Factors affecting microplastic retention and emission by a wastewater treatment plant on the southern coast of Caspian Sea.

Understanding how wastewater treatment plants (WWTPs) process microplastics (MPs) will help informing management practices to reduce MP emissions to the environment. We show that composite 24 h samples taken at three replications from the outflow of the grit chamber, primary settling tank and clarifier of the WWTP of Sari City, on the southern coast of the Caspian Sea, contained 12667 ± 668, 3514 ± 543 and 423 ± 44.9 MP/m3, respectively. Fibers accounted for 94.9%, 89.9% and 77.5% of the total number of MPs, respectively. The MP removal efficiency was 96.7%. MP shape (fiber, particle), size and structure were the most important factors determining their removal in different steps of the wastewater treatment process. The structure of microfibers (polyester, acrylic and nylon) and the consequent higher density than water explained their high removal (72.3%) in the primary settling tank. However, size was more important in microparticle removal with particles ≥500 µm being removed in the primary settling tank and <500 µm in the clarifier unit. The smallest particles (37-300 µm) showed the lowest removal efficiency. The predominant types of fibers and particles were polyester and polyethylene, respectively, which are likely to originate from the washing of synthetic textiles and from microbeads in toothpaste and cosmetics. Despite the efficiency of the Sari WWTP in removing MPs, it remains a major emission source of MPs to the Caspian Sea due to its high daily discharge load.

Non-hazardous biocatalytic oxidation in Nylon-9 monomer synthesis on a 40 g scale with efficient downstream processing.

This paper describes the development of a biocatalytic process on the multi-dozen gram scale for the synthesis of a precursor to Nylon-9, a specialty polyamide. Such materials are growing in demand, but their corresponding monomers are often difficult to synthesize, giving rise to biocatalytic approaches. Here, we implemented cyclopentadecanone monooxygenase as an Escherichia coli whole-cell biocatalyst in a defined medium, together with a substrate feeding-product removal concept, and an optimized downstream processing (DSP). A previously described hazardous peracid-mediated oxidation was thus replaced with a safe and scalable protocol, using aerial oxygen as oxidant, and water as reaction solvent. The engineered process converted 42 g (0.28 mol) starting material ketone to the corresponding lactone with an isolated yield of 70% (33 g), after highly efficient DSP with 95% recovery of the converted material, translating to a volumetric yield of 8 g pure product per liter. Biotechnol. Bioeng. 2017;114: 1670-1678. © 2017 Wiley Periodicals, Inc.

Efficient production of the Nylon 12 monomer ω-aminododecanoic acid methyl ester from renewable dodecanoic acid methyl ester with engineered Escherichia coli.

The expansion of microbial substrate and product scopes will be an important brick promoting future bioeconomy. In this study, an orthogonal pathway running in parallel to native metabolism and converting renewable dodecanoic acid methyl ester (DAME) via terminal alcohol and aldehyde to 12-aminododecanoic acid methyl ester (ADAME), a building block for the high-performance polymer Nylon 12, was engineered in Escherichia coli and optimized regarding substrate uptake, substrate requirements, host strain choice, flux, and product yield. Efficient DAME uptake was achieved by means of the hydrophobic outer membrane porin AlkL increasing maximum oxygenation and transamination activities 8.3 and 7.6-fold, respectively. An optimized coupling to the pyruvate node via a heterologous alanine dehydrogenase enabled efficient intracellular L-alanine supply, a prerequisite for self-sufficient whole-cell transaminase catalysis. Finally, the introduction of a respiratory chain-linked alcohol dehydrogenase enabled an increase in pathway flux, the minimization of undesired overoxidation to the respective carboxylic acid, and thus the efficient formation of ADAME as main product. The completely synthetic orthogonal pathway presented in this study sets the stage for Nylon 12 production from renewables. Its effective operation achieved via fine tuning the connectivity to native cell functionalities emphasizes the potential of this concept to expand microbial substrate and product scopes.

From zero to hero - production of bio-based nylon from renewable resources using engineered Corynebacterium glutamicum.

Polyamides are important industrial polymers. Currently, they are produced exclusively from petrochemical monomers. Herein, we report the production of a novel bio-nylon, PA5.10 through an integration of biological and chemical approaches. First, systems metabolic engineering of Corynebacterium glutamicum was used to create an effective microbial cell factory for the production of diaminopentane as the polymer building block. In this way, a hyper-producer, with a high diaminopentane yield of 41% in shake flask culture, was generated. Subsequent fed-batch production of C. glutamicum DAP-16 allowed a molar yield of 50%, a productivity of 2.2gL(-1)h(-1), and a final titer of 88gL(-1). The streamlined producer accumulated diaminopentane without generating any by-products. Solvent extraction from alkalized broth and two-step distillation provided highly pure diaminopentane (99.8%), which was then directly accessible for poly-condensation. Chemical polymerization with sebacic acid, a ten-carbon dicarboxylic acid derived from castor plant oil, yielded the bio-nylon, PA5.10. In pure form and reinforced with glass fibers, the novel 100% bio-polyamide achieved an excellent melting temperature and the mechanical strength of the well-established petrochemical polymers, PA6 and PA6.6. It even outperformed the oil-based products in terms of having a 6% lower density. It thus holds high promise for applications in energy-friendly transportation. The demonstration of a novel route for generation of bio-based nylon from renewable sources opens the way to production of sustainable bio-polymers with enhanced material properties and represents a milestone in industrial production.

Preparation and characterization of novel cationic pH-responsive poly(N,N'-dimethylamino ethyl methacrylate) microgels.

Novel monodisperse cationic pH-responsive microgels were successfully prepared by dispersion polymerization in ethanol/water mixture using N,N'-dimethylamino ethyl methacrylate (DMAEMA) as the monomer, poly(vinyl pyrrolidone) (PVP) as the steric stabilizer and N,N'-methylenebisacrylamide (MBA) as the cross-linker. The effects of various polymerization parameters, such as medium polarity, concentration of cross-linker, concentration of monomer, and concentration and molecular weight of stabilizer on the final diameter and monodispersity of poly(N,N'-dimethylamino ethyl methacrylate) (PDMAEMA) microgels were systematically studied. The pH-responsive characteristics of PDMAEMA microgels were also investigated. The experimental results showed that these microgels exhibited excellent pH-responsivity and significantly swelled at low pH values. The maximum ratio of volume change of the prepared microgels in response to pH variation was more than 11 times. It was found that the prepared microgels completely aggregated at the isoelectric point (IEP) around pH 6. On the other hand, the microgels were stable in aqueous solution at both low and high pH values. The results can be used for effectively controlled separation of particles.

Lipid, polyamide, and flavonol phagostimulants for adult western corn rootworm from sunflower (Helianthus annuus L.) pollen.

Adult Diabroticites including western corn rootworm (WCR), Diabrotica virgifera virgifera LeConte, consume pollen of corn, squash, sunflower, and other species. Short-chain neutral amino acids in methanol-water extracts of pollen have been previously identified in our laboratory as strong phagostimulants for Diabrotica. Bioassay-driven fractionation was used to characterize the interacting lipid and midpolarity phagostimulants for adult WCR in Giant Gray Stripe sunflower, Helianthus annuus L., pollen. Lipids rich in omega3-linolenic acid including triglycerides, free fatty acids, phosphatidylethanolamines, phosphatidic acids, and phosphatidylcholines were highly phagostimulatory. Other important phagostimulatory components included a hydroxycinnamic acid-polyamine amide, N(1),N(5),N(10)-tri[(E)-p-coumaroyl]spermidine, and a flavonol, quercetin beta-3-O-glucoside. The structural characteristics of these phagoactive compounds and their role in the pollinivory specialization of rootworm beetles are discussed.

Supercritical fluid extraction of nylon 6,6 oligomers and their characterization via liquid chromatography coupled with mass spectrometry.

This research extends previous studies regarding the application of supercritical fluid extraction (SFE) for the analysis of oligomers from nylon 6,6 fibers. The effects of CO2 pressure, extraction temperature, CO2-modifier percentage, static extraction time and dynamic extraction time on the SFE efficiency of nylon 6,6 oligomers were examined. Results from the SFE methods for oligomer extractions were compared to results from conventional solvent extraction. The extracted oligomers were identified by high-performance liquid chromatography (HPLC) with coupled on-line atmospheric pressure chemical ionization mass spectrometry and HPLC fractionation coupled with off-line liquid secondary ion mass spectrometry.

Polyamides (nylon) composition analysis by capillary zone electrophoresis.

A new and simple method of analysis for polyamide composition is described. Polymer samples were decomposed to their corresponding monomers by hydrobromic acid (HBr) and the decomposed products were analyzed by capillary zone electrophoresis (CZE). Amines from polyamides were derivatized with fluorescamine and detected by UV at 280 nm. Aliphatic acids were detected by direct UV at 205 nm. Sample treatment is much simpler than published methods, and electropherograms show a good separation of decomposed products under the proper conditions.

On the question of biological control methods for plastic materials.

Biological and chemical testing of plastic materials and devices needs the extraction of the analyzed sample. Polyamide was used as the model material and various effects of the extraction conditions on some biological (intracutaneous irritation, rat heart in situ, blood pressure on rats) and chemical (mass of the residue after evaporation) tests were studied. The material was extracted at 120, 55 and 37 degrees C for 0.5, 72 and 504 hr, respectively. Moreover, the polyamide was extracted at 120 degrees C for 5, 10, 15, 20, 25, 30, 60 and 120 min. Extracts were evaporated on the water bath. The increasing extraction period at 120 degrees C resulted in the increase in values of intracutaneous irritation as well as the residue mass after evaporation and in the decrease of rat heart amplitude and frequency. It was found that the extraction conditions at different temperature mentioned above were not equivalent. Various methods of extract concentration were also tested. Extracts evaporated at 35 degrees C in vacuo decreased the blood pressure more than those evaporated in the water bath.