FA Chain Research Articles

(Non)linear Interfacial Rheology of Tween, Brij and Span Stabilized Oil-Water Interfaces: Impact of the Molecular Structure of the Surfactant on the Interfacial Layer Stability.

During emulsification and further processing (e.g., pasteurizing), the oil-water interface is mechanically and thermally stressed, which can lead to oil droplet aggregation and coalescence, depending on the interfacial properties. Currently, there is a lack of insights into the impact of the molecular structure (headgroup and FA chain) of low molecular weight emulsifiers (LME) on the resulting interfacial properties. Additionally, the crystallization/melting of the oil/the emulsifier is often neglected within interfacial rheological experiments. Within this study, the stability of interfaces formed by Tween, Span or Brij was determined as a function of their molecular structure, taking crystallization effects of the LME into account. The headgroup was kept constant while varying the FA, or vice versa. The interfacial film properties (viscoelasticity) were investigated at different temperatures using dilatational and interfacial shear rheology. Both the headgroup and the FA chain impacted the interfacial properties. For the same FA composition, a rather small hydrophobic headgroup resulted in a higher packed interface. The interfacial elasticity increased with increased FA chain length (C12 to C18). This seemed to be particularly the case when the emulsifier crystallized on the interface among cooling. In the case of a densely packed interface, network formation due to chain crystallization of the LME's FA chains occurs during the cooling step. The resulting interface shows predominantly elastic behavior.

Structural characterization of fatty acid anions via gas-phase charge inversion using Mg(tri-butyl-terpyridine)2 2+ reagent ions.

Free fatty acids and lipid classes containing fatty acid esters are major components of lipidome. In the absence of a chemical derivatization step, FA anions do not yield all of the structural information that may be of interest under commonly used collision-induced dissociation (CID) conditions. A line of work that avoids condensed-phase derivatization takes advantage of gas-phase ion/ion chemistry to charge invert FA anions to an ion type that provides the structural information of interest using conventional CID. This work was motivated by the potential for significant improvement in overall efficiency for obtaining FA chain structural information. A hybrid triple quadrupole/linear ion-trap tandem mass spectrometer that has been modified to enable the execution of ion/ion reaction experiments was used to evaluate the use of 4,4',4″-tri-tert-butyl-2,2':6',2″-terpyridine (ttb-Terpy) as the ligand in divalent magnesium complexes for charge inversion of FA anions. Mg(ttb-Terpy)2 2+ complexes provide significantly improved efficiency in producing structurally informative products from FA ions relative to Mg(Terpy)2 2+ complexes, as demonstrated for straight-chain FAs, branched-chain FAs, unsaturated FAs, and cyclopropane-containing FAs. It was discovered that most of the structurally informative fragmentation from [FA-H + Mg(ttb-Terpy)]+ results from the loss of a methyl radical from the ligand followed by radical-directed dissociation (RDD), which stands in contrast to the charge-remote fragmentation (CRF) believed to be operative with the [FA-H + Mg(Terpy)]+ ions. This work demonstrates that a large fraction of product ions from the CID of ions of the form [FA-H + Mg(ttb-Terpy)]+ are derived from RDD of the FA backbone, with a very minor fraction arising from structurally uninformative dissociation channels. This ligand provides an alternative to previously used ligands for the structural characterization of FAs via CRF.

The acyl-acyl carrier protein thioesterases GmFATA1 and GmFATA2 are essential for fatty acid accumulation and growth in soybean.

Acyl-acyl carrier protein (ACP) thioesterases (FAT) hydrolyze acyl-ACP complexes to release FA in plastids, which ultimately affects FA biosynthesis and profiles. Soybean GmFATA1 and GmFATA2 are homoeologous genes encoding oleoyl-ACP thioesterases whose role in seed oil accumulation and plant growth has not been defined. Using CRISPR/Cas9 gene editing mutation of Gmfata1 or 2 led to reduced leaf FA content and growth defect at the early seedling stage. In contrast, no homozygous double mutants were obtained. Combined this indicates that GmFATA1 and GmFATA2 display overlapping, but not complete functional redundancy. Combined transcriptomic and lipidomic analysis revealed a large number of genes involved in FA synthesis and FA chain elongation are expressed at reduced level in the Gmfata1 mutant, accompanied by a lower triacylglycerol abundance at the early seedling stage. Further analysis showed that the Gmfata1 or 2 mutants had increased composition of the beneficial FA, oleic acid. The growth defect of Gmfata1 could be at least partially attributed to reduced acetyl-CoA carboxylase activity, reduced abundance of five unsaturated monogalactosyldiacylglycerol lipids, and altered chloroplast morphology. On the other hand, overexpression of GmFATA in soybean led to significant increases in leaf FA content by 5.7%, vegetative growth, and seed yield by 26.9%, and seed FA content by 23.2%. Thus, overexpression of GmFATA is an effective strategy to enhance soybean oil content and yield.

Starch molecular structures in relation to properties of ratoon rice produced by different ratooning practices

The development of forage-grain ratoon rice (RR) pattern could ensure food security and promote silage production. Herein three indica rice varieties were used to investigate the influence of different forage clipping stages (heading, milk-ripe, wax-ripe, and full-ripe) on starch molecular structures and RR properties. The apparent amylose contents (AAC) of starches increased, but pasting viscosities, gelatinization temperatures and starch sizes decreased with the postponement of clipping stages due to the retardation of endosperm development. The starches showed A-type crystalline structure with increased in vitro digestibility; however relative crystallinity decreased by 13.45 % to 23.89 %. The short fa (DP 6–12) chains of amylopectin increased while long fb3 (DP ≥ 37) chains decreased (p < 0.05). The proportions of amylose chains with DP 100–2000 increased but those with DP 2000–20,000 decreased. Rice grain strength was positively correlated with fb3 chains while negatively correlated with fa chain. The hardness of cooked RR was positively correlated with AAC while negatively correlated with fb2 (DP 25–36). RR clipping at milk-ripe stage had the highest grain strength and moderate texture properties. The elucidation of structure-property relationships is helpful for RR utilization and development of suitable cultivation conditions for RR production.

Multi-scale structures and physicochemical properties of waxy starches from different botanical origins

The multi-scale structures and physicochemical relationships of three different types of waxy starches (maize, tapioca, and potato) were investigated. The maize and tapioca starches exhibited A-type crystalline polymorph compared to potato starch (B-type). The WMS showed higher amorphous content (5.56 %) than other waxy starches. The WTS exhibited a low tendency of retrogradation with its high fa (DP 6–12) and low fb3 (DP ≥ 37) proportion of chains. Double helix content of WPS was observed highest with a high pasting viscosity (952.3 BU). Low fa (DP 6–12) and high fb3 (DP ≥ 37) chain proportions of the WPS retrograded easily. The compactness of the semi-crystalline aggregation structure influenced the retrogradation properties of waxy starches with a positive correlation. Furthermore, the peak viscosity of pastes was correlated with the proportion of fb3 (DP ≥ 37) chains, mass fractal dimension, and double helix content. The results provide guidance to design the application of waxy starches in the production of clean-labels.

Whole picture of human stratum corneum ceramides, including the chain-length diversity of long-chain bases

Ceramides are essential lipids for skin permeability barrier function, and a wide variety of ceramide species exist in the stratum corneum (SC). Although ceramides with long-chain bases (LCBs) of various lengths have been identified in the human SC, a quantitative analysis that distinguishes ceramide species with different LCB chain lengths has not been yet published. Therefore, the whole picture of human SC ceramides remains unclear. Here, we conducted LC/MS/MS analyses to detect individual ceramide species differing in both the LCB and FA chain lengths and quantified 1,327 unbound ceramides and 254 protein-bound ceramides: the largest number of ceramide species reported to date. Ceramides containing an LCB whose chain length was C16–26 were present in the human SC. Of these, C18 (28.6%) was the most abundant, followed by C20 (24.8%) and C22 (12.8%). Each ceramide class had a characteristic distribution of LCB chain lengths and was divided into five groups according to this distribution. There was almost no difference in FA composition between the ceramide species containing LCBs of different chain lengths. Furthermore, we demonstrated that one of the serine palmitoyltransferase (SPT) complexes, SPTLC1/SPTLC3/SPTSSB, was able to produce C16–24 LCBs. The expression levels of all subunits constituting the SPT complexes increased during keratinocyte differentiation, resulting in the observed chain-length diversity of LCBs in the human SC. This study provides a molecular basis for elucidating human SC ceramide diversity and the pathogenesis of skin disorders.

Differences in starch structural and physicochemical properties and texture characteristics of cooked rice between the main crop and ratoon rice

Ratoon rice (RR) is characterized by higher production combined with enhanced rice quality. However, limited information is available regarding the mechanism of quality enhancement of RR. In this study, three varieties were used to investigate differences in the components, the fine structural and physicochemical properties of starch, and the textural characteristics of cooked rice between the main crop and RR. Compared to the main crop, RR significantly increased the starch and amylose content, amylose to amylopectin ratio, weight average molecular weight of the starch granule, and fa (DP 6–12) and fb1 (DP 13–24) chain proportions of amylopectin. However, it decreased the amylopectin and protein content, mean diameter and number average molecular weight of the starch granule, and fb2 (DP25-36) and fb3 (DP > 37) chain proportions of amylopectin. This contributed to an increase in branching degree, polydispersity, ΔHgel, Tc-R, ΔHret, and retrogradation percentage, as well as a decrease in the average chain length and polymerization degree of amylopectin and crystallinity degree, and water solubility of RR. These differences might contribute to the increase in hardness and decrease in stickiness of cooked RR.

Prilling of API/fatty acid suspensions: Processability and characterisation.

Current study evaluated the processability and characteristics of prills made of an active pharmaceutical ingredient/fatty acid (API/FA) suspension instead of previously studied API/FA solutions to enlarge the application field of prilling. Metformin hydrochloride (MET) and paracetamol (PAR) were used as model APIs while both the effect of drug load (10-40%) and FA chain length (C14-C22) were evaluated. API/FA suspensions were processable on lab-scale prilling equipment without thermal degradation, nozzle obstruction or sedimentation in function of processing time. The collected prills were spherical (AR ≥ 0.898) with a smooth surface (sphericity ≥ 0.914) and a particle size of ±2.3 mm and 2.4 mm for MET and PAR prills, respectively, independent of drug load and/or FA chain length. In vitro drug release evaluation revealed a faster drug release at higher drug load, higher API water solubility and shorter FA chain length. Solid state characterisation via XRD and Raman spectroscopy showed that API and FA crystallinity was maintained after thermal processing via prilling and during storage. Evaluation of the similarity factor indicated a stable drug release (f2 > 50) from MET and PAR prills after 6 months storage at 25 °C or 40 °C.

Fatty acid binding profile of the liver X receptor α

Liver X receptor (LXR)α is a nuclear receptor that responds to oxysterols and cholesterol overload by stimulating cholesterol efflux, transport, conversion to bile acids, and excretion. LXRα binds to and is regulated by synthetic (T-0901317, GW3695) and endogenous (oxysterols) ligands. LXRα activity is also modulated by FAs, but the ligand binding specificity of FA and acyl-CoA derivatives for LXRα remains unknown. We investigated whether LXRα binds FA or FA acyl-CoA with affinities that mimic in vivo concentrations, examined the effect of FA chain length and the degree of unsaturation on binding, and investigated whether FAs regulate LXRα activation. Saturated medium-chain FA (MCFA) displayed binding affinities in the low nanomolar concentration range, while long-chain fatty acyl-CoA did not bind or bound weakly to LXRα. Circular dichroic spectra and computational docking experiments confirmed that MCFA bound to the LXRα ligand binding pocket similar to the known synthetic agonist of LXRα (T0901317), but with limited change to the conformation of the receptor. Transactivation assays showed that MCFA activated LXRα, whereas long-chain FA caused no effect. Our results suggest that LXRα functions as a receptor for saturated FA or acyl-CoA of C10 and C12 in length.

Photoswitchable fatty acids enable optical control of TRPV1.

Fatty acids (FAs) are not only essential components of cellular energy storage and structure, but play crucial roles in signalling. Here we present a toolkit of photoswitchable FA analogues (FAAzos) that incorporate an azobenzene photoswitch along the FA chain. By modifying the FAAzos to resemble capsaicin, we prepare a series of photolipids targeting the Vanilloid Receptor 1 (TRPV1), a non-selective cation channel known for its role in nociception. Several azo-capsaicin derivatives (AzCAs) emerge as photoswitchable agonists of TRPV1 that are relatively inactive in the dark and become active on irradiation with ultraviolet-A light. This effect can be rapidly reversed by irradiation with blue light and permits the robust optical control of dorsal root ganglion neurons and C-fibre nociceptors with precision timing and kinetics not available with any other technique. More generally, we expect that photolipids will find many applications in controlling biological pathways that rely on protein–lipid interactions.

A hybrid non-ribosomal peptide/polyketide synthetase containing fatty-acyl ligase (FAAL) synthesizes the β-amino fatty acid lipopeptides puwainaphycins in the Cyanobacterium Cylindrospermum alatosporum.

A putative operon encoding the biosynthetic pathway for the cytotoxic cyanobacterial lipopeptides puwainphycins was identified in Cylindrospermum alatosporum. Bioinformatics analysis enabled sequential prediction of puwainaphycin biosynthesis; this process is initiated by the activation of a fatty acid residue via fatty acyl-AMP ligase and continued by a multidomain non-ribosomal peptide synthetase/polyketide synthetase. High-resolution mass spectrometry and nuclear magnetic resonance spectroscopy measurements proved the production of puwainaphycin F/G congeners differing in FA chain length formed by either 3-amino-2-hydroxy-4-methyl dodecanoic acid (4-methyl-Ahdoa) or 3-amino-2-hydroxy-4-methyl tetradecanoic acid (4-methyl-Ahtea). Because only one puwainaphycin operon was recovered in the genome, we suggest that the fatty acyl-AMP ligase and one of the amino acid adenylation domains (Asn/Gln) show extended substrate specificity. Our results provide the first insight into the biosynthesis of frequently occurring β-amino fatty acid lipopeptides in cyanobacteria, which may facilitate analytical assessment and development of monitoring tools for cytotoxic cyanobacterial lipopeptides.

Synthesis and anticancer activity of long chain substituted 1,3,4-oxadiazol-2-thione, 1,2,4-triazol-3-thione and 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazine derivatives

In this paper, three novel series of 5-long chain alkenyl/hydorxyalkenyl-1,3,4-oxadiazol-2-thiones 2(a–d), 4-amino-5-long chain alkenyl/hydroxyalkenyl-1,2,4-triazol-3-thiones 3(a–d) and 3-long chain alkenyl/hydroxyalkenyl-6-phenyl-(7H)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazines 4(a–d) were synthesized with an aim to produce promising anticancer agents. We describe here the synthesis of compounds 2(a–d), 3(a–d) and 4(a–d) using long chain alkenyl/hydroxyalkenyl hydrazides 1(a–d) as starting material. Our investigation shows that the thione tautomer of 2(a–d) and 3(a–d) dominates. All the synthesized compounds were characterized by IR, 1H NMR, 13C NMR and mass spectral data. After characterization, all compounds were tested for in vitro anticancer activity against PBMCs and three different human cancer cell lines. On the basis of SAR, it may be concluded that the potency of drugs depends on the nature of FA chain and the heterocyclic ring system. Among all the tested compounds, compounds having fused ring system (triazolothiadiazine nucleus) and the hydroxyl group attached to the FA chain (4c and 4d) were found to be the most promising anticancer agents.

Synthesis and characterization of a new multifunctional polymeric prodrug paclitaxel–polyphosphoester–folic acid for targeted drug delivery

We report here a strategy that allows the preparation of a novel water-soluble polymeric prodrug, paclitaxel–poly(ethyl ethylene phosphate) conjugated with folic acid molecules (abbreviated as PTX–PEEP–FA). PTX was directly used as an initiator for the ring-opening polymerization (ROP) of 2-ethoxy-2-oxo-1,3,2-dioxaphospholane (EOP) under the catalysis of Sn(Oct)2 to fabricate an amphiphilic PTX–PEEP, followed by covalently conjugating a FA moiety via esterification to obtain the biodegradable and targeted polymeric prodrug PTX–PEEP–FA. The chemical structure of the prodrug was characterized by 1H NMR and MALDI-TOF mass spectroscopy. TEM and DLS measurements showed that these prodrugs could self-assemble in aqueous solution to form micelles with PTX as the core and PEEP–FA as the corona, and the average particle size was less than 130 nm. The hydrophobic PTX core could be further used to load more water-insoluble anti-cancer drugs, such as PTX or doxorubicin (DOX), while the hydrophilic PEEP–FA chain endowed micelles with good stability during systemic circulation and significantly improved controlled-release properties compared to free PTX or DOX. Live cell imaging system was utilized to monitor the cellular uptake process of DOX-loaded PTX–PEEP–FA micelles for HeLa and KB cells, respectively. The results revealed that these drug-loaded micelles with FA on their surface could remarkably improve cell endocytosis. In vitro biological evaluations confirmed that PTX–PEEP–FA, simultaneously acted as both a prodrug and drug delivery carrier, could achieve the aims of increased drug loading efficiency, reduced cytotoxicity, and enhanced targeting efficacy.

Enteric methane emissions and lactational performance of Holstein cows fed different concentrations of coconut oil

To determine if dietary medium-chain fatty acids (FA; C8 to C14) may mitigate enteric methane emissions, 24 cows were blocked by body size (n=2) and randomly assigned to 1 sequence of dietary treatments. Diets were fed for 35 d each in 2 consecutive periods. Diets differed in concentrations of coconut oil (CNO; ∼75% medium-chain FA): 0.0 (control) or 1.3, 2.7, or 3.3% CNO, dry matter basis. The control diet contained 50% forage (74% from corn silage), 16.5% crude protein (60% from rumen-degradable protein), 34% neutral detergent fiber (NDF; 71% from forage), and 28% starch, dry matter basis. Data and sample collections were from d 29 to 35 in environmentally controlled rooms to measure methane (CH4) production. Methane emitted was computed from the difference in concentrations of inlet and outlet air and flux as measured 8 times per day. Control cows emitted 464g of CH4/d, consumed 22.9kg of DM/d, and produced 34.8kg of solids-corrected milk/d and 1.3kg of milk fat/d. Treatment with 1.3, 2.7, or 3.3% dietary CNO reduced CH4 (449, 291, and 253g/d, respectively), but concomitantly depressed dry matter intake (21.4, 17.9, and 16.2kg/d, respectively), solids-corrected milk yield (36.3, 28.4, and 26.8kg/d, respectively), and milk fat yield (1.4, 0.9, and 0.9kg/d, respectively). The amount of NDF digested in the total tract decreased with increased dietary CNO concentrations; thus, CH4 emitted per unit of NDF digested rose from 118 to 128, 153, and 166g/kg across CNO treatments. Dietary CNO did not significantly affect apparent digestibility of CP but increased apparent starch digestibility from 92 to 95%. No FA C10 or shorter were detected in feces, and apparent digestibility decreased with increasing FA chain length. Coconut oil concentrations of 2.7 or 3.3% decreased yields of milk FA <C12 and >C14. The highest milk fat concentration (3.69%; 1.3% CNO) was due to the greatest yields of C12 to C16 milk FA. Milk FA concentrations of C18:2 trans-10,cis-12 were related to increased dietary CNO concentrations and presumably to depressed ruminal NDF digestion. Moderate dietary CNO concentrations (e.g., 1.3%) may benefit lactational performance; however, CNO concentrations greater than or equal to 2.7% depressed dry matter intake, milk yield, milk fat yield, and NDF utilization. If mitigation of enteric CH4 emissions is due to decreased digestion of dietary NDF, then this will lessen a major advantage of ruminants compared with nonruminants in food-production systems. Thus, CNO has limited use for enteric CH4 mitigation in lactating dairy cows.

Determination of lipoprotein lipase activity using a novel fluorescent lipase assay

A novel, real-time, homogeneous fluorogenic lipoprotein lipase (LPL) assay was developed using a commercially available substrate, the EnzChek lipase substrate, which is solubilized in Zwittergent. The triglyceride analog substrate does not fluoresce, owing to apposition of fluorescent and fluorescent quenching groups at the sn-1 and sn-2 positions, respectively, fluorescence becoming unquenched upon release of the sn-1 BODIPY FA derivative following hydrolysis. Increase in fluorescence intensity at 37°C was proportional to LPL concentration. The assay was more sensitive than a similar assay using 1,2-O-dilauryl-rac-glycero-3-glutaric acid-(6-methylresorufin ester) and was validated in biological samples, including determination of LPL-specific activity in postheparin mouse plasma. The simplicity and reproducibility of the assay make it ideal for in vitro, high-throughput screening for inhibitors and activators of LPL, thus expediting discovery of drugs of potential clinical value.

Physical properties of palm‐based diacylglycerol and palm‐based oils in the preparation of shelf‐stable margarine

Ternary mixtures containing palm olein (POL), palm kernel oil (PKO) and palm oil-based diacylglycerol (PO-DAG) were designed using mixture design. The corresponding physical properties such as solid fat content (SFC) as well as deviation from SFC (ΔSFC) using nuclear magnetic resonance (NMR) and melting and crystallization properties using differential scanning calorimetry (DSC) were studied. Ternary phase behaviour was analysed using isosolid diagrams. The most intensive eutectic interaction among the three binary blends studied was observed along the binary line of PKO/PO-DAG followed by POL/PKO and POL/PO-DAG. The higher ΔSFC did not always lead to the more intensive eutectic behaviour among the blends. Addition of pure POL, 33.33 and 66.66% POL, and no POL to 50/50 mixture of PKO/PO-DAG decreased heat of crystallization (ΔHc) as well as crystallization onset (TO). However, as the same amounts of PO-DAG and PKO were added to the 50/50 mixtures of POL/PKO and POL/PO-DAG, respectively, blend containing the equi-mixture of POL, PKO and PO-DAG (33.33/33.33/33.33) was found to have the lowest ΔHc. This was also reflected in the corresponding eutectic effect observed at 20–25 and 5–10°C, respectively. Palm-based DAG-enriched shelf-stable margarine consisting of POL/PKO/PO-DAG (42.5/42.5/15 w/w) was optimally formulated through analysis of multiple isosolid diagrams and was found to have quite similar SFC profile with commercial shelf-stable margarine. Practical applications: In this study, valuable information about complicated interactions among the palm oil-based diacylglycerol (PO-DAG) and palm-based oils with different FA chain length was obtained in the ternary system. These informative data may be useful in future exploitation of solid fat-based DAG in blend with natural fats for various DAG-enriched plastic fat products. Furthermore, Design Expert software was found to be a valuable tool to optimize the new fat blend formulation using the minimum number of blend preparation. By using this tool, assessment of complicated behaviour among the blend components through construction of the corresponding phase diagrams which are critical for optimization purposes as well as fat product development, would also be possible.

2-Hydroxy-ceramide synthesis by ceramide synthase family: enzymatic basis for the preference of FA chain length

Ceramide is unusually abundant in epidermal stratum corneum and is important for permeability barrier function. Ceramides in epidermis also comprise an unusual variety, including 2-hydroxy (alpha-hydroxy)-ceramide. Six mammalian ceramide synthase/longevity assurance homologue (CerS/LASS) family members have been identified as synthases responsible for ceramide (CER) production. We reveal here that of the six, CerS3/LASS3 mRNA is the most predominantly expressed in keratinocytes. Moreover, its expression is increased upon differentiation. CerS family members have known substrate specificities for fatty acyl-CoA chain length and saturation, yet their abilities to produce 2-hydroxy-CER have not been examined. In the present study, we demonstrate that all CerS members can produce 2-hydroxy-CER when overproduced in HEK 293T cells. Each produced a 2-hydroxy-CER with a chain length similar to that of the respective nonhydroxy-CER produced. In HeLa cells overproducing the FA 2-hydroxylase FA2H, knock-down of CerS2 resulted in a reduction in total long-chain 2-hydroxy-CERs, confirming enzyme substrate specificity for chain length. In vitro CerS assays confirmed the ability of CerS1 to utilize 2-hydroxy-stearoyl-CoA as a substrate. These results suggest that all CerS members can synthesize 2-hydroxy-CER with specificity for 2-hydroxy-fatty acyl-CoA chain length and that CerS3 may be important in CER and 2-hydroxy-CER synthesis in epidermis.

Fatty acid-induced NF-κB activation and insulin resistance in skeletal muscle are chain length dependent

The saturated fatty acid (SFA) palmitate induces insulin resistance in cultured skeletal muscle cells, which may be related to NF-kappaB activation. The aim of this study was to evaluate whether other SFAs also exert these effects on skeletal muscle and whether these relate to chain length. Therefore, we incubated L6 and C(2)C(12) skeletal muscle cells with four different fatty acids, caprylate (C8:0), laurate (C12:0), palmitate (C16:0), and stearate (C18:0), to study effects on GLUT4 translocation, deoxyglucose uptake, and NF-kappaB activation. Incubation of L6 cells with the long-chain FAs C16:0 and C18:0 reduced insulin-stimulated GLUT4 translocation and deoxyglucose uptake, whereas L6 cells incubated with the medium-chain FAs C8:0 and C12:0 remained insulin sensitive. Besides increasing NF-kappaB DNA binding activity in both L6 and C(2)C(12) cells, C16:0 also induced NF-kappaB transcriptional activity. C18:0 showed comparable effects, whereas the SFAs with shorter chain lengths were not able to elevate NF-kappaB transcriptional activity. Collectively, these results demonstrate that SFA-induced NF-kappaB activation coincides with insulin resistance and depends on FA chain length.

Zeolite‐catalyzed isomerization of oleic acid to branched‐chain isomers

AbstractBranched‐chain (bc) saturated fatty acids (SFA) have potential as oleochemical intermediates since they have better oxidative stability than linear unsaturated fatty acids (UFA) and have better low‐temperature properties than linear SFA. Previous studies in converting UFA to bc‐FA using clay catalysts have resulted in only modest yields and conversions. Recent reports, however, have suggested that certain zeolites can be effective catalysts for converting UFA to bc‐FA in higher yields and conversions. In this work, we examined the scope and potential of the zeolite‐catalyzed synthesis of bc‐FA starting from readily available monounsaturated linear FA. Our results show that common UFA such as oleic acid can be converted to bc‐isomers using modified Ferrierite zeolite catalysts with high conversions (98%) and high selectivity (85%) and that the zeolite catalysts are reusable for at least three cycles. The positions of branching (methyl) on the FA chain were determined from the GC‐MS spectra of the picolinyl esters of the bc‐FA.

Polymorphic transitions of cocoa butter affected by high hydrostatic pressure and sucrose polyesters

AbstractForm V to Form VI transitions of cocoa butter (CB) were investigated by varying the temperature between 28 and 21°C during storage. High hydrostatic pressure (HHP) treatments of CB melt at 60 or 21°C did not affect the rate of Form V to Form VI transitions in CB crystallized in Form V during temperature fluctuations. The HHP treatments with 100, 300, or 600 MPa of CB crystallized in Form V crystals did not alter the rate of Form V to Form VI transitions of CB. The addition of sucrose polyesters to CB melts altered the rate of Form V to Form VI transitions of CB and was dependent on the FA chain lengths and hydrophilelipophile balance (HLB) values of the SPE. The addition of most SPE to CB melts promoted the polymorphic transitions; however, sucrose polyester S‐170 containing FA of chain length similar to CB with small HLB values inhibited Form V to Form VI transitions of CB for 10 temperature fluctuation cycles. Therefore, HHP treatments can be applied to foods containing high fat with little effect on the polymorphic transitions, and selected SPE may be used to retard adverse polymorphic transitions.