Search results for: benzo[a]pyrene

Authors: Ali Bahri Lubis

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Tryptophan oxidation by Heme-dioxygenase enzyme is the initial rate-limiting step in the kynurenine pathway, which leads to the formation of NADH and dangerous metabolites, implicating several severe diseases such as Parkinson’s Disease, Huntington's Disease, poliomyelitis and cataract. This oxidation, generally, allows tryptophan to convert to N-Formylkynurenine (NFK). Observing the catalytic mechanism of Heme dioxygenase in tryptophan oxidation has been a debatably scientific interest 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) utilising various substrates: L-tryptophan, L-tryptophan (indole-ring-2-¹³C), L-fully-labelled¹³C-tryptophan, L-N-methyl-tryptophan, L-tryptophanol 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 synthesised enzyme products as our control in NMR measurements. The result exhibited that all substrates produced N-formyl kynurenine (NFK), and a side, the minor product of hydroxypyrrolloindoleamine carboxylic acid (HPIC) in cis and trans isomer, except 1-methyl tryptophan only generating cis HPIC. Interestingly, L- tryptophanol was oxidised to form HPIC derivative as a major product and 5-hydroxy tryptophan was converted to NFK derivative instead without any HPIC derivative. The bizarre result of oxidation underwent in 2-amino-3-(benzo(b)thiophene-3-yl) propanoic acid, which produced epoxide cyclic. Those phenomena have been explainable in our research based on the proposed mechanism of how tryptophan is oxidised by human indoleamine dioxygenase.

Keywords: tryptophan oxidation, heme-dioxygenases, human indoleamine dioxygenases, N-formylkynurenine, hydroxypyrroloindoleamine carboxylic acid

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Authors: Momita Das, Sofia Banu, Jibon Kotoky

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

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

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Authors: Kali Prasad Sarma, Nibedita Baul, Jinu Deka

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

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

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Authors: Huda Qari, I. A. Hassan

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The brown alga Padina boryanawas was used for bioassay of polycyclic aromatic hydrocarbons (PAHs) accumulation at the seashore of Jeddah city. PAHs were determined in the coastal water and algal tissues by GC-MS. Acenaphthene (Ace) and dibenzo (a,h) anthracene (dB(a,h)An) were the main PAHs in seawater (50.02 and 46.18) and algal tissues (64.67 and 72.45), respectively. The ratios of low molecular weight/high molecular weight hydrocarbons (1.76 – 1.44), fluoranthene/pyrene (1.57 – 1.52) and phenanthrene/anthracene (0.86 – 0.67) in seawater and algal tissues, respectively, indicated the origin of the PAHs to be mainly petrogenic. This study has demonstrated the utility of using Padina boryanawas as a biomonitor of PAH contamination and bioavailability in the coastal waters.

Keywords: polycyclic aromatic hydrocarbons, Padina boryanawas, bioaccumulation, waste water

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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: Mathew Tran, Deepa Patel, Breann Prophete, Irandokht Khaki Najafabadi

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Status epilepticus is a neurological disorder requiring emergent control with medical therapy. Based on guideline recommendations for adults with status epilepticus, the first-line treatment is to start a benzodiazepine, as they are quick at seizure control. The second step is to initiate a non-benzodiazepine anti-epileptic drug to prevent refractory seizures. Studies show that the anti-epileptic drugs are approximately equivalent in status epilepticus control once a benzodiazepine has been given. This review provides a brief overview of the management of status epilepticus based on evidence from the literature and evidence-based guidelines.

Keywords: neurological disorder, seizure, status epilepticus, benzo diazepines, antiepileptic agents

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Authors: Jyoti Singh, Ranju Bansal

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Fighting pain and inflammation is a common problem faced by physicians while dealing with a wide variety of diseases. Since ancient time nonsteroidal anti-inflammatory agents (NSAIDs) and opioids have been the cornerstone of treatment therapy, however, the usefulness of both these classes is limited due to severe side effects. NSAIDs, which are mainly used to treat mild to moderate inflammatory pain, induce gastric irritation and nephrotoxicity whereas opioids show an array of adverse reactions such as respiratory depression, sedation, and constipation. Moreover, repeated administration of these drugs induces tolerance to the analgesic effects and physical dependence. Further discovery of selective COX-2 inhibitors (coxibs) suggested safety without any ulcerogenic side effects; however, long-term use of these drugs resulted in kidney and hepatic toxicity along with an increased risk of secondary cardiovascular effects. The basic approaches towards inflammation and pain treatment are constantly changing, and researchers are continuously trying to develop safer and effective anti-inflammatory drug candidates for the treatment of different inflammatory conditions such as osteoarthritis, rheumatoid arthritis, ankylosing spondylitis, psoriasis and multiple sclerosis. Synthetic 3(2H)-pyridazinones constitute an important scaffold for drug discovery. Structure-activity relationship studies on pyridazinones have shown that attachment of a lactam at N-2 of the pyridazinone ring through a methylene spacer results in significantly increased anti-inflammatory and analgesic properties of the derivatives. Further introduction of the heterocyclic ring at lactam nitrogen results in improvement of biological activities. Keeping in mind these SAR studies, a new series of compounds were synthesized as shown in scheme 1 and investigated for anti-inflammatory, analgesic, anti-platelet activities and docking studies. The structures of newly synthesized compounds have been established by various spectroscopic techniques. All the synthesized pyridazinone derivatives exhibited potent anti-inflammatory and analgesic activity. Homoveratryl substituted derivative was found to possess highest anti-inflammatory and analgesic activity displaying 73.60 % inhibition of edema at 40 mg/kg with no ulcerogenic activity when compared to standard drugs indomethacin. Moreover, 2-substituted-4-benzo[d][1,3]dioxole-6-phenylpyridazin-3(2H)-ones derivatives did not produce significant changes in bleeding time and emerged as safe agents. Molecular docking studies also illustrated good binding interactions at the active site of the cyclooxygenase-2 (hCox-2) enzyme.

Keywords: anti-inflammatory, analgesic, pyridazin-3(2H)-one, selective COX-2 inhibitors

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Authors: Dheepshika Kodieswaran

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The persisting problem in the world that continuously impose our planet at risk is the increasing amounts of recalcitrant. One such issue is the disposal of the Petroleum Refinery Sludge (PRS) which constitutes hydrocarbons that are hazardous to terrestrial and aquatic life. The comparatively safe approach to handling these wastes is by microbial degradation, while the other chemical and physical methods are either expensive and/or produce secondary pollutants. The bacterial and algal systems have different pathways for the degradation of hydrocarbons, and their growth rates vary. This study shows how different bacterial and microalgal strains degrade the polyaromatic hydrocarbon PAHs individually and their symbiotic influence on degradation as well. In this system, the metabolites and gaseous exchange help each other in growth. This method using also aids in the accumulation of lipids in microalgal cells and from which bio-oils can also be extracted. The bacterial strains used in this experiment are reported to be indigenous strains isolated from PRS. The target PAH studied were anthracene and pyrene for a period of 28 days. The PAH degradation kinetics best fitted the Gompertz model, and the order of the kinetics, rate constants, and half-life was determined.

Keywords: petroleum refinery sludge, co-culturing, polycyclic hydrocarbons, microalgal-bacterial consortia

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Authors: Swapna Guntupalli, Leela Madhuri Chalasani, Kshatri Jyothi, C. V. Rao, Bondili J. S.

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The study hypothesizes that enhanced biodegradation of Polycyclic Aromatic Hydrocarbons (PAHs) is achievable with an assemblage of microorganisms that are capable of producing biofilm and biosurfactants. Accordingly, PAHs degrading microorganism’s (bacteria, fungi, actinomycetes and yeast) were screened and grouped into different consortia based on their capabilities to produce biofilm and biosurfactants. Among these, Consortium BTSN09 consisting of bacterial fungal cocultures showed highest degradation due to the synergistic action between them. Degradation effiencies were evaluated using HPLC and GC-MS. Within 7days, BTSN09 showed 51% and 50.7% degradation of Phenanthrene (PHE) and Pyrene (PYR) with 200mg/L and 100 mg/L concentrations respectively in a liquid medium. In addition, several degradative enzymes like laccases, 1hydroxy-2-naphthoicacid dioxygenase, 2-carboxybenzaldehyde dehydrogenase, catechol1,2 dioxygenase and catechol2,3 dioxygenase activity was observed during degradation. Degradation metabolites were identified using GC-MS analysis and from the results it was confirmed that the metabolism of degradation proceeds via pthalic acid pathway for both PAHs. Besides, Microbial consortia also demonstrated good biosurfactant production capacity, achieving maximum oil displacement area and emulsification activity of 19.62 cm2, 65.5% in presence of PAHs as sole carbon source. Scanning Electron Microscopy analysis revealed exopolysaccharides (EPS) production, micro and macrocolonies formation with different stages of biofim development in presence of PAHs during degradation.

Keywords: PAHs, biosurfactant, biofilm, biodegradation

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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: Pengwei Qiao, Sucai Yang, Wenxia Wei

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Soil pollution has become an important issue in China. Accurate spatial distribution prediction of pollutants with interpolation methods is the basis for soil remediation in the site. However, a relatively strong variability of pollutants would decrease the prediction accuracy. Theoretically, partition interpolation can result in accurate prediction results. In order to verify the applicability of partition interpolation for a site, benzo (b) fluoranthene (BbF) in four soil layers was adopted as the research object in this paper. IDW (inverse distance weighting)-, RBF (radial basis function)-and OK (ordinary kriging)-based partition interpolation accuracies were evaluated, and their influential factors were analyzed; then, the uncertainty and applicability of partition interpolation were determined. Three conclusions were drawn. (1) The prediction error of partitioned interpolation decreased by 70% compared to unpartitioned interpolation. (2) Partition interpolation reduced the impact of high CV (coefficient of variation) and high concentration value on the prediction accuracy. (3) The prediction accuracy of IDW-based partition interpolation was higher than that of RBF- and OK-based partition interpolation, and it was suitable for the identification of highly polluted areas at a contaminated site. These results provide a useful method to obtain relatively accurate spatial distribution information of pollutants and to identify highly polluted areas, which is important for soil pollution remediation in the site.

Keywords: accuracy, applicability, partition interpolation, site, soil pollution, uncertainty

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Authors: Young Nam Chun, Mun Sup Lim, Byeo Ri Jeong

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Sewage sludge is regarded as the residue produced by the waste water treatment process, during which liquids and solids are being separated. Thermal treatments are interesting techniques to stabilize the sewage sludge for disposal. Among the thermal treatments, pyrolysis and/or gasification has been being applied to the sewage sludge. The final goal of our NRF research is to develop a microwave In-line Drying-Pyrolysis-Gasification (IDPG) technology for the dewatered sewage sludge for the bio-waste to energy conversion. As a first step, the pyrolysis characteristics in a bench scale electric furnace was investigated at 800℃ for the dewatered sludge and dried sludge samples of which moisture contents are almost 80% and 0%, respectively. Main components of producer gas are hydrogen and carbon dioxide. Particularly, higher hydrogen for the dewatered sludge is shown as 75%. The hydrogen production for the dewatered sludge and dried sludge are 56% and 32%, respectively. However, the pyrolysis for the dried sludge produces higher carbon dioxide and other gases, while higher methane and carbon dioxide are given to 74% and 53%, respectively. Tar also generates during the pyrolysis process, showing lower value for case of the dewatered sludge. Gravimetric tar is 195 g/m3, and selected light tar like benzene, naphthalene, anthracene, pyrene are 9.4 g/m3, 2.1 g/m3, 0.5 g/m3, 0.3 g/m3, respectively. After the pyrolysis process, residual char for the dewatered sludge and dried sludge remain 1g and 1.3g, showing weight reduction rate of 93% and 57%, respectively. Through the results, this could be known that the dewatered sludge can be used to produce a clean hydrogen-rich gas fuel without the drying process. Therefore, the IDPG technology can be applied effectively to the energy conversion for dewater sludge waste without a drying pretreatment. Acknowledgment: This work was supported by the National Research Foundation of Korea(NRF) grant funded by the Korea government(MSIP) (No. 2015R1A2A2A03003044).

Keywords: pyrolysis, gasification, sewage sludge, tar generation, producer gas, sludge char, biomass energy

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Authors: Ismail Celik, Gulgun Ayhan Kilcigil, Berna Guven, Zumra Kara, Arzu Onay-Besikci

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Epidermal Growth Factor Receptor is the cell-surface receptor of the ErbB (erythroblastic leukemia viral oncogene homologue receptors) family of tyrosine kinases. It plays a vital role in regulating the proliferation and differentiation of cells. However, a variety of mechanisms, such as EGFR expression, mutation, and ligand-dependent receptor dimerization, are associated with the development of various activated EGFR tumors. EGFR is highly expressed in most solid tumors, including breast, head and neck cancer, non-small cell lung cancer (NSCLC), renal, ovarian, and colon cancers. Thus, specific EGFR inhibition plays one of the key roles in cancer treatment. The compounds used in the treatment as tyrosine kinase inhibitors are known to contain the benzimidazole isosterium indole, pazopanib, and axitinibin indazole rings. In addition, benzimidazoles have been shown to exhibit protein kinase inhibitory activity in addition to their different biological activities.Based on these data, it was planned and synthesized of some oxadiazole bearing benzimidazole derivatives [N-cyclohexyl-5-((2-phenyl/substitutedphenyl-1H-benzo[d]imidazole-1-yl) methyl)-1,3,4-oxadiazole-2-amine]. EGFR kinase inhibitory efficiency of the synthesized compounds was determined by comparing them with a known kinase inhibitor erlotinib in vitro, and two of the compounds bearing phenyl (19a) and 3,4-dibenzyloxyphenyl (21a) ring exhibited significant activities.

Keywords: benzimidazole, EGFR kinase inhibitory, oxadiazole, synthesis

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Authors: N. F. Hamid, A. Kipar, J. Stewart, D. J. Antoine, B. K. Park, D. P. Williams

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Acetaminophen (APAP) is a widely used analgesic that is safe at therapeutic doses. The mouse model of APAP has been extensively used for studies on pathogenesis and intervention of drug induced liver injury based on the CytP450 mediated formation of N-acetyl-p-benzo-quinoneimine and, more recently, as model for mechanism based biomarkers. Delay of the fasted CD1 mice to rebound to the basal level of hepatic GSH compare to fed mice is reported in this study. Histologically, 15 hours fasted mice prior to APAP treatment leading to overall more intense cell loss with no evidence of apoptosis as compared to non-fasted mice, where the apoptotic cells were clearly seen on cleaved caspase-3 immunostaining. After 15 hours post APAP administration, hepatocytes underwent stage of recovery with evidence of mitotic figures in fed mice and return to completely no histological difference to control at 24 hours. On the contrary, the evidence of ongoing cells damage and inflammatory cells infiltration are still present on fasted mice until the end of the study. To further measure the regenerative capacity of the hepatocytes, the inflammatory mediators of cytokines that involved in the progression or regression of the toxicity like TNF-α and IL-6 in liver and spleen using RT-qPCR were also included. Yet, quantification of proliferating cell nuclear antigen (PCNA) has demonstrated the time for hepatic regenerative in fasted is longer than that to fed mice. Together, these data would probably confirm that fasting prior to APAP treatment does not only modulate liver injury, but could have further effects to delay subsequent regeneration of the hepatocytes.

Keywords: acetaminophen, liver, proliferating cell nuclear antigen, regeneration, apoptosis

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Authors: V. E. Messerle, A. B. Ustimenko, O. A. Lavrichshev

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A large amount of manure and its irrational use negatively affect the environment. As compared with biomass fermentation, plasma processing of manure enhances makes it possible to intensify the process of obtaining fuel gas, which consists mainly of synthesis gas (CO + H₂), and increase plant productivity by 150–200 times. This is achieved due to the high temperature in the plasma reactor and a multiple reduction in waste processing time. This paper examines the plasma processing of biomass using the example of dried mixed animal manure (dung with a moisture content of 30%). Characteristic composition of dung, wt.%: Н₂О – 30, С – 29.07, Н – 4.06, О – 32.08, S – 0.26, N – 1.22, P₂O₅ – 0.61, K₂O – 1.47, СаО – 0.86, MgO – 0.37. The thermodynamic code TERRA was used to numerically analyze dung plasma gasification and pyrolysis. Plasma gasification and pyrolysis of dung were analyzed in the temperature range 300–3,000 K and pressure 0.1 MPa for the following thermodynamic systems: 100% dung + 25% air (plasma gasification) and 100% dung + 25% nitrogen (plasma pyrolysis). Calculations were conducted to determine the composition of the gas phase, the degree of carbon gasification, and the specific energy consumption of the processes. At an optimum temperature of 1,500 K, which provides both complete gasification of dung carbon and the maximum yield of combustible components (99.4 vol.% during dung gasification and 99.5 vol.% during pyrolysis), and decomposition of toxic compounds of furan, dioxin, and benz(a)pyrene, the following composition of combustible gas was obtained, vol.%: СО – 29.6, Н₂ – 35.6, СО₂ – 5.7, N₂ – 10.6, H₂O – 17.9 (gasification) and СО – 30.2, Н₂ – 38.3, СО₂ – 4.1, N₂ – 13.3, H₂O – 13.6 (pyrolysis). The specific energy consumption of gasification and pyrolysis of dung at 1,500 K is 1.28 and 1.33 kWh/kg, respectively. An installation with a DC plasma torch with a rated power of 100 kW and a plasma reactor with a dung capacity of 50 kg/h was used for dung processing experiments. The dung was gasified in an air (or nitrogen during pyrolysis) plasma jet, which provided a mass-average temperature in the reactor volume of at least 1,600 K. The organic part of the dung was gasified, and the inorganic part of the waste was melted. For pyrolysis and gasification of dung, the specific energy consumption was 1.5 kWh/kg and 1.4 kWh/kg, respectively. The maximum temperature in the reactor reached 1,887 K. At the outlet of the reactor, a gas of the following composition was obtained, vol.%: СO – 25.9, H₂ – 32.9, СO₂ – 3.5, N₂ – 37.3 (pyrolysis in nitrogen plasma); СO – 32.6, H₂ – 24.1, СO₂ – 5.7, N₂ – 35.8 (air plasma gasification). The specific heat of combustion of the combustible gas formed during pyrolysis and plasma-air gasification of agricultural waste is 10,500 and 10,340 kJ/kg, respectively. Comparison of the integral indicators of dung plasma processing showed satisfactory agreement between the calculation and experiment.

Keywords: agricultural waste, experiment, plasma gasification, thermodynamic calculation

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Authors: Lucero Gonzalez, Salvador Alfaro

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Carbon dioxide (CO2) and methane (CH4) are considered as the compounds with higher abundance among the greenhouse gases (CO2, NOx, SOx, CxHx, etc.), due to its higher concentration, this two gases have a greater impact in the environment pollution and provokes global warming. So, recovery, disposal and subsequent reuse, are of great interest, especially from the ecological and health perspective. By one hand, porous inorganic materials are good candidates to capture gases, because these type of materials are higher stability from the point view of thermal, chemical and mechanical under adsorption gas processes. By another hand, during the design and the synthetic preparation of the porous materials is possible add other intrinsic properties (physicochemical and structural) by adding chemical compounds as dopants or using structured directed agents or surfactants to improve the porous structure, the above features allow to have alternative materials for separation, capture and storage of greenhouse gases. In this work, ordered mesoporous materials base silica were prepared using Surfynol as surfactant. The surfactant micelles are commonly used as self-assembly templates for the development of new structure porous silica’s, adding a variety of textures and structures. By another hand, the Surfynol is a commercial surfactant, is non-ionic, for that is necessary determine its critical micelles concentration (cmc) by the pyrene I1/I3 ratio method, before to prepare silica particles. One time known the CMC, a precursor gel was prepared via sol-gel process at room temperature using TEOS as silica precursor, NH4OH as catalyst, Surfynol as template and H2O as solvent. Then, the gel precursor was treatment hydrothermally in a Teflon-lined stainless steel autoclave with a volume of 100 mL and kept at 100 ºC for 24 h under static conditions in a convection oven. After that, the porous silica particles obtained were impregnated with lithium to improve the CO2 adsorption capacity. Then the silica particles were characterized physicochemical, morphology and structurally, by XRD, FTIR, BET and SEM techniques. The thermal stability and the CO2 adsorption capacity was evaluated by thermogravimetric analysis (TGA). According the results, we found that the Surfynol is a good candidate to prepare silica particles with an ordered structure. Also the TGA analysis shown that the particles has a good thermal stability in the range of 250 °C and 800 °C. The best materials had, the capacity to adsorbing 70 and 90 mg per gram of silica particles and its CO2 adsorption capacity depends on the way to thermal pretreatment of the porous silica before of the adsorption experiments and of the concentration of surfactant used during the synthesis of silica particles. Acknowledgments: This work was supported by SIP-IPN through project SIP-20161862.

Keywords: CO2 adsorption, lithium as dopant, porous silica, surfynol as surfactant, thermogravimetric analysis

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Authors: Igor Jerkovic

Abstract:

Owing to the attractive sensory properties and low odour thresholds, norisoprenoids (degraded carotenoid-like structures with 3,5,5-trimethylcyclohex-2-enoic unit) have been identified as aroma contributors in a number of different matrices. C₁₃-Norisoprenoids have been found among volatile organic compounds of various honey types as well as C₉//C₁₀-norisoprenoids or C₁₄/C₁₅-norisoprenoids. Besides degradation of abscisic acid (which produces, e.g., dehydrovomifoliol, vomifoliol, others), the cleavage of the C(9)=C(10) bond of other carotenoid precursors directly generates nonspecific C₁₃-norisoprenoids such as trans-β-damascenone, 3-hydroxy-trans-β-damascone, 3-oxo-α-ionol, 3-oxo-α-ionone, β-ionone found in various honey types. β-Damascenone and β-ionone smelling like honey, exhibit the lowest odour threshold values of all C₁₃-norisoprenoids. The presentation is targeted on two uncommon C₁₃-norisoprenoids in the honey flavor that could be used as specific or nonspecific chemical markers of the botanical origin. Namely, after screening of different honey types, the focus was directed on Centaruea cyanus L. and Allium ursinum L. honey. The samples were extracted by headspace solid-phase microextraction (HS-SPME) and ultrasonic solvent extraction (USE) and the extracts were analysed by gas chromatography and mass spectrometry (GC-MS). SPME fiber with divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) coating was applied for the research of C. cyanus honey headspace and predominant identified compound was 3,4-dihydro-3-oxoedulan (2,5,5,8a-tetramethyl-2,3,5,6,8,8a-hexahydro-7H-chromen-7-one also known as 2,3,5,6,8,8a-hexahydro-2,5,5,8a-tetramethyl-7H-1-benzo-pyran-7-one). The oxoedulan structure contains epoxide and it is more volatile in comparison with its hydroxylated precursors. This compound has not been found in other honey types and can be considered specific for C. cyanus honey. The dichloromethane extract of A. ursinum honey contained abundant (E)-4-(r-1',t-2',c-4'-trihydroxy-3',6',6'-trimethylcyclohexyl)-but-3-en-2-one that was previously isolated as dominant substance from the ether extracts of New Zealand thyme honey. Although a wide variety of degraded carotenoid-like substances have been identified from different honey types, this appears to be rare situation where 3,4-dihydro-3-oxoedulan and (E)-4-(r-1',t-2',c-4'-trihydroxy-3',6',6'-trimethylcyclohexyl)-but-3-en-2-one have been found that is of great importance for chemical fingerprinting and identification of the chemical biomarkers that can complement the pollen analysis as the major method for the honey classification.

Keywords: 3, 4-dihydro-3-oxoedulan, (E)-4-(r-1', t-2', c-4'-trihydroxy-3', 6', 6'-trimethylcyclohexyl)-but-3-en-2-one, honey flavour, C₁₃-norisoprenoids

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Authors: N. Gopal, K. Jaasminerjiit, L. Z. Xiang

Abstract:

Quinazoline-4(3H)-one ring system has been consistently regarded as promising privileged structural icon owing to its pharmacodynamic versatility in many of its synthetic derivatives as well as in several naturally occurring alkaloids. The literature reveals that 2nd & 3rd positions of the quinazolin-4(3H)-one pharmacophore are the target for substitution with other moieties. On the other hand, sulphanilamide derivatives and isatin moiety also displayed valuable biological activities. Hence, it was thought worthwhile to study the effects of three pharmacophoric moieties like quinazolinone, sulphanilamide and isatin in a single molecule for the better analgesic activity with lower toxicity. Series of novel 2,3-disubstituted quinazolin-4(3H)-one derivatives have been synthesised from the intermediate Schiff base of 2-(4’-substitutedphenyl)-3-[(N-2-oxoindolin-3-ylidene)-4”-sulphonamidophenyl]-quinazolin-4(3H)-one derivatives, which was prepared from reacting 2-(substituted phenyl)-4H-benzo[d][1,3]-oxazin-4-one with sulphanilamide. The required benzoxazinone derivatives were prepared by reacting anthranilic acid with benzoyl chloride. All the compounds structure was characterised by using H1 NMR, IR and Mass spectroscopy. The intermediate Schiff base and final Mannich base compounds were evaluated for their analgesic activity by acetic acid-induced writhing method at the dose of 25mg/kg, 50 mg/kg, and 100 mg/kg (bw) and Diclofenac (25mg/kg of body weight) will be used as the reference drugs. From the results of the study, it has been observed that final Mannich base showed a better analgesic activity when compared to the parent Schiff bases, it was found that compound substituted with N-methyl piperazine at 1st position of the indole nucleus of the final quinazolinone derivatives (GA4B1) i.e. 2-(4’-methoxy phenyl)-3-[4-(N-(1-N-methyl piperazine amine) methyl-2-oxo indoilin-3-ylidene] benzenesulfonyl quinazolin-4(3H)-one increases the analgesic activity and among the synthesised compounds, GA4B1 exhibited quite superior analgesic activity. The remaining Schiff bases and Mannich base derivatives exhibited moderate analgesic activity. All the compounds showed a dose dependent activity. None of the synthesised compound showed ulcer index whereas the standard drug, diclofenac [25 mg/kg (bw)] showed significantly higher gross ulcer index values.

Keywords: analgesic activity, isatin, mannich base, quinazolin-4(3H)-one

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Authors: Pei-Ying Lo, Jing-Hao Ciou, Kai-Cheng Yang, Jia-Huei Zheng, Shih-Hsiang Huang, Kuen-Chan Lee, Er-Chieh Cho

Abstract:

As-produced CNTs are insoluble in all organic solvents and aqueous solutions have imposed limitations to the use of CNTs. Therefore, how to debundle carbon nanotubes and to modify them for further uses is an important issue. There are several methods for the dispersion of CNTs in water using covalent attachment of hydrophilic groups to the surface of tubes. These methods, however, alter the electronic structure of the nanotubes by disrupting the network of sp2 hybridized carbons. In order to keep the nanotubes’ intrinsic mechanical and electrical properties intact, non-covalent interactions are increasingly being explored as an alternative route for dispersion. Apart from conventional surfactants such as sodium dodecylsulfate (SDS) or sodium dodecylbenzenesulfonate (SDBS) which are highly effective in dispersing CNTs, biopolymers have received much attention as dispersing agents due to the anticipated biocompatibility of the dispersed CNTs. Also, The pyrenyl group is known to interact strongly with the basal plane of graphene via π-stacking. In this study, a highly re-dispersible biopolymer is reported for the synthesis of pyrene-modified poly-L-lysine (PBPL) and poly(D-Glu, D-Lys) (PGLP). To provide the evidence of the safety of the PBPL/CNT & PGLP/CNT materials we use in this study, H1299 and HCT116 cells were incubated with PBPL/CNT & PGLP/CNT materials for toxicity analysis, MTS assays. The results from MTS assays indicated that no significant cellular toxicity was shown in H1299 and HCT116 cells. Furthermore, the fluorescence marker fluorescein isothiocyanate (FITC) was added to PBPL & PGLP dispersions. From the fluorescent measurements showed that the chemical functionalisation of the PBPL/CNT & PGLP/CNT conjugates with the fluorescence marker were successful. The fluorescent PBPL/CNT & PGLP/CNT conjugates could find application in medical imaging. In the next step, the GFP gene is immobilized onto PBPL/CNT conjugates by introducing electrostatic interaction. GFP-transfected cells that emitted fluorescence were imaged and counted under a fluorescence microscope. Due to the unique biocompatibility of PBPL modified CNTs, the GFP gene could be transported into H1299 cells without using antibodies. The applicability of such soluble and chemically functionalised polypeptide/CNT conjugates in biomedicine is currently investigated. We expect that this polypeptide/CNT system will be a safe and multi-functional nanomedical delivery platform and contribute to future medical therapy.

Keywords: carbon nanotube, nanotoxicology, GFP transfection, polypeptide/CNT hybrids

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Authors: Parvesh Singh, Vipan Kumar, Vishu Mehra

Abstract:

Quinoline-4-ones represent an important class of heterocyclic scaffolds that have attracted significant interest due to their various biological and pharmacological activities. This heterocyclic unit also constitutes an integral component in drugs used for the treatment of neurodegenerative diseases, sleep disorders and in antibiotics viz. norfloxacin and ciprofloxacin. The synthetic accessibility and possibility of fictionalization at varied positions in quinoline-4-ones exemplifies an elegant platform for the designing of combinatorial libraries of functionally enriched scaffolds with a range of pharmacological profles. They are also considered to be attractive precursors for the synthesis of medicinally imperative molecules such as non-steroidal androgen receptor antagonists, antimalarial drug Chloroquine and martinellines with antibacterial activity. 2-Aryl-2,3-dihydroquinolin-4(1H)-ones are present in many natural and non-natural compounds and are considered to be the aza-analogs of favanones. The β-lactam class of antibiotics is generally recognized to be a cornerstone of human health care due to the unparalleled clinical efficacy and safety of this type of antibacterial compound. In addition to their biological relevance as potential antibiotics, β-lactams have also acquired a prominent place in organic chemistry as synthons and provide highly efficient routes to a variety of non-protein amino acids, such as oligopeptides, peptidomimetics, nitrogen-heterocycles, as well as biologically active natural and unnatural products of medicinal interest such as indolizidine alkaloids, paclitaxel, docetaxel, taxoids, cyptophycins, lankacidins, etc. A straight forward route toward the synthesis of quinoline-4-ones via the triflic acid assisted Fries rearrangement of N-aryl-βlactams has been reported by Tepe and co-workers. The ring expansion observed in this case was solely attributed to the inherent ring strain in β-lactam ring because -lactam failed to undergo rearrangement under reaction conditions. Theabovementioned protocol has been recently extended by our group for the synthesis of benzo[b]-azocinon-6-ones via a tandem Michael addition–Fries rearrangement of sorbyl anilides as well as for the single-pot synthesis of 2-aryl-quinolin-4(3H)-ones through the Fries rearrangement of 3-dienyl-βlactams. In continuation with our synthetic endeavours with the β-lactam ring and in view of the lack of convenient approaches for the synthesis of C-3 functionalized quinolin-4(1H)-ones, the present work describes the single-pot synthesis of C-3 functionalized quinolin-4(1H)-ones via the trific acid promoted Fries rearrangement of C-3 vinyl/isopropenyl substituted β-lactams. In addition, DFT calculations and MD simulations were performed to investigate the stability profles of synthetic compounds.

Keywords: dihydroquinoline, fries rearrangement, azetidin-2-ones, quinoline-4-ones

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Authors: O. O. Sufyani, M. E. Oraiby, S. A. Qumaiy, A. I. Alaamri, Z. M. Eisa, A. M. Hakami, M. A. Attafi, O. M. Alhassan, W. M. Elsideeg, E. M. Noureldin, Y. A. Hobani, Y. Q. Majrabi, I. A. Khardali, A. B. Maashi, A. A. Al Mane, A. H. Hakami, I. M. Alkhyat, A. A. Sahly, I. M. Attafi

Abstract:

According to the Food and Agriculture Organization (FAO) Pesticides Use Database, pesticide use in agriculture in Saudi Arabia has more than doubled from 4539 tons in 2009 to 10496 tons in 2019. Among pesticides, pyrethroids is commonly used in Saudi Arabia. Pesticides may increase susceptibility to a variety of diseases, particularly among pesticide workers, due to their extensive use, indiscriminate use, and long-term exposure. Therefore, analyzing blood chemo-profiles and evaluating the detected substances as biomarkers for pyrethroid pesticide exposure may assist to identify and predicting adverse effects of exposure, which may be used for both preventative and risk assessment purposes. The purpose of this study was to (a) analyze chemo-profiling by Gas Chromatography-Mass Spectrometry (GC-MS) analysis, (b) identify the most commonly detected chemicals in a time-exposure-dependent manner using a Venn diagram, and (c) identify their associated disease among pesticide workers using analyzer tools on the Comparative Toxicogenomics Database (CTD) website, (250 healthy male volunteers (20-60 years old) who deal with pesticides in the Jazan region of Saudi Arabia (exposure intervals: 1-2, 4-6, 6-8, more than 8 years) were included in the study. A questionnaire was used to collect demographic information, the duration of pesticide exposure, and the existence of chronic conditions. Blood samples were collected for biochemistry analysis and extracted by solid-phase extraction for gas chromatography-mass spectrometry (GC-MS) analysis. Biochemistry analysis reveals no significant changes in response to the exposure period; however, an inverse association between the albumin level and the exposure interval was observed. The blood chemo-profiling was differentially expressed in an exposure time-dependent manner. This analysis identified the common chemical set associated with each group and their associated significant occupational diseases. While some of these chemicals are associated with a variety of diseases, the distinguishing feature of these chemically associated disorders is their applicability for prevention measures. The most interesting finding was the identification of several chemicals; erucic acid, pelargonic acid, alpha-linolenic acid, dibutyl phthalate, diisobutyl phthalate, dodecanol, myristic Acid, pyrene, and 8,11,14-eicosatrienoic acid, associated with pneumoconiosis, asbestosis, asthma, silicosis and berylliosis. Chemical-disease association study also found that cancer, digestive system disease, nervous system disease, and metabolic disease were the most often recognized disease categories in the common chemical set. The hierarchical clustering approach was used to compare the expression patterns and exposure intervals of the chemicals found commonly. More study is needed to validate these chemicals as early markers of pyrethroid insecticide-related occupational disease, which might assist evaluate and reducing risk. The current study contributes valuable data and recommendations to public health.

Keywords: occupational, toxicology, chemo-profiling, pesticide, pyrethroid, GC-MS

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