Oil-derived Compounds Research Articles

Essential oil-derived robust and heat-resistant polybenzoxazine-POSS composites as low dielectric matrixes

Polybenzoxazines (PBozs) are regarded as prime candidates as low dielectric matrixes. However, the fabrication of high-performance PBozs that combines low dielectric property with high thermal stability using sustainable resources as the starting raw materials remains a significant challenge. In this work, we constructed a novel main-chain benzoxazine (Boz) oligomer from natural essential oil-derived compounds (eugenol and p-menthane diamine) to fulfill the principles of green chemistry. To enhance their low dielectric properties, polar C-Si unit on the main-chain and cellular structure of polyoctahedral silsesquioxanes (POSS) as the cross-linkers were introduced in PBoz-POSS composites. The obtained composites demonstrated excellent thermal stability, mechanical property, and with remarkable low dielectric constants. Coupled with their exceptional hydrophobicity and heat resistance, these materials are promising matrixes for low dielectric application in contemporary electronic industries.

Functionalization of Bacterial Cellulose With Bacterial Pigments: Optimization Using a Full Factorial Design Approach

Pigments from natural sources, such as bacterial pigments, have gained increased attention in recent years due to their biodegradability, non-toxicity, and noncarcinogenicity. The intention to replace synthetic and oil-derived compounds is not restricted to synthetic dyes; other applications include the replacement of oilderived polymers for more environmentally friendly options, such as biopolymers. In this work, the functionalization of a bacterial cellulose (BC) biopolymer with bacterial pigments was explored using a full factorial design methodology to evaluate the best functionalization conditions to produce colored BC. From the factors and interactions evaluated, it was possible to conclude that the variable duration of the functionalization procedure could be reduced to a low level without significantly affecting the functionalization of the BC samples with bacterial pigments. Moreover, BC is a product with high industrial applicability, versatility, and sustainability. Hence, the multifunctional colored BC can be applied in the packaging, paper, and textile industries, among others.
 Keywords: bacterial pigments, bacterial cellulose, full-factorial design, optimization

Transition Metal Phosphides (TMP) as a Versatile Class of Catalysts for the Hydrodeoxygenation Reaction (HDO) of Oil-Derived Compounds.

Hydrodeoxygenation (HDO) reaction is a route with much to offer in the conversion and upgrading of bio-oils into fuels; the latter can potentially replace fossil fuels. The catalyst’s design and the feedstock play a critical role in the process metrics (activity, selectivity). Among the different classes of catalysts for the HDO reaction, the transition metal phosphides (TMP), e.g., binary (Ni2P, CoP, WP, MoP) and ternary Fe-Co-P, Fe-Ru-P, are chosen to be discussed in the present review article due to their chameleon type of structural and electronic features giving them superiority compared to the pure metals, apart from their cost advantage. Their active catalytic sites for the HDO reaction are discussed, while particular aspects of their structural, morphological, electronic, and bonding features are presented along with the corresponding characterization technique/tool. The HDO reaction is critically discussed for representative compounds on the TMP surfaces; model compounds from the lignin-derivatives, cellulose derivatives, and fatty acids, such as phenols and furans, are presented, and their reaction mechanisms are explained in terms of TMPs structure, stoichiometry, and reaction conditions. The deactivation of the TMP’s catalysts under HDO conditions is discussed. Insights of the HDO reaction from computational aspects over the TMPs are also presented. Future challenges and directions are proposed to understand the TMP-probe molecule interaction under HDO process conditions and advance the process to a mature level.

Bioactive Foods and Medicinal Plants for Cardiovascular Complications of Type II Diabetes: Current Clinical Evidence and Future Perspectives.

Cardiovascular diseases (CVDs) are the main cause of mortality in type 2 diabetes mellitus (T2DM); however, not all patients are fully satisfied with the current available treatments. Medicinal plants have been globally investigated regarding their effect in CVD, yet the field is far from getting exhausted. The current paper aims to provide an evidence-based review on the clinically evaluated medicinal plants and their main therapeutic targets for the management of CVD in T2DM. Electronic databases including PubMed, Cochrane, Embase, Scopus, and Web of Science were searched from 2000 until November 2019, and related clinical studies were included. Lipid metabolism, glycemic status, systemic inflammation, blood pressure, endothelial function, oxidative stress, and anthropometric parameters are the key points regulated by medicinal plants in T2DM. Anti-inflammatory and antioxidant properties are the two most important mechanisms since inflammation and oxidative stress are the first steps triggering a domino of molecular pathological pathways leading to T2DM and, subsequently, CVD. Polyphenols with potent antioxidant and anti-inflammatory effects, essential oil-derived compounds with vasorelaxant properties, and fibers with demonstrated effects on obesity are the main categories of phytochemicals beneficial for CVD of T2DM. Some medicinal plants such as garlic (Allium sativum) and milk thistle (Silybum marianum) have strong evidences regarding their beneficial effects; however, others have low level of evidence which reveals the need for further clinical studies with larger sample sizes and longer follow-up periods to confirm the safety and efficacy of medicinal plants for the management of CVD in T2DM.

Biomarker responses and accumulation of polycyclic aromatic hydrocarbons in Mytilus trossulus and Gammarus oceanicus during exposure to crude oil

In the brackish water Baltic Sea, oil pollution is an ever-present and significant environmental threat mainly due to the continuously increasing volume of oil transport in the area. In this study, effects of exposure to crude oil on two common Baltic Sea species, the mussel Mytilus trossulus and the amphipod Gammarus oceanicus, were investigated. The species were exposed for various time periods (M. trossulus 4, 7, and 14 days, G. oceanicus 4 and 11 days) to three oil concentrations (0.003, 0.04, and 0.30 mg L−1 based on water measurements, nominally aimed at 0.015, 0.120, and 0.750 mg L−1) obtained by mechanical dispersion (oil droplets). Biological effects of oil exposure were examined using a battery of biomarkers consisting of enzymes of the antioxidant defense system (ADS), lipid peroxidation, phase II detoxification (glutathione S-transferase), neurotoxicity (acetylcholinesterase inhibition), and geno- and cytotoxicity (micronuclei and other nuclear deformities). In mussels, the results on biomarker responses were examined in connection with data on the tissue accumulation of polycyclic aromatic hydrocarbons (PAH). In M. trossulus, during the first 4 days of exposure the accumulation of all PAHs in the two highest exposure concentrations was high and was thereafter reduced significantly. Significant increase in ADS responses was observed in M. trossulus at 4 and 7 days of exposure. At day 14, significantly elevated levels of geno- and cytotoxicity were detected in mussels. In G. oceanicus, the ADS responses followed a similar pattern to those recorded in M. trossulus at day 4; however, in G. oceanicus, the elevated ADS response was still maintained at day 11. Conclusively, the results obtained show marked biomarker responses in both study species under conceivable, environmentally realistic oil-in-seawater concentrations during an oil spill, and in mussels, they are related to the observed tissue accumulation of oil-derived compounds.

Assessment of soil contamination by oil-derived compounds in the Kielce agglomeration using gas chromatography coupled with mass spectrometry (GC-MS)

Soil contamination with petroleum-derived compounds is one of the most serious ecological problems. Their main source in urbanized areas is public transport. According to the Regulation of the Polish Minister of Environment about the assessment of earth’s surface contamination, hydrocarbon compounds are divided into: gasolines and oils, aromatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs). The subject of the research is the use of a gas chromatography coupled with mass spectrometry (GC-MS) method to assess the degree of soil contamination in the vicinity of the main communication routes of the Kielce agglomeration. This method is useful for the detection and identification of many organic compounds occurring in samples in very small quantities, which cannot be determined by common methods. For the purpose of this study, 14 soil samples were collected. After carrying out extraction with various methods, the ultrasonic solvent extraction method was chosen as the most effective way of extracting hydrocarbon impurities for the GC-MS studies. During single analysis, both oil fraction and PAHs quantities were determined.

Oleocanthal and oleacein contribute to the in vitro therapeutic potential of extra virgin oil-derived extracts in non-melanoma skin cancer

Although the anticancer properties of extra virgin olive oil (EVOO) extracts have been recognized, the role of single compounds in non-melanoma skin cancer is still unknown. The in vitro chemopreventive and anticancer action of EVOO extracts and oil-derived compounds in non-melanoma skin cancer models were evaluated on cutaneous squamous cell carcinoma cells and on immortalized human keratinocytes stimulated with epidermal growth factor. Preparation of EVOO extracts and isolation of single compounds was carried out by chromatographic methods. Antitumor activity was assessed by cell-based assays (cell viability, migration, clonogenicity, and spheroid formation) and apoptosis documented by internucleosomal DNA fragmentation. Finally, inhibition of key oncogenic signaling nodes involved in the progression from actinic keratosis to cutaneous squamous cell carcinoma was studied by western blot. EVOO extracts reduced non-melanoma skin cancer cell viability and migration, prevented colony and spheroid formation, and inhibited proliferation of atypical keratinocytes stimulated with epidermal growth factor. Such a pharmacological activity was promoted by oleocanthal and oleacein through the inhibition of Erk and Akt phosphorylation and the suppression of B-Raf expression, whereas tyrosol and hydroxytyrosol did not have effect. The current study provides in vitro evidence for new potential clinical applications of EVOO extracts and/or single oil-derived compounds in the prevention and treatment of non-melanoma skin cancers.

How Persistent and Bioavailable Are Oxygenated Deepwater Horizon Oil Transformation Products?

About half of the surface oil floating on the Gulf of Mexico in the aftermath of the 2010 Deepwater Horizon spill was transformed into oxygenated hydrocarbons (OxHC) within days to weeks. These OxHC persist for years in oil/sand aggregates in nearshore and beach environments, and there is concern that these aggregates might represent a long-term source of toxic compounds. However, because this OxHC fraction is a continuum of transformation products that are not well chemically characterized, it is not included in current oil spill fate and effect models. This challenges an accurate environmental risk assessment of weathered oil. Here, we used molecular and bulk analytical techniques to constrain the chemical composition and environmental fate of weathered oil samples collected on the sea surface and beaches of the Gulf of Mexico. We found that approximately 50% of the weathering-related disappearance of saturated and aromatic compounds in these samples was compensated by an increase in OxHC. Furthermore, we identified and quantified a suite of oxygenated aliphatic compounds that are more water-soluble and less hydrophobic than its presumed precursors, but only represent <1% of the oil residues' mass. Lastly, dissolution experiments showed that compounds in the OxHC fraction can leach into the water; however, the mass loss of this process is small. Overall, this study shows that the OxHC fraction is prevalent and persistent in weathered oil/sand aggregates, which can act as a long-term source of dissolved oil-derived compounds.

Identifying oil/marine snow associations in mesocosm simulations of the Deepwater Horizon oil spill event using solid-state 13C NMR spectroscopy

The Deepwater Horizon oil spill stimulated the release of marine snow made up of dead/living plankton/bacteria and their exopolymeric polysaccharide substances (EPS), termed marine oil snow (MOS), promoting rapid removal of oil from the water column into sediments near the well site. Mesocosm simulations showed that Macondo surrogate oil readily associates with the marine snow. Quantitative solid-state 13C NMR readily distinguishes this oil from naturally formed marine snow and reveals that adding the dispersant Corexit enhances the amount of oil associated with the MOS, thus contributing to rapid removal from the water column. Solvent extraction of MOS removes the oil-derived compounds for analysis by one and two-dimensional GC/MS and evaluation of potential transformations they undergo when associated with the EPS. The results reveal that the oil associated with EPS is subjected to rapid transformation, in a matter of days, presumably by bacteria and fungi associated with EPS.

De novo assembly of a transcriptome from juvenile blue crabs (Callinectes sapidus) following exposure to surrogate Macondo crude oil

BackgroundThe blue crab, Callinectes sapidus, is economically and ecologically important in western Atlantic and Gulf of Mexico coastal estuaries. In 2010 blue crabs in the northern Gulf of Mexico were exposed to crude oil and chemical dispersants from the Deepwater Horizon oil spill. To characterize the blue crab transcriptome and identify genes that could be regulated in response to oil exposure we sequenced transcriptomes from hepatopancreas and gill tissues of juvenile blue crabs after exposing them to a water-accommodated fraction of surrogate Macondo crude oil in the laboratory and compared them to transcriptomes from an unexposed control group.ResultsIllumina sequencing provided 42.5 million paired-end sequencing reads for the control group and 44.9 million paired-end reads for the treatment group. From these, 73,473 transcripts and 52,663 genes were assembled. Comparison of control and treatment transcriptomes revealed about 100 genes from each tissue type that were differentially expressed. However, a much larger number of transcripts, approximately 2000 from each tissue type, were differentially expressed. Several examples of alternatively spliced transcripts were verified by qPCR, some of which showed significantly different expression patterns. The combined transcriptome from all tissues and individuals was annotated to assign putative gene products to both major gene ontology categories as well as specific roles in responses to cold and heat, metabolism of xenobiotic compounds, defence, hypoxia, osmoregulation and ecdysis. Among the annotations for upregulated and alternatively-spliced genes were candidates for the metabolism of oil-derived compounds.ConclusionsPreviously, few genomic resources were available for blue crabs or related brachyuran crabs. The transcriptome sequences reported here represent a major new resource for research on the biology of blue crabs. These sequences can be used for studies of differential gene expression or as a source of genetic markers. Genes identified and annotated in this study include candidates for responses of the blue crab to xenobiotic compounds, which could serve as biomarkers for oil exposure. Changes in gene expression also suggest other physiological changes that may occur as the result of exposure to oil.Electronic supplementary materialThe online version of this article (doi:10.1186/s12864-015-1739-2) contains supplementary material, which is available to authorized users.

Use of multiple cell and tissue-level biomarkers in mussels collected along two gas fields in the northern Adriatic Sea as a tool for long term environmental monitoring

As a consequence of the growing global demand of energy supplies, intense oil and gas exploration and exploitation programs have been carried out worldwide especially within the marine environments. The release of oil-derived compounds in the sea from anthropogenic sources both as effluents or accidental spill is perceived as a major environmental concern. An approach based on a combination of biomarkers and the distribution of some classes of environmentally relevant pollutants was used to investigate the occurrence of a stress syndrome in mussels (Mytilus galloprovincialis) collected at three gas platforms placed in two distinct oceanographic districts within the Adriatic Sea. Biological responses were integrated by a ranking algorithm which demonstrated both a range of biological effects reflecting exposure gradients and a temporal related trend in the investigated responses. The overall results demonstrate a moderate to absent pollution from studied gas platforms with low but remarkable biological disturbance in sentinel organisms.

Contact and fumigant toxicity of Armoracia rusticana essential oil, allyl isothiocyanate and related compounds to Dermatophagoides farinae

The toxicity to adult Dermatophagoides farinae of allyl isothiocyanate identified in horseradish, Armoracia rusticana, oil and another 27 organic isothiocyanates was evaluated using contact + fumigant and vapour-phase mortality bioassays. Results were compared with those of two conventional acaricides, benzyl benzoate and dibutyl phthalate. Horseradish oil (24 h LC(50), 1.54 µg cm(-2)) and allyl isothiocyanate (2.52 µg cm(-2)) were highly toxic. Benzyl isothiocyanate (LC(50) , 0.62 µg cm(-2)) was the most toxic compound, followed by 4-chlorophenyl, 3-bromophenyl, 3,5-bis(trifluoromethyl)phenyl, cyclohexyl, 2-chlorophenyl, 4-bromophenyl and 2-bromophenyl isothiocyanates (0.93-1.41 µg cm(-2)). All were more effective than either benzyl benzoate (LC(50) , 4.58 µg cm(-2)) or dibutyl phthalate (24.49 µg cm(-2)). The structure-activity relationship indicates that types of functional group and chemical structure appear to play a role in determining the isothiocyanate toxicities to adult D. farinae. In the vapour-phase mortality bioassay, these isothiocyanates were consistently more toxic in closed versus open containers, indicating that their mode of delivery was, in part, a result of vapour action. In the light of global efforts to reduce the level of highly toxic synthetic acaricides in indoor environments, the horseradish oil-derived compounds and the isothiocyanates described herein merit further study as potential acaricides for the control of house dust mite populations as fumigants with contact action.

The immune response of juvenile Atlantic cod ( Gadus morhua L.) to chronic exposure to produced water

Produced water (PW) is the main discharge from the offshore oil industry and contains oil-derived compounds such as poly-aromatic hydrocarbons, phenols, alkylphenols, and heavy metals. Studies suggest that PW discharges may affect the biota over larger areas from the oil drilling sites at sea than originally predicted. We investigated the effects of chronic exposure to PW on some aspects of juvenile Atlantic cod immunity, stress response and growth by intermittently exposing fish to 0, 100 or 200 ppm of PW for 22 weeks. No significant effects of PW were observed on growth, hepatosomatic index, condition factor or plasma cortisol. The respiratory burst (RB) of circulating leukocytes was significantly elevated in the 100 ppm group only, while the RB of head–kidney leukocytes was significantly decreased in both the 100 and 200 ppm groups. Significant up-regulation of the mRNA expression of β-2-microglobulin, immunoglobulin-M light chain and interleukins-1β and −8 was observed in the 200 ppm group, while the down-regulation of interferon stimulated gene 15 was obvious for both the 100 and 200 ppm groups. The results suggest that chronic exposure to environmentally relevant concentrations of PW causes modulations of the immune system of juvenile Atlantic cod with most immune parameters being stimulated, potentially resulting in an energetic cost that may be detrimental to the fish.

Cytotoxic and antiproliferative effects induced by a non terpenoid polar extract of A. indica seeds on 3T6 murine fibroblasts in culture

Neem oil is a natural product obtained from the seeds of the tree Azadirachta indica. Its composition is very complex and the oil exhibits a number of biological activities. The most studied component is the terpenoid azadirachtin which is used for its insecticidal and putative antimicrobial properties. In this report we investigate the biological activity of partially purified components of the oil obtained from A. indica. We show that the semi-purified fractions have moderate to strong cytotoxicity. However, this is not attributable to azadirachtin but to other active compounds present in the mixture. Each fraction was further purified by appropriate extraction procedures and we observed a differential cytotoxicity in the various sub-fractions. This led us to investigate the mode of cell death. After treatment with the oil fractions we observed positivity to TUNEL staining and extensive internucleosomal DNA degradation both indicating apoptotic death. The anti-proliferative properties of the neem oil-derived compounds were also assayed by evaluation of the nuclear PCNA levels (Proliferating Cell Nuclear Antigen). PCNA is significantly reduced in cells treated with a specific fraction of neem oil. Finally, our results strongly suggest a possible involvement of the mitochondrial pathway in the apoptotic death.

Ovicidal and adulticidal effects of Eugenia caryophyllata bud and leaf oil compounds on Pediculus capitis.

The toxicity of Eugenia caryophyllata bud and leaf oil-derived compounds (acetyleugenol, beta-caryophyllene, eugenol, alpha-humulene, and methyl salicylate) and congeners of eugenol (isoeugenol and methyleugenol) against eggs and females of Pediculus capitis was examined using direct contact application and fumigation methods and compared with those of the widely used delta-phenothrin and pyrethrum. In a filter paper diffusion bioassay with female P. capitis, the pediculicidal activity of the Eugenia bud and leaf oils was comparable to those of delta-phenothrin and pyrethrum on the basis of LT(50) values at 0.25 mg/cm(2). At 0.25 mg/cm(2), the compound most toxic to female P. capitis was eugenol followed by methyl salicylate. Acetyleugenol, beta-caryophyllene, alpha-humulene, isoeugenol, and methyleugenol were not effective. Eugenol at 0.25 mg/cm(2) was as potent as delta-phenothrin and pyrethrum but was slightly less effective than the pyrethroids at 0.125 mg/cm(2). Against P. capitis eggs, methyl salicylate and eugenol were highly effective at 0.25 and 1.0 mg/cm(2), respectively, whereas little or no activity at 5 mg/cm(2) was observed with the other test compounds as well as with delta-phenothrin and pyrethrum. In fumigation tests with female P. capitis at 0.25 mg/cm(2), eugenol and methyl salicylate were more effective in closed cups than in open ones, indicating that the effect of the compounds was largely due to action in the vapor phase. Neither delta-phenothrin nor pyrethrum exhibited fumigant toxicity. The Eugenia bud and leaf essential oils, particularly eugenol and methyl salicylate, merit further study as potential P. capitis control agents or lead compounds.