Search results for: aromatic solvents
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 725

Search results for: aromatic solvents

575 Photocatalysis with Fe/Ti-Pillared Clays for the Oxofunctionalization of Alkylaromatics by O2

Authors: Houria Rezala, Jose Luis Valverde, Amaya Romero, Alessandra Molinari, Andrea Maldotti

Abstract:

A pillared montmorillonite containing iron doped titania (Fe/Ti-PILC) has been prepared from a natural clay. This material has been characterized by X-ray diffraction, nitrogen adsorption, temperature programmed desorption of ammonia, inductively coupled plasma atomic emission spectroscopy, atomic absorption, and diffuse reflectance UV-VIS spectroscopy. The layer structure of Fe/Ti-PILC resulted to be ordered with an insertion of pillars, which caused a slight increase in the basal spacing of the clay. Its specific surface area was about three times larger than that of the parent Na-montmorillonite due principally to the creation of a remarkable microporous network. The doped material was a robust photocatalyst able to oxidize liquid alkyl aromatics to the corresponding carbonylic derivatives, using O2 as the oxidizing species, at mild pressure and temperature conditions. Accumulation of valuable carbonylic derivatives was possible since their over-oxidation to carbon dioxide was negligible. Fe/Ti-PILC was able to discriminate between toluene and cyclohexane in favor of the aromatic compound with an efficiency that is about three times higher than that of titanium pillared clays (Ti-PILC). It is likely that the addition of iron favored the formation of new acid sites able to interact with the aromatic substrate. Iron doping caused a significant TiO2 visible light-induced activity (wavelength > 400 nm) with only minor negative effects on its performance under UV-light irradiation (wavelength > 290 nm).

Keywords: alkyl aromatics oxidation, heterogeneous photocatalysis, iron doping, pillared clays

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574 Reactive Oxygen Species-Mediated Photoaging Pathways of Ultrafine Plastic Particles under UV Irradiation

Authors: Jiajun Duan, Yang Li, Jianan Gao, Runzi Cao, Enxiang Shang, Wen Zhang

Abstract:

Reactive oxygen species (ROS) generation is considered as an important photoaging mechanism of microplastics (MPs) and nanoplastics (NPs). To elucidate the ROS-induced MP/NP aging processes in water under UV365 irradiation, we examined the effects of surface coatings, polymer types, and grain sizes on ROS generation and photoaging intermediates. Bare polystyrene (PS) NPs generated hydroxyl radicals (•OH) and singlet oxygen (¹O₂), while coated PS NPs (carboxyl-modified PS (PS-COOH), amino-modified PS (PS-NH₂)) and PS MPs generated fewer ROS due to coating scavenging or size effects. Polypropylene, polyethylene, polyvinyl chloride, polyethylene terephthalate, and polycarbonate MPs only generated •OH. For aromatic polymers, •OH addition preferentially occurred at benzene rings to form monohydroxy polymers. Excess •OH resulted in H abstraction, C-C scission, and phenyl ring opening to generate aliphatic ketones, esters, aldehydes, and aromatic ketones. For coated PS NPs, •OH preferentially attacked the surface coatings to result in decarboxylation and deamination reactions. For aliphatic polymers, •OH attack resulted in the formation of carbonyl groups from peracid, aldehyde, or ketone via H abstraction and C-C scission. Moreover, ¹O₂ might participate in phenyl ring opening for PS NPs and coating degradation for coated PS NPs. This study facilitates understanding the ROS-induced weathering process of NPs/MPs in water under UV irradiation.

Keywords: microplastics, nanoplastics, photoaging, reactive oxygen species, surface coating

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573 Polycyclic Aromatic Hydrocarbons: Pollution and Ecological Risk Assessment in Surface Soil of the Tezpur Town, on the North Bank of the Brahmaputra River, Assam, India

Authors: Kali Prasad Sarma, Nibedita Baul, Jinu Deka

Abstract:

In the present study, pollution level of polycyclic aromatic hydrocarbon (PAH) in surface soil of historic Tezpur town located in the north bank of the River Brahmaputra were evaluated. In order to determine the seasonal distribution and concentration level of 16 USEPA priority PAHs surface soil samples were collected from 12 different sampling sites with various land use type. The total concentrations of 16 PAHs (∑16 PAHs) varied from 242.68µgkg-1to 7901.89µgkg-1. Concentration of total probable carcinogenic PAH ranged between 7.285µgkg-1 and 479.184 µgkg-1 in different seasons. However, the concentration of BaP, the most carcinogenic PAH, was found in the range of BDL to 50.01 µgkg-1. The composition profiles of PAHs in 3 different seasons were characterized by following two different types of ring: (1) 4-ring PAHs, contributed to highest percentage of total PAHs (43.75%) (2) while in pre- and post- monsoon season 3- ring compounds dominated the PAH profile, contributing 65.58% and 74.41% respectively. A high PAHs concentration with significant seasonality and high abundance of LMWPAHs was observed in Tezpur town. Soil PAHs toxicity was evaluated taking toxic equivalency factors (TEFs), which quantify the carcinogenic potential of other PAHs relative to BaP and estimate benzo[a]pyrene-equivalent concentration (BaPeq). The calculated BaPeq value signifies considerable risk to contact with soil PAHs. We applied cluster analysis and principal component analysis (PCA) with multivariate linear regression (MLR) to apportion sources of polycyclic aromatic hydrocarbons (PAHs) in surface soil of Tezpur town, based on the measured PAH concentrations. The results indicate that petrogenic and pyrogenic sources are the important sources of PAHs. A combination of chemometric and molecular indices were used to identify the sources of PAHs, which could be attributed to vehicle emissions, a mixed source input, natural gas combustion, wood or biomass burning and coal combustion. Source apportionment using absolute principle component scores–multiple linear regression showed that the main sources of PAHs are 22.3% mix sources comprising of diesel and biomass combustion and petroleum spill,13.55% from vehicle emission, 9.15% from diesel and natural gas burning, 38.05% from wood and biomass burning and 16.95% contribute coal combustion. Pyrogenic input was found to dominate source of PAHs origin with more contribution from vehicular exhaust. PAHs have often been found to co-emit with other environmental pollutants like heavy metals due to similar source of origin. A positive correlation was observed between PAH with Cr and Pb (r2 = 0.54 and 0.55 respectively) in monsoon season and PAH with Cd and Pb (r2 = 0.54 and 0.61 respectively) indicating their common source. Strong correlation was observed between PAH and OC during pre- and post- monsoon (r2=0.46 and r2=0.65 respectively) whereas during monsoon season no significant correlation was observed (r2=0.24).

Keywords: polycyclic aromatic hydrocarbon, Tezpur town, chemometric analysis, ecological risk assessment, pollution

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572 Fluoranthene Removal in Wastewater Using Biological and Physico-Chemical Methods

Authors: Angelica Salmeron Alcocer, Deifilia Ahuatzi Chacon, Felipe Rodriguez Casasola

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Polycyclic aromatic hydrocarbons (PAHs) are produced naturally (forest fires, volcanic eruptions) and human activity (burning fossil fuels). Concern for PAHs is due to their toxic, mutagenic and carcinogenic effects and so pose a potential risk to human health and ecology. Therefore these are considered the most toxic components of oil, they are highly hydrophobic, making them easily depositable on the floor, air and water. One method of removing PAHs of contaminated soil used surfactants such as Tween 80, which it has been reported as less toxic and also increases the solubility of the PAH compared to other surfactants, fluoranthene is a PAH with molecular formula C16H10, its name derives from the fluorescence which presents to UV light. In this paper, a study of the fluoranthene removal solubilized with Tween 80 in synthetic wastewater using a microbial community (isolated from soil of coffee plantations in the state of Veracruz, Mexico) and Fenton oxidation method was performed. The microbial community was able to use both tween 80 and fluoranthene as carbon sources for growth, when the biological treatment in batch culture was applied, 100% of fluoranthene was mineralized, this only occurred at an initial concentration of 100 ppm, but by increasing the initial concentration of fluoranthene the removal efficiencies decay and degradation time increases due to the accumulation of byproducts more toxic or less biodegradable, however when the Fenton oxidation was previously applied to the biological treatment, it was observed that removal of fluoranthene improved because it is consumed approximately 2.4 times faster.

Keywords: fluoranthene, polycyclic aromatic hydrocarbons, biological treatment, fenton oxidation

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571 Recovery of Polyphenolic Phytochemicals From Greek Grape Pomace (Vitis Vinifera L.)

Authors: Christina Drosou, Konstantina E. Kyriakopoulou, Andreas Bimpilas, Dimitrios Tsimogiannis, Magdalini C. Krokida

Abstract:

Rationale: Agiorgitiko is one of the most widely-grown and commercially well-established red wine varieties in Greece. Each year viticulture industry produces a large amount of waste consisting of grape skins and seeds (pomace) during a short period. Grapes contain polyphenolic compounds which are partially transferred to wine during winemaking. Therefore, winery wastes could be an alternative cheap source for obtaining such compounds with important antioxidant activity. Specifically, red grape waste contains anthocyanins and flavonols which are characterized by multiple biological activities, including cardioprotective, anti-inflammatory, anti-carcinogenic, antiviral and antibacterial properties attributed mainly to their antioxidant activity. Ultrasound assisted extraction (UAE) is considered an effective way to recover phenolic compounds, since it combines the advantage of mechanical effect with low temperature. Moreover, green solvents can be used in order to recover extracts intended for used in the food and nutraceutical industry. Apart from the extraction, pre-treatment process like drying can play an important role on the preservation of the grape pomace and the enhancement of its antioxidant capacity. Objective: The aim of this study is to recover natural extracts from winery waste with high antioxidant capacity using green solvents so they can be exploited and utilized as enhancers in food or nutraceuticals. Methods: Agiorgitiko grape pomace was dehydrated by air drying (AD) and accelerated solar drying (ASD) in order to explore the effect of the pre-treatment on the recovery of bioactive compounds. UAE was applied in untreated and dried samples using water and water: ethanol (1:1) as solvents. The total antioxidant potential and phenolic content of the extracts was determined using the 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging assay and Folin-Ciocalteu method, respectively. Finally, the profile of anthocyanins and flavonols was specified using HPLC-DAD analysis. The efficiency of processes was determined in terms of extraction yield, antioxidant activity, phenolic content and the anthocyanins and flavovols profile. Results & Discussion: The experiments indicated that the pre-treatment was essential for the recovery of highly nutritious compounds from the pomace as long as the extracts samples showed higher phenolic content and antioxidant capacity. Water: ethanol (1:1) was considered a more effective solvent on the recovery of phenolic compounds. Moreover, ASD grape pomace extracted with the solvent system exhibited the highest antioxidant activity (IC50=0.36±0.01mg/mL) and phenolic content (TPC=172.68±0.01mgGAE/g dry extract), followed by AD and untreated pomace. The major compounds recovered were malvidin3-O-glucoside and quercetin3-O-glucoside according to the HPLC analysis. Conclusions: Winery waste can be exploited for the recovery of nutritious compounds using green solvents such as water or ethanol. The pretreatment of the pomace can significantly affect the concentration of phenolic compounds, while UAE is considered a highly effective extraction process.

Keywords: agiorgitico grape pomace, antioxidants, phenolic compounds, ultrasound assisted extraction

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570 Molecular Engineering of High-Performance Nanofiltration Membranes from Intrinsically Microporous Poly (Ether-Ether-Ketone)

Authors: Mahmoud A. Abdulhamid

Abstract:

Poly(ether-ether-ketone) (PEEK) has received increased attention due to its outstanding performance in different membrane applications including gas and liquid separation. However, it suffers from a semi-crystalline morphology, bad solubility and low porosity. To fabricate membranes from PEEK, the usage of harsh acid such as sulfuric acid is essential, regardless its hazardous properties. In this work, we report the molecular design of poly(ether-ether-ketones) (iPEEKs) with intrinsic porosity character, by incorporating kinked units into PEEK backbone such as spirobisindane, Tröger's base, and triptycene. The porous polymers were used to fabricate stable membranes for organic solvent nanofiltration application. To better understand the mechanism, we conducted molecular dynamics simulations to evaluate the possible interactions between the polymers and the solvents. Notable enhancement in separation performance was observed confirming the importance of molecular engineering of high-performance polymers. The iPEEKs demonstrated good solubility in polar aprotic solvents, a high surface area of 205–250 m² g⁻¹, and excellent thermal stability. Mechanically flexible nanofiltration membranes were prepared from N-methyl-2-pyrrolidone dope solution at iPEEK concentrations of 19–35 wt%. The molecular weight cutoff of the membranes was fine-tuned in the range of 450–845 g mol⁻¹ displaying 2–6 fold higher permeance (3.57–11.09 L m⁻² h⁻¹ bar⁻¹) than previous reports. The long-term stabilities were demonstrated by a 7 day continuous cross-flow filtration.

Keywords: molecular engineering, polymer synthesis, membrane fabrication, liquid separation

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569 The Metabolite Profiling of Fulvestrant-3 Boronic Acid under Biological Oxidation

Authors: Changde Zhang, Qiang Zhang, Shilong Zheng, Jiawang Liu, Shanchun Guo, Qiu Zhong, Guangdi Wang

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Fulvestrant was approved by FDA to treat breast cancer as a selective estrogen receptor downregulator (SERD) with intramuscular injection administration. ZB716, a fulvestarnt-3 boronic acid, is an SERD with comparable anticancer effect to fulvestrant, but could produce good pharmacokinetic properties under oral administration with mice or rat models. To understand why ZB716 produced much better oral bioavailability, it was proposed that the boronic acid blocked the phase II direct biotransformation with the hydroxyl group on the 3 position of the aromatic ring on fulvestrant. In this study, ZB716 or fulvestrant was incubated with human liver microsome and oxidation cofactor NADPH in vitro. Their metabolites after oxidation were profiled with the Q-Exactive, a high-resolution mass spectrometer. The result showed that ZB716 blocked the forming of hydroxyl groups on its benzene ring except for the oxidation of C-B bond forming fulvestrant in its metabolites, and the concentration of fulvestrant with one more hydroxyl group found in the metabolites from incubation with fulvestrant was about 34 fold high as that formed from incubation with ZB716. Compared to fulvestrant, ZB716 is expected to be much difficult to be further bio-transformed into more hydrophilic compounds, to be difficult excreted out of blood system, and to have longer residence time in blood, which can lead to higher oral bioavailability. This study provided evidence to explain the high bioavailability of ZB716 after oral administration from the perspective of its difficulty of oxidation, a phase I biotransformation, on positions on its aromatic ring.

Keywords: biotransformation, fulvestrant, metabolite profiling, ZB716

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568 Effect of Biostimulants on Downstream Processing of Endophytic Fungi Hosted in Aromatic Plant, Ocimum basicilium

Authors: Kanika Chowdhary, Satyawati Sharma

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Endophytic microbes are hosted inside plants in a symbiotic and hugely benefitting relationship. Exploring agriculturally beneficial endophytes is quite a prospective field of research. In the present work fungal endophytes associated with aromatic plant Ocimum basicilium L. were investigated for biocontrol potential. The anti-plant pathogenic activity of fungal endophytes was tested against causal agent of stem rot Sclerotinia sclerotiorum. 75 endophytic fungi were recovered through culture-dependent approach. Fungal identification was performed both microscopically and by rDNA ITS sequencing. Curvuaria lunata (Sb-6) and Colletotrichum lindemuthianum (Sb-8) inhibited 86% and 72% mycelia growth of S. sclerotinia on Sabouraud dextrose agar medium at 7.4 pH. Small-scale fermentation was carried out on sterilised oatmeal grain medium. In another set of experiment, fungi were grown in oatmeal grain medium amended with certain biostimulants such as aqueous seaweed extract (10% v/w); methanolic seaweed extract (5% v/w); cow urine (20% v/w); biochar (10% w/w) in triplicate along with control of each to ascertain the degree of metabolic difference and anti-plant pathogenic activity induced. Phytochemically extracts of both the fungal isolates showed the presence of flavanoids, phenols, tannins, alkaloids and terpenoids. Ethylacetate extract of C. lunata and C. lindemuthianum suppressed S. sclerotinia conidial germination at IC50 values of 0.514± 0.02 and 0.913± 0.04 mg/ml. Therefore, fungal endophytes of O. basicilium are highly promising bio-resource agent, which can be developed further for sustainable agriculture.

Keywords: endophytic fungi, ocimum basicilium, sclerotinia sclerotiorum, biostimulants

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567 An Efficient and Low Cost Protocol for Rapid and Mass in vitro Propagation of Hyssopus officinalis L.

Authors: Ira V. Stancheva, Ely G. Zayova, Maria P. Geneva, Marieta G. Hristozkova, Lyudmila I. Dimitrova, Maria I. Petrova

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The study describes a highly efficient and low-cost protocol for rapid and mass in vitro propagation of medicinal and aromatic plant species (Hyssopus officinalis L., Lamiaceae). Hyssop is an important aromatic herb used for its medicinal values because of its antioxidant, anti-inflammatory and antimicrobial properties. The protocol for large-scale multiplication of this aromatic plant was developed using young stem tips explants. The explants were sterilized with 0.04% mercuric chloride (HgCl₂) solution for 20 minutes and washing three times with sterile distilled water in 15 minutes. The cultural media was full and half strength Murashige and Skoog medium containing indole-3-butyric acid. Full and ½ Murashige and Skoog media without auxin were used as controls. For each variant 20 glass tubes with two plants were used. In each tube two tip and nodal explants were inoculated. Maximum shoot and root number were obtained on ½ Murashige and Skoog medium supplemented with 0.1 mg L-1 indole-3-butyric acid at the same time after four weeks of culture. The number of shoots per explant and shoot height were considered. The data on rooting percentage, the number of roots per plant and root length were collected after the same cultural period. The highest percentage of survival 85% for this medicinal plant was recorded in mixture of soil, sand and perlite (2:1:1 v/v/v). This mixture was most suitable for acclimatization of all propagated plants. Ex vitro acclimatization was carried out at 24±1 °C and 70% relative humidity under 16 h illuminations (50 μmol m⁻²s⁻¹). After adaptation period, the all plants were transferred to the field. The plants flowered within three months after transplantation. Phenotypic variations in the acclimatized plants were not observed. An average of 90% of the acclimatized plants survived after transferring into the field. All the in vitro propagated plants displayed normal development under the field conditions. Developed in vitro techniques could provide a promising alternative tool for large-scale propagation that increases the number of homologous plants for field cultivation. Acknowledgments: This study was conducted with financial support from National Science Fund at the Bulgarian Ministry of Education and Science, Project DN06/7 17.12.16.

Keywords: Hyssopus officinalis L., in vitro culture, micro propagation, acclimatization

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566 Comparative Analysis on the Evolution of Chlorinated Solvents Pollution in Granular Aquifers and Transition Zones to Aquitards

Authors: José M. Carmona, Diana Puigserver, Jofre Herrero

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Chlorinated solvents belong to the group of nonaqueous phase liquids (DNAPL) and have been involved in many contamination episodes. They are carcinogenic and recalcitrant pollutants that may be found in granular aquifers as: i) pools accumulated on low hydraulic conductivity layers; ii) immobile residual phase retained at the pore-scale by capillary forces; iii) dissolved phase in groundwater; iv) sorbed by particulate organic matter; and v) stored into the matrix of low hydraulic conductivity layers where they penetrated by molecular diffusion. The transition zone between granular aquifers and basal aquitards constitute the lowermost part of the aquifer and presents numerous fine-grained interbedded layers that give rise to significant textural contrasts. These layers condition the transport and fate of contaminants and lead to differences from the rest of the aquifer, given that: i) hydraulic conductivity of these layers is lower; ii) DNAPL tends to accumulate on them; iii) groundwater flow is slower in the transition zone and consequently pool dissolution is much slower; iv) sorbed concentrations are higher in the fine-grained layers because of their higher content in organic matter; v) a significant mass of pollutant penetrates into the matrix of these layers; and vi) this contaminant mass back-diffuses after remediation and the aquifer becomes contaminated again. Thus, contamination sources of chlorinated solvents are extremely more recalcitrant in transition zones, which has far-reaching implications for the environment. The aim of this study is to analyze the spatial and temporal differences in the evolution of biogeochemical processes in the transition zone and in the rest of the aquifer. For this, an unconfined aquifer with a transition zone in the lower part was selected at Vilafant (NE Spain). This aquifer was contaminated by perchloroethylene (PCE) in the 80’s. Distribution of PCE and other chloroethenes in groundwater and porewater was analyzed in: a) conventional piezometers along the plume and in two multilevel wells at the source of contamination; and b) porewater of fine grained materials from cores recovered when drilled the two multilevel wells. Currently, the highest concentrations continue to be recorded in the source area in the transition zone. By contrast, the lowest concentrations in this area correspond to the central part of the aquifer, where flow velocities are higher and a greater washing of the residual phase initially retained has occurred. The major findings of the study were: i) PCE metabolites were detected in the transition zone, where conditions were more reducing than in the rest of the aquifer; ii) however, reductive dechlorination was partial since only the formation of cis-dicholoroethylene (DCE) was reached; iii) In the central part of the aquifer, where conditions were predominantly oxidizing, the presence of nitrate significantly hindered the reductive declination of PCE. The remediation strategies to be implemented should be directed to enhance dissolution of the source, especially in the transition zone, where it is more recalcitrant. For example, by combining chemical and bioremediation methods, already tested at the laboratory scale with groundwater and sediments of this site.

Keywords: chlorinated solvents, chloroethenes, DNAPL, partial reductive dechlorination, PCE, transition zone to basal aquitard

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565 The Studies of the Sorption Capabilities of the Porous Microspheres with Lignin

Authors: M. Goliszek, M. Sobiesiak, O. Sevastyanova, B. Podkoscielna

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Lignin is one of three main constituents of biomass together with cellulose and hemicellulose. It is a complex biopolymer, which contains a large number of functional groups, including aliphatic and aromatic hydroxyl groups, carbohylic groups and methoxy groups in its structure, that is why it shows potential capacities for process of sorption. Lignin is a highly cross-linked polymer with a three-dimentional structure which can provide large surface area and pore volumes. It can also posses better dispersion, diffusion and mass transfer behavior in a field of the removal of, e.g., heavy-metal-ions or aromatic pollutions. In this work emulsion-suspension copolymerization method, to synthesize the porous microspheres of divinylbenzene (DVB), styrene (St) and lignin was used. There are also microspheres without the addition of lignin for comparison. Before the copolymerization, modification lignin with methacryloyl chloride, to improve its reactivity with other monomers was done. The physico-chemical properties of the obtained microspheres, e.g., pore structures (adsorption-desorption measurements), thermal properties (DSC), tendencies to swell and the actual shapes were also studied. Due to well-developed porous structure and the presence of functional groups our materials may have great potential in sorption processes. To estimate the sorption capabilities of the microspheres towards phenol and its chlorinated derivatives the off-line SPE (solid-phase extraction) method is going to be applied. This method has various advantages, including low-cost, easy to use and enables the rapid measurements for a large number of chemicals. The efficiency of the materials in removing phenols from aqueous solution and in desorption processes will be evaluated.

Keywords: microspheres, lignin, sorption, solid-phase extraction

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564 Investigating the Effect of Plant Root Exudates and of Saponin on Polycyclic Aromatic Hydrocarbons Solubilization in Brownfield Contaminated Soils

Authors: Marie Davin, Marie-Laure Fauconnier, Gilles Colinet

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In Wallonia, there are 6,000 estimated brownfields (rising to over 3.5 million in Europe) that require remediation. Polycyclic Aromatic Hydrocarbons (PAHs) are a class of recalcitrant carcinogenic/mutagenic organic compounds of major concern as they accumulate in the environment and represent 17% of all encountered pollutants. As an alternative to environmentally aggressive, expensive and often disruptive soil remediation strategies, a lot of research has been directed to developing techniques targeting organic pollutants. The following experiment, based on the observation that PAHs soil content decreases in the presence of plants, aimed at improving our understanding of the underlying mechanisms involved in phytoremediation. It focusses on plant root exudates and whether they improve PAHs solubilization, which would make them more available for bioremediation by soil microorganisms. The effect of saponin, a natural surfactant found in some plant roots such as members of the Fabaceae family, on PAHs solubilization was also investigated as part of the implementation of the experimental protocol. The experiments were conducted on soil collected from a brownfield in Saint-Ghislain (Belgium) and presenting weathered PAHs contamination. Samples of soil were extracted with different solutions containing either plant root exudates or commercial saponin. Extracted PAHs were determined in the different aqueous solutions using High-Performance Liquid Chromatography and Fluorimetric Detection (HPLC-FLD). Both root exudates of alfalfa (Medicago sativa L.) or red clover (Trifolium pratense L.) and commercial saponin were tested in different concentrations. Distilled water was used as a control. First of all, results show that PAHs are more extracted using saponin solutions than distilled water and that the amounts generally rise with the saponin concentration. However, the amount of each extracted compound diminishes as its molecular weight rises. Also, it appears that passed a certain surfactant concentration, PAHs are less extracted. This suggests that saponin might be investigated as a washing agent in polluted soil remediation techniques, either for ex-situ or in-situ treatments, as an alternative to synthetic surfactants. On the other hand, preliminary results on experiments using plant root exudates also show differences in PAHs solubilization compared to the control solution. Further results will allow discussion as to whether or not there are differences according to the exudates provenance and concentrations.

Keywords: brownfield, Medicago sativa, phytoremediation, polycyclic aromatic hydrocarbons, root exudates, saponin, solubilization, Trifolium pratense

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563 New Off-Line SPE-GC-MS/MS Method for Determination of Mineral Oil Saturated Hydrocarbons/Mineral Oil Hydrocarbons in Animal Feed, Foods, Infant Formula and Vegetable Oils

Authors: Ovanes Chakoyan

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MOH (mineral oil hydrocarbons), which consist of mineral oil saturated hydrocarbons(MOSH) and mineral oil aromatic hydrocarbons(MOAH), are present in various products such as vegetable oils, animal feed, foods, and infant formula. Contamination of foods with mineral oil hydrocarbons, particularly mineral oil aromatic hydrocarbons(MOAH), exhibiting carcinogenic, mutagenic, and hormone-disruptive effects. Identifying toxic substances among the many thousands comprising mineral oils in food samples is a difficult analytical challenge. A method based on an offline-solid phase extraction approach coupled with gas chromatography-triple quadrupole(GC-MS/MS) was developed for the determination of MOSH/MOAH in various products such as vegetable oils, animal feed, foods, and infant formula. A glass solid phase extraction cartridge loaded with 7 g of activated silica gel impregnated with 10 % silver nitrate for removal of olefins and lipids. The MOSH/MOAH fractions were eluated with hexane and hexane: dichloromethane : toluene, respectively. Each eluate was concentrated to 50 µl in toluene and injected on splitless mode into GC-MS/MS. Accuracy of the method was estimated as measurement of recovery of spiked oil samples at 2.0, 15.0, and 30.0 mg kg -1, and recoveries varied from 85 to 105 %. The method was applied to the different types of samples (sunflower meal, chocolate ships, santa milk chocolate, biscuits, infant milk, cornflakes, refined sunflower oil, crude sunflower oil), detecting MOSH up to 56 mg/kg and MOAH up to 5 mg/kg. The limit of quantification(LOQ) of the proposed method was estimated at 0.5 mg/kg and 0.3 mg/kg for MOSH and MOAH, respectively.

Keywords: MOSH, MOAH, GC-MS/MS, foods, solid phase extraction

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562 Typical Characteristics and Compositions of Solvent System in Application of Maceration Technology to Isolate Antioxidative Activated Extract of Natural Products

Authors: Yohanes Buang, Suwari

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Increasing interest of society in use and creation of herbal medicines has encouraged scientists/researchers to establish an ideal method to produce the best quality and quantity of pharmaceutical extracts. To have highest the antioxidative extracts, the method used must be at optimum conditions. Hence, the best method is not only able to provide highest quantity and quality of the isolated pharmaceutical extracts but also it has to be easy to do, simple, fast, and cheap. The characterization of solvents in maceration technique, in present study, involved various variables influencing quantity and quality of the pharmaceutical extracts, such as solvent’s optimum acidity-alkalinity (pH), temperature, concentration, and contact time. The shifting polarity of the solvent by combinations of water with ethanol (70:30) and (50:50) were also performed to completely record the best solvent system in application of maceration technology. Among those three solvents threated within Myrmecodia pendens, as a model of natural product, the results showed that water solvent system with conditions of alkalinity pH, optimum temperature, concentration, and contact time, is the best system to perform the maceration in order to have the highest isolated antioxidative activated extracts. The optimum conditions of the water solvent are at the alkalinity pH 9 up, 30 mg/mL of concentration, 40 min of contact time, 100 °C of temperature, and no ethanol used to replace parts of the water solvent. The present study strongly recommended the best conditions of solvent system to isolate the pharmaceutical extracts of natural products in application of the maceration technology.

Keywords: extracts, herbal medicine, natural product, maceration technique

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561 Isolation, Characterization and Optimization of Alkalophilic and Thermotolerant Lipase from Bacillus subtilis Strain

Authors: Indu Bhushan Sharma, Rashmi Saraswat

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The thermotolerant, solvent stable and alkalophilic lipase producing bacterial strain was isolated from the water sample of the foothills of Trikuta Mountain in Kakryal (Reasi district) in Jammu and Kashmir, India. The lipase-producing microorganisms were screened using tributyrin agar plates. The selected microbe was optimized for maximum lipase production by subjecting to various carbon and nitrogen sources, incubation period and inoculum size. The selected strain was identified as Bacillus subtilis strain kakrayal_1 (BSK_1) using 16S rRNA sequence analysis. Effect of pH, temperature, metal ions, detergents and organic solvents were studied on lipase activity. Lipase was found to be stable over a pH range of 6.0 to 9.0 and exhibited maximum activity at pH 8. Lipolytic activity was highest at 37°C and the enzyme activity remained at 60°C for 24hrs, hence, established as thermo-tolerant. Production of lipase was significantly induced by vegetable oil and the best nitrogen source was found to be peptone. The isolated Bacillus lipase was stimulated by pre-treatment with Mn2+, Ca2+, K+, Zn2+, and Fe2+. Lipase was stable in detergents such as triton X 100, tween 20 and Tween 80. The 100% ethyl acetate enhanced lipase activity whereas, lipase activity were found to be stable in Hexane. The optimization resulted in 4 fold increase in lipase production. Bacillus lipases are ‘generally recognized as safe’ (GRAS) and are industrially interesting. The inducible alkaline, thermo-tolerant lipase exhibited the ability to be stable in detergents and organic solvents. This could be further researched as a potential biocatalyst for industrial applications such as biotransformation, detergent formulation, bioremediation and organic synthesis.

Keywords: bacillus, lipase, thermotolerant, alkalophilic

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560 Phosphorous Acid: An Efficient and Recyclable Liquid Catalyst for the Synthesis of α-Aminophosphonates

Authors: Hellal Abdelkader, Chafaa Salah, Touafri Lasnouni

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A simple, efficient and general method has been developed for the high diastereoselective synthesis of diethyl α-aminophosphonates in water through “one-pot” three-component reaction of aromatic aldehydes, aminophenols and dialkyl phosphites in the presence of a low catalytic amount (10mol%) of phosphorous acid as highly stable catalyst is described.

Keywords: DFT, HOMO-LUMO, phosphonic acid, aminophenols

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559 Back Extraction and Isolation of Alkaloids from Ionic Liquid-Based Extracts

Authors: Rozalina Keremedchieva, Ivan Svinyarov, Milen G. Bogdanov

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In continuation of a research project on the application of ionic liquids (ILs) as an alternative to the conventional organic solvents used in the recovery of value added chemicals of industrial interest1-3 we developed a procedure for back extraction and isolation in pure form of the biologically active alkaloid glaucine from IL-based aqueous solutions. One of the approaches applied was the formation of two-phase systems (IL-ATPS) by the addition of kosmotropic salts to the plant extract. The ability of the salts (Na2CO3, MgSO4, (NH4)2SO4, NaH2PO4) to induce the formation of two-phase systems and the influence of pH value on the partition coefficients of glaucine was comprehensively studied. As a result, it was found that the target alkaloid is preferably partitioned into the IL-rich phase regardless of the pH value of the medium and thus shows the inapplicability of the approach used for the isolation of the target compound from the ionic liquid. However, the results obtained can be used as a platform for the development of an analytical method for the quantitative determination of low concentrations of glaucine in biological samples. We further examined the ability of a series of organic solvents such as diethyl ether, Tert-butylmethyl ether, ethyl acetate, butyl acetate, toluene, chloroform, dichloromethane to recover glaucine form raw IL-based aqueous extracts. Optimal conditions for quantitative extraction of glaucine into chloroform were found from which, after removal of the solvent and subsequent recrystallization from ethanol, the target compound was isolated in a high purity as a hydrobromide salt – The form in which it entrance as an active ingredient in various medicines.

Keywords: natural products, ionic liquids, solid-liquid extraction, liquid-liquid extraction

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558 Biodegradation Ability of Polycyclic Aromatic Hydrocarbon (PAHs) Degrading Bacillus cereus Strain JMG-01 Isolated from PAHs Contaminated Soil

Authors: Momita Das, Sofia Banu, Jibon Kotoky

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Environmental contamination of natural resources with persistent organic pollutants is of great world-wide apprehension. Polycyclic aromatic hydrocarbons (PAHs) are among the organic pollutants, released due to various anthropogenic activities. Due to their toxic, carcinogenic and mutagenic properties, PAHs are of environmental and human concern. Presently, bioremediation has evolved as the most promising biotechnology for cleanup of such contaminants because of its economical and less cost effectiveness. In the present study, distribution of 16 USEPA priority PAHs was determined in the soil samples collected from fifteen different sites of Guwahati City, the Gateway of the North East Region of India. The total concentrations of 16 PAHs (Σ16 PAHs) ranged from 42.7-742.3 µg/g. Higher concentration of total PAHs was found more in the Industrial areas compared to all the sites (742.3 µg/g and 628 µg/g). It is noted that among all the PAHs, Naphthalene, Acenaphthylene, Anthracene, Fluoranthene, Chrysene and Benzo(a)Pyrene were the most available and contain the higher concentration of all the PAHs. Since microbial activity has been deemed the most influential and significant cause of PAH removal; further, twenty-three bacteria were isolated from the most contaminated sites using the enrichment process. These strains were acclimatized to utilize naphthalene and anthracene, each at 100 µg/g concentration as sole carbon source. Among them, one Gram-positive strain (JMG-01) was selected, and biodegradation ability and initial catabolic genes of PAHs degradation were investigated. Based on 16S rDNA analysis, the isolate was identified as Bacillus cereus strain JMG-01. Topographic images obtained using Scanning Electron Microscope (SEM) and Atomic Force Microscope (AFM) at scheduled time intervals of 7, 14 and 21 days, determined the variation in cell morphology during the period of degradation. AFM and SEM micrograph of biomass showed high filamentous growth leading to aggregation of cells in the form of biofilm with reference to the incubation period. The percentage degradation analysis using gas chromatography and mass analyses (GC-MS) suggested that more than 95% of the PAHs degraded when the concentration was at 500 µg/g. Naphthalene, naphthalene-2-methy, benzaldehyde-4-propyl, 1, 2, benzene di-carboxylic acid and benzene acetic acid were the major metabolites produced after degradation. Moreover, PCR experiments with specific primers for catabolic genes, ndo B and Cat A suggested that JMG-01 possess genes for PAHs degradation. Thus, the study concludes that Bacillus cereus strain JMG-01 has efficient biodegrading ability and can trigger the clean-up of PAHs contaminated soil.

Keywords: AFM, Bacillus cereus strain JMG-01, degradation, polycyclic aromatic hydrocarbon, SEM

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557 Reusability of Coimmobilized Enzymes

Authors: Aleksandra Łochowicz, Daria Świętochowska, Loredano Pollegioni, Nazim Ocal, Franck Charmantray, Laurence Hecquet, Katarzyna Szymańska

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Multienzymatic cascade reactions are nowadays widely used in pharmaceutical, chemical and cosmetics industries to produce high valuable compounds. They can be carried out in two ways, step by step and one-pot. If two or more enzymes are in the same reaction vessel is necessary to work out the compromise to run the reaction in optimal conditions for each enzyme. So far most of the reports of multienzymatic cascades concern on usage of free enzymes. Unfortunately using free enzymes as catalysts of reactions accomplish high cost. What is more, free enzymes are soluble in solvents which makes reuse impossible. To overcome this obstacle enzymes can be immobilized what provides heterogeneity of biocatalyst that enables reuse and easy separation of the enzyme from solvents and reaction products. Usually, immobilization increase also the thermal and operational stability of enzyme. The advantages of using immobilized multienzymes are enhanced enzyme stability, improved cascade enzymatic activity via substrate channeling, and ease of recovery for reuse. The one-pot immobilized multienzymatic cascade can be carried out in mixed or coimmobilized type. When biocatalysts are coimmobilized on the same carrier the are in close contact to each other which increase the reaction rate and catalytic efficiency, and eliminate the lag time. However, in this type providing the optimal conditions both in the process of immobilization and cascade reaction for each enzyme is complicated. Herein, we examined immobilization of 3 enzymes: D-amino acid oxidase from Rhodotorula gracilis, commercially available catalase and transketolase from Geobacillus stearothermophilus. As a support we used silica monoliths with hierarchical structure of pores. Then we checked their stability and reusability in one-pot cascade of L-erythrulose and hydroxypuryvate acid synthesis.

Keywords: biocatalysts, enzyme immobilization, multienzymatic reaction, silica carriers

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556 Predicting and Obtaining New Solvates of Curcumin, Demethoxycurcumin and Bisdemethoxycurcumin Based on the Ccdc Statistical Tools and Hansen Solubility Parameters

Authors: J. Ticona Chambi, E. A. De Almeida, C. A. Andrade Raymundo Gaiotto, A. M. Do Espírito Santo, L. Infantes, S. L. Cuffini

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The solubility of active pharmaceutical ingredients (APIs) is challenging for the pharmaceutical industry. The new multicomponent crystalline forms as cocrystal and solvates present an opportunity to improve the solubility of APIs. Commonly, the procedure to obtain multicomponent crystalline forms of a drug starts by screening the drug molecule with the different coformers/solvents. However, it is necessary to develop methods to obtain multicomponent forms in an efficient way and with the least possible environmental impact. The Hansen Solubility Parameters (HSPs) is considered a tool to obtain theoretical knowledge of the solubility of the target compound in the chosen solvent. H-Bond Propensity (HBP), Molecular Complementarity (MC), Coordination Values (CV) are tools used for statistical prediction of cocrystals developed by the Cambridge Crystallographic Data Center (CCDC). The HSPs and the CCDC tools are based on inter- and intra-molecular interactions. The curcumin (Cur), target molecule, is commonly used as an anti‐inflammatory. The demethoxycurcumin (Demcur) and bisdemethoxycurcumin (Bisdcur) are natural analogues of Cur from turmeric. Those target molecules have differences in their solubilities. In this way, the work aimed to analyze and compare different tools for multicomponent forms prediction (solvates) of Cur, Demcur and Biscur. The HSP values were calculated for Cur, Demcur, and Biscur using the chemical group contribution methods and the statistical optimization from experimental data. The HSPmol software was used. From the HSPs of the target molecules and fifty solvents (listed in the HSP books), the relative energy difference (RED) was determined. The probability of the target molecules would be interacting with the solvent molecule was determined using the CCDC tools. A dataset of fifty molecules of different organic solvents was ranked for each prediction method and by a consensus ranking of different combinations: HSP, CV, HBP and MC values. Based on the prediction, 15 solvents were selected as Dimethyl Sulfoxide (DMSO), Tetrahydrofuran (THF), Acetonitrile (ACN), 1,4-Dioxane (DOX) and others. In a starting analysis, the slow evaporation technique from 50°C at room temperature and 4°C was used to obtain solvates. The single crystals were collected by using a Bruker D8 Venture diffractometer, detector Photon100. The data processing and crystal structure determination were performed using APEX3 and Olex2-1.5 software. According to the results, the HSPs (theoretical and optimized) and the Hansen solubility sphere for Cur, Demcur and Biscur were obtained. With respect to prediction analyses, a way to evaluate the predicting method was through the ranking and the consensus ranking position of solvates already reported in the literature. It was observed that the combination of HSP-CV obtained the best results when compared to the other methods. Furthermore, as a result of solvent selected, six new solvates, Cur-DOX, Cur-DMSO, Bicur-DOX, Bircur-THF, Demcur-DOX, Demcur-ACN and a new Biscur hydrate, were obtained. Crystal structures were determined for Cur-DOX, Biscur-DOX, Demcur-DOX and Bicur-Water. Moreover, the unit-cell parameter information for Cur-DMSO, Biscur-THF and Demcur-ACN were obtained. The preliminary results showed that the prediction method is showing a promising strategy to evaluate the possibility of forming multicomponent. It is currently working on obtaining multicomponent single crystals.

Keywords: curcumin, HSPs, prediction, solvates, solubility

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555 Photoswitchable and Polar-Dependent Fluorescence of Diarylethenes

Authors: Sofia Lazareva, Artem Smolentsev

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Fluorescent photochromic materials collect strong interest due to their possible application in organic photonics such as optical logic systems, optical memory, visualizing sensors, as well as characterization of polymers and biological systems. In photochromic fluorescence switching systems the emission of fluorophore is modulated between ‘on’ and ‘off’ via the photoisomerization of photochromic moieties resulting in effective resonance energy transfer (FRET). In current work, we have studied both photochromic and fluorescent properties of several diarylethenes. It was found that coloured forms of these compounds are not fluorescent because of the efficient intramolecular energy transfer. Spectral and photochromic parameters of investigated substances have been measured in five solvents having different polarity. Quantum yields of photochromic transformation A↔B ΦA→B and ΦB→A as well as B isomer extinction coefficients were determined by kinetic method. It was found that the photocyclization reaction quantum yield of all compounds decreases with the increase of solvent polarity. In addition, the solvent polarity is revealed to affect fluorescence significantly. Increasing of the solvent dielectric constant was found to result in a strong shift of emission band position from 450 nm (nhexane) to 550 nm (DMSO and ethanol) for all three compounds. Moreover, the emission intensive in polar solvents becomes weak and hardly detectable in n-hexane. The only one exception in the described dependence is abnormally low fluorescence quantum yield in ethanol presumably caused by the loss of electron-donating properties of nitrogen atom due to the protonation. An effect of the protonation was also confirmed by the addition of concentrated HCl in solution resulting in a complete disappearance of the fluorescent band. Excited state dynamics were investigated by ultrafast optical spectroscopy methods. Kinetic curves of excited states absorption and fluorescence decays were measured. Lifetimes of transient states were calculated from the data measured. The mechanism of ring opening reaction was found to be polarity dependent. Comparative analysis of kinetics measured in acetonitrile and hexane reveals differences in relaxation dynamics after the laser pulse. The most important fact is the presence of two decay processes in acetonitrile, whereas only one is present in hexane. This fact supports an assumption made on the basis of steady-state preliminary experiments that in polar solvents occur stabilization of TICT state. Thus, results achieved prove the hypothesis of two channel mechanism of energy relaxation of compounds studied.

Keywords: diarylethenes, fluorescence switching, FRET, photochromism, TICT state

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554 Deasphalting of Crude Oil by Extraction Method

Authors: A. N. Kurbanova, G. K. Sugurbekova, N. K. Akhmetov

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The asphaltenes are heavy fraction of crude oil. Asphaltenes on oilfield is known for its ability to plug wells, surface equipment and pores of the geologic formations. The present research is devoted to the deasphalting of crude oil as the initial stage refining oil. Solvent deasphalting was conducted by extraction with organic solvents (cyclohexane, carbon tetrachloride, chloroform). Analysis of availability of metals was conducted by ICP-MS and spectral feature at deasphalting was achieved by FTIR. High contents of asphaltenes in crude oil reduce the efficiency of refining processes. Moreover, high distribution heteroatoms (e.g., S, N) were also suggested in asphaltenes cause some problems: environmental pollution, corrosion and poisoning of the catalyst. The main objective of this work is to study the effect of deasphalting process crude oil to improve its properties and improving the efficiency of recycling processes. Experiments of solvent extraction are using organic solvents held in the crude oil JSC “Pavlodar Oil Chemistry Refinery. Experimental results show that deasphalting process also leads to decrease Ni, V in the composition of the oil. One solution to the problem of cleaning oils from metals, hydrogen sulfide and mercaptan is absorption with chemical reagents directly in oil residue and production due to the fact that asphalt and resinous substance degrade operational properties of oils and reduce the effectiveness of selective refining of oils. Deasphalting of crude oil is necessary to separate the light fraction from heavy metallic asphaltenes part of crude oil. For this oil is pretreated deasphalting, because asphaltenes tend to form coke or consume large quantities of hydrogen. Removing asphaltenes leads to partly demetallization, i.e. for removal of asphaltenes V/Ni and organic compounds with heteroatoms. Intramolecular complexes are relatively well researched on the example of porphyinous complex (VO2) and nickel (Ni). As a result of studies of V/Ni by ICP MS method were determined the effect of different solvents-deasphalting – on the process of extracting metals on deasphalting stage and select the best organic solvent. Thus, as the best DAO proved cyclohexane (C6H12), which as a result of ICP MS retrieves V-51.2%, Ni-66.4%? Also in this paper presents the results of a study of physical and chemical properties and spectral characteristics of oil on FTIR with a view to establishing its hydrocarbon composition. Obtained by using IR-spectroscopy method information about the specifics of the whole oil give provisional physical, chemical characteristics. They can be useful in the consideration of issues of origin and geochemical conditions of accumulation of oil, as well as some technological challenges. Systematic analysis carried out in this study; improve our understanding of the stability mechanism of asphaltenes. The role of deasphalted crude oil fractions on the stability asphaltene is described.

Keywords: asphaltenes, deasphalting, extraction, vanadium, nickel, metalloporphyrins, ICP-MS, IR spectroscopy

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553 Densities and Volumetric Properties of {Difurylmethane + [(C5 – C8) N-Alkane or an Amide]} Binary Systems at 293.15, 298.15 and 303.15 K: Modelling Excess Molar Volumes by Prigogine-Flory-Patterson Theory

Authors: Belcher Fulele, W. A. A. Ddamba

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Study of solvent systems contributes to the understanding of intermolecular interactions that occur in binary mixtures. These interactions involves among others strong dipole-dipole interactions and weak van de Waals interactions which are of significant application in pharmaceuticals, solvent extractions, design of reactors and solvent handling and storage processes. Binary mixtures of solvents can thus be used as a model to interpret thermodynamic behavior that occur in a real solution mixture. Densities of pure DFM, n-alkanes (n-pentane, n-hexane, n-heptane and n-octane) and amides (N-methylformamide, N-ethylformamide, N,N-dimethylformamide and N,N-dimethylacetamide) as well as their [DFM + ((C5-C8) n-alkane or amide)] binary mixtures over the entire composition range, have been reported at temperature 293.15, 298.15 and 303.15 K and atmospheric pressure. These data has been used to derive the thermodynamic properties: the excess molar volume of solution, apparent molar volumes, excess partial molar volumes, limiting excess partial molar volumes, limiting partial molar volumes of each component of a binary mixture. The results are discussed in terms of possible intermolecular interactions and structural effects that occur in the binary mixtures. The variation of excess molar volume with DFM composition for the [DFM + (C5-C7) n-alkane] binary mixture exhibit a sigmoidal behavior while for the [DFM + n-octane] binary system, positive deviation of excess molar volume function was observed over the entire composition range. For each of the [DFM + (C5-C8) n-alkane] binary mixture, the excess molar volume exhibited a fall with increase in temperature. The excess molar volume for each of [DFM + (NMF or NEF or DMF or DMA)] binary system was negative over the entire DFM composition at each of the three temperatures investigated. The negative deviations in excess molar volume values follow the order: DMA > DMF > NEF > NMF. Increase in temperature has a greater effect on component self-association than it has on complex formation between molecules of components in [DFM + (NMF or NEF or DMF or DMA)] binary mixture which shifts complex formation equilibrium towards complex to give a drop in excess molar volume with increase in temperature. The Prigogine-Flory-Patterson model has been applied at 298.15 K and reveals that the free volume is the most important contributing term to the excess experimental molar volume data for [DFM + (n-pentane or n-octane)] binary system. For [DFM + (NMF or DMF or DMA)] binary mixture, the interactional term and characteristic pressure term contributions are the most important contributing terms in describing the sign of experimental excess molar volume. The mixture systems contributed to the understanding of interactions of polar solvents with proteins (amides) with non-polar solvents (alkanes) in biological systems.

Keywords: alkanes, amides, excess thermodynamic parameters, Prigogine-Flory-Patterson model

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552 Fabricating Method for Complex 3D Microfluidic Channel Using Soluble Wax Mold

Authors: Kyunghun Kang, Sangwoo Oh, Yongha Hwang

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PDMS (Polydimethylsiloxane)-based microfluidic device has been recently applied to area of biomedical research, tissue engineering, and diagnostics because PDMS is low cost, nontoxic, optically transparent, gas-permeable, and especially biocompatible. Generally, PDMS microfluidic devices are fabricated by conventional soft lithography. Microfabrication requires expensive cleanroom facilities and a lot of time; however, only two-dimensional or simple three-dimensional structures can be fabricated. In this study, we introduce fabricating method for complex three-dimensional microfluidic channels using soluble wax mold. Using the 3D printing technique, we firstly fabricated three-dimensional mold which consists of soluble wax material. The PDMS pre-polymer is cast around, followed by PDMS casting and curing. The three-dimensional casting mold was removed from PDMS by chemically dissolved with methanol and acetone. In this work, two preliminary experiments were carried out. Firstly, the solubility of several waxes was tested using various solvents, such as acetone, methanol, hexane, and IPA. We found the combination between wax and solvent which dissolves the wax. Next, side effects of the solvent were investigated during the curing process of PDMS pre-polymer. While some solvents let PDMS drastically swell, methanol and acetone let PDMS swell only 2% and 6%, respectively. Thus, methanol and acetone can be used to dissolve wax in PDMS without any serious impact. Based on the preliminary tests, three-dimensional PDMS microfluidic channels was fabricated using the mold which was printed out using 3D printer. With the proposed fabricating technique, PDMS-based microfluidic devices have advantages of fast prototyping, low cost, optically transparence, as well as having complex three-dimensional geometry. Acknowledgements: This research was supported by Supported by a Korea University Grant and Basic Science Research Program through the National Research Foundation of Korea(NRF).

Keywords: microfluidic channel, polydimethylsiloxane, 3D printing, casting

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551 Removal of Polycyclic Aromatic Hydrocarbons Present in Tyre Pyrolytic Oil Using Low Cost Natural Adsorbents

Authors: Neha Budhwani

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Polycyclic aromatic hydrocarbons (PAHs) are formed during the pyrolysis of scrap tyres to produce tyre pyrolytic oil (TPO). Due to carcinogenic, mutagenic, and toxic properties PAHs are priority pollutants. Hence it is essential to remove PAHs from TPO before utilising TPO as a petroleum fuel alternative (to run the engine). Agricultural wastes have promising future to be utilized as biosorbent due to their cost effectiveness, abundant availability, high biosorption capacity and renewability. Various low cost adsorbents were prepared from natural sources. Uptake of PAHs present in tyre pyrolytic oil was investigated using various low-cost adsor¬bents of natural origin including sawdust (shiham), coconut fiber, neem bark, chitin, activated charcol. Adsorption experiments of different PAHs viz. naphthalene, acenaphthalene, biphenyl and anthracene have been carried out at ambient temperature (25°C) and at pH 7. It was observed that for any given PAH, the adsorption capacity increases with the lignin content. Freundlich constant kf and 1/n have been evaluated and it was found that the adsorption isotherms of PAHs were in agreement with a Freundlich model, while the uptake capacity of PAHs followed the order: activated charcoal> saw dust (shisham) > coconut fiber > chitin. The partition coefficients in acetone-water, and the adsorption constants at equilibrium, could be linearly correlated with octanol–water partition coefficients. It is observed that natural adsorbents are good alternative for PAHs removal. Sawdust of Dalbergia sissoo, a by-product of sawmills was found to be a promising adsorbent for the removal of PAHs present in TPO. It is observed that adsorbents studied were comparable to those of some conventional adsorbents.

Keywords: natural adsorbent, PAHs, TPO, coconut fiber, wood powder (shisham), naphthalene, acenaphthene, biphenyl and anthracene

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550 Degradation of Petroleum Hydrocarbons Using Pseudomonas Aeruginosa Isolated from Oil Contaminated Soil Incorporated into E. coli DH5α Host

Authors: C. S. Jeba Samuel

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Soil, especially from oil field has posed a great hazard for terrestrial and marine ecosystems. The traditional treatment of oil contaminated soil cannot degrade the crude oil completely. So far, biodegradation proves to be an efficient method. During biodegradation, crude oil is used as the carbon source and addition of nitrogenous compounds increases the microbial growth, resulting in the effective breakdown of crude oil components to low molecular weight components. The present study was carried out to evaluate the biodegradation of crude oil by hydrocarbon-degrading microorganism Pseudomonas aeruginosa isolated from natural environment like oil contaminated soil. Pseudomonas aeruginosa, an oil degrading microorganism also called as hydrocarbon utilizing microorganism (or “HUM” bug) can utilize crude oil as sole carbon source. In this study, the biodegradation of crude oil was conducted with modified mineral basal salt medium and nitrogen sources so as to increase the degradation. The efficacy of the plasmid from the isolated strain was incorporated into E.coli DH5 α host to speed up the degradation of oil. The usage of molecular techniques has increased oil degradation which was confirmed by the degradation of aromatic and aliphatic rings of hydrocarbons and was inferred by the lesser number of peaks in Fourier Transform Infrared Spectroscopy (FTIR). The gas chromatogram again confirms better degradation by transformed cells by the lesser number of components obtained in the oil treated with transformed cells. This study demonstrated the technical feasibility of using direct inoculation of transformed cells onto the oil contaminated region thereby leading to the achievement of better oil degradation in a shorter time than the degradation caused by the wild strain.

Keywords: biodegradation, aromatic rings, plasmid, hydrocarbon, Fourier Transform Infrared Spectroscopy (FTIR)

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549 Comparative Correlation Investigation of Polynuclear Aromatic Hydrocarbons (PAHs) in Soils of Different Land Uses: Sources Evaluation Perspective

Authors: O. Onoriode Emoyan, E. Eyitemi Akporhonor, Charles Otobrise

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Polycyclic Aromatic Hydrocarbons (PAHs) are formed mainly as a result of incomplete combustion of organic materials during industrial, domestic activities or natural occurrence. Their toxicity and contamination of terrestrial and aquatic ecosystem have been established. Though with limited validity index, previous research has focused on PAHs isomer pair ratios of variable physicochemical properties in source identification. The objective of this investigation was to determine the empirical validity of Pearson correlation coefficient (PCC) and cluster analysis (CA) in PAHs source identification along soil samples of different land uses. Therefore, 16 PAHs grouped as endocrine disruption substances (EDSs) were determined in 10 sample stations in top and sub soils seasonally. PAHs was determined the use of Varian 300 gas chromatograph interfaced with flame ionization detector. Instruments and reagents used are of standard and chromatographic grades respectively. PCC and CA results showed that the classification of PAHs along kinetically and thermodyanamically-favoured and those derived directly from plants product through biologically mediated processes used in source signature is about the predominance PAHs are likely to be. Therefore the observed PAHs in the studied stations have trace quantities of the vast majority of the sixteen un-substituted PAHs which may ultimately inhabit the actual source signature authentication. Type and extent of bacterial metabolism, transformation products/substrates, and environmental factors such as: salinity, pH, oxygen concentration, nutrients, light intensity, temperature, co-substrates and environmental medium are hereby recommended as factors to be considered when evaluating possible sources of PAHs.

Keywords: comparative correlation, kinetically and thermodynamically-favored PAHs, pearson correlation coefficient, cluster analysis, sources evaluation

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548 HCIO4-SiO2 Nanoparticles as an Efficient Catalyst for Three-Component Synthesis of Triazolo[1,2-A]Indazole-Triones

Authors: Hossein Anaraki-Ardakani, Tayebe Heidari-Rakati

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An environmentally benign protocol for the one-pot, three-component synthesis of Triazolo[1,2-a]indazole-1,3,8-trione derivatives by condensation of dimedone, urazole and aromatic aldehydes catalyzed by HClO4/SiO2 NPS as an ecofriendly catalyst with high catalytic activity and reusability at 100 ºC under solvent-free conditions is reported. The reaction proceeds to completion within 20-30 min in 77-86 % yield.

Keywords: one-pot reaction, dimedone, triazoloindazole, urazole

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547 Oil-Oil Correlation Using Polar and Non-Polar Fractions of Crude Oil: A Case Study in Iranian Oil Fields

Authors: Morteza Taherinezhad, Ahmad Reza Rabbani, Morteza Asemani, Rudy Swennen

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Oil-oil correlation is one of the most important issues in geochemical studies that enables to classify oils genetically. Oil-oil correlation is generally estimated based on non-polar fractions of crude oil (e.g., saturate and aromatic compounds). Despite several advantages, the drawback of using these compounds is their susceptibility of being affected by secondary processes. The polar fraction of crude oil (e.g., asphaltenes) has similar characteristics to kerogen, and this structural similarity is preserved during migration, thermal maturation, biodegradation, and water washing. Therefore, these structural characteristics can be considered as a useful correlation parameter, and it can be concluded that asphaltenes from different reservoirs with the same genetic signatures have a similar origin. Hence in this contribution, an integrated study by using both non-polar and polar fractions of oil was performed to use the merits of both fractions. Therefore, five oil samples from oil fields in the Persian Gulf were studied. Structural characteristics of extracted asphaltenes were investigated by Fourier transform infrared (FTIR) spectroscopy. Graphs based on aliphatic and aromatic compounds (predominant compounds in asphaltenes structure) and sulphoxide and carbonyl functional groups (which are representatives of sulphur and oxygen abundance in asphaltenes) were used for comparison of asphaltenes structures in different samples. Non-polar fractions were analyzed by GC-MS. The study of asphaltenes showed the studied oil samples comprise two oil families with distinct genetic characteristics. The first oil family consists of Salman and Reshadat oil samples, and the second oil family consists of Resalat, Siri E, and Siri D oil samples. To validate our results, biomarker parameters were employed, and this approach completely confirmed previous results. Based on biomarker analyses, both oil families have a marine source rock, whereby marl and carbonate source rocks are the source rock for the first and the second oil family, respectively.

Keywords: biomarker, non-polar fraction, oil-oil correlation, petroleum geochemistry, polar fraction

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546 Isolation, Selection and Identification of Bacteria for Bioaugmentation of Paper Mills White Water

Authors: Nada Verdel, Tomaz Rijavec, Albin Pintar, Ales Lapanje

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Objectives: White water circuits of woodfree paper mills contain suspended, dissolved, and colloidal particles, such as cellulose, starch, paper sizings, and dyes. By closing the white water circuits, these particles start to accumulate and affect the production. Due to high amount of organic matter that scavenge radicals and adsorbs onto catalyst surfaces, treatment of white water with photocatalysis is inappropriate. The most suitable approach should be bioaugmentation-assisted bioremediation. Accordingly, objectives were: - to isolate bacteria capable of degrading organic compounds used for the papermaking process - to select the most active bacteria for bioaugmentation. Status: The state-of-the-art of bioaugmentation of pulp and paper mill effluents is mostly based on biodegradation of lignin. Whereas in white water circuits of woodfree paper mills only papermaking compounds are present. As far as one can tell from the literature, the study on degradation activities of bacteria for all possible compounds of the papermaking process is a novelty. Methodology: The main parameters of the selected white water were systematically analyzed during a period of two months. Bacteria were isolated on selective media with particular carbon source. Organic substances used as carbon source either enter white water circuits as base paper or as recycled broke. The screening of bacterial activities for starch, cellulose, latex, polyvinyl alcohol, alkyl ketene dimers, and resin acids was followed by addition of lugol. Degraders of polycyclic aromatic dyes were selected by cometabolism tests; cometabolism is simultaneous biodegradation of two compounds, in which the degradation of the second compound depends on the presence of the first. The obtained strains were identified by 16S rRNA sequencing. Findings: 335 autochthonous strains were isolated on plates with selected carbon source. The isolated strains were selected according to degradation of the particular carbon source. The ultimate degraders of cationic starch, cellulose, and sizings are Pseudomonas sp. NV-CE12-CF and Aeromonas sp. NV-RES19-BTP. The most active strains capable of degrading azo dyes are Aeromonas sp. NV-RES19-BTP and Sphingomonas sp. NV-B14-CF. Klebsiella sp. NV-Y14A-BTP degrade polycyclic aromatic direct blue 15 and also yellow dye, Agromyces sp. NV-RED15A-BF and Cellulosimicrobium sp. NV-A4-BF are specialists for whitener and Aeromonas sp. NV-RES19-BTP is general degrader of all compounds. To the white water adapted bacteria were isolated and selected according to their degradation activities for particular organic substances. Mostly isolated bacteria are specialized to lower the competition in the microbial community. Degraders of readily-biodegradable compounds do not degrade recalcitrant polycyclic aromatic dyes and vice versa. General degraders are rare.

Keywords: bioaugmentation, biodegradation of azo dyes, cometabolism, smart wastewater treatment technologies

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