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The direct incorporation of low viscosity organic liquids (OL) such as dodecane and tributylphosphate (TBP) into fresh geopolymers (GP) is difficult and generally leads to variable amounts of un-incorporated OL remaining outside the hardened geopolymer. Experimentally, it is observed that a regular torque increase during OL incorporation corresponds to a suitable dispersion of the OL in the form of fine micrometric droplets. This can be obtained for TBP and dodecane by adding a small quantity of quaternary ammoniums salts (QAs) such as cetyltrimethylammonium bromide (CTAB). Shorter alkyl chains QAs, such as hexamethyltrimethylammonium (HMTA) can also be used but with a reduced efficiency. The positive impact of CTAB is then confirmed by the Washburn capillary rise method, showing that the interactions between TBP and CTAB-modified metakaolin are weaker compared to untreated powder. Finally, it is observed that the incorporation of TBP into geopolymer slurries is much easier than the incorporation of dodecane. The low interfacial tension measured between TBP and the activating solution (around 8 mN·m -1 ), contrasting with dodecane (29 mN·m -1 ), explains that the dispersion of TBP droplets in fresh metakaolin suspensions is more efficient.

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The drying characteristics, rehydration capacity, color, infrared spectra and volatile components of iron stick yam slices were investigated under different alternating current (AC) voltages (13, 17, 21 kV), hot air drying (HAD) (60 °C) and natural drying (AD) by electrohydrodynamic (EHD) drying and HAD experimental devices. The results showed that slices of iron stick yam dried the quickest with HAD, which also had the fastest drying rate; while drying the slices of iron stick yam with EHD led to a better rehydration capacity, higher brightness L* and whiteness, a more stable protein secondary structure, and a greater variety and content of volatile components compared with AD and HAD. These finding indicated that EHD is a more promising method for drying iron stick yam.

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The adsorption and detachment processes of n-dodecane (C12H26) molecules were studied on silica surfaces with variable surface chemistry (Q2, Q3, Q4 environments), using molecular dynamics simulations. The area density of the silanol groups varied from 9.4 to 0 per nm2. The shrinking of the oil-water-solid contact line was a key step for the oil detachment, due to water diffusion on the three-phase contact line. The simulation results showed that oil detachment was easier and faster on a perfect Q3 silica surface which had (≡Si(OH))-type silanol groups, due to the H-bond formation between the water and silanol groups. When the surfaces contained more Q2 crystalline type which had (≡Si(OH)2)-type silanol groups, less oil detached, due to the formations of H-bonds among the silanol groups. There were no silanol groups on the Si-OH 0 surface. Water cannot diffuse on the water-oil-silica contact line, and oil cannot detach from the Q4 surface. The detachment efficiency of oil from the silica surface not only depended on the area density, but also on the types of silanol groups. The density and type of silanol groups depend on the crystal cleavage plane, particle size, roughness, and humidity.

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This paper addresses the impact of the particle initial wetting and the viscosity of the oil phase on the structure and rheological properties of direct (Oil/Water) and reverse (Water/Oil) Pickering emulsions. The emulsion structure was investigated via confocal microscopy and static light scattering. The flow and viscoelastic properties were probed by a stress-controlled rheometer. Partially hydrophobic silica particles have been employed at 1 and 4 wt.% to stabilize dodecane or paraffin-based emulsions at 20 vol.% of the dispersed phase. W/O emulsions were obtained when the particles were dispersed in the oily phase while O/W emulsions were prepared when the silica was introduced in the aqueous phase. We demonstrated that, although the particles adsorbed at the droplets interfaces for all the emulsions, their organization, the emulsion structure and their rheological properties depend in which phase they were previously dispersed in. We discuss these features as a function of the particle concentration and the oil viscosity.

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Thermal desorption technology can effectively remediate fuels-contaminated clayey soil. However, the microscopic mechanism for the contaminant desorption on clay is still unclear, especially with the existence of water on clay surfaces. In this study, a combination method including TGA experiments, multi-phase and multi-component kinetic models, and MD simulation was proposed to reveal the thermal desorption mechanism of n-dodecane in unsaturated clay. Results showed that the thermal desorption behavior of the free nonaqueous phase liquid (NAPL) and the adsorbed phase of n-dodecane or water could be identified by the multi-phase and multi-component kinetic models based on the desorption process rate obtained by thermogravimetric analysis (TGA) experiments. The activation energy of the NAPL phase (49-69.9 kJ/mol) was lower than the adsorbed phase (90 kJ/mol). The activation energy of the NAPL phase had the same linear relationship with its mass on kaolinite and montmorillonite, while adsorbed phase only existed on the kaolinite surface. MD simulation showed that water demonstrated competitive adsorption with n-dodecane on montmorillonite surfaces and prevented the formation of the adsorbed phase while having little influence on the n-dodecane adsorption on kaolinite surface, which agrees well with the kinetic analysis of the TGA experiments. With the combination of macroscopic experimental analysis and microscopic molecular simulation, it can be concluded that the mass of the NAPL phase limited the desorption behavior, while the interaction between the clay mineral surface and n-dodecane was the key factor that dominated the thermal desorption behavior of the adsorbed phase. The presented results provide new insight into the desorption mechanism of hydrocarbon on clay minerals, which is of significance for the design of thermal desorption remediation.

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Cooking improves food aroma, but few studies have explored how cooking affects food aromas. Here, aroma changes in mildly salted large yellow croaker (Larimichthys crocea, MSLYC) after steaming, baking, frying, and deep frying was investigated. The raw fish was dominated by fishy notes but after cooking, the aroma became dominated by fatty notes. Nine volatiles, including hexanal, nonanal, (E, Z)-2, 6-nonadienal, (E, E)-2, 4-decadienal, 1-octen-3-ol, linalool, ethyl hexanoate, acetic acid and anethole, were identified as key odor-active compounds using GC-MS, OAV, and omission tests analyses. Changes in the concentrations of key odor-active compounds were mainly due to evaporation, oxidation of linolenic acids, and thermal catalyzed reactions. Interestingly, anethole was the key odor-active compound, providing new insight into the underlying reactions of cooked fish aroma.

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The synthesis of substituted aza- and oxaazaisowurtzitanes via direct condensation is challenging. The selection of starting ammonia derivatives is very limited. The important step in developing alternative synthetic routes to these compounds is a detailed study on their formation process. Here, we explored an acid-catalyzed condensation between 4-tert-butyl-2,6-dimethylbenzenesulfonamide and glyoxal in aqueous H2SO4, aqueous acetonitrile and acetone, and established some new processes hindering the condensation. In particular, an irreversible rearrangement of the condensation intermediate was found to proceed and be accompanied by the 1,2-hydride shift and by the formation of symmetric disulfanes and sulfanes. It has been shown for the first time that aldehydes may act as a reducing agent when disulfanes are generated from aromatic sulfonamides, as is experimentally proved. The condensation between 4-tert-butyl-2,6-dimethylbenzenesulfonamide and formaldehyde resulted in 1,3,5-tris((4-(tert-butyl)-2,6-dimethylphenyl)sulfonyl)-1,3,5-triazinane. It was examined if diimine could be synthesized from 4-tert-butyl-2,6-dimethylbenzenesulfonamide and glyoxal by the most common synthetic procedures for structurally similar imines. It has been discovered for the first time that the Friedel-Crafts reaction takes place between sulfonamide and the aromatic compound. A new synthetic strategy has been suggested herein that can reduce the stages in the synthesis of in-demand organic compounds of symmetric and asymmetric aromatic sulfones via the Brønsted acid-catalyzed Friedel-Crafts reaction, starting from aromatic sulfonamides and arenes activated towards an electrophilic attack.

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Scholars from around the world have been attempting to simplify and cheapen the synthetic method for the promising high-energy compound CL-20 for decades. The lack of understanding of the formation mechanisms of hexaazaisowurtzitane derivatives-CL-20 precursors-is a barrier to solving the said problems. Here, we report the results from an in-depth study into the acid-catalyzed condensation between benzamide and glyoxal in a molar ratio of 2:1 in polar protic and aprotic solvents. Sixteen compounds were isolated and identified, of which eight were synthesized for the first time. A geminal diol, N,N'-(2,2-dihydroxyethane-1,1-diyl)dibenzamide, was synthesized. Two isomers of 1,2-bis(benzoylamino)-1,2-ethanediol were isolated and identified. N,N'-(1-oxoethane-1,2-diyl)dibenzamide and 2-oxo-2-[(phenylcarbonyl)amino]ethyl benzoate were produced that were likely formed due to the 1,2-hydride shift. N-polysubstituted 1,4-dioxane-2,3,5,6-tetramine was synthesized for the first time, whose structure may be of interest as a scaffold for new explosives. DMSO, THF and HCOOH were found to be able to engage in a reaction with benzamide, or condensation products thereof, and glyoxal under acid-catalyzed conditions.

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The treatment and disposal of spent radioactive organic solvents, i.e., tributyl phosphate (TBP) and diluent (such as kerosene, n-dodecane, etc.), produced in the reprocessing of spent fuel in the closed cycle are crucial for the sustainable development of the nuclear industry. In this study, the synthesized nanoscale zero-valent iron (nZVI) was used as the heterogeneous Fenton-like catalyst to promote the generation of hydroxyl radicals (•OH) by reacting with H2O2 to degrade the mixed organic solvents of TBP and n-dodecane. nZVI was characterized by scanning electron microscopy (SEM), nitrogen adsorption/desorption isotherms, and X-ray photoelectron spectroscopy (XPS) to investigate the micro-morphology, nano-particle size, and surface valence state. The change of Fe2+/Fe3+ concentration ratio during the reaction was measured to clarify the performance of nZVI. The effects of temperature, catalyst dosage, H2O2 dosage, and acidifier concentration on the degradation of TBP and n-dodecane were studied, and the results were complemented by the COD of the aqueous solution and the volume reduction rate of the organic phase. The mixed organic solvents of TBP and n-dodecane containing Co2+ were used to simulate the spent radioactive organic solvents and to study the distribution of nuclides after the reaction. The results showed that most of the radioactivity was in the residual solution, and the condensate contained almost no radioactivity. The degradation of TBP and n-dodecane was carried out separately, which showed that n-dodecane was more difficult to degrade. Density functional theory (DFT) calculations were applied to determine the adsorption energy of organic solvents and nZVI. According to the Fourier transform infrared spectra (FTIR) and their corresponding DFT calculations, liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS) of the sample after the reaction, the possible intermediates were analyzed, and the degradation mechanism was speculated.

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L-asparaginase II (ASNase) is the biopharmaceutical of choice for the treatment of acute lymphoblastic leukaemia. In this study, E. coli BL21 (DE3) transformed with the pET15b + asnB vector which expresses recombinant ASNase was used as a source to obtain this enzyme. The ideal conditions to produce ASNase would be a high level of secretion into the extracellular medium, which depends not only on the application of molecular biology techniques but also on the development of a strategy to modify cell permeability such as the addition of substances to the culture medium that stimulate destabilisation of structural components of the cell. Thus, the growth of E. coli BL21 (DE3) in modified Luria-Bertani broth, supplemented with 0.8% (w/v) glycine and 6% (v/v) n-dodecane, increased the total yield of ASNase by about 50% (15,108 IU L-1) and resulted in a 16-fold increase in extracellular enzymatic productivity (484 IU L-1 h-1), compared to production using the same medium without addition of these substances. Most of the enzyme (89%) was secreted into the culture medium 24 h after the induction step. This proposed approach presents a simple strategy to increase extracellular production of ASNase in E. coli.

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The aim of this study was the investigation of non-destructive lipid extraction from Chlorella vulgaris grown under stress conditions of nutrient limitation and salinity. To select a suitable solvent for extraction, the performances of decane, dodecane and hexadecane were tested based on their effect on lipid extraction and cell viability. The results showed that dodecane was the most suitable solvent for the extraction process. The concentration of extracted lipids from stressed cells was 2762.52 ± 11.38 mg L-1, i.e. a value 1.75 times higher than that obtained from unstressed cells. Long-term extraction was also evaluated with continuous dodecane recirculation during five-stage extraction and a recovery time of 24 h between the extraction steps, which yielded after the fifth extraction stage a total lipid amount as high as 9811.56 mg L-1. These results showed that non-destructive lipid recovery can be effectively performed by applying stress conditions and in repetitive extractions.

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Metabolic engineering of cyanobacteria has received much attention as a sustainable strategy to convert CO2 to various longer carbon chain fuels. Pinene has become increasingly attractive since pinene dimers contain high volumetric energy and have been proposed to act as potential aircraft fuels. However, cyanobacteria cannot directly convert geranyl pyrophosphate into pinene due to the lack of endogenous pinene synthase. Herein, we integrated the gene encoding Abies grandis pinene synthase into the model cyanobacterium Synechococcus sp. PCC 7002 through homologous recombination. The genetically modified cyanobacteria achieved a pinene titer of 1.525 ± 0.l45 mg L-1 in the lab-scale tube photobioreactor with CO2 aeration. Specifically, the results showed a mixture of α- and ß-pinene (∼33:67 ratio). The ratio of ß-pinene in the product was significantly increased compared with that previously reported in the engineered Escherichia coli. Furthermore, we investigated the photoautotrophic growth performances of Synechococcus overlaid with different concentrations of dodecane. The work demonstrates that the engineered Synechococcus is a suitable potential platform for ß-pinene production.

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Gum arabic (GA), an arabinogalactan-based gum, is a well-known powerful emulsifier. However, the poor stability of emulsion has often been pointed out. In order to clarify the origin, the structure-property relationship of GA, especially the interfacial property at oil/water interface, needs to be investigated. Here, we tried to correlate the primary structure with interfacial property at oil/water interface. A series of structural analyses by SEC-MALLS, SAXS, etc. showed that the primary structure of GA was a disk-like star shaped nanoparticle. The dynamic interfacial tension measurement showed that GA molecules adsorb onto oil surface in 2 steps: Firstly, the micron-aggregates of GA approach onto the oil surface, and then the aggregates are dissociated into nano-particles so that they cover the oil surface. Therefore, the emulsification and emulsion stability are controlled not by the property of the primary structure of GA but by the higher-order molecular network structure made of GA molecules.

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Lipid membranes, enveloping all living systems, are of crucial importance, and control over their structure and composition is a highly desirable functionality of artificial structures. However, the rational design of protein-inspired systems is still challenging. Here we have developed a highly functional nucleic acid construct that self-assembles and inserts into membranes, enabling lipid transfer between inner and outer leaflets. By designing the structure to account for interactions between the DNA, its hydrophobic modifications, and the lipids, we successfully exerted control over the rate of interleaflet lipid transfer induced by our DNA-based enzyme. Furthermore, we can regulate the level of lipid transfer by altering the concentration of divalent ions, similar to stimuli-responsive lipid-flipping proteins.

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Gold oxides (0.1 - 2.0 nm thick) prepared from gold films by an oxygen-dc glow discharge using a gold discharge ring for 0.17 - 30 min at room temperature were characterized by X-ray photoelectron spectroscopy. The oxide thickness increased with increasing discharge time in contrast to the use of an aluminum ring, and thicker oxide films were obtained. The O 1s spectra show four components: I, II, III, and IV. Components I, II, and IV appear during the early formation periods (≤0.5 min). Components I and II are stable and assigned to hydroxyl groups on the surfaces. Component IV changes into component III (gold oxide) after longer discharge times (≥1 min). The gold oxides (2.0 nm thick) decompose after 15 d at room temperature and decompose immediately at temperatures exceeding 117°C. They also decompose under ultraviolet light irradiation (254, 302, and 365 nm) and decompose more rapidly in water vapor at the shorter wavelengths. The thicker nature of the gold oxides is advantageous for their preservation, and they were preserved in their oxidized state for 196 d in anhydrous dodecane in a dark atmosphere.

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Room-temperature Raman spectra of n-dodecane and methyl oleate were acquired at pressures up to 4 GPa. Both have monoalkyl chains with characteristic Raman rotamer profiles (trans and gauche conformers) along the skeletal CC bonds. The trans conformer was dominant in the high-pressure solid phase of n-dodecane. In solid methyl oleate, most of the gauche conformers transformed to the trans conformers. The all-trans dominated in the high-pressure solid phase and a triclinic subcell structure was indicated on the basis of previous vibrational spectra of n-alkanes and lipids. The solidification pressure of methyl oleate was determined against temperature up to 413 K.

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One of the major environmental problems nowadays is petroleum hydrocarbons contamination. Bioremediation is widely used for cleaning ecosystems contaminated with petroleum hydrocarbons. This study was carried out to investigate the response of five microalgae strains isolated from different regions in Iran for 1% n-dodecane (DOD) degradation. The results revealed that Leptolyngbya fragilis ISC 108 is the most effective strain to utilize n-DOD as growth substrate under a mixotrophic condition. Currently, there is little information about mechanisms involved in microalgae response against DOD. The activity of antioxidant enzymes and total lipid and carbohydrate contents were observed to be greater in DOD-treated L. fragilis ISC 108. Lower values of lipid peroxidation and H2O2 along with an increase of dry weight and specific growth rate in L. fragilis ISC 108 under DOD treatment shows that at the cellular level this strain is better equipped with an efficient oxygen radical scavenging system. In conclusion, this study proposes that L. fragilis ISC 108 can be considered an ideal candidate for use in bioremediation of DOD contaminated sites.

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BACKGROUND: Long-chain free fatty acids (FFAs) are a type of backbone molecule that can react with alcohol to produce biodiesels. Various microorganisms have become potent producers of FFAs. Efforts have focused on increasing metabolic flux to the synthesis of either neutral fat or fatty acyl intermediates attached to acyl carrier protein (ACP), which are the source of FFAs. Membrane lipids are also a source of FFAs. As an alternative way of producing FFAs, exogenous phospholipase may be used after heterologous production and localization in the periplasmic space. In this work, we examined whether Rhodobacter sphaeroides, which forms an intracytoplasmic membrane, can be used for long-chain FFA production using phospholipase. RESULTS: The recombinant R. sphaeroides strain Rs-A2, which heterologously produces Arabidopsis thaliana phospholipase A2 (PLA2) in the periplasm, excretes FFAs during growth. FFA productivity under photoheterotrophic conditions is higher than that observed under aerobic or semiaerobic conditions. When the biosynthetic enzymes for FA (ß-ketoacyl-ACP synthase, FabH) and phosphatidate (1-acyl-sn-glycerol-3-phosphate acyltransferase, PlsC) were overproduced in Rs-A2, the FFA productivity of the resulting strain Rs-HCA2 was elevated, and the FFAs produced mainly consisted of long-chain FAs of cis-vaccenate, stearate, and palmitate in an approximately equimolar ratio. The high-cell-density culture of Rs-HCA2 with DMSO in two-phase culture with dodecane resulted in an increase of overall carbon substrate consumption, which subsequently leads to a large increase in FFA productivity of up to 2.0 g L-1 day-1. Overexpression of the genes encoding phosphate acyltransferase (PlsX) and glycerol-3-phosphate acyltransferase (PlsY), which catalyze the biosynthetic steps immediately upstream from PlsC, in Rs-HCA2 generated Rs-HXYCA2, which grew faster than Rs-HCA2 and showed an FFA productivity of 2.8 g L-1 day-1 with an FFA titer of 8.5 g L-1. CONCLUSION: We showed that long-chain FFAs can be produced from metabolically engineered R. sphaeroides heterologously producing PLA2 in the periplasm. The FFA productivity was greatly increased by high-cell-density culture in two-phase culture with dodecane. This approach provides highly competitive productivity of long-chain FFAs by R. sphaeroides compared with other bacteria. This method may be applied to FFA production by other photosynthetic bacteria with similar differentiated membrane systems.

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Tsukamurella sp. strain MH1, capable to use a wide range of n-alkanes as the only carbon source, was isolated from petroleum-contaminated soil (Pitești, Romania) and its complete genome was sequenced. The 4,922,396 bp genome contains only one circular chromosome with a G + C content of 71.12%, much higher than the type strains of this genus (68.4%). Based on the 16S rRNA genes sequence similarity, strain MH1 was taxonomically identified as Tsukamurella carboxydivorans. Genome analyses revealed that strain MH1 is harboring only one gene encoding for the alkB-like hydroxylase, arranged in a complete alkane monooxygenase operon. This is the first complete genome of the specie T. carboxydivorans, which will provide insights into the potential of Tsukamurella sp. MH1 and related strains for bioremediation of petroleum hydrocarbons-contaminated sites and into the environmental role of these bacteria.

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Oil and gas exploration in the Arctic will increase the risk for accidental oil spills and thereby have a potential impact on the ecosystem and the organisms inhabiting these areas. Lipid rich copepods are an important food source for higher trophic levels in Arctic marine ecosystems. However, high lipid content and a slower metabolism increase the risk for bioaccumulation in Arctic species. Here we exposed three late development stages of the lipid rich high-Arctic copepod species Calanus hyperboreus to two different 14C-marked crude oil model compounds, the alkane dodecane (log Kow 6.10) and the polycyclic aromatic hydrocarbon (PAH) phenanthrene (log Kow 4.46) on a short-term scale of 4days. Exposure was followed by a depuration phase of 3days. We observed a difference in estimated bioaccumulation of the two model compounds between stages and found a slower depuration of dodecane than of phenanthrene in the two largest and most lipid rich stages. However, depuration of dodecane and phenanthrene was non-significant for all three stages. The results indicate that even short-term exposure may result in long-term bioaccumulation and internal exposure of oil compounds in the lipid rich high-Arctic copepods C. hyperboreus. Slow elimination and depuration of oil components indicate a risk for transfer of oil component up the food web to pelagic fish, seabirds and baleen whales.

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