Glycerol Derivatives Research Articles

Preparation of adipic acid from glycerol derivative by photodehalogenative C–C homocoupling: Synergistic effect of Ag cocatalyst and alkali

Preparation of adipic acid from glycerol derivative by photodehalogenative C–C homocoupling: Synergistic effect of Ag cocatalyst and alkali

New sesquiterpenes from the soft coral Litophyton arboreum.

Two new sesquiterpenes; 8α,11-dihydroxy-β-cyperon (2), and 5-epi-7α-hydroxy-( +)-oplopanone (3), were isolated from the soft coral Litophyton arboreum, together with nine known ones, including five sesquiterpenes; 11-hydroxy-8-oxo-β-cyperon (1), alismoxide (4), 5β,8β-epidioxy-11-hydroxy-6-eudesmene (5), chabrolidione B (6), 7-oxo-tri-nor-eudesm-5-en-4β-ol (7), two sterols; 7β-acetoxy-24-methyl-cholesta-5,24(28)-diene-3β,19-diol (8), nebrosteroid M (9), and two glycerol derivatives; chimyl alcohol (10) and batyl alcohol (11). The structures of the isolated compounds were characterized using spectroscopic techniques, predominately HR-ESI-MS, 1D, 2D-NMR, and ECD analyses. Compounds 1-11 were evaluated for their cytotoxic activity against three human cancer-cell lines (A549, MCF-7 and HepG2), and anti-leishmanial potential against the causal parasite, Leishmania major. Compounds 4, 8, and 9 exhibited potent cytotoxic activity against the A549 cell line (IC50 = 17.0 ± 2.5, 13.5 ± 2.1, and 16.5 ± 1.3μg/ml, respectively) as compared with the standard antitumor agent etoposide (IC50 28.4 ± 4.5μg/ml). In addition, compound 9 exhibited remarkable cytotoxic activity against MCF-7 cell line (IC50 = 24.7 ± 2.1μg/ml: 22.2 ± 4.2μg/mL for etoposide).

Determination and correlation of liquid-liquid equilibrium data for the extraction of glycerol carbonate from glycerol using 2-pentanone, cyclohexanone, and 4-methyl-2-pentanone

Glycerol carbonate, a high-value derivative of glycerol, finds extensive applications in the cosmetics, pharmaceuticals, and food industries, as well as in plasticizers and battery electrolytes. This study assessed the feasibility of extracting glycerol carbonate from glycerol using three solvents: 2-pentanone, cyclohexanone, and 4-methyl-2-pentanone. The extraction performance of these solvents was evaluated through liquid-liquid equilibrium (LLE) measurements at atmospheric pressure and temperatures of 303.2 K, 313.2 K, and 323.2 K. Although 4-methyl-2-pentanone exhibited high extraction selectivity, the distribution coefficient of glycerol carbonate in it was less than one. Conversely, while cyclohexanone provided a high distribution coefficient, its extraction selectivity was low. In contrast, 2-pentanone demonstrated a relatively balanced extraction selectivity and capacity. The Non-Random Two-Liquid (NRTL) model was used as an activity model in the equilibrium data correlation, and the corresponding binary interaction parameters were estimated. The regressed parameters of the NRTL model successfully reproduced the phase equilibrium trends observed for all systems investigated, facilitating process design and solvent screening for glycerol carbonate extraction from glycerol.

LC.MS-based chemical profiling of Aristotle's lantern and viscera of the sea urchin Echinometra mathaei collected from the Red Sea and evaluation of their antiviral activity

BackgroundEchinometra mathaei (family Echinometridae), is one of the sea urchins widely distributed on the Egyptian coasts in the Red Sea. This organism contains edible and non-edible parts. The present study was carried out to analyze and identify the metabolites present in the non-edible parts (Aristotle's lantern and viscera) using LC/MS. Also, the cytotoxic activity on Vero cell line and antiviral activity against herpes simplex virus type 1 were evaluated using MTT colorimetric assay.ResultsChemical profiling of the crude extracts of Aristotle's lantern and viscera using LC/MS indicated the presence of 51 and 59 compounds, respectively. The main metabolites present in both non-edible parts were phospholipids, amino acids, peptides, fatty acids and glycerol derivatives. However, the characteristic difference was the presence of carotenoid pigments only in viscera. The crude extract of Aristotle's lantern and viscera showed no cytotoxic activity on Vero cell line and significant antiviral activity against herpes simplex virus with an IC50 value equal to 115.48 ± 1.20 and 122.4 ± 0.50 µg/mL, respectively.ConclusionsIn the present study, the crude extracts of the non-edible parts of E. mathaei were analyzed using LC.MS.MS.QTOF and indicated the existence of 110 chemical compounds, with significant antiviral activity against HSV-1 and no cytotoxic activity. The diversity of the identified compounds with two main categories of compounds, phospholipids and peptides, may contribute to the antiviral activity of Aristotle's lantern and viscera. Additionally, this research focused on clarification of nutritive, pharmaceutical and economic values of these parts. As future prospects, further studies are required to isolate the metabolites and assess the detailed mechanism of antiviral activity via in vitro, in vivo and in silico studies.

Glycerol Carbonate and Solketal Carbonate as Circular Economy Bricks for Supercapacitors and Potassium Batteries.

Considering the worldwide market of batteries and supercapacitors, the (partial or total) replacement of conventional fossil-derived carbonates with bio-based ones in electrolyte formulations would allow the production of safer and more sustainable devices. In this work, embracing the 7th principle of green chemistry, glycerol derivatives (namely glycerol carbonate and solketal carbonate) are tested as solvents and additives for electrolyte formulations. Glycerol carbonate is innovatively employed as promising electrolyte solvent for electric double-layer capacitors with excellent performances. On the other hand, a solketal carbonate-laden liquid electrolyte is investigated for potassium-based batteries, showing a rather stable electrochemical behaviour and performance close to those of commercial oil-derived alternatives.

Harnessing Cooperative Multivalency in Thioguanine for Surface-Enhanced Raman Scattering (SERS)-Based Differentiation of Polyfunctional Analytes Differing by a Single Functional Group.

Small-molecule receptors are increasingly employed to probe various functional groups for (bio)chemical analysis. However, differentiation of polyfunctional analogs sharing multiple functional groups remains challenging for conventional mono- and bidentate receptors because their insufficient number of binding sites limits interactions with the least reactive yet property-determining functional group. Herein, we introduce 6-thioguanine (TG) as a supramolecular receptor for unique tridentate receptor-analyte complexation, achieving ≥97 % identification accuracy among 16 polyfunctional analogs across three classes: glycerol derivatives, disubstituted propane, and vicinal diols. Crucially, we demonstrate distinct spectral changes induced by the tridentate interaction between TG's three anchoring points and all the analyte's functional groups, even the least reactive ones. Notably, hydrogen bond (H-bond) networks formed in the TG-analyte complexes demonstrate additive effects in binding strength originating from good bond linearity, cooperativity, and resonance, thus strengthening complexation events and amplifying the differences in spectral changes induced among analytes. It also enhances spectral consistency by selectively forming a sole configuration that is stronger than the respective analyte-analyte interaction. Finally, we achieve 95.4 % accuracy for multiplex identification of a mixture consisting of multiple polyfunctional analogs. We envisage that extension to other multidentate non-covalent interactions enables the development of interference-free small molecule-based sensors for various (bio)chemical analysis applications.

Recent Progress in Solketal Synthesis from Glycerol and Acetone

AbstractThe extensive use of biodiesel leads to the excess of glycerol as a by‐product. But as a carbon resource, it has been increasingly used in organic synthesis of high value‐added derivatives in recent years. Among them, solketal is one of the most important derivatives of glycerol, which is generated by the reaction of glycerol and acetone. Based on a large number of relevant literatures, this paper systematically summarized the relevant researches in recent ten years. We systematically summary the latest research progress on the synthesis of solketal by glycerol and acetone. We have focused on a systematic study of four different reaction mechanisms for the ketonation reaction of glycerol and acetone. And the types of catalysts were classified into two categories, homogeneous catalysts and non‐homogeneous catalysts, and the non‐homogeneous catalysts were further classified in more details for the study. This review provides a more comprehensive reference for the ketal reaction of glycerol and acetone, and develops some new ideas for the transformation.

Orthogonal Deprotection of Photolabile Protecting Groups and Its Application in Oligosaccharide Synthesis.

We herein report for the first time the inter- and intramolecular orthogonal cleavage of two ortho-nitrobenzyl (NB) analogues. It is shown that the nitroveratryl (NV) group can be photolyzed with high priority when NV and ortho-nitrobenzyl carbonate (oNBC) are used together as the protecting groups of glycans. Notably, the photolytic products could be used directly in the subsequent glycosylation without further purification. With the above-mentioned orthogonal photolabile protecting group strategy in hand, a Mycobacterium tuberculosis tetrasaccharide and a derivative of glucosyl glycerol were rapidly prepared.

Harnessing Cooperative Multivalency in Thioguanine for SERS Differentiation of Polyfunctional Analytes Differing by Single Functional Group

Small‐molecule receptors are increasingly employed to probe various functional groups for (bio)chemical analysis. However, differentiation of polyfunctional analogs sharing multiple functional groups remains challenging for conventional mono‐ and bidentate receptors because their insufficient number of binding sites limits interactions with the least reactive yet property‐determining functional group. Herein, we introduce 6‐thioguanine (TG) as a supramolecular receptor for unique tridentate receptor‐analyte complexation,achieving ≥ 95% identification accuracy among 16 polyfunctional analogs across three scenarios: glycerol derivatives, disubstituted propanes, and vicinal diols. Crucially, we demonstrate distinct spectral changes induced by the tridentate interaction between TG’s three anchoring points and all the analyte’s functional groups, even the least reactive ones. Notably, H‐bond networks formed in the TG‐analyte complexes demonstrate additive effect in binding strength originating from good bond linearity, cooperativity, and resonance, thus strengthens complexation events and amplifies the differences in spectral changes induced among analytes. It also enhances spectral consistency by selectively form a sole configuration that is stronger than the respective analyte‐analyte interaction. Finally, we achieve 95.4% accuracy for multiplex identification of a mixture consisting of multiple polyfunctional analogs. We envisage that extension to other multidentate non‐covalent interactions enables the development of interference‐free small molecule‐based sensors for various (bio)chemical analysis applications.

Experimental Investigation of Glycerol Derivatives and C1–C4 Alcohols as Gasoline Oxygenates

Certain oxygenated compounds, when blended with gasoline, have the ability to inhibit the occurrence and decrease the intensity of engine knock, helping improve engine efficiency. Although ethanol has had widespread use as an oxygenate, higher alcohols, such as butanol, exhibit superior properties in some respects. Besides alcohols, glycerol derivatives such as glycerol tert-butyl ether (GTBE), among others, also have the potential to be used as gasoline oxygenates. This work provides a direct comparison, performed on a modified Waukesha CFR engine, of C1–C4 alcohols and the glycerol derivatives GTBE, solketal, and triacetin, all blended with a gasoline surrogate in different concentrations. The tests focused on how these oxygenated compounds affected the knocking behavior of the fuel blends, since it directly impacts engine efficiency. The test matrices comprised spark-timing sweeps at two different compression ratios, at stoichiometric conditions and constant engine speed. The results showed that, in general, the C1–C4 alcohols and the glycerol derivatives were effective in decreasing knock intensity. n-Butanol and solketal were the noteworthy exceptions, due to their demonstrated inferior knock-inhibiting abilities. On the other hand, isopropanol, isobutanol, and GTBE performed particularly well, indicating their potential to be used as gasoline oxygenates for future engines, as alternatives to ethanol.

UTILIZAÇÃO DO BAGAÇO DE MALTE PARA PREPARAÇÃO DE BIOPLÁSTICOS: UMA PROPOSTA DE ECONOMIA CIRCULAR AO SETOR CERVEJEIRO

USE OF BREWERY SPENT GRAINS FOR THE PREPARATION OF BIOPLASTICS: A PROPOSAL FOR A CIRCULAR ECONOMY TO THE BREWING SECTOR. There is a demand for new technologies to replace fossil resources in activities due to environment concerns. In the circular economy, materials to be discarded are reused and reenter to the economy. An alternative for the plastic problem would be preparation of fiber-reinforced plastics from renewable sources. Herein polymeric films were prepared with starch, glycerol and bagasse derivatives. Some characterization techniques were presented to indicate the best applications. It was identified that higher glycerol ratio films are more malleable and have a higher humidity and solubility. The DSC scans for each film shows no increase in glass transition temperature. Biodiesel films are an alternative for the circular economy of waste and the biodiesel industry, since the study proved to be an alternative for the plastics currently used. This work will certainly attract the students’ interest, because the theme is in their daily lives, also bringing the precepts of sustainability and green chemistry.

Mechanochemistry and oleochemistry: a green combination for the production of high-value small chemicals

Mechanochemistry and oleochemistry and their combination have been known for centuries. Nevertheless, bioeconomy and circular economy concepts is much more recent and has motivated a regain of interest of dedicated research to improve alternative technologies for the valorization of biomass feedstocks. Accordingly, this review paper aims essentially at outlining recent breakthroughs obtained in the field of mechanochemistry and oleochemicals such as triglycerides, fatty acids, and glycerol derivatives. The review discusses advances obtained in the production of small chemicals derived from oils with a brief overview of vegetable oils, mechanochemistry and the use of mechanochemistry for the synthesis of biodiesel, lipidyl-cyclodextrine, dimeric and labelled fatty acids, calcium diglyceroxide, acylglycerols, benzoxazine and solketal. The paper also briefly overviews advances and limits for an industrial application.

Synthesis of Solketal Ethers as Cold Flow Improver for Palm‐Based Biodiesel

AbstractIn this study, glycerol derivatives, namely solketal ethers (SEs), were synthesized by Williamson etherification of solketal with alkyl bromide, catalyzed by tetrabutylammonium iodide (TBAI) and basic aqueous potassium hydroxide (KOH). Under optimized reaction conditions: solketal/alkyl bromide (1 : 1), TBAI (5 mol %), KOH solution (2 equiv), 100 °C, 24 hours, SE were obtained between 21 and 94 %. The influence of the incorporation of SE in palm‐based biodiesel was evaluated using kinematic viscosity, cloud point (CP), and pour point (PP). The addition of 5 wt % of 4‐((butoxy)methyl)‐2,2‐dimethyl‐1,3‐dioxolane reduced PP and CP by 5 and 3 °C, respectively, with viscosity values well within the range of ASTM D6751‐12 standard specifications.

Acid-Catalyzed Etherification of Glycerol with Tert-Butanol: Reaction Monitoring through a Complete Identification of the Produced Alkyl Ethers

Higher tert-Butyl glycerol ethers (tBGEs) are interesting glycerol derivatives that can be produced from tert-butyl alcohol (TBA) and glycerol using an acid catalyst. Glycerol tert-butylation is a complex reaction that leads to the formation of five tBGEs (two monoethers, two diethers, and one triether). In order to gain insight into the reaction progress, the present work reports on the monitoring of glycerol etherification with TBA and p-toluensulfonic acid (PTSA) as homogeneous catalysts. Two analytical techniques were used: gas chromatography (GC), which constitutes the benchmark method, and 1H nuclear magnetic resonance (1H NMR), whose use for this purpose has not been reported to date. A method for the quantitative analysis of tBGEs and glycerol based on 1H NMR is presented that greatly reduced the analysis time and relative error compared with GC-based methods. The combined use of both techniques allowed for a complete quantitative and qualitative description of the glycerol tert-butylation progress. The set of experimental results collected showed the influence of the catalyst concentration and TBA/glycerol ratio on the etherification reaction and evidenced the intrinsic difficulties of this process to achieve high selectivities and yields to the triether.

Chemoenzymatic Synthesis of Chiral Building Blocks Based on the Kinetic Resolution of Glycerol‐Derived Cyclic Carbonates

AbstractThe biocatalytic kinetic resolution of cyclic carbonates derived from glycerol is reported. A selection of 26 esterases and lipases was tested for the asymmetric hydrolysis of the model substrate (epichlorohydrin carbonate) in aqueous medium. Among them, Pig Liver Esterase and Novozym® 435 showed the best selectivity with E=38 and 49, respectively. Both enzymes were employed for the conversion of 12 glycerol derivatives under optimized conditions. The resolution of halogenated carbonates afforded the unconverted enantiomer in up to >99 : 1 er. Furthermore, Novozym® 435 was successfully recycled 10 times without significant loss of activity. Upscaling and isolation of the chiral carbonate was also demonstrated. Subsequent conversion of this chiral building block allowed the direct one‐pot synthesis of (S)‐Guaifenesin, (S)‐Mephenesin and (S)‐Chlorphenesin in up to 89 % yield and 94 : 6 er.

Glycerol Monooleate (GMO): A Valuable Biobased Lubricity and Pour Point Enhancer Blend Component for the ULSD Fuel.

Novel value-added usage of glycerol (biodiesel coproduct) derivatives has been indispensable due to the extensive production of biodiesel. The physical properties of ultralow-sulfur diesel (ULSD) improved with the addition of technical-grade glycerol monooleate (TGGMO) with increasing concentration from 0.01 to 5 wt %. The influence of increasing concentration of TGGMO was studied on the acid value, cloud point, pour point, cold filter plugging point, kinematic viscosity, and lubricity of its blend with ULSD. The results showed improved lubricity for the blended ULSD with TGGMO as shown by the reduced wear scar diameter from 493 to 90 μm. The low-temperature flow properties were also improved as shown by lower pour points of -36 °C for the 1% TGGMO/ULSD blend compared to -25 °C for ULSDTGGMO blends in ULSD of up to 1 wt %, which met the ASTM standard D975 specifications. We also investigated the blending effect of the pure-grade monooleate (PGMO, purity level >99.98%) on the physical properties of ULSD at a blend concentration of 0.5 and 1.0%. Compared to PGMO, TGGMO significantly improved the physical properties of ULSD with increasing concentration from 0.01 to 1 wt %. Nevertheless, PGMO/TGGMO did not significantly affect the acid value, cloud point, or cold filter plugging point of ULSD. A comparison between TGGMO and PGMO showed that TGGMO improves the ULSD fuel lubricity and pour point more effectively than PGMO. PDSC data indicated that although addition of TGGMO will lower the oxidation stability slightly, it is still better than the addition of PGMO. Thermogravimetric analysis (TGA) data showed higher thermal stability and lesser volatility for TGGMO blends compared to those for PGMO blends. The cost effectiveness of TGGMO makes it a better ULSD fuel lubricity enhancer than PGMO.

Synthesis and Fungicide Activity onAsperisporium caricaeof Glycerol Derivatives Bearing 1,2,3-Triazole Fragments

In agriculture, the control of fungal infections is essential to improve crop quality and productivity. This study describes the preparation and fungicidal activity evaluation of 12 glycerol derivatives bearing 1,2,3-triazole fragments. The derivatives were prepared from glycerol in four steps. The key step corresponded to the Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) click reaction between the azide 4-(azidomethyl)-2,2-dimethyl-1,3-dioxolane (3) and different terminal alkynes (57-91% yield). The compounds were characterized by infrared spectroscopy, nuclear magnetic resonance (1H and 13C), and high-resolution mass spectrometry. The in vitro assessment of the compounds on Asperisporium caricae, that is, the etiological agent of papaya black spot, at 750 mg L-1 showed that the glycerol derivatives significantly inhibited conidial germination with different degrees of efficacy. The most active compound 4-(3-chlorophenyl)-1-((2,2-dimethyl-1,3-dioxolan-4-yl) methyl)-1H-1,2,3-triazole (4c) presented a 91.92% inhibition. In vivo assays revealed that 4c reduced the final severity (70.7%) and area under the disease severity progress curve of black spots on papaya fruits 10 days after inoculation. The glycerol-bearing 1,2,3-triazole derivatives also present agrochemical-likeness properties. Our in silico study using molecular docking calculations show that all triazole derivatives bind favorably to the sterol 14α-demethylase (CYP51) active site at the same region of the substrate lanosterol (LAN) and fungicide propiconazole (PRO). Thus, the mechanism of action of the compounds 4a-4l may be the same as the fungicide PRO, blocking the entrance/approximation of the LAN into the CYP51 active site by steric effects. The reported results point to the fact that the glycerol derivatives may represent a scaffold to be explored for the development of new chemical agents to control papaya black spot.

Eicosanoid turnover in GtoPdb v.2023.1

Eicosanoids are 20-carbon fatty acids, where the usual focus is the polyunsaturated analogue arachidonic acid and its metabolites. Arachidonic acid is thought primarily to derive from phospholipase A2 action on membrane phosphatidylcholine, and may be re-cycled to form phospholipid through conjugation with coenzyme A and subsequently glycerol derivatives. Oxidative metabolism of arachidonic acid is conducted through three major enzymatic routes: cyclooxygenases; lipoxygenases and cytochrome P450-like epoxygenases, particularly CYP2J2. Isoprostanes are structural analogues of the prostanoids (hence the nomenclature D-, E-, F-isoprostanes and isothromboxanes), which are produced in the presence of elevated free radicals in a non-enzymatic manner, leading to suggestions for their use as biomarkers of oxidative stress. Molecular targets for their action have yet to be defined.

Ultra-thin CoNi0.2P nanosheets for plastics and biomass participated hybrid water electrolysis

Designing cost-efficient and active electrocatalysts are very crucial for their practical implementation in electrochemical energy conversion systems. Herein, a handy template-post phosphatization approach is adopted to achieve ultra-thin CoNi0.2P nanosheets attached to nickel foam (termed as CoNi0.2P-uNS/NF) nanohybrids. Profiting from ultra-thin construction and the optimization of electronic structure, CoNi0.2P-uNS/NF exhibits high electroactivity for hydrogen evolution reaction (HER), which only needs an overpotential of 43 mV to obtain the current density of 10 mA cm−2. Additionally, CoNi0.2P-uNS/NF also reveals prominent electroactivity for ethylene glycol oxidation reaction (EGOR) in an alkaline environment due to the surface electrochemical reconstruction. Additionally, CoNi0.2P-uNS/NF also reveals similar high electroactivity for glycerol and furfural derivatives oxidation reaction, revealing its potential as a composition-controlled platform catalyst. For practical application, CoNi0.2P-uNS/NF||CoNi0.2P-uNS/NF electrolyzer is assembled to directly electrolyze the hydrolysate of polyethylene terephthalate (i.e., the mixture of terephthalate and ethylene glycol) for the co-generation of formate and hydrogen, accompanying with lower integral electrolytic voltage (1.24 V) than traditional water splitting (1.53 V) at current density 50 mA cm−2. This work expands the territory for energy-saving co-generation of hydrogen and value-added chemical products.

Efficient and Reversible Capture of CO2 in CO2-Binding Organic Liquids Formed by 1,1,3,3-Tetramethylguanidine and Glycerol Derivatives

A class of CO2-binding organic liquids (CO2-BOLs) composed of 1,1,3,3-Tetramethylguanidine (TMG) and Glycerol (Gly) and Gly’s amino derivatives were developed for highly efficient and reversible CO2 capture. These CO2-BOLs exhibited high gravimetric CO2 solubility up to 0.196 g CO2·g–1 at 313.2 K and 1.0 atm, superior to most functionalized ILs and other absorbents. The influential factors of CO2 absorption, such as components of CO2-BOLs, absorption temperature, and CO2 partial pressure together with water contents were investigated, and the recyclability of CO2-BOLs was verified to be excellent. The absorption mechanism of CO2-BOLs was explored with the help of spectral analysis, quantum chemical calculation, and thermodynamic analysis. All the results revealed that chemisorption took place once these CO2-BOLs were exposed to CO2, and alkyl guanidine carbonates were produced. Besides, it is illustrated that introducing the amino group to Gly could reduce the nucleophilic reactivity of CO2-BOLs, along with the absorption enthalpy simultaneously.