Search results for: branched isomers

Authors: Zainab S. Ahmed, Mohammed S. Ali, Nadia A. Elshiekh, Sami Adam Ibrahim, Ghada M. El-Tayeb, Ahmed H. Elsadig, Rihab A. Omer, Sofia B. Mohamed

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Maple syrup urine (MSUD) is an autosomal recessive disease that causes a deficiency in the enzyme branched-chain alpha-keto acid (BCKA) dehydrogenase. The development of disease has been associated with SNPs in the DBT gene. Despite that, the computational analysis of SNPs in coding and noncoding and their functional impacts on protein level still remains unknown. Hence, in this study, we carried out a comprehensive in silico analysis of missense that was predicted to have a harmful influence on DBT structure and function. In this study, eight different in silico prediction algorithms; SIFT, PROVEAN, MutPred, SNP&GO, PhD-SNP, PANTHER, I-Mutant 2.0 and MUpo were used for screening nsSNPs in DBT including. Additionally, to understand the effect of mutations in the strength of the interactions that bind protein together the ELASPIC servers were used. Finally, the 3D structure of DBT was formed using Mutation3D and Chimera servers respectively. Our result showed that a total of 15 nsSNPs confirmed by 4 software (R301C, R376H, W84R, S268F, W84C, F276C, H452R, R178H, I355T, V191G, M444T, T174A, I200T, R113H, and R178C) were found damaging and can lead to a shift in DBT gene structure. Moreover, we found 7 nsSNPs located on the 2-oxoacid_dh catalytic domain, 5 nsSNPs on the E_3 binding domain and 3 nsSNPs on the Biotin Domain. So these nsSNPs may alter the putative structure of DBT’s domain. Furthermore, we detected all these nsSNPs are on the core residues of the protein and have the ability to change the stability of the protein. Additionally, we found W84R, S268F, and M444T have high significance, and they affected Leucine, Isoleucine, and Valine, which reduces or disrupt the function of BCKD complex, E2-subunit which the DBT gene encodes. In conclusion, based on our extensive in-silico analysis, we report 15 nsSNPs that have possible association with protein deteriorating and disease-causing abilities. These candidate SNPs can aid in future studies on Maple Syrup Urine Disease type II base in the genetic level.

Keywords: DBT gene, ELASPIC, in silico analysis, UCSF chimer

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Authors: J. Tomilla Ajayi, Werner E. Van Zyl

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This work presents an overview of the reaction of 2, 4-diferrocenyl-1, 3-dithiadiphosphetane-2, 4-disulfide (Ferrocenyl Lawesson’s reagent) with water to produce the non-symmetric, ferocenyl dithiophosphonic acid respectively in high yields. These acids were readily deprotonated by anhydrous Ammonia to yield the corresponding ammonium salt NH4S2PFcOH. These were complex to Ni (II) in molar ratio 1:1 and 1:2. The resulting complex from the reaction formed same compound with different isomers (Cis and Trans) and also compound with multimetallic coordination. Quality X-ray crystals were formed from THF/Ether. The compounds were characterized by 1H, 31P NMR, and FTIR. Bulk purity were confirmed by either ESI-MS or elemental analysis and The XRD images were obtained using single crystal X-ray crystallographic studies. The electrochemical investigation of the Compounds were carried out using cyclic voltammetry.

Keywords: ferrocenyl, dithiophosphonate, isomer, coordination

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Authors: Ali Bahri Lubis

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Tryptophan oxidation by Heme-dioxygenase enzyme is initial important stepTryptophan oxidation by Heme-dioxygenase enzyme is initial important step in kynurenine pathway implicating to several severe diseases such as Parkinson’s Disease, Huntington Disease, poliomyelitis and cataract. It is crucial to comprehend the oxidation mechanism with the hope to find decent treatment upon abovementioned diseases. The mechanism has been debatable since no one has been yet proved the mechanism obviously. In this research we have attempted to prove mechanistic steps of tryptophan oxidation via human indoleamine dioxygenase (h-IDO) using various substrates: L-tryptophan, L-tryptophan (indole-ring-2-13C), L-fully-labelled13C-tryptophan, L-N-methyl-tryptophan, L-tryptophan and 2-amino-3-(benzo(b)thiophene-3-yl) propanoic acid. All enzyme assay experiments were measured using a UV-Vis spectrophotometer, LC-MS, 1H-NMR, and HSQC. We also successfully synthesized enzyme products as our control in NMR measurements. The result exhibited that the distinct substrates produced N-formyl kynurenine (NFK) and hydroxypyrrolloindoleamine carboxylate acid (HPIC) in different concentrations and isomers, correlated to the proposal of considered mechanism reaction in kynurenine pathway implicating to several severe diseases such as Parkinson’s Disease, Huntington Disease, poliomyelitis and cataract. It is crucial to comprehend the oxidation mechanism with the hope to find decent treatment for the abovementioned diseases. The mechanism has been debatable since no one has yet proven the mechanism obviously. In this research we have attempted to prove mechanistic steps of tryptophan oxidation via human indoleamine dioxygenase (h-IDO) using various substrates: L-tryptophan, L-tryptophan (indole-ring-2-13C), L-fully-labelled13C-tryptophan, L-N-methyl-tryptophan, L-tryptophan and 2-amino-3-(benzo(b)thiophene-3-yl) propanoic acid. All enzyme assay experiments were measured using a UV-Vis spectrophotometer, LC-MS, 1H-NMR and HSQC. We also successfully synthesized enzyme products as our control in NMR measurements. The result exhibited that the distinct substrates produced N-formyl kynurenine (NFK) and hydroxypyrrolloindoleamine carboxylate acid (HPIC) in different concentrations and isomers, correlated to the proposal of considered mechanism reaction.

Keywords: heme-dioxygenase enzyme, tryptophan oxidation, kynurenine pathway, n-formyl kynurenine

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Authors: Natarajan Ramasamy, Gurulingamurthy Haralur, Ramesh Nivarthu, Nikhil Kumar Singha

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Elastomers are polymeric materials with varied backbone architectures ranging from linear to dendrimeric structures and wide varieties of monomeric repeat units. These elastomers show strongly viscous and weakly elastic when it is not cross-linked. But when crosslinked, based on the extent the properties of these elastomers can range from highly flexible to highly stiff nature. Lightly cross-linked systems are well studied and reported. Understanding the nature of highly cross-linked rubber based upon chemical structure and architecture is critical for varieties of applications. One of the critical parameters is cross-link density. In the current work, we have studied the highly cross-linked state of linear, lightly branched to star-shaped branched elastomers and determined the cross-linked density by using different models. Change in hardness, shift in Tg, change in modulus and swelling behavior were measured experimentally as a function of the extent of curing. These properties were analyzed using varied models to determine cross-link density. We used hardness measurements to examine cure time. Hardness to the extent of curing relationship is determined. It is well known that micromechanical transitions like Tg and storage modulus are related to the extent of crosslinking. The Tg of the elastomer in different crosslinked state was determined by DMA, and based on plateau modulus the crosslink density is estimated by using Nielsen’s model. Usually for lightly crosslinked systems, based on equilibrium swelling ratio in solvent the cross link density is estimated by using Flory–Rhener model. When it comes to highly crosslinked system, Flory-Rhener model is not valid because of smaller chain length. So models based on the assumption of polymer as a Non-Gaussian chain like 1) Helmis–Heinrich–Straube (HHS) model, 2) Gloria M.gusler and Yoram Cohen Model, 3) Barbara D. Barr-Howell and Nikolaos A. Peppas model is used for estimating crosslink density. In this work, correction factors are determined to the existing models and based upon it structure-property relationship of highly crosslinked elastomers was studied.

Keywords: dynamic mechanical analysis, glass transition temperature, parts per hundred grams of rubber, crosslink density, number of networks per unit volume of elastomer

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Authors: A. Özyer, N. G. Turan, Y. Ardalı

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The environmental fate of organic contaminants in soils is influenced significantly by the pH, texture of soil, water content and also presence of organic matter. In this study, biodegradation of endosulfan isomers was studied in two different soils (Soil A and Soil B) that have contrasting properties in terms of their texture, pH, organic content, etc. Two Nocardia sp., which were isolated from soil, were used for degradation of endosulfan. Soils were contaminated with commercial endosulfan. Six sets were maintained from two different soils, contaminated with different endosulfan concentrations for degradation experiments. Inoculated and uninoculated mineral media with Nocardia isolates were added to the soils and mixed. Soils were incubated at a certain temperature (30 °C) during ten weeks. Residue endosulfan and its metabolites’ concentrations were determined weekly during the incubation period. The changes of the soil microorganisms were investigated weekly.

Keywords: endosulfan, biodegradation, Nocardia sp. soil, organochlorine pesticide

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Authors: H.Yari, M. Mohseni, Z. Ranjbar

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In this work a typical automotive clearcoat is modified with a combination of hyperbranched polymer (HBP) and polyhedral oligomeric silsesquioxane (POSS) nanostructures to simultaneously enhance the scratch resistance and healing ability of the resulting films. Micro-scratch and healing data revealed that these goals were achieved at high loadings of modifiers. Enhanced scratch resistance was attributed to the improved elastic recovery of the clearcoats in presence of modifiers. In addition, improved healing performance due to the partial replacement of covalent cross-links with physical ones resulted from the unique globular highly branched structure of HBP and POSS macromolecules.

Keywords: automotive clearcoat, POSS building blocks scratch resistance, self-healing

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Authors: Mohamed Hefnawy, Abdulrahman Al-Majed, Aymen Al-Suwailem

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Enantioseparation of drugs with multiple stereogenic centers is challenging. This study objectives to evaluate the efficiency of different mobilized and/or immobilized polysaccharide-based chiral stationary phases to separate enantiomers of some drugs containing multiple stereogenic centers namely indenolol, nadolol, labetalol. The critical mobile phase variables (composition of organic solvents, acid/base ratios) were carefully studied to compare the retention time and elution order of all isomers. Different chromatographic parameters such as capacity factor (k), selectivity (α) and resolution (Rs) were calculated. Experimental conditions and the possible chiral recognition mechanisms have been discussed.

Keywords: HPLC, polysaccharide columns, enantio-resolution, indenolol, nadolol, labetalol

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Authors: Padmaja R. Jonnalagadda

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Dietary exposure assessment of fifteen pesticide residues was done in Andhra Pradesh. Twelve commonly consumed foods including water, which were representative of the diet, were collected, processed as table ready and analysed for the presence of various Organochlorines, organophosphates and synthetic pyrethroids. All the samples were contaminated with one or more of the 15 pesticide residues and all of them were within the MRLs. DDT and its isomers, Chlorpyriphos and Cypermethrin were frequently detected in many of the food samples. The mean concentration of the pesticide residues ranged from 0.02 μg kg-1 to 5.1 μg kg-1 (fresh weight) in the analysed foods. When exposure assessments was carried out for different age, sex and physiological groups it was found that the estimates of daily dietary intakes of the analysed pesticide residues in the present study are much lower than the violative levels in all age groups that were computed.

Keywords: table ready foods, pesticide residues, dietary intake, physiological groups, risk

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Authors: Subhojyoti Chatterjee, Peter J. Mahon, Feng Wang

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Resveratrol (RvL), a phenolic compound, is a key ingredient in wine and tomatoes that has been studied over the years because of its important bioactivities such as anti-oxidant, anti-aging and antimicrobial properties. Out of the two isomeric forms of resveratrol i.e. trans and cis, the health benefit is primarily associated with the trans form. Thus, studying the structural properties of the isomers will not only provide an insight into understanding the RvL isomers, but will also help in designing parameters for differentiation in order to achieve 99.9% purity of trans-RvL. In the present study, density function theory (DFT) study is conducted, using the B3LYP/6-311++G** model to explore the through bond and through space intramolecular interactions. Properties such as vibrational spectroscopy (IR and Raman), nuclear magnetic resonance (NMR) spectra, excess orbital energy spectrum (EOES), energy based decomposition analyses (EDA) and Fukui function are calculated. It is discovered that the structure of trans-RvL, although it is C1 non-planar, the backbone non-H atoms are nearly in the same plane; whereas the cis-RvL consists of two major planes of R1 and R2 that are not in the same plane. The absence of planarity gives rise to a H-bond of 2.67Å in cis-RvL. Rotation of the C(5)-C(8) single bond in trans-RvL produces higher energy barriers since it may break the (planar) entire conjugated structure; while such rotation in cis-RvL produces multiple minima and maxima depending on the positions of the rings. The calculated FT-IR spectrum shows very different spectral features for trans and cis-RvL in the region 900 – 1500 cm-1, where the spectral peaks at 1138-1158 cm-1 are split in cis-RvL compared to a single peak at 1165 cm-1 in trans-RvL. In the Raman spectra, there is significant enhancement of cis-RvL in the region above 3000cm-1. Further, the carbon chemical environment (13C NMR) of the RvL molecule exhibit a larger chemical shift for cis-RvL compared to trans-RvL (Δδ = 8.18 ppm) for the carbon atom C(11), indicating that the chemical environment of the C group in cis-RvL is more diverse than its other isomer. The energy gap between highest occupied molecular orbital (HOMO) and the lowest occupied molecular orbital (LUMO) is 3.95 eV for trans and 4.35 eV for cis-RvL. A more detailed inspection using the recently developed EOES revealed that most of the large energy differences i.e. Δεcis-trans > ±0.30 eV, in their orbitals are contributed from the outer valence shell. They are MO60 (HOMO), MO52-55 and MO46. The active sites that has been captured by Fukui function (f + > 0.08) are associated with the stilbene C=C bond of RvL and cis-RvL is more active at these sites than in trans-RvL, as cis orientation breaks the large conjugation of trans-RvL so that the hydroxyl oxygen’s are more active in cis-RvL. Finally, EDA highlights the interaction energy (ΔEInt) of the phenolic compound, where trans is preferred over the cis-RvL (ΔΔEi = -4.35 kcal.mol-1) isomer. Thus, these quantum mechanics results could help in unwinding the diversified beneficial activities associated with resveratrol.

Keywords: resveratrol, FT-IR, Raman, NMR, excess orbital energy spectrum, energy decomposition analysis, Fukui function

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Authors: A. Szabó Nagy, J. Szabó, Zs. Csanádi, J. Erdős

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An assessment of the air quality of Győr (Hungary) was performed by determining the ambient concentrations of PM10-bound carcinogenic polycyclic aromatic hydrocarbons (cPAHs) in different seasons. A high volume sampler was used for the collection of ambient aerosol particles, and the associated cPAH compounds (benzo[a]pyrene (BaP), benzo[a]anthracene, benzofluoranthene isomers, indeno[123-cd]pyrene and dibenzo[ah]anthracene) were analyzed by a gas chromatographic method. Higher mean concentrations of total cPAHs were detected in samples collected in winter (9.62 ng/m³) and autumn (2.69 ng/m³) compared to spring (1.05 ng/m³) and summer (0.21 ng/m³). The calculated BaP toxic equivalent concentrations have also reflected that the local population appears to be exposed to significantly higher cancer risk in the heating seasons. Moreover, the concentration levels of cPAHs determined in this study were compared to other Hungarian urban sites.

Keywords: air, carcinogenic, polycyclic aromatic hydrocarbons (PAH), PM10

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Authors: Behnaz Mahdavi, Hamidreza Khodaei, Leila Karshenas

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Conjugated Linoleic Acid is a group of long-chain unsaturated fatty acids with more than one double bond and a mixture of 28 isomers of Linoleic acid (C 18:2) and it is counted as one of the essential acids. The main purpose of this study was to investigate the effect of CLA on some reproductive hormones in rams. In this study, six rams 3 to 4 years old with an average weight of 90 kg were selected. Rams were randomly divided into 3 groups and were treated by CLA treatment for 30 days. The first group (as a control group) didn’t receive CLA, The second group received 0.5 gr and the third group received 1 gram of CLA. The blood testing was done on rams every 15 days using a 20 ml syringe. Data analysis was performed by SAS software. Also mean comparison was done using Duncan's test method (p<0.05). Obtained results showed that the serum concentration of testosterone hormone was decreased numerically as well as the concentration of FSH hormone however the concentration of LH was increased. CLA in oral form can reduce the concentration of testosterone in rams.

Keywords: CLA, ram, testosterone, DHT, Conjugated Linoleic Acid

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Authors: S. Dargouthi, S. Boughdiri, B. Tangour

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This work invoked two complementary parts. In the first, we performed a theoretical study of various dimers of molecular of titanium dioxide. Five structures were examined. Three among them, the (T), (C) and (T/P) isomers, may be considered as stable compounds because they represent absolute minima on their potential energy surfaces. (T) and (C) may coexist because they are separted by only 6.5 kcal mol-1 but (T/P) dimer is in a metastable state from an energetic point of view. Non bonded dimer (P) transforms into its homologue (O) which has been considered as transitory specie with low lifetime which evolves to (T) structure. In the second part, we highlight the possible stabilization of (T), (C) and (P) dimers by encapsulation in carbon nanotubes. This indicates the probable role that plays this transitory specie the polymerization process of molecular TiO2. Confinement is suitable to control the fast evolution process and could towards the synthesis of new titanium dioxide nanostructured materials. An alternative description of TiO2 polymorphs (Rutie, anatase et Brookite) is proposed from (T), (C) and (T/P) dimmers motifs.

Keywords: titanium dioxide, carbon nanotube, confinement. encapsulation, transitory specie

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Authors: Aliyu Adamu, Fahrul Huyop, Roswanira Abdul Wahab, Mohd Shahir Shamsir

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Halogenated organic compounds occur in huge amount in biosphere. This is attributable to the diverse use of halogen-based compounds in the synthesis of various industrially important products. Halogenated compound is toxic and may persist in the environment, thereby causing serious health and environmental pollution problems. L-2-haloacid dehalogenases (EC 3.8.1.2) catalyse the specific cleavage of carbon-halogen bond in L-isomers of halogenated compounds, which consequently reverse the effects of environmental halogen-associated pollution. To enhance the efficiency and utility of these enzymes, this study investigates the catalytic amino acid residues and the molecular functional mechanism of DehL, by classical molecular dynamic simulations, MM-PBSA and ab initio fragments molecular orbital (FMO) calculations. The results of the study will serve as the basis for the molecular engineering of the enzyme.

Keywords: DehL, Functional mechanism, Catalytic residues, L-2-haloacid dehalogenase

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Authors: Behnaz Mahdavi, Hamidreza Khodaei, Alireza Banitaba

Abstract:

Conjugated Linoleic Acid is a group of long-chain unsaturated fatty acids with more than one double bond and a mixture of 28 isomers of Linoleic acid (C 18:2) and it is counted as one of the essential acids. The main purpose of this study was to investigate the effect of CLA on some reproductive hormones in rams. In this study, six rams 3 to 4 years old with an average weight of 90 kg were selected. Rams were randomly divided into 3 groups and were treated by CLA treatment for 30 days. The first group (as a control group) did not receive CLA, The second group received 0.5 gr and the third group received 1 gram of CLA. The blood testing was done on rams every 15 days using a 20 ml syringe. Data analysis was performed by SAS software. Also mean comparison was done using Duncan's test method (p<0.05). Obtained results showed that the serum concentration of testosterone hormone was decreased numerically as well as the concentration of FSH hormone however the concentration of LH was increased. Also, the CLA had a significant effect on Leptin concentration. CLA in oral form can reduce the concentration of testosterone in rams.

Keywords: CLA, ram, testosterone, conjugated linoleic acid

Procedia PDF Downloads 305

Authors: Gomti Devi

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Photoisomerization has been attracting to researchers due to its wide range of applications in optical switches, polymeric chains, liquid-crystalline systems and bilayer membranes etc. Azobenzene is a photochromic molecule which exhibits a reversible isomerisation process between its trans and cis isomers of different stability. An investigation has been conducted of the effects of temperature on intensity and position of Raman band of N=N, C-N stretching modes of Azobenzene (AZBN). It was found that the N=N stretching mode of Raman band shape shifts to lower frequency region with the increase in temperature. The Raman intensity was also decreased with the increase of temperature. The change in bandwidth with the increase in temperature has been studied. The FTIR spectrum of the molecule is recorded so as to complement the Raman spectra. In order to investigate the possibility of undergoing dimerization and trimerization as well as the stability of this molecule, ab initio calculation for geometry optimization and vibrational wavenumber calculation have been performed. Theoretically calculated values are found in good agreement with the experimental results.

Keywords: azobenzene, temperature, ab-initio, frequency

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Authors: Omar Hussein El Ayadi, EmadY. El-Mansouri, Mohamed B. Dozan

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Production oil process require specific details i.e. oil composition. Generally, types of oil or differentiation between reservoir fluids depend specifically on composition. The main purpose of this study is to correlate and predict the Libyan oil (reservoir fluid and residual) composition utilizing tri-angle-coordinate plots discovered and tasked with Excel. The reservoir fluid data (61 old + 47 new), the residual oil data (33 new) collected from most of Libyan reservoirs were correlated with each others. Moreover, find a relation between stock tank molecular weight and stock tank oil gravity (oAPI), the molecular weight oh (C7+) versus residual oil gravity (oAPI). The average value of every oil composition was estimated including non-hydrocarbon (H2S, CO2, and N2). Nevertheless, the isomers (i-…) and normal (n-…) structure of (C4) and (C5) were also obtained. The summary of the conclusion is; utilizing excel Microsoft office to draw triangle coordinates to find two unknown component if only one is known. However, it is recommended to use the obtained oil composition plots and equations for any oil composition dependents i.e. optimum separator pressure.

Keywords: PVT, phase behavior, petroleum, chemical engineering

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Authors: Soumaya Sallem, Marc Olivas

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This contribution presents a method for detecting, locating, and characterizing soft faults in a complex wired network. The proposed method is based on multi-carrier reflectometry MCTDR (Multi-Carrier Time Domain Reflectometry) combined with a multi-objective genetic algorithm. In order to ensure complete network coverage and eliminate diagnosis ambiguities, the MCTDR test signal is injected at several points on the network, and the data is merged between different reflectometers (sensors) distributed on the network. An adapted multi-objective genetic algorithm is used to merge data in order to obtain more accurate faults location and characterization. The proposed method performances are evaluated from numerical and experimental results.

Keywords: wired network, reflectometry, network distributed diagnosis, multi-objective genetic algorithm

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Authors: Igor B. Sivaev

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Design of molecular machines is an extraordinary growing and very important area of research that it was recognized by awarding Sauvage, Stoddart and Feringa the Nobel Prize in Chemistry in 2016 'for the design and synthesis of molecular machines'. Based on the type of motion being performed, molecular machines can be divided into two main types: molecular motors and molecular switches. Molecular switches are molecules or supramolecular complexes having bistability, i.e., the ability to exist in two or more stable forms, among which may be reversible transitions under external influence (heating, lighting, changing the medium acidity, the action of chemicals, exposure to magnetic or electric field). Molecular switches are the main structural element of any molecular electronics devices. Therefore, the design and the study of molecules and supramolecular systems capable of performing mechanical movement is an important and urgent problem of modern chemistry. There is growing interest in molecular switches and other devices of molecular electronics based on transition metal complexes; therefore choice of suitable stable organometallic unit is of great importance. An example of such unit is bis(dicarbollide) complexes of transition metals [3,3’-M(1,2-C₂B₉H₁₁)₂]ⁿ⁻. The control on the ligand rotation in such complexes can be reached by introducing substituents which could provide stabilization of certain rotamers due to specific interactions between the ligands, on the one hand, and which can participate as Lewis bases in complex formation with external metals resulting in a change in the rotation angle of the ligands, on the other hand. A series of isomeric methyl sulfide derivatives of cobalt bis(dicarbollide) complexes containing methyl sulfide substituents at boron atoms in different positions of the pentagonal face of the dicarbollide ligands [8,8’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻, rac-[4,4’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻ and meso-[4,7’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻ were synthesized by the reaction of CoCl₂ with the corresponding methyl sulfide carborane derivatives [10-MeS-7,8-C₂B₉H₁₁)₂]⁻ and [10-MeS-7,8-C₂B₉H₁₁)₂]⁻. In the case of asymmetrically substituted cobalt bis(dicarbollide) complexes the corresponding rac- and meso-isomers were successfully separated by column chromatography as the tetrabutylammonium salts. The compounds obtained were studied by the methods of ¹H, ¹³C, and ¹¹B NMR spectroscopy, single crystal X-ray diffraction, cyclic voltammetry, controlled potential coulometry and quantum chemical calculations. It was found that in the solid state, the transoid- and gauche-conformations of the 8,8’- and 4,4’-isomers are stabilized by four intramolecular CH···S(Me)B hydrogen bonds each one (2.683-2.712 Å and 2.709-2.752 Å, respectively), whereas gauche-conformation of the 4,7’-isomer is stabilized by two intramolecular CH···S hydrogen bonds (2.699-2.711 Å). The existence of the intramolecular CH·S(Me)B hydrogen bonding in solutions was supported by the 1H NMR spectroscopy. These data are in a good agreement with results of the quantum chemical calculations. The corresponding iron and nickel complexes were synthesized as well. The reaction of the methyl sulfide derivatives of cobalt bis(dicarbollide) with various labile transition metal complexes results in rupture of intramolecular hydrogen bonds and complexation of the methyl sulfide groups with external metal. This results in stabilization of other rotational conformation of cobalt bis(dicarbollide) and can be used in design of molecular switches. This work was supported by the Russian Science Foundation (16-13-10331).

Keywords: molecular switches, NMR spectroscopy, single crystal X-ray diffraction, transition metal bis(dicarbollide) complexes, quantum chemical calculations

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Authors: Gaurav Verma

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Organoclay loaded (0-5 weight %) polyester-urethane (PU) coatings were prepared with a branched hydroxyl-bearing polyester and an aliphatic poly-isocyanate. TEM micrographs show partial exfoliation and intercalation of clay platelets in organoclay-polyester dispersions. AFM surface images reveals that the PU hard domains tend to regularise and also self-organise into spherical shapes of sizes 50 nm (0 wt %), 60 nm (2 wt %) and 190 nm (4 wt %) respectively. IR analysis shows that PU chains have increasing tendency to interact with exfoliated clay platelets through hydrogen bonding. This interaction strengthens inter-chain linkages in PU matrix and hence improves anti-ageing properties. 1000 hours of accelerated weathering was evaluated by ATR spectroscopy, while yellowing and overall discoloration was quantified by the Δb* and ΔE* values of the CIELab colour scale. Post-weathering surface properties also showed improvement as the loss of thickness and reduction in gloss in neat PU was 25% and 42%; while it was just 3.5% and 14% respectively for the 2 wt% nanocomposite coating. This work highlights the importance of modifying surface and bulk properties of PU coatings at nanoscale, which led to improved performance in accelerated weathering conditions.

Keywords: coatings, AFM, ageing, spectroscopy

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Authors: Sunil Kumar, Sandip Dhole, Deepak Salunke, Chung-ming Sun

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Heterocycles bearing nitrogen, oxygen, and selenium are present in innumerable biologically active compounds. For instance, coumarin containing dicoumarol acts as naturally occurring anticoagulant. 2-Acylamido selenazole works as Store-Operated Calcium (SOC) channel regulator. Therefore, due to biologically significance of selenazole and coumarin and our quest to develop efficient methodologies for the synthesis of complex heterocycles, the trisubstituted angular isocoumarinoselenazole synthesis was proposed and achieved by starting from nitrobenzoic acid derivative, available commercially. Synthetic procedure involves three steps: i) the construction of 2-aminobenzoselenazoles, ii) their regioselective N-alkylation at position-2 and iii) alkyne insertion via Ru catalyzed C-H activation. Transition metal free synthesis of benzoselenazoles was successfully brought about by the addition/elimination reaction via intramolecular C-Se bond formation. In the next step, N-alkylation of selenazole furnished two regioisomers. Both the isomers exhibited different reactivity towards [4+2] alkyne annulation reaction. The fusion of α-pyrone ring on the benzo[1,3-d]selenazole skeleton was achieved via Ru(II)-catalyzed C-H activation and alkyne insertion. As evident from mechanism, the selenazole 'N' plays an important role for the experiential selectivity.

Keywords: alkylation, alkyne insertion, coumarin, selenazole

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Authors: E. Esra Kasapbaşı, Büşra Yıldırım

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Weak oxidizing radicals, such as alkyl peroxyl derivatives, react with carotenoids through hydrogen atom transfer to form neutral carotenoid radicals. Using the DFT method, it has been observed that s-cis-β-carotene is more stable than all-transforms. In the context of this study, an attempt is made to explain the reaction mechanism of the isomers of β-carotene, which exhibits antioxidant properties, with n-pentyl peroxide, one of the alkyl peroxyl molecules, using the Density Functional Theory (DFT) method. The cis and transforms of β-carotene are used in the study to determine which form is more reactive. For this purpose, Natural Bond Orbital (NBO) charges of all optimized structures are calculated, and electron transfer is determined by examining electron transitions between Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO). Additionally, the radical character and reaction mechanism of β-carotene in a radical environment are attempted to be explained based on the calculations. The theoretical inclination of whether β-carotene in cis or transforms is more active in reaction is also discussed. All these calculations are performed in the gas phase using the Integral Equation Formalism Polarizable Continuum Model IEFPCM method with dichloromethane as the solvent.

Keywords: β-carotene, n-pentyl peroxyl radical, DFT, TD-DFT

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Authors: Reyna Singh, David Lokhat, Milan Carsky

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The world crude oil demand is projected to rise to 108.5 million bbl/d by the year 2035. With reserves estimated at 869 billion tonnes worldwide, coal is an abundant resource. This work was aimed at producing a high value hydrocarbon liquid product from the Direct Coal Liquefaction (DCL) process at, comparatively, mild operating conditions. Via hydrogenation, the temperature-staged approach was investigated. In a two reactor lab-scale pilot plant facility, the objectives included maximising thermal dissolution of the coal in the presence of a hydrogen donor solvent in the first stage, subsequently promoting hydrogen saturation and hydrodesulphurization (HDS) performance in the second. The feed slurry consisted of high grade, pulverized bituminous coal on a moisture-free basis with a size fraction of < 100μm; and Tetralin mixed in 2:1 and 3:1 solvent/coal ratios. Magnetite (Fe3O4) at 0.25wt% of the dry coal feed was added for the catalysed runs. For both stages, hydrogen gas was used to maintain a system pressure of 100barg. In the first stage, temperatures of 250℃ and 300℃, reaction times of 30 and 60 minutes were investigated in an agitated batch reactor. The first stage liquid product was pumped into the second stage vertical reactor, which was designed to counter-currently contact the hydrogen rich gas stream and incoming liquid flow in the fixed catalyst bed. Two commercial hydrotreating catalysts; Cobalt-Molybdenum (CoMo) and Nickel-Molybdenum (NiMo); were compared in terms of their conversion, selectivity and HDS performance at temperatures 50℃ higher than the respective first stage tests. The catalysts were activated at 300°C with a hydrogen flowrate of approximately 10 ml/min prior to the testing. A gas-liquid separator at the outlet of the reactor ensured that the gas was exhausted to the online VARIOplus gas analyser. The liquid was collected and sampled for analysis using Gas Chromatography-Mass Spectrometry (GC-MS). Internal standard quantification methods for the sulphur content, the BTX (benzene, toluene, and xylene) and alkene quality; alkanes and polycyclic aromatic hydrocarbon (PAH) compounds in the liquid products were guided by ASTM standards of practice for hydrocarbon analysis. In the first stage, using a 2:1 solvent/coal ratio, an increased coal to liquid conversion was favoured by a lower operating temperature of 250℃, 60 minutes and a system catalysed by magnetite. Tetralin functioned effectively as the hydrogen donor solvent. A 3:1 ratio favoured increased concentrations of the long chain alkanes undecane and dodecane, unsaturated alkenes octene and nonene and PAH compounds such as indene. The second stage product distribution showed an increase in the BTX quality of the liquid product, branched chain alkanes and a reduction in the sulphur concentration. As an HDS performer and selectivity to the production of long and branched chain alkanes, NiMo performed better than CoMo. CoMo is selective to a higher concentration of cyclohexane. For 16 days on stream each, NiMo had a higher activity than CoMo. The potential to cover the demand for low–sulphur, crude diesel and solvents from the production of high value hydrocarbon liquid in the said process, is thus demonstrated.

Keywords: catalyst, coal, liquefaction, temperature-staged

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Authors: Julide Hizal Yucesoy, Batuhan Yardimci, Aysem Arda, Resat Apak

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Humic substances produce reactive oxygene species such as hydroxyl, phenoxy and superoxide radicals by oxidizing in a wide pH and reduction potential range. Hydroxyl radicals, produced by reducing agents such as antioxidants and/or peroxides, attack on salicylate probe, and form 2,3-dihydroxybenzoate, 2,4-dihydroxybenzoate and 2,5-dihydroxybenzoate species. These species are quantitatively determined by using HPLC Method. Humic substances undergo photodegradation by UV radiation. As a result of their antioxidant properties, they produce hydroxyl radicals. In the presence of salicylate probe, these hydroxyl radicals react with salicylate molecules to form hydroxylated products (dihidroxybenzoate isomers). In this study, humic acid was photodegraded in a photoreactor at 254 nm (400W), formed hydroxyl radicals were caught by salicylate probe. The total concentration of hydroxylated salicylate species was measured by using spectrophotometric CUPRAC Method. And also, using results of time dependent experiments, kinetic of photohydroxylation was determined at different pHs. This method has been applied for the first time to measure the concentration of hydroxylated products. It allows to achieve the results easier than HPLC Method.

Keywords: CUPRAC method, humic acid, photohydroxylation, salicylate probe

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Authors: Yasser Gaber, Mohamed Ismail, Serena Bisagni, Mohamad Takwa, Rajni Hatti-Kaul

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Enzymes are safe and selective catalysts. They skillfully catalyze chemical reactions; however, the native form is not usually suitable for industrial applications. Enzymes are therefore engineered by several techniques to meet the required catalytic task. Clopidogrel is recorded among the five best selling pharmaceutical in 2010 under the brand name Plavix. The commonly used route for production of the drug on an industrial scale is the synthesis of the racemic mixture followed by diastereomeric resolution to obtain the pure S isomer. The process consumes a lot of solvents and chemicals. We have evaluated a biocatalytic cleaner approach for asymmetric hydrolysis of racemic clopidogrel. Initial screening of a selected number of hydrolases showed only one enzyme EST to exhibit activity and selectivity towards the desired stereoisomer. As the crude EST is a mixture of several isoenzymes, a homology model of EST-1 was used in molecular dynamic simulations to study the interaction of the enzyme with R and S isomers of clopidogrel. Analysis of the geometric hindrances of the tetrahedral intermediates revealed a potential site for mutagenesis in order to improve the activity and the selectivity. Single point mutation showed dramatic increase in activity and inversion of the enantioselectivity (400 fold change in E value).

Keywords: biocatalysis, biotechnology, enzyme, protein engineering, molecular modeling

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Authors: M. Nagaraja, H. M. Mahesh, K. Rajanna, M. Z. Kurian, J. Manjanna

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In recent years, composites of conjugated polymers with fullerenes (C60) has attracted considerable scientific and technological attention in the field of organic electronics because they possess a novel combination of electrical, optical, ferromagnetic, mechanical and sensor properties. These properties represent major advances in the design of organic electronic devices. With the addition of C60 in the conjugated polymer matrix, the primary photo-excitation of the conjugated polymer undergoes an ultrafast electron transfer, and it has been demonstrated that fullerene molecules may serve as efficient electron acceptors in polymeric solar cells. The present paper includes the systematic studies on the effect of electrical, structural and sensor properties of polyaniline (PANI) matrix by the presence of C60. Polyaniline-fullerene (PANI/C60) composite is prepared by the introduction of fullerene during polymerization of aniline with ammonium persulfate and dodechyl benzene sulfonic acid as oxidant and dopant respectively. FTIR spectroscopy indicated the interaction between PANI and C60. X-ray diffraction proved the formation of a PANI/C60 complex. SEM image shows the highly branched chain structure of the PANI in the presence of C60. The conductivity of the PANI/C60 was found to be more than ten orders of magnitude over the pure PANI.

Keywords: conductivity, fullerene, nanocomposite, polyaniline

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Authors: M. Helen

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Chemical graph serves as a convenient model for any real or abstract chemical system. Dendrimers are novel three dimensional hyper branched globular nanopolymeric architectures. Drug delivery scientists are especially enthusiastic about possible utility of dendrimers as drug delivery tool. Dendrimers like poly L lysine (PLL), poly-propylene imine (PPI) and poly-amidoamine (PAMAM), etc., are used as gene carrier in drug delivery system because of their chemical characteristics. These characteristics of chemical compounds are analysed using topological indices (invariants under graph isomorphism) such as Wiener index, Zagreb index, etc., Prof. V. R. Kulli motivated by the application of Zagreb indices in finding the total π energy and derived Gourava indices which is an improved version over Zagreb indices. In this paper, we study the structure of PLL-Dendrimer that has the following applications: reduction in toxicity, colon delivery, and topical delivery. Also, we determine first and second Gourava indices, first and second hyper Gourava indices, product and sum connectivity Gourava indices for PLL-Dendrimer. Gourava Indices have found applications in Quantitative Structure-Property Relationship (QSPR)/ Quantitative Structure-Activity Relationship (QSAR) studies.

Keywords: connectivity Gourava indices, dendrimer, Gourava indices, hyper GouravaG indices

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Authors: Rasha S. Kamal, Reham I. El-Shazly, Reem K. Farag

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Green nano-branched structural compounds were synthesized by adding 1% by weight of clay nanoparticle to different moles ratios of either dodecyl acrylate or triethylenetetramine using a simple one-pot method. The synthesized nano polymers were provided with different terminations. In order to confirm the chemical structure of the produced nanocomposites, FTIR and 1HNMR spectroscopy were performed. Additionally, Dynamic Light Scattering (DLS) analysis was used to assess the size and dispersion of the produced branching nano polymers. Using a Gel-permeation chromatograph, the molecular weights of the produced modified green nano hyperbranched polymer with various terminations were determined. the prepared nano samples with different molar feed ratios dodecyl acrylate: triethylenetetramine (DDA: TETA) was designed as An, Bn, Cn, Dn and En. Moreover, the synthesized compounds are expressed as viscosity index improvers (VII); The VI rises when prepared additive concentrations in the solution improve, as does the VI as prepared hyperbranched polymers' triethylenetetramine content rises, and the most effective VI is (E). All of the synthesized green hyperbranched nanocomposites have Newtonian rheological behavior as their rheological behavior.

Keywords: green hyperbranched polymer, DLS, viscosity index improver, Michael addition, nano clay

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Authors: Sushil Kumar Saraswat, K. K. Pant

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Co metal supported on SiO2 and Al2O3 catalysts with a metal loading varied from 30 of 70 wt.% were evaluated for decomposition of methane to CO/CO2 free hydrogen and carbon nano materials. The catalytic runs were carried out from 550-800 oC under atmospheric pressure using fixed bed vertical flow reactor. The fresh and spent catalysts were characterized by BET surface area analyzer, TPR, XRD, SEM, TEM, and TG analysis. The data showed that 50% Co/Al2O3 catalyst exhibited remarkable higher activity and stability up to 10 h time-on-stream at 750 oC with respect to H2 production compared to rest of the catalysts. However, the catalytic activity and durability was greatly declined at a higher temperature. The main reason for the catalytic inhibition of Co containing SiO2 catalysts is the higher reduction temperature of Co2SiO4. TEM images illustrate that the carbon materials with various morphologies, carbon nanofibers (CNFs), helical-shaped CNFs, and branched CNFs depending on the catalyst composition and reaction temperature, were obtained. The TG data showed that a higher yield of MWCNTs was achieved over 50% Co/Al2O3 catalyst compared to other catalysts.

Keywords: carbon nanotubes, cobalt, hydrogen production, methane decomposition

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Authors: A. Szabó Nagy, J. Szabó, Zs. Csanádi, J. Erdős

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In Hungary, the measurement of ambient PM10-bound polycyclic aromatic hydrocarbon (PAH) concentrations is great importance for a number of reasons related to human health, the environment and compliance with European Union legislation. However, the monitoring of PAHs associated with PM2.5 aerosol fraction is still incomplete. Therefore, the main aim of this study was to investigate the concentration levels of PAHs in PM2.5 urban aerosol fraction. PM2.5 and associated PAHs were monitored in November 2014 in an urban site of Győr (Northwest Hungary). The aerosol samples were collected every day for 24-hours over two weeks with a high volume air sampler provided with a PM2.5 cut-off inlet. The levels of 19 PAH compounds associated with PM2.5 aerosol fraction were quantified by a gas chromatographic method. Polluted air quality for PM2.5 (>25 g/m3) was indicated in 50% of the collected samples. The total PAHs concentrations ranged from 2.1 to 37.3 ng/m3 with the mean value of 12.4 ng/m3. Indeno(123-cd)pyrene (IND) and sum of three benzofluoranthene isomers were the most dominant PAH species followed by benzo(ghi)perylene and benzo(a)pyrene (BaP). Using BaP-equivalent approach on the concentration data of carcinogenic PAH species, BaP, and IND contributed the highest carcinogenic exposure equivalent (1.50 and 0.24 ng/m3 on average). A selected number of concentration ratios of specific PAH compounds were calculated to evaluate the possible sources of PAH contamination. The ratios reflected that the major source of PAH compounds in the PM2.5 aerosol fraction of Győr during the study period was fossil fuel combustion from automobiles.

Keywords: air, PM2.5, benzo(a)pyrene, polycyclic aromatic hydrocarbon

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Authors: Mbongeni Mabaso, Kandasamy Moodley, Gan Redhi

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The recovery of industrially valuable organic solvents from liquid waste, generated in chemical processes, is economically crucial to countries which need to import organic solvents. In view of this, the main objective of this study was to determine the ability of selected ionic liquids, namely, 1-ethyl-3-methylimidazolium ethylsulphate, [EMIM] [ESO4] and 1-ethyl-3-methylpyridinium ethylsulphate, [EMpy][ESO4] to recover aromatic components from spent paint solvents. Preliminary studies done on the liquid waste, received from a paint manufacturing company, showed that the aromatic components were present in the range 6 - 21 % by volume. The separation of the aromatic components was performed with the ionic liquids listed above. The phases, resulting from the separation of the mixtures, were analysed with a Gas Chromatograph (GC) coupled to a FID detector. Chromatograms illustrate that the chosen ZB-Wax-Plus column gave excellent separation of all components of interest from the mixtures, including the isomers of xylene. The concentrations of aromatics recovered from the spent solvents were found to be the % ranges 13-33 and 23-49 respectively for imidazolium and pyridinium ionic liquids. These results also show that there is a significant correlation between π-character of ionic liquids and the level of extraction. It is therefore concluded that ionic liquids have the potential for macro-scale recovery of re-useable solvents present in liquid waste emanating from paint manufacture.

Keywords: synthesis, ionic liquid, imidazolium, pyridinium, extraction, aromatic solvents, spent paint organic solvents

Procedia PDF Downloads 337