Catalytic upcycling of post-consumer multilayered plastic packaging wastes for the selective production of monoaromatic hydrocarbons.

In order to obtain extended storage life of food-grade materials and better barrier properties against environmental factors, a multilayer plastic packaging (MLP) is often used. The multilayer packaging plastics are labelled as "other" (SPI#7) category, and are manufactured with a combination of barrier plastics, rigid plastics and printing surface. Owing to their complex composition and difficulty in separating the layers of MLP, its mechanical recycling is challenging. In this study, MLP wastes (MLPWs) were collected from zero-waste garbage collection center of IIT Madras, India, and thoroughly characterized to determine their composition and plastic types. MLPWs were characterized using various physico-chemical methods such as thermogravimetric/differential scanning calorimetric analysis, Fourier transform infrared spectroscopy, bomb calorimetry, and proximate and ultimate analyses. The MLPWs were mainly made up of polyethylene (PE) and polyethylene terephthalate (PET). Further, the non-catalytic and zeolite-catalyzed fast pyrolysis of these MLPWs were studied using analytical pyrolysis coupled with gas chromatograph/mass spectrometer (Py-GC/MS). The non-catalytic fast pyrolysis of MLPWs primarily produced a mixture of aliphatic and alicyclic hydrocarbons, while zeolite catalyzed fast pyrolysis resulted in the formation of mono-aromatic hydrocarbons (MAHs). The activity of HZSM-5, zeolite Y (HY) and zeolite beta (Hß) catalysts were evaluated, and the salient products were quantified. The yields of MAHs like benzene, toluene, ethylbenzene and xylene using the zeolites followed the trend: HZSM-5 (14.9 wt%) > HY (8.1 wt%) > Hß (7.8 wt%), at 650 °C. The use of HZSM-5 resulted in highest yield of MAHs, viz. 16.1 wt%, at the optimum temperature of 550 °C and MLPW-to-catalyst ratio of 1:15 (w/w). The superior activity of HZSM-5 is due to its nominal acidity and larger pore size of 4.24 nm, as compared to HY and Hß. The MAHs yield from three other types of MLPWs varied in the range of 9-16 wt%. The present study demonstrates a promising pathway for the catalytic upcycling of highly heterogeneous MLPWs in the context of circular economy.

Research progress in human biological monitoring of aromatic hydrocarbon with emphasis on the analytical technology of biomarkers.

Aromatic hydrocarbons are unsaturated compounds containing carbon and hydrogen that form single aromatic ring, or double, triple, or multiple fused rings. This review focuses on the research progress of aromatic hydrocarbons represented by polycyclic aromatic hydrocarbons (including halogenated polycyclic aromatic hydrocarbons), benzene and its derivatives including toluene, ethylbenzene, xylenes (o-, m- and p-), styrene, nitrobenzene, and aniline. Due to the toxicity, widespread coexistence, and persistence of aromatic hydrocarbons in the environment, accurate assessment of exposure to aromatic hydrocarbons is essential to protect human health. The effects of aromatic hydrocarbons on human health are mainly derived from three aspects: different routes of exposure, the duration and relative toxicity of aromatic hydrocarbons, and the concentration of aromatic hydrocarbons which should be below the biological exposure limit. Therefore, this review discusses the primary exposure routes, toxic effects on humans, and key populations, in particular. This review briefly summarizes the different biomarker indicators of main aromatic hydrocarbons in urine, since most aromatic hydrocarbon metabolites are excreted via urine, which is more feasible, convenient, and non-invasive. In this review, the pretreatment and analytical techniques are compiled systematically for the qualitative and quantitative assessments of aromatic hydrocarbons metabolites such as gas chromatography and high-performance liquid chromatography with multiple detectors. This review aims to identify and monitor the co-exposure of aromatic hydrocarbons that provides a basis for the formulation of corresponding health risk control measures and guide the adjustment of the exposure dose of pollutants to the population.

Comparison of PAC and MOAH for understanding the carcinogenic and developmental toxicity potential of mineral oils.

The carcinogenicity and developmental toxicity of unrefined mineral oil is related to its 3-7 ring polycyclic aromatic compounds (PAC) content. Therefore, refining operations focus on the targeted removal PAC from mineral oil that may contain aromatics of low toxicological concern. There are thus, two types of aromatic substances in mineral oil: hazardous and non-hazardous. The first type consists of 3-7 ring PAC which may be naked (unsubstituted) or lowly alkylated. The second type or non-hazardous consists of 1-7 ring aromatics with high degree of alkylation or lack of bay or fjord regions. Although these are toxicologically different, they may both elute in the same fraction when using chromatography. To understand how these two aromatic types are related we have assessed the entire mineral oil refinement process by measuring total mineral oil aromatic hydrocarbons (MOAH) content by chromatography next to regulatory hazard tests which focus on 3-7 ring PAC. MOAH content is positively correlated to its molecular weight resulting in aromatic content bias for high viscosity substances. Hazard to 3-7 ring PAC is best controlled by the validated IP346 or modified Ames test. We explain the concept of high vs low alkylation by shortly reviewing new data on alkylated PAC.

Electrophysiological Responses of the Mediterranean Fruit Fly, Ceratitis capitata, to the Cera Trap® Lure: Exploring Released Antennally-Active Compounds.

The Mediterranean fruit fly (medfly), Ceratitis capitata, is a worldwide pest of agriculture able to use olfactory cues to locate habitat, food sources, mates and oviposition sites. The sensitivity of medfly olfaction has been exploited to develop olfactory-based attractants that are currently important tools for detection, control and eradication of its populations. Among these is Cera Trap® (BIOIBERICA, S.A.U.), a cost-effective bait. Here we used coupled gas chromatography/electroantennographic detection (GC-EAD) and GC/mass spectrometry (GC-MS) approaches to characterize the medfly antennally-active compounds released by this lure. We identified GC peaks corresponding to chemicals belonging to six different classes including heterocyclic aromatic compounds, aliphatic alcohols, aldehydes, esters, sesquiterpene hydrocarbons, and aromatic alcohols. We tested ten potential candidate volatiles belonging to these classes and predicted to be emitted by the lure and found that they were eliciting electroantennographic responses in medfly adults. These results will help in unravelling the physiological mechanisms of odor perception in both sexes, especially in relation to Cera Trap® attractant activity, which in the field has been shown to be female-specific. These findings and their developments will ultimately expand the toolbox for medfly control in the field.

A new and effective evaluation method for Radix Gentianae Macrophyllae herbs based on 2-phenylethyl ß-d-glucopyranoside, 2-methoxyanofinic acid and gentioxepine by UPLC-QTOF-MS exploring and HPLC-DAD quantification.

Radix Gentianae Macrophyllae (RGM) is a traditional Chinese medicine belonging to the Gentiana genus and including four species of herbs. Owing to the lack of characteristic constituents, it is difficult to discriminate RGMs of different origins or even differentiate between herbs in the same genus. The current research aimed to explore the characteristic aromatic compounds, verify their significance in distinguishing different origins of RGM herbs and provide a simple and effective quality evaluation method. A selective extraction method was developed for noniridoid compounds and the extract was then subjected to UPLC-QTOF-MS analysis to obtain the RGM-MS ion pair database for noniridoid components. An HPLC-DAD quantitative analysis method was further developed based on characteristic aromatic compounds (2-phenylethyl ß-d-glucopyranoside, 2-methoxyanofinic acid and gentioxepine) after the ion screening in the MS database. By means of principal component analysis and hierarchical clustering analysis analysis, the significant relationship between aromatic compounds contents and different species of RGM was revealed. As a result, the significance of 2-phenylethyl ß-d-glucopyranoside, 2-methoxyanofinic acid and gentioxepine in distinguishing four species of RGM herbs was verified and a sensitive and reproducible HPLC-DAD method was established using these markers, which can be used for the classification and quantitative analysis of RGMs.

Determination of 14 heterocyclic aromatic amines in meat products using solid-phase extraction and supercritical fluid chromatography coupled to triple quadrupole mass spectrometry.

A novel, simple, and sensitive method has been developed for simultaneous determination of 14 heterocyclic aromatic amines in meat product using solid-phase extraction combined with ultrahigh-performance supercritical fluid chromatography coupled to tandem quadrupole mass spectrometry. The analytes could be separated within 7 min and identified using their retention times and mass. The developed method was validated based on the linearity, limits of quantification, precision, and accuracy. The recovery ranged from 52.3 to 97.5% with an acceptable standard deviation, which is not higher than 6%. The limits of quantitation ranged from 0.03 to 0.17 µg/kg. The selectivity and sensitivity were satisfactory in multiple reaction monitoring mode. The method was applied to commercial meat products, and the results demonstrated that the novel method has potential for the analysis of the targets in food matrices. This is the first work reporting the simultaneous quantification of 14 heterocyclic aromatic amines by means of ultrahigh-performance supercritical fluid chromatography coupled to tandem quadrupole mass spectrometry.

Acute oral methylmercury exposure perturbs the gut microbiome and alters gut-brain axis related metabolites in rats.

Environmental pollutants like methylmercury (MeHg) can bring devastating neurotoxicity to animals and human beings. Gut microbiota has been found to demethylate MeHg and promote the excretion of Hg through feces. However, the impacts of MeHg on gut microbiota and metabolites related to gut-brain interactions were less studied in mammals. The object of this study was to investigate the impacts of acute MeHg exposure on gut microbiome and metabolites together with its impact on gut integrity and related biological responses in rats. Rats were exposed to MeHg through oral administration and were sacrificed after 24 h 16 S rRNA gene sequencing was used to study the perturbance to gut microbiome and liquid chromatography mass spectrometry (LC-MS) was used for metabolomics profiling. It was found that gut was one of the target tissues of MeHg. MeHg induce the changes of intestinal microbial community structure and induce the regulating neuron activity change of intestinal neurotransmitters and metabolites on intestinal neurotransmitters and metabolites regulating the neuron activity. This was supported by the increased BDNF level. These findings may suggest a potential new mechanism regarding the neurotoxicity of MeHg. The protocols used in this study may also be applied to understand the neurotoxicity of other environmental neurotoxins like Pb, Mn, polychlorinated biphenyls, and pesticides, etc and to screen the neurotoxicity of emerging environmental contaminants.

Repetitive Detection of Aromatic Hydrocarbon Contaminants with Bioluminescent Bioreporters Attached on Tapered Optical Fiber Elements.

In this study, we show the repetitive detection of toluene on a tapered optical fiber element (OFE) with an attached layer of Pseudomonas putida TVA8 bioluminescent bioreporters. The bioluminescent cell layer was attached on polished quartz modified with (3-aminopropyl)triethoxysilane (APTES). The repeatability of the preparation of the optical probe and its use was demonstrated with five differently shaped OFEs. The intensity of measured bioluminescence was minimally influenced by the OFE shape, possessing transmittances between 1.41% and 5.00%. OFE probes layered with P. putida TVA8 were used to monitor liquid toluene over a two-week period. It was demonstrated that OFE probes layered with positively induced P. putida TVA8 bioreporters were reliable detectors of toluene. A toluene concentration of 26.5 mg/L was detected after <30 min after immersion of the probe in the toluene solution. Additional experiments also immobilized constitutively bioluminescent cells of E. coli 652T7, on OFEs with polyethyleneimine (PEI). These OFEs were repetitively induced with Lauria-Bertani (LB) nutrient medium. Bioluminescence appeared 15 minutes after immersion of the OFE in LB. A change in pH from 7 to 6 resulted in a decrease in bioluminescence that was not restored following additional nutrient inductions at pH 7. The E. coli 652T7 OFE probe was therefore sensitive to negative influences but could not be repetitively used.

Structure prediction and molecular docking studies of aromatic hydrocarbon sensing proteins TbuT, HbpR and PhnR to detect priority pollutants.

On-line detection of aromatic hydrocarbon pollutants in aqueous environments can be achieved by biosensing strains having fusion of gene responsible for pollutant sensing protein with a reporter gene. Regulatory proteins TbuT, HbpR and PhnR are such proteins for recognizing one-, two-and three-ring aromatic hydrocarbon pollutants respectively, for which the structure is not known till date. Aim of the present study was to predict the structure of proteins and to determine their in-silico interaction with array of pollutants. Structure prediction of proteins was performed using I-TASSER and Phyre2 and refined with ModRefiner and 3DRefine. Total 14 models were obtained for each protein and the best model had more than 95% coverage in Ramachandran plot region. After successful structure prediction, molecular interaction of proteins with respective aromatic hydrocarbon pollutants categorized by United States Environmental Protection Agency was studied using AutoDockVina where the binding energy was found to fall in range of -4.6 to -8.4 kcal/mol. The types of protein-pollutant interaction were analyzed by LigPlus and Discovery Studio 2017 R2 Client which were found to be similar for standard and pollutant compounds. This study enables us to predict the range of pollutants possible to be detected using these regulatory protein-based biosensors.

Exposure to organic solvents and hepatotoxicity.

The purpose of this study was to identify the long-term effect of chemical exposure on the liver. Laboratory tests included alanine aminotransferase (ALT) dosage and oxidative stress tests, such as thiobarbituric acid reactive substances in plasma and superoxide dismutase (SOD) and glutathione S-transferase analysis in erythrocytes. The cross-sectional study comprised 70 workers, 30 of them exposed to organic solvents and 40 not exposed. All those exposed presented at least 5 years of exposure to solvents. Hepatitis B and C, known hepatic disease, comorbidities, use of alcohol, illicit drugs or hepatotoxic medications, smoking, body mass index >30, female sex and age (<18 or >65) were excluded from the sample. Results indicated that elevated ALT was more frequent in the exposed group compared to controls: 33% vs. 10.5%, with a statistical significance (p < 0.05). Thiobarbituric acid reactive substances were significantly elevated (p < 0.01) in the exposed group in comparison to controls. Antioxidant enzymes were more elevated in the exposed group compared to controls: SOD 7.29 (4.30-8.91) USOD/mg of protein vs. 3.48 (2.98-5.28) USOD/mg of protein and GST 2.57 µmol/min/mg of protein (1.80-4.78) vs. 1.81 µmol/min/mg of protein (1.45- 2.30) µM/min/mg of protein. The results suggest an association between exposure to organic solvents and hepatotoxicity.

Direct Analysis of Polyaromatic Hydrocarbons in Soil and Aqueous Samples Using Condensed Phase Membrane Introduction Tandem Mass Spectrometry with Low-Energy Liquid Electron Ionization.

Polyaromatic hydrocarbons (PAHs) are listed as priority pollutants by the United States Environmental Protection Agency (U.S. EPA). PAH-contaminated samples often require extensive sample cleanup before analysis, with the method used dependent upon the sample matrix. We present condensed phase membrane introduction mass spectrometry with liquid electron ionization (CP-MIMS-LEI) as a sensitive and universal technique that can directly analyze both aqueous and soil samples for PAHs without the need for sample clean up or instrumental modifications for different matrixes. The method uses a semipermeable hollow fiber membrane immersion probe to transfer analytes from complex samples into a solvent acceptor phase that is directly entrained at nanoliter/min flows to an LEI-interfaced mass spectrometer. The resulting aerosol is desolvated under vacuum leading to analyte vaporization and subsequent electron ionization. Electron energy and LEI vaporization capillary position were examined and optimized for PAHs. The CP-MIMS probe was directly immersed in complex aqueous matrixes, demonstrating low nanogram per liter PAH detection limits and response times of ≤1.6 min. For soil sample analysis, 2-propanol was found to be the optimal PAH sampling solvent. Soil samples were briefly sonicated in 2-propanol, followed by direct CP-MIMS measurement. Soil sample throughput was ca. 15 samples/h, with PAH quantitation successful at microgram per kilogram levels. The workflow is remarkably simple, fast, green, and leads to reproducible results that enable high-throughput screening of heterogeneous soil samples.

Mineral oil in food, cosmetic products, and in products regulated by other legislations.

For a few years, mineral oils and their potential adverse health effects have been a constant issue of concern in many regulatory areas such as food, cosmetics, other consumer products, and industrial chemicals. Analytically, two fractions can be distinguished: mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH). This paper aims at assessing the bioaccumulative potential and associated histopathological effects of MOSH as well as the carcinogenic potential of MOAH for consumer-relevant mineral oils. It also covers the absorption, distribution, metabolism, and excretion of MOSH and MOAH upon oral and dermal exposures. The use and occurrence of consumer-relevant, highly refined mineral oils in food, cosmetics and medicinal products are summarized, and estimates for the exposure of consumers are provided. Also addressed are the challenges in characterizing the substance identity of mineral oil products under REACH. Evidence from more recent autopsy and biopsy studies, along with information on decreasing food contamination levels, indicates a low risk for adverse hepatic lesions that may arise from the retention of MOSH in the liver. With respect to MOAH, at present there is no indication of any carcinogenic effects in animals dermally or orally exposed to highly refined mineral oils and waxes. Such products are used not only in cosmetics but also in medicinal products and as additives in food contact materials. The safety of these mineral oil-containing products is thus indirectly documented by their prevalent and long-term use, with a simultaneous lack of clinical and epidemiological evidence for adverse health effects.

Levels and temporal trends of persistent organic pollutants (POPs) in Atlantic cod (Gadus morhua) and haddock (Melanogrammus aeglefinus) from the southern Barents Sea.

Liver samples of two gadoid species, Atlantic cod (Gadus morhua) and haddock (Melanogrammus aeglefinus), sampled in the southern Barents Sea in the period 1992-2015, were studied for the levels of six types of persistent organic pollutants (POPs): polychlorinated biphenyls (PCBs), chlorinated organic pesticides (DDTs, hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB), trans-nonachlor (TNC)), and polybrominated diphenyl ethers (PBDEs). Higher average levels were found in cod than in haddock. Sampling approximately every third year allowed studies of temporal trends for all the compound groups except PBDEs. Time series are reported for 1992-2015 for Atlantic cod and for 1998-2015 for haddock. Decreasing temporal trends have been modeled in cod for the analyzed POPs for this time period. The decrease seems to be slowing down in the later years. HCB levels showed least decrease with time among all the contaminants, with the poorest fit to the proposed model. Similar time trends were found in haddock, but the decrease is less apparent due to shorter time series. The observed time trends of legacy POPs document the effectiveness of efforts during the 1990s to reduce the levels of these contaminants in the marine environment but question the possibility to eliminate them altogether from the marine environment in the foreseeable future.

Development of fluorescent protein-based biosensing strains: A new tool for the detection of aromatic hydrocarbon pollutants in the environment.

The major sources for release of hydrocarbons into the environment include the effluents generated from chemical processing industries and ports. The introduction of such hazardous compounds into natural water bodies creates considerable disturbances in aquatic life and causes a threat to humans. Thus, it is essential to detect and quantify pollutants at various stages of the wastewater generation and treatment before they reach natural aquatic environments and contaminate them. This study reports the development of "biosensing strains" by cloning hydrocarbon recognizing promoter-operator and a reporter gene in bacterial strains for sensing the presence of pollutants at their lowest possible concentration. So far, various biosensing strains have been constructed with a fused promoter-operator region of the hydrocarbon degrading operons, but most of them use luxAB as a reporter gene. A novel approach in the present study aimed at constructing strains harboring two different fluorescent protein (FP)-based reporter genes for the quantification of multiple pollutants at a time. Two vectors were designed with a fusion of tbuT-gfp and phnR-cfp for the quantification of mono- and poly-aromatic hydrocarbons, respectively. The designed vectors were transformed into E. coli DH5α, and these strains were designated as E. coli DH5α 2296-gfp (containing pPROBE-Tbut-RBS-gfp-npt) and E. coli DH5α 2301-cfp (containing pPROBE-phn-RBS-cfp-npt). Both the developed recombinant strains were capable of successfully detecting mono- and poly-aromatic hydrocarbons in the range of 1-100 µM. The sensing capacity of recombinant strains was successfully validated with actual wastewater samples against available physico-chemical analytical techniques. The development of such recombinant microbial strains indicates the future for online contaminant detection, treatment quality monitoring and protection of aquatic flora and fauna.

Electrochemical Determination of TNT, DNT, RDX, and HMX with Gold Nanoparticles/Poly(Carbazole-Aniline) Film-Modified Glassy Carbon Sensor Electrodes Imprinted for Molecular Recognition of Nitroaromatics and Nitramines.

Since nitroaromatic- and nitramine-type energetic materials, mostly arising from military activities, are persistent pollutants in soil and groundwater, on-site sensing of these hazardous chemicals has gained importance. A novel electrochemical sensor was designed for detecting nitroaromatic- and nitramine-type energetic materials, relying on gold nanoparticles (Aunano), modified glassy carbon (GC) electrode coated with nitro-energetic memory-poly(carbazole-aniline) copolymer (Cz- co-ANI) film (e.g., TNT memory-GC/P(Cz- co-ANI)-Aunano modified electrode). Current was recorded against concentration to build the calibration curves that were found to be linear within the range of 100-1000 µg L-1 for 2,4,6-trinitrotoluene (TNT) and 2,4-dinitrotoluene (DNT): 50-1000 µg L-1 for 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). The corresponding limits of detection were 25 µg L-1 for TNT, 30 µg L-1 for DNT, and 10 µg L-1 for both RDX and HMX, using nitro-energetic memory-GC/P(Cz- co-ANI)-Aunano electrodes. These electrodes were used separately, and specific determinations were made in various mixtures of nitro-energetic materials. The developed method could be efficiently used in electroanalyzing nitroaromatics and nitramines in military explosives (i.e., comp B, octol, and comp A5). The sensor electrodes were specific for the tested nitro-energetic compounds and did not respond to paracetamol-caffeine-based analgesic drug, acetylsalicylic acid (aspirin), sweetener, and sugar that can be used as camouflage materials in passenger belongings. The developed method was statistically validated against the standard LC-MS reference method in contaminated clay soil samples containing TNT and RDX explosives.

Nitroaromatic detection and infrared communication from wild-type plants using plant nanobionics.

Plant nanobionics aims to embed non-native functions to plants by interfacing them with specifically designed nanoparticles. Here, we demonstrate that living spinach plants (Spinacia oleracea) can be engineered to serve as self-powered pre-concentrators and autosamplers of analytes in ambient groundwater and as infrared communication platforms that can send information to a smartphone. The plants employ a pair of near-infrared fluorescent nanosensors-single-walled carbon nanotubes (SWCNTs) conjugated to the peptide Bombolitin II to recognize nitroaromatics via infrared fluorescent emission, and polyvinyl-alcohol functionalized SWCNTs that act as an invariant reference signal-embedded within the plant leaf mesophyll. As contaminant nitroaromatics are transported up the roots and stem into leaf tissues, they accumulate in the mesophyll, resulting in relative changes in emission intensity. The real-time monitoring of embedded SWCNT sensors also allows residence times in the roots, stems and leaves to be estimated, calculated to be 8.3 min (combined residence times of root and stem) and 1.9 min mm-1 leaf, respectively. These results demonstrate the ability of living, wild-type plants to function as chemical monitors of groundwater and communication devices to external electronics at standoff distances.

Investigating the Influence of Aromatic Moieties on the Formulation of Hydrophobic Natural Products and Drugs in Poly(2-oxazoline)-Based Amphiphiles.

Many natural compounds with interesting biomedical properties share one physicochemical property, namely, low water solubility. Polymer micelles are, among others, a popular means to solubilize hydrophobic compounds. The specific molecular interactions between the polymers and the hydrophobic drugs are diverse, and recently it has been discussed that macromolecular engineering can be used to optimize drug-loaded micelles. Specifically, π-π stacking between small molecules and polymers has been discussed as an important interaction that can be employed to increase drug loading and formulation stability. Here, we test this hypothesis using four different polymer amphiphiles with varying aromatic content and various natural products that also contain different relative amounts of aromatic moieties. In the case of paclitaxel, having the lowest relative content of aromatic moieties, the drug loading decreases with increasing relative aromatic amount in the polymer, whereas the drug loading of curcumin, having a much higher relative aromatic content, is increased. Interestingly, the loading using schizandrin A, a dibenzo[ a, c]cyclooctadiene lignan with intermediate relative aromatic content is not influenced significantly by the aromatic content of the polymers employed. The very high drug loading, long-term stability, ability to form stable highly loaded binary coformulations in different drug combinations, small-sized formulations, and amorphous structures in all cases corroborate earlier reports that poly(2-oxazoline)-based micelles exhibit an extraordinarily high drug loading and are promising candidates for further biomedical applications. The presented results underline that the interaction between the polymers and the incorporated small molecules may be more complex and are significantly influenced by both sides, the used carrier and drug, and must be investigated in each specific case.

Determination of major aromatic constituents in vanilla using an on-line supercritical fluid extraction coupled with supercritical fluid chromatography.

An on-line supercritical fluid extraction coupled with supercritical fluid chromatography method was developed for the determination of four major aromatic constituents in vanilla. The parameters of supercritical fluid extraction were systematically investigated using single factor optimization experiments and response surface methodology by a Box-Behnken design. The modifier ratio, split ratio, and the extraction temperature and pressure were the major parameters which have significant effects on the extraction. While the static extraction time, dynamic extraction time, and recycle time had little influence on the compounds with low polarity. Under the optimized conditions, the relative extraction efficiencies of all the constituents reached 89.0-95.1%. The limits of quantification were in the range of 1.123-4.747 µg. The limits of detection were in the range of 0.3368-1.424 µg. The recoveries of the four analytes were in the range of 76.1-88.9%. The relative standard deviations of intra- and interday precision ranged from 4.2 to 7.6%. Compared with other off-line methods, the present method obtained higher extraction yields for all four aromatic constituents. Finally, this method has been applied to the analysis of vanilla from different sources. On the basis of the results, the on-line supercritical fluid extraction-supercritical fluid chromatography method shows great promise in the analysis of aromatic constituents in natural products.

Enhanced headspace single drop microextraction method using deep eutectic solvent based magnetic bucky gels: Application to the determination of volatile aromatic hydrocarbons in water and urine samples.

A facile headspace single drop microextraction method was developed using deep eutectic solvent-based magnetic bucky gel as the extraction solvent for the first time. The hydrophobic magnetic bucky gel was formed by combining choline chloride/chlorophenol deep eutectic solvent and magnetic multiwalled carbon nanotube nanocomposite. Magnetic susceptibility, high viscosity, high sorbing ability, and tunable extractability of organic analytes are the desirable advantages of the prepared gel. Using a rod magnet as a suspensor in combination with the magnetic susceptibility of the prepared gel resulted in a highly stable droplet. This stable droplet eliminated the possibility of drop dislodgement. The prepared droplet made it possible to complete the extraction process in high temperatures and elevated agitation rates. Furthermore, using larger micro-droplet volumes without any operational problems became possible. These facts resulted in shorter sample preparation time, higher sensitivity of the method, and lower detection limits. Under the optimized conditions, an enrichment factor of 520-587, limit of detection of 0.05-0.90 ng/mL, and linearity range of 0.2-2000 ng/mL (coefficient of determination = 0.9982-0.9995) were obtained. Relative standard deviations were < 10%. This method was successfully coupled with gas chromatography and used for the determination of benzene, toluene, ethylbenzene, and xylene isomers as harmful volatile organic compounds in water and urine samples.

Biodegradation and detoxification of aliphatic and aromatic hydrocarbons by new yeast strains.

Seeking new efficient hydrocarbon-degrading yeast stains was the main goal of this study. Because microorganisms are greatly affected by the environmental factors, the biodegradation potentiality of the microorganisms varies from climatic area to another. This induces research to develop and optimize the endemic organisms in bioremediation technology. In this study, 67 yeast strains were tested for their growth potentiality on both aliphatic and aromatic hydrocarbons. The most efficient six strains were identified using sequence analysis of the variable D1/D2 domain of the large subunit 26S ribosomal DNA. The identity of these strains was confirmed as Yamadazyma mexicana KKUY-0160, Rhodotorula taiwanensis KKUY-0162, Pichia kluyveri KKUY-0163, Rhodotorula ingeniosa KKUY-0170, Candida pseudointermedia KKUY-0192 and Meyerozyma guilliermondii KKUY-0214. These species are approved for their ability to degrade both aliphatic and aromatic hydrocarbons for the first time in this study. Although, all of them were able to utilize and grow on both hydrocarbons, Rhodotorula taiwanensis KKUY-0162 emerged as the best degrader of octane, and Rhodotorula ingeniosa KKUY-170 was the best degrader of pyrene. GC-MS analysis approved the presence of many chemical compounds that could be transitional or secondary metabolites during the utilization of the hydrocarbons. Our results recommend the application of these yeast species on large scale to approve their efficiency in bioremediation of oil-contamination of the environment. Using these yeasts, either individually or in consortia, could offer a practical solution for aquatic or soil contamination with the crude oil and its derivatives in situ.