Search results for: polyhedral oligomeric silsesquioxanes
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 29

Search results for: polyhedral oligomeric silsesquioxanes

29 Thermal Properties of Polyhedral Oligomeric Silsesquioxanes/Polyimide Nanocomposite

Authors: Seyfullah Madakbas, Hatice Birtane, Memet Vezir Kahraman

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In this study, we aimed to synthesize and characterize polyhedral oligomeric silsesquioxanes containing polyimide nanocomposite. Polyimide nanocomposites widely have been used in membranes in fuel cell, solar cell, gas filtration, sensors, aerospace components, printed circuit boards. Firstly, polyamic acid was synthesized and characterized by Fourier Transform Infrared. Then, polyhedral oligomeric silsesquioxanes containing polyimide nanocomposite was prepared with thermal imidization method. The obtained polyimide nanocomposite was characterized by Fourier Transform Infrared, Scanning Electron Microscope, Thermal Gravimetric Analysis and Differential Scanning Calorimetry. Thermal stability of polyimide nanocomposite was evaluated by thermal gravimetric analysis and differential scanning calorimetry. Surface morphology of composite samples was investigated by scanning electron microscope. The obtained results prove that successfully prepared polyhedral oligomeric silsesquioxanes are containing polyimide nanocomposite. The obtained nanocomposite can be used in many industries such as electronics, automotive, aerospace, etc.

Keywords: polyimide, nanocomposite, polyhedral oligomeric silsesquioxanes

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28 Poly (Lactic Acid)/Poly (Butylene Adipate-Co-terephthalate) Films Reinforced with Polyhedral Oligomeric Silsesquioxane Nanoparticles

Authors: Elahe Moradi, Hossein Ali Khonakdar

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In the context of the growing interest in renewable polymers, this study presents an innovative approach to environmental conservation through the development of an eco-friendly structure. The research focused on enhancing the compatibility between two immiscible polymers, poly (lactic acid) (PLA) and poly (butylene adipate-co-terephthalate) (PBAT), using polyhedral oligomeric silsesquioxanes (POSS) nanoparticles with an epoxy functional group (Epoxy-POSS). This was achieved through a solution casting method. The study found that the modulus in the glassy region for blends containing Epoxy-POSS was significantly higher than that of the PLA/PBAT blend without Epoxy-POSS. However, in the transition and rubbery regions, the modulus of the Epoxy-POSS-containing blends was only marginally greater. From a mechanical properties’ perspective, the study demonstrated that the incorporation of POSS-EPOXY at varying concentrations enhanced the tensile strength of the PLA/PBAT blend by 30%, thereby acting as a reinforcement. This finding underscores the potential of this approach in the development of renewable polymers.

Keywords: Polyhedral oligomeric silsesquioxane, mechanical behavior, PLA, PBAT, nanocomposite

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27 Polyhedral Oligomeric Silsesquioxane in Poly Lactic Acid and Poly Butylene Adipate-Co-Terephthalate Blend

Authors: Elahe Moradi, Hoseinali A. Khonakdar

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The escalating interest in renewable polymers is undeniable, albeit accompanied by inherent challenges. In our study, we endeavored to make a significant contribution to environmental conservation by introducing an eco-friendly structure, developed through an innovative approach. Specifically, we enhanced the compatibility between two immiscible polymers, namely poly (lactic acid) (PLA) and poly (butylene adipate-co-terephthalate) (PBAT). Our strategy involved the use of polyhedral oligomeric silsesquioxanes (POSS) nanoparticles, equipped with an epoxy functional group (Epoxy-POSS), to accomplish this objective with solution casting method. The incorporation of 1% nanoparticles into the PLA blend resulted in a decrease in its cold crystallization temperature. Furthermore, these nanoparticles possess the requisite capability to enhance molecular mobility, facilitated by the induction of a lubrication effect. The emergence of a PLA-CO-POSS-CO-PBAT structure at the interface between PLA and PBAT led to a significant amplification of the interactions at the interface of the matrix and the dispersed phase.

Keywords: compatibilization, thermal behavior, structure-properties, nanocomposite, PLA, PBAT

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26 Self-Healing Composites of Silicone Rubber

Authors: Anna Strakowska, Marian Zaborski

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This abstract focuses an overview of the methods used to create self-healing silicone composites. It has been shown how incorporating of polyhedral oligomeric silsesquioxanes (POSS) molecules with acid and basic groups to silicone rubber affects the barrier properties, mechanical properties in room and reduced temperature or the influence on relaxation rates of the methylvinylsilicone rubber vulcanizates. Moreover, the presence of silsesquioxanes, their content and the way of composites preparing affect the amount of ionic bonds, as indicated by dynamic - mechanical thermal analysis (DMTA) as well as measurements of equilibrium swelling in toluene. The aim of this work was to study the influence of concentration and different functional groups types selected silsesquioxanes compounds on self-healing effect of silicone rubber and obtain elastomers with good barrier and mechanical properties. Composites based on the methylvinylsilicone rubber with fumed silica as the fillers were manufactured and studied. To obtain self-healing effect various silsesquioxanes with amino and acid groups were used. Every tested sample demonstrated the ability to the self-treatment. The most significant effect was observed for system containing amic-acid isobytyl POSS/ aminopropylisobutyl POSS. Composite with this silsesquioxanes was exhibited the best improvement of gas permeability after heal. Moreover, the addition of POSS with acid and basic groups clearly affects the mechanical properties of the vulcanizates. The most significant effect was observed for the composite material consisting of amic-acid isobytyl POSS / aminoethylaminopropylisobutyl POSS, which tensile strength was even greater than the reference vulcanizate with fumed silica. The development of autonomous self-healing materials could have an enormous influence on all industry branches from motorization to power industry. Self-repairing materials would have a massive impact on lengthening product lifetimes, increasing safety, and lowering product costs by reducing maintenance requirements.

Keywords: barrier properties, mechanical properties, POSS, self-healing composites

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25 Novel Scratch Resistant Self-Healing Automotive Clearcoats Using Hyperbranched Polymers and POSS Nanostructures

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

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

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

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24 Preparation of Fluoroalkyl End-Capped Oligomers/Silica Nanocomposites Possessing a Nonflammable Characteristic Even After Calcination at 800 oC

Authors: Hideo Sawada

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Fluoroalkyl end-capped oligomers [RF-(M)n-RF; RF = fluoroalkyl groups; M = radical polymerizable monomers] can form nanometre size-controlled self-assembled oligomeric aggregates through the aggregations of end-capped fluoroalkyl groups. Fluoroalkyl end-capped oligomeric aggregates can also interact with guest molecules to afford fluorinated aggregate/guest molecule nanocomposites; although the corresponding non-fluorinated oligomers cannot form such molecular aggregates to interact with guest molecules. For example, silica nanoparticles should act as guest molecules in fluorinated oligomeric aggregate cores to give new fluorinated oligomer-coated silica nanoparticles (fluorinated oligomer/silica nanocomposites). In these fluoroalkyl end-capped oligomers/silica nanocomposites, some fluorinated oligomers/silica nanocomposites were found to exhibit no weight loss behavior corresponding to the contents of oligomers in the silica matrices even after calcination at 800 oC. Fluoroalkyl end-capped vinyltrimethoxysilane oligomer-coated silica nanoparticles can be prepared by the sol-gel reaction of the corresponding fluorinated oligomer under alkaline conditions. The modified glass surface treated with this fluorinated oligomeric nanoparticle exhibited a completely super-hydrophobic characteristic. These fluorinated nanoparticles were also applied to the surface modification possessing a super-oleophobic characteristic. Not only fluoroalkyl end-capped oligomers but also low molecular weight fluorinated surfactants such as perfluoro-1,3-propanedisulfonic acid (PFPS) were applied to the preparation of fluorinated surfactants/silica nanocomposites to give no weight loss in proportion to the content of the surfactants in the nanocomposites even after calcination at 800 oC.

Keywords: fluorinated oligomer, silica nanocomposite, nonflammable characteristic, superamphiphobic chracteristic

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23 Self-Healing Coatings and Electrospun Fibers

Authors: M. Grandcolas, N. Rival, H. Bu, S. Jahren, R. Schmid, H. Johnsen

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The concept of an autonomic self-healing material, where initiation of repair is integrated to the material, is now being considered for engineering applications and is a hot topic in the literature. Among several concepts/techniques, two are most interesting: i) Capsules: Integration of microcapsules in or at the surface of coatings or fibre-like structures has recently gained much attention. Upon damage-induced cracking, the microcapsules are broken by the propagating crack fronts resulting in a release of an active chemical (healing agent) by capillary action, subsequently repairing and avoiding further crack growth. ii) Self-healing polymers: Interestingly, the introduction of dynamic covalent bonds into polymer networks has also recently been used as a powerful approach towards the design of various intrinsically self-healing polymer systems. The idea behind this is to reconnect the chemical crosslinks which are broken when a material fractures, restoring the integrity of the material and thereby prolonging its lifetime. We propose here to integrate both self-healing concepts (capsules, self-healing polymers) in electrospun fibres and coatings. Different capsule preparation approaches have been investigated in SINTEF. The most advanced method to produce capsules is based on emulsification to create a water-in-oil emulsion before polymerisation. The healing agent is a polyurethane-based dispersion that was encapsulated in shell materials consisting of urea-benzaldehyde resins. Results showed the successful preparation of microcapsules and release of the agent when capsules break. Since capsules are produced in water-in-oil systems we mainly investigated organic solvent based coatings while a major challenge resides in the incorporation of capsules into water-based coatings. We also focused on developing more robust microcapsules to prevent premature rupture of the capsules. The capsules have been characterized in terms of size, and encapsulation and release might be visualized by incorporating fluorescent dyes and examine the capsules by microscopy techniques. Alternatively, electrospinning is an innovative technique that has attracted enormous attention due to unique properties of the produced nano-to-micro fibers, ease of fabrication and functionalization, and versatility in controlling parameters. Especially roll-to-roll electrospinning is a unique method which has been used in industry to produce nanofibers continuously. Electrospun nanofibers can usually reach a diameter down to 100 nm, depending on the polymer used, which is of interest for the concept with self-healing polymer systems. In this work, we proved the feasibility of fabrication of POSS-based (POSS: polyhedral oligomeric silsesquioxanes, tradename FunzioNano™) nanofibers via electrospinning. Two different formulations based on aqueous or organic solvents have shown nanofibres with a diameter between 200 – 450nm with low defects. The addition of FunzioNano™ in the polymer blend also showed enhanced properties in term of wettability, promising for e.g. membrane technology. The self-healing polymer systems developed are here POSS-based materials synthesized to develop dynamic soft brushes.

Keywords: capsules, coatings, electrospinning, fibers

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22 Generating 3D Anisotropic Centroidal Voronoi Tessellations

Authors: Alexandre Marin, Alexandra Bac, Laurent Astart

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New numerical methods for PDE resolution (such as Finite Volumes (FV) or Virtual Elements Method (VEM)) open new needs in terms of meshing of domains of interest, and in particular, polyhedral meshes have many advantages. One way to build such meshes consists of constructing Restricted Voronoi Diagrams (RVDs) whose boundaries respect the domain of interest. By minimizing a function defined for RVDs, the shapes of cells can be controlled, e.g., elongated according to user-defined directions or adjusted to comply with given aspect ratios (anisotropy) and density variations. In this paper, our contribution is threefold: First, we introduce a new gradient formula for the Voronoi tessellation energy under a continuous anisotropy field. Second, we describe a meshing algorithm based on the optimisation of this function that we validate against state-of-the-art approaches. Finally, we propose a hierarchical approach to speed up our meshing algorithm.

Keywords: anisotropic Voronoi diagrams, meshes for numerical simulations, optimisation, volumic polyhedral meshing

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21 Influence of Synergistic/Antagonistic Mixtures of Oligomeric Stabilizers on the Biodegradation of γ-Sterilized Polyolefins

Authors: Sameh A. S. Thabit Alariqi

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Our previous studies aimed to investigate the biodegradation of γ-sterilized polyolefins in composting and microbial culture environments at different doses and γ-dose rates. It was concluded from the previous studies that the pretreatment of γ-irradiation can accelerate the biodegradation of neat polymer matrix in biotic conditions significantly. A similar work was carried out to study the stabilization of γ-sterilized polyolefins using different mixtures of stabilizers which are approved for food-contact applications. Ethylene-propylene (EP) copolymer has been melt-mixed with hindered amine stabilizers (HAS), phenolic antioxidants and hydroperoxide decomposers. Results were discussed by comparing the stabilizing efficiency, combination and consumption of stabilizers and the synergistic and antagonistic effects was explained through the interaction between the stabilizers. In this attempt, we have aimed to study the influence of the synergistic and antagonistic mixtures of oligomeric stabilizers on the biodegradation of the γ-irradiated polyolefins in composting and microbial culture. Neat and stabilized films of EP copolymer irradiated under γ-radiation and incubated in compost and fungal culture environments. The changes in functional groups, surface morphology, mechanical properties and intrinsic viscosity in polymer chains were characterized by FT-IR spectroscopy, SEM, instron, and viscometric measurements respectively. Results were discussed by comparing the effect of different stabilizers, stabilizers mixtures on the biodegradation of the γ-irradiated polyolefins. It was found that the biodegradation significantly depends on the components of stabilization system, mobility, interaction, and consumption of stabilizers.

Keywords: biodegradation, γ-irradiation, polyolefins, stabilization

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20 Sterilization Effects of Low Concentration of Hydrogen Peroxide Solution on 3D Printed Biodegradable Polyurethane Nanocomposite Scaffold for Heart Valve Regeneration

Authors: S. E. Mohmad-Saberi, W. Song, N. Oliver, M. Adrian, T.C. Hsu, A. Darbyshire

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Biodegradable polyurethane (PU) has emerged as a potential material to promote repair and regeneration of damaged/diseased tissues in heart valve regeneration due to its excellent biomechanical profile. Understanding the effects of sterilization on their properties is vital since they are more sensitive and more critical of porous structures compared to bulk ones. In this study, the effects of low concentration of hydrogen peroxide (H₂O₂) solution sterilization has been investigated to determine whether the procedure would be efficient and non-destructive to porous three-dimensional (3D) elastomeric nanocomposite, polyhedral oligomeric silsesquioxane-terminated poly (ethylene-diethylene glycol succinate-sebacate) urea-urethane (POSS-EDSS-PU) scaffold. All the samples were tested for sterility following sterilization using phosphate buffer saline (PBS) as control and 5 % v/v H₂O₂ solution. The samples were incubated in tryptic soy broth for the cultivation of microorganisms under agitation at 37˚C for 72 hours. The effects of the 5 % v/v H₂O₂ solution sterilization were evaluated in terms of morphology, chemical and mechanical properties using scanning electron microscopy (SEM), Fourier transform infrared (FTIR) and tensile tester apparatus. Toxicity effects of the 5 % v/v H₂O₂ solution decontamination were studied by in vitro cytotoxicity test, where the cellular responses of human dermal fibroblast (HDF) were examined. A clear, uncontaminated broth using 5 % v/v H₂O₂ solution method indicated efficient sterilization after 3 days, while the non-sterilized control shows clouding broth indicated contamination. The morphology of 3D POSS-EDSS-PU scaffold appeared to have similar morphology after sterilization with 5 % v/v H₂O₂ solution regarding of pore size and surface. FTIR results show that the sterilized samples and non-sterilized control share the same spectra pattern, confirming no significant alterations over the surface chemistry. For the mechanical properties of the H₂O₂ solution-treated scaffolds, the tensile strain was not significantly decreased, however, become significantly stiffer after the sterilization. No cytotoxic effects were observed after the 5 % v/v H₂O₂ solution sterilization as confirmed by cell viability assessed by Alamar Blue assay. The results suggest that low concentration of 5 % v/v hydrogen peroxide solution can be used as an alternative method for sterilizing biodegradable 3D porous scaffold with micro/nano-architecture without structural deformation. This study provides the understanding of the sterilization effects on biomechanical profile and cell proliferation of 3D POSS-EDSS-PU scaffolds.

Keywords: biodegradable, hydrogen peroxide solution, POSS-EDSS-PU, sterilization

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19 Dido: An Automatic Code Generation and Optimization Framework for Stencil Computations on Distributed Memory Architectures

Authors: Mariem Saied, Jens Gustedt, Gilles Muller

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We present Dido, a source-to-source auto-generation and optimization framework for multi-dimensional stencil computations. It enables a large programmer community to easily and safely implement stencil codes on distributed-memory parallel architectures with Ordered Read-Write Locks (ORWL) as an execution and communication back-end. ORWL provides inter-task synchronization for data-oriented parallel and distributed computations. It has been proven to guarantee equity, liveness, and efficiency for a wide range of applications, particularly for iterative computations. Dido consists mainly of an implicitly parallel domain-specific language (DSL) implemented as a source-level transformer. It captures domain semantics at a high level of abstraction and generates parallel stencil code that leverages all ORWL features. The generated code is well-structured and lends itself to different possible optimizations. In this paper, we enhance Dido to handle both Jacobi and Gauss-Seidel grid traversals. We integrate temporal blocking to the Dido code generator in order to reduce the communication overhead and minimize data transfers. To increase data locality and improve intra-node data reuse, we coupled the code generation technique with the polyhedral parallelizer Pluto. The accuracy and portability of the generated code are guaranteed thanks to a parametrized solution. The combination of ORWL features, the code generation pattern and the suggested optimizations, make of Dido a powerful code generation framework for stencil computations in general, and for distributed-memory architectures in particular. We present a wide range of experiments over a number of stencil benchmarks.

Keywords: stencil computations, ordered read-write locks, domain-specific language, polyhedral model, experiments

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18 Influence of Shear Deformation on Carbon Onions Stability under High Pressure

Authors: D. P. Evdokimov, A. N. Kirichenko, V. D. Blank, V. N. Denisov, B. A. Kulnitskiy

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In this study we investigated the stability of polyhedral carbon onions under influence of shear deformation and high pressures above 43 GPa by means of by transmission electron microscopy (TEM) and Raman spectroscopy (RS). It was found that at pressures up to 29 GPa and shear deformations of 40 degrees the onions are stable. At shear deformation applying at pressures above 30 GPa carbon onions collapsed with formation of amorphous carbon. At pressures above 43 GPa diamond-like carbon (DLC) was obtained.

Keywords: carbon onions, Raman spectroscopy, transmission electron spectroscopy

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17 An Investigation into the Use of Overset Mesh for a Vehicle Aerodynamics Case When Driving in Close Proximity

Authors: Kushal Kumar Chode, Remus Miahi Cirstea

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In recent times, the drive towards more efficient vehicles and the increase in the number of vehicle on the roads has driven the aerodynamic researchers from studying the vehicle in isolation towards understanding the benefits of vehicle platooning. Vehicle platooning is defined as a series of vehicles traveling in close proximity. Due to the limitations in size and load measurement capabilities for the wind tunnels facilities, it is very difficult to perform this investigation experimentally. In this paper, the use of chimera or overset meshing technique is used within the STARCCM+ software to model the flow surrounding two identical vehicle models travelling in close proximity and also during an overtaking maneuver. The results are compared with data obtained from a polyhedral mesh and identical physics conditions. The benefits in terms of computational time and resources and the accuracy of the overset mesh approach are investigated.

Keywords: chimera mesh, computational accuracy, overset mesh, platooning vehicles

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16 Silver Nanoparticles in Drinking Water Purification

Authors: S. Pooja Pragati, B. Sudarsan, S. Rajkumar

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Silver nanoparticles (AgNP) are known for their excellent antimicrobial agents, and thus can be used as alternative disinfectant agents. However, released silver nanoparticles is a threat to naturally occurring microorganisms. This paper exhibits information on the environmental fate, toxicological effects, and application of AgNP and the current estimate on the physicochemical and antimicrobial properties of AgNP in different aqueous solutions, as well as their application as alternative disinfectants in water-treatment systems. It also gives a better approximation and experimental data of AgNP’s antimicrobial properties at different water chemistry conditions. A saturation-type fitting curve was established, showing the survival of bacteria under different water chemistry conditions as a function of the size of the nanoparticles. The results obtained show that silver nanoparticles in surface water, ground water, and brackish water are stable. The paper demonstrates the comparative study of AgNP-impregnated point-of-use ceramic water filters and ceramic filters impregnated with silver nitrate. It is observed that AgNP-impregnated ceramic water filters are more appropriate for this application due to the lesser amount of silver desorbed. Experimental data of the comparison of a polymer-based quaternary amine functionalized silsesquioxanes compound and AgNP are also tabulated and conclusions are analysed with the goal of optimizing. The simplicity of synthesis and application of Silver nanoparticles enables us to consider its effective modified version for the purification of water.

Keywords: disinfectant agent, purification of water, nano particles, water treatment

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15 Synthesis, Characterization and Cytotoxic Effect of Eu2O3-doped ZnO Nanostructures

Authors: Otilia R. Vasile, Florina C. Ilie, Irina F. Nicoara, Cristina D. Ghitulica, Roxana Trusca, Ovidiu Oprea, Vasile A. Surdu, Bogdan S. Vasile, Ecaterina Adronescu

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In this work ZnO nanostructures (nanopowders and nanostars) have been synthesized via a simple sol-gel method. The used methods for synthesizing the nanostructures involve two steps as follows: (1) precipitation of zinc acetate precursor for the synthesis of ZnO nanopowders and zinc chloride precursor for the synthesis of ZnO nanostars and (2) addition of Eu2O3 in different concentrations (1%, 3%, and 5%) using europium acetate as precursor. Detailed crystalline parameters for each of the synthetized species were analysed using X-ray diffraction. Structural transitions were also discussed. The structure and morphology of the as-prepared ZnO nanopowders and nanostars were investigated by electron microscopy. TEM investigations have shown an average particle size range from 23 to 29 nm and polyhedral and spherical morphology with tendency to form aggregates for nanopowders. For nanostars structures, a star-like morphology could be observed. Cytotoxicity tests on MG-63 cell lines were also performed. Photocatalytic activity of ZnO nanopowders have reached higher values compared to ZnO nanostars.

Keywords: cytotoxicity, photocatalytic activity, TEM, ZnO

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14 Phosphoproteomic Analysis of the Response of Rice Leaves to Chitosan under Drought Stress

Authors: Narumon Phaonakrop, Janthima Jaresitthikunchai, Sittiruk Roytrakul, Wasinee Pongprayoon

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Chitosan has been proposed as a natural polymer, and it is derived from chitin. The objective of this research was to determine the growth promoting responses induced by chitosan at the molecular physiology level in Khao Dawk Mali 105 (KDML 105) rice (Oryza sativa L.) seedlings under drought stress by adding of 2% polyethylene glycol 4000 (PEG4000) to the nutrient solution and after removal of the drought stress (re-water). Oligomeric chitosan at 40 ppm could enhance shoot fresh weight and shoot dry weight during drought stress and re-water. After 7 days of drought stress and re-water, significant increases in chlorophyll a and chlorophyll b contents in KDML 105 cultivar were observed. The 749 phosphoproteins in rice leaf treated with chitosan could be resolved by phosphoprotein enrichment, tryptic digestion and liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. They can be classified into 10 groups. Proteins involved in the metabolic process and biological regulation were upregulated in response to chitosan during drought stress. This work will help us to understand protein phosphorylation relating to chitosan response during drought stress in aromatic rice seedlings.

Keywords: Chitosan, drought, phosphoproteome, rice

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13 Effects of Copper and Cobalt Co-Doping on Structural, Optical and Electrical Properties of Tio2 Thin Films Prepared by Sol Gel Method

Authors: Rabah Bensaha, Badreeddine Toubal

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Un-doped TiO2, Co single doped TiO2 and (Cu-Co) co-doped TiO2 thin films have been growth on silicon substrates by the sol-gel dip coating technique. We mainly investigated both effects of the dopants and annealing temperature on the structural, optical and electrical properties of TiO2 films using X-ray diffraction (XRD), Raman and FTIR spectroscopy, Atomic force microscopy (AFM), Scanning electron microscopy (SEM), UV–Vis spectroscopy. The chemical compositions of Co-doped and (Cu-Co) co-doped TiO2 films were confirmed by XRD, Raman and FTIR studies. The average grain sizes of CoTiO3-TiO2 nanocomposites were increased with annealing temperature. AFM and SEM reveal a completely the various nanostructures of CoTiO3-TiO2 nanocomposites thin films. The films exhibit a high optical reflectance with a large band gap. The highest electrical conductivity was obtained for the (Cu-Co) co-doped TiO2 films. The polyhedral surface morphology might possibly improve the surface contact between particle sizes and then contribute to better electron mobility as well as conductivity. The obtained results suggest that the prepared TiO2 films can be used for optoelectronic applications.

Keywords: sol-gel, TiO2 thin films, CoTiO3-TiO2 nanocomposites films, Electrical conductivity

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12 Tetra Butyl Ammonium Cyanate Mediated Selective Synthesis of Sulfonyltriuret and Their Investigation towards Trypsin Protease Modulation

Authors: Amarjyoti Das Mahapatra, Umesh Kumar, Bhaskar Datta

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A pseudo peptide can mimic the biological or structural properties of natural peptides. They have become an increasing attention in medicinal chemistry because of their interesting advantages like more bioavailability and less biodegradation than compare to the physiologically active native peptides which increase their therapeutic applications. Many biologically active compounds contain urea as functional groups, and they have improved pharmacokinetic properties because of their bioavailability and metabolic stability. Recently we have reported a single-step synthesis of sulfonyl urea and sulfonyltriuret from sulfonyl chloride and sodium cyanate. But the yield of sulfonyltriuret was less around 40-60% because of the formation of other products like sulfonamide and sulfonylureas. In the present work, we mainly focused on the selective synthesis of sulfonyltriuret using tetrabutylammonium cyanate and sulfonyl chloride. More precisely, we are interested in the controlled synthesis of oligomeric urea mainly sulfonyltriuret as a new class of pseudo peptide and their application as protease modulators. The distinctive architecture of these molecules in the form of their pseudo-peptide backbone offers promise as a potential pharmacophore. The synthesized molecules have been screened on trypsin enzyme, and we observed that these molecules are the efficient modulator of trypsin enzyme.

Keywords: pseudo peptide, pharmacophore, sulfonyltriuret, trypsin

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11 Metabolic Syndrome and Its Effects on Cartilage Degeneration vs Regeneration: A Pilot Study Using Osteoarthritis Biomarkers

Authors: Neena Kanojia, R. K. Kanojia

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Background: Osteoarthritis OA of the knee is one of the leading causes of disability characterized by degeneration of hyaline cartilage combined with reparative processes. Its strong association with metabolic syndrome is postulated to be due to both mechanical and biochemical factors. Our study aims to study differential effect of metabolic risk factors on cartilage degeneration and regeneration at biomarker level. Design: After screening 281 patients presenting with knee pain, 41 patients who met the selection criteria were included and were divided into metabolic MetS OA and non-metabolic Non-MetS OA phenotypes using National Cholesterol Education Programme-Adult Treatment Panel-III NCEP ATP III criteria for metabolic syndrome. Serum Cartilage Oligomeric Matrix Protein COMP and Procollagen type IIA N terminal Propeptide PIIANP levels were used as tools to assess cartilage degeneration and regeneration, respectively. Results: 22 among 41 patients 53.66% had metabolic syndrome. Covariates like age, gender, Kellgren Lawrence KL grades were comparable in both groups. MetS OA group showed significant increase in serum COMP levels (p 0.03 with no significant effect on serum PIIANP levels (p 0.46. Hypertriglyceridemia showed independent association with both cartilage anabolism (p 0.03 and catabolism (p 0.03. Conclusion: Metabolic syndrome, though has no effect on cartilage regeneration tends to shift cartilage homeostasis towards degeneration with hypertriglyceridemia showing significant independent effect on cartilage metabolism.

Keywords: metabolic, syndrome, cartilage, degernation

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10 Can We Meet the New Challenges of NonIsocyanates Polyurethanes (NIPU) towards NIPU Foams?

Authors: Adrien Cornille, Marine Blain, Bernard Boutevin, Sylvain Caillol

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Generally, linear polyurethanes (PUs) are obtained by the reaction between an oligomeric diol, a short diol as chain extender and a diisocyanate. However the use of diisocyanate should be avoided since they are generally very harmful for human health. Therefore the synthesis of NIPUs (non isocyanate PUs) from step growth polymerization of dicyclocarbonates and diamines should be favoured. This method is particularly interesting since no hazardous isocyanates are used. Thus, this reaction, extensively studied by Endo et al. is currently gaining a lot of attention as a substitution route for the synthesis of NIPUs, both from industrial and academic community. However, the reactivity of reaction between amine and cyclic carbonate is a major scientific issue, since cyclic carbonates are poorly reactive. Thus, our team developed several synthetic ways for the synthesis of various di-cyclic carbonates based on C5-, C6- and dithio- cyclic carbonates, from different biobased raw materials (glycerin isosorbide, vegetable oils…). These monomers were used to synthesize NIPUs with various mechanical and thermal properties for various applications. We studied the reactivity of reaction with various catalysts and find optimized conditions for room temperature reaction. We also studied the radical copolymerization of cyclic carbonate monomers in styrene-acrylate copolymers for coating applications. We also succeeded in the elaboration of biobased NIPU flexible foams. To the best of our knowledge, there is no report in literature on the preparation of non-isocyanate polyurethane foams.

Keywords: foam, nonisocyanate polyurethane, cyclic carbonate, blowing agent, scanning electron microscopy

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9 Synthetic Access to Complex Metal Carbonates and Hydroxycarbonates via Sol-Gel Chemistry

Authors: Schirin Hanf, Carlos Lizandara-Pueyo, Timmo P. Emmert, Ivana Jevtovikj, Roger Gläser, Stephan A. Schunk

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Metal alkoxides are very versatile precursors for a broad array of complex functional materials. However, metal alkoxides, especially transition metal alkoxides, tend to form oligomeric structures due to the very strong M–O–M binding motif. This fact hinders their facile application in sol-gel-processes and complicates access to complex carbonate or oxidic compounds after hydrolysis of the precursors. Therefore, the development of a synthetic alternative with the aim to grant access to carbonates and hydroxycarbonates from simple metal alkoxide precursors via hydrolysis is key to this project. Our approach involves the reaction of metal alkoxides with unsaturated isoelectronic molecules, such as carbon dioxide. Subsequently, a stoichiometric insertion of the CO₂ into the alkoxide M–O bond takes place and leads to the formation of soluble metal alkyl carbonates. This strategy is a very elegant approach to solubilize metal alkoxide precursors to make them accessible for sol-gel chemistry. After hydrolysis of the metal alkyl carbonates, crystalline metal carbonates, and hydroxycarbonates can be obtained, which were then utilized for the synthesis of Cu/Zn based bulk catalysts for methanol synthesis. Using these catalysts, a comparable catalytic activity to commercially available MeOH catalysts could be reached. Based on these results, a complement for traditional precipitation techniques, which are usually utilized for the synthesis of bulk methanol catalysts, have been found based on an alternative solubilization strategy.

Keywords: metal alkoxides, metal carbonates, metal hydroxycarbonates, CO₂ insertion, solubilization

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8 Mitigating the Aggregation of Human Islet Amyloid Polypeptide with Nanomaterials

Authors: Ava Faridi, Pouya Faridi, Aleksandr Kakinen, Ibrahim Javed, Thomas P. Davis, Pu Chun Ke

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Human islet amyloid polypeptide (IAPP) is a hormone associated with glycemic control and type 2 diabetes. Biophysically, the chirality of IAPP fibrils has been little explored with respect to the aggregation and toxicity of the peptide. Biochemically, it remains unclear as for how protein expression in pancreatic beta cells may be altered by cell exposure to the peptide, and how such changes may be mitigated by nanoparticle inhibitors for IAPP aggregation. In this study, we first demonstrated the elimination of the IAPP nucleation phase and shortening of its elongation phase by silica nanoribbons. This accelerated IAPP fibrillization translated to reduced toxicity, especially for the right-handed silica nanoribbons, as revealed by cell viability, helium ion microscopy, as well as zebrafish embryo survival, developmental and behavioral assays. We then examined the proteomes of βTC6 pancreatic beta cells exposed to the three main aggregation states of monomeric, oligomeric and amyloid fibrillar IAPP, and compared that with cellular protein expression modulated by graphene quantum dots (GQDs). A total of 29 proteins were significantly regulated by different forms of IAPP, and the majority of these proteins were nucleotide-binding proteins. A regulatory capacity of GQDs against aberrant protein expression was confirmed. These studies have demonstrated the great potential of employing nanomaterials targeting the mesoscopic enantioselectivity and protein expression dysregulation in pancreatic beta cells.

Keywords: graphene quantum dots, IAPP, silica nanoribbons, protein expression, toxicity

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7 Stabilization of y-Sterilized Food, Packaging Materials by Synergistic Mixtures of Food-Contact Approval Stabilizers

Authors: Sameh A. S. Thabit Alariqi

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Food is widely packaged with plastic materials to prevent microbial contamination and spoilage. Ionizing radiation is widely used to sterilize the food-packaging materials. Sterilization by γ-radiation causes degradation for the plastic packaging materials such as embrittlement, stiffening, softening, discoloration, odour generation, and decrease in molecular weight. Many antioxidants can prevent γ-degradation but most of them are toxic. The migration of antioxidants to its environment gives rise to major concerns in case of food packaging plastics. In this attempt, we have aimed to utilize synergistic mixtures of stabilizers which are approved for food-contact applications. Ethylene-propylene-diene terpolymer (EPDM) have been melt-mixed with hindered amine stabilizers (HAS), phenolic antioxidants and organo-phosphites (hydroperoxide decomposer). Results were discussed by comparing the stabilizing efficiency of mixtures with and without phenol system. Among phenol containing systems where we mostly observed discoloration due to the oxidation of hindered phenol, the combination of secondary HAS, tertiary HAS, organo-phosphite and hindered phenol exhibited improved stabilization efficiency than single or binary additive systems. The mixture of secondary HAS and tertiary HAS, has shown antagonistic effect of stabilization. However, the combination of organo-phosphite with secondary HAS, tertiary HAS and phenol antioxidants have been found to give synergistic even at higher doses of -sterilization. The effects have been explained through the interaction between the stabilizers. After γ-irradiation, the consumption of oligomeric stabilizer significantly depends on the components of stabilization mixture. The effect of the organo-phosphite antioxidant on the overall stability has been discussed.

Keywords: ethylene-propylene-diene terpolymer, synergistic mixtures, gamma sterilization, gamma stabilization

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6 An Enzyme Technology - Metnin™ - Enables the Full Replacement of Fossil-Based Polymers by Lignin in Polymeric Composites

Authors: Joana Antunes, Thomas Levée, Barbara Radovani, Anu Suonpää, Paulina Saloranta, Liji Sobhana, Petri Ihalainen

Abstract:

Lignin is an important component in the exploitation of lignocellulosic biomass. It has been shown that within the next years, the yield of added-value lignin-based chemicals and materials will generate renewable alternatives to oil-based products (e.g. polymeric composites, resins and adhesives) and enhance the economic feasibility of biorefineries. In this paper, a novel technology for lignin valorisation (METNIN™) is presented. METNIN™ is based on the oxidative action of an alkaliphilic enzyme in aqueous alkaline conditions (pH 10-11) at mild temperature (40-50 °C) combined with a cascading membrane operation, yielding a collection of lignin fractions (from oligomeric down to mixture of tri-, di- and monomeric units) with distinct molecular weight distribution, low polydispersity and favourable physicochemical properties. The alkaline process conditions ensure the high processibility of crude lignin in an aqueous environment and the efficiency of the enzyme, yielding better compatibility of lignin towards targeted applications. The application of a selected lignin fraction produced by METNIN™ as a suitable lignopolyol to completely replace a commercial polyol in polyurethane rigid foam formulations is presented as a prototype. Liquid lignopolyols with a high lignin content were prepared by oxypropylation and their full utilization in the polyurethane rigid foam formulation was successfully demonstrated. Moreover, selected technical specifications of different foam demonstrators were determined, including closed cell count, water uptake and compression characteristics. These specifications are within industrial standards for rigid foam applications. The lignin loading in the lignopolyol was a major factor determining the properties of the foam. In addition to polyurethane foam demonstrators, other examples of lignin-based products related to resins and sizing applications will be presented.

Keywords: enzyme, lignin valorisation, polyol, polyurethane foam

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5 Structural Evolution of Na6Mn(SO4)4 from High-Pressure Synchrotron Powder X-ray Diffraction

Authors: Monalisa Pradhan, Ajana Dutta, Irshad Kariyattuparamb Abbas, Boby Joseph, T. N. Guru Row, Diptikanta Swain, Gopal K. Pradhan

Abstract:

Compounds with the Vanthoffite crystal structure having general formula Na6M(SO₄)₄ (M= Mg, Mn, Ni , Co, Fe, Cu and Zn) display a variety of intriguing physical properties intimately related to their structural arrangements. The compound Na6Mn(SO4)4 shows antiferromagnetic ordering at low temperature where the in-plane Mn-O•••O-Mn interactions facilitates antiferromagnetic ordering via a super-exchange interaction between the Mn atoms through the oxygen atoms . The inter-atomic bond distances and angles can easily be tuned by applying external pressure and can be probed using high resolution X-ray diffraction. Moreover, because the magnetic interaction among the Mn atoms are super-exchange type via Mn-O•••O-Mn path, the variation of the Mn-O•••O-Mn dihedral angle and Mn-O bond distances under high pressure inevitably affects the magnetic properties. Therefore, it is evident that high pressure studies on the magnetically ordered materials would shed light on the interplay between their structural properties and magnetic ordering. This will indeed confirm the role of buckling of the Mn-O polyhedral in understanding the origin of anti-ferromagnetism. In this context, we carried out the pressure dependent X-ray diffraction measurement in a diamond anvil cell (DAC) up to a maximum pressure of 17 GPa to study the phase transition and determine equation of state from the volume compression data. Upon increasing the pressure, we didn’t observe any new diffraction peaks or sudden discontinuity in the pressure dependences of the d values up to the maximum achieved pressure of ~17 GPa. However, it is noticed that beyond 12 GPa the a and b lattice parameters become identical while there is a discontinuity in the β value around the same pressure. This indicates a subtle transition to a pseudo-monoclinic phase. Using the third order Birch-Murnaghan equation of state (EOS) to fit the volume compression data for the entire range, we found the bulk modulus (B0) to be 44 GPa. If we consider the subtle transition at 12 GPa, we tried to fit another equation state for the volume beyond 12 GPa using the second order Birch-Murnaghan EOS. This gives a bulk modulus of ~ 34 GPa for this phase.

Keywords: mineral, structural phase transition, high pressure XRD, spectroscopy

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4 Applying Computer Simulation Methods to a Molecular Understanding of Flaviviruses Proteins towards Differential Serological Diagnostics and Therapeutic Intervention

Authors: Sergio Alejandro Cuevas, Catherine Etchebest, Fernando Luis Barroso Da Silva

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The flavivirus genus has several organisms responsible for generating various diseases in humans. Special in Brazil, Zika (ZIKV), Dengue (DENV) and Yellow Fever (YFV) viruses have raised great health concerns due to the high number of cases affecting the area during the last years. Diagnostic is still a difficult issue since the clinical symptoms are highly similar. The understanding of their common structural/dynamical and biomolecular interactions features and differences might suggest alternative strategies towards differential serological diagnostics and therapeutic intervention. Due to their immunogenicity, the primary focus of this study was on the ZIKV, DENV and YFV non-structural proteins 1 (NS1) protein. By means of computational studies, we calculated the main physical chemical properties of this protein from different strains that are directly responsible for the biomolecular interactions and, therefore, can be related to the differential infectivity of the strains. We also mapped the electrostatic differences at both the sequence and structural levels for the strains from Uganda to Brazil that could suggest possible molecular mechanisms for the increase of the virulence of ZIKV. It is interesting to note that despite the small changes in the protein sequence due to the high sequence identity among the studied strains, the electrostatic properties are strongly impacted by the pH which also impact on their biomolecular interactions with partners and, consequently, the molecular viral biology. African and Asian strains are distinguishable. Exploring the interfaces used by NS1 to self-associate in different oligomeric states, and to interact with membranes and the antibody, we could map the strategy used by the ZIKV during its evolutionary process. This indicates possible molecular mechanisms that can explain the different immunological response. By the comparison with the known antibody structure available for the West Nile virus, we demonstrated that the antibody would have difficulties to neutralize the NS1 from the Brazilian strain. The present study also opens up perspectives to computationally design high specificity antibodies.

Keywords: zika, biomolecular interactions, electrostatic interactions, molecular mechanisms

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3 Fast Transient Workflow for External Automotive Aerodynamic Simulations

Authors: Christina Peristeri, Tobias Berg, Domenico Caridi, Paul Hutcheson, Robert Winstanley

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In recent years the demand for rapid innovations in the automotive industry has led to the need for accelerated simulation procedures while retaining a detailed representation of the simulated phenomena. The project’s aim is to create a fast transient workflow for external aerodynamic CFD simulations of road vehicles. The geometry used was the SAE Notchback Closed Cooling DrivAer model, and the simulation results were compared with data from wind tunnel tests. The meshes generated for this study were of two types. One was a mix of polyhedral cells near the surface and hexahedral cells away from the surface. The other was an octree hex mesh with a rapid method of fitting to the surface. Three different grid refinement levels were used for each mesh type, with the biggest total cell count for the octree mesh being close to 1 billion. A series of steady-state solutions were obtained on three different grid levels using a pseudo-transient coupled solver and a k-omega-based RANS turbulence model. A mesh-independent solution was found in all cases with a medium level of refinement with 200 million cells. Stress-Blended Eddy Simulation (SBES) was chosen for the transient simulations, which uses a shielding function to explicitly switch between RANS and LES mode. A converged pseudo-transient steady-state solution was used to initialize the transient SBES run that was set up with the SIMPLEC pressure-velocity coupling scheme to reach the fastest solution (on both CPU & GPU solvers). An important part of this project was the use of FLUENT’s Multi-GPU solver. Tesla A100 GPU has been shown to be 8x faster than an Intel 48-core Sky Lake CPU system, leading to significant simulation speed-up compared to the traditional CPU solver. The current study used 4 Tesla A100 GPUs and 192 CPU cores. The combination of rapid octree meshing and GPU computing shows significant promise in reducing time and hardware costs for industrial strength aerodynamic simulations.

Keywords: CFD, DrivAer, LES, Multi-GPU solver, octree mesh, RANS

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2 Reactions of 4-Aryl-1H-1,2,3-Triazoles with Cycloalkenones and Epoxides: Synthesis of 2,4- and 1,4-Disubstituted 1,2,3-Triazoles

Authors: Ujjawal Kumar Bhagat, Kamaluddin, Rama Krishna Peddinti

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The Huisgen’s 1,3-dipolar [3+2] cycloaddition of organic azides and alkynes often give the mixtures of both the regioisomers 1,4- and 1,5- disubstituted 1,2,3-triazoles. Later, in presence of metal salts (click chemistry) such as copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) was used for the synthesis of 1,4-disubstituted 1,2,3-triazoles as a sole products regioselectively. Also, the ‘click reactions’ of Ruthenium-catalyzed azides-alkynes cycloaddition (RuAAC) is used for the synthesis of 1,5-disubstituted 1,2,3-triazoles as a single isomer. The synthesis of 1,4- and 1.5-disubstituted 1,2,3-triazoles has become the gold standard of ‘click chemistry’ due to its reliability, specificity, and biocompatibility. The 1,4- and 1,5-disubstituted 1,2,3-triazoles have emerged as one of the most powerful entities in the varieties of biological properties like antibacterial, antitubercular, antitumor, antifungal and antiprotozoal activities. Some of the 1,4,5-trisubstituted 1,2,3-triazoles exhibit Hsp90 inhibiting properties. The 1,4-disubstituted 1,2,3-triazoles also play a big role in the area of material sciences. The triazole-derived oligomeric, polymeric structures are the potential materials for the preparation of organic optoelectronics, silicon elastomers and unimolecular block copolymers. By the virtue of hydrogen bonding and dipole interactions, the 1,2,3-triazole moiety readily associates with the biological targets. Since, the 4-aryl-1H-1,2,3-triazoles are stable entities, they are chemically robust and very less reactive. In this regard, the addition of 4-aryl-1H-1,2,3-triazoles as nucleophiles to α,β-unsaturated carbonyls and nucleophilic substitution with the epoxides constitutes a powerful and challenging synthetic approach for the generation of disubstituted 1,2,3-triazoles. Herein, we have developed aza-Michael addition of 4-aryl-1H-1,2,3-triazoles to 2-cycloalken-1-ones in the presence of an organic base (DABCO) in acetonotrile solvent leading to the formation of disubstituted 1,2,3-triazoles. The reaction provides 1,4-disubstituted triazoles, 3-(4-aryl-1H-1,2,3-triazol-1-yl)cycloalkanones in major amount along with 1,5-disubstituted 1,2,3-triazoles, minor regioisomers with excellent combined chemical yields (upto99%). The nucleophilic behavior of 4-aryl-1H-1,2,3-triazoles was also tested in the ring opening of meso-epoxides in the presence of organic bases (DABCO/Et3N) in acetonotrile solvent furnishing the two regioisomers1,4- and 1,5-disubstituted 1,2,3-triazoles. Thus, the novelty of this methodology is synthesis of diversified disubstituted 1,2,3-triazoles under metal free condition.The results will be presented in detail.

Keywords: aza-Michael addition, cycloalkenones, epoxides, triazoles

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1 Erosion Wear of Cast Al-Si Alloys

Authors: Pooja Verma, Rajnesh Tyagi, Sunil Mohan

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Al-Si alloys are widely used in various components such as liner-less engine blocks, piston, compressor bodies and pumps for automobile sector and aerospace industries due to their excellent combination of properties like low thermal expansion coefficient, low density, excellent wear resistance, high corrosion resistance, excellent cast ability, and high hardness. The low density and high hardness of primary Si phase results in significant reduction in density and improvement in wear resistance of hypereutectic Al-Si alloys. Keeping in view of the industrial importance of the alloys, hypereutectic Al-Si alloys containing 14, 16, 18 and 20 wt. % of Si were prepared in a resistance furnace using adequate amount of deoxidizer and degasser and their erosion behavior was evaluated by conducting tests at impingement angles of 30°, 60°, and 90° with an erodent discharge rate of 7.5 Hz, pressure 1 bar using erosion test rig. Microstructures of the cast alloys were examined using Optical microscopy (OM) and scanning electron microscopy (SEM) and the presence of Si particles was confirmed by x-ray diffractometer (XRD). The mechanical properties and hardness were measured using uniaxial tension tests at a strain rate of 10-3/s and Vickers hardness tester. Microstructures of the alloys and X-ray examination revealed the presence of primary and eutectic Si particles in the shape of cuboids or polyhedral and finer needles. Yield strength (YS), ultimate tensile strength (UTS), and uniform elongation of the hypereutectic Al-Si alloys were observed to increase with increasing content of Si. The optimal strength and ductility was observed for Al-20 wt. % Si alloy which is significantly higher than the Al-14 wt. % Si alloy. The increased hardness and the strength of the alloys with increasing amount of Si has been attributed presence of Si in the solid solution which creates strain, and this strain interacts with dislocations resulting in solid-solution strengthening. The interactions between distributed primary Si particles and dislocations also provide Orowan strengthening leading to increased strength. The steady state erosion rate was found to decrease with increasing angle of impact as well as Si content for all the alloys except at 900 where it was observed to increase with the increase in the Si content. The minimum erosion rate is observed in Al-20 wt. % Si alloy at 300 and 600 impingement angles because of its higher hardness in comparison to other alloys. However, at 90° impingement angle the wear rate for Al-20 wt. % Si alloy is found to be the minimum due to deformation, subsequent cracking and chipping off material.

Keywords: Al-Si alloy, erosion wear, cast alloys, dislocation, strengthening

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