Search results for: polar molecule impurities

Authors: V. J. Pillewan, D. N. Raut, K. N. Patil, D. K. Shinde

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Forging, milling, turning, grinding and shaping etc. are the various industrial manufacturing processes which generate the metal waste. Grinding is extensively used in the finishing operation. The waste generated contains significant impurities apart from the metal particles. Due to these significant impurities, it becomes difficult to process and gets usually dumped in the landfills which create environmental problems. Therefore, it becomes essential to reuse metal waste to create value added products. Powder injection molding process is used for producing the porous metal matrix framework. This paper discusses the presented design of the porous framework to be used for the liquid filter application. Different parameters are optimized to obtain the better strength framework with variable porosity. Carbon nanotubes are used as reinforcing materials to enhance the strength of the metal matrix framework.

Keywords: grinding waste, powder injection molding (PIM), carbon nanotubes (CNTs), matrix composites (MMCs)

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Authors: Marta Kwiatkowska, Paweł Jarosiewicz, Bożena Bukowska

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Glyphosate (N-phosphonomethylglycine) is a non-selected broad spectrum ingredient in the herbicide (Roundup) used for over 35 years for the protection of agricultural and horticultural crops. Glyphosate was believed to be environmentally friendly but recently, a large body of evidence has revealed that glyphosate can negatively affect on environment and humans. It has been found that glyphosate is present in the soil and groundwater. It can also enter human body which results in its occurrence in blood in low concentrations of 73.6 ± 28.2 ng/ml. Research conducted for potential genotoxicity and cytotoxicity can be an important element in determining the toxic effect of glyphosate. Due to regulation of European Parliament 1107/2009 it is important to assess genotoxicity and cytotoxicity not only for the parent substance but also its impurities, which are formed at different stages of production of major substance – glyphosate. Moreover verifying, which of these compounds are more toxic is required. Understanding of the molecular pathways of action is extremely important in the context of the environmental risk assessment. In 2002, the European Union has decided that glyphosate is not genotoxic. Unfortunately, recently performed studies around the world achieved results which contest decision taken by the committee of the European Union. World Health Organization (WHO) in March 2015 has decided to change the classification of glyphosate to category 2A, which means that the compound is considered to "probably carcinogenic to humans". This category relates to compounds for which there is limited evidence of carcinogenicity to humans and sufficient evidence of carcinogenicity on experimental animals. That is why we have investigated genotoxicity and cytotoxicity effects of the most commonly used pesticide: glyphosate and its impurities: N-(phosphonomethyl)iminodiacetic acid (PMIDA) and bis-(phosphonomethyl)amine on human peripheral blood mononuclear cells (PBMCs), mostly lymphocytes. DNA damage (analysis of DNA strand-breaks) using the single cell gel electrophoresis (comet assay) and ATP level were assessed. Cells were incubated with glyphosate and its impurities: PMIDA and bis-(phosphonomethyl)amine at concentrations from 0.01 to 10 mM for 24 hours. Evaluating genotoxicity using the comet assay showed a concentration-dependent increase in DNA damage for all compounds studied. ATP level was decreased to zero as a result of using the highest concentration of two investigated impurities, like bis-(phosphonomethyl)amine and PMIDA. Changes were observed using the highest concentration at which a person can be exposed as a result of acute intoxication. Our survey leads to a conclusion that the investigated compounds exhibited genotoxic and cytotoxic potential but only in high concentrations, to which people are not exposed environmentally. Acknowledgments: This work was supported by the Polish National Science Centre (Contract-2013/11/N/NZ7/00371), MSc Marta Kwiatkowska, project manager.

Keywords: cell viability, DNA damage, glyphosate, impurities, peripheral blood mononuclear cells

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Authors: Seyed Mostafa Jafari Raad, Hassan Hassanzadeh

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Injection of impurities along with CO₂ into saline aquifers provides an exceptional prospect for low-cost carbon capture and storage technologies and can potentially accelerate large-scale implementation of geological storage of CO₂. We have conducted linear stability analyses and numerical simulations to investigate the effects of permitted impurities in CO₂ streams on the onset of natural convection and dynamics of subsequent convective mixing. We have shown that the rate of dissolution of an impure CO₂ stream with H₂S highly depends on the operating conditions such as temperature, pressure, and composition of impurity. Contrary to findings of previous studies, our results show that an impurity such as H₂S can potentially reduce the onset time of natural convection and can accelerate the subsequent convective mixing. However, at the later times, the rate of convective dissolution is adversely affected by the impurities. Therefore, the injection of an impure CO₂ stream can be engineered to improve the rate of dissolution of CO₂, which leads to higher storage security and efficiency. Accordingly, we have identified the most favorable CO₂ stream compositions based on the geophysical properties of target aquifers. Information related to the onset of natural convection such as the scaling relations and the most favorable operating conditions for CO₂ storage developed in this study are important in proper design, site screening, characterization and safety of geological storage. This information can be used to either identify future geological candidates for acid gas disposal or reviewing the current operating conditions of licensed injection sites.

Keywords: CO₂ storage, solubility trapping, convective dissolution, storage efficiency

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Authors: Shagufta Tabassum, V. P. Pawar

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The study of static dielectric properties in a binary mixture of 1,2 dichloroethane (DE) and n,n dimethylformamide (DMF) polar liquids has been carried out in the frequency range of 10 MHz to 30 GHz for 11 different concentration using time domain reflectometry technique at 10ºC temperature. The dielectric relaxation study of solute-solvent mixture at microwave frequencies gives information regarding the creation of monomers and multimers as well as interaction between the molecules of the binary mixture. The least squares fit method is used to determine the values of dielectric parameters such as static dielectric constant (ε₀), dielectric constant at high frequency (ε_∞) and relaxation time (τ).

Keywords: shagufta shaikhexcess parameters, relaxation time, static dielectric constant, time domain reflectometry

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Authors: SHWETA SRIKUMAR

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Winter stratospheric dynamics is a highly variable and spectacular field of research in middle atmosphere. It is well believed that the interaction of energetic planetary waves with mean flow causes the temperature to increase in the stratosphere and associated circulation reversal. This wave driven sudden disturbances in the polar stratosphere is defined as Sudden Stratospheric Warming. The main objective of the present work is to investigate the mid-winter major stratospheric warming events on equatorial dynamics over Peninsular India. To explore the effect of mid-winter stratospheric warming on Indian region (60oE -100oE), we have selected the winters 2003/04, 2005/06, 2008/09, 2012/13 and 2018/19. This study utilized the data from ERA-Interim Reanalysis, Outgoing Longwave Radiation (OLR) from NOAA and TRMM satellite data from NASA mission. It is observed that a sudden drop in OLR (averaged over Indian Region) occurs during the course of warming for the winters 2005/06, 2008/09 and 2018/19. But in winters 2003/04 and 2012/13, drop in OLR happens prior to the onset of major warming. Significant amplitude of planetary wave activity is observed in equatorial lower stratosphere which indicates the propagation of extra-tropical planetary waves from high latitude to equator. During the course of warming, a strong downward propagation of EP flux convergence is observed from polar to equator region. The polar westward wind reaches upto 20oN and the weak eastward wind dominates the equator during the winters 2003/04, 2005/06 and 2018/19. But in 2012/13 winter, polar westward wind reaches upto equator. The equatorial wind at 2008/09 is dominated by strong westward wind. Further detailed results will be presented in the conference.

Keywords: Equatorial dynamics, Outgoing Longwave Radiation, Sudden Stratospheric Warming, Planetary Waves

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Authors: Sweta Iyer, Nemeshwaree Behary, Jinping Guan, Guoqiang Chen, Vincent Nierstrasz

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Flavin mononucleotide widely known as 'FMN' is a biobased resource derived from riboflavin. The isoalloxazine ring present in the FMN molecule attributes the photoluminescence phenomenon, whereas FMN molecule in the presence of bacterial luciferase enzyme and co-factors such as NADH, long chain aldehyde leads to bioluminescence reaction. In this study, the FMN molecule was treated on cellulosic textile using chromojet technique and the photoluminescence property was characterized using spectroscopy technique. Further, the FMN was used as a substrate along with enzymes and co-factors to treat the non-woven textile, and the bioluminescence property was explored using luminometer equipment. The investigation revealed photoluminescence property on cellulosic textile, and the emission peak was observed at a wavelength around 530 nm with an average corrected spectral intensity of 10×106 CPS/Microamps. In addition, the measurement of nonwoven textile using bioluminescence reaction system exhibited light intensity measured in the form of relative light units (RLU). The study enabled to explore the use of FMN as both photoluminescent and bioluminescent textile. Further investigation would require for stability study of the same to provide an eco-efficient approach to obtain luminescent textile.

Keywords: flavin mononucleotide, photoluminescence, bioluminescence, luminescent textile

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Authors: K. Eryilmaz, G. Mercanoglu

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Aim: Purification of the final product, which is the last step in the synthesis of lanthanide-labeled peptide compounds, can be accomplished by different methods. Among these methods, the two most commonly used methods are C18 solid phase extraction (SPE) and weak cation exchanger cartridge elution. SPE C18 solid phase extraction method yields high purity final product, while elution from the weak cation exchanger cartridge is pH dependent and ineffective in removing colloidal impurities. The aim of this work is to develop an additional purification method for the lanthanide-labeled peptide compound in cases where the desired radionuclidic and radiochemical purity of the final product can not be achieved because of pH problem or colloidal impurity. Material and Methods: For colloidal impurity formation, 3 mL of water for injection (WFI) was added to 30 mCi of 177LuCl3 solution and allowed to stand for 1 day. 177Lu-DOTATATE was synthesized using EZAG ML-EAZY module (10 mCi/mL). After synthesis, the final product was mixed with the colloidal impurity solution (total volume:13 mL, total activity: 40 mCi). The resulting mixture was trapped in SPE-C18 cartridge. The cartridge was washed with 10 ml saline to remove impurities to the waste vial. The product trapped in the cartridge was eluted with 2 ml of 50% ethanol and collected to the final product vial via passing through a 0.22μm filter. The final product was diluted with 10 mL of saline. Radiochemical purity before and after purification was analysed by HPLC method. (column: ACE C18-100A. 3µm. 150 x 3.0mm, mobile phase: Water-Acetonitrile-Trifluoro acetic acid (75:25:1), flow rate: 0.6 mL/min). Results: UV and radioactivity detector results in HPLC analysis showed that colloidal impurities were completely removed from the 177Lu-DOTATATE/ colloidal impurity mixture by purification method. Conclusion: The improved purification method can be used as an additional method to remove impurities that may result from the lanthanide-peptide synthesis in which the weak cation exchange purification technique is used as the last step. The purification of the final product and the GMP compliance (the final aseptic filtration and the sterile disposable system components) are two major advantages.

Keywords: lanthanide, peptide, labeling, purification, radionuclide, radiopharmaceutical, synthesis

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Authors: Avijit Datta

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We have presented a phase control scheme in population transfer using chirped laser fields. A chirped pulse can do population transfer from one level to another level via adiabatic rapid passage accessible by one photon dipole transition. We propose to use a pair of phase-locked chirped pulses of the same frequency w(t) instead of a singly chirped-pulse frequency w(t). Simultaneous action of phase controlled interference in addition to rapid adiabatic passages due to chirped pulses lead to phase control over this population transfer dynamics. We have demonstrated the proposed phase control scheme over the population distribution from the initial level X(v=0,j=0) to C(v=2,j=1) level of hydrogen molecule using a pair of phase-locked and similarly chirped laser pulses. We have extended this two-level system to three-level 1+1 ladder system of hydrogen molecule from X level to final J(v=2,j=2) level via C intermediate level using two pairs of laser pulses having frequencies w(t) and w'(t) respectively and obtained laudable control over the population distribution among three levels. We also have presented some results of interference effects of w₁(t) and its third harmonics w₃(t).

Keywords: phase control, population transfer, chirped laser pulses, rapid adiabatic passage, laser-molecule interaction

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Authors: Hiroyuki Aoki

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The physical properties of polymer materials are dependent on the conformation and molecular motion of a polymer chain. Therefore, the structure and dynamic behavior of the single polymer chain have been the most important concerns in the field of polymer physics. However, it has been impossible to directly observe the conformation of the single polymer chain in a bulk medium. In the current work, the novel techniques to study the conformation and dynamics of a single polymer chain are proposed. Since a fluorescence method is extremely sensitive, the fluorescence microscopy enables the direct detection of a single molecule. However, the structure of the polymer chain as large as 100 nm cannot be resolved by conventional fluorescence methods because of the diffraction limit of light. In order to observe the single chains, we developed the labeling method of polymer materials with a photo-switchable dye and the super-resolution microscopy. The real-space conformational analysis of single polymer chains with the spatial resolution of 15-20 nm was achieved. The super-resolution microscopy enables us to obtain the three-dimensional coordinates; therefore, we succeeded the conformational analysis in three dimensions. The direct observation by the nanometric optical microscopy would reveal the detailed information on the molecular processes in the various polymer systems.

Keywords: polymer materials, single molecule, super-resolution techniques, conformation

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Authors: Maziar Noei

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Adsorption of a boron nitride nanotube (BNNT) was examined toward ethylacetylene (C4H6) molecule by using density functional theory (DFT) calculations at the B3LYP/6-31G (d) level, and it was found that the adsorption energy (Ead) of ethylacetylene the pristine nanotubes is about -1.60kcal/mol. But when nanotube have been doped with Si and Al atomes, the adsorption energy of ethylacetylene molecule was increased. Calculation showed that when the nanotube is doping by Al, the adsorption energy is about -24.19kcal/mol and also the amount of HOMO/LUMO energy gap (Eg) will reduce significantly. Boron nitride nanotube is a suitable adsorbent for ethylacetylene and can be used in separation processes ethylacetylene. It is seem that nanotube (BNNT) is a suitable semiconductor after doping, and the doped BNNT in the presence of ethylacetylene an electrical signal is generating directly and therefore can potentially be used for ethylacetylene sensors.

Keywords: sensor, nanotube, DFT, ethylacetylene

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Authors: S. V. Boroznin, I. V. Zaporotskova, N. P. Polikarpova

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Studing of nanotubes sorption properties is very important for researching. These processes for carbon and boron nanotubes described in the high number of papers. But the sorption properties of boron containing nanotubes, susch as BC3-nanotubes haven’t been studied sufficiently yet. In this paper we present the results of theoretical research into the mechanism of atomic surface adsorption on the two types of boron-carbon nanotubes (BCNTs) within the framework of an ionic-built covalent-cyclic cluster model and an appropriately modified MNDO quantum chemical scheme and DFT method using B3LYP functional with 6-31G basis. These methods are well-known and the results, obtained using them, were in good agreement with the experiment. Also we studied three position of atom location above the nanotube surface. These facts suggest us to use them for our research and quantum-chemical calculations. We studied the mechanism of sorption of Cl, O and F atoms on the external surface of single-walled BC3 arm-chair nanotubes. We defined the optimal geometry of the sorption complexes and obtained the values of the sorption energies. Analysis of the band structure suggests that the band gap is insensitive to adsorption process. The electron density is located near atoms of the surface of the tube. Also we compared our results with others, which have been obtained earlier for pure carbon and boron nanotubes. The most stable adsorption complex has been between boron-carbon nanotube and oxygen atom. So, it suggests us to make a research of oxygen molecule adsorption on the BC3 nanotube surface. We modeled five variants of molecule orientation above the nanotube surface. The most stable sorption complex has been defined between the oxygen molecule and nanotube when the oxygen molecule is located above the nanotube surface perpendicular to the axis of the tube.

Keywords: Boron-carbon nanotubes, nanostructures, nanolayers, quantum-chemical calculations, nanoengineering

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Authors: Hasanpasha N. Sholapur, Basanagouda M.Patil

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Alcoholic extract of the bark of Moringa oleifera Lam. (MO), (Moringaceae), has been evaluated experimentally in the past for its insulin sensitizing potentials. In order to explore the possibility of the class of phytochemical(s) responsible for this experimental claim, the alcoholic extract was fractionated into non-polar [petroleum ether (PEF)], moderately non-polar [ethyl acetate (EAF)] and polar [aqueous (AQF)] fractions. All the fractions and pioglitazone (PIO) as standard (10mg/kg were p.o., once daily for 11 d) were investigated for their chronic effect on fasting plasma glucose, triglycerides, total cholesterol, insulin, oral glucose tolerance and acute effect on oral glucose tolerance in dexamethasone-induced (1 mg/kg s.c., once daily for 11 d) chronic model and acute model (1 mg/kg i.p., for 4 h) respectively for insulin resistance (IR) in rats. Among all the fractions tested, chronic treatment with EAF (140 mg/kg) and PIO (10 mg/kg) prevented dexamethasone-induced IR, indicated by prevention of hypertriglyceridemia, hyperinsulinemia and oral glucose intolerance, whereas treatment with AQF (95 mg/kg) prevented hepatic IR but not peripheral IR. In acute study single dose treatment with EAF (140 mg/kg) and PIO (10 mg/kg) prevented dexamethasone-induced oral glucose intolerance, fraction PEF did not show any effect on these parameters in both the models. The present study indicates that the triterpenoidal and the phenolic class of phytochemicals detected in EAF of alcoholic extract of MO bark may be responsible for the prevention of dexamethasone-induced insulin resistance in rats.

Keywords: Moringa oleifera, insulin resistance, dexamethasone, serum triglyceride, insulin, oral glucose tolerance test

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Authors: A. Burakowska, M. Piotrowski, M. Kubicki, H. Trzaskowska, R. Sosnowiec, B. Myslek-Laurikainen

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The most important source of atmospheric radioactivity are radionuclides generated as a result of the impact of primary and secondary cosmic radiation, with the nuclei of nitrogen oxygen and carbon in the upper troposphere and lower stratosphere. This creates about thirty radioisotopes of more than twenty elements. For organisms, the four of them are most important: ³H, ⁷Be, ²²Na, ¹⁴C. The natural radionuclides, which are present in Earth crust, also settle on dust and particles of water vapor. By this means, the derivatives of uranium and thorium, and long-life 40K get into the air. ¹³⁷Cs is the most widespread isotope, that is implemented by humans into the environment. To determine the concentration of radionuclides in the atmosphere, high volume air samplers were used, where the aerosol collection took place on a special filter fabric (Petrianov filter tissue FPP-15-1.5). In 2002 the high volume air sampler AZA-1000 was installed at the Polish Polar Observatory of the Polish Academy of Science in Hornsund, Spitsbergen (77°00’N, 15°33’E), designed to operate in all weather conditions of the cold polar region. Since 1991 (with short breaks) the ASS-500 air sampler has been working, which is located in Swider at the Kalinowski Geophysical Observatory of Geophysics Institute of the Polish Academy of Science (52°07’N, 21°15’E). The following results of radionuclides concentrations were obtained from both stations using gamma spectroscopy analysis: ⁷Be, ¹³⁷Cs, ¹³⁴Cs, ²¹⁰Pb, ⁴⁰K. For gamma spectroscopy analysis HPGe (High Purity Germanium) detector were used. These data were compared with each other. The preliminary results gave evidence that radioactivity measured in aerosols is not proportional to the amount of dust for both studied regions. Furthermore, the results indicate annual variability (seasonal fluctuations) as well as a decrease in the average activity of ⁷Be with increasing latitude. The content of ⁷Be in surface air also indicates the relationship with solar activity cycles.

Keywords: aerosols, air filters, atmospheric beryllium, environmental radionuclides, gamma spectroscopy, mid-latitude regions radionuclides, polar regions radionuclides, solar cycles

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Authors: А. V. Panko, Е. V. Ablets, I. G. Kovzun, М. А. Ilyashov

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Based upon generalized analysis of modern know-how in the sphere of processing, concentration and purification of iron-ore raw materials (IORM), in particular, the most widespread ferrioxide-silicate materials (FOSM), containing impurities of phosphorus and other elements compounds, noted special role of nano technological initiatives in improvement of such processes. Considered ideas of role of nano particles in processes of FOSM carbonization with subsequent direct reduction of ferric oxides contained in them to metal phase, as well as in processes of alkali treatment and separation of powered iron from phosphorus compounds. Using the obtained results the wasteless solid-phase processing, concentration and purification of IORM and FOSM from compounds of phosphorus, silicon and other impurities excelling known methods of direct iron reduction from iron ores and metallurgical slimes.

Keywords: iron ores, solid-phase reduction, nanoparticles in reduction and purification of iron from silicon and phosphorus, wasteless method of ores processing

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Authors: Neha Singh

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Background: Nowadays, the nanoparticle is gaining unexceptional attention in targeted drug delivery. But before proceeding to this episode of accomplishment, the journey and closure of these nanoparticles inside the cells should be disentangle. Being foreign for the cells, nanoparticles will easily getcleared off without any effective outcome. As the cancer cells withhold these nanoparticles for a longer period of time, more will be the drug’s effect. Chlorpromazine is a cationic amphiphilic drug which is believed to inhibit clathrin-coated pit formation by a reversible translocation of clathrin and its adapter proteins from the plasma membrane to intracellular vesicles. Chlorpromazine has a role in increasing the retention of nanoparticles in cancer cells. The mechanism of action how this small molecule increases the retention of nanoparticles is still uncovered. Method: Polymeric nanoparticle (PLGA) with Cyanine3.5 dye were synthesized by solvent evaporation method and characterized for size and zeta potential. FTIR was also done. Pulse and chase studies with and without inhibitor were done to check the retention of nanoparticle using fluorescence microscopy. Mean fluorescence intensity was measured by ImageJ software. Results: Increased retention of nanoparticle with inhibitor was observed in both pulse and chase studies. Conclusion: Our results demonstrate that by repurposing these small molecule inhibitor, we can increase the retention of nanoparticle at the targeted site.

Keywords: nanoparticle, endocytosis, clathrin inhibitor, cancer cell

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Authors: Ibrahim A. Adeniran, Rui F. Zhu, Man S. Wong

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Owing to the insufficiency in the spatial representativeness and continuity of in situ temperature measurements from weather stations (WS), the use of temperature measurement from WS for large-range diurnal analysis in heterogenous landscapes has been limited. This has made the accurate estimation of land surface temperature (LST) from remotely sensed data more crucial. Moreover, the study of dynamic interaction between the atmosphere and the physical surface of the Earth could be enhanced at both annual and diurnal scales by using optimal LST data derived from satellite sensors. The tradeoff between the spatial and temporal resolution of LSTs from satellite’s thermal infrared sensors (TIRS) has, however, been a major challenge, especially when high spatiotemporal LST data are recommended. It is well-known from existing literature that polar satellites have the advantage of high spatial resolution, while geostationary satellites have a high temporal resolution. Hence, this study is aimed at designing a framework for the cross-comparison of LST data from polar and geostationary satellites in a heterogeneous landscape. This could help to understand the relationship between the LST estimates from the two satellites and, consequently, their integration in diurnal LST analysis. Landsat-8 satellite data will be used as the representative of the polar satellite due to the availability of its long-term series, while the Himawari-8 satellite will be used as the data source for the geostationary satellite because of its improved TIRS. For the study area, Hong Kong Special Administrative Region (HK SAR) will be selected; this is due to the heterogeneity in the landscape of the region. LST data will be retrieved from both satellites using the Split window algorithm (SWA), and the resulting data will be validated by comparing satellite-derived LST data with temperature data from automatic WS in HK SAR. The LST data from the satellite data will then be separated based on the land use classification in HK SAR using the Global Land Cover by National Mapping Organization version3 (GLCNMO 2013) data. The relationship between LST data from Landsat-8 and Himawari-8 will then be investigated based on the land-use class and over different seasons of the year in order to account for seasonal variation in their relationship. The resulting relationship will be spatially and statistically analyzed and graphically visualized for detailed interpretation. Findings from this study will reveal the relationship between the two satellite data based on the land use classification within the study area and the seasons of the year. While the information provided by this study will help in the optimal combination of LST data from Polar (Landsat-8) and geostationary (Himawari-8) satellites, it will also serve as a roadmap in the annual and diurnal urban heat (UHI) analysis in Hong Kong SAR.

Keywords: automatic weather station, Himawari-8, Landsat-8, land surface temperature, land use classification, split window algorithm, urban heat island

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Authors: Sanjay Kumar

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This paper reports the solvent effects on the electronic absorption and fluorescence emission spectra of 6-OH-4-CH3, 7-OH-4-CH3 and 7-OH-4-CF3 coumarin derivatives having -OH, -CH3 and -CF3 substituent at different positions in various solvents (Polar and Non-Polar). The first excited singlet state dipole moment and ground state dipole moment were calculated using Bakhshiev, Kawski-Chamma-Viallet and Reichardt-Dimroth equations and were compared for all the coumarin studied. In all cases the dipole moments were found to be higher in the excited singlet state than in the ground state indicating a substantial redistribution of Π-electron density in the excited state. The angle between the excited singlet state and ground state dipole moment is also calculated. The red shift of the absorption and fluorescence emission bands, observed for all the coumarin studied upon increasing the solvent polarity indicating that the electronic transitions were Π → Π* nature.

Keywords: coumarin, solvent effects, absorption spectra, emission spectra, excited singlet state dipole moment, ground state dipole moment, solvatochromism

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Authors: Simran Baweja, Bhavika Kalal, Surajit Maity

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Photoinduced tautomerization reactions have been the centre of attention among the scientific community over the past several decades because of their significance in various biological systems. 7-azaindole (7AI) is considered a model system for DNA base pairing and to understand the role of such tautomerization reactions in mutations. To the best of our knowledge, extensive studies have been carried out on 7-azaindole and its solvent clusters exhibiting proton/ hydrogen transfer in both solution as well as gas phases. Derivatives of the above molecule, like 2,7- and 2,6-diazaindoles are proposed to have even better photophysical properties due to the presence of -aza group on the 2nd position. However, there are studies in the solution phase that suggest the relevance of these molecules, but there are no experimental studies reported in the gas phase yet. In our current investigation, we present the first gas phase spectroscopic data of 2,7-diazaindole (2,7-DAI) and its solvent cluster (2,7-DAI-H2O). In this, we have employed state-of-the-art laser spectroscopic methods such as fluorescence excitation (LIF), dispersed fluorescence (DF), resonant two-photon ionization-time of flight mass spectrometry (2C-R2PI), photoionization efficiency spectroscopy (PIE), IR-UV double resonance spectroscopy, i.e., fluorescence-dip infrared spectroscopy (FDIR) and resonant ion-dip infrared spectroscopy (IDIR) to understand the electronic structure of the molecule. The origin band corresponding to the S1 ← S0 transition of the bare 2,7-DAI is found to be positioned at 33910 cm-1, whereas the origin band corresponding to S1 ← S0 transition of the 2,7-DAI-H2O is positioned at 33074 cm-1. The red-shifted transition in the case of solvent cluster suggests the enhanced feasibility of excited state hydrogen/ proton transfer. The ionization potential for the 2,7-DAI molecule is found to be 8.92 eV which is significantly higher than the previously reported 7AI (8.11 eV) molecule, making it a comparatively complex molecule to study. The ionization potential is reduced by 0.14 eV in the case of 2,7-DAI-H2O (8.78 eV) cluster compared to that of 2,7-DAI. Moreover, on comparison with the available literature values of 7AI, we found the origin band of 2,7-DAI and 2,7-DAI-H2O to be red-shifted by -729 and -280 cm-1 respectively. The ground and excited state N-H stretching frequencies of the 27DAI molecule were determined using fluorescence-dip infrared spectra (FDIR) and resonant ion dip infrared spectroscopy (IDIR), obtained at 3523 and 3467 cm-1, respectively. The lower value of vNH in the electronically excited state of 27DAI implies the higher acidity of the group compared to the ground state. Moreover, we have done extensive computational analysis, which suggests that the energy barrier in the excited state reduces significantly as we increase the number of catalytic solvent molecules (S= H2O, NH3) as well as the polarity of solvent molecules. We found that the ammonia molecule is a better candidate for hydrogen transfer compared to water because of its higher gas-phase basicity. Further studies are underway to understand the excited state dynamics and photochemistry of such N-rich chromophores.

Keywords: excited state hydrogen transfer, supersonic expansion, gas phase spectroscopy, IR-UV double resonance spectroscopy, laser induced fluorescence, photoionization efficiency spectroscopy

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Authors: N. Harun, E. E. Masiren, W. H. W. Ibrahim, F. Adam

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Amine absorption process is an approach for mitigation of CO2 from flue gas that produces from power plant. This process is the most common system used in chemical and oil industries for gas purification to remove acid gases. On the challenges of this process is high energy requirement for solvent regeneration to release CO2. In the past few years, mixed alkanolamines have received increasing attention. In most cases, the mixtures contain N-methyldiethanolamine (MDEA) as the base amine with the addition of one or two more reactive amines such as PZ. The reason for the application of such blend amine is to take advantage of high reaction rate of CO2 with the activator combined with the advantages of the low heat of regeneration of MDEA. Several experimental and simulation studies have been undertaken to understand this process using blend MDEA/PZ solvent. Despite those studies, the mechanism of CO2 absorption into the aqueous MDEA is not well understood and available knowledge within the open literature is limited. The aim of this study is to investigate the intermolecular interaction of the blend MDEA/PZ using Molecular Dynamics (MD) simulation. MD simulation was run under condition 313K and 1 atm using NVE ensemble at 200ps and NVT ensemble at 1ns. The results were interpreted in term of Radial Distribution Function (RDF) analysis through two system of interest i.e binary and tertiary. The binary system will explain the interaction between amine and water molecule while tertiary system used to determine the interaction between the amine and CO2 molecule. For the binary system, it was observed that the –OH group of MDEA is more attracted to water molecule compared to –NH group of MDEA. The –OH group of MDEA can form the hydrogen bond with water that will assist the solubility of MDEA in water. The intermolecular interaction probability of –OH and –NH group of MDEA with CO2 in blended MDEA/PZ is higher than using single MDEA. This findings show that PZ molecule act as an activator to promote the intermolecular interaction between MDEA and CO2.Thus, blend of MDEA with PZ is expecting to increase the absorption rate of CO2 and reduce the heat regeneration requirement.

Keywords: amine absorption process, blend MDEA/PZ, CO2 capture, molecular dynamic simulation, radial distribution function

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Authors: Simran Baweja, Bhavika Kalal, Surajit Maity

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Photoinduced tautomerization reactions have been the centre of attention among scientific community over past several decades because of their significance in various biological systems. 7-azaindole (7AI) is considered as a model system for DNA base pairing and to understand the role of such tautomerization reactions in mutations. To the best of our knowledge, extensive studies have been carried on 7-azaindole and its solvent clusters exhibiting proton/ hydrogen transfer in both solution as well as gas phase. Derivatives of above molecule, like 2,7- and 2,6-diazaindoles are proposed to have even better photophysical properties due to the presence of -aza group on the 2nd position. However, there are a few studies in the solution phase which suggest the relevance of these molecules, but there are no experimental studies reported in the gas phase yet. In our current investigation, we present the first gas phase spectroscopic data of 2,7-diazaindole (2,7-DAI) and its solvent cluster (2,7-DAI-H2O). In this, we have employed state-of-the-art laser spectroscopic methods such as fluorescence excitation (LIF), dispersed fluorescence (DF), resonant two-photon ionization time of flight mass spectrometry (2C-R2PI), photoionization efficiency spectroscopy (PIE), IR-UV double resonance spectroscopy i.e. fluorescence-dip infrared spectroscopy (FDIR) and resonant ion-dip infrared spectroscopy (IDIR) to understand the electronic structure of the molecule. The origin band corresponding to S1 ← S0 transition of the bare 2,7-DAI is found to be positioned at 33910 cm-1 whereas the origin band corresponding to S1 ← S0 transition of the 2,7-DAI-H2O is positioned at 33074 cm-1. The red shifted transition in case of solvent cluster suggests the enhanced feasibility of excited state hydrogen/ proton transfer. The ionization potential for the 2,7-DAI molecule is found to be 8.92 eV, which is significantly higher that the previously reported 7AI (8.11 eV) molecule, making it a comparatively complex molecule to study. The ionization potential is reduced by 0.14 eV in case of 2,7-DAI-H2O (8.78 eV) cluster compared to that of 2,7-DAI. Moreover, on comparison with the available literature values of 7AI, we found the origin band of 2,7-DAI and 2,7-DAI-H2O to be red shifted by -729 and -280 cm-1 respectively. The ground and excited state N-H stretching frequencies of the 27DAI molecule were determined using fluorescence-dip infrared spectra (FDIR) and resonant ion dip infrared spectroscopy (IDIR), obtained at 3523 and 3467 cm-1, respectively. The lower value of vNH in the electronic excited state of 27DAI implies the higher acidity of the group compared to the ground state. Moreover, we have done extensive computational analysis, which suggests that the energy barrier in excited state reduces significantly as we increase the number of catalytic solvent molecules (S= H2O, NH3) as well as the polarity of solvent molecules. We found that the ammonia molecule is a better candidate for hydrogen transfer compared to water because of its higher gas-phase basicity. Further studies are underway to understand the excited state dynamics and photochemistry of such N-rich chromophores.

Keywords: photoinduced tautomerization reactions, gas phse spectroscopy, ), IR-UV double resonance spectroscopy, resonant two-photon ionization time of flight mass spectrometry (2C-R2PI)

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Authors: Alena Semeradtova, Marcel Stofik, Lucie Mareckova, Petr Maly, Ondrej Stanek, Jan Maly

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Recently, novel strategies based on so-called molecular evolution were shown to be effective for the production of various peptide ligand libraries with high affinities to molecular targets of interest comparable or even better than monoclonal antibodies. The major advantage of these peptide scaffolds is mainly their prevailing low molecular weight and simple structure. This study describes a new high-affinity binding molecules based immunesensor using a simple optical system for human serum albumin (HSA) detection as a model molecule. We present a comparison of two variants of recombinant binders based on albumin binding domain of the protein G (ABD) performed on micropatterned glass chip. Binding domains may be tailored to any specific target of interest by molecular evolution. Micropatterened glass chips were prepared using UV-photolithography on chromium sputtered glasses. Glass surface was modified by (3-aminopropyl)trietoxysilane and biotin-PEG-acid using EDC/NHS chemistry. Two variants of high-affinity binding molecules were used to detect target molecule. Firstly, a variant is based on ABD domain fused with TolA chain. This molecule is in vivo biotinylated and each molecule contains one molecule of biotin and one ABD domain. Secondly, the variant is ABD domain based on streptavidin molecule and contains four gaps for biotin and four ABD domains. These high-affinity molecules were immobilized to the chip surface via biotin-streptavidin chemistry. To eliminate nonspecific binding 1% bovine serum albumin (BSA) or 6% fetal bovine serum (FBS) were used in every step. For both variants range of measured concentrations of fluorescently labelled HSA was 0 – 30 µg/ml. As a control, we performed a simultaneous assay without high-affinity binding molecules. Fluorescent signal was measured using inverse fluorescent microscope Olympus IX 70 with COOL LED pE 4000 as a light source, related filters, and camera Retiga 2000R as a detector. The fluorescent signal from non-modified areas was substracted from the signal of the fluorescent areas. Results were presented in graphs showing the dependence of measured grayscale value on the log-scale of HSA concentration. For the TolA variant the limit of detection (LOD) of the optical immunosensor proposed in this study is calculated to be 0,20 µg/ml for HSA detection in 1% BSA and 0,24 µg/ml in 6% FBS. In the case of streptavidin-based molecule, it was 0,04 µg/ml and 0,07 µg/ml respectively. The dynamical range of the immunosensor was possible to estimate just in the case of TolA variant and it was calculated to be 0,49 – 3,75 µg/ml and 0,73-1,88 µg/ml respectively. In the case of the streptavidin-based the variant we didn´t reach the surface saturation even with the 480 ug/ml concentration and the upper value of dynamical range was not estimated. Lower value was calculated to be 0,14 µg/ml and 0,17 µg/ml respectively. Based on the obtained results, it´s clear that both variants are useful for creating the bio-recognizing layer on immunosensors. For this particular system, it is obvious that the variant based on streptavidin molecule is more useful for biosensing on glass planar surfaces. Immunosensors based on this variant would exhibit better limit of detection and wide dynamical range.

Keywords: high affinity binding molecules, human serum albumin, optical immunosensor, protein G, UV-photolitography

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Authors: Seyed Mohamad Rasool Mirkarimi, David Chiaramonti, Samir Bensaid

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Catalytic methane decomposition (CMD, reaction 4) is a one-step process for hydrogen production where carbon in the methane molecule is sequestered in the form of stable and higher-value carbon materials. Metallic catalysts and carbon-based catalysts are two major types of catalysts utilized for the CDM process. Although carbon-based catalysts have lower activity compared to metallic ones, they are less expensive and offer high thermal stability and strong resistance to chemical impurities such as sulfur. Also, it would require less costly separation methods as some of the carbon-based catalysts may not have an active metal component in them. Since the regeneration of metallic catalysts requires burning of the C on their surfaces, which emits CO/CO2, in some cases, using carbon-based catalysts would be recommended because regeneration can be completely avoided, and the catalyst can be directly used in other processes. This work focuses on the effect of biochar as a carbon-based catalyst for the conversion of methane into hydrogen and carbon. Biochar produced from the pyrolysis of poplar wood and activated biochar are used as catalysts for this process. In order to observe the impact of carbon-based catalysts on methane conversion, methane cracking in the absence and presence of catalysts for a gas stream with different levels of methane concentration should be performed. The results of these experiments prove conversion of methane in the absence of catalysts at 900 °C is negligible, whereas in the presence of biochar and activated biochar, significant growth has been observed. Comparing the results of the tests related to using char and activated char shows the enhancement obtained in BET surface area of the catalyst through activation leads to more than 10 vol.% methane conversion.

Keywords: hydrogen production, catalytic methane decomposition, biochar, activated biochar, carbon-based catalyts

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Authors: H. Yilmaz Atay

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Huntite and hydromagnesite minerals have been used as additive materials to achieve incombustible material due to their inflammability property. Those fire retardants materials can help to extinguish in the early stages of fire. Thus dispersion of the flame can be prevented even if the fire started. Huntite and hydromagnesite minerals are known to impart fire-proofing of the polymer composites. However, the additives used in the applications led to deterioration in the mechanical properties due to the usage of high amount of the powders in the composites. In this study, by enriching huntite and hydromagnesite, it was aimed to use purer minerals to reinforce the polymer composites. Thus, predictably, using purer mineral will lead to use lower amount of mineral powders. By this manner, the minerals free from impurities by various processes were added to the polymer matrix with different loading level and grades. Different types of samples were manufactured, and subsequently characterized by XRD, SEM-EDS, XRF and flame-retardant tests. Tensile strength and elongation at break values were determined according to loading levels and grades. Besides, a comparison on the properties of the polymer composites produced by using of minerals with and without impurities was performed. As a result of the work, it was concluded that it is required to use beneficiated minerals to provide better fire-proofing behaviors in the polymer composites.

Keywords: flame retardant, huntite and hydromagnesite, mechanical property, polymer composites

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Authors: Yezli-Touiker Samira, Amrani-Kirane Leila, Soltani Mazouni Nadia

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Due to secondary effects of conventional insecticides on the environment, the agrochemical research has resulted in the discovery of novel molecules. That research work will help in the development of a new group of pesticides that may be cheaper and less hazardous to the environment and non-target organisms which is the main desired outcome of the present work. Angiotensin-converting enzyme as a target for the development of novel insect growth regulators. Captopril is an inhibitor of angiotensin converting enzyme (ACE) it was tested in vivo by topical application on reproduction of Ephestia kuehniella Zeller (Lepidoptera: Pyralidae). The compound is diluted in acetone and applied topically to newly emerged pupae (10µg/ 2µl). The effects of this molecule was studied,on the biochemistry of ovary (on amounts nucleic acid, proteins, the qualitative analysis of the ovarian proteins and the reproductive potential (duration of the pre-oviposition, duration of the oviposition, number of eggs laid and hatching percentage). Captopril reduces significantly quantity of ovarian proteins and nucleic acid. The electrophoresis profile reveals the absence of tree bands at the treated series. This molecule reduced the duration of the oviposition period, the fecundity and the eggviability.

Keywords: environment, ephestia kuehniella, captopril, reproduction, the agrochemical research

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Authors: Mohammad Ahmad, Sander Gersen, Erwin Wilbers

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Carbon capture, transport and underground storage have become a major solution to reduce CO2 emissions from power plants and other large CO2 sources. A big part of this captured CO2 stream is transported at high pressure dense phase conditions and stored in offshore underground depleted oil and gas fields. CO2 is also transported in offshore pipelines to be used for enhanced oil and gas recovery. The captured CO2 stream with impurities may contain water that causes severe corrosion problems, flow assurance failure and might damage valves and instrumentations. Thus, free water formation should be strictly prevented. The purpose of this work is to study the solubility of water in pure CO2 and in CO2 mixtures under real pipeline pressure (90-150 bar) and temperature operation conditions (5-35°C). A set up was constructed to generate experimental data. The results show the solubility of water in CO2 mixtures increasing with the increase of the temperature or/and with the increase in pressure. A drop in water solubility in CO2 is observed in the presence of impurities. The data generated were then used to assess the capabilities of two mixture models: the GERG-2008 model and the EOS-CG model. By generating the solubility data, this study contributes to determine the maximum allowable water content in CO2 pipelines.

Keywords: carbon capture and storage, water solubility, equation of states, fluids engineering

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

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

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

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Authors: Zhengkun Guo, Yanbin Li, Wenqing Wang, Bo Zou

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The statically fused converted position and doppler measurements Kalman filter (SF-CMKF) with additive debiased measurement conversion has been previously presented to combine the resulting states of converted position measurements Kalman filter (CPMKF) and converted doppler measurement Kalman filter (CDMKF) to yield the final state estimates under minimum mean squared error (MMSE) criterion. However, the exact compensation for the bias in the polar-to-cartesian and spherical-to-cartesian conversion are multiplicative and depend on the statistics of the cosine of the angle measurement errors. As a result, the consistency and performance of the SF-CMKF may be suboptimal in large-angle error situations. In this paper, the multiplicative unbiased position and Doppler measurement conversion for 2D (polar-to-cartesian) tracking are derived, and the SF-CMKF is improved to use those conversions. Monte Carlo simulations are presented to demonstrate the statistical consistency of the multiplicative unbiased conversion and the superior performance of the modified SF-CMKF (SF-UCMKF).

Keywords: measurement conversion, Doppler, Kalman filter, estimation, tracking

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Authors: Oyugi Ngure Robert, Kallen Mulilo Nalyanya, Tabitha A. Amollo

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Nanomaterials have attracted significant attention in research because of their exemplary properties, making them suitable for diverse applications. This paper reports the successful synthesis as well as the structural properties of silver sulfide/reduced graphene oxide (Ag_2 S-rGO) nanocomposite. The nanocomposite was synthesized by the chemical reduction method. Scanning electron microscopy (SEM) showed that the reduced graphene oxide (rGO) sheets were intercalated within the Ag_2 S nanoparticles during the chemical reduction process. The SEM images also showed that Ag_2 S had the shape of nanowires. Further, SEM energy dispersive X-ray (SEM EDX) showed that Ag_2 S-rGO is mainly composed of C, Ag, O, and S. X-ray diffraction analysis manifested a high crystallinity for the nanowire-shaped Ag2S nanoparticles with a d-spacing ranging between 1.0 Å and 5.2 Å. Thermal gravimetric analysis (TGA) showed that rGO enhances the thermal stability of the nanocomposite. Ag_2 S-rGO nanocomposite exhibited strong optical absorption in the UV region. The formed nanocomposite is dispersible in polar and non-polar solvents, qualifying it for solution-based device processing.

Keywords: silver sulfide, reduced graphene oxide, nanocomposite, structural properties, optical properties

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Authors: Bunindro Nameirakpam, Sonia Sougrapakam, Shannon B. Olsson, Rajashekar Yallappa

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Natural sources for new pesticidal compounds hold promise in view of their eco-friendly nature, selectivity and mammalian safety. Despite a large number of plants that show insecticidal activity and diversity of natural chemistry with inherent eco-friendly nature, newer classes of insecticides have eluded discovery. Artemisia vulgaris, known as Mugwort, is a universal herb used for folk medicine and religious purposes throughout the ancient world. In India, the essential oils of Artemisia vulgaris are used for its insecticidal, anti parasiticidal and antimicrobial properties. Traditionally, the dried leaves of Artemisia vulgaris are used to repel insects as well as rats in and around the granaries in the North-East India. Artemisia vulgaris collected during November from different ecological sites were studied for the bio-pesticidal utility against the stored grain pests. The insecticidal activities were found in the crude extracts of n-hexane and methanol from the samples collected in Sikkim and Manipur respectively. Using silica gel column chromatography protocol, we have isolated one novel bioactive molecule from the aerial parts of Artemisia vulgaris L based on various physical-chemical and spectroscopic techniques (IR, 1H NMR, 13C NMR and mass). The novel bioactive molecule is highly toxic and very low concentration (4.35 µg/l) is needed to control the stored product insects. In additional experiment results clearly showed the involvement of sodium pumps inhibition in the insecticidal action of purified compound in the Sitophilus oryzae. The knockdown activity of the purified compound is concomitant with the in vivo inhibition of Na+/ K+- ATPase. Further, our study showed insignificant differences in the seed germination of control and the treated grains. The lack of adverse effect of the novel bioactive molecule on the seed germination is highly desirable for seed/grain protectant and showing the potential to be developed as possible natural fumigants for the control of stored grain pests. The novel bioactive molecule is selective insecticide with a high margin of safety to mammals and showed promise as novel biopesticide candidate for grain protection. It is believed that Bio-pesticides can serve as the most important pest management tools as far as global safety is concerned.

Keywords: Indian traditional plant, Artemisia vulgaris, bio-pesticides, Na+/ K+- ATPase, seed germination

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Authors: Dessie Tibebe, Yeshifana Ayenew, Marye Mulugeta, Yezbie Kassa, Zerubabel Moges, Dereje Yenealem, Tarekegn Fentie, Agmas Amare, Hailu Sheferaw Ayele

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Electrochemical treatment technology is a technique used for wastewater treatment due to its ability to eliminate impurities that are not easily removed by chemical processes. The objective of the study is the treatment and characterization of textile wastewater by an electrochemical process. The results obtained at various operational parameters indicated that at 20 minutes of electrochemical process at ( pH =7), initial concentration 10 mg/L, current density 37.5 mA/cm², voltage 9 v and temperature 25⁰C the highest removal efficiency was achieved. The kinetics of removal of selected metal by electrochemical treatment has been successfully described by the first-order rate equation. The results of microscopic techniques using SEM for the scarified electrode before treatment were uniform and smooth, but after the electrochemical process, the morphology was completely changed. This is due to the detection of the adsorbed aluminum hydroxide coming from adsorption of the conducting electrolyte, chemicals used in the experiments, alloying and the scrap impurities of the anode and cathode. The FTIR spectroscopic analysis broad bands at 3450 cm-¹ representing O-H functional groups, while the presence of H-O-H and Al-H groups are indicated by the bands at 2850-2750 cm-¹ and 1099 representing C-H functional groups.

Keywords: electrochemical, treatment, textile wastewater, kinetics, removal efficiency

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