Bio-based crotonic acid from polyhydroxybutyrate: synthesis and photocatalyzed hydroacylation

Parodi, Adriano; Jorea, Alexandra; Fagnoni, Maurizio; Ravelli, Davide; Samorì, Chiara; Torri, Cristian; Galletti, Paola

doi:10.1039/d1gc00421b

Cited by 33 publications

(47 citation statements)

References 49 publications

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“…CA was obtained following a previously reported procedure. 27 Hence, a single-neck round-bottom flask equipped with a distillation apparatus was charged with PHB (20 g) or PHB inclusions (35 g of SSC-57) and then kept under reduced pressure (150 mbar). The flask was inserted in a heating mantle already set at 175 °C and kept at this temperature until no vapors were observed (approximately 1 h).…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

“…PHB was purchased from Biomer (DE). SSC (Cupriavidus necator) and MMC containing PHB were cultivated following previously reported procedures. , The types of bacteria used (SSC or MMC) and their PHB content (22, 35, 39, or 57 wt %) are reported in Table . A sulfonated acidic heterogeneous catalyst from potato starch (C-SO 3 H) was obtained following an already reported procedure …”

Section: Methodsmentioning

confidence: 99%

“…CA was obtained following a previously reported procedure . Hence, a single-neck round-bottom flask equipped with a distillation apparatus was charged with PHB (20 g) or PHB inclusions (35 g of SSC-57) and then kept under reduced pressure (150 mbar).…”

Section: Methodsmentioning

confidence: 99%

“…Recently, we reported that PHB thermolytic distillation is a very convenient technique to obtain high-purity CA from PHB in high yields (95%). 27 In this study, we focus on the optimization of the esterification and oxa-Michael addition steps. Even if MC is an already known ester, 41,42 not much is reported in the literature regarding alternative ways for its synthesis from crotonic acid, apart from the use of high loadings of H 2 SO 4 .…”

Section: Mass Of Wastes (G) Mass Of Products (G)mentioning

confidence: 99%

“…Hydrothermal depolymerization has been performed on polyhydroxybutyrate (PHB), the homopolymer of hydroxybutyric acid, to obtain hydroxybutyric acid or propylene, useful building blocks for the synthesis of β-hydroxy esters or isopropanol, respectively. α,β-unsaturated acids and oligomers can be produced through pyrolysis or thermolytic distillation and used as convenient feedstock to reobtain PHAs through methanotrophic bacteria . Microwave-assisted PHB degradation in alkaline MeOH has been proposed as a sustainable way to produce PHB monomers, while the use of acidic or basic functionalized ionic liquids in methanol leads to the synthesis of methyl 3-hydroxybutyrate (MHB). , …”

Section: Introductionmentioning

confidence: 99%

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Chemical Recycling of Polyhydroxybutyrate (PHB) into Bio-Based Solvents and Their Use in a Circular PHB Extraction

Parodi

D’Ambrosio

Mazzocchetti

et al. 2021

ACS Sustainable Chem. Eng.

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Two novel protocols for the chemical valorization of polyhydroxybutyrate (PHB) were developed, aiming at the production of two bio-based molecules: methyl 3-hydroxybutyrate (MHB) and methyl 3-methoxybutyrate (MMB). Optimized reaction conditions were applied to pure PHB and PHB inclusions inside bacterial cells as starting materials. MHB was synthesized through a single-step catalytic methanolysis, while MMB was synthesized through a three-step process: thermolytic distillation to give crotonic acid (CA), esterification to give methyl crotonate (MC), and oxa-Michael addition of MeOH. The obtained MHB and MMB were tested as solvents for the recovery of PHB itself both from freeze-dried single strain cultures (SSC) and mixed microbial cultures (MMC) with low to medium contents of PHB (22–57 wt %). High PHB recovery was achieved: up to 96 ± 1% through MHB and up to 98 ± 1% through MMB. Extraction from MMC slurry (with a PHB content of 39% on dry weight) was also performed, recovering 77 ± 2% using MHB and 92 ± 2% using MMB. High purities and excellent molecular weights and polydispersity indexes of extracted PHB were obtained with both MHB and MMB. Solubility in water, octanol/water partition coefficients (log K ow), and aerobic ready biodegradability of both solvents were also evaluated.

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Section: ■ Materials and Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Mass Of Wastes (G) Mass Of Products (G)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Chemical Recycling of Polyhydroxybutyrate (PHB) into Bio-Based Solvents and Their Use in a Circular PHB Extraction

Parodi

D’Ambrosio

Mazzocchetti

et al. 2021

ACS Sustainable Chem. Eng.

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Tailored recycling chemicals and fuels from poly‐3‐hydroxybutyrate: A review

Kang

Liang

Yuan

et al. 2022

Biofuels Bioprod Bioref

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With the threat of ‘white pollution’, the large‐scale production and application of biodegradable plastics have become crucial. Poly‐3‐hydroxybutyrate (PHB) is the simplest and most used member of the polyhydroxyalkanoate family, with a uniform C4 structural unit (C4H6O2). To reduce the impact of PHB on waste treatment, various recycling strategies have been developed for the tailored conversion of PHB to targeted chemicals and fuels. Given the special structural unit, PHB and its plastic forms have the potential to serve as a sustainable feedstock for producing a series of value‐added chemicals and fuels, including (i) crotonic acid via pyrolysis, (ii) (R)‐β‐hydroxybutyric acid via hydrolysis, (iii) propylene via depolymerization and decarboxylation, (iv) liquid fuels via deoxygenation and oligomerization, (v) n‐biobutanol via catalytic hydrogenolysis, (vi) methyl crotonate via thermolysis and esterification, (vii) (R)‐3‐hydroxybutyrate methyl ester via catalytic methanolysis, and (viii) β‐aminobutyric acid via ammonolysis. This review article provides a systematic review focusing on the reaction pathways, primary applications and market potential of the target products, and the pros and cons of current bio‐refineries in comparison with conventional petroleum refineries. The thermochemical processes developed for PHB degradation and polypropylene (a typical petroleum‐derived plastic to be replaced by PHB) are also comprehensively evaluated to reveal the future opportunities and challenges of PHB's broad‐scale production and utilization. PHB‐derived chemicals and fuels have a mature market already, and it is confirmed that the tailored valorization of PHB is a promising pathway to expand the market and gain more environmental and energy benefits. © 2022 Society of Chemical Industry and John Wiley & Sons, Ltd.

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Decatungstate‐Photocatalyzed Dearomative Hydroacylation of Indoles: Direct Synthesis of 2‐Acylindolines

Varlet

Bouchet

Elslande

et al. 2022

Chemistry A European J

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We report herein a convenient and scalable dearomative hydroacylation reaction of indoles. Employing readily available aldehydes as the acyl source and TBADT as an inexpensive direct HAT photocatalyst, a variety of indoles derivatives were converted into synthetically interesting 2acylindolines in good to excellent yields as well as great diastereoselectivity under mild conditions. An asymmetric version of the reaction was successfully developed and an experimental mechanistic investigation was carried out in order to gain further insights on the assumed reaction pathway.

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Bio-based crotonic acid from polyhydroxybutyrate: synthesis and photocatalyzed hydroacylation

Abstract: A novel thermolytic distillation process was developed to depolymerize polyhydroxybutyrate (PHB) for the selective production of crotonic acid. The conditions adopted (170°C, 150 mbar) were applied to pure PHB and...

Cited by 33 publications

References 49 publications

Chemical Recycling of Polyhydroxybutyrate (PHB) into Bio-Based Solvents and Their Use in a Circular PHB Extraction

Chemical Recycling of Polyhydroxybutyrate (PHB) into Bio-Based Solvents and Their Use in a Circular PHB Extraction

Tailored recycling chemicals and fuels from poly‐3‐hydroxybutyrate: A review

Decatungstate‐Photocatalyzed Dearomative Hydroacylation of Indoles: Direct Synthesis of 2‐Acylindolines

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