terminals by virtue of a N-hydroxysuccinimide-ester-functionalized Grubbs initiator following the modification of polymer end groups. DSPAAC click reaction is then used to ring-close the linear polymer precursors and prepare the corresponding well-defined cyclic polynorbornenes using the sym-dibenzo-1,5-cyclooctadiene-3,7-diyne (DIBOD) as small linkers. The self-accelerating DSPAAC ring-closing reaction facilitates this method to efficiently prepare pure cyclic polynorbornenes in the presence of a molar excess of DIBOD small linkers to the linear polynorbornene precursors. This is the first report to prepare well-defined polynorbornenes with cyclic topology based on the ring-closure strategy for cyclic polymers.

Harmonizing analytical chemistry and clinical epidemiology for human biomonitoring studies. A case-study of plastic product chemicals in urine.

There is an interdisciplinary interface between analytical chemistry and epidemiology studies with respect to the design, execution, and analysis of environmental epidemiology cohorts and studies. Extracting meaningful results linking chemical exposure to human health outcomes begins at study design and spans the entire workflow. Here we discuss analytical experimental design from an exposure science perspective, and propose a reporting checklist for the design of human biomonitoring studies. We explain key analytical chemistry concepts of blanks and limits of reporting and present a case series of plastic product chemical exposure in prenatal urine specimens from the Barwon Infant Study.

Synthesis and Application of a Thermoplastic Plate of Poly(lactide-ε-caprolactone) for Radiation Therapy.

In this study, the poly(lactide-ε-caprolactone) (P(LA-CL)) copolymer is synthesized by ring-opening polymerization with glycol used as a molecular weight regulator to adjust the molecular weight of the polymer. The proton nuclear magnetic resonance spectroscopy and gel permeation chromatography (GPC) results demonstrate that the P(LA-CL) copolymer is successfully synthesized, and that the molecular weight can be controlled by the glycol content. The thermoplastic plate is processed with triallyl isocyanurate as a cross-linking agent by a single-screw extruder followed by γ-ray irradiation. Shape memory test results show that the material had the desired shape memory effect, with deformation recovery rates reaching 100%. After secondary stretching of samples, deformation recovery rates are unchanged. The results of mechanical property measurements indicate that with added lactide, the tensile strength is improved and shore hardness is increased by 20%-30%. Data from clinical trials also reveal that the material has good clinical effects in thermoplastic membrane fixation.

Preparation and characterization of coffee hull fiber for reinforcing application in thermoplastic composites.

Nowadays, there is an increasing concern toward substituting the scarce wood fibers with alternative lignocellulosic fibers that originate from crop residue to reinforce biocomposites. In this paper, the potential application of coffee hull (CH) of the reinforced polyethylene (PE) matrix composites was studied for the first time. Experiments of composite that enhanced with CH on mechanical properties, hydroscopicity, thermogravimetric analysis, fiber treatment, and microstructures were tested in this study. The PE matrix was reinforced with varying volume fractions of CH and was studied. The results show that incorporation of coffee hull markedly improved the mechanical properties of the reinforced high-density polyethylene (HDPE) matrix composites. Micrographs show a strong interfacial adhesion between the CH fiber particles. This property may be the main reason for the stability between composites. At the same time this work investigated the effect of different treatments on the mechanical properties and water absorption behavior of composites. The fiber surface treatments were done using active chemicals such as calcium hydroxide (Ca(OH)2), silane coupling agent (SCA), maleic anhydride grafted polypropylene (MA-g-PP), stearic acid (SA), ethylene bis stearamide (EBS) and the combination (MA-g-PP, SA, EBS). The results show that (Ca(OH)2)treatment is the best way to improve its properties. Probably because attributed to removal of surface active functional groups (-OH) from the CH fiber and induction of hydrophobicity that in turn improved the compatibility with the polymer matrix. As a result, the use of coffee hull in composites could have great significance for the industry.

Determination and analysis of harmful components in synthetic running tracks from Chinese primary and middle schools.

In China, incidences involving pupils suffering health problems caused by synthetic running tracks have attracted the public's attention. However, the existence of known and unknown harmful chemicals in the tracks have not yet been explored. Here, the levels of 16 known harmful ingredients were firstly analyzed in 167 school running tracks. In all samples, the recognized toxic solvents and additives, such as the benzene series, soluble mercury, 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA) and toluene diisocyanate monomer (TDI) were under the limits of detection. In contrast, polycyclic aromatic hydrocarbons (PAHs), phthalates, Short chain chlorinated paraffins (SCCPs) soluble lead, cadmium and chromium were found in 86%, 88%, 46%, 81%, 43% and 83% of the specimens, respectively. The levels, toxicology and distribution of these known chemicals were evaluated. Then, a static-headspace gas chromatography-mass spectrometer (GC-MS) method in full scan mode was employed to screen for unknown volatile chemicals. Three groups of chemicals reflecting different kinds of pollution sources were discovered: new solvents, such as N, N-Dimethylformamide, new additives, such as 2-ethylhexanoic acid, and by-products, such as carbon disulfide. In summary, the existence of potential risk factors in school plastic tracks was revealed through exhaustive testing. Moreover, most of the hazardous components detected have been recently included in a new national standard to improve the safety performance of synthetic running tracks.

Improving physical properties and retrogradation of thermoplastic starch by incorporating agar.

To develop functional and sustainable packaging materials from starch and to enhance their properties, agar was added to thermoplastic corn starch (TPS) in a wide concentration range and the products were prepared either by casting or melt blending with a high glycerol content. The role of agar in the mechanical and barrier performance of films, as well as the compatibility of TPS and agar was systematically evaluated. In addition, the retrogradiation of starch in various blends after long storage periods was widely characterized. Results proved that the addition of agar to TPS resulted in films with promising barrier and tensile properties. Stiffness and strength increased considerably by increasing agar content, while deformability of blends was better than those of pure TPS. Agar incorporation decreased water permeability and solubility and improved light transmittance. Retrogradation of the dry blends was significantly smaller than that of pure TPS owing to the strong starch/agar interaction.

Miscibility studies of plastic-mimetic polypeptide with hydroxypropylmethylcellulose blends and generation of non-woven fabrics.

In the current investigation, the results of viscometric measurements, thermal property, SEM, XRD and FTIR of the polymer blends containing synthetic plastic-based polypeptide (PLP) with hydroxypropylmethylcellulose (HPMC) on miscibility is discussed. Various interaction parameters; KH, Δ[η]m, ΔB, µ, α, ß and ΔK indicated the miscibility of polypeptide/HPMC up to 40% of the PLP in the blend at room temperature. The calorimetric results a single glass transition event for miscible systems. Further, the results were aligned with the scanning electron microscope and XRD analysis. Details concerning the nature of interactions in these systems and how they are influenced by the peptide proportion in the blends are discussed. The thermo gravimetric analysis manifested the improved thermal stability of the blends than their individual polymers. Additionally, the blend solutions were fabricated into non-woven fabrics with electrospinning technique, which may be a good candidate for pharmaceutical and biomedical applications.

Homogeneous acylation of Cellulose diacetate: Towards bioplastics with tuneable thermal and water transport properties.

In this study, we report a simple, non-degrading and efficient homogeneous acylation of cellulose diacetate (CDA) by using a large panel of commercially available acylating aliphatic moieties, differing in their structure (fatty, ramified, bulky, cycloaliphatic, aromatic, more or less spaced from the cellulose backbone), in view of generating a library of well-defined cellulose mixed esters with enhanced thermoplasticity. As reflected by a lowering of the glass temperature (Tg), the covalent grafting confers an improved mobility to the cellulose chains, by disrupting the initial H-bonds. In particular, it appears that the gain in free volume is tailored by the substituent structure and that acylating reagents consisting in a terminal bulky moieties spaced from CDA chains by a linear chain efficiently separate macromolecular chains without generating detrimental stiffening interactions (low Tg around 125 °C). Moreover, free-standing films easily prepared by solvent casting exhibit relevant water transport properties, which are closely dictated and tuned by the water solubility of the cellulose mixed ester.

Crosslinked chitosan films with controllable properties for commercial applications.

In this research, sustainable and green bioproducts with controlled sorption and good mechanical properties have been developed from chitosan for commercial applications. Addition of citric acid, a biocompatible crosslinker, and later treating with alkali imparts excellent tensile strength and aqueous stability to the chitosan films. Films were developed from chitosan and studied for their sorption capabilities, mechanical properties, oxygen/water vapour transmission rates and antimicrobial abilities. Moisture sorption of up to 1466% based on the dry weight of chitosan was seen when the films were untreated. However, treating the films with alkali decreased their water sorption to 100-250% and made the films resistant even to boiling water. Modified chitosan could be moulded into various forms and made into bioproducts that could replace plastic based materials. The chitosan bioproducts developed have the potential to replace plastic based products and will help to provide a greener alternative for the plastic based commodity products in current use.

Characterization of bio-based plastic made from a mixture of Momordica charantia bioactive polysaccharide and choline chloride/glycerol based deep eutectic solvent.

Momordica charantia bioactive polysaccharide (MCBP) was used as an alternative source for the production of bio-based plastics (BPs) with choline chloride/glycerol-based deep eutectic solvent (DES) as a plasticizer. In this study, MCBP was initially extracted using 0.1 M citric acid at temperature 80 °C for 2 h, precipitated using ethanol, and then lyophilized. Subsequently, seven BPs were prepared: MCBP without plasticizer (MCBP), with 1% (w/w) of glycerol (MCBP-G), or with 1% (w/w) of DES at different choline chloride/glycerol molar ratios (i.e. 1.5:1, 1:1, 1:1.5, 1:2, and 1:3). The properties of these BPs were then investigated. Results showed that the tensile strains, stresses and moduli were in the range of 1.3-13.3%, 4.8-19.1 MPa and 132-2487 MPa, respectively. The melting temperatures were found in the range of 92.6-111.4 °C whereas the moisture absorptions and water vapour transmission rates (WVTR) of BPs were 1.4-6.5% and 3.6-5.4 mg/m2·s, respectively. The results also showed that these BPs exhibited bioactivities, such as microbial inhibitory activity (19.5-32.3 mm), free radical scavenging activity (10.3-18.3%) and ferric reducing antioxidant power (FRAP, 16.1-20.0 mM). In addition, it was observed that using DES as a plasticizer had improved the properties of BP, such as tensile strain (354.7-937.5%), melting temperature (4.6-20.3%), radical scavenging activity (0.6-88.6%), FRAP (0.9-18.7%) and antimicrobial activity (12.3-33.6%) compared to MCBP, due to the fact DES has caused different degrees of plasticization via hydrogen bonds and ionic bonds with the polymer chains, and induced a lower pH condition. Therefore, it was suggested that these BPs with DES could contribute to food preservation properties.

Luminescence-Tunable Polynorbornenes for Simultaneous Multicolor Imaging in Subcellular Organelles.

Through modular ROMP (ring-opening metathesis polymerization), biofunctional polynorbornenes are designed and fabricated from panchromatic fluorophores, bioactive peptides, and polyethylene glycol solubilizer for organelle-specific multicolor imaging. Attributed to the free permutation and combination of highly fluorescent red rhodamine B, green dichlorofluorescein and blue 9,10-diphenylanthracene fluorophores as well as signaling peptide sequences of F xrF xK and TAT, we successfully realize simultaneous multicolor imaging toward lysosomes and mitochondria in living cells first utilizing polymeric scaffolds. If more biofunctions could be incorporated, modularly designed copolymer would provide a promising opportunity to facilitate multitasking application to monitoring intracellular alterations and elucidating complex biological processes.