Search results for: solvent activation

Authors: Fatemeh Saadat Ghareh Bagh, Srimanta Ray, Jerald Lalman

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Lignin, the largest inventory of organic carbon with a high caloric energy value is a major component in woody and non-woody biomass. In pulping mills, a large amount of the lignin is burned for energy. At the same time, the phenolic structure of lignin enables it to be converted to value-added compounds.This study has focused on extracting lignin from black liquor using deep eutectic solvents (DESs). Therefore, three choline chloride (ChCl)-DESs paired with lactic acid (LA) (1:11), oxalic acid.2H₂O (OX) (1:4), and malic acid (MA) (1:3) were synthesized at 90oC and atmospheric pressure. The kinetics of lignin recovery from black liquor using DES was investigated at three moderate temperatures (338, 353, and 368 K) at time intervals from 30 to 210 min. The extracted lignin (acid soluble lignin plus Klason lignin) was characterized by Fourier transform infrared spectroscopy (FTIR). The FTIR studies included comparing the extracted lignin with a model Kraft lignin. The extracted lignin was characterized spectrophotometrically to determine the acid soluble lignin (ASL) [TAPPI UM 250] fraction and Klason lignin was determined gravimetrically using TAPPI T 222 om02. The lignin extraction reaction using DESs was modeled by first-order reaction kinetics and the activation energy of the process was determined. The ChCl:LA-DES recovered lignin was 79.7±2.1% at 368K and a DES:BL ratio of 4:1 (v/v). The quantity of lignin extracted for the control solvent, [emim][OAc], was 77.5+2.2%. The activation energy measured for the LA-DES system was 22.7 KJ mol⁻¹, while the activation energy for the OX-DES and MA-DES systems were 7.16 KJ·mol⁻¹ and 8.66 KJ·mol⁻¹ when the total lignin recovery was 75.4 ±0.9% and 62.4 ±1.4, % respectively.

Keywords: black liquor, deep eutectic solvents, kinetics, lignin

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Authors: Kuheli Chakrabarty, Animesh Ghosh, Atanu Roy, Gourab Kanti Das

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Aldol reaction is an important class of carbon-carbon bond forming reactions. One of the popular ways to impose asymmetry in aldol reaction is the introduction of chiral auxiliary that binds the approaching reactants and create dissymmetry in the reaction environment, which finally evolves to enantiomeric excess in the aldol products. The last decade witnesses the usage of natural amino acids as chiral auxiliary to control the stereoselectivity in various carbon-carbon bond forming processes. In this context, L-proline was found to be an effective organocatalyst in asymmetric aldol additions. In last few decades the use of water as solvent or co-solvent in asymmetric organocatalytic reaction is increased sharply. Simple amino acids like L-proline does not catalyze asymmetric aldol reaction in aqueous medium not only that, In organic solvent medium high catalytic loading (~30 mol%) is required to achieve moderate to high asymmetric induction. In this context, huge efforts have been made to modify L-proline and 4-hydroxy-L-proline to prepare organocatalyst for aqueous medium asymmetric aldol reaction. Here, we report the result of our DFT calculations on asymmetric aldol reaction of benzaldehyde, p-NO2 benzaldehyde and t-butyraldehyde with a number of ketones using L-proline hydrazide as organocatalyst in wet solvent free condition. Gaussian 09 program package and Gauss View program were used for the present work. Geometry optimizations were performed using B3LYP hybrid functional and 6-31G(d,p) basis set. Transition structures were confirmed by hessian calculation and IRC calculation. As the reactions were carried out in solvent free condition, No solvent effect were studied theoretically. Present study has revealed for the first time, the direct involvement of two water molecules in the aldol transition structures. In the TS, the enamine and the aldehyde is connected through hydrogen bonding by the assistance of two intervening water molecules forming a supramolecular network. Formation of this type of supramolecular assembly is possible due to the presence of protonated -NH2 group in the L-proline hydrazide moiety, which is responsible for the favorable entropy contribution to the aldol reaction. It is also revealed from the present study that, water assisted TS is energetically more favorable than the TS without involving any water molecule. It can be concluded from this study that, insertion of polar group capable of hydrogen bond formation in the L-proline skeleton can lead to a favorable aldol reaction with significantly high enantiomeric excess in wet solvent free condition by reducing the activation barrier of this reaction.

Keywords: aldol reaction, DFT, organocatalysis, transition structure

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Authors: Ravid Inbar

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CaMKII (calcium-calmodulin dependent protein kinase II) makes up 2% of the protein in our brain and has a critical role in memory formation and long-term potentiation of neurons. Despite this, research has yet to uncover the role of one of the domains on the activation of this kinase. The following proposes to express the protein without the hub domain in E. coli, leaving only the kinase and regulatory segment of the protein. Next, a series of kinase assays will be conducted to elucidate the role the hub domain plays on CaMKII sensitivity to calcium/calmodulin activation. The hub domain may be important for activation; however, it may also be a variety of domains working together to influence protein activation and not the hub alone. Characterization of a protein is critical to the future understanding of the protein's function, as well as for producing pharmacological targets in cases of patients with diseases.

Keywords: CaMKII, hub domain, kinase assays, kinase + reg seg

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Authors: Yuting Wu, Faraz Choudhury, Daniel Benjamin, James Whalin, Joshua Blatz, Leon Shohet, Michael Sussman, Mark Richards

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Plasma-Induced Modification of Biomolecules (PLIMB) has been developed as a technology, which, together with mass spectrometry, measures three-dimensional structural characteristics of proteins. This technique uses hydroxyl radicals generated by atmospheric-pressure plasma discharge to react with the solvent-accessible side chains of protein in an aqueous solution. In this work, we investigate the three-dimensional structure of hemoglobin and myoglobin using PLIMB. Additional modifications to these proteins, such as oxidation, fragmentations, and conformational changes caused by PLIMB are also explored. These results show that PLIMB, coupled with mass spectrometry, is an effective way to determine solvent access to hemoproteins. Furthermore, we show that many factors, including pH and the electrical parameters used to generate the plasma, have a significant influence on solvent accessibility.

Keywords: plasma, hemoglobin, myoglobin, solvent access

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Authors: Samiul Islam Hazarika, Domngam Boje, Ananta Kumar Atta

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It is well familiar that solvents play a significant role in modern chemistry. Solvents can change the reactivity and physicochemical properties of molecules in a solution. Keeping this in mind, we have designed and synthesized a mono-triazolyl-linked pyrenyl-appended xylofuranose derivative for the detection of metal ions with changing solvent systems. The incorporation of a sugar backbone in the sensor increases the water solubility and biocompatibility. The experimental study revealed that the xylofuranose-based fluorescence probe did not exhibit any specific selectivity towards metal ions in acetonitrile (CH₃CN) solvent. Whereas, we revealed that triazole-linked pyrenyl-appended xylofuranose-based fluorescent sensor would exhibit high selectivity and sensitivity towards Au³⁺ ions in CH₃CN-H₂O (1/1, v/v) system. This observation might be explained by the viscosity and polarity differences of CH₃CN and CH₃CN-H₂O solvent systems. The formation of the sensor-Au³⁺ complex was also established by high-resolution mass spectrometry (HRMS) data of the complex.

Keywords: triazole, furanose, fluorometric, solvent dependent

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Authors: Abdallah Sofiane Berrouk, Dara Satyadileep

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This paper investigates the feasibility of retrofitting a middle-east based commercial amine sweetening unit with a split-flow scheme which involves withdrawing a portion of partially stripped semi-lean solvent from the stripping column and re-injecting it in the absorption column to reduce the overall energy consumption of the unit. This method is comprehensively explored by performing parametric analysis of the split fraction of the semi-lean solvent using a kinetics based process simulator ProMax V 3.2. Re-boiler duty, condenser duty, solvent cooling and pumping loads are analysed as functions of a split fraction of the semi-lean solvent from the stripper. It is shown that the proposed method significantly reduces the overall energy consumption of the unit resulting in an annual savings of 325,000 USD. The thorough economic analysis is performed using Aspen Economic Evaluation V 8.4 to reveal that the retrofit scheme pays back the capital cost in less than eight years and is highly recommended for any commercial plant having suitable provisions for solvent inlet/withdrawal on the columns.

Keywords: split flow, Amine, gas processing, optimization

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Authors: Ng Mei Han, Nu'man Abdul Hadi

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Extraction of ferulic acid from palm pressed fiber using deep eutectic solvent (DES) of choline chloride-acetic acid (ChCl-AA) and choline chloride-citric acid (ChCl-CA) are reported. Influence of water content in DES on the extraction efficiency was investigated. ChCl-AA and ChCl-CA experienced a drop in viscosity from 9.678 to 1.429 and 22.658 ± 1.655 mm2/s, respectively as the water content in the DES increased from 0 to 50 wt% which contributed to higher extraction efficiency for the ferulic acid. Between 41,155 ± 940 mg/kg ferulic acid was obtained after 6 h reflux when ChCl-AA with 30 wt% water was used for the extraction compared to 30,940 ± 621 mg/kg when neat ChCl-AA was used. Although viscosity of the DES could be improved with the addition of water, there is a threshold where the DES could tolerate the presence of water without changing its solvent behavior. The optimum condition for extraction of ferulic acid from palm pressed fiber was heating for 6 h with DES containing 30 wt% water.

Keywords: deep eutectic solvent, extraction, ferulic acid, palm fibre

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Authors: M. Münch, R. Brandt

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Martensitic steels with an ultimate tensile strength beyond 2000 MPa are applied in the powertrain of vehicles due to their excellent fatigue strength and high creep resistance. However, the creep controlling mechanism in martensitic steels at ambient temperatures up to 423 K is not evident. The purpose of this study is to review the low temperature creep (LTC) behavior of martensitic steels at temperatures from 363 K to 523 K. Thus, the validity of a logarithmic creep law is reviewed and the stress and temperature dependence of the creep parameters α and β are revealed. Furthermore, creep tests are carried out, which include stepped changes in temperature or stress, respectively. On one hand, the change of the creep rate due to a temperature step provides information on the magnitude of the activation energy of the LTC controlling mechanism and on the other hand, the stress step approach provides information on the magnitude of the activation volume. The magnitude, the temperature dependency, and the stress dependency of both material specific activation parameters may deliver a significant contribution to the disclosure of the nature of the LTC rate controlling mechanism.

Keywords: activation parameters, creep mechanisms, high strength steels, low temperature creep

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Authors: Su Bin Wang, Jin Hee Ahn, Tong-Shin Chang

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The peroxisome proliferator-activated receptors (PPARs) are member of nuclear receptor superfamily that act as a ligand-activated transcription factors. Although platelets lack a nucleus, previous studies have shown that PPARγ agonists, rosiglitazone, inhibited platelet activation induced by collagen. In this study, we investigated the inhibitory effects of KR-62980, a newly synthesized PPARγ agonist, on collagen receptor-stimulated platelet activation. The specific tyrosine phosphorylations of key components (Syk, Vav1, Btk and PLCγ2) for collagen receptor signaling pathways were suppressed by KR-62980. KR-62980 also attenuated downstream responses including cytosolic calcium elevation, P-selectin surface exposure, and integrin αIIbβ3 activation. PPARγ was found to associate with multiple proteins within the LAT signaling complex in collagen-stimulated platelets. This association was prevented by KR-62980, indicating a potential mechanism for PPARγ function in collagen-stimulated platelet activation. Furthermore, KR-62980 inhibited platelet aggregation and adhesion in response to collagen in vitro and prolonged in vivo thrombotic response in carotid arteries of mice. Collectively, these data suggest that KR-62980 inhibits collagen-stimulated platelet activation and thrombus formation through modulating the collagen receptor signaling pathways.

Keywords: KR-62980, PPARγ, antiplatelet, thrombosis

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Authors: Daniel S. Brox

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Starting from earthquake fault dynamic equations, a correspondence between earthquake occurrence statistics in a seismic region before a major earthquake and eigenvalue statistics of a differential operator whose bound state eigenfunctions characterize the distribution of stress in the seismic region is derived. Modeling these eigenvalue statistics with a 2D Coulomb gas statistical physics model, previously reported deviation of seismic activation earthquake occurrence statistics from Gutenberg-Richter statistics in time intervals preceding the major earthquake is derived. It also explains how statistical physics modeling predicts a finite-dimensional nonlinear dynamic system that describes real-time velocity model evolution in the region undergoing seismic activation and how this prediction can be tested experimentally.

Keywords: seismic activation, statistical physics, geodynamics, signal processing

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Authors: Thierry Pauporté, Sana Koussi, Fabrice Odobel

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The preparation of semiconductor oxide layers and structures by soft techniques is an important field of research. Higher performances are expected from the optimizing of the oxide films and then use of new methods of preparation for a better control of their chemical, morphological, electrical and optical properties. We present the preparation of NiO by electrodeposition from pure polar aprotic medium and mixtures with water. The effect of the solvent, of the electrochemical deposition parameters and post-deposition annealing treatment on the structural, morphological and optical properties of the films is investigated. We remarkably show that the solvent is inserted in the deposited layer and act as a blowing agent, giving rise to mesoporous films after elimination by thermal annealing. These layers of p-type oxide have been successfully used, after sensitization by a dye, in p-type dye-sensitized solar cells. The effects of the solvent on the layer properties and the application of these layers in p-type dye-sensitized solar cells are described.

Keywords: NiO, layer, p-type sensitized solar cells, electrodeposition

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Authors: Ferhat Mohamed, Boukhatem Mohamed Nadjib, Chemat Farid

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Simultaneous distillation–extraction (SDE) is routinely used by analysts for sample preparation prior to gas chromatography analysis. In this work, a new process design and operation for microwave assisted simultaneous distillation – solvent extraction (MW-SDE) of volatile compounds was developed. Using the proposed method, isolation, extraction and concentration of volatile compounds can be carried out in a single step. To demonstrate its feasibility, MW-SDE was compared with the conventional technique, Simultaneous distillation–extraction (SDE), for gas chromatography-mass spectrometry (GC-MS) analysis of volatile compounds in a fresh orange juice and a dry spice “carvi seeds”. SDE method required long time (3 h) to isolate the volatile compounds, and large amount of organic solvent (200 mL of hexane) for further extraction, while MW-SDE needed little time (only 30 min) to prepare sample, and less amount of organic solvent (10 mL of hexane). These results show that MW-SDE–GC-MS is a simple, rapid and solvent-less method for determination of volatile compounds from aromatic plants.

Keywords: essential oil, extraction, distillation, carvi seeds

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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: F. T. Senberber, N. Tugrul, E. Moroydor Derun

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As a nutraceutical, sumac (Rhus Coriaria) was extracted by using different solvents of methanol, ethanol, and water. The DPPH (2,2-diphenyl-1-picryl-hydrazyl-hydrate) method of free radical scavenging capacity was used to determine the effects of solvent on antioxidant activities of the plant. The total phenolic content was studied by The Folin Ciocalteu Reagent method. The antioxidant activities of extracts exhibit minor changes in different solvents and varied in the range of 84.3–86.4 %. The total phenolic contents are affected by the selected solvent. The highest total phenolic content was determined at the liquid phase of water and it was estimated as 26.3 mg/g in gallic acid.

Keywords: DPPH, solvent, sumac, total phenolic content

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Authors: Sharareh Mohseni

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Purpose: The objective of this study was to find a suitable solvent to produce saffron edible extract with improved chemical properties. Design/methodology/approach: Dried and pulverized stigmas of C. sativus L. (10g) was extracted with 300 ml of solvents including: distillated water (DW), ethanol/DW, methanol/DW, propylene glycol/DW, heptan/DW, and hexan/DW, for 3 days at 25°C and then centrifuged at 3000 rpm. Then the extracts were evaporated using rotary evaporator at 40°C. The fiber and solvent-free extracts were then analyzed by UV spectrophotometer to detect saffron quality parameters including crocin, picrocrocin and safranal. Findings: Distilled water/ethanol mixture as the extraction solvent, caused larger amounts of the plant constituents to diffuse out to the extract compared to other treatments and also control. Polar solvents including distilled water, ethanol, and propylene glycol (except methanol) were more effective in extracting crocin, picrocrocin, and saffranal than non-polar solvents. Social implications: Due to an enhancement of color and flavor, saffron extract is economical compared to natural saffron. Saffron Extract saves on preparation time and reduces the amount of saffron required for imparting the same flavor, as compared to dry saffron. Liquid extract is easier to use and standardize in food preparations compared to dry stamens and can be dosed precisely compared to natural saffron. Originality/value: No research had been done on production of saffron edible extract using the solvent studied in this survey. The novelty of this research is high and the results can be used industrially.

Keywords: Crocus sativus L., saffron extract, solvent extraction, distilled water

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Authors: Durata Haciu, Berti Manisa, Ozgur Birer

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ZnO nanoparticles have been synthesized by ultrasonic irradiation from simple linear alcohols and water/ethanolic mixtures, at 50 oC. By changing the composition of the solvent, the shape could be altered. While no product was obtained from methanolic solutions, in ethanol, sheet like lamellar structures prevail.n-propanol and n-butanol resulted in needle like structures. The morphology of ZnO could be thus tailored in a simple way, by varying the solvent, under ultrasonic irradiation, in a relatively less time consuming method. Variation of the morphology and size of Zn also provides a means for modulating the band-gap. Although the chemical effects of ultrasound do not come from direct interaction with molecular species, the high energy derived from acoustic cavitation creates a unique interaction of energy and matter with great potential for synthesis.

Keywords: ultrasound, ZnO, linear alcohols, morphology

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Authors: S. Bouameur, S. Chirani

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The aim of this study was to evaluate the potential use of EthylCellulose in the preparation of microspheres as a Drug Delivery System for sustained release of phenobarbital. The microspheres were prepared by solvent evaporation technique using ethylcellulose as polymer matrix with a ratio 1:2, dichloromethane as solvent and Polyvinyl alcohol 1% as processing medium to solidify the microspheres. Size, shape, drug loading capacity and entrapement efficiency were studied.

Keywords: phenobarbital, microspheres, ethylcellulose, polyvinylacohol

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Authors: Imad Eddine Charif, Sidi Mohamed Mekelleche, Didier Villemin

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The solvent effects on the keto-enol tautomeric equilibriums of acetylacetone and dimedone are theoretically investigated at the correlated Becke-3-parameter-Lee-Yang-Parr (B3LYP) and second-order Møller-Plesset (MP2) computational levels. The present study shows that the most stable keto tautomer of acetylacetone corresponds to the trans-diketo, E,Z form; while the most stable enol tautomer corresponds to the closed cis-enol,Z,Z form. The keto tautomer of dimedone prefers the trans diketo, E, E form; while the most stable enol tautomer corresponds to trans-enol form. The calculated free Gibbs enthalpies indicate that, in polar solvents, the keto-enol equilibrium of acetylacetone is shifted toward the keto tautomer; whereas the keto-enol equilibrium of dimedone is shifted towards the enol tautomer. The experimental trends of the change of equilibrium constants with respect to the change of solvent polarity are well reproduced by both B3LYP and MP2 calculations.

Keywords: acetylacetone, dimedone, solvent effects, keto-enol equilibrium, theoretical calculations

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Authors: Rhoda Afriyie Mensah, Lin Jiang, Solomon Asante-Okyere, Xu Qiang, Cong Jin

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Flammability analysis of extruded polystyrene (XPS) has become crucial due to its utilization as insulation material for energy efficient buildings. Using the Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa methods, the degradation kinetics of two pure XPS from the local market, red and grey ones, were obtained from the results of thermogravity analysis (TG) and microscale combustion calorimetry (MCC) experiments performed under the same heating rates. From the experiments, it was discovered that red XPS released more heat than grey XPS and both materials showed two mass loss stages. Consequently, the kinetic parameters for red XPS were higher than grey XPS. A comparative evaluation of activation energies from MCC and TG showed an insignificant degree of deviation signifying an equivalent apparent activation energy from both methods. However, different activation energy profiles as a result of the different chemical pathways were presented when the dependencies of the activation energies on extent of conversion for TG and MCC were compared.

Keywords: flammability, microscale combustion calorimetry, thermogravity analysis, thermal degradation, kinetic analysis

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Authors: Karen E. Supan

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Thermal degradation kinetics of switchgrass (Panicum virgatum) from the field, as well as in a pellet form, are presented. Thermogravimetric analysis tests were performed at heating rates of 10-40 K min⁻¹ in an inert atmosphere. The activation energy and the pre-exponential factor were calculated using the Ozawa/Flynn/Wall method as suggested by the ASTM Standard Test Method for Decomposition Kinetics by Thermogravimetry. Four stages were seen in the degradation: dehydration, active pyrolysis of hemicellulose, active pyrolysis of cellulose, and passive pyrolysis. The derivative mass loss peak for active pyrolysis of cellulose in the field-dried sample was much higher than the pelletized. The range of activation energy in the 0.15 – 0.70 conversion interval was 191 – 242 kJ mol⁻¹ for the field-dried and 130-192 kJ mol⁻¹ for the pellets. The highest activation energies were achieved at 0.50 conversion and were 242 kJ mol⁻¹ and 192 kJ mol⁻¹ for the field-dried and pellets, respectively. The thermal degradation and activation energies were comparable to switchgrass and other biomass reported in the literature.

Keywords: biomass, switchgrass, thermal degradation, thermogravimetric analysis

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Authors: Natália C. C. Lobato, Ângela M. Ferreira, Marcelo B. Mansur

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In solvent extraction operations, large sedimentation areas in the mixer-settler are required when the disengagement of the aqueous and the organic phases is slow and/or difficult. The use of a magnetic organic liquid (also known as ferrofluid), consisting of magnetite nanoparticles coated by oleic acid dispersed in the organic diluent, has proven successful to speed up phase disengagement. The method, however, has never been used industrially; therefore, the aim of this study is to raise its main limitations. Tests were carried out using a ferrofluid containing 30 g/l of magnetite dissolved in commercial aliphatic kerosene Exxsol D80. The efficiency of cobalt extraction ([Co] = 1 g/l) with 10% v/v Cyanex 272 (bis-2,4,4-trimethylpentyl phosphinic acid) at changing pH of the aqueous phase (2 to 7) was found unaffected in the conditions studied. However, the chemical resistance of the ferrofluid in contact with deionized water at changing acidity (from 10-7 to 2 mol/l) revealed that the nanoparticles are not resistant when contacted to aqueous solutions with a pH ≤ 2. Such result represents a serious limitation to the applicability of the method mainly to hydrometallurgical systems because solvent extraction operations are normally done in acid conditions, therefore more effective strategies to coat the particles are required.

Keywords: magnetic solvent extraction, oleic acid, magnetite nanoparticles, cyanex 272

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Authors: Geeta Kumari, Prabu Vairakannu

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Underground coal gasification (UCG) technology is an efficient and an economic in-situ clean coal technology, which converts unmineable coals into calorific valuable gases. This technology avoids ash disposal, coal mining, and storage problems. CO₂ gas can be a potential gasifying medium for UCG. CO₂ is a greenhouse gas and, the liberation of this gas to the atmosphere from thermal power plant industries leads to global warming. Hence, the capture and reutilization of CO₂ gas are crucial for clean energy production. However, the reactivity of high ash Indian coals with CO₂ needs to be assessed. In the present study, two varieties of Indian coals (low ash and high ash) are used for thermogravimetric analyses (TGA). Two low ash north east Indian coals (LAC) and a typical high ash Indian coal (HAC) are procured from the coal mines of India. Low ash coal with 9% ash (LAC-1) and 4% ash (LAC-2) and high ash coal (HAC) with 42% ash are used for the study. TGA studies are carried out to evaluate the activation energy for pyrolysis and gasification of coal under N₂ and CO₂ atmosphere. Coats and Redfern method is used to estimate the activation energy of coal under different temperature regimes. Volumetric model is assumed for the estimation of the activation energy. The activation energy estimated under different temperature range. The inherent properties of coals play a major role in their reactivity. The results show that the activation energy decreases with the decrease in the inherent percentage of coal ash due to the ash layer hindrance. A reverse trend was observed with volatile matter. High volatile matter of coal leads to the estimation of low activation energy. It was observed that the activation energy under CO₂ atmosphere at 400-600°C is less as compared to N₂ inert atmosphere. At this temperature range, it is estimated that 15-23% reduction in the activation energy under CO₂ atmosphere. This shows the reactivity of CO₂ gas with higher hydrocarbons of the coal volatile matters. The reactivity of CO₂ with the volatile matter of coal might occur through dry reforming reaction in which CO₂ reacts with higher hydrocarbon, aromatics of the tar content. The observed trend of Ea in the temperature range of 150-200˚C and 400-600˚C is HAC > LAC-1 >LAC-2 in both N₂ and CO₂ atmosphere. At the temperature range of 850-1000˚C, higher activation energy is estimated when compared to those values in the temperature range of 400-600°C. Above 800°C, char gasification through Boudouard reaction progressed under CO₂ atmosphere. It was observed that 8-20 kJ/mol of activation energy is increased during char gasification above 800°C compared to volatile matter pyrolysis between the temperature ranges of 400-600°C. The overall activation energy of the coals in the temperature range of 30-1000˚C is higher in N₂ atmosphere than CO₂ atmosphere. It can be concluded that higher hydrocarbons such as tar effectively undergoes cracking and reforming reactions in presence of CO₂. Thus, CO₂ gas is beneficial for the production of high calorific value syngas using high ash Indian coals.

Keywords: clean coal technology, CO₂ gasification, activation energy, underground coal gasification

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Authors: Yu-Wen Cheng, Jau-Der Ho, Liang-Huan Wu, Fan-Li Lin, Li-Huei Chen, Hung-Ming Chang, Yueh-Hsiung Kuo, George Hsiao

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Retina glial activation and neuroinflammation have been confirmed to cause devastating responses in retinodegenerative diseases. The expression and activation of matrix metalloproteinase (MMP)-9 and inducible nitric oxide synthase (iNOS) could be exerted as the crucial pathological factors in glaucoma- and blue light-induced retinal injuries. The present study aimed to investigate the retinoprotective effects and mechanisms of fungal ingredient 3,4-dihydroxybenzalacetone (DBL) isolated from Phellinus linteus in the retinal glial activation and retinodegenerative animal models. According to the cellular studies, DBL significantly and concentration-dependently abrogated MMP-9 activation and expression in TNFα-stimulated retinal Müller (rMC-1) cells. We found the inhibitory activities of DBL were strongly through the STAT- and ERK-dependent pathways. Furthermore, DBL dramatically attenuated MMP-9 activation in the stimulated Müller cells exposed to conditioned media from LPS-stimulated microglia BV-2 cells. On the other hand, DBL strongly suppressed LPS-induced production of NO and ROS and expression of iNOS in microglia BV-2 cells. Consistently, the phosphorylation of STAT was substantially blocked by DBL in LPS-stimulated microglia BV-2 cells. In the evaluation of retinoprotective functions, the high IOP-induced scotopic electroretinographic (ERG) deficit and blue light-induced abnormal pupillary light response (PLR) were assessed. The deficit scotopic ERG responses markedly recovered by DBL in a rat model of glaucoma-like ischemia/reperfusion (I/R)-injury. DBL also reduced the aqueous gelatinolytic activity and retinal MMP-9 expression in high IOP-injured conditions. Additionally, DBL could restore the abnormal PLR and reduce retinal MMP-9 activation. In summary, DBL could ameliorate retinal neuroinflammation and MMP-9 activation by predominantly inhibiting STAT3 activation in the retinal Müller cells and microglia, which exhibits therapeutic potential for glaucoma and other retinal degenerative diseases.

Keywords: glaucoma, blue light, DBL, retinal Müller cell, MMP-9, STAT, Microglia, iNOS, ERG, PLR

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Authors: Kenichi Hirota, Jifeng Wang, Sadao Araki, Koji Endo, Hideki Yamamoto

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Zirconium (Zr) has been used as a fuel cladding tube for nuclear reactors, because of the excellent corrosion resistance and the low adsorptive material for neutron. Generally speaking, the natural resource of Zr is often containing Hf that has similar properties. The content of Hf in the Zr resources is about 2~4 wt%. In the industrial use, the content of Hf in Zr resources should be lower than the 100 ppm. However, the separation of Zr and Hf is not so easy, because of similar chemical and physical properties such as melting point, boiling point and things. Solvent extraction method has been applied for the separation of Zr and Hf from Zr natural resources. This method can separate Hf with high efficiency (Hf < 100ppm), however, it needs much amount of organic solvents for solvent extraction and the cost of its disposal treatment is high. Therefore, we attached attention for the fractional crystallization. This separation method depends on the solubility difference of Zr and Hf in the solvent. In this work, hexafluorozirconate (hafnate) (K2Zr(Hf)F6) was used as model compound. Solubility of K2ZrF6 in water showed lower than that of K2HfF6. By repeating of this treatment, it is possible to purify Zr, practically. In this case, 16-18 times of recrystallization stages were needed for its high purification. The improvement of the crystallization process was carried out in this work. Water, hydrofluoric acid (HF) and hydrofluoric acid (HF) +hydrochloric acid (HCl) mixture were chosen as solvent for dissolution of Zr and Hf. In the experiment, 10g of K2ZrF6 was added to each solvent of 100mL. Each solution was heated for 1 hour at 353K. After 1h of this operation, they were cooled down till 293K, and were held for 5 hours at 273K. Concentration of Zr or Hf was measured using ICP analysis. It was found that Hf was separated from Zr-Hf mixed compound with high efficiency, when HF-HCl solution was used for solvent of crystallization. From the comparison of the particle size of each crystal by SEM, it was confirmed that the particle diameter of the crystal showed smaller size with decreasing of Hf content. This paper concerned with purification of Zr from Zr-Hf mixture using crystallization method.

Keywords: crystallization, zirconium, hafnium, separation

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Authors: Korban Oosthuizen, Robert C. Luckay

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Due to the growing popularity of electric vehicles and the importance of cobalt as part of the cathode material for lithium-ion batteries, demand for this metal is on the rise. Recycling of the cathode materials by means of solvent extraction is an attractive means of recovering cobalt and easing the pressure on limited natural resources. In this study, a series of straight chain and macrocyclic diamine ligands were developed for the selective recovery of cobalt from the solution containing nickel and manganese by means of solvent extraction. This combination of metals is the major cathode material used in electric vehicle batteries. The ligands can be protonated and function as ion-pairing ligands targeting the anionic [CoCl₄]²⁻, a species which is not observed for Ni or Mn. Selectivity for Co was found to be good at very high chloride concentrations and low pH. Longer chains or larger macrocycles were found to enhance selectivity, and linear chains on the amide side groups also resulted in greater selectivity over the branched groups. The cation of the chloride salt used for adjusting chloride concentrations seems to play a major role in extraction through salting-out effects. The ligands developed in this study show good selectivity for Co over Ni and Mn but require very high chloride concentrations to function. This research does, however, open the door for further investigations into using diamines as solvent extraction ligands for the recovery of cobalt from spent lithium-ion batteries.

Keywords: hydrometallurgy, solvent extraction, cobalt, lithium-ion batteries

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Authors: Jamshaid Ul Rahman, Faiza Makhdoom, Dianchen Lu

Abstract:

Activation functions play a decisive role in determining the capacity of Deep Neural Networks (DNNs) as they enable neural networks to capture inherent nonlinearities present in data fed to them. The prior research on activation functions primarily focused on the utility of monotonic or non-oscillatory functions, until Growing Cosine Unit (GCU) broke the taboo for a number of applications. In this paper, a Convolutional Neural Network (CNN) model named as ASU-CNN is proposed which utilizes recently designed activation function ASU across its layers. The effect of this non-monotonic and oscillatory function is inspected through feature map visualizations from different convolutional layers. The optimization of proposed network is offered by Adam with a fine-tuned adjustment of learning rate. The network achieved promising results on both training and testing data for the classification of CIFAR-10. The experimental results affirm the computational feasibility and efficacy of the proposed model for performing tasks related to the field of computer vision.

Keywords: amplifying sine unit, activation function, convolutional neural networks, oscillatory activation, image classification, CIFAR-10

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Authors: Getenet Aseged Zeleke

Abstract:

The aim of this project was to study the synthesis of activated carbon from low-cost animal beef and the characterization of the product obtained. The bone was carbonized in an inert atmosphere at three different temperatures (500°C, 700oC and 900°C) in an electric furnace, followed by activation with hydrochloric acid. The activated animal bone charcoals obtained were characterized by using scanning electron microscopy (SEM)to observe the effect of activation compared to the unactivated bone charcoal. The following parameters were also determined: ash content, moisture content, volatile content, fixed carbon, pH, pore volume and bulk (apparent) density. The characterization result showed that the activated bone charcoal has good properties and is compared favorably with other reference activated carbons.

Keywords: bones, carbonization, activation, characterization, activated carbon

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Authors: Yi-Hui Lai, Chih-Hsiang Yang, Li-Chung Hsu

Abstract:

The inflammasome is a protein complex that modulates caspase-1 activity, resulting in proteolytic cleavage of proinflammatory cytokines such as IL-1β and IL-18, into their bioactive forms. It has been shown that the inflammasomes play a crucial role in the clearance of pathogenic infection and tissue repair. However, dysregulated inflammasome activation contributes to a wide range of human diseases such as cancers and auto-inflammatory diseases. Yet, regulation of NLRP3 inflammasome activation remains largely unknown. We discovered a novel DEAD box protein, whose biological function has not been reported, not only negatively regulates NLRP3 inflammasome activation by interfering NLRP3 inflammasome assembly and cellular localization but also mitigate pyroptosis upon pathogen evasion. The DEAD-box protein is the first DEAD-box protein gets involved in modulation of the inflammasome activation. In our study, we found that caspase-1 activation and mature IL-1β production were largely enhanced upon LPS challenge in the DEAD box-containing protein- deleted THP-1 macrophages and bone marrow-derived macrophages (BMDMs). In addition, this DEAD box-containing protein migrates from the nucleus to the cytoplasm upon LPS stimulation, which is required for its inhibitory role in NLRP3 inflammasome activation. The DEAD box-containing protein specifically interacted with the LRR motif of NLRP3 via its DEAD domain. Furthermore, due to the crucial role of the NLRP3 LRR domain in the recruitment of NLRP3 to mitochondria and binding to its adaptor ASC, we found that the interaction of NLRP3 and ASC was downregulated in the presence of the DEAD box-containing protein. In addition to the mechanical study, we also found that this DEAD box protein protects host cells from inflammasome-triggered cell death in response to broad-ranging pathogens such as Candida albicans, Streptococcus pneumoniae, etc., involved in nosocomial infections and severe fever shock. Collectively, our results suggest that this novel DEAD box molecule might be a key therapeutic strategy for various infectious diseases.

Keywords: inflammasome, inflammation, innate immunity, pyroptosis

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Authors: Ian Marc G. Cabugsa, Kim Ryan A. Won

Abstract:

Fast, reliable and simultaneous HPLC analysis of theobromine and caffeine in cacao and cocoa products was optimized in this study. The samples tested were raw, fermented, and roasted cacao beans as well as commercially available cocoa products. The HPLC analysis was carried out using step gradient solvent system with acetonitrile and water buffered with H3PO4 as the mobile phase. The HPLC system was optimized using 273 nm wavelength at 35 °C for the column temperature with a flow rate of 1.0 mL/min. Using this method, the theobromine percent recovery mean, Limit of Detection (LOD) and Limit of Quantification (LOQ) is 118.68(±3.38)%, 0.727 and 1.05 respectively. The percent recovery mean, LOD and LOQ for caffeine is 105.53(±3.25)%, 2.42 and 3.50 respectively. The inter-day and intra-day precision for theobromine is 4.31% and 4.48% respectively, while 7.02% and 7.03% was for caffeine respectively. Compared to the standard method in AOAC using methanol in isocratic solvent system, the results of the study produced lesser chromatogram noise with emphasis on theobromine and caffeine. The method is readily usable for cacao and cocoa substances analyses using HPLC with step gradient capability.

Keywords: cacao, caffeine, HPLC, step gradient solvent system, theobromine

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Authors: Azhar Jabareen, Mahmoud Huleihel

Abstract:

BRCA-1 is a multifunctional tumor suppressor, whose expression is activated by the estrogen (E2)-liganded ERα receptor. The activated ERα is a transcriptional factor which activates various genes either by direct binding to the DNA at E2-responsive elements (EREs) and indirectly associated with a range of alternative non-ERE elements. Interference with BRCA-1 expression and/or functions leads to high risk of breast or/and ovarian cancer. Our lab investigated the involvement of Human T-cell leukemia Virus Type 1 (HTLV-1) in breast cancer, since HTLV-1 Tax was found to strongly inhibit BRCA-1 expression. In addition, long exposure of 12-O-tetradecanoylphorbol-13-acetate (TPA), which is one of the stress-inducing agents activated the HTLV-1 promoter. So here the involvement of TPA in breast cancer had been examined by testing the effect of TPA on BRCA-1 and ERE expression. The results showed that TPA activated both BRCA-1 and ERE expression. In the 12 hours TPA activated the tow promoters more than others time, and after 24 hours the level of the tow promoters was decreased. Tax inhibited BRCA-1 expression but did not succeed to inhibit the effect of TPA. Then the activation of the two promoters was not through ERα pathway because TPA had no effect on ERα binding to the two promoters of the BRCA-1 and ERE. Also, the activation was not via nuclear factor kappa B (NF-κB) pathway because when the inhibitory of NF-κB had been added to the TPA, it still activated the tow promoters. However, it seems that 53BP1 may be involved in TPA activation of these promoters because ectopic high expression of 53BP1 significantly reduced the TPA activity. In addition, in the presence of Bisindolylmaleimide-I (BI)- the inhibitor of Protein Kinase C (PKC)- there was no activation for the two promoters, so the PKC is agonized BRCA-1 and ERE activation.

Keywords: BRCA-1, ERE, HTLV-1, TPA

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