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In this work, a microchip gas chromatography (GC) column assembly utilizing a three-dimensional (3D) printed micro oven and a flexible stainless steel capillary column was developed. The assembly's performance and separation capabilities were characterized. The key components include a 3D printed aluminum plate (7.50 × 7.50 × 0.16 cm) with a 3-meter-long circular spiral channel, serving as the oven, and the column coiled on the channel with an inner diameter of 320 μm and a stationary phase of OV-1. A heating ceramic plate was affixed on the opposite side of the plate. The assembly weighed 40.3 g. The design allows for easy disassembly, or stacking of heating devices and columns, enabling flexibility in adjusting column length. When using n-C 13 as the test analyte at 140 °C, a retention factor (k) was 8.5, and 7797 plates (2599 plates/m) were obtained. The assembly, employing resistance heating, demonstrated effective separation performance for samples containing alkanes, aromatics, alcohols and ketones, with good reproducibility. The reduction in theoretical plates compared to oven heating was only 2.95 %. In the boiling point range of C 6 to C 18 , rapid temperature programming (120 °C/min) was achieved with a power consumption of 119.512 W. The assembly was successfully employed to separate benzene series compounds, gasoline and volatile organic compounds (VOCs), demonstrating excellent separation performance. This innovative design addresses the challenges of the complexity and low repeatability of the fabrication process and the high cost associated with microchip columns. Furthermore, its versatility makes it suitable for outdoor analysis applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Orchids are rich treasure troves of various important phytomolecules. Among the various medicinal orchids, Ansellia africana stands out prominently in the preparing of various herbal medicines due to its high therapeutic importance. The nodal explants of A. africana were sampled from asymbiotically germinated seedlings on basal Murashige and Skoog (MS) medium and were micropropagated in MS medium supplemented with 3% sucrose and 10 µM meta topolin ( m T) + 5 µM naphthalene acetic acid (NAA) +15 µM indole butyric acid (IBA) + 30 µM phloroglucinol (PG). In the present study, the essential oil was extracted by hydrodistillation and the oleoresins by the solvent extraction method from the micropropagated A. africana . The essential oil and the oleoresins were analysed by Gas Chromatography (GC) and GC/MS (Mass spectrometry). A total of 84 compounds were identified. The most predominant components among them were linoleic acid (18.42%), l -ascorbyl 2,6-dipalmitate (11.50%), linolenic acid (10.98%) and p -cresol (9.99%) in the essential oil; and eicosane (26.34%), n-butyl acetate (21.13%), heptadecane (16.48%) and 2-pentanone, 4-hydroxy-4-methyl (11.13%) were detected in the acetone extract; heptadecane (9.40%), heneicosane (9.45%), eicosane (6.40%), n-butyl acetate (14.34%) and styrene (22.20%) were identified and quantified in the ethyl acetate extract. The cytotoxic activity of essential oil and oleoresins of micropropagated A. africana was evaluated by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium Bromide) assay on Vero cells compared to the standard drug doxorubicin chloride. The present research contains primary information about the therapeutic utility of the essential oil and oleoresins of A. africana with a promising future research potential of qualitative and quantitative improvement through synchronised use of biotechnological techniques.

Larval Diaphania indica (Saunders) (Lepidoptera: Crambidae) cause complete defoliation of Trichosanthes anguina L. and reduce crop yield in India. Females lay eggs on the leaf surface, and therefore leaf surface waxes are potentially involved in host selection. Alkanes and free fatty acids are the major constituents of leaf surface waxes, so a study was conducted to determine whether these wax constituents from three T. anguina cultivars (MNSR-1, Baruipur Long, and Polo No.1) could act as short-range attractants and oviposition stimulants in D. indica females. Twenty n-alkanes from n-C 14 to n-C 36 and 13 free fatty acids from C12:0 to C21:0 were detected in the leaf surface waxes of these cultivars. Heptadecane and stearic acid were predominant among n-alkanes and free fatty acids, respectively, in these cultivars. Females showed attraction towards one leaf equivalent surface wax of each of these cultivars against solvent controls (petroleum ether) in Y-tube olfactometer bioassays. A synthetic blend of heptadecane, eicosane, hexacosane, and stearic acid, a synthetic blend of hexacosane and stearic acid, and a synthetic blend of pentadecane and stearic acid comparable to amounts present in one leaf equivalent surface wax of MNSR-1, Baruipur Long, and Polo No.1, respectively, were short-range attractants and oviposition stimulants in D. indica. Female egg laying responses were similar to each of these blends, providing information that could be used to developing baited traps in integrated pest management (IPM) programs., (© 2021. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

This work highlights the effect of the stationary phase coating process on the separation efficiency of gas chromatography microcolumns. The stationary phase coating quality was characterized by three different bis(trifluoromethylsulfonyl)imide (NTf 2 ) anion based ionic liquids. The ionic liquids containing NTf 2 anion are used for gas chromatography due to their high temperature stability. In this work, the chemical and physical approaches of column deactivation as well as the temperature treatment were evaluated by separating a mixture of 20 organic components and saturated alkanes. The results show that higher oven temperature treatment provides higher efficiency while losing a bit of peak symmetry. The thermal treated 1-butylpyridinum bis(trifluoromethylsulfonyl) imide [BPY][NTf 2 ] stationary phase at 240°C demonstrated as high as 8300 plates per meter for naphthalene. This was a 5-fold increase in separation efficiency in comparison to those of the columns treated at 200°C. Albeit being within acceptable ranges, the peak tailing degraded from 1.17 to 1.46 for naphthalene when the processing temperature for coating increased. Both chemical and physical deactivation process increased separation efficiencies and peak resolution., Competing Interests: Declaration of Competing Interest The authors declare no competing financial interest., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Bee products are a well-known remedy against numerous diseases. However, from the consumers' perspective, it is essential to define factors that can affect their sensory acceptance. This investigation aimed to evaluate the volatile and sensory profiles, and sugar composition of beeswax, beebread, pollen, and honey. According to the HS-SPME/GC-MS results, 20 volatiles were identified in beeswax and honey, then 32 in beebread, and 33 in pollen. Alkanes were found to dominate in beeswax, beebread, and pollen, while aldehydes and monoterpenes in honey. In the case of sugars, a higher content of fructose was determined in beebread, bee pollen, and honey, whereas the highest content of glucose was assayed in beeswax. In the QDA, the highest aroma intensity characterized as honey-like and sweet was found in honey, while the acid aroma was typical of beebread. Other odor descriptors, including waxy, pungent, and plant-based aromas were noted only in beeswax, honey, and pollen, respectively.

A stable preparation of agaricinic acid nanoparticles was obtained. The mean hydrodynamic size of nanoparticles according to photon correlation spectroscopy was 200 nm and zeta potential was -57 mV. Cytotoxic activity of agaricinic acid nanoparticles against human HepG2 hepatoma cells was evaluated. Nanoparticles with a low concentration of agaricinic acid stimulated and with high concentration - suppressed metabolic activity and viability of hepatoma cells. The EC 50 for the stimulating effect was 32.8 μg/ml, and the IC 50 =602.1 mg/ml. The preparation of agaricinic acid nanoparticles can be used in medicine as a potential antitumor agent.

Fusicoccane-derived diterpenoids bearing a unique bridgehead double-bond-containing tricyclo[9.2.1.0 3,7 ]tetradecane (5-9-5 ring system) core skeleton represent a rarely reported class of rearranged terpenoids, which traced back to fusicoccanes with a classical dicyclopenta[a,d]cyclooctane (5-8-5 ring system) core skeleton via a crucial Wagner-Meerwein rearrangement reaction. In this research, alterbrassicenes B-D (1-3), three new rearranged fusicoccane diterpenoids bearing a rare bridgehead double-bond-containing tricyclo[9.2.1.0 3,7 ]tetradecane core skeleton, together with two known congeners, brassicicenes O and K (4 and 5), were isolated from the modified cultures of fungus Alternaria brassicicola. Their structures were elucidated by comprehensive analyses of the NMR and HRESIMS data, and the absolute configurations of 1 and 4 were further confirmed via a combination of 13 C NMR and ECD calculations and single-crystal X-ray diffraction analysis (Cu Kα). Interestingly, alterbrassicene B (1) represented the second case of bridgehead C-10-C-11 double-bond-containing natural products with a bicyclo[6.2.1]undecane core skeleton, and also featured an undescribed oxygen bridge between C-6 and C-14 to construct an unprecedentedly caged tetracyclic system. Alterbrassicenes B-D showed moderate cytotoxic activity against certain human tumor cell lines with IC 50 values in the range of 15.87-36.85 μM., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Phosphine resistance is a worldwide issue threatening the grain industry. The cuticles of insects are covered with a layer of lipids, which protect insect bodies from the harmful effects of pesticides. The main components of the cuticular lipids are hydrocarbon compounds. In this research, phosphine-resistant and -susceptible strains of two main stored-grain insects, T. castaneum and R. dominica , were tested to determine the possible role of their cuticular hydrocarbons in phosphine resistance. Direct immersion solid-phase microextraction followed by gas chromatography-mass spectrometry (GC-MS) was applied to extract and analyze the cuticular hydrocarbons. The results showed significant differences between the resistant and susceptible strains regarding the cuticular hydrocarbons that were investigated. The resistant insects of both species contained higher amounts than the susceptible insects for the majority of the hydrocarbons, sixteen from cuticular extraction and nineteen from the homogenized body extraction for T. castaneum and eighteen from cuticular extraction and twenty-one from the homogenized body extraction for R. dominica . 3-methylnonacosane and 2-methylheptacosane had the highest significant difference between the susceptible and resistant strains of T. castaneum from the cuticle and the homogenized body, respectively. Unknown5 from the cuticle and 3-methylhentriacontane from the homogenized body recorded the highest significant differences in R. dominica . The higher hydrocarbon content is a key factor in eliminating phosphine from entering resistant insect bodies, acting as a barrier between insects and the surrounding phosphine environment., Competing Interests: The authors declare no conflict of interest.

European badgers, Meles meles, are group-living in the UK, and demarcate their ranges with shared latrines. As carnivores, badgers possess paired anal glands, but olfactory information on the content of badger anal gland secretion (AGS) is largely uninvestigated. Here, we examined the volatile organic compounds (VOCs) of AGS samples from 57 free-living badgers using solid-phase microextraction (SPME) and gas chromatography-mass spectrometry. AGS was rich in alkanes (C7-C15, 14.3% of identified compounds), aldehydes (C5-C14, 9.7%), phenols (C6-C15, 9.5%), alcohols (C5-C10, 7.3%), aromatic hydrocarbons (C6-C13, 6.8%), ketones (C6-C13, 6.3%) and carboxylic acids (C3-C12, 5.6%) and contained a variety of esters, sulfurous and nitrogenous compounds, and ethers. The number of VOCs per profile ranged from 20 to 111 (mean = 65.4; ± 22.7 SD), but no compound was unique for any of the biological categories. After normalization of the raw data using Probabilistic Quotient Normalization, we produced a resemblance matrix by calculating the Euclidian distances between all sample pairs. PERMANOVA revealed that AGS composition differs between social groups, and concentration and complexity in terms of number of measurable VOCs varies between seasons and years. AGS VOC profiles encode individual identity, sex and vary with female reproductive state, indicating an important function in intraspecific communication. Because AGS is excreted together with fecal deposits, we conclude that chemical complexity of AGS enables particularly latrine-using species, such as badgers, to advertise more complex individual-specific information than in feces alone.

This work presents the investigation of two triptycene-based materials (TP-3OB and TP-3Im) as the stationary phases for gas chromatographic (GC) separations. The TP-3OB and TP-3Im capillary columns fabricated by static coating exhibited column efficiency of 3000-3500 plates/m for n-dodecane at 120 °C. Also, their McReynolds constants and Abraham system constants were determined to characterize their polarity and molecular interactions with analytes. On the basis of the unique 3D TP architecture, the TP-3OB and TP-3Im stationary phases exhibited complementary high-resolution performance for analytes of a wide ranging polarity, including alkylbenzenes, alkylnaphthalenes, halobenzenes, phenols and anilines, respectively. Moreover, the TP-based columns exhibited good repeatability and reproducibility on the retention times of analytes with the relative standard deviation (RSD) values in the range of 0.01-0.14% for run-to-run, 0.11-0.47% for day-to-day and 0.68-4.7% for column-to-column, respectively. Additionally, their applications for the determination of isomer impurities in the commercial reagents of o-dichlorobenzene, p-/m-diethylbenzene, o-toluidine and 2,3-/3,5-xylidine proved their good potential for practical analysis. This work demonstrates the promising future of the triptycene-based stationary phases for chromatographic separations., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Thermodynamic retention modeling to a thermally modulated comprehensive two-dimensional gas chromatography (GC × GC) system run under constant flow is performed. Significant errors in modeled second dimension retention time (t r,2 ) were observed, in line with past work on thermally modulated GC × GC modeling. A comprehensive study of t r,2 modeling error for alkane separations across a wide range of heating ramp rates and carrier gas flow rates was performed. Modeling errors were found to be systematic and a function of analyte elution temperature and mobile phase velocity. A model to account for these systematic errors was generated, and associated coefficients were determined which reduced average t r,2 retention time error in 144 hydrocarbon separations by an order of magnitude resulting in significant improvement in prediction accuracy. The model was used to correct the separation of 139 Grob mix analyte separations, providing an average t r,2 modeling error of 0.030 ± 0.022 s. The model successfully predicted the separation of n-alkanes on a longer second dimension column configuration., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Cuticular hydrocarbons (CHCs), the dominant fraction of the insects' epicuticle and the primary barrier to desiccation, form the basis for a wide range of chemical signaling systems. In eusocial insects, CHCs are key mediators of nestmate recognition, and colony identity appears to be maintained through a uniform CHC profile. In the unicolonial Argentine ant Linepithema humile, an unparalleled invasive expansion has led to vast supercolonies whose nestmates can still recognize each other across thousands of miles. CHC profiles are expected to display considerable variation as they adapt to fundamentally differing environmental conditions across the Argentine ant's expanded range, yet this variation would largely conflict with the vastly extended nestmate recognition based on CHC uniformity. To shed light on these seemingly contradictory selective pressures, we attempt to decipher which CHC classes enable adaptation to such a wide array of environmental conditions and contrast them with the overall CHC profile uniformity postulated to maintain nestmate recognition. n-Alkanes and n-alkenes showed the largest adaptability to environmental conditions most closely associated with desiccation, pointing at their function for water-proofing. Trimethyl alkanes, on the other hand, were reduced in environments associated with higher desiccation stress. However, CHC patterns correlated with environmental conditions were largely overriden when taking overall CHC variation across the expanded range of L. humile into account, resulting in conserved colony-specific CHC signatures. This delivers intriguing insights into the hierarchy of CHC functionality integrating both adaptation to a wide array of different climatic conditions and the maintenance of a universally accepted chemical profile.

In this study, nanoscale zerovalent Fe 0 /Cu 0 bimetallic composites were synthesized by liquid-phase reduction of Fe(II)/Cu(II) and applied for decomposition of tridecane dicarboxylic acid (DC13). The removal performance of Fe 0 /Cu 0 bimetallic composites for DC13 in terms of Fe/Cu ratios, addition amount, reaction time and initial pH were studied. The as-prepared nanoscale composites were characterized by a transmission electron micrographs (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), BET surface area, fourier transform infrared spectroscopy (FT-IR) and inductively coupled plasma-atomic emission spectrometry (ICP). Finally, the degradation mechanisms of DC13 utilizing the Fe 0 /Cu 0 nanocomposites were investigated by using mass spectrumetry (MS). The results indicated that the Fe 0 /Cu 0 bimetallic composites exerted a remarkable removal capacity for DC13 through the multiple reactions, e.g., coagulation, adsorption and •OH reduction in the Fe 0 /Cu 0 system. XPS indicated that the Fe 0 /Cu 0 reduction reaction of hydroxyl radicals (•OH) system played a significant role in degradation of DC13 and the LC-MS result suggested that DC13 was degraded into inorganic small molecules by •OH radicals generated from the corrosion of Fe 0 . The experimental results indicated that the nanoscale Fe 0 /Cu 0 could be used as a potential material to remove DC13 because of its remarkable degradability., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Microbes appear to play a key role in bioremediation of petroleum hydrocarbons pollution and little attention has been paid to the enzyme activity in the process of alkane bioremediation. Oil field bacterium identified as Pseudomonas synxantha LSH-7' was chosen as the tested strain. Periodically collected samples were analyzed by GC-FID (Gas Chromatography- Flame Ionization Detector) and RT-qPCR (Quantitative-Real-Time-PCR). GC-FID results showed this bacterial strain has great degradation ability on crude oil n-alkanes and RT-qPCR data indicated the differences between the three genes expression including AlkB-, Cytochromes P450-, and almA- related when grown on different-chain alkanes. Meanwhile, enzyme activity like alkane hydroxylase, alcohol dehydrogenase, dehydrogenase, protease, phosphatase, catalase and lipase were measured. Extracellular alkane hydroxylase was induced in a higher degree than intracellular in the early incubation time, alcohol dehydrogenase increased/decreased along with alkane hydroxylase, and the pH of the medium obviously decreased. Other enzymes were also described including dehydrogenase activity that reached a highest point that was slower than alcohol dehydrogenase, protease activity started multiplying after a period of culture while biomass was immediately increased, catalase activity dramatically enhanced in the presence of alkanes, phosphatase activity was closely linked to pH approximately but lipase activity was found to be moderate., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The pharaoh ant is a notorious and hard to eradicate pest, which poses a threat in hospitals, spreading pathogens and contaminating sterile equipment. When applied on ants, zeolites adsorb part of their epicuticular wax layer. The ants are then vulnerable to desiccation, since this layer regulates water exchange. We analyzed the chemical composition of this wax layer using GC-MS (Gas Chromatography-Mass Spectrometry). A hexane wash of M. pharaonis foragers resulted in the identification of 53 components, four of which were not previously defined in Monomorium species. Selective adsorption of specific compounds on zeolites assisted in the identification of compounds which could not be separated on the GC column and allowed for the identification of three additional compounds. Zeolites show different affinities for the wax compounds depending on pore structure and chemical composition. Selective adsorption of alkanes on zeolites is also investigated in the fields of refinery processes and catalysis. Pore mouth and key lock adsorption mechanisms and selectivity according to molecular weight and branching, investigated in these fields, are also involved in adsorption processes of epicuticular waxes. The insecticidal activity of a zeolite is related to adsorption selectivity rather than capacity. One of the best adsorbing zeolites showed limited insecticidal activity and can be considered as a non-lethal alternative for epicuticular wax sampling.

A highly ordered chiral mesoporous silica-coated capillary column has been used for high-resolution gas chromatographic separations. The column has excellent selectivity, not only for the separation of isomers, polycyclic aromatic hydrocarbons, linear alkanes, long chain alkanes, Grob's test mixture and aromatic hydrocarbons, but also for the resolution of different classes of chiral compounds. Additionally, the column exhibits high column efficiency, excellent temperature resistance, and analysis times are short. This is the first report of a highly ordered chiral inorganic mesoporous silica used in separation science., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Application of monolithic columns in gas chromatography is still considered very limited. In this work, several polymethacrylate-based monolithic capillary columns were fabricated, characterized and used in gas chromatography. The five monomers used were: methyl methacrylate, (MMA), hexyl methacrylate (HMA), glycidyl methacrylate (GMA), 2-butoxyethyl methacrylate (BEMA) and isobornyl methacrylate (IBMA), while ethylene dimethacrylate was the crosslinker. The monoliths were synthesized in 30 cm length capillaries possessing inner diameters (i.d.) of 0.25 mm. The prepared monolithic columns were applied for separation of 3 series of homologous alkanes, alcohols and alkylbenzenes, as well as some isomeric mixtures. Van Deemter plots were used to optimize and compare the columns performance. The smaller methacrylates (MMA and GMA) exhibited higher porosity and permeability with low column backpressure values and poorer efficiency than the larger methacrylate monomers (HMA and BEMA). The columns prepared from IBMA monomer showed the highest pressure and the least separation efficiency. The fastest full separation of alkanes was achieved on HMA-co-EDMA column in about 3.0 min with resolution better than 2.73, while the fastest full separation of alcohols and alkylbenzenes was carried out using BEMA-co-EDMA column in less than 0.8 and 1.75 min with chromatographic resolution better than 1.27 and 1.85, respectively. Again, BEMA-co-EDMA column gave the best performance with the fastest and complete separation of all studied isomeric mixtures. For all tested series of solutes, the better separation efficiency was reached with tridecane, which gave 25,200 plates/m on the HMA-co-EDMA column. Another application was carried out using HMA-co-EDMA column for determination of myrcene and limonene, two monoterpenic isomers, in some fruit peels. Under the optimum GC conditions, a rapid separation of myrcene and limonene was achieved in less than 1.0 min with chromatographic resolution of 2.56. The highest contents of myrcene (0.131 mg/g) and limonene (1.225 mg/g) were measured in the hexane extracts of grapefruit and Egyptian orange, respectively. Finally, a comparison between the prepared columns and a commercial capillary column was performed. Based on the measured run time and HETP values, HMA-co-EDMA and BEMA-co-EDMA monolithic columns exhibited faster separation and higher efficiency for n-alkanes and alkylbenzenes than the TR-5 open tubular column, although they are 100 times shorter., (Copyright © 2018. Published by Elsevier B.V.)

Two new compounds a flavanolignan (1), and an alkane (2) along with four known compounds including two fatty acid esters (3-4) and two isocoumarins (5-6) were isolated from the methanolic extract of the stem bark of Newtonia griffoniana. Their structures were elucidated using spectroscopic methods including extensive 1-D and 2-D NMR experiments.

Miniaturization of gas chromatography (GC) instrumentation is of interest because it addresses current and future issues relating to compactness, portability and field application. While incremental advancements continue to be reported in GC with columns fabricated in microchips (referred to in this paper as "microchip columns"), the current performance is far from acceptable. This lower performance compared to conventional GC is due to factors such as pooling of the stationary phase in corners of non-cylindrical channels, adsorption of sensitive compounds on incompletely deactivated surfaces, shorter column lengths and less than optimum interfacing to injector and detector. In this work, a GC system utilizing microchip columns was developed that solves the latter challenge, i.e., microchip interfacing to injector and detector. A microchip compression clamp was constructed to heat the microchip (i.e., primary heater), and seal the injector and detector fused silica interface tubing to the inlet and outlet ports of the microchip channels with minimum extra-column dead volume. This clamp allowed occasional operation up to 375°C and routine operation up to 300°C. The compression clamp was constructed of a low expansion alloy, Kovar™, to minimize leaking due to thermal expansion mismatch at the interface during repeated thermal cycling, and it was tested over several months for more than one hundred injections without forming leaks. A 5.9m long microcolumn with rectangular cross section of 158μm×80μm, which approximately matches a 100μm i.d. cylindrical fused silica column, was fabricated in a silicon wafer using deep reactive ion etching (DRIE) and high temperature fusion bonding; finally, the channel was coated statically with a 1% vinyl, 5% phenyl, 94% methylpolysiloxane stationary phase. High temperature separations of C10-C40 n-alkanes and a commercial diesel sample were demonstrated using the system under both temperature programmed GC (TPGC) and thermal gradient GC (TGGC) conditions. TGGC analysis of a complex essential oil sample was also demonstrated. Addition of a secondary heater and polyimide insulation proved to be helpful in achieving the desired elution temperature without having to raise the primary heater temperature above 300°C for high boiling point compounds., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Fruits of Pinang Yaki (Areca vestiaria) are used by the people around Bogani Nani Wartabone as contraseption for men. Extracts from the fruit contain tannin, triterpenoid, flavonoid and saponin which are potential as bioactive compounds. This research aimed at exploring the fractions or bioactive compounds contained in the fruit. The extract was prepared by fractionation using hexane. The fractions were separated and analysed by gas chromatography mass spectrometry (GC-MS) technique. The fractions revealed the presence of five compounds. These compounds were identified by interpretation of mass spectra and comparing their retention time and covate indexes with those from literature. The five compounds are pentadecane, methyl-dodecanate, methyl-tetradecanoate, hexadecanoic acid and methyl-octadecanate.

Ionic liquids can form biphasic solvent systems with many organic solvents and water, and these solvent systems can be used in liquid-liquid separations and countercurrent chromatography. The wide range of ionic liquids that can by synthesised, with specifically tailored properties, represents a new philosophy for the separation of organic, inorganic and bio-based materials. A customised countercurrent chromatograph has been designed and constructed specifically to allow the more viscous character of ionic liquid-based solvent systems to be used in a wide variety of separations (including transition metal salts, arenes, alkenes, alkanes, bio-oils and sugars).

This study compared four treatment techniques for the removal of a toluene/n-decane as NAPL (Non Aqueous Phase Liquid) phase mixture in identical 1 cubic meter tanks filled with different kind of sand. These four treatment techniques were: oxidation with persulfate, surfactant washing with Tween80®, sparging with air followed by ozone, and thermal treatment at 80°C. The sources were made with three lenses of 26×26×6.5cm, one having a hydraulic conductivity similar to the whole tank and the two others a value 10 times smaller. The four techniques were studied after conditioning the tanks with tap water during approximately 80days. The persulfate treatment tests showed average removal of the contaminants but significant flux decrease if density effects are considered. Surfactant flushing did not show a highly significant increase of the flux of toluene but allowed an increased removal rate that could lead to an almost complete removal with longer treatment time. Sparging removed a significant amount but suggests that air was passing through localized gas channels and that the removal was stagnating after removing half of the contamination. Thermal treatment reached 100% removal after the target temperature of 80°C was kept during more than 10d. The experiments emphasized the generation of a high-spatial heterogeneity in NAPL content. For all the treatments the overall removal was similar for both n-decane and toluene, suggesting that toluene was removed rapidly and n-decane more slowly in some zones, while no removal existed in other zones. The oxidation and surfactant results were also analyzed for the relation between contaminant fluxes at the outlet and mass removal. For the first time, this approach clearly allowed the differentiation of the treatments. As a conclusion, experiments showed that the most important differences between the tested treatment techniques were not the global mass removal rates but the time required to reach 99% decrease in the contaminant fluxes, which were different for each technique., (Copyright © 2017 Elsevier B.V. All rights reserved.)

This work presents the investigation of permethyl pillar[5]arene (MP5) as stationary phase for capillary gas chromatographic (GC) separations. The MP5 capillary column fabricated by the sol-gel coating method exhibited weak polarity and high column efficiency over 4200 plates/m for n-dodecane, n-octanol and naphthalene. Particularly, the MP5 stationary phase displays unique retention for dibromoalkanes, which was found to be closely related with the linker length, and shows high resolving capability for a wide range of positional and structural isomers, including alkylbenzenes, chlorobenzenes and chloronitrobenzenes, naphthalene derivatives, phenols and anilines. Moreover, the MP5 column showed good thermal stability and repeatability and reproducibility with the relative standard deviation in the range of 0.02-0.04% for intra-day, 0.32-0.46% for inter-day and 1.5-3.4% for between-column, respectively. This work demonstrates an promising future of pillar[n]arenes as a new type of stationary phase in chromatographic separations., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Seaweed-like graphitic carbon nitride (g-C 3 N 4 ) has a unique porous architecture composed of interlocking g-C 3 N 4 nanofibers (NF-C 3 N 4 ) with much higher surface area than bulk g-C 3 N 4 and shows good potential in separation science. This work investigated the separation performance of NF-C 3 N 4 as stationary phase for capillary gas chromatographic (GC) separations. The NF-C 3 N 4 column exhibits weak polarity and high column efficiency of 4728 plates/m for n-dodecane. Importantly, it displays good separation performance for a wide range of analytes and shows different retention behaviors from the bulk g-C 3 N 4 column and commercial HP-5MS column with 5% phenylpolysiloxane. Particularly, it shows high resolving capability for both aliphatic and aromatic isomers. In addition, NF-C 3 N 4 column has high thermal stability up to 280°C and good separation repeatability with relative standard deviation (RSD) values in the range of 0.29-0.61% for intra-day, 0.56-1.1% for inter-day and 2.0-4.9% for between-column, respectively. Moreover, it was applied for the determination of isomer impurities in real samples, showing good potential in GC applications., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The rapid and complete baseline separation of both volatile (C 5 to C 16 alkanes in gasoline or terpenes in plant extracts) and non-volatile (>C 20 alkanes) organic compounds was achieved by combining (1) low-density fluid chromatography (LDFC) using carbon dioxide at elevated temperature (>90°C) and low pressure (1500psi) designed to increase the retention of the most volatile compounds and (2) high-vacuum technology (<10 -4 Torr) in order to preserve the maximum efficiency of short analytical columns (3.0mm×150mm packed with 1.8μm fully porous HSS-SB-C 18 particles) when used in LDFC. The volatile compounds are eluted first under isobaric conditions (1500psi) in less than a minute followed by a linear gradient of the column back pressure (from 1500 to 3500psi in 5min) for the elution of the non-volatile compounds up to C 40 . The experimental results demonstrate that LDFC performed with short 3.0mm i.d. columns packed with sub-2μm particles and placed under adiabatic conditions enables the analysts to deliver a single, fast, and high-resolution separation of both volatile and non-volatile compounds., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Biosynthesis of alkanes in microbial foundries offers a sustainable and green supplement to traditional fossil fuels. The dynamic equilibrium of fatty aldehydes, key intermediates, played a critical role in microbial alkanes production, due to the poor catalytic capability of aldehyde deformylating oxygenase (ADO). In our study, exploration of competitive pathway together with multi-modular optimization was utilized to improve fatty aldehydes balance and consequently enhance alkanes formation in Escherichia coli. Endogenous fatty alcohol formation was supposed to be competitive with alkane production, since both of the two routes consumed the same intermediate-fatty aldehyde. Nevertheless, in our case, alkanes production in E. coli was enhanced from trace amount to 58.8mg/L by the facilitation of moderate fatty alcohol biosynthesis, which was validated by deletion of endogenous aldehyde reductase (AHR), overexpression of fatty alcohol oxidase (FAO) and consequent transcriptional assay of aar, ado and adhP genes. Moreover, alkanes production was further improved to 81.8mg/L, 86.6mg/L or 101.7mg/L by manipulation of fatty acid biosynthesis, lipids degradation or electron transfer system modules, which directly referenced to fatty aldehydes dynamic pools. A titer of 1.31g/L alkanes was achieved in 2.5L fed-batch fermentation, which was the highest reported titer in E. coli. Our research has offered a reference for chemical overproduction in microbial cell factories facilitated by exploring competitive pathway., (Copyright © 2016 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.)

Wortmannolol (1), a new furanosteroid, along with five known compounds, wortmannolone (2), ergosterol (3), p-hydroxyphenyl ethanol (4), trans-6-dodecene (5), (2Z, 4E) -5-(8-hydroxy-1,5-dimethyl-3-oxo-6-oxabicyclo [3.2.1] octan-8-yl) -3-methylpenta-2,4-dienoic acid (6) were isolated from a fungal endophyte Talaromyces sp. lgt-4. Their structures were elucidated by IR, MS, 1D and 2D NMR spectra. Compound 1 show weak monoamine oxidase inhibitory activity.

Alkanes of defined carbon chain lengths can serve as alternatives to petroleum-based fuels. Recently, microbial pathways of alkane biosynthesis have been identified and enabled the production of alkanes in non-native producing microorganisms using metabolic engineering strategies. The chemoautotrophic bacterium Cupriavidus necator has great potential for producing chemicals from CO2: it is known to have one of the highest growth rate among natural autotrophic bacteria and under nutrient imbalance it directs most of its carbon flux to the synthesis of the acetyl-CoA derived polymer, polyhydroxybutyrate (PHB), (up to 80% of intracellular content). Alkane synthesis pathway from Synechococcus elongatus (2 genes coding an acyl-ACP reductase and an aldehyde deformylating oxygenase) was heterologously expressed in a C. necator mutant strain deficient in the PHB synthesis pathway. Under heterotrophic condition on fructose we showed that under nitrogen limitation, in presence of an organic phase (decane), the strain produced up to 670mg/L total hydrocarbons containing 435mg/l of alkanes consisting of 286mg/l of pentadecane, 131mg/l of heptadecene, 18mg/l of heptadecane, and 236mg/l of hexadecanal. We report here the highest level of alka(e)nes production by an engineered C. necator to date. We also demonstrated the first reported alka(e)nes production by a non-native alkane producer from CO2 as the sole carbon source., (Copyright © 2016 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.)

Natural peloids from sulfurous thermal springs are largely used in cosmetic and pelotherapy for the treatment of different dermatological conditions, including skin aging, dermatitis, and other eczemas. The beneficial effects are correlated to mineralogical and other thermal properties, as well as to the presence of natural substances with specific antioxidant activity. Few data are available for the comparison between natural peloids and synthetic (i.e., artificially maturated) muds. In this context, the natural substances and antioxidant activity of natural white mud (WM) and dark mud (DM) peloids from the sulfurous thermal spring pool Bagnaccio (Viterbo, Italy) have been studied in detail to evaluate possible relationships between physicochemical properties and therapeutic effect. A large panel of natural substances in WM and DM were characterized for the first time by ³¹P-nuclear magnetic resonance and gas chromatography associated to mass spectrometry analysis. Polar fractions of WM and DM peloids were characterized by the presence of several bioactive natural compounds, showing high antioxidant activity and DNA protective effect, as evaluated by 2,2-diphenyl-1-picrylhydrazyl assay, and hydrogen peroxide–induced DNA breakage in the alkaline comet assay. The antioxidant activity and DNA protective effect could be attributed to radical scavenging rather than a modulatory effect on the induced DNA repair, and are of order of intensity higher than that reported for synthetic muds.

This article reports biodegradation rates for a commercial dispersant, JD-2000, South Louisiana crude oil (SLC) alone, and SLC dispersed with JD-2000 at 5 and 25 °C. Results from the biodegradation experiments revealed that Component X, a chemical marker for JD-2000, rapidly degraded at both temperatures. The application of JD-2000 decreased by half the overall biodegradation rate of aliphatic compounds at 25 °C. At 5 °C, a residual fraction consisting of iso- and n-alkanes (C29-C35) persisted after 56 d. The combination of dispersant and higher temperature resulted in faster removal rates for 2- and 3-ring polycyclic aromatic hydrocarbons. When compared with Corexit 9500, our results suggest that the chemistry of the surfactant (or surfactants) in JD-2000 might have favored oil dissolution (substrate transport to the aqueous phase) as an uptake mechanism over adhesion, which requires direct contact of the biomass with the oil., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Addition of granular materials to floating crude oil slicks can be effective in capturing and densifying the floating hydrophobic phase, which settles by gravity. Interaction of light hydrophobic liquids (LHL) with quartz sand was investigated in LHL-salt water systems. The LHLs studied were decane, tetradecane, hexadecane, benzene, toluene, ethylbenzene, m-xylene, and 2-cholorotoluene. Experiments were conducted with fine quartz sand (passing sieve No. 40 with openings 0.425 mm). Each LHL was dyed with few crystals of Sudan IV dye for ease of visual observation. A volume of 0.5 mL of each LHL was added to 100 mL salt water (34 g/L). Addition of one gram of quartz sand to the floating hydrophobic liquid layer resulted in formation of sand-encapsulated globules, which settled due to increased density. All LHLs (except for a few globules of decane) formed globules covered with fine sand particles that were heavy enough to settle by gravity. The encapsulated globules were stable and retained their shape upon settling. Polarity of hydrophobic liquids as the main factor of aggregation with minerals was found to be insufficient to explain LHL aggregation with sand. Contact angle measurements were made by submerging a large quartz crystal with the LHL drop on its surface into salt water. A positive correlation was observed between the wetting angle of LHL and the LHL volume captured (r = 0.75). The dependence of the globule density on globule radius was analyzed in relation to the coverage (%) of globule surface (LHL-salt water interface) by fine quartz particles., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Typical renewable liquid fuel alternatives to gasoline are not entirely compatible with current infrastructure. We have engineered Escherichia coli to selectively produce alkanes found in gasoline (propane, butane, pentane, heptane, and nonane) from renewable substrates such as glucose or glycerol. Our modular pathway framework achieves carbon-chain extension by two different mechanisms. A fatty acid synthesis route is used to generate longer chains heptane and nonane, while a more energy efficient alternative, reverse-β-oxidation, is used for synthesis of propane, butane, and pentane. We demonstrate that both upstream (thiolase) and intermediate (thioesterase) reactions can act as control points for chain-length specificity. Specific free fatty acids are subsequently converted to alkanes using a broad-specificity carboxylic acid reductase and a cyanobacterial aldehyde decarbonylase (AD). The selectivity obtained by different module pairings provides a foundation for tuning alkane product distribution for desired fuel properties. Alternate ADs that have greater activity on shorter substrates improve observed alkane titer. However, even in an engineered host strain that significantly reduces endogenous conversion of aldehyde intermediates to alcohol byproducts, AD activity is observed to be limiting for all chain lengths. Given these insights, we discuss guiding principles for pathway selection and potential opportunities for pathway improvement., (Copyright © 2015 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.)

A high-temperature diaphragm valve-based comprehensive two-dimensional gas chromatography (GC×GC) instrument is demonstrated which readily allows separations up to 325°C. Previously, diaphragm valve-based GC×GC was limited to 175°C if the valve was mounted in the oven, or limited to 265°C if the valve was faced mounted on the outside of the oven. A new diaphragm valve has been commercially developed, in which the temperature sensitive O-rings that previously limited the separation temperatures have been replaced with Kalrez O-rings, a perfluoroelastomer, allowing for significantly higher temperatures permitting a greater range of volatile and semi-volatile compounds to be readily separated. In the current investigation, a separation temperature up to 325°C is demonstrated with the valve mounted directly in the oven. Since the temperature limit for most commonly used GC columns is at or below 325°C, the scope of diaphragm valve-based GC×GC is now dramatically broadened to encompass a majority of all column stationary phase chemistries. A 44-component mixture of alkanes, alcohols, and polyaromatic hydrocarbons is used to study this new configuration whose boiling points range from 98°C (n-heptane) to 450°C (n-triacontane). For the test mixture using a modulation period PM of 1.0s, peak shapes on second dimension separations, (2)D, are symmetric with average widths at base of 79.4ms, producing a (2)D peak capacity of (2)nc∼12. Based on the average peak width of 2.4s for the first dimension separation with a run time of 32.5min, the (1)D peak capacity is (1)nc∼800. Thus, the ideal two-dimensional peak capacity [Formula: see text] is 9600. Little variation in within-analyte (2)D peak width was observed with an average %RSD of less than 3.0%. Furthermore, retention time on (2)D was very reproducible with an average %RSD less than 0.5%. Measured peak areas (sum of all (2)D peaks for given analyte) had an average %RSD of 4.4%. The transfer fraction from (1)D to (2)D was experimentally determined to be ∼30%, while the detection sensitivity for valve-based GC×GC was ∼8 times higher than one dimensional GC due to zone compression. After a year of use with temperatures consistently up to 325°C, there has been no deterioration of the valve or its performance for GC×GC. Separations of vacuum pump oil and orange oil are also reported to demonstrate practical utility., (Copyright © 2015 Elsevier B.V. All rights reserved.)

An analytical method has been developed for the pressurized liquid extraction (PLE) of a wide range of semi-volatile organic compounds (SVOCs) from atmospheric particulate matter. Approximately 130 SVOCs from eight compound classes were selected as molecular markers of (1) agricultural activity (30 current and historic-use pesticides), (2) industrial activity (18 PCBs), (3) consumer products and building materials (16 PBDEs, 11 OPEs), and (4) motor vehicle exhaust (22 PAHs, 16 alkanes, 9 hopanes, 8 steranes). Currently, there is no analytical method validated for the extraction of all eight compound classes in a single automated technique. The extraction efficiencies of varying solvents and solvent combinations at high temperatures and pressures were examined. Extracts were concentrated and analyzed by gas chromatography coupled with mass spectrometry. The optimized PLE method utilized methylene chloride:acetone (2:1 v/v) at 100 °C with three (5 min) static cycles, flush volume of 80%, and a 100 s N2 purge. Spike and recovery experiments (n=7) provided average percent recoveries for pesticides, PCBs, PBDEs, OPEs, PAHs, alkanes, hopanes, and steranes of 88.8±4.0%, 86.9±2.6%, 83.8±2.9%, 101±6%, 90.3±6.1%, 74.4±8.8%, 104±8%, and 86.5±8.6%, respectively. The developed method was applied to atmospheric particulate matter samples collected in the greater Houston, TX metropolitan area. Ambient concentrations of eight classes of compounds (92 SVOCs) were reported in pg m(-3)., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

In this study the preparation of various mesoporous silica thin films as new stationary phases for gas chromatography (GC) columns is presented. The synthesis was performed inside capillaries via a sol-gel process using a templating route. The as-obtained columns were found to be highly efficient for the fast separation of light n-alkanes (C1-C5) mixture; these columns exhibiting a normalized retention 30 times higher than that of a commercially available silica column used as standard. A particular effort was directed towards the characterization of the stationary phase physical features: thin film inspection by Scanning Electron Microscopy and, for the first time to our knowledge, in situ SAXS characterization using synchrotron radiation were used to study the impact of the pore-network structuration on the GC properties. Worm-like, cubic and hexagonal phases were observed for specific preparation conditions. Unexpectedly, the normalized retention relative to film thickness appeared higher with disordering of the pores network., (Copyright © 2015 Elsevier B.V. All rights reserved.)

An organic monolithic column based on the co-polymerization of 2-naphthyl methacrylate (NAPM) as the functional monomer and trimethylolpropane trimethacrylate (TRIM) as the crosslinker was introduced for high performance reversed-phase liquid chromatography (RPC). The co-polymerization was performed in situ in a stainless steel column of 4.6mm i.d. in the presence of a ternary porogen consisting of 1-dodecanol and cyclohexanol. This monolithic column (referred to as naphthyl methacrylate monolithic column or NMM column) showed high mechanical stability at relatively high mobile phase flow velocity indicating that the column has excellent hydrodynamic characteristics. To characterize the NMM column, different probe molecules including alkyl benzenes, and aniline, benzene, toluene and phenol derivatives were chromatographed on the column and the results in terms of k, selectivity and plate counts were compared to those obtained on an octadecyl silica (ODS) column in order to assess the presence of π-π and hydrophobic interactions on the NMM column under otherwise the same elution conditions. The NMM column offered additional π-π interactions with aromatic molecules in addition to hydrophobic interactions under RPC elution conditions. Run-to-run and column-to-column reproducibility of solute k values were evaluated, and percent relative standard deviation of <1% and ∼2-3.5%, respectively, were obtained. Six standard proteins were readily separated on the NMM column using shallow (30min at 1.0mL/min), steep (10min at 1.0mL/min) and ultra steep (1min at 3.0mL/min) linear gradient elution at increasing ACN concentration in the mobile phase using a 10cm×4.6mm i.d. column in case of shallow and steep linear gradients and a 3cm×4.6mm i.d. column for ultra steep linear gradient., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Subcritical water extraction of organic matter containing sedimentary rocks at 300°C and 1500 psi produces extracts comparable to conventional solvent extraction. Subcritical water extraction of previously solvent extracted samples confirms that high molecular weight organic matter (kerogen) degradation is not occurring and that only low molecular weight organic matter (free compounds) are being accessed in analogy to solvent extraction procedures. The sedimentary rocks chosen for extraction span the classic geochemical organic matter types. A type I organic matter-containing sedimentary rock produces n-alkanes and isoprenoidal hydrocarbons at 300°C and 1500 psi that indicate an algal source for the organic matter. Extraction of a rock containing type II organic matter at the same temperature and pressure produces aliphatic hydrocarbons but also aromatic compounds reflecting the increased contributions from terrestrial organic matter in this sample. A type III organic matter-containing sample produces a range of non-polar and polar compounds including polycyclic aromatic hydrocarbons and oxygenated aromatic compounds at 300°C and 1500 psi reflecting a dominantly terrestrial origin for the organic materials. Although extraction at 300°C and 1500 psi produces extracts that are comparable to solvent extraction, lower temperature steps display differences related to organic solubility. The type I organic matter produces no products below 300°C and 1500 psi, reflecting its dominantly aliphatic character, while type II and type III organic matter contribute some polar components to the lower temperature steps, reflecting the chemical heterogeneity of their organic inventory. The separation of polar and non-polar organic compounds by using different temperatures provides the potential for selective extraction that may obviate the need for subsequent preparative chromatography steps. Our results indicate that subcritical water extraction can act as a suitable replacement for conventional solvent extraction of sedimentary rocks, but can also be used for any organic matter containing mineral matrix, including soils and recent sediments, and has the added benefit of tailored extraction for analytes of specific polarities., (Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.)

Several biotechnological processes can show an undesirable formation of emulsions making difficult phase separation and product recovery. The breakup of oil-in-water emulsions stabilized by yeast was studied using different physical and chemical methods. These emulsions were composed by deionized water, hexadecane and commercial yeast (Saccharomyces cerevisiae). The stability of the emulsions was evaluated varying the yeast concentration from 7.47 to 22.11% (w/w) and the phases obtained after gravity separation were evaluated on chemical composition, droplet size distribution, rheological behavior and optical microscopy. The cream phase showed kinetic stability attributed to mechanisms as electrostatic repulsion between the droplets, a possible Pickering-type stabilization and the viscoelastic properties of the concentrated emulsion. Oil recovery from cream phase was performed using gravity separation, centrifugation, heating and addition of demulsifier agents (alcohols and magnetic nanoparticles). Long centrifugation time and high centrifugal forces (2 h/150,000×g) were necessary to obtain a complete oil recovery. The heat treatment (60°C) was not enough to promote a satisfactory oil separation. Addition of alcohols followed by centrifugation enhanced oil recovery: butanol addition allowed almost complete phase separation of the emulsion while ethanol addition resulted in 84% of oil recovery. Implementation of this method, however, would require additional steps for solvent separation. Addition of charged magnetic nanoparticles was effective by interacting electrostatically with the interface, resulting in emulsion destabilization under a magnetic field. This method reached almost 96% of oil recovery and it was potentially advantageous since no additional steps might be necessary for further purifying the recovered oil., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Mathematical kinetic plot expressions have been established for the correct extrapolation of the kinetic performance measured in a thin-film capillary GC column with fixed length into the performance that can be expected in a longer column used at the same outlet velocity but at either the maximal inlet pressure or at the optimal inlet pressure, i.e., the one leading to an operation at the kinetic performance limit of the given capillary size. To determine this optimal pressure, analytical solutions have been established for the three roots of the corresponding cubic equation. Experimental confirmation of the kinetic plot extrapolations in GC has been obtained measuring the efficiency of a simple test mixture on 30, 60, 90 and 120m long (coupled) columns., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Ranunculus nipponicus var. submersus is an aquatic macrophyte; it is known as a wild edible plant in Japan for a long time. In this study, the essential oils from the fresh and dried aerial parts of R. nipponicus var. submersus were extracted by hydrodistillation and analyzed by gas chromatography (GC) and GC-mass spectrometry (GC-MS). Moreover, important aroma-active compounds were also detected in the oil using GC-olfactometry (GC-O) and aroma extract dilution analysis (AEDA). Thus, 98 compounds (accounting for 93.86%) of the oil were identified. The major compounds in fresh plant oil were phytol (41.94%), heptadecane (5.92%), and geranyl propionate (5.76%), while those of. Dried plant oil were β-ionone (23.54%), 2-hexenal (8.75%), and dihydrobovolide (4.81%). The fresh and dried oils had the green-floral and citrus-floral odor, respectively. The GC-O and AEDA results show that phenylacetaldehyde (green, floral odor, FD-factor = 8) and β-ionone (violet-floral odor, FD-factor = 8) were the most characteristic odor compounds of the fresh oils. β-Cyclocitral (citrus odor, FD-factor = 64) and β-ionone (violet-floral odor, FD-factor = 64) were the most characteristic odor compounds of the dried oil. These compounds are thought to contribute to the flavor of R. nipponicus var. submersus.

In this study, the chemical compositions of the essential oils from aerial parts (JmA) and radices (JmR) of Jacobaea maritima (L.) Pelser & Meijden, collected in Croatia, and of Jacobaea maritima subsp. bicolor (Willd.) B. Nord. & Greuter, collected in Sicily, were evaluated by using gas chromatography and gas chromatography-mass spectrometry. The main components of the essential oil from J. maritima, both in JmA and JmR, were pentacosane (15.7%), heptacosane (13.1%) and nonacosane (8.1%) whereas the essential oil from J. maritima subsp. bicolor was characterised by the presence of hexadecanoic acid (14.6%), caryophyllene oxide (9.3%) and hexahydrofarnesylacetone (6.5%). The comparison of the essential oil with other studied oils of the genus Jacobaea is discussed.

Thermodynamic parameters of ΔH(T0), ΔS(T0), and ΔCP for 156 compounds comprising alkanes, alkyl halides and alcohols were determined for a 5% phenyl 95% methyl stationary phase. The determination of thermodynamic parameters relies on a Nelder-Mead simplex optimization to rapidly obtain the parameters. Two methodologies of external and leave one out cross validations were applied to assess the robustness of the estimations of thermodynamic parameters. The largest absolute errors in predicted retention time across all temperature ramps and all compounds were 1.5 and 0.3s for external and internal sets, respectively. The possibility of an in silico extension of the thermodynamic library was tested using a quantitative structure-retention relationship (QSRR) methodology. The estimated thermodynamic parameters were utilized to develop QSRR models. Individual partial least squares (PLS) models were developed for each of the three classes of the molecules. R(2) values for the test sets of all models across all temperature ramps were larger than 0.99 and the average of relative errors in retention time predictions of the test sets for alkanes, alcohols, and alkyl halides were 1.8%, 2.4%, and 2.5%, respectively., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Larvae of the European earwig, Forficula auricularia, possess a paired pygidial gland with yet unknown content and function. We used gas chromatography-mass spectrometry to analyze the larval secretions revealing the presence of 2-methyl-1,4-benzoquinone, 2-ethyl-1,4-benzoquinone, n-tridecane and n-pentadecane. Based on our recent discovery that the morphologically-distinct abdominal glands of adult earwigs produce secretions with antibacterial, antifungal and nematicidal activity, we propose that the pygidial glands mediate chemical defenses in the larvae. We next considered whether the defensive functions of larval secretions include repellent activity against sympatric predators. Therefore, we tested the effects of larval secretions on foraging workers of the ant species Myrmica rubra, the actively hunting spiders Anyphaena accentuata and Philodromus aureolus and the net-hunting spider Pholcus phalangioides in laboratory feeding assays. The secretion is released in response to ant attacks, and discourages feeding in M. rubra, however, it does not discourage feeding in spiders. Our results suggest that earwigs use different glands during ontogenesis to produce secretions that play roles in chemical defense against predators such as ants., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The composition of the cuticular n-alkanes isolated from the leaves of nine populations of Juniperus deltoides R.P.Adams from continental and coastal areas of the Balkan Peninsula was characterized by GC-FID and GC/MS analyses. In the leaf waxes, 14 n-alkane homologues with chain-lengths ranging from C22 to C35 were identified. n-Tritriacontane (C33 ) was dominant in the waxes of all populations, but variations between the populations in the contents of all n-alkanes were observed. Several statistical methods (ANOVA, principal component, discriminant, and cluster analyses) were used to investigate the diversity and variability of the cuticular-leaf-n-alkane patterns of the nine J. deltoides populations. This is the first report on the n-alkane composition for this species. The multivariate statistical analyses evidenced a high correlation of the leaf-n-alkane pattern with the geographical distribution of the investigated samples, differentiating the coastal from the continental populations of this taxon., (Copyright © 2014 Verlag Helvetica Chimica Acta AG, Zürich.)

The acaricidal activity of the petroleum ether extract of leaves of Tetrastigma leucostaphylum (Dennst.) Alston (family: Vitaceae) against Rhipicephalus (Boophilus) annulatus was assessed using adult immersion test (AIT). The per cent of adult mortality, inhibition of fecundity, and blocking of hatching of eggs were studied at different concentrations. The extract at 10% concentration showed 88.96% inhibition of fecundity, 58.32% of adult tick mortality, and 50% inhibition of hatching. Peak mortality rate was observed after day 5 of treatment. Mortality of engorged female ticks, inhibition of fecundity, and hatching of eggs were concentration dependent. The LC50 value of the extract against R. (B.) annulatus was 10.46%. The HPTLC profiling of the petroleum ether extract revealed the presence of at least seven polyvalent components. In the petroleum ether extract, nicotine was identified as one of the components up to a concentration of 5.4%. However, nicotine did not reveal any acaricidal activity up to 20000 ppm (2%). Coconut oil, used as diluent for dissolving the extract, did not reveal any acaricidal effects. The results are indicative of the involvement of synergistic or additive action of the bioactive components in the tick mortality and inhibition of the oviposition.

Increasing concerns about limited fossil fuels and global environmental problems have focused attention on the need to develop sustainable biofuels from renewable resources. Although microbial production of diesel has been reported, production of another much in demand transport fuel, petrol (gasoline), has not yet been demonstrated. Here we report the development of platform Escherichia coli strains that are capable of producing short-chain alkanes (SCAs; petrol), free fatty acids (FFAs), fatty esters and fatty alcohols through the fatty acyl (acyl carrier protein (ACP)) to fatty acid to fatty acyl-CoA pathway. First, the β-oxidation pathway was blocked by deleting the fadE gene to prevent the degradation of fatty acyl-CoAs generated in vivo. To increase the formation of short-chain fatty acids suitable for subsequent conversion to SCAs in vivo, the activity of 3-oxoacyl-ACP synthase (FabH), which is inhibited by unsaturated fatty acyl-ACPs, was enhanced to promote the initiation of fatty acid biosynthesis by deleting the fadR gene; deletion of the fadR gene prevents upregulation of the fabA and fabB genes responsible for unsaturated fatty acids biosynthesis. A modified thioesterase was used to convert short-chain fatty acyl-ACPs to the corresponding FFAs, which were then converted to SCAs by the sequential reactions of E. coli fatty acyl-CoA synthetase, Clostridium acetobutylicum fatty acyl-CoA reductase and Arabidopsis thaliana fatty aldehyde decarbonylase. The final engineered strain produced up to 580.8 mg l(-1) of SCAs consisting of nonane (327.8 mg l(-1)), dodecane (136.5 mg l(-1)), tridecane (64.8 mg l(-1)), 2-methyl-dodecane (42.8 mg l(-1)) and tetradecane (8.9 mg l(-1)), together with small amounts of other hydrocarbons. Furthermore, this platform strain could produce short-chain FFAs using a fadD-deleted strain, and short-chain fatty esters by introducing the Acinetobacter sp. ADP1 wax ester synthase (atfA) and the E. coli mutant alcohol dehydrogenase (adhE(mut)).

Biotechnological research on marine organisms, such as ex situ or in situ aquaculture and in vitro cell culture, is being conducted to produce bioactive metabolites for biomedical and industrial uses. The Caribbean marine sponge Discodermia dissoluta is the source of (+)-discodermolide, a potent antitumoural polyketide that has reached clinical trials. This sponge usually lives at depths greater than 30 m, but at Santa Marta (Colombia) there is a shallower population, which has made it logistically possible to investigate for the first time, on ways to supply discodermolide. We thus performed in situ, 6-month fragment culture trials to assess the performance of this sponge in terms of growth and additional discodermolide production and studied possible factors that influence the variability of discodermolide concentrations in the wild. Sponge fragments cultured in soft mesh bags suspended from horizontal lines showed high survivorship (93 %), moderate growth (28 % increase in volume) and an overall rise (33 %) in the discodermolide concentration, equivalent to average additional production of 8 μg of compound per millilitre of sponge. The concentration of discodermolide in wild sponges ranged from 8 to 40 μg mL(-1). Locality was the only factor related to discodermolide variation in the wild, and there were greater concentrations in peripheral vs. basal portions of the sponge, and in clean vs. fouled individuals. As natural growth and regeneration rates can be higher than culture growth rates, there is room for improving techniques to sustainably produce discodermolide.

The molecular scale sorption, diffusion and distribution of asphaltene, resin, aromatic and saturate fractions of heavy crude oil on quartz surface were studied using molecular dynamic simulation. Sorption of saturates on quartz decreased by 31% when temperature increased from 298 to 398K while opposite trend was observed for resins, but insignificant changes were found in asphaltenes and aromatics. Despite of this variety, the main contribution of interactions was van der Waals energy (>90%) irrespective of molecular components and temperatures. The diffusion coefficient of saturates was predicted as 10.8×10(-10)m(2)s(-1) while that of the remaining fractions was about 4×10(-10)m(2)s(-1) at 298K. The most likely oil distribution on quartz surface was that aromatics and saturates transported randomly into and out of the complex consisting of asphaltenes surrounded by resins, which was influenced by temperature. Overall, the knowledge on quartz-oil and oil-oil interactions gained in this study is essential for future risk assessment and remediation activities as previous studies on soil remediation either limited to light oil fractions with <40 carbons or treated the heavy crude oil as a single pseudo entity ignoring the interactions between oil fractions., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Gas chromatography (GC) is considered the least common application of both polymer and silica-based monolithic columns. This study describes the fabrication of alkyl methacrylate monolithic materials for use as stationary phases in capillary gas chromatography. Following the deactivation of the capillary surface with 3-(trimethoxysilyl)propyl methacrylate (TMSM), the monoliths were formed by the co-polymerization of either hexyl methacrylate (HMA) or lauryl methacrylate (LMA) with different percentage of ethylene glycol dimethacrylate (EDMA) in presence of an initiator (azobisisobutyronitrile, AIBN) and a mixture of porogens include 1-propanol, 1,4-butanediol and water. The monoliths were prepared in 500mm length capillaries possessing inner diameters of 250μm. The efficiencies of the monolithic columns for low molecular weight compounds significantly improved as the percentage of crosslinker was increased, because of the greater proportion of pores less than 50nm. The columns containing lower percentages of crosslinker were able to rapidly separate a series of 8 alkane members in 0.7min, but the separation was less efficient for the light alkanes. Columns prepared with the lauryl methacrylate monomer yielded a different morphology for the monolith-interconnected channels. The channels were more branched, which increased the separation time, and unlike the other columns, allowed for temperature programming., (Copyright © 2013 Elsevier B.V. All rights reserved.)