Search results for: membrane synthesis

Authors: A. S. Gorobtsov, A. S. Polyanina, A. E. Andreev

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The movement of points feet of the anthropomorphous robot in space occurs along some stable trajectory of a known form. A large number of modifications to the methods of control of biped robots indicate the fundamental complexity of the problem of stability of the program trajectory and, consequently, the stability of the control for the deviation for this trajectory. Existing gait generators use piecewise interpolation of program trajectories. This leads to jumps in the acceleration at the boundaries of sites. Another interpolation can be realized using differential equations with fractional derivatives. In work, the approach to synthesis of generators of program trajectories is considered. The resulting system of nonlinear differential equations describes a smooth trajectory of movement having rectilinear sites. The method is based on the theory of an asymptotic stability of invariant sets. The stability of such systems in the area of localization of oscillatory processes is investigated. The boundary of the area is a bounded closed surface. In the corresponding subspaces of the oscillatory circuits, the resulting stable limit cycles are curves having rectilinear sites. The solution of the problem is carried out by means of synthesis of a set of the continuous smooth controls with feedback. The necessary geometry of closed trajectories of movement is obtained due to the introduction of high-order nonlinearities in the control of stabilization systems. The offered method was used for the generation of trajectories of movement of point’s feet of the anthropomorphous robot. The synthesis of the robot's program movement was carried out by means of the inverse method.

Keywords: control, limits cycle, robot, stability

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Authors: Taoufik Bettaieb, Sihem Soufi

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As a bioactive metalloid, silicon (Si) is an essential element for plant growth and development. It also plays a crucial role in enhancing plants’ resilience to different abiotic and biotic stresses. The morpho-physiological, biochemical, and molecular background of Si-mediated stress tolerance in plants were unraveled. Cold stress is a severe abiotic stress response to the decrease of plant growth and yield by affecting various physiological activities in plants. Several approaches have been used to alleviate the adverse effects generated from cold stress exposure, but the cost-effective, environmentally friendly, and defensible approach is the supply of silicon. Silicon has the ability to neutralize the harmful impacts of cold stress. Therefore, based on these hypotheses, this study was designed in order to investigate the morphological and physiological background of silicon effects applied at different concentrations on cold stress mitigation during early growth of a turfgrass, namely Paspalum vaginatum Sw. Results show that silicon applied at different concentrations improved the morphological development of Paspalum subjected to cold stress. It is also effective on the photosynthetic apparatus by maintaining stability the photochemical efficiency. As the primary component of cellular membranes, lipids play a critical function in maintaining the structural integrity of plant cells. Silicon application decreased membrane lipid peroxidation and kept on membrane frontline barrier relatively stable under cold stress.

Keywords: crops, cold stress, silicon, abiotic stress

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Authors: Eduardo Padilla, Luis Daniel Rodriguez, Ivan Sanchez, Angelica Sofia Go

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The synthesis and application of metallic nanoparticles have increased in recent years. Biological methods go beyond the chemical and physical synthesis that is expensive and not friendly to the environment. Therefore, in this study, silver nanoparticles were synthesized biologically in an environmentally friendly way by Handroanthus chrysanthus flower aqueous extract (AgNPs) that contains phytochemicals capable of reducing silver nitrate. AgNPs were characterized visually by UV-visible spectroscopy and TEM. The antimicrobial activity of the AgNPs was tested by determining the minimum inhibitory concentration (MIC), and minimal bactericidal concentration (MBC) in Escherichia coli and Staphylococcus aureus strains AgNPs showed potent antimicrobial activity against gram-negative and gram-positive bacteria. MIC and MBC values were as low as 41.6, and 83.2 ug/mL using AgNPs biosynthesized by H. chrysanthus flower extract. This nanoparticle could be the basis for the formulation of disinfectants for use in the food and pharmaceutical industry.

Keywords: antimicrobial, silver nanoparticles, flower extract, Handroanthus

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Authors: Surjyakanta Rana, Sreekantha B. Jonnalagadda

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Synthesis of well distributed Pd nanoparticles (3 – 7 nm) on organo amine-functionalized graphene is reported, which demonstrated excellent catalytic activity towards Suzuki coupling reaction. The active material was characterized by X-ray diffraction (XRD), BET surface area, X-ray photoelectron spectra (XPS), Fourier-transfer infrared spectroscopy (FTIR), Raman spectra, Scanning electron microscope (SEM), Transmittance electron microscopy (TEM) analysis and HRTEM. FT-IR revealed that the organic amine functional group was successfully grafted onto the graphene oxide surface. The formation of palladium nanoparticles was confirmed by XPS, TEM and HRTEM techniques. The catalytic activity in the coupling reaction was superb with 100% conversion and 98 % yield and also activity remained almost unaltered up to six cycles. Typically, an extremely high turnover frequency of 185,078 h-1 is observed in the C-C Suzuki coupling reaction using organo di-amine functionalized graphene as catalyst.

Keywords: Di-amine, graphene, Pd nanoparticle, suzuki coupling

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Authors: Rachid El Aidani, Phuong Nguyen-Tri, Toan Vu-Khanh

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The filter media in synthetic fibre is the most geotextile materials used in aerosol and drainage filtration, particularly for buildings soil reinforcement in civil engineering due to its appropriated properties and its low cost. However, the current understanding of the durability and stability of this material in real service conditions, especially under severe long-term conditions are completely limited. This study has examined the effects of the chemical aging of a filter media in polyester nonwoven under different temperatures (50, 70 and 80˚C) and pH (2. 7 and 12). The effect of aging conditions on mechanical properties, morphology, permeability, thermal stability and molar weigh changes is investigated. The results showed a significant reduction of mechanical properties in term of tensile strength, puncture force and tearing forces of the filter media after chemical aging due to the chemical degradation. The molar mass and mechanical properties changes in different temperature and pH showed a complex dependence of material properties on environmental conditions. The SEM and AFM characterizations showed a significant impact of the thermal aging on the morphological properties of the fibres. Based on the obtained results, the lifetime of the material in different temperatures was determined by the use of the Arrhenius model. These results provide useful information to better understand phenomena occurring during chemical aging of the filter media and may help to predict the service lifetime of this material in real used conditions.

Keywords: nonwoven membrane, chemical aging, mechanical properties, lifetime, filter media

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Authors: Abdelkader Anouzla, Soukaina Bouaouda, Roukaya Bouyakhsass, Salah Souabi, Abdeslam Taleb

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During storage and under the combined action of rainwater and natural fermentation, these wastes produce over 800.000 m3 of landfill leachates. Due to population growth and changing global economic activities, the amount of waste constantly generated increases, making more significant volumes of leachate. Leachate, when leaching into the soil, can negatively impact soil, surface water, groundwater, and the overall environment and human life. The leachate must first be treated because of its high pollutant load before being released into the environment. This article reviews the different leachate treatments in September 2022 techniques. Different techniques can be used for this purpose, such as biological, physical-chemical, and membrane methods. Young leachate is biodegradable; in contrast, these biological processes lose their effectiveness with leachate aging. They are characterized by high ammonia nitrogen concentrations that inhibit their activity. Most physical-chemical treatments serve as pre-treatment or post-treatment to complement conventional treatment processes or remove specific contaminants. After the introduction, the different types of pollutants present in leachates and their impacts have been made, followed by a discussion highlighting the advantages and disadvantages of the various treatments, whether biological, physicochemical, or membrane. From this work, due to their simplicity and reasonable cost compared to other treatment procedures, biological treatments offer the most suitable alternative to limit the effects produced by the pollutants in landfill leachates.

Keywords: landfill leachate, landfill pollution, impact, wastewater

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Authors: Sirous Eydivandi

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Diacylglycerol-O-acyltransferase (DGAT1) gene encodes diacylglycerol transferase enzyme that plays an important role in glycerol lipid metabolism. DGAT1 is considered to be the key enzyme in controlling the synthesis of triglycerides in adipocytes. This enzyme catalyzes the final step of triglyceride synthesis (transform triacylglycerol (DAG) into triacylglycerol (TAG). A total of 20 DGAT1 gene sequences and corresponding amino acids belonging to 4 species include cattle, goats, sheep and yaks were analyzed, and the differentiation within and among the species was also studied. The length of the DGAT1 gene varies greatly, from 1527 to 1785 bp, due to deletion, insertion, and stop codon mutation resulting in elongation. Observed genetic diversity was higher among species than within species, and Goat had more polymorphisms than any other species. Novel amino acid variation sites were detected within several species which might be used to illustrate the functional variation. Differentiation of the DGAT1 gene was obvious among species, and the clustering result was consistent with the taxonomy in the National Center for Biotechnology Information.

Keywords: DGAT1gene, bioinformatic, ruminnants, biotechnology information

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Authors: F. Z. Abir, M. Mesnaoui, Y. Abouliatim, L. Nibou, Y. El Hafiane, A. Smith

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The cement industry has been taking significant steps for years to reduce its carbon footprint by opting for an eco-friendly alternative such as Calcium Sulfoaluminate Cements (CSA). These binders, compared to Ordinary Portland Cements (OPC), have two advantages: reduction of the CO2 emissions and energy-saving because the sintering temperature of CSA cements is between 1250 and 1350 °C, which means 100 to 200 °C less than OPC. The aim of this work is to study the impurities effect, such as iron oxide, on the formation of the ye'elimite phase, which represents the main phase of Calcium Sulfoaluminate Cements and the consequence on its hydration. Several elaborations and characterization techniques were used to study the structure and microstructure of ye'elimite, such as X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), thermal analysis, specific surface area measurement, and electrical conductivity of diluted solutions. This study details the protocol for the solid-state synthesis of ye'elimite containing increasing amounts of iron (general formula: Ca4Al(6-2x)Fe2xSO16 with x = 0.00 to 1.13). Ye'elimite is formed by solid-state reactions between Al2O3, CaO and CaSO4 and the maximum ye'elimite content is reached at a sintering temperature of 1300 °C. The presence of iron promotes the formation of cubic ye'elimite at the expense of the orthorhombic phase. The total incorporation of iron in ye'elimite structure is possible when x < 0.12. Beyond this content, the ferritic phase (CaO)2(Al2O3,Fe2O3) appears as a minor phase and develops two different morphologies during cooling: dendritic crystals and melt morphology. The formation of the ferrous liquid phase affects the evolution of grain size of the ye’elimite and calcium aluminates.

Keywords: calcium sulfoaluminate cement, ferritic phase, sintering, solid-state synthesis, ye’elimite

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Authors: Hyunuk Kim, Yang No Yun, Muhammad Sohail, Jong-Ho Moon, Young Cheol Park

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Metal-organic frameworks (MOFs), which are emerging absorbents assembled from metal ions and organic ligands, have attracted attention for their permanent porosity and design of tunable pore size. These microporous materials showed interesting properties for CO₂ storage and separation. In particular, MOFs with high surface area and open metal sites showed the remarkable adsorption capacity and selectivity for CO₂. [Mg₂ (DOBDC)] (DOBDC = 2,5-dioxidobenzene-1,4-dicarboxylate) (MOF-74 or CPO-27) is a well-known absorbent showing an exceptionally high CO₂ sorption capacity at low partial pressure and room temperature. In this work, we synthesized [M₂(DOBDC)(DMF)₂] (M = Mg, Co, Ni) and determined their single-crystal structures by X-ray crystallography. The removal of coordinated guest molecules generates Lewis acidic sites and showed high CO₂ adsorption affinity. Both CO₂ adsorption capacity and surface area are much higher than reported values in literature. To fabricate MMMs, microcrystalline [M₂ (DOBDC)(DMF)₂] was synthesized by microwave reaction and dispersed in PDMS solution. The MMMs with a various amount of [M₂ (DOBDC)(DMF) ₂] in PDMS were fabricated by a solution casting method. [M₂ (DOBDC)(DMF)₂]@PDMS membrane showed higher CO2 permeability and CO₂/N₂ selectivity than those of PDMS. Therefore, we believe that MMMs combining polymer and MOFs provide new materials for CO₂ separation technology.

Keywords: metal-organic frameworks, mixed matrix membrane, CO2/N2 separation, polydimethylsiloxane (PDMS)

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Authors: Boukary Lam, Sebastien Deon, Patrick Fievet, Nadia Crini, Gregorio Crini

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Treatment of heavy metal-contaminated industrial wastewater has become a major challenge over the last decades. Conventional processes for the treatment of metal-containing effluents do not always simultaneously satisfy both legislative and economic criteria. In this context, coupling of processes can then be a promising alternative to the conventional approaches used by industry. The polymer-assisted ultrafiltration (PAUF) process is one of these coupling processes. Its principle is based on a sequence of steps with reaction (e.g., complexation) between metal ions and a polymer and a step involving the rejection of the formed species by means of a UF membrane. Unlike free ions, which can cross the UF membrane due to their small size, the polymer/ion species, the size of which is larger than pore size, are rejected. The PAUF process was deeply investigated herein in the case of removal of nickel ions by adding chitosan and carboxymethyl cellulose (CMC). Experiments were conducted with synthetic solutions containing 1 to 100 ppm of nickel ions with or without the presence of NaCl (0.05 to 0.2 M), and an industrial discharge water (containing several metal ions) with and without polymer. Chitosan with a molecular weight of 1.8×105 g mol⁻¹ and a degree of acetylation close to 15% was used. CMC with a degree of substitution of 0.7 and a molecular weight of 9×105 g mol⁻¹ was employed. Filtration experiments were performed under cross-flow conditions with a filtration cell equipped with a polyamide thin film composite flat-sheet membrane (3.5 kDa). Without the step of polymer addition, it was found that nickel rejection decreases from 80 to 0% with increasing metal ion concentration and salt concentration. This behavior agrees qualitatively with the Donnan exclusion principle: the increase in the electrolyte concentration screens the electrostatic interaction between ions and the membrane fixed the charge, which decreases their rejection. It was shown that addition of a sufficient amount of polymer (greater than 10⁻² M of monomer unit) can offset this decrease and allow good metal removal. However, the permeation flux was found to be somewhat reduced due to the increase in osmotic pressure and viscosity. It was also highlighted that the increase in pH (from 3 to 9) has a strong influence on removal performances: the higher pH value, the better removal performance. The two polymers have shown similar performance enhancement at natural pH. However, chitosan has proved more efficient in slightly basic conditions (above its pKa) whereas CMC has demonstrated very weak rejection performances when pH is below its pKa. In terms of metal rejection, chitosan is thus probably the better option for basic or strongly acid (pH < 4) conditions. Nevertheless, CMC should probably be preferred to chitosan in natural conditions (5 < pH < 8) since its impact on the permeation flux is less significant. Finally, ultrafiltration of an industrial discharge water has shown that the increase in metal ion rejection induced by the polymer addition is very low due to the competing phenomenon between the various ions present in the complex mixture.

Keywords: carboxymethyl cellulose, chitosan, heavy metals, nickel ion, polymer-assisted ultrafiltration

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Authors: Afsheen Aman, Shah Ali Ul Qader

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Dextransucrase [EC 2.4.1.5] is a glucosyltransferase that catalysis the biosynthesis of a natural biopolymer called dextran. It can catalyze the transfer of D-glucopyranosyl residues from sucrose to the main chain of dextran. This unique biopolymer has multiple applications in several industries and the key utilization of dextran lies on its molecular weight and the type of branching. Extracellular dextransucrase from Leuconostoc mesenteroides is most extensively studied and characterized. Limited data is available regarding cell-bound or intracellular dextransucrase and on the characterization of dextran produced by in-vitro reaction of intracellular dextransucrase. L. mesenteroides AA1 is reported to produce extracellular dextransucrase that catalyzes biosynthesis of a high molecular weight dextran with only α-(1→6) linkage. Current study deals with the characterization of an intracellular dextransucrase and in vitro biosynthesis of low molecular weight dextran from L. mesenteroides AA1. Intracellular dextransucrase was extracted from cytoplasm and purified to homogeneity for characterization. Kinetic constants, molecular weight and N-terminal sequence analysis of intracellular dextransucrase reveal unique variation with previously reported extracellular dextransucrase from the same strain. In vitro synthesized biopolymer was characterized using NMR spectroscopic techniques. Intracellular dextransucrase exhibited Vmax and Km values of 130.8 DSU ml-1 hr-1 and 221.3 mM, respectively. Optimum catalytic activity was detected at 35°C in 0.15 M citrate phosphate buffer (pH-5.5) in 05 minutes. Molecular mass of purified intracellular dextransucrase is approximately 220.0 kDa on SDS-PAGE. N-terminal sequence of the intracellular enzyme is: GLPGYFGVN that showed no homology with previously reported sequence for the extracellular dextransucrase. This intracellular dextransucrase is capable of in vitro synthesis of dextran under specific conditions. This intracellular dextransucrase is capable of in vitro synthesis of dextran under specific conditions and this biopolymer can be hydrolyzed into different molecular weight fractions for various applications.

Keywords: characterization, dextran, dextransucrase, leuconostoc mesenteroides

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Authors: Samira Naghdi, Kyong Yop Rhee

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Transfer-free synthesis of graphene on dielectric substrates is highly desirable but remains challenging. Here, by using a thin sacrificial platinum layer as a catalyst, graphene was deposited on a silicon substrate through a simple and transfer-free synthesis method. During graphene growth, the platinum layer evaporated, resulting in direct deposition of graphene on the silicon substrate. In this work, different growth conditions of graphene were optimized. Raman spectra of the produced graphene indicated that the obtained graphene was bilayer. The sheet resistance obtained from four-point probe measurements demonstrated that the deposited graphene had high conductivity. Reflectance spectroscopy of graphene-coated silicon showed a decrease in reflectance across the wavelength range of 200-800 nm, indicating that the graphene coating on the silicon surface had antireflection capabilities.

Keywords: antireflection coating, chemical vapor deposition, graphene, the sheet resistance

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Authors: N. Moudir, N. Moulai-Mostefa, Y. Boukennous, I. Bozetine, N. Kamel, D. Moudir

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the study focuses on a novel process of silver powders synthesis for the preparation of conductive pastes used for solar cells metalization. Butyl-Carbitol and butyl-carbitol Acetate have been used as solvents and reducing agents of silver nitrate (AgNO3) as precursor to get silver powders. XRD characterization revealed silver powders with a cubic crystal system. SEM micro graphs showed spherical morphology of the particles. Laser granulometer gives similar particles distribution for the two agents. Using same glass frit and organic vehicle for comparative purposes, two conductive pastes were prepared with the synthesized silver powders for the front-side metalization of multi-crystalline cells. The pastes provided acceptable fill factor of 59.5 % and 60.8 % respectively.

Keywords: chemical reduction, conductive paste, silver nitrate, solar cell

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Authors: Azad Khalid, Sifa Dogan

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Because of its persistence in conventional treatment plants and broad prevalence in water bodies, the pharmaceutical chemical carbamazepine (CBZ) has been suggested as an anthropogenic marker to evaluate water quality. This study provides a thorough examination of the origins and occurrences of CBZ in water bodies, as well as the drug's toxicological effects and laws. Given CBZ's well-documented negative consequences on the human body when used medicinally, cautious monitoring in water is advised. CBZ residues in drinking water may enter embryos and newborns via intrauterine exposure or breast-feeding, causing congenital abnormalities and/or neurodevelopmental issues over time. The insufficiency of solo solutions was shown after an in-depth technical study of traditional and sophisticated treatment technologies. Nanofiltration and reverse osmosis membranes are more successful at removing CBZ than traditional activated sludge and membrane bioreactor techniques. Recent research has shown that severe chemical cleaning, which is essential to prevent membrane fouling, may lower long-term removal efficiency. Furthermore, despite the efficacy of activated carbon adsorption and advanced oxidation processes, a few issues such as chemical cost and activated carbon renewal must be carefully examined. Individual technology constraints lead to the benefits of combined and hybrid systems, namely the heterogeneous advanced oxidation process.

Keywords: carbamazepine, occurrence, toxicity, conventical treatment, advanced oxidation process (AOPs)

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Authors: Zohreh Derikvand

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Nanoreactors Zr-MCM-41were prepared via the reaction of ZrOCl2, Fumed silica, sodium hydroxide and cethyltrimethyl ammonium bromide under hydrothermal condition. The prepared nanoreactors were characterized by FT-IR spectroscopy, X-ray diffraction (XRD), Scanning electron micrographs (SEM) and nitrogen adsorption-desorption. The XRD pattern of Zr-MCM-41 exhibits a high-intensity (100) and two low-intensity reflections (110 and 200) which are characteristic of hexagonal structure, exhibiting the long-range order and good textural uniformity of mesoporous structure. Based on the green chemistry approach, we report an efficient and environmentally benign protocol to study the catalytic activity of Zr-MCM-41 in the Biginelli type reactions initially. Nanoreactors Zr-MCM-41 were used as highly recoverable and reusable catalyst for synthesis of 3,4-dihydropyrimidin-2(1H)-one, octahydroquinazolinone, benzimidazolo-quinazolineone and 4,6-diarylpyrimidin-2(1H)-one. The methodology offers several advantages such as short reaction time, high yields and simple operation. The catalyst was active up to three cycles.

Keywords: Zr-MCM-41 nanoreactors, Biginelli like reactions, 3, 4-dihydropyrimidin-2(1H)-ones, ctahydroquinazolinones

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Authors: Fei Xu, Guofan Zhang, Xiao Liu

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Many major marine invertebrate phyla are characterized by indirect development. These animals transit from planktonic larvae to benthic adults via settlement and metamorphosis, which has many advantages for organisms to adapt marine environment. Studying the biological process of metamorphosis is thus a key to understand the origin and evolution of indirect development. Although the mechanism of metamorphosis has been largely studied on their relationships with the marine environment, microorganisms, as well as the neurohormones, little is known on the gene regulation network (GRN) during metamorphosis. We treated competent oyster pediveligers with epinephrine, which was known to be able to effectively induce oyster metamorphosis, and analyzed the dynamics of gene and proteins with transcriptomics and proteomics methods. The result indicated significant upregulation of protein synthesis system, as well as some transcription factors including Homeobox, basic helix-loop-helix, and nuclear receptors. The result suggested the GRN complexity of the transition stage during oyster metamorphosis.

Keywords: indirect development, gene regulation network, protein synthesis, transcription factors

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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: Laura Mejias, Sandra Monteagudo, Oscar Martinez-Avila, Sergio Ponsa

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Bioplastics are gaining attention as potential substitutes of conventional fossil-derived plastics and new components of specialized applications in different industries. Besides, these constitute a sustainable alternative since they are biodegradable and can be obtained starting from renewable sources. Thus, agro-industrial wastes appear as potential substrates for bioplastics production using microorganisms, considering they are a suitable source for nutrients, low-cost, and available worldwide. Therefore, this approach contributes to the biorefinery and circular economy paradigm. The present study assesses the solid-state fermentation (SSF) technology for the co-synthesis of exopolysaccharides (EPS) and polyhydroxyalkanoates (PHA), two attractive biodegradable bioplastics, using the leftover of the brewery industry brewer's spent grain (BSG). After an initial screening of diverse PHA-producer bacteria, it was found that Burkholderia cepacia presented the highest EPS and PHA production potential via SSF of BSG. Thus, B. cepacia served to identify the most relevant aspects affecting the EPS+PHA co-synthesis at a lab-scale (100g). Since these are growth-dependent processes, they were monitored online through oxygen consumption using a dynamic respirometric system, but also quantifying the biomass production (gravimetric) and the obtained products (EtOH precipitation for EPS and solid-liquid extraction coupled with GC-FID for PHA). Results showed that B. cepacia has grown up to 81 mg per gram of dry BSG (gDM) at 30°C after 96 h, representing up to 618 times higher than the other tested strains' findings. Hence, the crude EPS production was 53 mg g-1DM (2% carbohydrates), but purity reached 98% after a dialysis purification step. Simultaneously, B. cepacia accumulated up to 36% (dry basis) of the produced biomass as PHA, mainly composed of polyhydroxybutyrate (P3HB). The maximum PHA production was reached after 48 h with 12.1 mg g⁻¹DM, representing threefold the levels previously reported using SSF. Moisture content and aeration strategy resulted in the most significant variables affecting the simultaneous production. Results show the potential of co-synthesis via SSF as an attractive alternative to enhance bioprocess feasibility for obtaining these bioplastics in residue-based systems.

Keywords: bioplastics, brewer’s spent grain, circular economy, solid-state fermentation, waste to product

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Authors: Nayana T. Nivangune, Vivek V. Ranade, Ashutosh A. Kelkar

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Organic carbamates are versatile compounds widely employed as pesticides, fungicides, herbicides, dyes, pharmaceuticals, cosmetics and in the synthesis of polyurethanes. Carbamates can be easily transformed into isocyanates by thermal cracking. Isocyantes are used as precursors for manufacturing agrochemicals, adhesives and polyurethane elastomers. Manufacture of polyurethane foams is a major application of aromatic ioscyanates and in 2007 the global consumption of polyurethane was about 12 million metric tons/year and the average annual growth rate was about 5%. Presently Isocyanates/carbamates are manufactured by phosgene based process. However, because of high toxicity of phoegene and formation of waste products in large quantity; there is a need to develop alternative and safer process for the synthesis of isocyanates/carbamates. Recently many alternative processes have been investigated and carbamate synthesis by methoxycarbonylation of aromatic amines using dimethyl carbonate (DMC) as a green reagent has emerged as promising alternative route. In this reaction methanol is formed as a by-product, which can be converted to DMC either by oxidative carbonylation of methanol or by reacting with urea. Thus, the route based on DMC has a potential to provide atom efficient and safer route for the synthesis of carbamates from DMC and amines. Lot of work is being carried out on the development of catalysts for this reaction and homogeneous zinc salts were found to be good catalysts for the reaction. However, catalyst/product separation is challenging with these catalysts. There are few reports on the use of supported Zn catalysts; however, deactivation of the catalyst is the major problem with these catalysts. We wish to report here methoxycarbonylation of aniline to methylphenylcarbamate (MPC) using amino acid complexes of Zn as highly active and selective catalysts. The catalysts were characterized by XRD, IR, solid state NMR and XPS analysis. Methoxycarbonylation of aniline was carried out at 170 °C using 2.5 wt% of the catalyst to achieve >98% conversion of aniline with 97-99% selectivity to MPC as the product. Formation of N-methylated products in small quantity (1-2%) was also observed. Optimization of the reaction conditions was carried out using zinc-proline complex as the catalyst. Selectivity was strongly dependent on the temperature and aniline:DMC ratio used. At lower aniline:DMC ratio and at higher temperature, selectivity to MPC decreased (85-89% respectively) with the formation of N-methylaniline (NMA), N-methyl methylphenylcarbamate (MMPC) and N,N-dimethyl aniline (NNDMA) as by-products. Best results (98% aniline conversion with 99% selectivity to MPC in 4 h) were observed at 170oC and aniline:DMC ratio of 1:20. Catalyst stability was verified by carrying out recycle experiment. Methoxycarbonylation preceded smoothly with various amine derivatives indicating versatility of the catalyst. The catalyst is inexpensive and can be easily prepared from zinc salt and naturally occurring amino acids. The results are important and provide environmentally benign route for MPC synthesis with high activity and selectivity.

Keywords: aniline, heterogeneous catalyst, methoxycarbonylation, methylphenyl carbamate

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Authors: Talat Baran

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The Suzuki C(sp2)-C(sp2) coupling reaction is considered to be one of the best ways for the synthesis of biaryl compounds. There are many studies reporting the catalytic performance of palladium catalyst in Suzuki coupling reactions. Natural biopolymer (such as zeolite, carbon, silica, and chitosan) supporting catalysts have been lately attracted interest because of their low-cost, nontoxicity, and eco-friendliness. One of the most important natural biopolymer is cellulose, which is widely considered as an eco-friendly biopolymer due to its biodegradable, non-toxic and renewable nature. In this study, (1) cellulose supported Pd(II) catalyst was synthesized (2) its chemical structure was characterized by FT-IR, SEM/EDAX, XRD, TG-DTG, ICP-OES techniques (3) to investigate the performance of the catalyst in Suzuki coupling reactions by using microwave irradiation technique (4) reusability of the catalyst was done under optimum conditions. This cellulose supported Pd(II) catalyst exhibited high selectivity and efficiency in Suzuki coupling reactions under mild conditions (50°C). High TON and TOF values were recorded for the catalyst. Also, the reusability tests showed the catalysts could be used for several times in consequence of reusability tests.

Keywords: palladium, cellulose, Schiff base, reusability

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Authors: Opeyemi A. Oyewo, Seshibe Makgato

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This paper presents the synthesis, characterization, and application of pelletized chitosan immobilized sawdust cellulose nanocrystals (PCCN) in a fixed-bed column for the continuous adsorption of methyl blue (MB) from water. The product was characterized using FT-IR, XRD, and SEM analysis. Microstructural examination revealed that the pellets are porous and spherical. XRD examination revealed phases that can be attributed to the presence of chitosan in PCCN. The effects of starting concentration, bed depth, and flow rate on synthetic water were explored. To identify MB breakthrough behaviour, performance indices such as bed volume, adsorbent exhaustion rate, and service time were investigated. Furthermore, the breakthrough data were incorporated into both the Thomas and Bohart-Adams models. The Thomas model was suitable for describing MB breakthrough curves. However, more research with diverse water matrices may be required to assess the resilience of PCCN.

Keywords: adsorption, dynamic, methyl blue, pelletization

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Authors: Cristina Lavilla, Andreas Heise

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The synthesis of sequence-controlled polymers has received increasing attention in the last years. Well-defined polyacrylates, polyacrylamides and styrene-maleimide copolymers have been synthesized by sequential or kinetic addition of comonomers. However this approach has not yet been introduced to the synthesis of polypeptides, which are in fact polymers developed by nature in a sequence-controlled way. Polypeptides are natural materials that possess the ability to self-assemble into complex and highly ordered structures. Their folding and properties arise from precisely controlled sequences and compositions in their constituent amino acid monomers. So far, solid-phase peptide synthesis is the only technique that allows preparing short peptide sequences with excellent sequence control, but also requires extensive protection/deprotection steps and it is a difficult technique to scale-up. A new strategy towards sequence control in the synthesis of polypeptides is introduced, based on the sequential addition of α-amino acid-N-carboxyanhydrides (NCAs). The living ring-opening process is conducted to full conversion and no purification or deprotection is needed before addition of a new amino acid. The length of every block is predefined by the NCA:initiator ratio in every step. This method yields polypeptides with a specific sequence and controlled molecular weights. A series of polypeptides with varying block sequences have been synthesized with the aim to identify structure-property relationships. All of them are able to adopt secondary structures similar to natural polypeptides, and display properties in the solid state and in solution that are characteristic of the primary structure. By design the prepared polypeptides allow selective modification of individual block sequences, which has been exploited to introduce functionalities in defined positions along the polypeptide chain. Poly(ethylene glycol)(PEG) was the functionality chosen, as it is known to favor hydrophilicity and also yield thermoresponsive materials. After PEGylation, hydrophilicity of the polypeptides is enhanced, and their thermal response in H2O has been studied. Noteworthy differences in the behavior of the polypeptides having different sequences have been found. Circular dichroism measurements confirmed that the α-helical conformation is stable over the examined temperature range (5-90 °C). It is concluded that PEG units are the main responsible of the changes in H-bonding interactions with H2O upon variation of temperature, and the position of these functional units along the backbone is a factor of utmost importance in the resulting properties of the α-helical polypeptides.

Keywords: α-amino acid N-carboxyanhydrides, multiblock copolymers, poly(ethylene glycol), polypeptides, ring-opening polymerization, sequence control

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Authors: Hugo Daneluzzo, Christelle Rabbat, Alan Jean-Marie

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Water electrolysis is one of the most advanced technologies for producing hydrogen and can be easily combined with electricity from different sources. Under the influence of electric current, water molecules can be split into oxygen and hydrogen. The production of hydrogen by water electrolysis favors the integration of renewable energy sources into the energy mix by compensating for their intermittence through the storage of the energy produced when production exceeds demand and its release during off-peak production periods. Among the various electrolysis technologies, anion exchange membrane (AEM) electrolyser cells are emerging as a reliable technology for water electrolysis. Modeling and simulation are effective tools to save time, money, and effort during the optimization of operating conditions and the investigation of the design. The modeling and simulation become even more important when dealing with multiphysics dynamic systems. One of those systems is the AEM electrolysis cell involving complex physico-chemical reactions. Once developed, models may be utilized to comprehend the mechanisms to control and detect flaws in the systems. Several modeling methods have been initiated by scientists. These methods can be separated into two main approaches, namely equation-based modeling and graph-based modeling. The former approach is less user-friendly and difficult to update as it is based on ordinary or partial differential equations to represent the systems. However, the latter approach is more user-friendly and allows a clear representation of physical phenomena. In this case, the system is depicted by connecting subsystems, so-called blocks, through ports based on their physical interactions, hence being suitable for multiphysics systems. Among the graphical modelling methods, the bond graph is receiving increasing attention as being domain-independent and relying on the energy exchange between the components of the system. At present, few studies have investigated the modelling of AEM systems. A mathematical model and a bond graph model were used in previous studies to model the electrolysis cell performance. In this study, experimental data from literature were simulated using OpenModelica using bond graphs and mathematical approaches. The polarization curves at different operating conditions obtained by both approaches were compared with experimental ones. It was stated that both models predicted satisfactorily the polarization curves with error margins lower than 2% for equation-based models and lower than 5% for the bond graph model. The activation polarization of hydrogen evolution reactions (HER) and oxygen evolution reactions (OER) were behind the voltage loss in the AEM electrolyzer, whereas ion conduction through the membrane resulted in the ohmic loss. Therefore, highly active electro-catalysts are required for both HER and OER while high-conductivity AEMs are needed for effectively lowering the ohmic losses. The bond graph simulation of the polarisation curve for operating conditions at various temperatures has illustrated that voltage increases with temperature owing to the technology of the membrane. Simulation of the polarisation curve can be tested virtually, hence resulting in reduced cost and time involved due to experimental testing and improved design optimization. Further improvements can be made by implementing the bond graph model in a real power-to-gas-to-power scenario.

Keywords: hydrogen production, anion-exchange membrane, electrolyzer, mathematical modeling, multiphysics modeling

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Authors: Todd R. Walton

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Social media would seem to be an ideal mechanism for crisis communication, yet it has been met with varied results. Natural disasters, such as hurricanes, provide a slow moving view of how social media can be leveraged to guide stakeholders and the public through a crisis. Crisis communication managers have struggled to reach target audiences with credible messaging. This Qualitative Evidence Synthesis (QES) analyzed the findings of eight studies published in the last year to determine how organizations effectively utilize social media for crisis communication. Additionally, the evidence was analyzed to note strategies for establishing credibility in a medium fraught with misinformation. Studies indicated wide agreement on the use of multiple social media channels in addition to frequent accurate messaging in order to establish credibility. Studies indicated mixed agreement on the use of text based emergency notification systems. The findings in this QES will help crisis communication professionals plan for social media use for crisis communication.

Keywords: crisis communication, crisis management, emergency response, social media

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Authors: H. Ishii, S. Araki, H. Yamamoto

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In recent years, the carbon dioxide (CO2) separation technology is required in terms of the reduction of emission of global warming gases and the efficient use of fossil fuels. Since the emission amount of CO2 gas occupies the large part of greenhouse effect gases, it is considered that CO2 have the most influence on global warming. Therefore, we need to establish the CO2 separation technologies with high efficiency at low cost. In this study, we focused on the membrane separation compared with conventional separation technique such as distillation or cryogenic separation. In this study, we prepared carbonate-ceramic dual-phase membranes to separate CO2 at high temperature. As porous ceramic substrate, the (Pr0.9La0.1)2(Ni0.74Cu0.21Ga0.05)O4+σ, La0.6Sr0.4Ti0.3 Fe0.7O3 and Ca0.8Sr0.2Ti0.7Fe0.3O3-α (PLNCG, LSTF and CSTF) were examined. PLNCG, LSTF and CSTF have the perovskite structure. The perovskite structure has high stability and shows ion-conducting doped by another metal ion. PLNCG, LSTF and CSTF have perovskite structure and has high stability and high oxygen ion diffusivity. PLNCG, LSTF and CSTF powders were prepared by a solid-phase process using the appropriate carbonates or oxides. To prepare porous substrates, these powders mixed with carbon black (20 wt%) and a few drops of polyvinyl alcohol (5 wt%) aqueous solution. The powder mixture were packed into stainless steel mold (13 mm) and uniaxially pressed into disk shape under a pressure of 20 MPa for 1 minute. PLNCG, LSTF and CSTF disks were calcined in air for 6 h at 1473, 1573 and 1473 K, respectively. The carbonate mixture (Li2CO3/Na2CO3/K2CO3: 42.5/32.5/25 in mole percent ratio) was placed inside a crucible and heated to 793 K. Porous substrates were infiltrated with the molten carbonate mixture at 793 K. Crystalline structures of the fresh membranes and after the infiltration with the molten carbonate mixtures were determined by X-ray diffraction (XRD) measurement. We confirmed the crystal structure of PLNCG and CSTF slightly changed after infiltration with the molten carbonate mixture. CO2 permeation experiments with PLNCG-carbonate, LSTF-carbonate and CSTF-carbonate membranes were carried out at 773-1173 K. The gas mixture of CO2 (20 mol%) and He was introduced at the flow rate of 50 ml/min to one side of membrane. The permeated CO2 was swept by N2 (50 ml/min). We confirmed the effect of ceramic materials and temperature on the CO2 permeation at high temperature.

Keywords: membrane, perovskite structure, dual-phase, carbonate

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Authors: Preeti Makkar, R. C. Agarwala, Vijaya Agarwala

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The present study focuses on the preparation of Al2O3 nanoparticles by top down approach i.e. mechanical milling using high energy planetary ball mill at 250 rpm for 40h. The milled Al2O3 nanoparticles are then used as the second phase to develop electroless (EL) Ni-P- Al2O3 nanocomposite coatings on mild steel substrate. An alkaline bath was used with a suspension of Al2O3 particles (4 g/L) for the synthesis of Ni-P-Al2O3 nanocomposite coating. The surface morphology, size range and phase analysis of as-prepared Al2O3 particles and the coatings were characterized using X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). The coatings were heat treated at 400°C for 1h in argon atmosphere and the hardness of the nanocomposite coatings was investigated with respect to Ni-P before and after heat treatment. The results showed that as milled Al2O3 nanoparticles exhibit irregular shaped and size ranges around 40-45 nm. The Al2O3 particles are uniformly distributed in Ni-P matrix. The microhardness of the coatings is found to be significantly improved after heat treatment (1126 VHN).

Keywords: Electroless (EL), Ni-P-Al2O3, nanocomposite, mechanical milling, microhardness

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Authors: Sinwook Park, Gilad Yossifon

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The presence of a floating electrode array located within the depletion layer formed due to concentration-polarization (CP) across a microchannel-membrane device, produces not only induced-charge electro-osmosis (ICEO) vortex and but also a bipolar current resulting from faradaic reactions. It has been shown that there exists an optimal SiO2 layer thickness of ~50nm which is sufficient to suppress bipolar currents (at least up to 5V applied voltage) but still enables ICEO vortices that stir the depletion layer, thereby affecting its I-V response. This effect is pronounced beyond the limiting current where the existence of the depletion layer results in increased local electric field due to decreased solution conductivity. This comprehensive study of the interaction of embedded electrodes with the induced CP in microchannel-perm selective medium systems, allows one to choose the thickness of the thin dielectric coating to either enhance the mixing as a means to control the diffuse layer, or suppress it, for example, in the case where electrodes are intended for local measurements of the solution conductivity with minimal invasion. In addition, the use of alternating-current electro-osmosis by activating electrodes results in further enhancement of the fluid stirring and opens new routes for on-demand spatiotemporal control of the CP length. In addition, the use of embedded heaters within the depletion layer generates electro-thermal vortices that in turn also control the CP length.

Keywords: AC electrokinetics, microchannel, concentration-polarization, bipolar current

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Authors: M. S. M. Yusof, R. Ramli, S. K. C. Soh, N. Ismail, N. Ngah

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This study presents the synthesis of a series of methoxybenzoylthiourea amino acid derivatives. The compounds were obtained from the reactions between 2/3/4-methoxybenzoyl isothiocyanate with threonine. All of the compounds were characterized via mass spectrometry, ¹H and ¹³C NMR spectrometry, UV-Vis spectrophotometer and FT-IR spectroscopy. Mass spectra for all of the compounds showed the presence of molecular ion [M]⁺ peaks at m/z 312, which are in agreement to the calculated molecular weight. For ¹H NMR spectra, the presence of OCH₃, C=S-NH and C=O-NH protons were observed within range of δ_H 3.8-4.0 ppm, 11.1-11.5 ppm and 10.0-11.5 ppm, respectively. ¹³C NMR spectra in all compounds displayed the presence of OCH₃, C=O-NH, C=O-OH and C=S carbon resonances within range of δ_C 55.0-57.0 ppm, 165.0-168.0 ppm, 170.0-171.0 ppm and 180.0-182.0 ppm, respectively. In UV spectra, two absorption bands have been observed and both were assigned to the n-π* and π-π* transitions. Six vibrational modes of v(N-H), v(O-H), v(C=O-OH), v(C=O-NH), v(C=C) aromatic and v(C=S) appeared in the FT-IR spectra within the range of 3241-3467 cm^-1, 2976-3302 cm^-1, 1720-1768 cm^-1, 1655-1672 cm^-1, 1519-1525 cm^-1 and 754-763 cm^-1, respectively. The antibacterial activity for all of the compounds was screened against Staphylococcus aureus, Staphylococcus epidermidis, Salmonella typhimurium and Escherichia coli. However, no activity was observed.

Keywords: methoxybenzoyl isothiocyanate, amino acid, threonine, antibacterial

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Authors: Dorith Tavor, Adi Wolfson

Abstract:

In the past two decades a variety of green solvents have been proposed, including water, ionic liquids, fluorous solvents, and supercritical fluids. However, their implementation in industrial processes is still limited due to their tedious and non-sustainable synthesis, lack of experimental data and familiarity, as well as operational restrictions and high cost. Several years ago we presented, for the first time, the use of glycerol-based solvents as alternative sustainable reaction mediums in both catalytic and non-catalytic organic synthesis. Glycerol is the main by-product from the conversion of oils and fats in oleochemical production. Moreover, in the past decade, its price has substantially decreased due to an increase in supply from the production and use of fatty acid derivatives in the food, cosmetics, and drugs industries and in biofuel synthesis, i.e., biodiesel. The renewable origin, beneficial physicochemical properties and reusability of glycerol-based solvents, enabled improved product yield and selectivity as well as easy product separation and catalyst recycling. Furthermore, their high boiling point and polarity make them perfect candidates for non-conventional heating and mixing techniques such as ultrasound- and microwave-assisted reactions. Finally, in some reactions, such as catalytic transfer-hydrogenation or transesterification, they can also be used simultaneously as both solvent and reactant. In our ongoing efforts to design a viable protocol that will facilitate the acceptance of glycerol and its derivatives as sustainable solvents, pure glycerol and glycerol triacetate (triacetin) as well as various glycerol-triacetin mixtures were tested as sustainable solvents in several representative organic reactions, such as nucleophilic substitution of benzyl chloride to benzyl acetate, Suzuki-Miyaura cross-coupling of iodobenzene and phenylboronic acid, baker’s yeast reduction of ketones, and transfer hydrogenation of olefins. It was found that reaction performance was affected by the glycerol to triacetin ratio, as the solubility of the substrates in the solvent determined product yield. Thereby, employing optimal glycerol to triacetin ratio resulted in maximum product yield. In addition, using glycerol-based solvents enabled easy and successful separation of the products and recycling of the catalysts.

Keywords: glycerol, green chemistry, sustainability, catalysis

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Authors: Charmaine Lamiel, Van Hoa Nguyen, Jae-Jin Shim

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Supercapacitors are energy storage devices capable of storing more energy than conventional capacitors and have higher power density than batteries. The advantages of this method include the non-use of reducing agents and acidic medium, and no further use of a post-heat treatment unlike the conventional processes, in which calcination is generally employed after obtaining the initial product. Furthermore, it also offers a shorter reaction time at low temperatures and low power requirements, which allows low fabrication and energy cost. In this study, microwave irradiation was used for the facile and rapid synthesis of mesoporous RGO@(Co,Mn)3O4 nanosheets as an electrode material. The as-prepared electrode exhibited a high capacitance of 953 F•g^−1 at 1 A•g^−1 in a 6 M KOH electrolyte solution. Moreover, the electrode exhibited a high energy density of 76.2 Wh•kg^−1 at a power density of 720 W•kg^−1, and a high power density of 7200 W•kg^−1 at an energy density of 38 Wh•kg^−1. The successful methodology was considered to be efficient and cost-effective, thereby providing an active electrode material with very promising electrochemical performance.

Keywords: cobalt-manganese oxide, electrochemical, graphene, microwave synthesis, supercapacitor

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