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For water-soluble polymers (WSPs) that enter environmental systems at their end-of-life, biodegradability is a key functionality. For the development and regulation of biodegradable WSPs, testing methods that are both scientifically validated and economically practicable are needed. Here, we used respirometric laboratory tests to study the biodegradation of poly(amino acids), poly(ethylene glycol), and poly(vinyl alcohol), together with appropriate low-molecular-weight reference substrates. We varied key protocol steps of commonly used testing methods, which were originally established for small molecules and tested for effects on WSP biodegradation. We found that avoiding aeration of the wastewater inoculate prior to WSP addition, incubating WSP with filter-sterilized wastewater prior to biodegradation testing, and lowering the WSP concentration can increase biodegradation rates of WSPs. Combining the above-mentioned protocol variations substantially affected the results of the biodegradation testing for the two poly(amino acids) tested herein (i.e., poly(lysine) and poly(aspartic acid)). Our findings were consistent between microbial inocula derived from two municipal wastewater treatment plants. Our study presents promising biodegradation dynamics for poly(amino acids) and highlights the importance, strengths, and limitations of respirometric laboratory methods for WSP biodegradation testing.
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Water-soluble polymers (WSPs) are used in diverse applications, including agricultural formulations, that can result in the release of WSPs to soils. WSP biodegradability in soils is desirable to prevent long-term accumulation and potential associated adverse effects. In this work, we assessed adsorption of five candidate biodegradable WSPs with varying chemistry, charge, and polarity characteristics (i.e., dextran, diethylaminoethyl dextran, carboxymethyl dextran, polyethylene glycol monomethyl ether, and poly-l-lysine) and of one nonbiodegradable WSP (poly(acrylic acid)) to sand and iron oxide-coated sand particles that represent important soil minerals. Combined adsorption studies using solution-depletion measurements, direct surface adsorption techniques, and column transport experiments over varying solution pH and ionic strengths revealed electrostatics dominating interactions of charged WSPs with the sorbents as well as WSP conformations and packing densities in the adsorbed states. Hydrogen bonding controls adsorption of noncharged WSPs. Under transport in columns, WSP adsorption exhibited fast and slow kinetic adsorption regimes with time scales of minutes to hours. Slow adsorption kinetics in soil may lead to enhanced transport but also shorter lifetimes of biodegradable WSPs, assuming more rapid biodegradation when dissolved than adsorbed. This work establishes a basis for understanding the coupled adsorption and biodegradation dynamics of biodegradable WSPs in agricultural soils.
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Dextranos , Solo , Solo/química , Estrutura Molecular , Adsorção , Areia , Água , MineraisRESUMO
Water-soluble polymers (WSPs) have unique properties that are valuable in diverse applications ranging from home and personal care products to agricultural formulations. For applications that result in the release of WSPs into natural environments or engineered systems, such as agricultural soils and wastewater streams, biodegradable as opposed to nonbiodegradable WSPs have the advantage of breaking down and, thereby, eliminating the risk of persistence and accumulation. In this Commentary, we emphasize central steps in WSP biodegradation, discuss how these steps depend on both WSP properties and characteristics of the receiving environment, and highlight critical requirements for testing WSP biodegradability.
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Polímeros , Água , Biodegradação Ambiental , Águas ResiduáriasRESUMO
To achieve a sustainable circular economy, polymer production must start transitioning to recycled and biobased feedstock and accomplish CO2 emission neutrality. This is not only true for structural polymers, such as in packaging or engineering applications, but also for functional polymers in liquid formulations, such as adhesives, lubricants, thickeners or dispersants. At their end of life, polymers must be either collected and recycled via a technical pathway, or be biodegradable if they are not collectable. Advances in polymer chemistry and applications, aided by computational material science, open the way to addressing these issues comprehensively by designing for recyclability and biodegradability. This Review explores how scientific progress, together with emerging regulatory frameworks, societal expectations and economic boundary conditions, paint pathways for the transformation towards a circular economy of polymers.
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We report a novel polyester material generated from readily available biobased 1,18-octadecanedicarboxylic acid and ethylene glycol possesses a polyethylene-like solid-state structure and also tensile properties similar to high density polyethylene (HDPE). Despite its crystallinity, high melting point (Tm =96 °C) and hydrophobic nature, polyester-2,18 is subject to rapid and complete hydrolytic degradation in in vitro assays with isolated naturally occurring enzymes. Under industrial composting conditions (ISO standard 14855-1) the material is biodegraded with mineralization above 95 % within two months. Reference studies with polyester-18,18 (Tm =99 °C) reveal a strong impact of the nature of the diol repeating unit on degradation rates, possibly related to the density of ester groups in the amorphous phase. Depolymerization by methanolysis indicates suitability for closed-loop recycling.
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Poliésteres , Polietileno , Biodegradação Ambiental , Poliésteres/química , HidróliseRESUMO
The release of fragments from plastic products, that is, secondary microplastics, is a major concern in the context of the global plastic pollution. Currently available (thermoplastic) polyurethanes [(T)PU] are not biodegradable and therefore should be recycled. However, the ester bond in (T)PUs might be sufficiently hydrolysable to enable at least partial biodegradation of polyurethane particles. Here, we investigated biodegradation in compost of different types of (T)PU to gain insights into their fragmentation and biodegradation mechanisms. The studied (T)PUs varied regarding the chemistry of their polymer backbone (aromatic/aliphatic), hard phase content, cross-linking degree, and presence of a hydrolysis-stabilizing additive. We developed and validated an efficient and non-destructive polymer particle extraction process for partially biodegraded (T)PUs based on ultrasonication and density separation. Our results showed that biodegradation rates and extents decreased with increasing cross-linking density and hard-segment content. We found that the presence of a hydrolysis stabilizer reduced (T)PU fragmentation while not affecting the conversion of (T)PU carbon into CO2. We propose a biodegradation mechanism for (T)PUs that includes both mother particle shrinkage by surface erosion and fragmentation. The presented results help to understand structure-degradation relationships of (T)PUs and support recycling strategies.
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Plásticos , Poliuretanos , Humanos , Microplásticos , Polímeros , Biodegradação Ambiental , SupuraçãoRESUMO
Polypeptides are successfully incorporated into poly(l-lactide) (PLLA) chains in a ring-opening polymerization (ROP) of l-lactide by using them as initiators. The resulting ABA triblock copolymers possess molecular weights up to 11000 g·mol(-1) and polydispersities as low as 1.13, indicating the living character of the polymerization process. In a nonaqueous emulsion, peptide-initiated polymerization of l-lactide leads to well-defined nanoparticles, consisting of PLLA-block-peptide-block-PLLA copolymer. These nanoparticles are easily loaded by dye-encapsulation and transferred into aqueous media without aggregation (average diameter of 100 nm) or significant dye leakage. Finally, internalization of PLLA-block-peptide-block-PLLA nanoparticles by HeLa cells is demonstrated by a combination of coherent anti-Stokes Raman spectroscopy (CARS) and fluorescence microscopy. This demonstrates the promise of their utilization as cargo delivery vehicles.
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Portadores de Fármacos/síntese química , Nanopartículas/química , Peptídeos/síntese química , Poliésteres/síntese química , Portadores de Fármacos/metabolismo , Composição de Medicamentos , Endocitose , Corantes Fluorescentes , Células HeLa , Humanos , Microscopia Eletrônica de Varredura , Microscopia de Fluorescência , Nanopartículas/metabolismo , Nanopartículas/ultraestrutura , Tamanho da Partícula , Peptídeos/metabolismo , Poliésteres/metabolismo , PolimerizaçãoRESUMO
Cellulose acetate (CA) was partially acrylated, and the resulting cellulose acetate acrylate (acryl-substitution degree of 0.2) underwent quantitative thio-Michael click reactions with various thiols. A toolbox of functional CA polymers was obtained in this way, and their properties were studied. The modification with fatty alkyl thiols led to hydrophobic materials with large water drop contact angles. Octadecylthio-, butoxycarbonylpropylthio-, and furanylthio-modifications formed highly transparent materials. The new derivative CAASFur disintegrated completely under industrial composting conditions. Films of modified CA polymers were cast and investigated in terms of barrier properties. The nanocomposite of CAAS18 compounded with a synthetic layered silicate (hectorite) of a large aspect ratio showed permeabilities as low as 0.09 g mm m-2 day-1 for water vapor and 0.16 cm3 mm m-2 day-1 atm-1 for oxygen. This portfolio of functional CA polymers opens the door to new applications.
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This research evaluated the intra- and interlaboratory variability when applying OECD 301F and OECD 301B Ready Biodegradation respirometric test methods to quantify polymer biodegradation as well as the impact of method modifications including test duration, inoculum level and test substance concentration on results. This assessment synthesizes results of mineralization studies on 5 polymers of varying structural components, molecular weight, charge, and solubility, evaluated at 8 different laboratories in 4 different countries, providing significant geographic variation in inoculum source as well as lab to lab variations in test setup. Across all laboratories, intralaboratory variability was low (≤18 % absolute difference) indicating the reproducibility of results between replicates and uniformity of test setup in each laboratory. Interlaboratory variation was also low for all 5 polymers with extent of mineralization being comparable in all OECD 301F and 301B studies even when test methods were modified. Across all studies mean mineralization was 89 ± 5.5 % for polyethylene glycol 35,000, 85 ± 7.4 % for polyvinyl alcohol 18-88, 44 ± 13 % for carboxymethyl cellulose (DS 0.6), 48 ± 4.1 % for a modified guar gum, and 88 ± 6.2 % for microcrystalline cellulose (MCC) at study completion. Due to the lack of polymeric reference materials, MCC was evaluated and found to be a suitable reference material for polymers that biodegrade rapidly in screening studies. An additional respirometric study was conducted quantifying mineralization of the 5 polymers in river water to evaluate the relationship with OECD 301 results using activated sludge as the inoculum. A similar extent of mineralization was observed for all 5 polymers in the OECD 301 and river water studies but time to reach the maximum extent of mineralization was longer using river water as the inoculum source likely due to the lower microbial counts (106 CFU/L) in the test system.
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Laboratórios , Polímeros , Reprodutibilidade dos Testes , Biodegradação Ambiental , ÁguaRESUMO
Clearly visible: A water-soluble and highly fluorescent perylenediimide is synthesized via ruthenium-catalyzed alkylation with outstanding yields. For the first time, the possibility to use phosphonate derivatives in a Murai-type reaction is demonstrated.
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Corantes Fluorescentes/química , Imidas/química , Perileno/análogos & derivados , Água/química , Alquilação , Catálise , Membrana Celular/química , Células HeLa , Humanos , Microscopia Confocal , Perileno/química , Rutênio/químicaRESUMO
Describing wetting of a liquid on a rough or structured surface is a challenge because of the wide range of involved length scales. Nano- and micrometer-sized textures cause pinning of the contact line, reflected in a hysteresis of the contact angle. To investigate contact angles at different length scales, we imaged water drops on arrays of 5 µm high poly(dimethylsiloxane) micropillars. The drops were imaged by laser scanning confocal microscopy (LSCM), which allowed us to quantitatively analyze the local and large-scale drop profile simultaneously. Deviations of the shape of drops from a sphere decay at two different length scales. Close to the pillars, the amplitude of deviations decays exponentially within 1-2 µm. The drop profile approached a sphere at a length scale 1 order of magnitude larger than the pillars' height. The height and position dependence of the contact angles can be understood from the interplay of pinning of the contact line, the principal curvatures set by the topography of the substrate, and the minimization of the air-water interfaces.
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Using biodegradable instead of conventional plastics in agricultural applications promises to help overcome plastic pollution of agricultural soils. However, analytical limitations impede our understanding of plastic biodegradation in soils. Utilizing stable carbon isotope (13C-)labelled poly(butylene succinate) (PBS), a synthetic polyester, we herein present an analytical approach to continuously quantify PBS mineralization to 13CO2 during soil incubations and, thereafter, to determine non-mineralized PBS-derived 13C remaining in the soil. We demonstrate extensive PBS mineralization (65 % of added 13C) and a closed mass balance on PBS-13C over 425 days of incubation. Extraction of residual PBS from soils combined with kinetic modeling of the biodegradation data and results from monomer (i.e., butanediol and succinate) mineralization experiments suggest that PBS hydrolytic breakdown controlled the overall PBS biodegradation rate. Beyond PBS biodegradation in soil, the presented methodology is broadly applicable to investigate biodegradation of other biodegradable polymers in various receiving environments.
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Carbono , Solo , Biodegradação Ambiental , Butileno Glicóis/metabolismo , Dióxido de Carbono/metabolismo , Isótopos de Carbono , Marcação por Isótopo , Plásticos , Poliésteres/metabolismo , Polímeros/metabolismo , SuccinatosRESUMO
Repeated precipitation of colloidal semiconductor quantum dots (QD) from a good solvent by adding a poor solvent leads to an increasing number of QD oligomers after redispersion in the good solvent. By using density gradient ultracentrifugation we have been able to separate QD monomer, dimer, and trimer fractions from higher oligomers in such solutions. In the corresponding fractions QD dimers and trimers have been enriched up to 90% and 64%, respectively. Besides directly coupled oligomers, QD dimers and trimers were also assembled by linkage with a rigid terrylene diimide dye (TDI) and separated again by ultracentrifugation. High-resolution transmission electron micrographs show that the interparticle distances are clearly larger than those for directly coupled dots proving that the QDs indeed are cross-linked by the dye. Moreover, energy transfer from the QDs to the TDI "bridge" has been observed. Individual oligomers (directly coupled or dye-linked) can be readily deposited on a substrate and studied simultaneously by scanning force and optical microscopy. Our simple and effective scheme is applicable to a wide range of ligand stabilized colloidal nanoparticles and opens the way to a detailed study of electronic coupling in, e.g., QD molecules.
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Pontos Quânticos , Dimerização , Tamanho da Partícula , Semicondutores , Propriedades de SuperfícieRESUMO
The pollution of the natural environment, especially the world's oceans, with conventional plastic is of major concern. Biodegradable plastics are an emerging market bringing along potential chances and risks. The fate of these materials in the environment and their possible effects on organisms and ecosystems has rarely been studied systematically and is not well understood. For the marine environment, reliable field test methods and standards for assessing and certifying biodegradation to bridge laboratory respirometric data are lacking. In this work we present newly developed field tests to assess the performance of (biodegradable) plastics under natural marine conditions. These methods were successfully applied and validated in three coastal habitats (eulittoral, benthic and pelagic) and two climate zones (Mediterranean Sea and tropical Southeast Asia). Additionally, a stand-alone mesocosm test system which integrated all three habitats in one technical system at 400-L scale independent from running seawater is presented as a methodological bridge. Films of polyhydroxyalkanoate copolymer (PHA) and low density polyethylene (LD-PE) were used to validate the tests. While LD-PE remained intact, PHA disintegrated to a varying degree depending on the habitat and the climate zone. Together with the existing laboratory standard test methods, the field and mesocosm test systems presented in this work provide a 3-tier testing scheme for the reliable assessment of the biodegradation of (biodegradable) plastic in the marine environment. This toolset of tests can be adapted to other aquatic ecosystems.
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Ambiente Controlado , Oceanos e Mares , Plásticos/metabolismo , Biodegradação Ambiental , Cadeia Alimentar , Sedimentos Geológicos/química , Plásticos/química , Plásticos/isolamento & purificação , Água do Mar/química , TemperaturaRESUMO
We report on the synthesis of a novel perylene monoimide derivative that shows high response and selectivity for zinc ion detection. The complexation of Zn(2+) by the dye is followed by FD-MS, (1)H NMR, UV-vis spectroscopy, and isothermal titration calorimetry. Quantum chemical calculations are performed to gain further insight into the electronic processes responsible for the spectroscopic changes observed upon complexation. Finally, the perylene dye is incorporated in a sol-gel silica layer coated on optical fibers that are then used for Zn(2+) detection in aqueous solution.
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Tecnologia de Fibra Óptica , Imidas/química , Perileno/análogos & derivados , Zinco/análise , Imidas/síntese química , Íons/análise , Estrutura Molecular , Perileno/síntese química , Perileno/químicaRESUMO
Selective solvent vapour annealing is used on a photovoltaic blend to enhance the interaction between the electron acceptor and the electron donor, simplifying thin films post-processing for photovoltaic applications. A remarkable improvement in the interfacial charge transfer in the bulk hetero-junction is attained, as measured by Kelvin Probe Force Microscopy.
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Gases/química , Energia Solar , Solventes/química , Elétrons , Microscopia de Força Atômica , Perileno/química , Polietilenoglicóis/químicaRESUMO
Via an unprecedentedly reported ruthenium catalyzed reaction, an efficient and straightforward method was developed for the synthesis of 2,5,8,11-tetraboronate perylenediimide derivatives. A possible reaction mechanism is proposed. The synthesis of 2,5,8,11-tetra-iodo and tetra-amino perylenediimides derivatives is also reported.
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Via one-step copper catalyzed procedures it was possible to synthesize 2,5,8,11-tetrabromo, tetrachloro, and tetracyano derivatives of perylenediimides. Characterization of optical and electrochemical properties of these materials proves substantial enhancement of the electron affinity, with a LUMO level as low as -4.4 eV in the case of the tetracyano perylenediimide.
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We present relevant results dealing with the transparency/optical nonlinearity trade-off in high-frequency electro-optic applications. The very simple, stable and high optical gap chromophore, the zwitterion 1-methyl-4-(tetrazol-5-ate)pyridinium, represents the best transparency/optical nonlinearity trade-off so far described in the literature. We rationalize this remarkable performance in the framework of the Bond Length Alternation theory by means of a multidisciplinary approach including: single crystal X-ray structure, Electric Field Induced Second-Harmonic Generation, solvatochromism, electrochemistry and thermal analyses.