Chemical Depolymerization Research Articles

The use of extracted-ion chromatograms to quantify the composition of condensed tannin subunits.

RationaleThe analysis of tannins is currently usually done by liquid chromatography after the chemical depolymerization of tannins. However, one of the main limitations of this method is the difficulty in specifically detecting each constitutive tannin monomer in a complex matrix, as numerous compounds co‐elute with the monomers, thereby compromising the analysis.MethodsThe depolymerization of tannins under acidic conditions and in the presence of thioglycolic acid releases the various constitutive monomers, either as terminal units or as extension units. The tannin subunits were then quantified using extracted‐ion chromatogram (EIC) mass spectrometry, which required the determination of the ionization efficiency of the monomers. Thus, we used AgBF4‐assisted coupling for the hemisynthesis of the noncommercial epicatechin gallate dimer.ResultsThe EIC showed that the derivatives of the extension units were twice as ionized as the terminal units. Unlike the UV chromatograms, this new EIC‐based method is more specific and accurate because it is not impacted by the co‐elution phenomenon. This result, when added to the linearity obtained on a large range of the calibration curves, allowed for quantification of tannin subunits from EIC in complex mixtures with less pretreatment of the samples.ConclusionsDue to its specificity and sensitivity, this EIC‐based method represents a significant step toward improving the quantification of the tannin composition of samples. The results of this study should allow the oxidation markers to be quantified more accurately and taken into account, thereby providing a better indication of the actual tannin composition.

New Mortar Mixes with Chemically Depolymerized Waste PET Aggregates

Nanoparticles are used in innovative mortars in order to improve their engineering properties. In this paper, recycled PET (polyethylene terephthalate) nanoparticles were used as a substitute for sand in mortars. PET aggregates were obtained cutting water bottles wastes into many small sized pieces and the plastic fibres were treated through chemical depolymerization process. Mortars with different percentages of PET were tested to determine their physical and mechanical (flexural and compressive strength) properties. Specific attention is given to the heat‐transfer capacity of the cement pastes investigated. The results of the mechanical tests showed a reduction of the flexural and compressive strength values when the amount of PET nanoparticles increase. The thermal conductivity tests showed that chemically depolymerized PET nanoparticles derived from plastic wastes reduced the heat conduction capacity of the mortar. Therefore, the innovative mortars here tested can be considered for thermal insulation applications in the construction field with the advantage of recycling waste PET.

Conversion of polyethylene terephthalate to high-quality terephthalic acid by hydrothermal hydrolysis: the study of process parameters

A new circular economy concept is presented for the textile sector to convert unwearable polyester textile waste into valuable chemical feedstock. The idea behind it is to develop a new circular economy concept for the most used material in the textile industry, that is, polyester. Hydrothermal hydrolysis, an environmentally friendly process, has been studied for recovering polyester monomeric units. Under high-temperature and high-pressure conditions complete chemical depolymerization of pure poly(ethylene terephthalate) (PET) to terephthalic acid (TPA) was achieved at high yield. The produced TPA was characterized by potentiometric titrations, Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy and elemental analysis. A series of experiments were performed on the PET material with different intrinsic viscosities to define the appropriate depolymerization conditions related to the temperature ( T), time ( t) and PET:H2O ratio, which enables total conversion of the polymer. Maximal conversion (92%) to TPA was defined at 250℃, pressure of 39–40 bar, PET:water ratio of 1:10 and hydrolysis time of 30 min after reaching steady-state conditions in the reactor. The applied depolymerization route resulted in moderate purity of the originated TPA, which was applied successfully in a laboratory-scale two-step re-polymerization to produce PET resins.

Polymeric materials in sustainable development – from the need to use to the need for wear. Part II. Return to monomers

The critical analysis of the strategies of the prevention of the rise and accumulation of polymeric wastes was performed and the proposals for their processing according to the Packet for the Circular Economy have been presented. The weak points of these strategies resulting from contradictions with economic criteria, thermodynamics rules, real aims of the environment protection and the community expectations, finally also from the knitted influence of the EU administration onto structure of household and industrial articles dominating on the European market were demonstrated. The estimation of the real chances of the polymeric wastes recycling according to the principal goal of the CE, which is the come-back to the row material streams allowing the reduction of the crude oil and other mineral sources consumption have been also carried out. It was shown that the most realistic resolutions of the problem are: the return to the monomers on the way of gasification (or co-gasification) of plastic wastes (polyolefins) and processing of methanol synthesized from syngas by MTO or MTP methods and by the thermal or chemical depolymerization carried out in the case of susceptible to these processes (e.g. PET or PUR).

Isolation of a novel platform bacterium for lignin valorization and its application in glucose-free cis,cis-muconate production.

Microbial production of cis,cis-muconate (ccMA) from phenolic compounds obtained by chemical depolymerization of lignin is a promising approach to valorize lignin. Because microbial production requires a large amount of carbon and energy source, it is desirable to establish a ccMA-producing strain that utilizes lignin-derived phenols instead of general sources like glucose. We isolated Pseudomonas sp. strain NGC7 that grows well on various phenolic compounds derived from p-hydroxyphenyl, guaiacyl, and syringyl units of lignin. An NGC7 mutant of protocatechuate (PCA) 3,4-dioxygenase and ccMA cycloisomerase genes (NGC703) lost the ability to grow on vanillate and p-hydroxybenzoate but grew normally on syringate. Introduction of a plasmid carrying genes encoding PCA decarboxylase, flavin prenyltransferase, vanillate O-demethylase, and catechol 1,2-dioxygenase into NGC703 enabled production of 3.2g/L ccMA from vanillate with a yield of 75% while growing on syringate. This strain also produced ccMA from birch lignin-derived phenols. All these results indicate the utility of NGC7 in glucose-free ccMA production.

Comparative study of the characteristics and fluorescent properties of three different biochar derived‑carbonaceous nanomaterials for bioimaging and heavy metal ions sensing

Three types of biochar (microalgae, rice straw and sorghum straw) from biomass thermal conversion production were tested for producing biochar-derived carbonaceous nanomaterials (BCN). BCN were obtained after using chemical depolymerisation and solvent extraction, NanoRefinery process. Microalgae biochar-derived carbonaceous nanomaterials (MAB-CN), rice straw biochar-derived carbonaceous nanomaterials (RSB-CN) and sorghum straw biochar-derived carbonaceous nanomaterials (SSB-CN) were characterised using spectroscopic and microscopic techniques. This characterisation evidenced significant differences among the three BCN with MAB-CN exhibiting greater structural differences compared to RSB-CN and SSB-CN. Biocompatibility, cellular uptake, and cellular localisation were evaluated using three yeast species, Saccharomyces cerevisiae, Candida albicans, and Yarrowia lipolytica. While all BCN were biocompatible, the degree of biocompatibility for each species was dependent on pH, BCN concentration and BCN type. Additionally, BCN were evaluated as transducers for the detection of 12 heavy metal ions. MAB-CN, RSB-CN, and SSB-CN had different responses to the 12 heavy metal ions. The SSB-CN/Cu (II) and the MAB-CN/Zn (II) combinations evidenced selectivity over the other metal ions with these combinations having limits of detection of 0.0125 μM and 9 μM, respectively. The results from this research pave the way for BCN novel applications for bioimaging and heavy metal ions sensing probes.

Strategy for Structural Elucidation of Polysaccharides: Elucidation of a Maize Mucilage that Harbors Diazotrophic Bacteria.

The recruitment of a bacterial consortium by the host is a strategy not limited to animals but is also used in plants. A maize aerial root mucilage has been found that harbors nitrogen fixing bacteria that are attracted to the carbohydrate rich environment. This synbiotic relationship is facilitated by a polysaccharide, whose complicated structure has been previously unknown. In this report, we present the characterization of the maize polysaccharide by employing new analytical strategies combining chemical depolymerization, oligosaccharide sequencing, and monosaccharide and glycosidic linkage quantitation. The mucilage contains a single heterogeneous polysaccharide composed of a highly fucosylated and xylosylated galactose backbone with arabinan and mannoglucuronan branches. This unique polysaccharide structure may select for the diazotrophic community by containing monosaccharides and linkages that correspond to the glycosyl hydrolases associated with the microbial community. The elucidation of this complicated structure illustrates the power of the analytical methods, which may serve as a general platform for polysaccharide analysis in the future.

Bacterial conversion of depolymerized Kraft lignin

BackgroundLignin is a potential feedstock for microbial conversion into various chemicals. However, the microbial degradation rate of native or technical lignin is low, and chemical depolymerization is needed to obtain reasonable conversion rates. In the current study, nine bacterial strains belonging to the Pseudomonas and Rhodococcus genera were evaluated for their ability to grow on alkaline-treated softwood lignin as a sole carbon source.ResultsPseudomonas fluorescens DSM 50090 and Rhodococcus opacus DSM1069 showed the best growth of the tested species on plates with lignin. Further evaluation of P. fluorescens and R. opacus was made in liquid cultivations with depolymerized softwood Kraft lignin (DL) at a concentration of 1 g/L. Size-exclusion chromatography (SEC) showed that R. opacus consumed most of the available lower-molecular weight compounds (approximately 0.1–0.4 kDa) in the DL, but the weight distribution of larger fractions was almost unaffected. Importantly, the consumed compounds included guaiacol—one of the main monomers in the DL. SEC analysis of P. fluorescens culture broth, in contrast, did not show a large conversion of low-molecular weight compounds, and guaiacol remained unconsumed. However, a significant shift in molecular weight distribution towards lower average weights was seen after cultivation with P. fluorescens.ConclusionsRhodococcus opacus and P. fluorescens were identified as two potential microbial candidates for the conversion/consumption of base-catalyzed depolymerized lignin, acting on low- and high-molecular weight lignin fragments, respectively. These findings will be of relevance for designing bioconversion of softwood Kraft lignin.

Effective catalysts derived from waste ostrich eggshells for glycolysis of post-consumer PET bottles

Herein, we report an effective chemical recycling of poly(ethylene terephthalate) (PET) using sustainable sources of catalysts, calcium oxide (CaO) derived from ostrich eggshells. The active catalysts were demonstrated in the chemical depolymerization of post-consumer PET bottles. Beverage bottles were proceeded with 1 wt% catalyst derived from ostrich eggshells in the presence of ethylene glycol at 192 °C under atmospheric pressure to give the major product as bis(2-hydroxyethyl terephthalate) (BHET) which was confirmed by melting point, IR spectroscopy, 1H-, 13C-NMR spectroscopy and mass spectrum. The catalyst could fully depolymerize PET within 2 h, producing a good yield of highly pure BHET monomer. The catalysts were successfully characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy with energy dispersive X-ray spectroscopy analysis (FE-SEM), and thermo-gravimetric analysis (TGA). Furthermore, catalysts derived from chicken eggshells, geloina, mussel, and oyster shells were run to compare the catalytic activities. For better understanding of catalytic parameters, effects of calcination temperatures of catalyst, weight ratio of catalyst, ratio of weight of solvent, and time of depolymerization for the ostrich eggshells catalyst were also investigated.

Thermodynamics of amyloid fibril formation from chemical depolymerization.

Amyloid fibrils are homo-molecular protein polymers that play an important role in disease and biological function. While much is known about their kinetics and mechanisms of formation, the origin and magnitude of their thermodynamic stability has received significantly less attention. This is despite the fact that the thermodynamic stability of amyloid fibrils is an important determinant of their lifetimes and processing in vivo. Here we use depolymerization by chemical denaturants of amyloid fibrils of two different proteins (PI3K-SH3 and glucagon) at different concentrations and show that the previously applied isodesmic linear polymerization model is an oversimplification that does not capture the concentration dependence of chemical depolymerization of amyloid fibrils. We show that cooperative polymerization, which is compatible with the picture of amyloid formation as a nucleated polymerization process, is able to quantitatively describe the thermodynamic data. We use this combined experimental and conceptual framework in order to probe the ionic strength dependence of amyloid fibril stability. In combination with previously published data on the ionic strength dependence of amyloid fibril growth kinetics, our results provide strong evidence for the product-like nature of the transition state of amyloid fibril growth.

Assessment of the Possibility of Polymer Composite Materials Recycling by Chemical Method

The research of chemical utilization, which is mainly aimed at chemical depolymerization or removal of matrix by carbon fiber preservation, is presented. The article reflects the research results of carbon fiber composites disposal through chemical method providing the reinforcing filler extraction of the total matrix volume, which further can be reused in the polymer composite materials production, thereby the costly resource is saved. The obtained results allow to assess the possibility of establishing a fundamental basis for the waste and polymer composite materials articles disposal technology.

Solar binary chemical depolymerization of lignin for efficient production of small molecules and hydrogen

In this paper, solar binary chemical depolymerization, that is Solar Thermal Electrochemical Process (STEP), was implemented for an effective breaking of lignin into small molecules and hydrogen. Compared with the conventional unitary chemical thermolysis, solar binary chemical depolymerization of lignin has high efficiencies of the liquefaction and gasification with the low coke, and accompanied by the abundant production of hydrogen. And the reaction temperature of the STEP process was greatly lowered by an intervention of the electrolysis. The results showed that the total conversion and liquefaction of the lignin yielded 87.22% and 57.72% under a constant current of 0.4 A at 340 °C. Further characterizations show that lignin has been successfully decomposed into small molecules with high added-value and hydrogen by a combination of the thermolysis and electrolysis. And the particle size of aggregates and the color degree in the lignin aqueous solution was obviously decreased after the STEP process.

THE INHIBITION OF HUMAN PLATELET AGGREGATION BY A LOW-MOLECULAR WEIGHT CHITOSAN

Chitosan derivatives were obtained by chemical (MW of 6 kDa, DD 99% - Ch6/99; MW13 kDa, DD 98% - Ch13/98) and enzymatic (MW of 5 kDa, DD 85% - Ch5/85; MW of 10 kDa, DD 85% - Ch10/85) depolymeri-sation of chitosan with a MW of 334 and 1000 kDa. Chitosan derivatives (almost identical MW pairs and different DD) possessed insignificant an-ticoagulant activity, did not promote human platelet aggregation and re-duced ADP or collagen-induced platelet aggregation. The studied sam-ples at a concentration of 2 mg/ml reduced the aggregation of platelets more than twice induced in 2x10-6M and 1x10-5M concentrations; at weak activation in 2x10-6M, the Ch10/85 sample was the most effective. The Ch6/99 and Ch13/98 samples were 20 times more effective at the inhibi-tion of collagen-induced platelet aggregation than the Ch10/85 sample. The latter can be explained by the greater value of positive charge (DD) and polydispersity (Mw/Mn) of chitosan samples obtained by chemical de-polymerisation.

Effect of the silica nanofiller on the properties of castor oil-based waterborne polyurethane hybrid dispersions based on recycled PET waste

The paper describes the chemical depolymerization of the polyethylene terephthalate (PET) waste from postconsumer soft drink bottles and a search for the way to use this product. The depolymerized oligoester obtained from glycolysis of PET waste using tiethylene glycol was transesterified with castor oil which resulted in the formation of hydroxyl-functional polyester polyol, with hydroxyl value of 391 mg KOH g−1. In the presented paper, series of castor oil-based waterborne polyurethane (CPU)/silica hybrid dispersions were prepared using dimethylolpropionic acid as an ionic center. The polyurethane prepolymers with pendent castor oil groups were prepared first, and then different concentrations of hydrophilic fumed silicas (0, 0.5, 0.75, 1.0 and 2.0 wt%) were added. For waterborne polyurethane dispersions of hydrophilic fumed silica with the surface area (50 ± 15 m2/g) and a primary particle size of 40 nm in the polymer matrix, ultrasound waves were used. The hybrid dispersions were prepared by adding the required amount of triethylamine and water. The molecular structures and mass of glycolyzed PET oligoesters, castor oil-based polyol and castor oil-based polyurethane–silica hybrid dispersions were estimated by FTIR method and gel permeation chromatography.The incorporation effect of SiO2 nanoparticles into the PU matrix on the thermal and mechanical properties of resulting polyurethane films has been examined by Fourier transform infrared spectroscopy (FTIR), thermogravimetry analysis, differential scanning calorimetry (DSC), SEM microscope, and measurement of the coatings properties. The DSC data results suggest that hard segment glass temperature decreases, but mixed-phase glass transition temperature increases with increasing SiO2 content. The FTIR deconvolution result of the degree of phase separation between oxide nanoparticles and hard segment supports to the DSC analysis. The addition of silica oxide caused the increase in the thermal stability. The T10% and T50% of CPU films (the temperatures where 10 and 50% weight loss occurred) increased with increasing the SiO2 content. UV–Vis spectrophotometry showed that introduction of nanosilica particles into polyurethane enhanced the shielding property of obtained films for UV light. The hardness, adhesion, and gloss quality of the polyurethane films were also determined considering the effect of the phase separation and the SiO2 content, so this paper confirmed the suitability of using these castor oil-based waterborne polyurethane/silica hybrid dispersions as new materials with high-performance coatings materials.

The current and emerging sources of technical lignins and their applications.

Technical lignins are bulk feedstocks. They are generated as byproducts from pulping or cellulosic ethanol production. Since lignin undergoes significant structural changes in the chemical and physical treatments, all technical lignins are unique in terms of chemical structure, molecular weight, polydispersity, and impurity profile. Kraft lignin is potentially the largest source of technical lignin as new isolation technologies have been implemented on industrial scale in recent years. Lignosulfonate has been an integral product in sulfite pulping biorefinery. It has a well-established market in construction industry. Organosolv-like lignin production is increasing as cellulosic ethanol has been promoted as the substitute of fossil fuel. It may have unique applications because it has low molecule weight and is free from sulfur. Technical lignin application is expected to expand as the characteristics are improved with fractionation or chemical modification. The application of technical lignin has been focusing on developing products equivalent to those made by petroleum chemicals. The recent development in technical lignin supply should increase its market share as additives in polyurethanes and as the substitute of phenol-formaldehyde adhesives. Quality improvement of technical lignin may also encourage the study of lignin as an alternative feedstock for carbon fiber. In addition, technical lignin depolymerization has been extensively explored to provide renewable aromatic chemicals. Starting from controlled pyrolysis and thermal liquefaction as the baseline technologies, many different chemical depolymerization have been invented with a wide range of underlying chemical principles.

Thermosetting Polymers from Lignin Model Compounds and Depolymerized Lignins.

Lignin is the most abundant source of renewable ready-made aromatic chemicals for making sustainable polymers. However, the structural heterogeneity, high polydispersity, limited chemical functionality and solubility of most technical lignins makes them challenging to use in developing new bio-based polymers. Recently, greater focus has been given to developing polymers from low molecular weight lignin-based building blocks such as lignin monomers or lignin-derived bio-oils that can be obtained by chemical depolymerization of lignins. Lignin monomers or bio-oils have additional hydroxyl functionality, are more homogeneous and can lead to higher levels of lignin substitution for non-renewables in polymer formulations. These potential polymer feed stocks, however, present their own challenges in terms of production (i.e., yields and separation), pre-polymerization reactions and processability. This review provides an overview of recent developments on polymeric materials produced from lignin-based model compounds and depolymerized lignin bio-oils with a focus on thermosetting materials. Particular emphasis is given to epoxy resins, polyurethanes and phenol-formaldehyde resins as this is where the research shows the greatest overlap between the model compounds and bio-oils. The common goal of the research is the development of new economically viable strategies for using lignin as a replacement for petroleum-derived chemicals in aromatic-based polymers.

Enzymatic depolymerization of the GY785 exopolysaccharide produced by the deep-sea hydrothermal bacterium Alteromonas infernus: Structural study and enzyme activity assessment

Polysaccharides have attracted much attention due to their interesting physico-chemical and also biological properties that are explored in food, cosmetic and pharmaceutical industries. GY785 exopolysaccharide (EPS) presenting an unusual structure is secreted by the deep-sea hydrothermal bacterium, Alteromonas infernus. Low-molecular weight (LMW) derivatives obtained by chemical depolymerization of the native high molecular weight (HMW) EPS were previously shown to exhibit biological properties similar to glycosaminoglycans (GAG). In the present study, in order to generate well defined derivatives with a better control of the depolymerization, an enzymatic approach was applied for the first time. Various commercially available enzymes were firstly screened for their depolymerizing activities, however none of them was able to degrade the polysaccharide. Enzymatic assays performed with A. infernus protein extracts have shown that the bacterium produces by itself endogenous enzymes able to depolymerize its own EPS. The oligosaccharides released by the enzymes were analyzed and their structures allowed to assess that the protein extract contains several depolymerizing activities.

Mannan and phosphomannan from Kuraishia capsulata yeast

Linear mannan and branched phosphomannan were identified as exopolysaccharides produced by Kuraishia capsulata yeast. Their structures were determined using nuclear magnetic resonance spectroscopy. The repeating unit of mannan was found to be a trisaccharide →6)-α-Manp-(1→2)-α-Manp-(1→2)-α-Manp-(1→, while the phosphomannan was shown to be built of β-Manp-(1→2)-α-Manp-(1 disaccharide blocks linked by phosphodiester bonds via C-1 and C-6 of the reducing unit. The production of both polysaccharides was shown to depend on the phosphate concentration in the culture medium. In the absence of phosphate, only mannan was obtained, while an excess of KH2PO4 led to the exclusive production of phosphomannan. Chemical depolymerisation of phosphomannan led to the formation of disaccharide β-Manp-(1→2)-(6-P)-Manp, representing the repeating unit of the hydrolysed polysaccharide. The treatment of the disaccharide with alkaline phosphatase resulted in the formation of disaccharide β-Manp-(1→2)-Manp. The latest products can be transformed into glycosyl donors applicable further in the synthesis of oligosaccharides related to Candida cell wall polysaccharides.

Quantitative analysis of antithrombin III binding site in low molecular weight heparins by exhausetive heparinases digestion and capillary electrophoresis.

The antithrombin III (ATIII)-binding site, which contains a special 3-O-sulfated, N-sulfated glucosamine residue with or without 6-O-sulfation, is mainly responsible for the anticoagulant activity of heparin. Undergoing the chemical depolymerization process, the preservation of the ATIII-binding site in low molecular weight heparins (LMWHs) are varied leading to the fluctuation of the anticoagulant activity. Herein we report a capillary electrophoresis (CE) method in combination with heparinase digestion and affinity chromatography for the measurement of molar percentage of ATIII-binding site of LMWHs. After exhaustively digesting LMWHs with the mixture of heparinase I, II and III, almost all the resulting oligosaccharide building blocks, including the three 3-O-sulfated tetrasaccharides derived from the ATIII-binding site, were resolved by CE separation. The peak area of each building block permits quantification of the molar percentage of the ATIII-binding site. The peaks corresponding to the 3-O-sulfated tetrasaccharides were assigned based on the linear relationship between the electrophoretic mobilities of the oligosaccharides and their charge to mass ratios. The peak assignment was further confirmed by analysis of the high ATIII affinity fractions, which contains much high 3-O-sulfated tetrasaccharides. With the method, the molar percentage of the ATIII-binding site of enoxaparin from different batches and different manufactures were measured and compared. It was demonstrated that the CE method provides more precise data for assessing the anti-FXa activity than that of the biochemical assay method.

Lignin Valorization: Two Hybrid Biochemical Routes for the Conversion of Polymeric Lignin into Value-added Chemicals

Naturally, many aerobic organisms degrade lignin-derived aromatics through conserved intermediates including protocatechuate and catechol. Employing this microbial approach offers a potential solution for valorizing lignin into valuable chemicals for a potential lignocellulosic biorefinery and enabling bioeconomy. In this study, two hybrid biochemical routes combining lignin chemical depolymerization, plant metabolic engineering, and synthetic pathway reconstruction were demonstrated for valorizing lignin into value-added products. In the biochemical route 1, alkali lignin was chemically depolymerized into vanillin and syringate as major products, which were further bio-converted into cis, cis-muconic acid (ccMA) and pyrogallol, respectively, using engineered Escherichia coli strains. In the second biochemical route, the shikimate pathway of Tobacco plant was engineered to accumulate protocatechuate (PCA) as a soluble intermediate compound. The PCA extracted from the engineered Tobacco was further converted into ccMA using the engineered E. coli strain. This study reports a direct process for converting lignin into ccMA and pyrogallol as value-added chemicals, and more importantly demonstrates benign methods for valorization of polymeric lignin that is inherently heterogeneous and recalcitrant. Our approach also validates the promising combination of plant engineering with microbial chassis development for the production of value added and speciality chemicals.