scholarly journals Multi-Step Enzymatic Synthesis of 1,9-Nonanedioic Acid from a Renewable Fatty Acid and Its Application for the Enzymatic Production of Biopolyesters

Polymers ◽  
2019 ◽  
Vol 11 (10) ◽  
pp. 1690
Author(s):  
Lee ◽  
Kang ◽  
Kim ◽  
Seo ◽  
Pyo ◽  
...  
Keyword(s):  
Oleic Acid ◽  
Immobilized Lipase ◽  
Diphenyl Ether ◽  
Average Molecular Weight ◽  
Reaction Medium ◽  
Building Blocks ◽  
Biological Synthesis ◽  
Enzymatic Production ◽  
Nonanedioic Acid ◽  
Long Chain

1,9-Nonanedioic acid is one of the valuable building blocks for producing polyesters and polyamides. Thereby, whole-cell biosynthesis of 1,9-nonanedioic acid from oleic acid has been investigated. A recombinant Corynebacterium glutamicum, expressing the alcohol/aldehyde dehydrogenases (ChnDE) of Acinetobacter sp. NCIMB 9871, was constructed and used for the production of 1,9-nonanedioic acid from 9-hydroxynonanoic acid, which had been produced from oleic acid. When 9-hydroxynonanoic acid was added to a concentration of 20 mM in the reaction medium, 1,9-nonanedioic acid was produced to 16 mM within 8 h by the recombinant C. glutamicum. The dicarboxylic acid was isolated via crystallization and then used for the production of biopolyester by a lipase. For instance, the polyesterification of 1,9-nonanedioic acid and 1,8-octanediol in diphenyl ether by the immobilized lipase B from Candida antarctica led to formation of the polymer product with the number-average molecular weight (Mn) of approximately 21,000. Thereby, this study will contribute to biological synthesis of long chain dicarboxylic acids and their application for the enzymatic production of long chain biopolyesters.

scholarly journals Enzymatic Polycondensation of 1,6-Hexanediol and Diethyl Adipate: A Statistical Approach Predicting the Key-Parameters in Solution and in Bulk

Polymers ◽  
2020 ◽  
Vol 12 (9) ◽  
pp. 1907
Author(s):  
Kifah Nasr ◽  
Julie Meimoun ◽  
Audrey Favrelle-Huret ◽  
Julien De Winter ◽  
Jean-Marie Raquez ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Atmospheric Pressure ◽  
Statistical Approach ◽  
Immobilized Lipase ◽  
Diphenyl Ether ◽  
Average Molecular Weight ◽  
Statistical Technique ◽  
Influential Factor ◽  
Enzyme Loading

Among the various catalysts that can be used for polycondensation reactions, enzymes have been gaining interest for three decades, offering a green and eco-friendly platform towards the sustainable design of renewable polyesters. However, limitations imposed by their delicate nature, render them less addressed. As a case study, we compare herein bulk and solution polycondensation of 1,6-hexanediol and diethyl adipate catalyzed by an immobilized lipase from Candida antarctica. The influence of various parameters including time, temperature, enzyme loading, and vacuum was assessed in the frame of a two-step polymerization with the help of response surface methodology, a statistical technique that investigates relations between input and output variables. Results in solution (diphenyl ether) and bulk conditions showed that a two-hour reaction time was enough to allow adequate oligomer growth for the first step conducted under atmospheric pressure at 100 °C. The number-average molecular weight (Mn) achieved varied between 5000 and 12,000 g·mol−1 after a 24 h reaction and up to 18,500 g∙mol−1 after 48 h. The statistical analysis showed that vacuum was the most influential factor affecting the Mn in diphenyl ether. In sharp contrast, enzyme loading was found to be the most influential parameter in bulk conditions. Recyclability in bulk conditions showed a constant Mn of the polyester over three cycles, while a 17% decrease was noticed in solution. The following work finally introduced a statistical approach that can adequately predict the Mn of poly(hexylene adipate) based on the choice of parameter levels, providing a handy tool in the synthesis of polyesters where the control of molecular weight is of importance.

scholarly journals Synthesis and Characterization of Partially Renewable Oleic Acid-Based Ionomers for Proton Exchange Membranes

Polymers ◽  
2020 ◽  
Vol 13 (1) ◽  
pp. 130
Author(s):  
Carlos Corona-García ◽  
Alejandro Onchi ◽  
Arlette A. Santiago ◽  
Araceli Martínez ◽  
Daniella Esperanza Pacheco-Catalán ◽  
...  
Keyword(s):  
Oleic Acid ◽  
Proton Conductivity ◽  
Electrochemical Impedance ◽  
Proton Exchange Membranes ◽  
Proton Exchange ◽  
Molar Ratio ◽  
Aromatic Diamines ◽  
Chemical Structures ◽  
Long Chain

The future availability of synthetic polymers is compromised due to the continuous depletion of fossil reserves; thus, the quest for sustainable and eco-friendly specialty polymers is of the utmost importance to ensure our lifestyle. In this regard, this study reports on the use of oleic acid as a renewable source to develop new ionomers intended for proton exchange membranes. Firstly, the cross-metathesis of oleic acid was conducted to yield a renewable and unsaturated long-chain aliphatic dicarboxylic acid, which was further subjected to polycondensation reactions with two aromatic diamines, 4,4′-(hexafluoroisopropylidene)bis(p-phenyleneoxy)dianiline and 4,4′-diamino-2,2′-stilbenedisulfonic acid, as comonomers for the synthesis of a series of partially renewable aromatic-aliphatic polyamides with an increasing degree of sulfonation (DS). The polymer chemical structures were confirmed by Fourier transform infrared (FTIR) and nuclear magnetic resonance (1H, 13C, and 19F NMR) spectroscopy, which revealed that the DS was effectively tailored by adjusting the feed molar ratio of the diamines. Next, we performed a study involving the ion exchange capacity, the water uptake, and the proton conductivity in membranes prepared from these partially renewable long-chain polyamides, along with a thorough characterization of the thermomechanical and physical properties. The highest value of the proton conductivity determined by electrochemical impedance spectroscopy (EIS) was found to be 1.55 mS cm−1 at 30 °C after activation of the polymer membrane.

scholarly journals Bacterial precursors and unsaturated long-chain fatty acids are biomarkers of North-Atlantic demosponges

2020 ◽  
Author(s):  
Anna de Kluijver ◽  
Klaas G.J. Nierop ◽  
Teresa M. Morganti ◽  
Martijn C. Bart ◽  
Beate M. Slaby ◽  
...  
Keyword(s):  
Fatty Acids ◽  
North Atlantic ◽  
Deep Sea ◽  
North Atlantic Ocean ◽  
Carbon Isotopic Composition ◽  
Building Blocks ◽  
Functional Ecology ◽  
The North ◽  
A Chain ◽  
Long Chain

AbstractSponges produce distinct fatty acids (FAs) that (potentially) can be used as chemotaxonomic and ecological biomarkers to study endosymbiont-host interactions and the functional ecology of sponges. Here, we present FA profiles of five common habitat-building deep-sea sponges (class Demospongiae, order Tetractinellida), which are classified as high microbial abundance (HMA) species. Geodia hentscheli, G. parva, G. atlantica, G. barretti, and Stelletta rhaphidiophora were collected from boreal and Arctic sponge grounds in the North-Atlantic Ocean. Bacterial FAs dominated in all five species and particularly isomeric mixtures of mid-chain branched FAs (MBFAs, 8- and 9-Me-C16:0 and 10 and 11-Me-C18:0) were found in high abundance (together ≥ 20% of total FAs) aside more common bacterial markers. In addition, the sponges produced long-chain linear, mid- and a(i)-branched unsaturated FAs (LCFAs) with a chain length of 24‒28 C atoms and had predominantly the typical Δ5,9 unsaturation, although also Δ9,19 and (yet undescribed) Δ11,21 unsaturations were identified. G. parva and S. rhaphidiophora each produced distinct LCFAs, while G. atlantica, G. barretti, and G. hentscheli produced similar LCFAs, but in different ratios. The different bacterial precursors varied in carbon isotopic composition (δ13C), with MBFAs being more enriched compared to other bacterial (linear and a(i)-branched) FAs. We propose biosynthetic pathways for different LCFAs from their bacterial precursors, that are consistent with small isotopic differences found in LCFAs. Indeed, FA profiles of deep-sea sponges can serve as chemotaxonomic markers and support the conception that sponges acquire building blocks from their endosymbiotic bacteria.

scholarly journals Cochineal Waxy Residues as Source of Policosanol: Chemical Hydrolysis and Enzymatic Transesterification

2019 ◽  
Vol 2019 ◽  
pp. 1-10 ◽  
Author(s):  
Emilia Ramos-Zambrano ◽  
Pedro Herrera-Serrano ◽  
Jorge García-Dávila ◽  
Gabriel Ríos-Cortés ◽  
Antonio Ruperto Jiménez-Aparicio ◽  
...  
Keyword(s):  
Molecular Sieves ◽  
Reaction Medium ◽  
Value Added ◽  
Carminic Acid ◽  
Enzymatic Transesterification ◽  
Chemical Hydrolysis ◽  
Agroindustrial Waste ◽  
Main Component ◽  
Long Chain ◽  
Value Added Products

The aim of this study was to obtain and characterise the long-chain alcohols present in policosanol derived from waste from the production of carminic acid, a natural colouring agent widely used in the food industry. The effectiveness of different methods designed for extraction of policosanol from waxy waste was investigated and its content and composition was determined. Triacontanol was the main component in policosanol produced by chemical processes, and it yields up to 13% by alkaline hydrolysis in water and chloroform extraction. Regarding enzymatic transesterification, policosanol was obtained using lipase Candida antarctica recombinant in Aspergillus niger (CAL-Bn) in a reaction medium with toluene. To improve the reaction, different acyl receptors, propanol, butanol, and isopropanol, were tested and molecular sieves were employed to maintain an anhydrous reaction medium. In this case, the policosanol was made up of other long-chain alcohols, but triacontanol was obtained in yields of up to 19% using isopropanol as an acyl receptor. Triacontanol has a great commercial value due to its effect as a promoter of plant growth, and these results contribute to the use and application of this agroindustrial waste in obtaining value-added products.

scholarly journals Interesterification of Egg-Yolk Phosphatidylcholine with p-Methoxycinnamic Acid Catalyzed by Immobilized Lipase B from Candida Antarctica

Catalysts ◽  
2020 ◽  
Vol 10 (10) ◽  
pp. 1181
Author(s):  
Magdalena Rychlicka ◽  
Anna Gliszczyńska
Keyword(s):  
Reaction Time ◽  
Design Method ◽  
Immobilized Lipase ◽  
Reaction Medium ◽  
Solvent System ◽  
Novozym 435 ◽  
Molar Ratio ◽  
Binary Solvent ◽  
Methoxycinnamic Acid ◽  
Substrate Molar Ratio

The p-methoxycinnamic acid (p-MCA) is one of the most popular phenylpropanoids, the beneficial impact of which on the human health is well documented in the literature. This compound has shown many valuable activities including anticancer, antidiabetic, and neuro- and hepatoprotective. However, its practical application is limited by its low bioavailability resulting from rapid metabolism in the human body. The latest strategy, aimed at overcoming these limitations, is based on the production of more stability in systemic circulation bioconjugates with phospholipids. Therefore, the aim of this research was to develop the biotechnological method for the synthesis of phospholipid derivatives of p-methoxycinnamic acid, which can play a role of new nutraceuticals. We developed and optimized enzymatic interesterification of phosphatidylcholine (PC) with ethyl p-methoxycinnamate (Ep-MCA). Novozym 435 and a binary solvent system of toluene/chloroform 9:1 (v/v) were found to be the effective biocatalyst and reaction medium for the synthesis of structured p-MCA phospholipids, respectively. The effects of the other reaction parameters, such as substrate molar ratio, enzyme dosage, and reaction time, on the degree of incorporation of p-MCA into PC were evaluated by use of an experimental factorial design method. The results showed that substrate molar ratio and biocatalyst load have significant effects on the synthesis of p-methoxycinnamoylated phospholipids. The optimum conditions were: Reaction time of three days, 30% (w/w) of Novozym 435, and 1/10 substrate molar ratio PC/Ep-MCA. Under these parameters, p-methoxycinnamoylated lysophosphatidylcholine (p-MCA-LPC) and p-methoxycinnamoylated phosphatidylcholine (p-MCA-PC) were obtained in isolated yields of 32% and 3% (w/w), respectively.

scholarly journals Screening and Evaluation of New Hydroxymethylfurfural Oxidases for Furandicarboxylic Acid Production

2020 ◽  
Vol 86 (16) ◽  
Author(s):  
Mario Viñambres ◽  
Marta Espada ◽  
Angel T. Martínez ◽  
Ana Serrano
Keyword(s):  
Hydrogen Peroxide ◽  
Heterologous Expression ◽  
Half Life ◽  
Enzyme Stability ◽  
Bacterial Species ◽  
Building Blocks ◽  
Enzymatic Production ◽  
Content Type ◽  
Furandicarboxylic Acid ◽  
Total Turnover

ABSTRACT The enzymatic production of 2,5-furandicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF) has gained interest in recent years, as FDCA is a renewable precursor of poly(ethylene-2,5-furandicarboxylate) (PEF). 5-Hydroxymethylfurfural oxidases (HMFOs) form a flavoenzyme family with genes annotated in a dozen bacterial species but only one enzyme purified and characterized to date (after heterologous expression of a Methylovorus sp. HMFO gene). This oxidase acts on both furfuryl alcohols and aldehydes and, therefore, is able to catalyze the conversion of HMF into FDCA through 2,5-diformylfuran (DFF) and 2,5-formylfurancarboxylic acid (FFCA), with only the need of oxygen as a cosubstrate. To enlarge the repertoire of HMFO enzymes available, genetic databases were screened for putative HMFO genes, followed by heterologous expression in Escherichia coli. After unsuccessful trials with other bacterial HMFO genes, HMFOs from two Pseudomonas species were produced as active soluble enzymes, purified, and characterized. The Methylovorus sp. enzyme was also produced and purified in parallel for comparison. Enzyme stability against temperature, pH, and hydrogen peroxide, three key aspects for application, were evaluated (together with optimal conditions for activity), revealing differences between the three HMFOs. Also, the kinetic parameters for HMF, DFF, and FFCA oxidation were determined, the new HMFOs having higher efficiencies for the oxidation of FFCA, which constitutes the bottleneck in the enzymatic route for FDCA production. These results were used to set up the best conditions for FDCA production by each enzyme, attaining a compromise between optimal activity and half-life under different conditions of operation. IMPORTANCE HMFO is the only enzyme described to date that can catalyze by itself the three consecutive oxidation steps to produce FDCA from HMF. Unfortunately, only one HMFO enzyme is currently available for biotechnological application. This availability is enlarged here by the identification, heterologous production, purification, and characterization of two new HMFOs, one from Pseudomonas nitroreducens and one from an unidentified Pseudomonas species. Compared to the previously known Methylovorus HMFO, the new enzyme from P. nitroreducens exhibits better performance for FDCA production in wider pH and temperature ranges, with higher tolerance for the hydrogen peroxide formed, longer half-life during oxidation, and higher yield and total turnover numbers in long-term conversions under optimized conditions. All these features are relevant properties for the industrial production of FDCA. In summary, gene screening and heterologous expression can facilitate the selection and improvement of HMFO enzymes as biocatalysts for the enzymatic synthesis of renewable building blocks in the production of bioplastics.

scholarly journals Improved Method for Gas Chromatographic–Mass Spectrometric Analysis of 1-13C-labeled Long-Chain Fatty Acids in Plasma Samples

2002 ◽  
Vol 48 (6) ◽  
pp. 906-912 ◽  
Author(s):  
José M Hernández-Pérez ◽  
Eduard Cabré ◽  
Lourdes Fluvià ◽  
Ágata Motos ◽  
Cruz Pastor ◽  
...  
Keyword(s):  
Fatty Acids ◽  
Oleic Acid ◽  
Fatty Acid ◽  
Isotopic Ratio ◽  
Internal Standard ◽  
Mass Spectrometric ◽  
Spectrometric Analysis ◽  
Calibration Curves ◽  
Long Chain ◽  
Chromatographic Mass

Abstract Background: Gas chromatographic–mass spectrometric (GC/MS) tracking of stable-isotope-labeled substrates is useful in metabolic studies. However, GC/MS analysis of long-chain fatty acid methyl esters yields results that mostly depend on their concentration in the system. We describe a protocol aimed to obviate this and other drawbacks in plasma [1-13C]palmitic and [1-13C]oleic acid measurements. Methods: Lipoproteins were separated by sequential ultracentrifugation. Free or esterified heptadecanoic acid was used as internal standard. Fatty acids were derivatized to trimethylsilyl (TMS) esters. GC separation was in isothermal mode at 210 °C for 27 min. For both TMS-palmitate and TMS-oleate, M and [M + 1] signals were simultaneously acquired with a dual acquisition program in single-ion monitoring mode. Calibration mixtures containing increasing amounts of labeled fatty acids were prepared gravimetrically to construct calibration curves for isotopic enrichment. Likewise, five calibration curves (for increasing concentrations) were constructed for each fatty acid; this allowed selection of the most appropriate curve for the concentration in a plasma sample. Results: Oleic acid-TMS ester was clearly separated from that of its stereoisomer, elaidic acid. Within a 10-fold concentration range, the isotopic ratio was independent on the amount of the analyte in the sample, with a maximum uncertainty of 0.34% in terms of molar percent excess. In addition, the within- and between-day imprecision (CV) of the method was <1%. Conclusion: Results obtained with this method are independent of concentration and sufficiently precise for tracking 1-13C-labeled palmitic and oleic acids in biological samples

scholarly journals A straightforward electrospray ionization high resolution mass spectrometry method for underivatized long chain polysaccharides

2015 ◽  
Vol 13 (1) ◽  
Author(s):  
Roxana M. Ghiulai ◽  
Mirela Sarbu ◽  
Constantin Ilie ◽  
Alina D. Zamfir
Keyword(s):  
Mass Spectrometry ◽  
Molecular Weight ◽  
Electrospray Ionization ◽  
High Resolution Mass Spectrometry ◽  
Average Molecular Weight ◽  
Ionization Mass ◽  
Esi Ms ◽  
Singly Charged ◽  
Charged Ions ◽  
Long Chain

AbstractStructural analysis of long chain polysaccharides by electrospray ionization mass spectrometry (ESI-MS) is challenging since these molecules do not contain readily ionizable groups. Their mass spectra are dominated by singly charged ions, limiting the detection of high molecular weight species. Derivatization can enhance ionization, but analyte loss on purification decreases sensitivity. We report a method based on nanoESI-MS and MS/MS by collision induced dissociation (CID) for underivatized long chain polysaccharides. The procedure was tested on underivatized polydisperse dextrans (average molecular weight 4,000) at 2.6 kV ESI voltage and CID MS/MS at energies between 30-60 eV. 113 ions corresponding to species from Glc2 to Glc35 were detected. Ions at m/z 1,409.48, 1,107.35 and 1,438.47, assigned to [G17+2Na]2+,[G20+H+Na+K]3+ and [G35+2H+Na+K]4+, were sequenced and characterized by MS/MS. The component containing 35 Glc repeats is the longest polysaccharide chain detected by ESI-MS and structurally analyzed by MS/MS without prior derivatization and/or separation.

Corrigendum to the paper “Enzymatic production of biodiesel from Pistacia chinensis bge seed oil using immobilized lipase” [Fuel 92 (2012) 89–93]

Fuel ◽  
2012 ◽  
Vol 96 ◽  
pp. 611
Author(s):  
Xun Li ◽  
Xiao-Yun He ◽  
Zhi-Lin Li ◽  
You-Dong Wang ◽  
Chun-Yu Wang ◽  
...  
Keyword(s):  
Seed Oil ◽  
Immobilized Lipase ◽  
Enzymatic Production

scholarly journals Conversion of Oleic Acid into Azelaic and Pelargonic Acid by a Chemo-Enzymatic Route

Molecules ◽  
2020 ◽  
Vol 25 (8) ◽  
pp. 1882 ◽  
Author(s):  
Elisabetta Brenna ◽  
Danilo Colombo ◽  
Giuseppe Di Lecce ◽  
Francesco G. Gatti ◽  
Maria Chiara Ghezzi ◽  
...  
Keyword(s):  
Oleic Acid ◽  
Azelaic Acid ◽  
Atmospheric Oxygen ◽  
Reaction Medium ◽  
Chemical Oxidation ◽  
Pelargonic Acid ◽  
Dihydroxystearic Acid ◽  
Chemical Purity ◽  
Enzymatic Route

A chemo-enzymatic approach for the conversion of oleic acid into azelaic and pelargonic acid is herein described. It represents a sustainable alternative to ozonolysis, currently employed at the industrial scale to perform the reaction. Azelaic acid is produced in high chemical purity in 44% isolation yield after three steps, avoiding column chromatography purifications. In the first step, the lipase-mediated generation of peroleic acid in the presence of 35% H2O2 is employed for the self-epoxidation of the unsaturated acid to the corresponding oxirane derivative. This intermediate is submitted to in situ acid-catalyzed opening, to afford 9,10-dihydroxystearic acid, which readily crystallizes from the reaction medium. The chemical oxidation of the diol derivative, using atmospheric oxygen as a stoichiometric oxidant with catalytic quantities of Fe(NO3)3∙9∙H2O, (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), and NaCl, affords 9,10-dioxostearic acid which is cleaved by the action of 35% H2O2 in mild conditions, without requiring any catalyst, to give pelargonic and azelaic acid.

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