10-undecenoic Acid Research Articles

Preparation and Characterization of a Novel Terbium Complex Coordinated with 10-Undecenoic Acid for UV-Cured Coatings

A UV-cured composite containing a rare earth complex was prepared for this study. First, the photoluminescent terbium complex was synthesized with a long-chain unsaturated fatty acid (10-Undecenoic acid) by a solution precipitation method, resulting in the 10-UA-Tb(III) complex. Its structure was proven by FTIR, elemental analysis, XRD, and TGA. The results indicated that the organic acid ligand successfully coordinated with the Tb3+ ion and that the complex had a chelate bidentate structure. The emission spectrum of the 10-UA-Tb(III) complex indicated that the complex can emit a bright green light with the unique luminescence of the Tb3+ ion. Furthermore, the luminescence properties of complexes with different ratios of Tb3+ and ligand were studied, and the ratio of Tb3+ and the ligand had an obvious impact on the luminescence intensity of the 10-UA-Tb(III) complex. Subsequently, the prepared rare earth complex was doped into a UV-cured coating in different proportions to obtain a UV-cured composite. The morphology of the rare earth UV-cured composite was observed by SEM. The images showed that the rare earth complex was dispersed uniformly in the polymer matrix. Moreover, the composites could emit fluorescence. Additionally, it has good thermal stability and compatibility with the resin. Therefore, these composites should have potential applications in UV curable materials, such as luminescence coatings.

Synthesis and Physicochemical Characterization of Undecylenic Acid Grafted to Hyaluronan for Encapsulation of Antioxidants and Chemical Crosslinking.

In this work, a new amphiphilic derivative made of 10-undecylenic acid grafted to hyaluronan was prepared by mixed anhydrides. The reaction conditions were optimized, and the effect of the molecular weight (Mw), reaction time, and the molar ratio of reagents was explored. Using this methodology, a degree of substitution up to 50% can be obtained. The viscosity of the conjugate can be controlled by varying the substitution degree. The physicochemical characterization of the modified hyaluronan was performed by infrared spectroscopy, Nuclear Magnetic Resonance, Size-Exclusion Chromatography combined with Multiangle Laser Light Scattering (SEC-MALLS), and rheology. The low proton motility and self-aggregation of the amphiphilic conjugate produced overestimation of the degree of substitution. Thus, a novel method using proton NMR was developed. Encapsulation of model hydrophobic guest molecules, coenzyme Q10, curcumin, and α-tocopherol into the micellar core was also investigated by solvent evaporation. HA-UDA amphiphiles were also shown to self-assemble into spherical nanostructures (about 300 nm) in water as established by dynamic light scattering. Furthermore, HA-UDA was crosslinked via radical polymerization mediated by ammonium persulphate (APS/TEMED). The cross-linking was also tested by photo-polymerization catalyzed by Irgacure 2959. The presence of the hydrophobic moiety decreases the swelling degree of the prepared hydrogels compared to methacrylated-HA. Here, we report a novel hybrid hyaluronan (HA) hydrogel system of physically encapsulated active compounds and chemical crosslinking for potential applications in drug delivery.

Curing behavior and properties of high biosourced epoxy resin blends based on a triepoxy monomer and a tricarboxylic acid hardener from 10-undecenoic acid

Renewable propane-1,2,3-triyl tris(9-(oxiran-2-yl) nonanoate) (EGU, 100 wt% biogenic) and a tricarboxylic acid triglyceride (CGTU) hardener (85.7 wt% biogenic) were synthesized from 10-undecenoic acid (10-UDA) and used to produce epoxy resins with 52–92 wt% biobased carbon. CGTU was prepared by thermally activated thiol-ene coupling of thioglycolic acid onto propane-1,2,3-triyl tris(undec-10-enoate), (GUD) in the absence of solvent. The characterized CGTU was used as a green hardener of blends based on EGU and a conventional bisphenol A-based epoxy pre-polymer (DGEBA) at various mass percentages (0–100 wt%) with an stoichiometric epoxy/acid equivalent ratio. Calorimetric studies revealed higher peak temperature, lower reaction heats, and longer gelation times in resins with high EGU proportion, evidencing the lower reactivity of aliphatic EGU compared with aromatic DGEBA. Cured resins were yellowish transparent rubber-like materials with glass transition temperatures (Tg) varying from −14 °C to −42 °C and tensile strength in the range of 1750 kPa–790 kPa, for 0 and 100 wt % EGU, respectively. The soluble fraction of all resins was less than 4.3%, reflecting a high level of crosslinking. Thermosets with high biobased content showed both UV-light protection and visible light transparency.

Influence of Unusual Co-substrates on the Biosynthesis of Medium-Chain-Length Polyhydroxyalkanoates Produced in Multistage Chemostat.

A two-stage chemostat cultivation was used to investigate the biosynthesis of functionalized medium-chain-length polyhydroxyalkanoate (mcl-PHA) in the β-oxidation weakened strain of Pseudomonas putida KTQQ20. Chemostats were linked in sequence and allowed separation of biomass production in the first stage from the PHA synthesis in the second stage. Four parallel reactors in the second stage provided identical growth conditions and ensured that the only variable was the ratio of decanoic acid (C10) to an unusual PHA monomer precursor, such as 10-undecenoic acid (C11:1) or phenylvaleric acid (PhVA). Obtained PHA content was in the range of 10 to 25 wt%. When different ratios of C10 and C11:1 were fed to P. putida, the produced PHA had a slightly higher molar ratio in favor of C11:1-based 3-hydroxy-10-undecenoate. However, in case of PhVA a significantly lower incorporation of 3-hydroxy-5-phenylvalerate over 3-hydroxydecanoate took place when compared to the ratio of their precursors in the feed medium. A result that is explained by a less efficient uptake of PhVA compared to C10 and a 24% lower yield of polymer from the aromatic fatty acid ( = 0.25). In addition, PHA isolated from cultivations with PhVA resulted in the number average molecular weight two times lower than the PHA produced from C10 alone. Detection of products from PhVA metabolism in the culture supernatant showed that uptaken PhVA was not entirely converted into PHA, thus explaining the difference in the yield polymer from substrate. It was concluded that PhVA or its related metabolites increased the chain transfer rate during PHA biosynthesis in P. putida KTQQ20, resulting in a reduction of the polymer molecular weight.

Biobased Ester 2-(10-Undecenoyloxy)ethyl Methacrylate as an Asymmetrical Diene Monomer in Thiol–Ene Polymerization

In this work, a diene ester monomer, 2-(10-undecenoyloxy)ethyl methacrylate (MHU), was synthesized by the enzymatic esterification of 10-undecenoic acid (derived from castor oil) and 2-hydroxyethyl methacrylate and employed in two different ways: (1) in thiol–ene polymerization with 1,4-butanedithiol (1,4-BDT) and (2) as a precursor in a Michael addition reaction with hexamethylenediamine. In thiol–ene bulk polymerization of the asymmetrical diene monomer MHU, which presents different reactivities for each double bond, higher molecular weights (up to 44.3 kDa) were reached when nonstoichiometric thiol–ene ratios were used. In the second approach, Michael addition allowed us to obtain a symmetrical diene monomer that was used to produce a polymer (11.3 kDa) containing both amine and ester groups by thiol–ene polymerization. Finally, for the same MHU/1,4-BDT molar ratio, miniemulsion thiol–ene polymerization resulted in higher molecular weights (up to 17 kDa) when compared with those from bulk polymerizatio...

Identification and characterization of Zika virus NS5 RNA-dependent RNA polymerase inhibitors

The current outbreak of Zika virus (ZIKV) is the impetus for novel, safe and efficacious anti-ZIKV agents. ZIKV non-structural protein 5 RNA-dependent RNA polymerase (RdRp) is essential for viral replication and is logically regarded as an attractive drug target. This study used a fluorescence-based polymerase assay to find an anti-infective drug 10-undecenoic acid zinc salt (UA) which could inhibit RdRp activity with a half maximal inhibitory concentration (IC50) of 1.13-1.25 µM. Molecular docking and site-directed mutagenesis analyses identified D535 as the key amino acid in the interaction between RdRp and UA. Importantly, the surface plasmon resonance assay showed that UA had strong direct binding with ZIKV wild-type RdRp and a relatively weak interaction with D535A-RdRp. As a control, the nucleoside inhibitor sofosbuvir triphosphate (PSI-7409) conferred insensitivity to the fluorescence-based RdRp assay and cannot bind directly with RdRp. Moreover, UA showed anti-ZIKV activity comparable to sofosbuvir. All these results indicate that UA is likely to be a promising lead compound against ZIKV, exhibiting a different mechanism than sofosbuvir.

Enzymatic Synthesis of a Diene Ester Monomer Derived from Renewable Resource.

The total or partial substitution of fossil raw materials by biobased materials from renewable resources is one of the great challenges of our society. In this context, the reaction under mild condition as enzyme-catalyzed esterification was applied to investigate the esterification of the biobased 10-undecenoic acid with 2-hydroxyethyl methacrylate (HEMA) to obtain a new diene ester monomer. The environmentally friendly enzymatic reaction presented up to 100% of conversion; moreover, the production of possible by-products was minimized controlling reaction time and amount of enzyme. Furthermore, the presence of chloroform was evaluated during the enzymatic reactions and despite high conversions with higher enzyme concentration, the solvent-free system showed fast kinetics even with 1.13U/g substrates. In addition, the commercial immobilized lipases Novozym 435 and NS 88011 could be applied for up to 10 cycles keeping conversions about 90%. The scale-up of the reaction was possible and a purification procedure was applied in order to isolate the diene ester monomer 2-(10-undecenoyloxy)ethyl methacrylate, preserving its double bonds, which could allow a potential use of this product in the synthesis of new renewable polymers through techniques as metathesis, thiol-ene, or free-radical polymerization.

Synthesis of a Fully Biobased Polyfunctional Vinyl Oligomer and Their UV Cured Films Prepared via Thiol-ene Coupling

In this paper, a fully bio-based vinyl oligomer with high functionalities was successfully prepared by three steps: epoxidation of rapeseed oil, solvent-free and catalyst-free ring opening by 10-undecylenic acid, and esterification with 10-undecenoyl chloride. Then, the renewable polymers were prepared by photo-polymerization of these modified vegetable oils and typical thiol monomers (pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate) and 1,2-ethanedithiol). The synthesis of the vinyl oligomer was monitored by nuclear magnetic resonance and Fourier-transform infrared spectroscopy. The average number of the carbon-carbon double bonds of the resulting vinyl oligomer is high to be 7.2. The kinetic of thiol-ene photo-polymerization of vegetable oil based vinyl oligomer was studied by FTIR-ATR analyses. In addition, the thermo-physical properties and thermal stability of UV-curable films were characterized. The resulting polymers exhibit excellent water resistance and thermals stability, which is promising to find application in coatings and adhesives.

Polymacrocycles Derived via Ugi Multi-Component Reactions.

The synthesis of macrocycles based on the Ugi-4CR has been thoroughly explored by Wessjohann and coworkers, while polymerizations utilizing the Ugi-4CR are already patented by Ugi and recently studied more in detail, developing a new trend in polymer chemistry. Here, the combination of both, that is, the synthesis of polymacrocycles, is demonstrated. As diverse functional groups can be easily introduced in a macrocycle via Ugi-4CR, a straightforward design of polymacrocycles is achieved in a two-step procedure. First, the Ugi-4CR of 10-undecenoic acid, a diamine, a diisocyanide, and an aldehyde results in diversely substituted macrocycles having two terminal double bonds. Subsequently, these macrocycles are polymerized by ADMET (acyclic diene metathesis) or thiol-ene polymerization to generate polymacrocycles with potential application in coordination chemistry as, for example, sensors, filters, or phase-transfer catalysts. Moreover, the setup of the literature-known Ugi macrocyclization is simplified by systematic reaction screening.

Linear and branched acetal polymers from castor oil via acetal metathesis polymerization

Synthetic protocols to prepare new diols were developed to revalorize heptanal and 10-undecenoic acid castor oil derivatives. The Acetal Metathesis Polymerization of these diols yielded linear and branched renewable polyacetals and copolyacetals with number average molecular weights in the range 14,000–27,000 g mol−1. Thermally robust semicrystalline or amorphous materials were obtained. Polyacetals were hydrolytically degradable down to parent diols under slightly acidic media and no significant differences on the degradation pattern were observed among them.

Palladium-Catalyzed Direct Synthesis of Various Branched, Carboxylic Acid-Functionalized Polyolefins: Characterization, Derivatization, and Properties

Ethylene-co-acrylic acid (E–AA) copolymers are typically produced via high-pressure free radical copolymerization and have great industrial importance because of their many applications. The radical polymerization mechanism usually leads to highly branched products with poor mechanical properties. Transition-metal-catalyzed E–AA copolymerization represents a direct and economical route to access these copolymers with potentially better control over their microstructures and material properties. However, this is highly challenging due to catalyst poisoning from both the oxygen and carboxylic acid moieties in the monomers. In this contribution, we demonstrate that a series of α-diimine-based palladium catalysts can mediate efficient copolymerizations of ethylene with AA, allylacetic acid, and 10-undecenoic acid, leading to the formation of various branched, carboxylic acid-functionalized polyolefin materials. These comonomers exist as carboxylic acid-based dimeric species at ambient temperatures, which is p...

Quantifying the Thermodynamics of Ligand Binding to CsPbBr3 Quantum Dots.

Cesium lead halide perovskites are an emerging class of quantum dots (QDs) that have shown promise in a variety of applications; however, their properties are highly dependent on their surface chemistry. To this point, the thermodynamics of ligand binding remain unstudied. Herein, 1 H NMR methods were used to quantify the thermodynamics of ligand exchange on CsPbBr3 QDs. Both oleic acid and oleylamine native ligands dynamically interact with the CsPbBr3 QD surface, having individual surface densities of 1.2-1.7 nm-2 . 10-Undecenoic acid undergoes an exergonic exchange equilibrium with bound oleate (Keq =1.97) at 25 °C while 10-undecenylphosphonic acid undergoes irreversible ligand exchange. Undec-10-en-1-amine exergonically exchanges with oleylamine (Keq =2.52) at 25 °C. Exchange occurs with carboxylic acids, phosphonic acids, and amines on CsPbBr3 QDs without etching of the nanocrystal surface; increases in the steady-state PL intensities correlate with more strongly bound conjugate base ligands.

Hydroxyl functionalized renewable polyesters derived from 10-undecenoic acid: Polymer structure and post-polymerization modification

A simple synthetic route is used for the preparation of hydroxyl functionalized polyesters from an AB-type monomer carrying an epoxy and carboxylic acid group. A systematic study of the reaction conditions suggested that tetrabutylphosphonium bromide was the better polymerization catalyst to obtain the highest conversion of linear polymers with moderate molecular weights. Enzymatic catalyst (CALB), in contrast, yielded branched polymers with polyether units. The synthesized polymers were structurally characterized in detail, using model compounds previously synthesized, by 1H, 13C, and 19F NMR. Polyesters were characterized by FTIR, SEC, DSC and TGA too. The post-polymerization modification of the reactive hydroxyl sites present along the polymer backbone with N-Boc protected l-phenylalanine and l-serine was essayed to test the ability of these polyesters to prepare polymer bioconjugates.

Mutation in MON2, Which Encodes a Protein Implicated in Vesicular Transport, Affects Response to Exogenous Fatty Acids in Yeast

Metabolism of exogenous fatty acids requires cells to take up, traffic, and molecularly respond to fed fatty acids. Our lab has determined that a mutation in mon2 results in defective growth on the fatty acid 10‐undecenoic acid. Like wild type cells, mon2Δ mutants are capable of normal response to the feeding of long chain unsaturated fatty acids (UFAs) by reducing transcription of OLE1, (which encodes the Δ9 desaturase), and by reducing the accumulation of endogenously produced UFAs. However, wild type cells when fed 10‐undecenoic acid will continue to express OLE1 and increase their content of endogenously produced UFAs. In contrast, mon2Δ mutants do not differentially respond to the two fatty acids. Staining with a BODIPY‐labeled fluorescent fatty acid analog indicates that there is a difference in localization/amount of the supplied fatty acid in mon2Δ cells compared to wild type cells. Thus, it appears that the mon2 mutation decreases the cell's ability to differentiate between fatty acids, perhaps due to mislocalization of the fed fatty acid or regulatory proteins.Support or Funding InformationThis work was supported by a Jacob Nyenhuis Faculty Award (VM), NSF‐REU (AG, MS, BG) and a Summer Scholar award from the Dean for Natural and Applied Science (RD).This abstract is from the Experimental Biology 2018 Meeting. There is no full text article associated with this abstract published in The FASEB Journal.

Synthesis of water dispersible boron core silica shell (B@SiO2) nanoparticles

Water dispersible boron nanoparticles have great potential as materials for boron neutron capture therapy of cancer and magnetic resonance imaging, if they are prepared on a large scale with uniform size and shape and hydrophilic modifiable surface. We report the first method to prepare spherical, monodisperse, water dispersible boron core silica shell nanoparticles (B@SiO2 NPs) suitable for aforementioned biomedical applications. In this method, 40 nm elemental boron nanoparticles, easily prepared by mechanical milling and carrying 10-undecenoic acid surface ligands, are hydrosilylated using triethoxysilane, followed by base-catalyzed hydrolysis of tetraethoxysilane, which forms a 10-nm silica shell around the boron core. This simple two-step process converts irregularly shaped hydrophobic boron particles into the spherically shaped uniform nanoparticles. The B@SiO2 NPs are dispersible in water and the silica shell surface can be modified with primary amines that allow for the attachment of a fluorophore and, potentially, of targeting moieties.

Experimental determination and development of solution theory based model for the mixture solubilities of 10-undecenoic acid with methyl 10-undecenoate and methyl ricinoleate in supercritical carbon dioxide

The solubilities of liquid mixtures of 10-undecenoic acid + methyl 10-undecenoate, and 10-undecenoic acid + methyl ricinoleate in SCCO2 were determined at T = 313–333 K and P = 10–18 MPa. The selectivity is higher towards methyl 10-undecenoate in a mixture of 10-undecenoic acid + methyl 10-undecenoate, whereas the selectivity is higher towards 10-undecenoic acid in a mixture of 10-undecenoic acid + methyl ricinoleate. A new model was developed based on the solution theory coupled with regular solution theory. The absolute average relative deviation (AARD%) obtained using the new model for the system of 10-undecenoic acid + methyl 10-undecenoate was 10.5 and 9.10 for the 10-undecenoic acid and methyl 10-undecenoate, respectively, whereas for the system of 10-undecenoic acid + methyl ricinoleate, the AARD% was 4.71 and 4.91 for the 10-undecenoic acid and methyl ricinoleate, respectively. These AARDs were significantly lower than the existing models indicating utility of the new model.

Synthesis of Cr/Al<sub>2</sub>O<sub>3</sub>- Bentonite Nanocomposite as the Hydrocracking Catalyst of Castor Oil

Synthesis and characterization of Cr/Al2O3-bentonite nanocomposite as a hydrocracking catalyst of castor oil have been conducted. The catalyst was prepared according to the following method. At the first step, bentonite was activated using H2SO4 to obtain H-bentonite, after that the activated clay was pillarized by Al2O3, Next, a salt solution of Cr (NO3)3·9H2O was impregnated in the pillared bentonite sample, followed by calcination and reduction to obtain the final catalyst, i.e. Cr/Al2O3-bentonite. The catalysts including unpillared bentonite were characterized using infrared spectrometer (FT-IR), X-Ray diffractometer (XRD), X-ray Fluorescence spectrometer (XRF), Transmission Electron Microscope (TEM) and gas sorption analyzer. GC-MS analysis was conducted to characterize the hydrocracking product. The research results showed that pillarization of bentonite caused an increasing of the basal spacing of bentonite in an amount of 1.01 nm. Although Chrom was unevenly dispersed on the bentonite and it probably blocked the bentonite framework resulted in the decrease of catalyst specific surface area, Cr/Al2O3-bentonite catalyst gave the best conversion of 64.03%. The GC-MS analysis data showed that the hydrocracking products contained various kinds of organic compounds such as acetone, acetic acid, methyl benzene, octane, heptanal, 2-octene, 1-undecanoic acid, 9-octadecenal and 10-undecenoic acid.

Flexible, hard, and tough biobased polyurethane thermosets from renewable materials: glycerol and 10-undecenoic acid

The main theme of this work is to develop 100% biobased low viscous polyols from renewable resources. An epoxide compound (UA-GLY-E) was synthesized through esterification of glycerol and 10-undecenoic acid preceded by peroxidation. For the first time, UA-GLY-E was utilized as a building block in the generation of low viscous polyols and polyurethanes therefrom. The biobased polyols were synthesized by epoxide ring opening of UA-GLY-E with different nucleophiles, namely glycerol, water, and methanol. The advantage of these biobased polyols is their low viscosity and at the same time high functionality. These biobased polyols were further converted into poly(urethane–urea) coatings by reacting with methylene diphenyl diisocyanate. The impact of peripheral structural change in the polyols on the properties of polyols and their polyurethane coatings was studied. Flexible, hard, and tough thermosets have been prepared successfully from the same epoxy compound by altering the peripheral moiety in the polyol structure. Biobased polyurethanes prepared from glycerol and water-based polyols have shown better crosslinking density over the methanol-based polyol. Moreover, these biobased polyurethane films have shown good thermal stability, mechanical strength, and chemical resistance as well.

Biodegradable and High-Performance Poly(butylene adipate-co-terephthalate)–Lignin UV-Blocking Films

Renewable and biodegradable UV-blocking films are in high demand for the increasing need of sustainable environment. Lignin can offer significant UV absorption, but it deteriorates the mechanical properties of films at a high content. In this effort, biobased 10-undecenoic and oleic acids were successfully grafted on soda lignin via solvent- and catalyst-free processes, as confirmed by 31P and 1H NMR and Fourier transform infrared (FTIR). The resulting lignin ester derivatives and neat lignin were then melt-blended with a biodegradable poly(butylene adipate-co-terephthalate) (PBAT) to prepare UV-protective films. The incorporation of the modified lignins into the PBAT matrix exhibited good dispersion of lignin particles with almost unaffected tensile properties as well as good thermal stability for up to 20 wt % loading of lignin derivatives. The resulting films showed excellent UV-barrier property with 10 wt % lignin loading, having full protection in the whole UV-irradiation range (280–400 nm). The UV p...

Properties of polymers as a nanoscale material for fibers in leather

Hyperbranched polymers, an innovative class of nano-polymers, could enhance the properties of fibers owning to their unique structures. In this study, the ester compound (HPAE) of 3-(bis(2-hydroxyethyl)amino)propionic acid and pentaerythritol was treated with undecylenic acid to obtain novel hyperbranched multiterminal alkenyl polymers (HPAE-UAs). The sizes of the HPAE-UAs could be controlled conveniently from 400 to 1300 nm by adjusting the capped fraction of the hydroxyl groups with undecylenic acids. The molecular structures of HPAE-UAs were characterized by means of FT-IR and 1H-NMR. Then, the effect of the HPAE-UAs on the structures, thermal, and mechanical properties of the wet blue leather were investigated. TEM and SEM demonstrated that the spacing between fibers was enlarged. The thermogravimetric analysis showed that the residual volume of leather could reach up to 30.3 % at about 500 °C. Furthermore, the shrinkage temperature increased to 89.4 °C. It was found that the HPAE-UAs used in leather could improve the thermal performance, physical and mechanical properties. All of these results indicate that HPAE-UAs can be used as a fatliquor with retanning in leather process.