Search results for: chlorinated solvents

Authors: Maria Bercea, Bernhard A. Wolf

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The thermodynamic behavior for solutions of poly (methyl methacrylate-ran-t-butyl methacrylate) of variable composition as compared with the corresponding homopolymers was investigated by light scattering measurements carried out for dilute solutions and vapor pressure measurements of concentrated solutions. The complex dependencies of the Flory Huggins interaction parameter on concentration and copolymer composition in solvents of different polarity (toluene and chloroform) can be understood by taking into account the ability of the polymers to rearrange in a response to changes in their molecular surrounding. A recent unified thermodynamic approach was used for modeling the experimental data, being able to describe the behavior of the different solutions by means of two adjustable parameters, one representing the effective number of solvent segments and another one accounting for the interactions between the components. Thus, it was investigated how the solvent quality changes with the composition of the copolymers through the Gibbs energy of mixing as a function of polymer concentration. The largest reduction of the Gibbs energy at a given composition of the system was observed for the best solvent. The present investigation proves that the new unified thermodynamic approach is a general concept applicable to homo- and copolymers, independent of the chain conformation or shape, molecular and chemical architecture of the components and of other dissimilarities, such as electrical charges.

Keywords: random copolymers, Flory Huggins interaction parameter, Gibbs energy of mixing, chemical architecture

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Authors: M. K. Bin Subhan, P. Cullen, C. Howard

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A recent study by the World Corrosion Organization estimated that corrosion related damage causes $2.5tr worth of damage every year. As such, a low cost easily scalable solution is required to the corrosion problem which is economically viable. Graphene is an ideal anti-corrosion barrier layer material due to its excellent barrier properties and chemical stability, which makes it impermeable to all molecules. However, attempts to employ graphene as a barrier layer has been hampered by the fact that defect sites in graphene accelerate corrosion due to the inert nature of graphene which promotes galvanic corrosion at the expense of the metal. The recent discovery of spontaneous dissolution of charged graphite intercalation compounds in aprotic solvents enables defect free graphene platelets to be employed for anti-corrosion applications. These ‘inks’ of defect-free charged graphene platelets in solution can be coated onto a metallic surfaces via electroplating to form a homogeneous barrier layer. In this paper, initial data showing homogeneous coatings of graphene barrier layers on steel coupons via electroplating will be presented. This easily scalable technique also provides a controllable method for applying different barrier thicknesses from ultra thin layers to thick opaque coatings making it useful for a wide range of applications.

Keywords: anti-corrosion, defect-free, electroplating, graphene

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Authors: Rihana Hadjeb, Djamel Barkat

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Schiff bases derived from o-hydroxybenzaldehyde has attracted a great interest not only for its promising applications towards linear and non-linear optical properties, biological activity and technological applications but also used as model compounds for the theory of hydrogen bonding. Due to its intramolecular hydrogen bonding, depending on the position of proton in the hydrogen bond o-hydroxy salicylidene Schiff bases exhibit two tautomeric forms, enol-imine (E-form) and keto-enamine (K-form) both in solution and in crystalline state. A zwitterionic structure also appears due to a proton transfer in enol – imine and keto – amine tautomer. These classes of compounds also exhibit thermochromic and photochromic behavior. We undertook in this study the synthesis of ten compounds of hydroxy Schiff bases from the condensation of salicylic aldehyde and aniline substituted in the ortho, meta and para by the methyl, chloro and nitro groups. To study the keto-enol equilibrium of the compounds; UV-VIS spectra were studied in different polarity solvents. The compounds were in tautomeric equilibrium (enol imine O–H•••N, keto-amine O•••H–N forms). For some derivatives of salicylideneanilines the keto-amine form was observed in both ethanol and dioxane. IR results showed that all Schiff bases studied favor the enol-imine form over the keto form.

Keywords: salicylideneaniline, tautomerism, keto-enol equilibrium, UV-VIS spectroscopy, solvent effect

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Authors: Adnan Lanjawi

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This paper is carried out to investigate the management of hazardous waste in the chemistry section which belongs to Dubai Police forensic laboratory. The chemicals are the main contributor toward the accumulation of hazardous waste in the section. This is due to the requirement to use it in analysis, such as of explosives, drugs, inorganic and fire debris cases. This leads to negative effects on the environment and to the employees’ health and safety. The research investigates the quantity of chemicals there, the labels, the storage room and equipment used. The target is to reduce the need for disposal by looking at alternative options, such as elimination, substitution and recycling. The data was collected by interviewing the top managers there who have been working in the lab more than 20 years. Also, data was collected by observing employees and how they carry out experiments. Therefore, a survey was made to assess their knowledge about the hazardous waste. The management of hazardous chemicals in the chemistry section needs to be improved. The main findings illustrate that about 110 bottles of reference substances were going to be disposed of in 2014. These bottles were bought for about 100,000 UAE Dirhams (£17,600). This means that the management of substances purchase is not organised. There is no categorisation programme in place, which makes the waste control very difficult. In addition, the findings show that chemical are segregated according to alphabetical order, whereas the efficient way is to separate them according to their nature and property. In addition, the research suggested technology and experiments to follow to reduce the need for using solvents and chemicals in the sample preparation.

Keywords: control, hazard, laboratories, waste,

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Authors: Xin Zhao

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3D printing is used in creating bone grafts of various architectures by printing materials in a layer-by-layer manner. Traditionally, to make materials printable, heating up or dissolving materials in organic solvents have been used, compromising their capability in loading biomolecules. Photocrosslinkable materials which are initially liquid and printable, and solidified upon light exposure are therefore developed. However, the existing photocrosslinkable materials are either too soft to bear load or non-degradable with potential long-term biocompatibility problems. Here, photocrosslinkable nanocomposite ink is developed composed of poly (lactide-co-propylene glycol-co-lactide) dimethacrylate (PmLnDMA) and hydroxyethyl methacrylate-functionalized hydroxyapatite nanoparticles (nHAMA) mimicking the hairy setae of gecko that can strongly interact with its surroundings to bear high load. Incorporation of nHAMA into PmLnDMA endows the nanocomposite ink with several advantages in (1) improved organic/inorganic interfacial compatibility to increase mechanical strength, (2) readily modulated rheological behaviors, wettability, and biodegradation, (3) enhanced osteoconductivity and osteoinductivity. Moreover, the ink can be rapidly crosslinked upon light exposure, load, and long-term release growth factors, and be printed into 3D bone scaffolds of various shapes and structures according to the patients’ needs. Altogether, this innovation will benefit patients all over the world who suffer from bone fractures, tumors, infections.

Keywords: photocrosslinkable nanocomposite, 3D printing, bone ink, personalized medicine

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Authors: Jawad Alzeer

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Natural products are well recognized as sources of drugs in several human ailments. To investigate the impact of variable extraction techniques on the cytotoxic effects of medicinal plant extracts, 5 well-known medicinal plants from Palestine were extracted with 90% ethanol, 80% methanol, acetone, coconut water, apple vinegar, grape vinegar or 5% acetic acid. The resulting extracts were screened for cytotoxic activities against three different cancer cell lines (B16F10, MCF-7, and HeLa) using a standard resazurin-based cytotoxicity assay and Nile Blue A as the positive control. Highly variable toxicities and tissue sensitivity were observed, depending upon the solvent used for extraction. Acetone consistently gave lower extraction yields but higher cytotoxicity, whereas other solvent systems gave much higher extraction yields with lower cytotoxicity. Interestingly, coconut water was found to offer a potential alternative to classical organic solvents; it gave consistently highest extraction yields, and in the case of S. officinalis L., highly toxic extracts towards MCF-7 cells derived from human breast cancer. These results demonstrate how the cytotoxicity of plant extracts can be inversely proportional to the yield, and that solvent selection plays an important role in both factors.

Keywords: plant extract, natural products, anti cancer drug, cytotoxicity

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Authors: Harshani Uggallage, Kapila D. Dissanayaka

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A Sulforhodamine-B assay-guided fractionation on Nigella sativa seeds was conducted to determine the presence of cytotoxic compounds against human hepatoma (HepG2) cells. Initially, a freeze-dried sample of Nigella sativa seeds was sequentially extracted into solvents of increasing polarities. Crude extracts from the sequential extraction of Nigella sativa seeds in chloroform and ethyl acetate showed the highest cytotoxicity. The combined mixture of these two extracts was subjected to bioassay guided fractionation using a modified Kupchan method of partitioning, followed by Sephadex® LH-20 chromatography. This chromatographic separation process resulted in a column fraction with a convincing IC50 (half-maximal inhibitory concentration) value of 13.07µg/ml, which is considerable for developing therapeutic drug leads against human hepatoma. Reversed phase High-Performance Liquid Chromatography (HPLC) was finally conducted for the same column fraction, and the result indicates the presence of one or several main cytotoxic compounds against human HepG2 cells.

Keywords: cytotoxic compounds, half-maximal inhibitory concentration, high-performance liquid chromatography, human HepG2 cells, nigella sativa seeds, Sulforhodamine-B assay

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Authors: Amanda C. Evans

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Enabling technologies such as continuous processing (CP) approaches can provide the tools needed to control and manipulate reactivities and transform chemical reactions into micro-controlled in-flow processes. Traditional synthetic approaches can be radically transformed by the application of CP, facilitating the pairing of chemical methodologies with technologies from other disciplines. CP supports sustainable processes that controllably generate reaction specificity utilizing supramolecular interactions. Continuous photochemical processing is an emerging field of investigation. The use of light to drive chemical reactivity is not novel, but the controlled use of specific and tunable wavelengths of light to selectively generate molecular structure under continuous processing conditions is an innovative approach towards chemical synthesis. This investigation focuses on the use of circularly polarized (cp) light as a sustainable catalyst for the CP generation of asymmetric molecules. Chiral photolysis has already been achieved under batch, solid-phase conditions: using synchrotron-sourced cp light, asymmetric photolytic selectivities of up to 4.2% enantiomeric excess (e.e.) have been reported. In order to determine the optimal wavelengths to use for irradiation with cp light for any given molecular building block, CD and anisotropy spectra for each building block of interest have been generated in two different solvents (water, hexafluoroisopropanol) across a range of wavelengths (130-400 nm). These spectra are being used to support a series of CP experiments using cp light to generate enantioselectivity.

Keywords: anisotropy, asymmetry, flow chemistry, active pharmaceutical ingredients

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Authors: Maíra O. Palm, Cintia Marangoni, Ozair Souza, Noeli Sellin

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Wastes from a vegetal extracts industry (cocoa, oak, Guarana and mate) were characterized by particle size, proximate and ultimate analysis, lignocellulosic fractions, high heating value, thermal analysis (Thermogravimetric analysis – TGA, and Differential thermal analysis - DTA) and energy density to evaluate their potential as biomass in the form of briquettes for power generation. All wastes presented adequate particle sizes to briquettes production. The wastes showed high moisture content, requiring previous drying for use as briquettes. Cocoa and oak wastes had the highest volatile matter contents with maximum mass loss at 310 ºC and 450 ºC, respectively. The solvents used in the aroma extraction process influenced in the moisture content of the wastes, which was higher for mate due to water has been used as solvent. All wastes showed an insignificant loss mass after 565 °C, hence resulting in low ash content. High carbon and hydrogen contents and low sulfur and nitrogen contents were observed ensuring a low generation of sulfur and nitrous oxides. Mate and cocoa exhibited the highest carbon and lignin content, and high heating value. The dried wastes had high heating value, from 17.1 MJ/kg to 20.8 MJ/kg. The results indicate the energy potential of wastes for use as fuel in power generation.

Keywords: agro-industrial waste, biomass, briquettes, combustion

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Authors: Hassan M. Albishri, Fatimah Al-Shehri, Deia Abd El-Hady

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Among the analytical techniques, reverse phase liquid chromatography (RPLC) is currently used in pharmaceutical industry. Ecofriendly analytical chemistry offers the advantages of decreasing the environmental impact with the advantage of increasing operator safety which constituted a topic of industrial interest. Recently, ionic liquids have been successfully used to reduce or eliminate the conventional organic toxic solvents. In the current work, a simple and ecofriendly ionic liquid modified RPLC (IL-RPLC) method has been firstly developed and compared with RPLC under acidic and neutral mobile phase conditions for simultaneous determination of atorvastatin-calcium, rosuvastatin and simvastatin. Several chromatographic effective parameters have been changed in a systematic way. Adequate results have been achieved by mixing ILs with ethanol as a mobile phase under neutral conditions at 1 mL/min flow rate on C18 column. The developed IL-RPLC method has been validated for the quantitative determination of drugs in pharmaceutical formulations. The method showed excellent linearity for analytes in a wide range of concentrations with acceptable precise and accurate data. The current IL-RPLC technique could have vast applications particularly under neutral conditions for simple and greener (bio)analytical applications of pharmaceuticals.

Keywords: ionic liquid, RPLC, anti-hyperlipidemic drugs, ecofriendly

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Authors: Diana Serbezeanu, Ionela-Daniela Carja, Tachita Vlad-Bubulac, Sergiu Sova

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New phosphorus-containing monomers having methoxy end functional groups were prepared from methyl 4-hydroxybenzoate and two different dichlorides with phosphorus, namely phenyl phosphonic dichloride and phenyl dichlorophosphate. The structures of the monomers were confirmed by FTIR and NMR spectroscopy. The assignments for the 1H, 13C and 31P chemical shifts are based on 1D and 2D NMR homo- and heteronuclear correlations (H,H-COSY (Correlation Spectroscopy), H,C-HMQC (Heteronuclear Multiple Quantum Correlation and H,C-HMBC (Heteronuclear Multiple Bond Correlation)) and 31P-13C couplings. The monomers exhibited good solubility in common organic solvents. Dimethyl sulfoxide was to be a good solvent to grow crystals of considerable size which were investigated by X-ray analysis. One of these two new monomers presented thermotropic liquid crystalline behaviour, as revealed by differential scanning calorimetry (DSC), polarized light microscopy (PLM) and X-ray diffraction (XRD). The transition temperature from crystal to liquid crystalline state (K→LC) was 143°C and from the LC to isotropic state (LC→I) was 167°C. Upon heating, bis(4-(methoxycarbonyl)phenyl formed fine textures, difficult to be ascribed to smectic or nematic phases. Upon cooling from the isotropic state, bis(4-(methoxycarbonyl)phenyl exhibited a mosaic-type texture. X-ray diffraction measurements at small angles (SAXS) of bis(4-(methoxycarbonyl)phenyl showed two peaks at 1.8 Å and 3.5 Å, respectively suggesting organization at supramolecular level.

Keywords: phosphorus-containing monomers, polarized light microscopy, structure investigation, thermotropic liquid crystalline properties

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Authors: Nurlan Akhmetov, Abilmansur Yeshmuratov, Aliya Kurbanova, Gulnar Sugurbekova, Murat Baisariyev

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Extraction of the vanadium and nickel compounds is complex due to the high stability of porphyrin, nickel is catalytic poison which deactivates catalysis during the catalytic cracking of the oil, while vanadyl is abrasive and valuable metal. Thus, high concentration of the Ni and V in the crude oil makes their removal relevant. Two methods of the demetallization of crude oil were tested, therefore, the present research is conducted for comparative analysis of the deasphalting with organic solvents (cyclohexane, carbon tetrachloride, chloroform) and electrochemical method. Percentage of Ni extraction reached maximum of approximately 55% by using the electrochemical method in electrolysis cell, which was developed for this research and consists of three sections: oil and protonating agent (EtOH) solution between two conducting membranes which divides it from two capsules of 10% sulfuric acid and two graphite electrodes which cover all three parts in electrical circuit. Ions of metals pass through membranes and remain in acid solutions. The best result was obtained in 60 minutes with ethanol to oil ratio 25% to 75% respectively, current fits in to the range from 0.3A to 0.4A, voltage changed from 12.8V to 17.3V. Maximum efficiency of deasphalting, with cyclohexane as the solvent, in Soxhlet extractor was 66.4% for Ni and 51.2% for V. Thus, applying the voltammetry, ICP MS (Inductively coupled plasma mass spectrometry) and AAS (atomic absorption spectroscopy), these mentioned types of metal extraction methods were compared in this paper.

Keywords: electrochemistry, deasphalting of crude oil, demetallization of crude oil, petrolium engineering

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Authors: Kaarunya Sampathkumar, Say Chye Joachim Loo

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Oral delivery is regarded as the facile method for the administration of active pharmaceutical ingredients (API) and drug carriers. In an initiative towards sustainable nanotechnology, an oral nano-delivery system has been developed that is made entirely of food-based materials and can also act as a site-specific delivery device depending on the stimulus encountered in different parts of the gastrointestinal tract (GIT). The delivery system has been fabricated from food grade polysaccharide materials like chitosan and starch through electrospraying technique without the use of any organic solvents. A nutraceutical extracted from an Indian medicinal plant, has been loaded into the nano carrier to test its efficacy in encapsulation and stimuli based release of the active ingredient. The release kinetics of the nutraceutical from the carrier was evaluated in simulated gastric, intestinal and colonic fluid and was found to be triggered both by the enzymes and the pH in each part of the intestinal tract depending on the polysaccharide being used. The toxicity of the nanoparticles on the intestinal epithelial cells was tested and found to be relatively safe for up to 24 hours at a concentration of 0.2 mg/mL with cellular uptake also being observed. The developed nano carrier thus serves as a promising delivery vehicle for targeted delivery to different parts of the GIT with the inherent conditions of the GIT itself acting as the stimulus. In addition, being fabricated from food grade materials, the carrier could be potentially used for the targeted delivery of nutrients through functional foods.

Keywords: bioavailability, chitosan, delivery systems, encapsulation

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Authors: Iman Adnan Annon, Kadhim F. Alsultan

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This study investigate the internal corrosion of low carbon steel pipelines in the crude oil, as well as prepare and use natural and locally available plant as a natural corrosion inhibiter, the nature extraction achieved by two types of solvents in order to show the solvent effect on inhibition process, the first being distilled water and the second is diethyl ether. FT-IR spectra and using a chemical reagents achieved to detection the presence of many active groups and the presence of tannins, phenols, and alkaloids in the natural extraction. Some experiments were achieved to estimate the performance of a new inhibitor, one of these tests include corrosion measurement by simple immersion in crude oil within and without inhibitors which added in different amounts 30,40,50and 60 ppm at tow temperature 300 and 323k, where the best inhibition efficiencies which get when added the inhibitors in a critical amounts or closest to it, since for the aqueous extract (EB-A) the inhibition efficiency reached (94.4) and (86.71)% at 300 and 323k respectively, and for diethyl ether extract (EB-D) reached (82.87) and (84.6)% at 300 and 323k respectively. Optical microscopy examination have been conducted to evaluate the corrosion nature where it show a clear difference in the topography of the immersed samples surface after add the inhibitors at two temperatures. The results show that the new corrosion inhibitor is not only equivalent to a chemical inhibitor but has greatly improvement properties such as: high efficiency, low cost, non-toxic, easily to produce, and nonpolluting as compared with chemical inhibitor.

Keywords: corrosion in pipeline, inhibitors, crude oil, carbon steel, types of solvent

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Authors: Trabelsi Mohamed, Kharrat Mohamed, Dammak Maher

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Guide rings play an important role in the performance and durability of hydraulic actuating cylinders. In service, guide rings surfaces are subjected to friction and wear against steel counterface. A good mastery of these phenomena is required for the improvement of the energy safeguard and the durability of the actuating cylinder. Polytetrafluoroethylene (PTFE) polymer is extensively used in guide rings thanks to its low coefficient of friction, its good resistance to solvents as well as its high temperature stability. In this study, friction and wear behavior of two PTFE composites filled with bronze and bronze plus MoS2 were evaluated under oil-lubricated condition, aiming as guide rings for hydraulic actuating cylinder. Wear tests of the PTFE composite specimen sliding against steel ball were conducted using reciprocating linear tribometer. The wear mechanisms of the composites under the same sliding condition were discussed, based on Scanning Electron Microscopy examination of the worn composite surface and the optical micrographs of the steel counter surface. As for the results, comparative friction behaviors of the PTFE composites and lower friction coefficients were recorded under oil lubricated condition. The wear behavior was considerably improved to compare with this in dry sliding, while the oil adsorbed layer limited the transfer of the PTFE to the steel counter face during the sliding test.

Keywords: PTFE, composite, bronze, MoS2, friction, wear, oil-lubrication

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Authors: A. Douka, S. Vouyiouka, L. M. Papaspyridi, D. Korres, C. Papaspyrides

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A "green" process was studied for the preparation of partially renewable aliphatic polyesters based on 1,4-butanediol and 1,8-octanediol with various diacids and derivatives, namely diethyl succinate, adipic acid, sebacic acid, 1,12-dodecanedioic acid and 1,14-tetradecanedioic acid. A first step of enzymatic prepolymerization was carried out in the presence of two different solvents, toluene and diphenylether, applying molecular sieves and vacuum, respectively, to remove polycondensation by-products. Poly(octylene adipate) (PE 8.6), poly(octylene dodecanate)(PE 8.12) and poly(octylene tetradecanate) (PE 8.14) were firstly enzymatically produced in toluene using molecular sieves giving however, low-molecular-weight products. Thereafter, the synthesis of PE 8.12 and PE 8.14 was examined under optimized conditions using diphenylether as solvent and a more vigorous by-product removal step, such as application of vacuum. Apart from these polyesters, the optimized process was also implemented for the production of another long-chain polyester-poly(octylene sebacate) (PE 8.10) and a short-chain polyester-poly(butylene succinate) (PE 4.4). Subsequently, bulk post-polymerization in the melt or solid state was performed. SSP runs involved absence of biocatalyst and reaction temperatures (T) in the vicinity of the prepolymer melting point (Tm-T varied between 15.5 up to 4oC). Focusing on PE 4.4 and PE 8.12, SSP took place under vacuum or flowing nitrogen leading to increase of the molecular weight and improvement of the end product physical appearance and thermal properties.

Keywords: aliphatic polyester, enzymatic polymerization, solid state polymerization, Novozym 435

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Authors: Aleksandrs Kovalcuks, Mara Duma

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Egg yolk oil is a concentrated source of egg bioactive compounds, such as fat-soluble vitamins, phospholipids, cholesterol, carotenoids and others. To extract lipids and other fat-soluble nutrients from liquid egg yolk, a two-step extraction process involving polar (ethanol) and non-polar (hexane) solvents were used. This extraction technique was based on egg yolk bioactive compounds polarities, where non-polar compound was extracted into non-polar hexane, but polar in to polar alcohol/water phase. But many egg yolk bioactive compounds are not strongly polar or non-polar. Egg yolk phospholipids, cholesterol and pigments are amphipatic (have both polar and non-polar regions) and their behavior in ethanol/hexane solvent system is not clear. The aim of this study was to clarify the behavior of phospholipids, cholesterol and carotenoids during extraction of egg yolk oil with ethanol and hexane and determine the loss of these compounds in egg yolk oil. Egg yolks and egg yolk oil were analyzed for phospholipids (phosphatidylcholine (PC) and phosphatidylethanolamine (PE)), cholesterol and carotenoids (lutein, zeaxanthin, canthaxanthin and β-carotene) content using GC-FID and HPLC methods. PC and PE are polar lipids and were extracted into polar ethanol phase. Concentration of PC in ethanol was 97.89% and PE 99.81% from total egg yolk phospholipids. Due to cholesterol’s partial extraction into ethanol, cholesterol content in egg yolk oil was reduced in comparison to its total content presented in egg yolk lipids. The highest amount of lutein and zeaxanthin was concentrated in ethanol extract. The opposite situation was observed with canthaxanthin and β-carotene, which became the main pigments of egg yolk oil.

Keywords: cholesterol, egg yolk oil, lutein, phospholipids, solvent extraction

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Authors: M. Nazim, S. Ameen, H. K. Seo, H. S. Shin

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Energy is the basis of life and strong attention has been growing for the cost-effective energy production. Recently, solution-processed small molecule organic solar cells (SMOSCs) have grown much attention due to the wages such as well-defined molecular structures, definite molecular weight, easy synthesis and easy purification techniques. In particular, the size of donor (D) and acceptor (A) unit is a crucial factor for the exciton-diffusion towards D-A interface and then charge-separation for the effective charge-transport to the electrodes. Furan-bridged materials are more electron-rich, high fluorescence, with better molecular-packing, and greater rigidity and greater solubility than their thiophene-counterparts In this work, a furan-bridged thiazolo[5,4-d]thiazole based organic small molecule (RFTzR) was formulated and applied for BHJ organic solar cells (OSCs). The introduction of furan spacer with two terminal alkyl units improved its absorption and solubility in the common organic solvents, significantly. RFTzR exhibited a HOMO and LUMO energy levels of -5.36 eV and -3.14 eV, respectively. The fabricated solar cell devices of RFTzR (donor) with PC60BM (acceptor) as photoactive materials showed high performance of 2.72% (RFTzR:PC60BM, 2:1, w/w) ratio with open-circuit voltage of 0.756 V and high photocurrent density of 10.13 mA/cm².

Keywords: chromophore, organic solar cells, photoactive materials, small molecule

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Authors: Hanjie Xie, Raphael Semiat, Ziyi Zhong

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It is well known that many oxidation reactions in nature are closely related to the origin and life activities. One of the features of these natural reactions is that they can proceed under mild conditions employing the oxidant of molecular oxygen (O₂) in the air and enzymes as catalysts. Catalysis is also a necessary part of life for human beings, as many chemical and pharmaceutical industrial processes need to use catalysts. However, most heterogeneous catalytic reactions must be run at high operational reaction temperatures and pressures. It is not strange that, in recent years, research interest has been redirected to green catalysis, e.g., trying to run catalytic reactions under relatively mild conditions as much as possible, which needs to employ green solvents, green oxidants such O₂, particularly air, and novel catalysts. This work reports the efficient binary Fe-Mn metal oxide catalysts for low-temperature formaldehyde (HCHO) oxidation, a toxic pollutant in the air, particularly in indoor environments. We prepared a series of nanosized FeMn oxide catalysts and found that when the molar ratio of Fe/Mn = 1:1, the catalyst exhibited the highest catalytic activity. At room temperature, we realized the complete oxidation of HCHO on this catalyst for 20 h with a high GHSV of 150 L g⁻¹ h⁻¹. After a systematic investigation of the catalyst structure and the reaction, we identified the reaction intermediates, including dioxymethylene, formate, carbonate, etc. It is found that the oxygen vacancies and the derived active oxygen species contributed to this high-low-temperature catalytic activity. These findings deepen the understanding of the catalysis of these binary Fe-Mn metal oxide catalysts.

Keywords: oxygen vacancy, catalytic oxidation, binary transition oxide, formaldehyde

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Authors: Dinesh Pathaka, Tomas Wagnera, J. M. Nunzib

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We investigated blends of MdPVV.PCBM.AIS for photovoltaic application. AgInSe2 powder was synthesized by sealing and heating the stoichiometric constituents in evacuated quartz tube ampule. Fine grinded AIS powder was dispersed in MD-MOPVV and PCBM with and without surfactant. Different concentrations of these particles were suspended in the polymer solutions and spin casted onto ITO glass. Morphological studies have been performed by atomic force microscopy and optical microscopy. The blend layers were also investigated by various techniques like XRD, UV-VIS optical spectroscopy, AFM, PL, after a series of various optimizations with polymers/concentration/deposition/ suspension/surfactants etc. XRD investigation of blend layers shows clear evidence of AIS dispersion in polymers. Diode behavior and cell parameters also revealed it. Bulk heterojunction hybrid photovoltaic device Ag/MoO3/MdPVV.PCBM.AIS/ZnO/ITO was fabricated and tested with standard solar simulator and device characterization system. The best performance and photovoltaic parameters we obtained was an open-circuit voltage of about Voc 0.54 V and a photocurrent of Isc 117 micro A and an efficiency of 0.2 percent using a white light illumination intensity of 23 mW/cm2. Our results are encouraging for further research on the fourth generation inorganic organic hybrid bulk heterojunction photovoltaics for energy. More optimization with spinning rate/thickness/solvents/deposition rates for active layers etc. need to be explored for improved photovoltaic response of these bulk heterojunction devices.

Keywords: thin films, photovoltaic, hybrid systems, heterojunction

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Authors: Lin Huang, Bo Wang, Armando Borgna

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Dehydration of glycerol to acrolein was conducted with solid acid catalysts in liquid phase in a batch reactor and in gas phase in a fix-bed reactor, respectively. In the liquid-phase reaction, ZSM-5, H3PO4-modified ZSM-5 and heteropolyacids including H3PW12O40•xH2O (HPW) and Cs2.5H0.5PW12O40 (CsPW) were studied as catalysts. High temperatures and high boiling point solvents such as sulfolane improved the selectivity to acrolein through suppressing the formation of polyglycerols and coke. Catalytic results and temperature-programmed desorption of ammonia showed that the yield of acrolein increased with increasing catalyst acidity within the range of weak acid strength. Weak acid sites favored the selectivity to acrolein whereas strong acid sites promoted the formation of coke. ZSM-5 possessing only acid sites led to a high acrolein yield, while heteropolyacid catalysts with strong acid sites produced a low acrolein yield. In the gas-phase reaction, HPW and CsPW supported on metal oxides such as SiO2, γ-Al2O3, SiO2-Al2O3, ZrO2 and silicate TUD-1 were studied as catalysts. HPW/TUD-1 was most active for the production of acrolein, followed by HPW/SiO2. An acrolein yield of 61 % was obtained over HPW/TUD-1. X-ray diffraction study suggested that HPW and CsPW were stable and more dispersed on SiO2, silicate TUD-1 and SiO2-Al2O3. It was found that the structures of HPW and CsPW were destroyed by interaction with γ-Al2O3 and ZrO2. Compared to CsPW/TUD-1, the higher acrolein yield with HPW/TUD-1 may be attributed to more Brønsted acid sites on HPW/TUD-1, based on preliminary pyridine adsorption IR study.

Keywords: dehydration, glycerol, acrolein, solid acid catalysts, gas-phase, liquid-phase

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Authors: Anupalli Roja Rani, Saraswathi Jaggali

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Rose-scented geranium (Pelargonium graveolens L’Hér.) is an erect, much-branched shrub. It is indigenous to various parts of southern Africa, and it is often called Geranium. Pelargonium species are widely used by traditional healers in the areas of Southern Africa by Sotho, Xhosa, Khoi-San and Zulus for its curative and palliative effects in the treatment of diarrhea, dysentery, fever, respiratory tract infections, liver complaints, wounds, gastroenteritis, haemorrhage, kidney and bladder disorders. We have used Plant materials for extracting active compounds from analytical grades of solvents methanol, ethyl acetate, chloroform and water by a soxhlet apparatus. The phytochemical screening reveals that extracts of Pelargonium graveolens contains alkaloids, glycosides, steroids, tannins, saponins and phenols in ethyl acetate solvent. The antioxidant activity was determined using 1, 1-diphenyl-2-picrylhydrazyl (DPPH) bleaching method and the total phenolic content in the extracts was determined by the Folin–Ciocalteu method. Due to the presence of different phytochemical compounds in Pelargonium the anti-microbial activity against different micro-organisms like E.coli, Streptococcus, Klebsiella and Bacillus. Fractionation of plant extract was performed by column chromatography and was confirmed with HPLC analysis, NMR and FTIR spectroscopy for the compound identification in different organic solvent extracts.

Keywords: Pelargonium graveolens L’Hér, DPPH, micro-organisms, HPLC analysis, NMR, FTIR spectroscopy

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Authors: Srikanth Korla, Mahesh Sharnangat

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Composite materials are being widely used in Aerospace, Naval, Defence and other branches of engineering applications. Studies on natural fibers is another emerging research area as they are available in abundance, and also due to their eco-friendly in nature. India being one of the major producer of coir, there is always a scope to study the possibilities of exploring coir as reinforment, and with different combinations of other elements of the composite. In present investigation effort is made to utilize properties possessed by natural fiber and make them enable with polymer/epoxy resin. In natural fiber coconut coir is used as reinforcement fiber in epoxy resin with varying weight percentages of fiber and filler material. Titanium dioxide powder (TiO2) is used as filler material with varying weight percentage including 0%, 2% and 4% are considered for experimentation. Environmental effects on the performance of the composite plate are also studied and presented in this project work; Moisture absorption test for composite specimens is conducted using different solvents including Kerosene, Mineral Water and Saline Water, and its absorption capacity is evaluated. Analysis is carried out in different combinations of Coir as fiber and TiO2 as filler material, and the best suitable composite material considering the strength and environmental effects is identified in this work. Therefore, the significant combination of the composite material is with following composition: 2% TiO2 powder 15% of coir fibre and 83% epoxy, under unique mechanical and environmental conditions considered in the work.

Keywords: composite materials, moisture test, filler material, natural fibre composites

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Authors: Mathias Schlenk, Susanne Seibt, Sabine Rosenfeldt, Josef Breu, Stephan Foerster

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Thin liquid jets on micrometer scale play an important role in processing such as in fiber fabrication, inkjet printing, but also for sample delivery in modern synchrotron X-ray devices. In all these cases the liquid jets contain solvents and dissolved materials such as polymers, nanoparticles, fibers pigments or proteins. As liquid flow in liquid jets differs significantly from flow in capillaries and microchannels, particle localization and orientation will also be different. This is of critical importance for applications, which depend on well-defined homogeneous particle and fiber distribution and orientation in liquid jets. Investigations of particle orientation in liquid microjets of diluted solutions have been rare, despite their importance. With the arise of micro-focused X-ray beams it has become possible to scan across samples with micrometer resolution to locally analyse structure and orientation of the samples. In the present work, we used this method to scan across liquid microjets to determine the local distribution and orientation of anisotropic particles. The compromise wormlike block copolymer micelles as an example of long flexible fibrous structures, hectorite materials as a model of extended nanosheet structures, and gold nanorods as an illustration of short stiff cylinders to comprise all relevant anisotropic geometries. We find that due to the different velocity profile in the liquid jet, which resembles plug flow, the orientation of the particles which was generated in the capillary is lost or changed into non-oriented or bi-axially orientations depending on the geometrical shape of the particle.

Keywords: anisotropic particles, liquid microjets, reorientation, SAXS

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Authors: Amina Merghad, Cherif Abdennour

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Solvents are widely used in paint industry, where humans are highly exposed, especially from inhalation. A case report describes how paint affects reproductive markers and the health of workers. Sixty four subjects were chosen and divided into two groups; a control and an exposed group. A questionnaire was given to male workers from similar socio-economic status in order to know their ages, working conditions, clinical symptoms, working period, smoking history, shift, medical history and nutrition. Blood was withdrawn in the morning from volunteers. The measurement of blood testosterone and prolactin concentrations was then carried out. Results showed that the ages of the two groups were almost similar and were up to 47 and 43 years. The period of employment was 17 years and 14 years for the control and the exposed workers, respectively. Concerning clinical symptoms, the frequency of neuropsychological symptoms of the two groups are presented. It is clear that the symptom of memory loss, headaches are the highest among exposed workers followed by poor coordination, poor concentration and insomnia. On the other hand, the symptoms’ frequency in the control was less than that of the exposed group. Testosterone concentration has significantly decreased in group 2 (4.61±2,005 ng/ml) and group 3 (4.25±1.67 ng/ml) of exposed workers. On the other hand, prolactin concentration was higher in group 3 compared to other groups. To conclude, paint industry has disturbed reproductive markers and created high frequency of neuropsychological symptoms.

Keywords: blood, paint, prolactin, occupational exposure, organic solvent, reproductive toxicity, testosterone

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Authors: Monthon Tangjitmungman

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Numerous diseases have been linked to oxidative stress, in which a disproportion of free radicals in the body leads to tissue or cell damage. Polyphenols are the most abundant antioxidants found in plants, and they are highly effective at scavenging oxidative free radicals. Due to the presence of phenolic compounds in Caesalpinia sappan has been discovered to have antioxidant activity. It has several health benefits, the most important of which is preventing cardiovascular and cancer diseases. This study aimed to determine the phenolic content and antioxidant activity of C. sappan extract using a variety of antioxidant assays. The extract of C. sappan was made using a mixture of solvents (ethyl alcohol: water in ratio 8:2). The total phenolic content of C. sappan extract was determined and expressed as gallic acid equivalents using the Folin-Cioucalteu method (GAE). The antioxidant activity of C. sappan extract was assessed using the 2, 2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging assay and the ABTS radical scavenging capacity assay. An association was found between antioxidant activity and total phenol content. The antioxidant activity of C. sappan extract was also determined by DPPH and ABTS assays. The IC50 values for C. sappan extract from DPPH and ABTS assays were 54.48 μg/mL ± 0.545 and 25.46 μg/mL ± 0.790, respectively, in the DPPH assay. In the DPPH assay, vitamin C was used as a positive control, whereas Trolox was used as a positive control in the ABTS assay. In conclusion, C. sappan extract contains a high level of total phenolics and exhibits significant antioxidant activity. Nevertheless, more research should be done on the antioxidant activity, such as SOD and ROS scavenging assays and in vivo experiments, to determine whether the compound has antioxidant activity.

Keywords: ABTS assay, antioxidant activity, Caesalpinia sappan, DPPH assays, total phenolic content

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Authors: Nacéra Benoussaid, Lehalali Meriem, Benchabane Messaoud

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Our work focuses on the production of compound antibiotic effect of volatile nature namely hydrogen cyanide and the production and identification of molecules phénazinique by some strains of fluorescent Pseudomonas spp isolated from the rhizosphere of some trees for a possible use as bio pesticides antifungal effect and/or antibiotic. We tested the production of hydrogen cyanide of 21 strains of Pseudomonas spp. fluorescent among them 19 strains (90, 47%) showed a positive cyanogenesis.The antagonism test executed in vitro showed that Pseudomonas strains have a higher anti fungal effect relative to their antibacterial effect with diameters of inhibition zones up to 3, 9 cm recorded by the strain F48 against Coleosporiumsp compared with recorded results against bacteria with a maximum inhibition of 1, 26 cm among this antagonistic strain.Three strains were selected by testing for producing phénazines namely PI9, BB9 and F20. The effect of the antimicrobial activity was performed on different culture media (GN, King B, ISP2 and PDA). The results of our study allowed us to retain the King B medium as ideal medium for the production of secondary metabolite. The produced phenazinique compounds was extracted from various organic solvents, and after the results of antibiographie against germs - targets, the extracts of ethyl acetate gave the best results compared to dichloromethane and hexane.The Analysis of these compounds of antibiotic phenazinique effect within layer chromatography (CCM) and high performance liquid chromatography( HPLC) indicate that both strains PI9 and F20 are productive of phenazine-1-carboxylic acid (PCA). The BB9 strain is suspected to be productive of another phenazinique compound.

Keywords: Pseudomonas ssp. fluorescents, antagonism in vitro, secondary metabolite, phenazines, biopesticide.

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Authors: Aliya Kurbanova, Nurlan Akhmetov, Abilmansur Yeshmuratov, Yerzhigit Sugurbekov, Ramiz Zulkharnay, Gulzat Demeuova, Murat Baisariyev, Gulnar Sugurbekova

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Last decades crude oils have tended to become more challenge to process due to increasing amounts of sour and heavy crude oils. Some crude oils contain high vanadium and nickel content, for example Pavlodar LLP crude oil, which contains more than 23.09 g/t nickel and 58.59 g/t vanadium. In this study, we used two types of metal removing methods such as solvent extraction and electrochemical. The present research is conducted for comparative analysis of the deasphalting with organic solvents (cyclohexane, carbon tetrachloride, chloroform) and electrochemical method. Applying the cyclic voltametric analysis (CVA) and Inductively coupled plasma mass spectrometry (ICP MS), these mentioned types of metal extraction methods were compared in this paper. Maximum efficiency of deasphalting, with cyclohexane as the solvent, in Soxhlet extractor was 66.4% for nickel and 51.2% for vanadium content from crude oil. Percentage of Ni extraction reached maximum of approximately 55% by using the electrochemical method in electrolysis cell, which was developed for this research and consists of three sections: oil and protonating agent (EtOH) solution between two conducting membranes which divides it from two capsules of 10% sulfuric acid and two graphite electrodes which cover all three parts in electrical circuit. Ions of metals pass through membranes and remain in acid solutions. The best result was obtained in 60 minutes with ethanol to oil ratio 25% to 75% respectively, current fits into the range from 0.3A to 0.4A, voltage changed from 12.8V to 17.3V.

Keywords: demetallization, deasphalting, electrochemical removal, heavy metals, petroleum engineering, solvent extraction

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Authors: Sharmin Sultana, Nicolas Nuns, Pardis Simon, Jean-Marc Giraudon, Jean-Francois Lamonior, Nathalie D. Geyter, Rino Morent

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Environmental issues, especially air pollution, have become a huge concern of environmental legislation as a consequence of growing awareness in our global world. In this regard, control of volatile organic compounds (VOCs) emission has become an important issue due to their potential toxicity, carcinogenicity, and mutagenicity. The research of innovative technologies for VOC abatement is stimulated to accommodate the new stringent standards in terms of VOC emission. One emerging strategy is the coupling of 2 existing complementary technologies, namely here non-thermal plasma (NTP) and heterogeneous catalysis, to get a more efficient process for VOC removal in air. The objective of this current work is to investigate the abatement of trichloroethylene (TCE-highly toxic chlorinated VOC) from moist air (RH=15%) as a function of time by combined use of multi-pin-to-plate negative DC corona/glow discharge with Fe-doped cryptomelanes catalyst downstream i.e. post plasma-catalysis (PPC) process. For catalyst alone case, experiments reveal that, initially, Fe doped cryptomelane (regardless the mode of Fe incorporation by co-precipitation (Fe-K-OMS-2)/ impregnation (Fe/K-OMS-2)) exhibits excellent activity to decompose TCE compared to cryptomelane (K-OMS-2) itself. A maximum obtained value of TCE abatement after 6 min is as follows: Fe-KOMS-2 (73.3%) > Fe/KOMS-2 (48.5) > KOMS-2 (22.6%). However, with prolonged operation time, whatever the catalyst under concern, the abatement of TCE decreases. After 111 min time of exposure, the catalysts can be ranked as follows: Fe/KOMS-2 (11%) < K-OMS-2 (12.3%) < Fe-KOMS-2 (14.5%). Clearly, this phenomenon indicates catalyst deactivation either by chlorination or by blocking the active sites. Remarkably, in PPC configuration (energy density = 60 J/L, catalyst temperature = 150°C), experiments reveal an enhanced performance towards TCE removal regardless the type of catalyst. After 6 min time on stream, the TCE removal efficiency amount as follows: K-OMS-2 (60%) < Fe/K-OMS-2 (79%) < Fe-K-OMS-2 (99.3%). The enhanced performances over Fe-K-OMS-2 catalyst are attributed to its high surface oxygen mobility and structural defects leading to high O₃ decomposition efficiency to give active species able to oxidize the plasma processed hazardous\by-products and the possibly remaining VOC into CO₂. Moreover, both undoped and doped catalysts remain strongly capable to abate TCE with time on stream. The TCE removal efficiencies of the PPC processes with Fe/KOMS-2 and KOMS-2 catalysts are not affected by time on stream indicating an excellent catalyst stability. When using the Fe-K-OMS-2 as catalyst, TCE abatement slightly reduces with time on stream. However, it is noteworthy to stress that still a constant abatement of 83% is observed during at least 30 minutes. These results prove that the combination of NTP with catalysts not only increases the catalytic activity but also allows to avoid, to some extent, the poisoning of catalytic sites resulting in an enhanced catalyst stability. In order to better understand the different surface processes occurring in the course of the total TCE oxidation in PPC experiments, a detailed X-ray Photoelectron Spectroscopy (XPS) and Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS) study on the fresh and used catalysts is in progress.

Keywords: Fe doped cryptomelane, non-thermal plasma, plasma-catalysis, stability, trichloroethylene

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Authors: Nabila Mohamed, Santiago Aparicio, Bahman Tohidi, Mert Atilhan

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Qatar's one of the biggest problem in processing its natural resource, which is natural gas, is the often occurring blockage in the pipelines caused due to uncontrolled gas hydrate formation in the pipelines. Several millions of dollars are being spent at the process site to dehydrate the blockage safely by using chemical inhibitors. We aim to establish national database, which addresses the physical conditions that promotes Qatari natural gas to form gas hydrates in the pipelines. Moreover, we aim to design and test novel hydrate inhibitors that are suitable for Qatari natural gas and its processing facilities. From these perspectives we are aiming to provide more effective and sustainable reservoir utilization and processing of Qatari natural gas. In this work, we present the initial findings of a QNRF funded project, which deals with the natural gas hydrate formation characteristics of Qatari type gas in both experimental (PVTx) and computational (molecular simulations) methods. We present the data from the two fully automated apparatus: a gas hydrate autoclave and a rocking cell. Hydrate equilibrium curves including growth/dissociation conditions for multi-component systems for several gas mixtures that represent Qatari type natural gas with and without the presence of well known kinetic and thermodynamic hydrate inhibitors. Ionic liquids were designed and used for testing their inhibition performance and their DFT and molecular modeling simulation results were also obtained and compared with the experimental results. Results showed significant performance of ionic liquids with up to 0.5 % in volume with up to 2 to 4 0C inhibition at high pressures.

Keywords: gas hydrates, natural gas, ionic liquids, inhibition, thermodynamic inhibitors, kinetic inhibitors

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