Excess Oleic Acid Research Articles

Exogenous Metal Cations in the Synthesis of CsPbBr3 Nanocrystals and Their Interplay with Tertiary Amines.

Current syntheses of CsPbBr3 halide perovskite nanocrystals (NCs) rely on overstoichiometric amounts of Pb2+ precursors, resulting in unreacted lead ions at the end of the process. In our synthesis scheme of CsPbBr3 NCs, we replaced excess Pb2+ with different exogenous metal cations (M) and investigated their effect on the synthesis products. These cations can be divided into two groups: group 1 delivers monodisperse CsPbBr3 cubes capped with oleate species (as for the case when Pb2+ is used in excess) and with a photoluminescence quantum yield (PLQY) as high as 90% with some cations (for example with M = In3+); group 2 yields irregularly shaped CsPbBr3 NCs with broad size distributions. In both cases, the addition of a tertiary ammonium cation (didodecylmethylammonium, DDMA+) during the synthesis, after the nucleation of the NCs, reshapes the NCs to monodisperse truncated cubes. Such NCs feature a mixed oleate/DDMA+ surface termination with PLQY values of up to 97%. For group 1 cations this happens only if the ammonium cation is directly added as a salt (DDMA-Br), while for group 2 cations this happens even if the corresponding tertiary amine (DDMA) is added, instead of DDMA-Br. This is attributed to the fact that only group 2 cations can facilitate the protonation of DDMA by the excess oleic acid present in the reaction environment. In all cases studied, the incorporation of M cations is marginal, and the reshaping of the NCs is only transient: if the reactions are run for a long time, the truncated cubes evolve to cubes.

Abstract PR015: Excess dietary oleic acid primes the pancreas for cancer

Abstract Human epidemiologic studies support a strong link between increased pancreatic adenocarcinoma (PDAC) risk and high fat diet (HFD) consumption, obesity, and overall energy imbalance. Given the rapid rise in worldwide obesity rates and the prevalence of western diets rich in fat, deciphering these mechanisms is not only a societal imperative but also represents a key untapped target to develop novel strategies for prevention and therapy. The translational relevance of diet research, however, has been limited by inconsistencies in fat source and consumption across human populations and mouse studies. Therefore, whether and how specific dietary fatty acids drive cancer development is poorly understood. To identify commonly consumed dietary fats capable of promoting pancreatic tumorigenesis, we fed a novel panel of 12 isocaloric HFDs – differing solely in fat source and representing the diversity of modern human fat consumption (as per statistics from the USDA) – to an oncogenic Kras-driven mouse model (KC: Pdx1-Cre; KrasLSL-G12D/+) that closely mimics the genetic and histologic features of human PDAC progression. Surprisingly, we found that diets rich in oleic acid (OA), a monounsaturated fat typically associated with good health, were strongly correlated with enhanced precancerous pancreatic intraepithelial neoplasia (PanIN) formation, arguing that OA enhances Kras-induced cellular transformation and early progression. High-oleic diets (HODs) and OA treatment of primary acinar cells induced loss of acinar cell identity and acquisition of ductal markers, consistent with a direct role for OA in acinar-to-ductal metaplasia (ADM), a prerequisite step in early PDAC development. Lipidomic analyses of plasma, liver, and muscle of mice fed HODs revealed greater circulating OA levels and increased tissue incorporation of OA into the acyl chains of phospholipids and sphingolipids, which make up the plasma membrane of cells and mediate intracellular and extracellular signaling. Furthermore, plasma and tissue OA levels more strongly correlated with tumor development, suggesting that direct OA pancreatic tissue incorporation could drive tumorigenesis. Indeed, molecular and biochemical analyses confirmed upregulation in the expression of de novo lipogenesis genes, alterations in lipid metabolism, and enhanced mTOR signaling in pancreata of mice fed HODs. Overall, these results directly link dietary OA to pancreatic lipid metabolism and transformation during PDAC development and highlight the complex pleiotropic effects of dietary fatty acids on health and disease: OA, while beneficial for heart health, may promote the development of certain cancers, such as PDAC. Uncovering the links between specific dietary fats and tumorigenesis are critical to enable precision nutritional guidance for the prevention and treatment of PDAC and potentially other obesity-associated cancers. Citation Format: Christian F. Ruiz, Rylee McDonnell, Jennifer Kaplan, Jasper de Jong, Christine Shugrue, Michael C. Rudolph, Fred S. Gorelick, John Wysolmerski, Matthew Rodeheffer, Mandar D. Muzumdar. Excess dietary oleic acid primes the pancreas for cancer [abstract]. In: Proceedings of the AACR Special Conference on Pancreatic Cancer; 2022 Sep 13-16; Boston, MA. Philadelphia (PA): AACR; Cancer Res 2022;82(22 Suppl):Abstract nr PR015.

Nanoparticle size and surface chemistry effects on mechanical and physical properties of nano-reinforced polymers: The case of PVDF-Fe3O4 nano-composites

In the present work, PVDF - Fe3O4 nanoparticle (NP) nanocomposite films were produced using the electrospinning method. We investigated the effect of NP size on the film's morphology (fiber size), mechanical properties, and physical properties (β-phase percentage). Surprisingly, while nanoparticle size acts as an enhancer for mechanical properties, it appeared to act as an inhibitor in terms of its effects on the crystallization of the β-polymorph. This result seemed in discordance with many previous results. A focus on local interactions between the NP surface chemistry and PVDF chains revealed the influence of grafted ligands at the nanoparticle surface on the crystallization of the piezoelectric phase of PVDF. The results from the molecular dynamics (MD) simulations for systems of PVDF chains with slabs of –OH and oleic acid-grafted magnetite, showed that the probability of beta phase configuration decreases when the nanoparticles are functionalized with oleic acid and becomes more probable for –OH terminated magnetite. These computational results are in accordance with our experimental results. To verify this hypothesis, we prepared films with washed nanoparticles to eliminate the excess oleic acid that acts as a β-polymorph inhibitor. As a result, the amount of β-phase obtained for washed nanoparticles increased and the difference in the amount of β-phase between the different samples decreased. Moreover, when heated, the films of nanocomposite with washed NP developed more β-phase for smaller sizes of nanoparticles. At 140 °C, isomerization occurred, and oleic acid was converted into elaidic acid, reducing the steric hindrance, and promoting the interaction between PVDF chains and the surface of the nanoparticles. This isomerization reaction seems to be an enhancer of the α- to β-phase transition. Our results prove that optimizing multiple properties in nano-reinforced polymers requires consideration of different aspects, such as NP size, surface chemistry, and processing methods.Our results based on mixed experimental and modeling approach proved the usefulness of simulation in understanding and guiding our experimental results. Our results suggest that for enhancing piezoelectric properties in PVDF magnetite nano-composites, the chemistry and the molecular morphology of the grafted ligands when combined with NP size could lead to multi-properties enhancement simultaneously.

Insight into effects of long-chain fatty acids on propionic acid production in anaerobic fermentation: A case study of oleic acid and palmitic acid

This study revealed long-chain fatty acids(LCFAs) on propionic acid production by lipid anaerobic acidogenesis. Oleic acid and palmitic acid, the two most common LCFAs, were added into the acidogenic system to evaluate LCFAs type and concentration on the propionic acid production capacity. The results showed that when the concentration of oleic acid was 4 g/L, the content of volatile fatty acids(VFAs) was 1.3 times higher than that of the blank group(propionic acid was the main product, >70%). In contrast, palmitic acid and excess oleic acid inhibited propionic acid production(butyric acid was the main product). Propionic acid-producing bacteria were the dominant bacteria in an oleic acid production system. According to response surface analysis, the optimal concentration of oleic acid favoring for propionic acid production was 2.3 g/L and fermentation time was 7.4 days in this study. The results showed that a proper concentration of oleic acid has a promotion to propionic acid production. This study provides a theoretical basis for oleic acid to promote propionic acid production.

Saponification with calcium has different impacts on anaerobic digestion of saturated/unsaturated long chain fatty acids

Little is known about the influence of the saturation degree of long chain fatty acids (LCFAs) on the bio-methane potential of calcium-LCFAs salts. In this study, palmitic acid and oleic acid were chosen as the model compounds to investigate the impact of saponification between calcium and saturated/unsaturated LCFAs on the methane recovery from LCFAs in anaerobic digestion. A 2.2-fold enhancement of methane yield was obtained due to the formation of calcium palmitate, which was primarily attributed to the enhanced bio-aggregation and significant change of microbial community. However, saponification between calcium and oleic acid decreased the methane recovery from oleic acid digestion. Only partial saponification with excess oleic acid led to 4% increment of methane production. The low bio-accessibility of calcium oleate and the little change of microbial community may be responsible for the small difference of methane recovery due to the formation of calcium oleate.

An Aggregation-Induced Emission Optical Highlighter for the Studies of Endoplasmic Reticulum-Lipid Droplet Content Dynamics

An Aggregation-Induced Emission Optical Highlighter for the Studies of Endoplasmic Reticulum-Lipid Droplet Content Dynamics

Lipozyme 435-Mediated Synthesis of Xylose Oleate in Methyl Ethyl Ketone.

In this paper, we have performed the Lipozyme 435-catalyzed synthesis of xylose oleate in methyl ethyl ketone (MEK) from xylose and oleic acid. The effects of substrates’ molar ratios, reaction temperature, reaction time on esterification rates, and Lipozyme 435 reuse were studied. Results showed that an excess of oleic acid (xylose: oleic acid molar ratio of 1:5) significantly favored the reaction, yielding 98% of xylose conversion and 31% oleic acid conversion after 24 h-reaction (mainly to xylose mono- and dioleate, as confirmed by mass spectrometry). The highest Lipozyme 435 activities occurred between 55 and 70 °C. The predicted Ping Pong Bi Bi kinetic model fitted very well to the experimental data and there was no evidence of inhibitions in the range assessed. The reaction product was purified and presented an emulsion capacity close to that of a commercial sugar ester detergent. Finally, the repeated use of Lipozyme 435 showed a reduction in the reaction yields (by 48 and 19% in the xylose and oleic acid conversions, respectively), after ten 12 h-cycles.

Toxoplasma gondii serine hydrolases regulate parasite lipid mobilization during growth and replication within the host

The intracellular protozoan parasite Toxoplasma gondii must scavenge cholesterol and other lipids from the host to facilitate intracellular growth and replication. Enzymes responsible for neutral lipid synthesis have been identified but there is no evidence for enzymes that catalyze lipolysis of cholesterol esters and esterified lipids. Here, we characterize several T.gondii serine hydrolases with esterase and thioesterase activities that were previously thought to be depalmitoylating enzymes. We find they do not cleave palmitoyl thiol esters but rather hydrolyze short-chain lipid esters. Deletion of one of the hydrolases results in alterations in levels of multiple lipids species. We also identify small-molecule inhibitors of these hydrolases and show that treatment of parasites results in phenotypic defects reminiscent of parasites exposed to excess cholesterol or oleic acid. Together, these data characterize enzymes necessary for processing lipids critical for infection and highlight the potential for targeting parasite hydrolases for therapeutic applications.

Adsorption mechanism of oleic acid on the surface of aluminum nanoparticle: ReaxFF molecular dynamics simulation and experimental study

The adsorption mechanism of oleic acid(OA) on the surface of aluminum(Al) nanoparticle was studied using ReaxFF molecular dynamics simulation. A surface-oxidized Al nanoparticle was constructed to simulate the single-molecule and multi-molecule adsorption processes of OA on the surface of Al nanoparticle. It was found that single OA molecule adsorbed on the surface of the Al nanoparticles through its –COOH group to form a carboxylate structure, thereby forming a chemical adsorption monolayer on the surface of Al nanoparticle. During the multi-molecule adsorption process, the chemical adsorption layer will become denser with the increase of initial density of OA in the system. When the initial density is large enough, excess OA molecules were adsorbed outside the chemical adsorption layer by physical adsorption and form a chemical-physical bilayer adsorption structure on the surface of the particles. The simulation results were verified by the adsorption layer thickness determined with XPS and the bonding structure detected with FTIR. The adsorption mechanism of OA on the surface of Al nanoparticle was found to changes from a chemical monolayer adsorption to a chemical-physical bilayer adsorption with the increase of OA concentration.

Morphology and optical properties of CeF3 and CeF3:Tb nanocrystals: The dominant role of the reaction thermal mode

Quite recently, nanosized rare-earth (RE) fluorides have been gaining importance due to their ability to form nanocomposites that are capable to absorb ionizing radiation. The efficiency of these materials may vary under the influence of external factors and under the growing conditions of nanocrystals. In this paper a novel effective approach to the synthesis of CeF3 nanocrystals (NCs) with a high yield of the desired material was proposed. The developed approach allows different modifications within the synthesis, thereby making it possible to change the growth conditions of QDs. The main exchange reaction between cerium oleate and ammonium fluoride was carried out in a non-coordinating solvent 1-octadecene (ODE) diluted with an excess of oleic acid (OA). The influence of the reaction temperature on the nucleation and the formation of a nanocrystals was presented. The possibility of introducing Tb3+ (1–5%) into nanosized CeF3 at one of the lowest reaction temperatures (180 °C) was also studied. The introduction of Tb3+ into the CeF3 crystal lattice led to changes in the nanocrystal's structure, an increase in their size and also to the expected changes in the photoluminescence (PL) spectra. The prepared CeF3 and CeF3:Tb QDs were well dispersible in low-polar media, which makes them promising candidates for the role of active agents or wavelength shifters in the matrix of polymer scintillators.

<i>Toxoplasma gondii</i> Serine Hydrolases Regulate Parasite Lipid Mobilization During Growth and Replication within the Host

The intracellular protozoan parasite Toxoplasma gondii must scavenge cholesterol and other lipids from the host to facilitate intracellular growth and replication. Enzymes responsible for neutral lipid synthesis have been identified but there is no evidence for enzymes that catalyze lipolysis of cholesterol esters and esterified lipids. Here we characterize several T. gondii serine hydrolases with esterase and thioesterase activities that were previously thought to be depalmitoylating enzymes. We find they do not cleave palmitoyl thiol esters but rather hydrolyze short chain lipid esters. Deletion of one of the hydrolases results in alterations in levels of multiple lipids species. We also identify small molecule inhibitors of these hydrolases and show that treatment of parasites results in phenotypic defects reminiscent of parasites exposed to excess cholesterol or oleic acid. Together, these data characterize enzymes necessary for processing lipids critical for infection and highlight the potential for targeting parasite hydrolases for therapeutic applications.

Oleic acid influences the adipogenesis of 3T3-L1 cells via DNA Methylation and may predispose to obesity and obesity-related disorders

BackgroundAdipogenesis is the process of adipocytes formation from unspecialized progenitor cells called mesenchymal stromal cells. Numerous mechanisms including epigenetic regulation modulate the correct progress of this process. Dietary exposures occurring over a specific period of time might cause long-lasting and even permanent changes in gene expression regulated by epigenetic mechanisms. For that reason, we investigated the adipogenesis of 3 T3-L1 cells with the excess of saturated and monounsaturated fatty acids and their influence on global and site-specific DNA methylation in these cells.Materials and methods3T3-L1 cells were cultured in vitro to obtain 100% of confluence, then the adipogenesis was induced by a differentiation cocktail with the addition of the excess of 0.25 mM and 0.5 mM of palmitic (16:0), stearic (18:0) and oleic (18:1n-9) acids. DNA and RNA were extracted at five-time points to assess the adipogenesis process. The phenotype of mature adipocytes (insulin sensitivity, adipokines secretion, fat content) was estimated in fully mature adipocytes. DNA methylation was investigated both during adipogenesis and in mature adipocytes.ResultsOleic acids stimulated expression of C/ebpα and Pparγ, which was correlated with lower methylation levels at promoters sites. Furthermore, cells cultured with an excess of oleic acid were characterized by higher lipid accumulation rate, higher leptin, and lower adiponectin secretion. Moreover, in all experimental cells, insulin signaling and glucose utilization were impaired.ConclusionOleic acid affected the methylation of Pparγ and C/ebpα promoters, what correlated with higher expression. Furthermore, examined free fatty acids influenced the phenotype of mature adipocytes, especially insulin signaling pathway and adipokine secretion.

Studies on the effect of acetate ions on the optical properties of InP/ZnSeS core/shell quantum dots

The effect of residual acetate ions in indium oleate (In(OA)3) precursor on the photoluminescence quantum yield (PL QY) and size distribution of InP-based core/shell quantum dots (QDs) was studied. For comparison, the synthesis conditions of In(OA)3 were varied to control the amount of acetate ions that remained in the In(OA)3 precursor. The acetate ions resulted in smaller crystallites in single QD and in surfaces with a greater defect concentration, yielding low PL QYs and broader size distributions. For a complete exchange of acetate ligand in indium acetate (In(Ac)3) with oleate, In(Ac)3 was reacted with excess oleic acid. Pure In(OA)3 precursor led to bright InP/ZnSeS core/shell QDs with a uniform size after a shell was formed on the InP core QDs.

Revealing the Relative Electronic Landscape of Colloidal ZnO and TiO2 Nanoparticles via Equilibration Studies

Interest in metal oxide semiconductors for energy processes has increased due to their prominent roles in photocatalysis, electrical energy storage, and conversion. However, an understanding of the thermochemistry of electron transfer (ET) reactions of these systems has lagged behind photophysical studies. This report investigates ET equilibria between reduced forms of well-characterized, ligated ZnO and TiO2 nanoparticles (NPs) suspended in toluene. Multiple electrons were added to each type of NP, either photochemically or with a chemical reductant. Equilibration experiments monitoring these added electrons are used to construct a qualitative band diagram. Surprisingly, the difference between the “reducible” oxide TiO2 and the formally “nonreducible” ZnO is reflected not in the relative band energies but rather in the relative width of the bands (the density of trap and/or band states). Moreover, the position of the electron equilibrium shifts upon addition of excess dodecylamine or oleic acid capping ligands. The directions of the equilibrium shifts suggest that they are due to the acid/base or hydrogen bond donor/acceptor properties of capping ligands. This suggests a coupling of protons with the electron transfers in these systems. These findings provide a more nuanced and detailed picture of ET thermodynamic landscapes at nanoparticles than what is provided in a typical nanoparticle band energy scheme. Aspects of this understanding could be valuable for the use of nanoscale oxides in energy technologies.

Controlled Self-Assembly and Tuning of Large PbS Nanoparticle Supercrystals

Self-assembly of colloidal nanocrystals (NCs) into ordered superlattices (SLs) and supercrystals (SCs) enables new artificial NC solids for nanoelectronic and nanophotonic applications, which requires critical control of nucleation and growth conditions. Herein large SCs of PbS NCs up to ∼100 μm size were synthesized by two controlled self-assembly methods from NC solutions. Both translational symmetry and orientational ordering of the nanocrystals in the SCs were readily tuned by excess oleic acid ligands and antisolvents. Slow evaporation and the counterdiffusion method of solvents resulted in the formation of single SCs with two different SLs from the same PbS NCs: a face-centered cubic SL with weak yet complex orientational order or a body-centered cubic SL with strong and uniform particle orientation, respectively. The translational ordering was mainly determined by the effective shape of the NCs while the difference in orientational order was a result of the balance between ligand–ligand attraction and rotational entropy. The ease of the growth of large SC solids could lead to diverse NC systems and facilitate essential investigation of nanoparticle interactions and coupling based nanoelectronic and nanophotonic properties.

Unveiling the Shape Evolution and Halide-Ion-Segregation in Blue-Emitting Formamidinium Lead Halide Perovskite Nanocrystals Using an Automated Microfluidic Platform.

Hybrid organic-inorganic perovskites and in particular formamidinium lead halide (FAPbX3, X = Cl, Br, I) perovskite nanocrystals (NCs) have shown great promise for their implementation in optoelectronic devices. Specifically, the Br and I counterparts have shown unprecedented photoluminescence properties, including precise wavelength tuning (530-790 nm), narrow emission linewidths (<100 meV) and high photoluminescence quantum yields (70-90%). However, the controlled formation of blue emitting FAPb(Cl1-xBrx)3 NCs lags behind their green and red counterparts and the mechanism of their formation remains unclear. Herein, we report the formation of FAPb(Cl1-xBrx)3 NCs with stable emission between 440 and 520 nm in a fully automated droplet-based microfluidic reactor and subsequent reaction upscaling in conventional laboratory glassware. The thorough parametric screening allows for the elucidation of parametric zones (FA-to-Pb and Br-to-Cl molar ratios, temperature, and excess oleic acid) for the formation of nanoplatelets and/or NCs. In contrast to CsPb(Cl1-xBrx)3 NCs, based on online parametric screening and offline structural characterization, we demonstrate that the controlled synthesis of Cl-rich perovskites (above 60 at% Cl) with stable emission remains a challenge due to fast segregation of halide ions.

Site-Specific Ligand Interactions Favor the Tetragonal Distortion of PbS Nanocrystal Superlattices

We analyze the structure and morphology of mesocrystalline, body-centered tetragonal (bct) superlattices of PbS nanocrystals functionalized with oleic acid. On the basis of combined scattering and real space imaging, we derive a three-dimensional (3D) model of the superlattice and show that the bct structure benefits from a balanced combination of {100}PbS-{100}PbS and {111}PbS-{111}PbS interactions between neighboring layers of nanocrystals, which uniquely stabilizes this structure. These interactions are enabled by the coaxial alignment of the atomic lattices of PbS with the superlattice. In addition, we find that this preferential orientation is already weakly present within isolated monolayers. By adding excess oleic acid to the nanocrystal solution, tetragonal distortion is suppressed, and we observe assembly into a bilayered hexagonal lattice reminiscent of a honeycomb with grain sizes of several micrometers.

Metal Oleate Induced Etching and Growth of Semiconductor Nanocrystals, Nanorods, and Their Heterostructures.

Unexpected etching of nanocrystals, nanorods, and their heterostructures by one of the most commonly used metal precursors, metal oleates, is reported. Zn oleate is shown to etch CdS nanorods anisotropically, where the length decreases without a significant change in the diameter. Sodium oleate enhances the etch rate, whereas oleic acid alone does not cause etching, indicating the importance of the countercation on the rate of oleate induced etching. Subsequent addition of Se precursors to the partially etched nanorods in Zn oleate solution can lead to epitaxial growth of CdSe particles rather than the expected ZnSe growth, despite an excess amount of Zn precursors being present. The composition of this epitaxial growth can be varied from CdSe to ZnSe, depending on the amount of excess oleic acid or the reaction temperature. Similar tuning of composition can be observed when starting with collinear CdSe/CdS/CdSe rod/rod/rod heterostructures and spherical CdS (or CdSe/CdS core/shell) nanocrystals. Conversion of collinear rod/rod/rod structures to barbells and interesting rod growth from nearly spherical particles among other structures can also result due to the initial etching effect of metal oleates. These observations have important implications on our understanding of nanocrystal heterostructure synthesis and open up new routes to varying the composition and morphology of these materials.

ChemInform Abstract: Self‐Assembly of Magnetite Nanocubes into Helical Superstructures.

AbstractCubic nanocrystals of magnetite self‐assemble into arrays of helical superstructures in a template‐free manner with &lt;99% yield by placing a drop of hexane solution of magnetite nanocubes containing excess oleic acid at the interface of diethylene glycol—air in the presence of an external magnetic field, followed by evaporation of the solvent.

Size control of magnetite nanoparticles in excess ligands as a function of reaction temperature and time.

The novel synthesis of monodisperse magnetite Fe3O4 nanoparticles of varying sizes using a solventless synthetic method was developed. Iron salt was treated in excess oleylamine and oleic acid as ligands. The effect of the reaction temperature and time on the particle size was investigated and the particle sizes were easily tuned from 5.3 to 20.4 nm by changing the reaction temperature and time.