Epoxy Derivatives Research Articles

Advanced Vitrimer with Spiropyran Beads: A Multi-Responsive, Shape Memory, Self-Healing, and Reprocessable Smart Material.

Thermosetting materials have limitations in terms of reshaping and recycling due to their irreversible bond structures, leading to significant plastic waste issues. Recently, epoxy vitrimers based on dynamic covalent bond exchange have been introduced as promising alternatives to traditional thermosets. Particularly, they demonstrate significant potential applications in the field of multi-responsive materials. In this research, a self-healable and mechano-responsive vitrimer (EB-V) is successfully prepared, incorporating epoxide spiropyran beads (ESP beads) derived from citric acid and epoxy derivatives. To enable self-reporting of cracks through color changes, ESP beads are covalently bonded to the vitrimer via an epoxy-carboxylic acid reaction. The photochromic properties of EB-V are demonstrated by color and fluorescence changes, and its tensile strength increased from 2.0 to 6.8MPa compared to the control sample. Dynamic mechanical analysis confirmed the covalent exchange reaction of the vitrimer, revealing its reconfigurable behavior and stress relaxation at elevated temperatures. Furthermore, EB-V exhibited exceptional properties, including self-healing and reprocessability. As a smart material, it holds great promise for a wide range of applications, such as sensors, actuators, 4D printing, and industrial safety diagnostics.

Quantification of Epoxyeicosatrienoic acids Enantiomers: The development of reliable and practical liquid chromatography mass Spectrometry assay

Epoxyeicosatrienoic acids (EETs) are increasingly recognized as key metabolites in the arachidonic acid (AA) metabolic pathway. EETs are epoxy derivatives of AA with two chiral centers formed by cytochrome P450 (CYP) enzymes. EETs have reported biological activities as racemates; however, knowledge on specific optical isomers of EET is lacking. A main reason is the absence of practical assay to quantify EETs isomers associated with specific pathological conditions and enzymes. The reported underivatized chiral LC-MS/MS assays utilize different mobile phases and flow rates or required long run times to achieve separation of EET stereoisomers. Others incorporated a derivatization step before the separation of EETs in their assays. Therefore, the objective of this study was to develop and validate a stereoselective assay for the simultaneous quantitation of underivatized EET enantiomers using Liquid Chromatography Mass Spectrometry (LC-MS/MS) with an optimum baseline separation using binary mobile phase and gradient elution. Herein, we report the development and validation of an LC-MS/MS assay, and its application to quantify the formation of EET enantiomers mediated by human liver microsomes. Assay linearity extends over 10–600 ng/mL with r2 > 0.99 for all EETs enantiomers. The inter-run accuracy was within ± 15 %, and precision was ≤ 15 %, and < 20 % for the LLOQ. The matrix effect for the current assay was within ≤ ±20 %, and the mean recovery for quantitative methods was 70–125 %. The assay proved to be reliable and practical for chiral analysis.

Solvent-controlled tunable Knoevenagel-epoxidation reaction: Synthesis of diverse epoxide derivatives by aldehydes and nitrile methylenes

Here, we report a solvent-controlled tandem Knoevenagel-epoxidation reaction capable of efficiently and selectively synthesizing α-formamidoepoxide and epoxidized benzylidene derivatives of malononitrile dimers. By carefully selecting the solvent system, we demonstrate the tunability of this reaction towards different product outcomes, thereby providing a switchable synthetic platform for various epoxy derivatives. The reaction proceeds under mild conditions with short reaction times, high efficiency, and good tolerance towards diverse functional groups. Furthermore, this method is scalable to gram-scale production.

Controlling Hybrid Polyhydroxyurethane Adhesive and Rheological Properties by Partial Carbonation of Biobased Epoxy Monomer.

Controlling hybrid material properties by simple monomer design offers an elegant pathway to prepare thermoset adhesives with tunable properties. Herein, biobased hybrid polyhydroxyurethane/polyepoxy is prepared starting from partially carbonated cashew nut shell epoxy derivatives (NC514) and m-xylene diamine (MXDA). The curing reactions, that is, epoxy-amine and cyclic carbonate aminolysis, monitored by ATR-IR spectroscopy at 50°C are found to be concomitant yielding highly homogeneous materials. Hybrid networks are extensively characterized by swelling tests, TGA, DMA, DSC, tensile tests, rheology, and lap-shear-test on aluminum substrates. The introduction of hydroxyurethane moieties within the epoxy-amine networks enhanced the adhesion properties (up to 20% compare to neat epoxy resins) by combining hydrogen bonding capability and vitrimeric properties (thermoset able to flow). Rheological characterizations and reprocessing tests demonstrated that hybrid adhesives with up to 47 mol% of cyclic carbonate groups are capable of covalent exchange (internally catalyzed by tertiary amine) while keeping similar thermomechanical properties and enhanced adhesion strength compare to the permanent epoxy network.

Multiple Traces of Families of Epoxy Derivatives as New Inhibitors of the Industrial Polymerization Reaction of Propylene.

In this study, the impact of ethylene oxide, propylene oxide, 1,2-butene oxide, and 1,2-pentene oxide on the polymerization of propylene at an industrial level was investigated, focusing on their influence on the catalytic efficiency and the properties of polypropylene (PP) without additives. The results show that concentrations between 0 and 1.24 ppm of these epoxides negatively affect the reaction's productivity, the PP's mechanical properties, the polymer's fluidity index, and the PP's thermal properties. Fourier transform infrared spectroscopy (FTIR) revealed bands for the Ti-O bond and the Cl-Ti-O-CH2 bonds at 430 to 475 cm-1 and 957 to 1037 cm-1, respectively, indicating the interaction between the epoxides and the Ziegler-Natta catalyst. The thermal degradation of PP in the presence of these epoxides showed a similar trend, varying in magnitude depending on the concentration of the inhibitor. Sample M7, with 0.021 ppm propylene oxide, exhibited significant mass loss at both 540 °C and 600 °C, suggesting that even small concentrations of this epoxide can markedly increase the thermal degradation of PP. This pattern is repeated in samples with 1,2-butene oxide and 1,2-pentene oxide. These results highlight the need to strictly control the presence of impurities in PP production to optimize both the final product's quality and the polymerization process's efficiency.

Overview of the Biochemical Potential of Solanum Nigrum

Solanum nigrum is known locally as the nightshadesamily, and it is considered one of the widespread plants that possess great biochemical potential. This review dealt with providing a comprehensive summary of the biochemistry of this plant, as it contains Solanum nigrum. It contains an important group of biologically active substances, including flavonoids, and some phenolic derivatives. It also contains some alkaloids, epoxy derivatives, and other important compounds. These substances have important biological activity, including significant and powerful antioxidant and anti-inflammatory properties, as well as strong antimicrobial and anti-cancer properties, and other medically important properties. This plant has been used for medicinal purposes for a long time in treating many diseases. Finally, this review indicates the wide biological diversity in biochemistry. The study also touched on some potential applications in various fields, including nutrition and medicine.

Multiple approaches to exploit ferulic acid bio-based epoxy monomer for green thermoset

Bio-based monomers are under investigation to replace fossil-based materials due to the concerns regarding climate change and depletion of fossil raw materials. Lignin, cellulose and hemicellulose represent the main interesting platform to use for developing new monomers due to their significant abundance. Ferulic acid is one of the moieties derived from lignin which can be suitable for many applications. In this study, the ferulic acid was epoxidated and it was investigated in cationic UV-curing. Due to the limited performance obtained during UV-curing, two alternative strategies were developed to overcome the initial problem of poor material properties. A thiol-ene epoxy system based on the ferulic epoxy derivative and a commercially available thiol as well as a thermally cured system based on pure cationic curing of ferulic acid diepoxy were chosen as alternative methods. The different curing processes were thoroughly investigated by means of FTIR (Fourier transform infrared spectroscopy) and photo-DSC (differential scanning calorimetry). The thermo-mechanical properties of the thermosets employing DMA- (dynamic mechanical analysis) and tensile analysis were deeply evaluated. Finally, the possibility to use the best cured system as an adhesive was raised investigating the shear strength of metallic and composite joined samples using the single lap offset (SLO) test under compression.

AIE-active vitrimer with photoluminescence, reprocessability and shape memory effects

An AIE-active vitrimer is successfully synthesized through the crosslinking of epoxy derivatives of tetraphenylethylene. This vitrimer demonstrates photoluminescence and remarkable properties in terms of reshaping, reprocessing, and shape memory.

Fetal valproate syndrome (review and case report)

Toxic damages in fetuses and newborns rank highly in perinatal pathology structure, though their true importance is not understood thoroughly. Among toxic encephalopathies of newborns the accent should be given to the conditions caused by administration of medicines by a pregnant woman. The use of medicines, especially neurotropic, during pregnancy is often forced. The widespread prevalence of epilepsy in women of reproductive age leads, in certain cases, to anticonvulsants administration during pregnancy. The dominance of valproic acid in epilepsy treatment in recent decades requires studying its teratogenic effect in newborns fetal valproate syndrome. The fetal valproate syndrome has casuistic nature and polymorphic phenomenology.&#x0D; The clinical case study is presented of a newborn with fetal valproate syndrome (born to a mother who took valproic acid in dose 14 mg/kg per day or 750 mg per day while pregnant, due to Janz syndrome), confirmed by valproic acid presence in the blood of a newborn (47.36 mol/l), with the main clinical manifestation of incomplete cleft palate (hard and soft) without other typical disturbances.&#x0D; Most anticonvulsants have a teratogenic effect, and may cause malformations and toxic encephalopathies in fetus and newborns. The similarity of clinical manifestations of intrauterine exposure to various anticonvulsants is associated with the presence of common metabolic links (epoxy and dihydrodiol derivatives of phenytoin, phenobarbital and carbamazepine). In spite of similarity of some teratogenic effect mechanisms, the anticonvulsants nature introduces specific clinical manifestations of these disorders.

Optimal combination of UV‐induced cationic ring opening polymerization monomers for light‐weight automotive plastic coating

AbstractCROP reactivity of organic coatings composed of three structurally different monomers with epoxy or oxetane derivatives was investigated, focusing on rheological and surface mechanical properties. Real‐time crosslinking behavior of CROP monomers was monitored using a rotational rheometer. Results of differential scanning calorimetry with in situ UV irradiation revealed that the ring opening reactivity of CROP monomers protonated by a photoacid generator (PAG) was correlated with the heat released during the exothermic polymerization reaction. In addition, reaction conversions of monomers with epoxy and oxetane groups were compared using Fourier transform infrared spectroscopy (FT‐IR) under dark curing conditions. Surface and internal mechanical properties of coating films, including adhesion with polycarbonate substrate, were comprehensively evaluated by nano‐indentation, nano‐scratch, and surface and interfacial cutting analysis system (SAICAS) tests. By understanding the unique crosslinking characteristics of each CROP monomer, the ternary CROP monomer system, optimally containing with ECC of 53.6 wt%, DOX of 22.9 wt%, and DEO of 15.3 wt%, exhibited improved crosslinking density (G′ from 104 to 107 Pa) and exceptional mechanical (with scratch resistance increasing from 7.11 to 16.17 mN for Lc1), adhesion (with crosscut resistance increasing from 0 to 5B), and transparency properties, surpassing the performance of unitary ECC coating system.

Investigating the Synthesis and Characteristics of UV-Cured Bio-Based Epoxy Vegetable Oil-Lignin Composites Mediated by Structure-Directing Agents.

Bio-based composites were developed from the epoxy derivatives of Lallemantia iberica oil and kraft lignin (ELALO and EpLnK), using UV radiation as a low energy consumption tool for the oxiranes reaction. To avoid the filler sedimentation or its inhomogeneous distribution in the oil matrix, different structure-directing agents (SDA) were employed: 1,3:2,4-dibenzylidene-D-sorbitol (DBS), 12-hydroxystearic acid (HSA) and sorbitan monostearate (Span 60). The SDA and EpLnK effect upon the ELALO-based formulations, their curing reaction and the performance of the resulting materials were investigated. Fourier-transform Infrared Spectrometry (FTIR) indicates different modes of molecular arrangement through H bonds for the initial ELALO-SDA or ELALO-SDA-EpLnK systems, also confirming the epoxy group's reaction through the cationic mechanism for the final composites. Gel fraction measurements validate the significant conversion of the epoxides for those materials containing SDAs or 1% EpLnK; an increased EpLnK amount (5%), with or without SDA addition, conduced to an inefficient polymerization process, with the UV radiation being partially absorbed by the filler. Thermo-gravimetric and dynamic-mechanical analyses (TGA and DMA) revealed good properties for the ELALO-based materials. By loading 1% EpLnK, the thermal stability was improved to with 10 °C (for Td3%) and the addition of each SDA differently influenced the Tg values but also gave differences in the glassy and rubbery states when the storage moduli were interrogated, depending on their chemical structures. Water affinity and morphological studies were also carried out.

Study of the Interference in Target Seed Germination Caused by Dienamides and Epoxy Derivatives, in the Search for New Herbicides

The indiscriminate use of herbicides makes weeds resistant, increasing the demand for more efficient herbicides. Novel potential herbicides were prepared from sorbic acid, being 8 dienamides and 6 epoxides. Subsequently, phytotoxic activities of sorbic acid and 14 synthesized compounds were evaluated against sorghum, onion, cucumber, lettuce, and beggartick seeds. Furthermore, the protein target of the most active substance in plants was identified in silico. Among the tested compounds, (2E,4E)-N-(p-fluorophenyl)hexa-2,4-dienamide (2c), (2E,4E)-N-(o-naphthyl) hexa-2,4-dienamide (2d), (E)-N-methylphenyl-3-((2R,3R)-3-methyloxiran-2-yl)acrylamide (3b), (E)-N-bromophenyl-3-((2R,3R)-3-methyloxiran-2-yl)acrylamide (3e), and (E)-N-methoxyphenyl3-((2R,3R)-3-methyloxiran-2-yl)acrylamide (3f) showed pronounced inhibitory activities, both of shoots and roots, making them candidates for promising herbicides. All compounds altered seed development, and compounds 2c, 2d, 3b, 3e, and 3f presented equal or superior results to the commercial control herbicide S-metolachlor. Docking studies suggest that enzyme mitogenactivated protein kinase can be the target of those compounds.

Computational and experimental investigation of photoresponsive behavior of 4,4′-dihydroxyazobenzene diglycidyl ether

The photochromic properties of 4,4′-dihydroxyazobenzene diglycidyl ether have been investigated to gain further insight into the photoisomerization pathways. The light induced trans–cis isomerization, thermal cis–trans recovery and light induced cis–trans isomerization were monitored using electronic absorption spectroscopy. The pohotoisomerization and thermal relaxation kinetics of azobenzene chromophores were investigated in solution. It was found that the trans–cis isomerization process occurs very fast and a high content of cis isomer was obtained (94 %). The optimization of the ground and transition state geometries as well as the electronic structure of the azo epoxy derivative was performed by the density functional theory (DFT) and time-dependent DFT with PBE0 and CAM-B3LYP functionals, using 6-31 + G(d,p) as basis set. Also, the theoretical UV–vis absorption spectra were calculated. The mechanism of isomerization along the S2, S1 and S0 energy levels has been described. It was shown how each internal coordinate contributes to the isomerization mechanism. TD-DFT and DFT methods revealed that modification of the NN bond length was the internal coordinate responsible for the trans to cis as well as cis to trans conversion.

Epoxides: methods of synthesis, reactivity, practical significance

This review systematically summarizes recent literature data on the chemistry of epoxides published from 2010 to 2021 and, in part, in 2022. Epoxides are an important class of compounds, which are valuable building blocks in the design of new structures serving as the basis for many practically important compounds. Epoxy derivatives have long attracted the attention of synthetic chemists, as confirmed by a number of name reactions associated with their synthesis. The review describes methods for the synthesis of epoxy compounds, including both improved classical and new approaches, considers chemical reactions involving epoxides, discusses the practical significance of such compounds in relation to the synthesis of natural products, drugs and polymer structures and the CO and CO&lt;sub&gt;2&lt;/sub&gt; utilization. Much attention is paid to the issues of asymmetric synthesis, which enable one to get a general idea on the current trends in the chemistry of epoxides. The most unexpected rearrangements of functionalized epoxides are considered and the role of epoxy compounds in the synthesis of various carbo- and heterocyclic systems is discussed. &lt;br&gt; The bibliography includes 555 references.

Effective enrichment and detection of bisphenol diglycidyl ether, novolac glycerol ether and their derivatives in canned food using a novel magnetic sulfonatocalix[6]arene covalent cross-linked polymer as the adsorbent

A core–shell magnetic sulfonatocalix[6]arene covalently cross-linked polymer was proposed as a magnetic adsorbent, combined with ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) for the enrichment and determination of epoxy derivatives in canned foods. The adsorbent has high density of host–guest recognition functional groups, abundant binding sites and suitable cavity size, showing good extraction performance for epoxy derivatives. Quantum chemical simulation calculations provedmultiple interaction forces in the adsorption process. Theextractionparameterswere investigated. Under optimized experimental conditions, 13 kinds of target analytes showed low detection limits (0.0072–0.023 ng/g) and good precisions (RSDs of 0.8 %-9.4 %). This method has been successfully applied to the simultaneous determination of 13 kinds of epoxy derivatives in different food samples including canned beverage, fish, meat, and milk powder. Satisfactory recoveries (74.9 %–118 %) were obtained. The results showed the potential application prospects in the enrichment and detection of hazardous substances in food.

Modification of epoxidized methyl esters of sunflower oil fatty acids with some diols

It is possible to obtain products with a wide range of useful properties as a result of the modification of epoxidized vegetable oils and their derivatives. The aim of this work was to develop methods for the synthesis of new products by the reaction of epoxidized sunflower oil fatty acid methyl esters (FAME) with dihydric alcohols: ethylene glycol, butanediol-1,4, diethylene glycol, as well as in the study of their structure and properties. Dependences of the structure of the obtained products on the conditions of the process and the type of the modifier have been established. It was shown that carrying out the modification at a higher temperature (100 ° C) leads to the formation of crosslinked products as a result of intermolecular dehydration with the participation of both hydroxyl groups of the diol molecule. In addition to the opening of the oxirane ring, the transesterification process with the participation of the ester fragment is realized. Certain characteristics of the obtained products, including the acid number, saponification number, were determined, and the emulsifying effect was evaluated. In addition, the solidification temperature and pour point were determined for the products obtained. It was found that the products of modification of epoxy derivatives of FAME of sunflower oil obtained at 50 ° C have the greatest emulsifying effect.

Synthesis of 14-deoxy-benzylidene-8,17-epoxy-diene-andrographolide derivatives and evaluation of their anticancer activities

Synthesis of 14-deoxy-benzylidene-8,17-epoxy-diene-andrographolide derivatives from andrographolide and evaluation of their anticancer activities were described herein. 3,19 hydroxy groups of andrographolide were protected by benzylidene which undergo m-chloroperbenzoic acid mediated epoxydation in moderate yield to form corresponding epoxy derivatives. Thereafter mild basic condition was applied to perform de-hydroxylation at C-14 which resulted in conjugated diene derivatives of benzylidene epoxy andrographolide. These compounds were examined against different human cancer cell lines and were found to inhibit their proliferation at IC50 in the range of 3–20 μM in order to elucidated the role of allylic hydroxyl group at C-14.

Pd-Catalyzed Enantioselective (3+2)-Cycloaddition of Vinyl-Substituted Oxyallyl Carbonates with Isocyanates and Ketones.

The vinyl-substituted oxyallyl carbonates were exploited as a new C,O-dipole for enantioselective Pd-catalyzed (3+2) cycloaddition. The corresponding oxyallyl-Pd species was weakly nucleophilic to react with activated carbonyl compounds, affording multisubstituted and enantioenriched oxazolidinones and 1,3-dioxolanes with a high degree of chemo- and stereoselectivity. The synthetic transformations of oxazolidinone product were carried out to build enantioenriched α-chiral aminoketone and epoxy derivatives.

Sintesis Senyawa-Senyawa Epoksi dari Asam Lemak Minyak Nyamplung (Calophyllum inophyllum L.)

Epoxidation is a reaction of a carbon double bond with active oxygen, which results in the addition of an oxygen atom, converting the original double bond into a three-membered epoxide (oxirane) ring. Generally, the raw material for making epoxy comes from petroleum. Nyamplung kernel oil is a non-edible oil that can be used as an alternative raw material for making epoxy derivatives. The purpose of this study was to determine the optimum conditions and characterization of epoxy materials. The fatty acids of Nyamplung kernel oil were reacted formic acid and hydrogen peroxide with sulfuric acid as a catalyst. The optimum condition of the following parameters on the study of this process was investigated: the epoxidation time, temperature, and the mole ratio of formic acid and hydrogen peroxide. The results showed that the optimum reaction conditions with the temperature was 65 oC, the mole ratio of formic acid and hydrogen peroxide was 1:6, and the reaction time was 75 minutes. The results of the characterization under optimum conditions showed the oxirane value of 1.69, the iodine number of 9.63 mg iod/100 g, and the epoxy conversion of 67.6 %. The results of FTIR characterization showed absorption at a wavenumber of 820.03 cm-1 which is a specific absorption from the oxirane ring of the epoxy compound.

Investigation of changes in rat’s blood metabolomic profile, caused by lead exposure

Introduction. The prevalence of lead in the environment, due to human production and economic activities, and the xenobiotic nature of the element substantiate the relevance of studying the changes caused by the action of this metal. Materials and methods. A non-target metabolomic screening of the blood of rats exposed to intraperitoneal administration of lead acetate by HPLC-mass spectrometry was carried out. The expression of the selected masses was compared with those for the control group of animals. The masses that significantly changed the intensity compared to the control were subjected to fragmentation to obtain characteristic fragments. The annotation of metabolites was performed by searching in MS/MS databases and by comparison with in silico fragmentation spectra. The involvement of annotated metabolites in metabolic processes was established by literature analyzing. Results. Non-target metabolomic screening revealed 37 m/z values for the exposed group, significantly changing the intensity compared to the control. Annotation using fragmentation spectra and in silico fragmentation allows establishing the structure of eight metabolites, including an epoxy derivative of linolic acid, 15-hydroxyeicosatetraenoic acid, four oxo- and hydroxyacylcarnitine derivatives of long-chain fatty acids, one acylcarnitine derivatives of medium-chain fatty acids and one lysophosphoserine. Conclusion. Analyzing the literature, the known functions of the identified metabolites were established and attributed to the known metabolic processes. So, oxo- and hydroxyacylcarnitines are derivatives for intermediate products of β-oxidation fatty acids - it is increased concentration compared to the control indicates a violation of this process under the influence of oxidative stress caused by lead. Epoxy and 15-hydroxy derivatives of fatty acids (increased content relative to the control group) act as regulatory metabolites (vasodynamic activity), on the one hand, and markers of lead-induced hypoxia on the other hand. The increase of the concentration for the lysophosphatidylserine derivative indicates the intensification of apoptotic processes in the organism of the exposed group in contrast to the control.