C6 C18 Research Articles

Effect of Interactions between Alkyl Chains and Solvent Structures on Lewis Acid Catalyzed Epoxidations

Solvent molecules within zeolite pores provide interactions that influence the stability of reactive intermediates and impact rates and selectivities for catalytic reactions. We show the kinetic and thermodynamic consequences of these interactions and reveal their origins using alkene epoxidations in titanium-substituted *BEA (Ti-BEA) zeolites. Epoxidation turnover rates vary widely among primary n-alkenes (C6–C18) in hydrophilic (Ti-BEA-OH) and hydrophobic (Ti-BEA-F) catalysts in aqueous acetonitrile (CH3CN). Apparent activation enthalpies (ΔHapp‡) and entropies (ΔSapp‡) increase with alkene carbon number in both catalysts; however, the span of ΔHapp‡ values in Ti-BEA-OH (68 kJ mol–1) greatly exceeds that in Ti-BEA-F (18 kJ mol–1). These trends, and commensurate gains in ΔSapp‡, reflect the displacement and reorganization of solvent molecules that scale with the size of transition states and the numbers of solvent molecules stabilized by silanol defects near active sites. Experimental and computational assessments of intrapore solvent composition from 1H NMR, infrared spectroscopy, and grand canonical molecular dynamics (GCMD) simulations show that Ti-BEA-OH uptakes larger quantities of both CH3CN and H2O than Ti-BEA-F. The Born–Haber decomposition of simulated enthalpies of adsorption (ΔHads,epox) for C6–C18 epoxides attributes ΔHads,epox that become more endothermic for larger adsorbates to the displacement of greater numbers of solvent molecules bound to silanol defects into the bulk solvent. A strong correlation between ΔHapp‡ and ΔHads,epox (from GCMD and isothermal titration calorimetry) gives evidence that the disruption of solvent structures provides excess thermodynamic contributions (e.g., Gε) that depend on the solvent composition in the pores, the excluded volume of reactive species, and the density of silanol groups near active sites. Altering Gε values offers opportunities to control selectivities and rates of reactions through the design of extended active site environments.

Lyophilic and Sorption Properties of Chitosan Aerogels Modified with Copolymers Based on Glycidyl Methacrylate and Alkyl Methacrylates.

This paper discusses the influence of the structure of copolymers based on glycidyl methacrylate and alkyl methacrylates with C6–C18 hydrocarbon side groups on the wettability and sorption properties of surface-modified chitosan aerogels. The grafting of copolymers onto the surface of aerogels was confirmed by elemental analysis, X-ray photoelectron spectroscopy, and Fourier-transform infrared spectroscopy. As a result of the modification, with an increase in the amount of the hydrocarbon substituent alkyl methacrylate, the surface of the resulting materials became hydrophobic with contact angles in the range of 146–157°. At the same time, the water absorption of the aerogels decreased by a factor of 30 compared to that for unmodified aerogels, while the sorption capacity for light oil, diesel fuel, and synthetic motor oil remained at the level of more than 30 g/g. Chitosan aerogels with grafted copolymers based on glycidyl methacrylate and alkyl methacrylates retain biodegradation capacity; however, compared to unmodified chitosan, this process has an induction period.

Lignin-based jet fuel and its blending effect with conventional jet fuel

Sustainable aviation fuels (SAFs) must demonstrate specific physical and chemical properties as well as material compatibility (i.e., seal swell) to be used as aviation turbine fuels. Several alternative jet fuels incorporated in ASTM D7566 are comprised mainly of n/iso-alkanes and can only be blended up to 50 vol% due to material compatibility and density issues. Prior work illustrated the ability of cycloalkanes to replace the swelling potential of aromatics required for material compatibility. Here, we report the first archival documentation of a feedstock and chemical process to yield a product composition that could complement 5 existing SAF ASTM D7566 annexes. A lignin-based jet fuel (LJF) blend component is generated and composed of mostly C6–C18 mono, di, and tri-cycloalkanes. The neat LJF was blended with conventional jet fuel at 10 vol% (LJF blend) to simulate a potential qualification goal. Fuel properties critical to engine operability (ATSM D4054 Tier 3 & 4) were either predicted or experimentally tested based on the volume availability. All LJF-blended operability properties fall within the experience range of conventional jet fuel, with neat o-ring swelling exceeding the typical range of conventional fuels. These results support the potential use of this LJF pathway to complement other SAF pathways and achieve 100% drop-in SAF.

Transcriptomic response of Saccharomyces cerevisiae to octanoic acid production.

ABSTRACTThe medium-chain fatty acid octanoic acid is an important platform compound widely used in industry. The microbial production from sugars in Saccharomyces cerevisiae is a promising alternative to current non-sustainable production methods, however, titers need to be further increased. To achieve this, it is essential to have in-depth knowledge about the cell physiology during octanoic acid production. To this end, we collected the first RNA-Seq data of an octanoic acid producer strain at three time points during fermentation. The strain produced higher levels of octanoic acid and increased levels of fatty acids of other chain lengths (C6–C18) but showed decreased growth compared to the reference. Furthermore, we show that the here analyzed transcriptomic response to internally produced octanoic acid is notably distinct from a wild type's response to externally supplied octanoic acid as reported in previous publications. By comparing the transcriptomic response of different sampling times, we identified several genes that we subsequently overexpressed and knocked out, respectively. Hereby we identified RPL40B, to date unknown to play a role in fatty acid biosynthesis or medium-chain fatty acid tolerance. Overexpression of RPL40B led to an increase in octanoic acid titers by 40%.

Characterization of complexes formed between debranched starch and fatty acids having different carbon chain lengths

Recently, amylose–lipid complexes have attracted widespread attention because of their various applications. However, DBS complexed with fatty acids of different carbon chain length are rarely studied. This study aimed to probe the complexation of DBS with saturated fatty acids having different carbon chain lengths (C6–C18). The results revealed that DBS was able to form V-type complexes with all the fatty acids considered. Compared to DBS, the relative crystallinity of the complexes increased 2–3 times. DBS with lauric acid and myristic acid formed three types V-type complexes (type I, type IIa, and type IIb). The complexing index followed the order of hexanoic acid > octanoic acid > capric acid > lauric acid > myristic acid > palmitic acid > stearic acid. Furthermore, lauric acid and myristic acid formed complexes with DBS more easily compared with other fatty acids.

In Vivo Reduction of Medium‐ to Long‐Chain Fatty Acids by Carboxylic Acid Reductase (CAR) Enzymes: Limitations and Solutions

AbstractFatty aldehyde production by chemical synthesis causes an immense burden to the environment. Within this study, we explored a sustainable, aldehyde‐selective and mild alternative approach by utilizing carboxylic acid reductases (CARs). CARs from Neurospora crassa (NcCAR), Thermothelomyces thermophila (TtCAR), Nocardia iowensis (NiCAR), Mycobacterium marinum (MmCAR) and Trametes versicolor (TvCAR) were overexpressed in E. coli K‐12 MG1655 RARE (DE3) and screened for medium‐ to long‐chain fatty acid (C6–C18) reduction. MmCAR showed the broadest tolerance towards all carbon‐chain lengths and was selected for further investigations of fatty aldehyde synthesis in whole cells. To yield relevant product concentrations, different limitations of CAR whole‐cell conversions were elucidated and compensated. We coupled an in vitro cofactor recycling system to a whole‐cell biocatalyst to support cofactor supply and achieved 12.36 g L−1 of octanal (STY 0.458 g L−1 h−1) with less than 1.5 % of 1‐octanol.

Synthesis of the C6–C18 bis-tetrahydrofuran fragment of the proposed structure of iriomoteolide-2a via stepwise double SN2 cyclization reactions

The C6–C18 bis-tetrahydrofuran (bis-THF) fragment of the proposed structure of iriomoteolide-2a has been synthesized via stepwise double intramolecular SN2-type etherifications. The C11 and C16 stereogenic centers could be secured in the forms of propargyl alcohols by asymmetric transfer hydrogenation of the corresponding propargyl ketones. The C9–C12 THF ring was first constructed via a tandem asymmetric dihydroxylation (AD)–SN2 sequence while the C13–C16 THF ring was later installed via an intramolecular SN2 reaction of a chiral propargyl mesylate. During the latter THF ring formation, epimerization at the propargylic carbon was not observed. Since the initially proposed (9R,11S,12R) configuration of iriomoteolide-2a has recently been revised to (9S,11R,12S), the established synthesis of the C6–C18 bis-THF fragment could be easily amended by using the opposite enantiomers of the chiral ligands for AD and asymmetric transfer hydrogenation.

Thermocatalytic Degradation of High Density Polyethylene into Liquid Product

Thermocatalytic degradation of high density polyethylene (HDPE) was carried out using acid activated fire clay catalyst in a semi batch reactor. Thermal pyrolysis was performed in the temperature range of 420–500 °C. The liquid and gaseous yields were increased with increase in temperature. The liquid yield was obtained 30.1 wt% with thermal pyrolysis at temperature of 450 °C, which increased to 41.4 wt% with catalytic pyrolysis using acid activated fire clay catalyst at 10 wt% of catalyst loading. The composition of liquid products obtained by thermal and catalytic pyrolysis was analyzed by gas chromatography-mass spectrometry and compounds identified for catalytic pyrolysis were mainly paraffins and olefins with carbon number range of C6–C18. The boiling point was found in the range of commercial fuels (gasoline, diesel) and the calorific value was calculated to be 42 MJ/kg.

Molecular flexibility operated mesomorphism by end groups in azoester series

ABSTRACTA novel azoester homologous series, RO‒C6H4‒COO‒C6H4‒N = N‒C6H4‒OC7H15(n) (para) has been synthesized and studied with a view to understanding and establishing the effects of molecular structure on mesomorphic properties with reference to tthe flexible terminal chain. The novel azoester series consists of thirteen (C1–C18) members. Mesomorphism commences from C5 homologue. C1–C4 homologues are nonmesomorphic, C5 homologue is only nematogenic and C6–C18 homologues are smectogenic and nematogenic. All mesogenic homologues are enantiotropically mesomorphic. Transition temperatures and textures were determined by polarizing optical microscopy (POM) and a heating stage. Cr-M/I transition curve follows a zigzag path of rising and falling values and behaves in a normal manner. The Sm-N and N-I transition curves of a phase diagram behave in the normal established manner except for a small deviation for the higher homologues (C14 and C16). An odd-even effect is exhibited by Sm-N and N-I transition curves. Analytical spectral and thermal data support the molecular structures. Smectic and nematic thermal stabilities are 93.62°C and 114.3°C, respectively. Smectic and nematic mesophas elengths range from 12.0°C to 18.0°C and 11.0°C to 31.0°C. The series is predominantly nematogenic and partly smectogenic and of middle order melting type. Group efficiency order derived for smectic and nematic. Smectic and nematic: ‒OCH3 > ‒OC4H9 > ‒OC7H15(n).

A Fatty Acids Mixture Reduces Anxiety-Like Behaviors in Infant Rats Mediated by GABAA Receptors.

Fatty acids (C6–C18) found in human amniotic fluid, colostrum, and maternal milk reduce behavioral indicators of experimental anxiety in adult Wistar rats. Unknown, however, is whether the anxiolytic-like effects of fatty acids provide a natural mechanism against anxiety in young offspring. The present study assessed the anxiolytic-like effect of a mixture of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, and linoleic acid in Wistar rats on postnatal day 28. Infant rats were subjected to the elevated plus maze, defensive burying test, and locomotor activity test. Diazepam was used as a reference anxiolytic drug. A group that was pretreated with picrotoxin was used to explore the participation of γ-aminobutyric acid-A (GABAA) receptors in the anxiolytic-like effects. Similar to diazepam, the fatty acid mixture significantly increased the frequency of entries into and time spent on the open arms of the elevated plus maze and decreased burying behavior in the defensive burying test, without producing significant changes in spontaneous locomotor activity. These anxiolytic-like effects were blocked by picrotoxin. Results suggest that these fatty acids that are contained in maternal fluid may reduce anxiety-like behavior by modulating GABAergic neurotransmission in infant 28-day-old rats.

The effect of side-chain length of cellulose fatty acid esters on their thermal, barrier and mechanical properties

Currently, long-chain cellulose esters are not produced commercially because of high price, and since their preparation typically requires a large quantity of chemicals. To reduce the chemical consumption, cellulose reactivity needs to be increased without losing its quality. One way to increase the reactivity of cellulose is to decrease its molar mass in a controlled manner. In this study, we have synthesized cellulose esters with different side-chain length (C6–C18) in a homogeneous system using ozone molar mass-controlled cellulose. The target was to keep the degree of substitution as low as possible while still ensuring the suitability of cellulose esters for solvent casting. Thermal, barrier and mechanical properties were studied depending on cellulose fatty acid ester side-chain length. All our molar mass-controlled cellulose esters form optically transparent, flexible and heat-sealable films with good water barrier properties and are processable without the addition of an external plasticizer. Furthermore, the films have mechanical properties comparable to some generally used plastics. These good properties suggest that our molar mass-controlled cellulose esters could be potential candidates for various applications such as films and composites.

Study of mesomorphism dependence on molecular flexibility of an azoester series containing a napthyl unit

ABSTRACTA novel azoester homologous series of liquid crystalline (LC) compounds: RO‒C6H4-COO‒C10H6-N:N-C6H4‒OC4H9(n) without lateral substitution has been synthesized and studied with a view to understanding and establishing the effects of molecular structure on thermotropic LC substances with reference to tailed-end group. The novel homologous series consists of 13 homologs (C1 to C18) whose nematogenic and smectogenic mesomorphism commences enantiotropically from C6 and C12 members of the series, respectively. The C12–C18 homologs are smectogenic and C6–C18 are nematogenic, of which C12–C18 homologs are smectogenic plus nematogenic. The C1–C5 homologs are nonmesogenic. Transition temperatures and the textures of the homologs were determined and identified by an optical polarizing microscope (POM) equipped with a heating stage. Textures of a nematic phase are threaded or Schlieren and that of the smectic phase are of the type A or C. Transition curves Cr-M/I, Sm-N and N-I of a phase diagram behaved in normal manner except N-I transition temperature of C10 homolog which deviated by 9°C–10°C from normal behavior. N-I transition curve exhibited odd-even effect. Analytical, spectral, and thermal data confirms the molecular structures of homologs. Thermal stability for smectic and nematic are 115.5°C and 138.5°C, respectively whose corresponding mesophaselengths are varied from 10.0°C to 16.0°C and 13.0°C to 24.0°C, respectively. Group efficiency order for smectic and nematic are derived from comparative study of structurally similar analogous series; as smectic: ‒OC4H9 (n) > ‒CH3 > ‒H; Nematic: ‒H > ‒OC4H9 (n) > ‒CH3

A gasoline-grade biofuel formed from renewable polyhydroxybutyrate on solid phosphoric acid

Polyhydroxybutyrate (PHB) is an energy storage material formed from renewable feedstock in many bacterial species. The biopolyester (C4H6O2)n was degraded, deoxygenated and reformed into hydrocarbon oil (C6–C18) on solid phosphoric acid (SPA) in one-pot reaction. The reaction started at 213°C and completed below 240°C as measured with a differential scanning calorimeter. In addition to the oil, other products included carbon dioxide (CO2), propylene (C3H6), water (H2O) and some char-like solid. The mass yields in a typical reaction were determined with a total mass recovery of 94wt%. About 80% of oxygen in PHB was removed as CO2 via decarboxylation. By using a gas chromatograph–mass spectrometer, the oil composition was analyzed according to the chemical structure and carbon number of major compounds. In contrast to conventional biofuels derived from plant biomass, the PHB–oil has a high content of alkenes or aromatics, depending on the solid acid catalyst. The catalyst properties that affected the reaction include the calcination temperature in catalyst preparation, the catalyst dosage in the reaction, the total acid and free acid contents of fresh or used catalyst, and working time when the catalyst was repeatedly reused. The hydrocarbon oil (30wt% yield) was separated into two fractions according to their boiling temperature range: a light oil (bp 40–240°C) with 23wt% yield and a heavy oil (bp 240–310°C) with 7wt% yield. The light oil has the same elemental composition and high heating value (HHV 41.4/kg) of a commercial gasoline and the heavy oil (HHV 38.4MJ/kg) has the similar elemental composition of biodiesel. The oil is a good source of bio-based alkenes and aromatics that can improve the performance of bio-based fuels in modern motor engines.

One-step production of C1–C18 alcohols via Fischer-Tropsch reaction over activated carbon-supported cobalt catalysts: Promotional effect of modification by SiO2

The promotional effect of SiO2 on the catalytic synthesis of mixed C1–C18 alcohols from syngas using the Fischer-Tropsch reaction over activated carbon-supported cobalt catalysts was investigated. X-ray diffraction, H2 temperature-programmed reduction, pulsed CO chemisorption and N2 physisorption techniques were all employed to assess the catalyst. Although the addition of SiO2 decreased the reducibility of the Co component, Co dispersion was significantly increased and its aggregation during reaction was inhibited, resulting in greatly enhanced reaction activity. Appropriate amounts of SiO2 also promoted the formation of Co2C, leading to an increased selectivity for C1–C18 alcohols. More importantly, the addition of SiO2 favored the formation of higher molecular mass alcohols (C6–C18) by suppressing Co reduction, thus producing an abundance of Co(II) species capable of facilitating CO insertion.

Lauryl-poly-L-lysine: A New Antimicrobial Agent?

The development of multiple antibiotic resistance is a global problem. It is necessary to find new tools whose mechanisms of action differ from those of currently used antibiotics. It is known that fatty acids and cationic polypeptides are able to fight bacteria. Here, we describe the synthesis of fatty acids linked to a polypeptide with antibacterial activity. The linkage of fatty acids to a polypeptide is reported to increase the antibacterial effect of the linked fatty acid in comparison with free fatty acids (FA) or free poly-L-lysine (PLL) or a mixture of both (FA free + PLL free). A number of C6–C18 fatty acids were linked to PLL to obtain new synthetic products. These compounds were assessed in vitro to evaluate their antibacterial activity. Some fatty acid-PLLs showed a good ability to fight bacteria. Their bactericidal activity was evaluated, and, lauryl linked to PLL was found to be the most active product against both Gram-positive and Gram-negative bacteria. This new active component showed a good degree of specificity and reproducibility and its minimum inhibitory concentration (MIC) was comparatively good. The antibacterial activity of the lauryl-PLL compound suggests that it is a new and promising antimicrobial agent.

Heats of Combustion of Fatty Acids and Fatty Acid Esters

AbstractThe military uses JP‐8, a kerosene type hydrocarbon, to fuel most of its vehicles and is seeking a renewable alternative fuel that meets strict JP‐8 specifications. Biodiesel is typically a mixture of different alkyl esters produced from the transesterification of triglycerides readily available in plant oils and used cooking oil. To date, no traditional biodiesel meets the requirements for heat of combustion, freezing point, viscosity and oxidative stability to be a stand‐alone replacement for JP‐8. This work is a fundamental survey of the heat of combustion of single fatty acid esters and a predictive model for estimating the heat of combustion given a known molecular structure. The gross heat of combustion of various C6–C18 fatty acids and the methyl, propyl and isopropyl esters of these fatty acids was measured. This study sought to relate the effect of chain length, degree of unsaturation and branching to the critical fuel property of the gross heat of combustion (Hc). It was found that Hc (kJ/g) increased with chain length. A nearly linear relationship was found between wt% carbon and hydrogen, and Hc. Group contribution models previously published for hydrocarbons and polymers were modified to more accurately predict the heat of combustion of the fatty acids and esters. Modification of the molar heat values of carboxylic acid, methyl, and methylene groups improved correlation of the model with the experimental results.

Synthesis and properties of fatty acid starch esters

Being completely bio-based, fatty acid starch esters (FASEs) are attractive materials that represent an alternative to crude oil-based plastics. In this study, two synthesis methods were compared in terms of their efficiency, toxicity and, especially, product solubility with starch laurate (C12) as model compound. Laurates (DS>2) were obtained through transesterification of fatty acid vinylesters in DMSO or reaction with fatty acid chlorides in pyridine. The latter lead to higher DS-values in a shorter reaction time. But due to the much better solubility of the products compared to lauroyl chloride esterified ones, vinylester-transesterification was preferred to optimize reaction parameters, where reaction time could be shortened to 2h. FASEs C6–C18 were also successfully prepared via transesterification. To determine the DS of the resulting starch laurates, the efficient ATR-IR method was compared with common methods (elementary analysis, 1H NMR). Molar masses (Mw) of the highly soluble starch laurates were analyzed using SEC-MALLS (THF). High recovery rates (>80%) attest to the outstanding solubility of products obtained through transesterification, caused by a slight disintegration during synthesis. Particle size distributions (DLS) demonstrated stable dissolutions in CHCl3 of vinyl laurate esterified – contrary to lauroyl chloride esterified starch. For all highly soluble FASEs (C6–C18), formation of concentrated solutions (10wt%) is feasible.

Nucleophilic and Electrophilic Reactions of Polyynes Catalyzed by an Electric Field: Toward Barcoding of Carbon Nanotubes Like Long Homogeneous Substrates

Computational studies at the B3LYP/6-31+G* level were carried out on the addition of pyridine to polyynes (C6-C18) and on the protonation of polyynes by methyl ammonium fluoride under electric fields of 2.5 and 5 MV/cm. The electric field in each case was oriented along the polyyne axis in a direction that enhances the reaction by stabilizing the incipient dipole. It was found that the reaction of pyridine addition is endothermic with a late transition state. The longer the polyynes and the stronger the field, the electric field catalysis was more efficient. Extrapolation of the data to long polyynes shows that at 1000 nm an electric field of 50 000 V/cm will reduce the barrier by 10 kcal/mol. This reduction is equivalent to 7 orders of magnitude in rate enhancement. A similar barrier reduction could be achieved with a 2.5 MV/cm field at a polyyne length of 20 nm. Protonation reactions were found to be much more affected by the electric field. A reduction of the reaction barrier by 10 kcal/mol using a 2.5 MV/cm electric field could be achieved at a polyyne length of 10 nm. Thus the electric field along the long axis of a substrate could induce a gradient of reactivity which could, in principle, enable the barcoding of substrates by using a sequence of reactants having different reactivities.

Carboxylic acid reductase is a versatile enzyme for the conversion of fatty acids into fuels and chemical commodities

Aliphatic hydrocarbons such as fatty alcohols and petroleum-derived alkanes have numerous applications in the chemical industry. In recent years, the renewable synthesis of aliphatic hydrocarbons has been made possible by engineering microbes to overaccumulate fatty acids. However, to generate end products with the desired physicochemical properties (e.g., fatty aldehydes, alkanes, and alcohols), further conversion of the fatty acid is necessary. A carboxylic acid reductase (CAR) from Mycobacterium marinum was found to convert a wide range of aliphatic fatty acids (C(6)-C(18)) into corresponding aldehydes. Together with the broad-substrate specificity of an aldehyde reductase or an aldehyde decarbonylase, the catalytic conversion of fatty acids to fatty alcohols (C(8)-C(16)) or fatty alkanes (C(7)-C(15)) was reconstituted in vitro. This concept was applied in vivo, in combination with a chain-length-specific thioesterase, to engineer Escherichia coli BL21(DE3) strains that were capable of synthesizing fatty alcohols and alkanes. A fatty alcohol titer exceeding 350 mg·L(-1) was obtained in minimal media supplemented with glucose. Moreover, by combining the CAR-dependent pathway with an exogenous fatty acid-generating lipase, natural oils (coconut oil, palm oil, and algal oil bodies) were enzymatically converted into fatty alcohols across a broad chain-length range (C(8)-C(18)). Together with complementing enzymes, the broad substrate specificity and kinetic characteristics of CAR opens the road for direct and tailored enzyme-catalyzed conversion of lipids into user-ready chemical commodities.

Micellization of Alkyl Trimethyl Ammonium Bromides in Aqueous Solutions–Part 1: Critical Micelle Concentration (CMC) and Ionization Degree

Abstract Conductivities of alkyl trimethyl ammonium bromides (alkyl = hexyl-, octyl-, decyl-, dodecyl-, tetradecyl-, hexadecyl-, and octadecyl-) in aqueous solutions were measured as afunction of molarity of surfactants, length of chain and temperature. Critical micelle concentrations (CMC) were estimated from the dependence of the specific conductivity on molarity of the surfactants. It was determined that the temperature dependence of CMC is U-shaped with aminimum shifting toward higher temperatures with decreasing chain length of the alkyl group. Quantities characterizing behaviors of surfactants below and above CMC were calculated and compared from conductivity measurements. Measured and calculated values of studied compounds were also compared with results of many other authors. The paper has the form of a minireview. It is a comparison of the presented experimental data of alkyltrimethylammonium bromides (C6–C18) with earlier works reported.