Search results for: ring opening polymerization (ROP)
1150 Use Process Ring-Opening Polymerization to Melt Processing of Cellulose Nanowhisker from Coconut Husk Fibers-Filled Polylactide-Based Nanocomposites
Authors: Imam Wierawansyah Eltara, Iftitah, Agus Ismail
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In the present work, cellulose nanowhiskers (CNW) extracted from coconut husk fibers, were incorporated in polylactide (PLA)-based composites. Prior to the blending, PLA chains were chemically grafted on the surface of CNW to enhance the compatibilization between CNW and the hydrophobic polyester matrix. Ring-opening polymerization of L-lactide was initiated from the hydroxyl groups available at the CNW surface to yield CNW-g-PLA nanohybrids. PLA-based nanocomposites were prepared by melt blending to ensure a green concept of the study thereby limiting the use of organic solvents. The influence of PLA-grafted cellulose nanoparticles on the mechanical and thermal properties of the ensuing nanocomposites was deeply investigated. The thermal behavior and mechanical properties of the nanocomposites were determined using differential scanning calorimetry (DSC) and dynamical mechanical and thermal analysis (DMTA), respectively. In theory, evidenced that the chemical grafting of CNW enhances their compatibility with the polymeric matrix and thus improves the final properties of the nanocomposites. Large modification of the crystalline properties such as the crystallization half-time was evidenced according to the nature of the PLA matrix and the content of nanofillers.Keywords: cellulose nanowhiskers, nanocomposites, coconut husk fiber, ring opening polymerization
Procedia PDF Downloads 3171149 The Tadpole-Shaped Polypeptides with Two Regulable (Alkyl Chain) Tails
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The biocompatible tadpole-shaped polypeptides with one cyclic polypeptides ring and two alkyl chain tails were synthesized by N-heterocyclic carbine (NHC)-mediated ring-opening polymerization (ROP) of α-amino acid N-carboxyanhydrides (NCAs). First, the NHC precursor, denoted as [NHC(H)][HCO₃], with two alkyl chains at the nitrogen was prepared by a simple anion metathesis of imidazole(in)ium chlorides with KHCO₃. Then NHC releasing from the [NHC(H)][HCO₃] directly initiated the ROP of NCA to produce the cyclic polypeptides. Finally, the tadpole-shaped polypeptides with two regulable tails were obtained. The target polypeptides were characterized by nuclear magnetic resonance spectrum (1H NMR), Fourier transform infrared spectroscopy (FT-IR), gel permeation chromatography (GPC) and matrix-assisted laser desorption ionization-time of flight mass spectra (MALDI-TOF MS). This pioneering approach simplifies the synthesis procedures of tadpole-shaped polypeptides compared to other methods, which usually requires specific intramolecular ring-closure reaction.Keywords: cyclic polypeptides, α-amino acid N-carboxyanhydrides, N-heterocyclic carbene, ring-opening polymerization, tadpole-shaped
Procedia PDF Downloads 2051148 Bulk Amounts of Linear and Cyclic Polypeptides on Our Hand within a Short Time
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Polypeptides with defined peptide sequences illustrate the power of remarkable applications in drug delivery, tissue engineering, sensing and catalysis. Especially the cyclic polypeptides, the distinctive topological architecture imparts many characteristic properties comparing to linear polypeptides. Here, a facile and highly efficient strategy for the synthesis of linear and cyclic polypeptides is reported using N-heterocyclic carbenes (NHCs)-mediated ring-opening polymerization (ROP) of α-amino acid N-carboxyanhydrides (NCA) in the presence or absence of primary amine initiator. The polymerization proceeds rapidly in a quasi-living manner, allowing access to linear and cyclic polypeptides of well-defined chain length and narrow polydispersity, as evidenced by nuclear magnetic resonance spectrum (1H NMR and 13C NMR spectra) and size exclusion chromatography (SEC) analysis. The cyclic architecture of the polypeptides was further verified by matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectra (MALDI-TOF MS) and electrospray ionization (ESI) mass spectra, as well as viscosity studies. This approach can also simplify workup procedures and make bulk scale synthesis possible, which thereby opens avenues for practical uses in diverse areas, opening up the new generation of polypeptide synthesis.Keywords: α-amino acid N-carboxyanhydrides, living polymerization, polypeptides, N-heterocyclic carbenes, ring-opening polymerization
Procedia PDF Downloads 1671147 Direct In-Situ Ring Opening Polymerization of E-caprolactone to Produce Biodegradable PCL/Montmorillonite Nanocomposites
Authors: Amine Harrane, Mahmoud Belalia
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During the last decade, polymer layered silicate nanocomposites have received increasing attention from scientists and industrial researchers because they generally exhibit greatly improved mechanical, thermal, barrier and flame-retardant properties at low clay content in comparison with unfilled polymers or more conventional micro composites. Poly(ε-caprolactone) (PCL)-layered silicate nanocomposites have the advantage of adding biocompatibility and biodegradability to the traditional properties of nanocomposites. They can be prepared by in situ ring-opening polymerization of ε-caprolactone using a conventional initiator to induce polymerization in the presence of an organophilic clay, such as organomodified montmorillonite. Messersmith and Giannelis used montmorillonite exchanged with protonated 12-amino dodecanoic acid and Cr3+ exchanged fluorohectorite, a synthetic mica type of silicate. Sn-based catalysts such as tin (II) octoate and dibutyltin (IV) dimethoxide have been reported to efficiently promote the polymerization of ε-caprolactone in the presence of organomodified clays. In this work, we have used an alternative method to prepare PCL/montmorillonite nanocomposites. The cationic polymerization of ε-caprolactone was initiated directly by Maghnite-TOA, organomodified montmorillonite clay, to produce nanocomposites (Scheme 1). Resulted from nanocomposites were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), force atomic microscopy (AFM) and thermogravimetry.Keywords: polycaprolactone, polycaprolactone/clay nanocomposites, biodegradables nanocomposites, Maghnite, Insitu polymeriation
Procedia PDF Downloads 781146 Copolymers of Epsilon-Caprolactam Received via Anionic Polymerization in the Presence of Polypropylene Glycol Based Polymeric Activators
Authors: Krasimira N. Zhilkova, Mariya K. Kyulavska, Roza P. Mateva
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The anionic polymerization of -caprolactam (CL) with bifunctional activators has been extensively studied as an effective and beneficial method of improving chemical and impact resistances, elasticity and other mechanical properties of polyamide (PA6). In presence of activators or macroactivators (MAs) also called polymeric activators (PACs) the anionic polymerization of lactams proceeds rapidly at a temperature range of 130-180C, well below the melting point of PA-6 (220C) permitting thus the direct manufacturing of copolymer product together with desired modifications of polyamide properties. Copolymers of PA6 with an elastic polypropylene glycol (PPG) middle block into main chain were successfully synthesized via activated anionic ring opening polymerization (ROP) of CL. Using novel PACs based on PPG polyols (with differ molecular weight) the anionic ROP of CL was realized and investigated in the presence of a basic initiator sodium salt of CL (NaCL). The PACs were synthesized as N-carbamoyllactam derivatives of hydroxyl terminated PPG functionalized with isophorone diisocyanate [IPh, 5-Isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane] and blocked then with CL units via an addition reaction. The block copolymers were analyzed and proved with 1H-NMR and FT-IR spectroscopy. The influence of the CL/PACs ratio in feed, the length of the PPG segments and polymerization conditions on the kinetics of anionic ROP, on average molecular weight, and on the structure of the obtained block copolymers were investigated. The structure and phase behaviour of the copolymers were explored with differential scanning calorimetry, wide-angle X-ray diffraction, thermogravimetric analysis and dynamic mechanical thermal analysis. The crystallinity dependence of PPG content incorporated into copolymers main backbone was estimate. Additionally, the mechanical properties of the obtained copolymers were studied by notched impact test. From the performed investigation in this study could be concluded that using PPG based PACs at the chosen ROP conditions leads to obtaining well-defined PA6-b-PPG-b-PA6 copolymers with improved impact resistance.Keywords: anionic ring opening polymerization, caprolactam, polyamide copolymers, polypropylene glycol
Procedia PDF Downloads 4151145 Polymerization of Epsilon-Caprolactone Using Lipase Enzyme for Medical Applications
Authors: Sukanya Devi Ramachandran, Vaishnavi Muralidharan, Kavya Chandrasekaran
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Polycaprolactone is polymer belonging to the polyester family that has noticeable characteristics of biodegradability and biocompatibility which is essential for medical applications. Polycaprolactone is produced by the ring opening polymerization of the monomer epsilon-Caprolactone (ε-CL) which is a closed ester, comprising of seven-membered ring. This process is normally catalysed by metallic components such as stannous octoate. It is difficult to remove the catalysts after the reaction, and they are also toxic to the human body. An alternate route of using enzymes as catalysts is being employed to reduce the toxicity. Lipase enzyme is a subclass of esterase that can easily attack the ester bonds of ε-CL. This research paper throws light on the extraction of lipase from germinating sunflower seeds and the activity of the biocatalyst in the polymerization of ε-CL. Germinating Sunflower seeds were crushed with fine sand in phosphate buffer of pH 6.5 into a fine paste which was centrifuged at 5000rpm for 10 minutes. The clear solution of the enzyme was tested for activity at various pH ranging from 5 to 7 and temperature ranging from 40oC to 70oC. The enzyme was active at pH6.0 and at 600C temperature. Polymerization of ε-CL was done using toluene as solvent with the catalysis of lipase enzyme, after which chloroform was added to terminate the reaction and was washed in cold methanol to obtain the polymer. The polymerization was done by varying the time from 72 hours to 6 days and tested for the molecular weight and the conversion of the monomer. The molecular weight obtained at 6 days is comparably higher. This method will be very effective, economical and eco-friendly to produce as the enzyme used can be regenerated as such at the end of the reaction and can be reused. The obtained polymers can be used for drug delivery and other medical applications.Keywords: lipase, monomer, polycaprolactone, polymerization
Procedia PDF Downloads 2961144 Sensitivity Improvement of Optical Ring Resonator for Strain Analysis with the Direction of Strain Recognition Possibility
Authors: Tayebeh Sahraeibelverdi, Ahmad Shirazi Hadi Veladi, Mazdak Radmalekshah
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Optical sensors became attractive due to preciseness, low power consumption, and intrinsic electromagnetic interference-free characteristic. Among the waveguide optical sensors, cavity-based ones attended for the high Q-factor. Micro ring resonators as a potential platform have been investigated for various applications as biosensors to pressure sensors thanks to their sensitive ring structure responding to any small change in the refractive index. Furthermore, these small micron size structures can come in an array, bringing the opportunity to have any of the resonance in a specific wavelength and be addressed in this way. Another exciting application is applying a strain to the ring and making them an optical strain gauge where the traditional ones are based on the piezoelectric material. Making them in arrays needs electrical wiring and about fifty times bigger in size. Any physical element that impacts the waveguide cross-section, Waveguide elastic-optic property change, or ring circumference can play a role. In comparison, ring size change has a larger effect than others. Here an engineered ring structure is investigated to study the strain effect on the ring resonance wavelength shift and its potential for more sensitive strain devices. At the same time, these devices can measure any strain by mounting on the surface of interest. The idea is to change the" O" shape ring to a "C" shape ring with a small opening starting from 2π/360 or one degree. We used the Mode solution of Lumbrical software to investigate the effect of changing the ring's opening and the shift induced by applied strain. The designed ring radius is a three Micron silicon on isolator ring which can be fabricated by standard complementary metal-oxide-semiconductor (CMOS) micromachining. The measured wavelength shifts from1-degree opening of the ring to a 6-degree opening have been investigated. Opening the ring for 1-degree affects the ring's quality factor from 3000 to 300, showing an order of magnitude Q-factor reduction. Assuming a strain making the ring-opening from 1 degree to 6 degrees, our simulation results showing negligible Q-factor reduction from 300 to 280. A ring resonator quality factor can reach up to 108 where an order of magnitude reduction is negligible. The resonance wavelength shift showed a blue shift and was obtained to be 1581, 1579,1578,1575nm for 1-, 2-, 4- and 6-degree ring-opening, respectively. This design can find the direction of the strain-induced by applying the opening on different parts of the ring. Moreover, by addressing the specified wavelength, we can precisely find the direction. We can open a significant opportunity to find cracks and any surface mechanical property very specifically and precisely. This idea can be implemented on polymer ring resonators while they can come with a flexible substrate and can be very sensitive to any strain making the two ends of the ring in the slit part come closer or further.Keywords: optical ring resonator, strain gauge, strain sensor, surface mechanical property analysis
Procedia PDF Downloads 1261143 Synthesis and Use of Bio Polyols in Rigid Polyurethane Foam Production
Authors: A. Esra Pişkin, L. Yusuf Yivlik
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Polyurethane consumption in the world increases every year. Polyetherpolyol, which is the main raw material of polyurethane, is produced from petroleum, and bioresources are needed in polyol production due to the damage it causes to the environment and the consumption of too much energy during the production phase. In this present work, bio polyol was synthesized with castor oil and soybean oil, and its use in rigid polyurethane systems was investigated. Transesterification and ring opening methods were applied for polyol synthesis, and the obtained bio polyols were compared with polyols derived petroleum. The goal of the present study was to synthesize biopolyols and to investigate the mechanical, thermal, and chemical properties of the synthesized polyurethane in terms of bio polyols.Keywords: polyurethane, polyol, biopolyol, vegetable oil, foam, rigid polyurethane foam, ring opening, transesterification
Procedia PDF Downloads 4651142 Rings Characterized by Classes of Rad-plus-Supplemented Modules
Authors: Manoj Kumar Patel
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In this paper, we introduce and give various properties of weak* Rad-plus-supplemented and cofinitely weak* Rad-plus-supplemented modules over some special kinds of rings, in particular, artinian serial ring and semiperfect ring. Also prove that ring R is artinian serial if and only if every right and left R-module is weak* Rad-plus-supplemented. We provide the counter example which proves that weak* Rad-plus-supplemented module is the generalization of plus-supplemented and Rad-plus-supplemented modules. Furthermore, as an application of above finding results of this research article, our main focus is to characterized the semisimple ring, artinian principal ideal ring, semilocal ring, semiperfect ring, perfect ring, commutative noetherian ring and Dedekind domain in terms of weak* Rad-plus-supplemented module.Keywords: cofinitely weak* Rad-plus-supplemented module , Dedekind domain, Rad-plus-supplemented module, semiperfect ring
Procedia PDF Downloads 2611141 Mathematical Modeling for Continuous Reactive Extrusion of Poly Lactic Acid Formation by Ring Opening Polymerization Considering Metal/Organic Catalyst and Alternative Energies
Authors: Satya P. Dubey, Hrushikesh A Abhyankar, Veronica Marchante, James L. Brighton, Björn Bergmann
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Aims: To develop a mathematical model that simulates the ROP of PLA taking into account the effect of alternative energy to be implemented in a continuous reactive extrusion production process of PLA. Introduction: The production of large amount of waste is one of the major challenges at the present time, and polymers represent 70% of global waste. PLA has emerged as a promising polymer as it is compostable, biodegradable thermoplastic polymer made from renewable sources. However, the main limitation for the application of PLA is the traces of toxic metal catalyst in the final product. Thus, a safe and efficient production process needs to be developed to avoid the potential hazards and toxicity. It has been found that alternative energy sources (LASER, ultrasounds, microwaves) could be a prominent option to facilitate the ROP of PLA via continuous reactive extrusion. This process may result in complete extraction of the metal catalysts and facilitate less active organic catalysts. Methodology: Initial investigation were performed using the data available in literature for the reaction mechanism of ROP of PLA based on conventional metal catalyst stannous octoate. A mathematical model has been developed by considering significant parameters such as different initial concentration ratio of catalyst, co-catalyst and impurity. Effects of temperature variation and alternative energies have been implemented in the model. Results: The validation of the mathematical model has been made by using data from literature as well as actual experiments. Validation of the model including alternative energies is in progress based on experimental data for partners of the InnoREX project consortium. Conclusion: The model developed reproduces accurately the polymerisation reaction when applying alternative energy. Alternative energies have a great positive effect to increase the conversion and molecular weight of the PLA. This model could be very useful tool to complement Ludovic® software to predict the large scale production process when using reactive extrusion.Keywords: polymer, poly-lactic acid (PLA), ring opening polymerization (ROP), metal-catalyst, bio-degradable, renewable source, alternative energy (AE)
Procedia PDF Downloads 3621140 Development and in vitro Evaluation of Polymer-Drug Conjugates Containing Potentiating Agents for Combination Therapy
Authors: Blessing A. Aderibigbe
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Combination therapy is a treatment approach that is used to prevent the emergence of drug resistance. This approach is used for the treatment of many chronic and infectious diseases. Potentiating agents are currently explored in combination therapy, resulting in excellent therapeutic outcomes. Breast cancer and malaria are two chronic conditions responsible globally for high death rates. In this research, a class of polymer-drug conjugates containing potentiating agents with either antimalarial or anticancer drugs were prepared by Michael Addition Polymerization reaction and ring-opening polymerization reaction. Conjugation of potentiating agents with bioactive compounds into the polymers resulted in conjugates with good water solubility, highly selective and non-toxic. In vitro cytotoxicity and in vitro antiplasmodial evaluation on the conjugates revealed that the conjugates were more effective when compared to the free drugs. The drug release studies further showed that the release profile of the drugs from the conjugates was sustained. The findings revealed the potential of polymer-drug conjugates to overcome drug toxicity and drug resistance, which is common with the currently used antimalarial and anticancer drugs.Keywords: anticancer, antimalarials, combination therapy, polymer-drug conjugates
Procedia PDF Downloads 1331139 Liquid Tin(II) Alkoxide Initiators for Use in the Ring-Opening Polymerisation of Cyclic Ester Monomers
Authors: Sujitra Ruengdechawiwat, Robert Molloy, Jintana Siripitayananon, Runglawan Somsunan, Paul D. Topham, Brian J. Tighe
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The main aim of this research has been to design and synthesize some completely soluble liquid tin(II) alkoxide initiators for use in the ring-opening polymerisation (ROP) of cyclic ester monomers. This is in contrast to conventional tin(II) alkoxides in solid form which tend to be molecular aggregates and difficult to dissolve. The liquid initiators prepared were bis(tin(II) monooctoate) diethylene glycol ([Sn(Oct)]2DEG) and bis(tin(II) monooctoate) ethylene glycol ([Sn(Oct)]2EG). Their efficiencies as initiators in the bulk ROP of ε-caprolactone (CL) at 130oC were studied kinetically by dilatometry. Kinetic data over the 20-70% conversion range was used to construct both first-order and zero-order rate plots. It was found that the rate data fitted more closely to first-order kinetics with respect to the monomer concentration and gave higher first-order rate constants than the corresponding tin(II) octoate/diol initiating systems normally used to generate the tin(II) alkoxide in situ. Since the ultimate objective of this work is to produce copolymers suitable for biomedical use as absorbable monofilament surgical sutures, poly(L-lactide-co-ε-caprolactone) 75:25 mol %, P(LL-co-CL), copolymers were synthesized using both solid and liquid tin(II) alkoxide initiators at 130°C for 48 hrs. The statistical copolymers were obtained in near-quantitative yields with compositions (from 1H-NMR) close to the initial comonomer feed ratios. The monomer sequencing (from 13C-NMR) was partly random and partly blocky (gradient-type) due to the much differing monomer reactivity ratios (rLL >> rCL). From GPC, the copolymers obtained using the soluble liquid tin(II) alkoxides were found to have higher molecular weights (Mn = 40,000-100,000) than those from the only partially soluble solid initiators (Mn = 30,000-52,000).Keywords: biodegradable polyesters, poly(L-lactide-co-ε-caprolactone), ring-opening polymerisation, tin(II) alkoxide
Procedia PDF Downloads 1941138 Simulation Analysis of Optical Add Drop Multiplexer in a Ring Network
Authors: Surinder Singh, Meenakshi
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In this paper MZI-FBG based optical add drop multiplexer is designed and its performance is analyzed in the ring network. In the ring network nodes are composed of optical add drop multiplexer, transmitter and receiver. OADM is used to add or drop any frequency at intermediate nodes without affecting other channels. In this paper the performance of the ring network is carried out by varying various kinds of fiber with or without amplifiers.Keywords: OADM, ring network, MZI-FBG, transmitter
Procedia PDF Downloads 5741137 On the Girth of the Regular Digraph of Ideals of a Commutative Ring
Authors: Masoud Karimi
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Let R be a commutative ring. The regular digraph of ideals of R, which is denoted by Γ(R), is a digraph whose vertex-set is the set of all non-trivial ideals of R and, for every two distinct vertices I and J, there is an arc from I to J, whenever I contains a non-zero-divisor on J. In this article, we show that an indecomposable Noetherian ring R is Artinian local if and only if Z(I)=Z(R) for every non-nilpotent ideal I. Then we conclude that the girth of Γ(R) is not equal to four.Keywords: commutative ring, girth, regular digraph, zero-divisor
Procedia PDF Downloads 2791136 On Modules over Dedekind Prime Rings
Authors: Elvira Kusniyanti, Hanni Garminia, Pudji Astuti
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This research studies an interconnection between finitely generated uniform modules and Dedekind prime rings. The characterization of modules over Dedekind prime rings that will be investigated is an adoption of Noetherian and hereditary concept. Dedekind prime rings are Noetherian and hereditary rings. This property of Dedekind prime rings is a background of the idea of adopting arises. In Noetherian area, it was known that a ring R is Noetherian ring if and only if every finitely generated R-module is a Noetherian module. Similar to that result, a characterization of the hereditary ring is related to its projective modules. That is, a ring R is hereditary ring if and only if every projective R-module is a hereditary module. Due to the above two results, we suppose that characterization of a Dedekind prime ring can be analyzed from finitely generated modules over it. We propose a conjecture: a ring R is a Dedekind prime ring if and only if every finitely generated uniform R-module is a Dedekind module. In this article, we will generalize a concept of the Dedekind module for non-commutative ring case and present a part of the above conjecture.Keywords: dedekind domains, dedekind prime rings, dedekind modules, uniform modules
Procedia PDF Downloads 4411135 Structural Analysis of Hydro-Turbine Spiral Casing and Stay Ring Using Ansys
Authors: Surjit Angra, Pooja Rani, Vinod Kumar
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In hydro power plant spiral casing and Stay ring is meant to guide the water flow to guide vane and runner. Spiral casing and Stay ring is subjected to static i.e. pressure load as well as fluctuating load acting on the structure due to water hammer effect in water conductor system. Finite element method has been used to calculate stresses on spiral casing and stay ring. These calculations were done for the maximum possible loading under operating condition "LC1 Quick Shut Down”. The design load is reached for the spiral casing and stay ring during the emergency closure of the guide apparatus "LC1 Quick Shut Down”. During this operation the forces from the head cover to the stay ring also reach their maximum.Keywords: hydro-turbine, spiral casing, stay ring, structural analysis
Procedia PDF Downloads 5161134 Polysulfide as Active ‘Stealth’ Polymers with Additional Anti-Inflammatory Activity
Authors: Farah El Mohtadi, Richard d'Arcy, Nicola Tirelli
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Since 40 years, poly (ethylene glycol) (PEG) has been the gold standard in biomaterials and drug delivery, because of its combination of chemical and biological inertness. However, the possibility of its breakdown under oxidative conditions and the demonstrated development of anti-PEG antibodies highlight the necessity to develop carriers based on materials with increased stability in a challenging biological environment. Here, we describe the synthesis of polysulfide via anionic ring-opening polymerization. In vitro, the synthesized polymer was characterized by low toxicity and a level of complement activation (in human plasma) and macrophage uptake slightly lower than PEG and poly (2‐methyl-2‐oxazoline) (PMOX), of a similar size. Importantly, and differently from PEG, on activated macrophages, the synthesized polymer showed a strong and dose-dependent ROS scavenging activity, which resulted in the corresponding reduction of cytokine production. Therefore, the results from these studies show that polysulfide is highly biocompatible and are potential candidates to be used as an alternative to PEG for various applications in nanomedicine.Keywords: PEG, low toxicity, ROS scavenging, biocompatible
Procedia PDF Downloads 1291133 Improved of Elliptic Curves Cryptography over a Ring
Authors: Abdelhakim Chillali, Abdelhamid Tadmori, Muhammed Ziane
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In this article we will study the elliptic curve defined over the ring An and we define the mathematical operations of ECC, which provides a high security and advantage for wireless applications compared to other asymmetric key cryptosystem.Keywords: elliptic curves, finite ring, cryptography, study
Procedia PDF Downloads 3721132 Transformation of Glycals to Chiral Fused Aromatic Cores via Annulative π-Extension Reaction with Arynes
Authors: Nazar Hussain, Debaraj Mukherjee
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Carbohydrate-derived chiral intermediates which contain arrays of defined stereocenters have found enormous applications in organic synthesis due to their inherent functional group, stereochemical and structural diversities as well as their ready availability. Stereodiversity of these classes of molecules has motivated synthetic organic chemistry over the years. One major challenge is control of relative configuration during construction of acyclic fragments. Here, we show that The Diels Alder addition of arynes to appropriately substituted vinyl/aryl glycals followed by π-extension via pyran ring opening smoothly furnished meta-disubstituted fused aromatic cores containing a stereo-defined orthogonally protected chiral side chain. The method is broad in terms of aryl homologation affording benzene, naphthalene, and phenanthrene derivatives. Base-induced deprotonation followed by cleavage of the allylic C-O bond appears to be the crucial steps leading to the development of aromaticity, which is the driving force behind the annulative π-extension process. The present protocol can be used for the synthesis of meta-disubstituted naphthalene aldehydes and substrates for aldolases.Keywords: vinyl/C-2 aryl glycal, arynes, cyclization, ring opening
Procedia PDF Downloads 2551131 Optimization of the Conditions of Oligomerization and Polymerization Processes of Selected Olefins with the Use of Complex Compounds of Transition Metal Ions
Authors: Joanna Drzeżdżon, Marzena Białek
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Polyolefins are a group of materials used today in all areas of life. They are used in the food, domestic and other industries. In particular, polyethylene and polypropylene have found application in the production of packaging materials, pipes, containers, car parts as well as elements of medical equipment, e.g. syringes. Optimization of the polymerization and oligomerization processes of selected olefins is a very important stage before the technological implementation of polyolefin production. The purpose of the studies is to determine the conditions for ethylene polymerization as well as 3-buten-2-ol and 2-chloro-2-propen-1-ol oligomerization with the use of oxovanadium(IV) dipicolinate complexes with N-heterocyclic ligands. Additionally, the studies aims to determine the catalytic activities of the dipicolinate oxovanadium(IV) complexes with N-heterocyclic ligands in the studied polymerization and oligomerization processes.Keywords: buten-2-ol, dipicolinate, ethylene, polymerization, oligomerization, vanadium
Procedia PDF Downloads 1961130 Photopolymerization of Dimethacrylamide with (Meth)acrylates
Authors: Yuling Xu, Haibo Wang, Dong Xie
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A photopolymerizable dimethacrylamide was synthesized and copolymerized with the selected (meth)acrylates. The polymerization rate, degree of conversion, gel time, and compressive strength of the formed neat resins were investigated. The results show that in situ photo-polymerization of the synthesized dimethacrylamide with comonomers having an electron-withdrawing and/or acrylate group dramatically increased the polymerization rate, degree of conversion, and compressive strength. On the other hand, an electron-donating group on either carbon-carbon double bond or the ester linkage slowed down the polymerization. In contrast, the triethylene glycol dimethacrylate-based system did not show a clear pattern. Both strong hydrogen-bonding between (meth)acrylamide and organic acid groups may be responsible for higher compressive strengths. Within the limitation of this study, the photo-polymerization of dimethacrylamide can be greatly accelerated by copolymerization with monomers having electron-withdrawing and/or acrylate groups. The monomers with methacrylate group can significantly reduce the polymerization rate and degree of conversion.Keywords: photopolymerization, dimethacrylamide, the degree of conversion, compressive strength
Procedia PDF Downloads 1561129 Heterocyclic Ring Extension of Estrone: Synthesis and Cytotoxicity of Fused Pyrin, Pyrimidine and Thiazole Derivatives
Authors: Rafat M. Mohareb
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Several D-ring alkylated estrone analogues display exceptionally high affinity for estrogen receptors. In particular, compounds in which an E-ring is formed are known to be involved in the inhibition of steroidogenic enzymes. Such compounds also have an effect on steroid dehydrogenase activity and the ability to inhibit the detrimental action of the steroid sulfatase enzyme. Generally, E-ring extended steroids have been accessed by modification of the C17-ketone in the D-ring by either arylimine or oximino formation, addition of a carbon nucleophile or hydrazone formation. Other approaches have included ketone reduction, silyl enol ether formation or ring-closing metathesis (giving five- or six-membered E-rings). Chemical modification of the steroid D-ring provides a way to alter the functional groups, sizes and stereochemistry of the D-ring, and numerous structure-activity relationships have been established by such synthetic alterations. Steroids bearing heterocycles fused to the D-ring of the steroid nucleus have been of pharmaceutical interest. In the present paper, we report on the efficient synthesis of estrone possessing pyran, pyrimidine and thiazole ring systems. This study focused on the synthesis and biochemical evaluation of newly synthesized heterocyclic compounds which were then subjected through inhibitory evaluations towards human cancer and normal cell lines.Keywords: estrone, heterocyclization, cytotoxicity, biomedicine
Procedia PDF Downloads 2951128 Three-Dimensional Numerical Investigation for Reinforced Concrete Slabs with Opening
Authors: Abdelrahman Elsehsah, Hany Madkour, Khalid Farah
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This article presents a 3-D modified non-linear elastic model in the strain space. The Helmholtz free energy function is introduced with the existence of a dissipation potential surface in the space of thermodynamic conjugate forces. The constitutive equation and the damage evolution were derived as well. The modified damage has been examined to model the nonlinear behavior of reinforced concrete (RC) slabs with an opening. A parametric study with RC was carried out to investigate the impact of different factors on the behavior of RC slabs. These factors are the opening area, the opening shape, the place of opening, and the thickness of the slabs. And the numerical results have been compared with the experimental data from literature. Finally, the model showed its ability to be applied to the structural analysis of RC slabs.Keywords: damage mechanics, 3-D numerical analysis, RC, slab with opening
Procedia PDF Downloads 1741127 Research on the Effect of Coal Ash Slag Structure Evolution on Its Flow Behavior During Co-gasification of Coal and Indirect Coal Liquefaction Residue
Authors: Linmin Zhang
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Entrained-flow gasification technology is considered the most promising gasification technology because of its clean and efficient utilization characteristics. The stable fluidity of slag at high temperatures is the key to affecting the long-period operation of the gasifier. The diversity and differences of coal ash-slag systems make it difficult to meet the requirements for stable slagging in entrained-flow gasifiers. Therefore, coal blending or adding fluxes has been used in industry for a long time to improve the flow behavior of coal ash. As a by-product of the indirect coal liquefaction process, indirect coal liquefaction residue (ICLR) is a kind of industrial solid waste that is usually disposed of by stacking or landfilling. However, this disposal method will not only occupy land resources but also cause serious pollution to soil and water bodies by leachate containing toxic and harmful metals. As a carbon-containing matrix, ICLR is not only a kind of waste but also a kind of energy substance. Utilizing existing industrial gasifiers to blend combustion ICLR can not only transform industrial solid waste into fuel but also save coal resources. Moreover, the ICLR usually contains a unique ash chemical composition different from coal, which will affect the slagging performance of the gasifier. Therefore, exploring the effect of the ash addition in ICLR on the coal ash flow behavior can not only improve the slagging performance and gasification efficiency of entrained-flow gasifier by using the unique ash chemical composition of ICLR but also provide some theoretical support for the large-scale consumption of industrial solid waste. Combining molecular dynamics simulation with Raman spectroscopy experiment, the effect of ICLR addition on slag structure and fluidity was explained, and the relationship between the evolution law of slag short/medium range microstructure and macroscopic flow behavior was discussed. The research found that the high silicon and aluminum content in coal ash led to the formation of complex [SiO₄]⁴- tetrahedron and [AlO₄]⁵- tetrahedron structures at high temperature, and the [SiO₄]⁴- tetrahedron and [AlO₄]⁵- tetrahedron were connected by oxygen atoms to form a multi-membered ring structure with high polymerization degree. Due to the action of the multi-membered ring structure, the internal friction in the slag increased, and the viscosity value was higher on the macro-level. As a network-modified ion, Fe2+ could replace Si4+ and Al3+ in the multi-membered ring structure and combine with O2-, which will destroy the bridge oxygen (BO) structure and transform more complex tri cluster oxygen (TO) and bridge oxygen (BO) into simple non-bridge oxygen (NBO) structure. As a result, a large number of multi-membered rings with high polymerization degrees were depolymerized into low-membered rings with low polymerization degrees. The evolution of oxygen types and ring structures in slag reduced the structure complexity and polymerization degree of coal ash slag, resulting in a decrease in the viscosity of coal ash slag.Keywords: ash slag, coal gasification, fluidity, industrial solid waste, slag structure
Procedia PDF Downloads 291126 Highly Conductive Polycrystalline Metallic Ring in a Magnetic Field
Authors: Isao Tomita
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Electrical conduction in a quasi-one-dimensional polycrystalline metallic ring with a long electron phase coherence length realized at low temperature is investigated. In this situation, the wave nature of electrons is important in the ring, where the electrical current I can be induced by a vector potential that arises from a static magnetic field applied perpendicularly to the ring’s area. It is shown that if the average grain size of the polycrystalline ring becomes large (or comparable to the Fermi wavelength), the electrical current I increases to ~I0, where I0 is a current in a disorder-free ring. The cause of this increasing effect is examined, and this takes place if the electron localization length in the polycrystalline potential increases with increasing grain size, which gives rise to coherent connection of tails of a localized electron wave function in the ring and thus provides highly coherent electrical conduction.Keywords: electrical conduction, electron phase coherence, polycrystalline metal, magnetic field
Procedia PDF Downloads 3881125 Development of Forging Technology of Cam Ring Gear for Truck Using Small Bar
Authors: D. H. Park, Y. H. Tak, H. H. Kwon, G. J. Kwon, H. G. Kim
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This study focused on developing forging technology of a large-diameter cam ring gear from the small bar. The analyses of temperature variation and deformation behavior of the material are important to obtain the optimal forging products. The hot compression test was carried out to know formability at high temperature. In order to define the optimum forging conditions including material temperature, strain and forging load, the finite element method was used to simulate the forging process of cam ring gear parts. Test results were in good agreement with the simulations. An existing cam ring gear is presented the chips generated by cutting the rod material and the durability issues, but this would be to develop a large-diameter cam ring gear forging parts for truck in order to solve the durability problem and the material waste.Keywords: forging technology, cam ring, gear, truck, small bar
Procedia PDF Downloads 2971124 Frobenius Manifolds Pairing and Invariant Theory
Authors: Zainab Al-Maamari, Yassir Dinar
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The orbit space of an irreducible representation of a finite group is a variety with the ring of invariant polynomials as a coordinate ring. The invariant ring is a polynomial ring if and only if the representation is a reflection representation. Boris Dubrovin shows that the orbits spaces of irreducible real reflection representations acquire the structure of polynomial Frobenius manifolds. Dubrovin's method was also used to construct different examples of Frobenius manifolds on certain reflection representations. By successfully applying Dubrovin’s method on non-polynomial invariant rings of linear representations of dicyclic groups, it gives some results that magnify the relation between invariant theory and Frobenius manifolds.Keywords: invariant ring, Frobenius manifold, inversion, representation theory
Procedia PDF Downloads 981123 Synthesis and Gas Transport Properties of Polynorbornene Dicarboximides Bearing Trifluoromethyl Isomer Moieties
Authors: Jorge A. Cruz-Morales, Joel Vargas, Arlette A. Santiago, Mikhail A. Tlenkopatchev
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In industrial processes such as oil extraction and refining, products are handled or generated in the gas phase, which represents a challenge in terms of treatment and purification. During the past three decades, new scientific findings and technological advances in separation based on the use of membranes have led to simpler and more efficient gas separation processes, optimizing the use of energy and generating less pollution. This work reports the synthesis and ring-opening metathesis polymerization (ROMP) of new structural isomers based on norbornene dicarboximides bearing trifluoromethyl moieties, specifically N-2-trifluoromethylphenyl-exo,endo-norbornene-5,6-dicarboximide (2a) and N-3-trifluoromethylphenyl-exo,endo-norbornene-5,6-dicarboximide (2b), using tricyclohexylphosphine [1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][benzylidene] ruthenium dichloride (I), bis(tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride (II), and bis(tricyclohexylphosphine) p-fluorophenylvinylidene ruthenium (II) dichloride (III). It was observed that the -CF3 moiety attached at the ortho position of the aromatic ring increases thermal and mechanical properties of the polymer, whereas meta substitution has the opposite effect. A comparative study of gas transportation in membranes, based on these fluorinated polynorbornenes, showed that -CF3 ortho substitution increases permeability of the polymer membrane as a consequence of the increase in both gas solubility and gas diffusion. In contrast, gas permeability coefficients of the meta-substituted polymer membrane are rather similar to those of that which is non-fluorinated; this can be attributed to a lower fractional free volume. The meta-substituted polymer membrane, besides showing the largest permselectivity coefficients of all the isomers studied here, was also found to have one of the largest permselectivity coefficients for separating H2/C3H6 into glassy polynorbornene dicarboximides.Keywords: gas transport membranes, polynorbornene dicarboximide, ROMP, structural isomers
Procedia PDF Downloads 2541122 Investigation of Film and Mechanical Properties of Poly(Lactic Acid)
Authors: Reyhan Özdoğan, Özgür Ceylan, Mehmet Arif Kaya, Mithat Çelebi
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Food packaging is important for the food industry. Bioplastics have been used as food packaging materials. According to the European Bioplastics organization, bioplastics can be defined as plastics based on renewable resources (bio-based) or as plastics which are biodegradable and/or compostable. Poly(lactic acid) (PLA) has an industrially importance of bioplastic polymers. PLA is a family of biodegradable thermoplastic polyester made from renewable resources. It is produced by conversion of corn, or other carbohydrate sources, into dextrose, followed by fermentation into lactic acid through direct polycondensation of lactic acid monomers or through ring-opening polymerization of lactide. The processing possibilities of this transparent material are very wide, ranging from injection molding and extrusion over cast film extrusion to blow molding and thermoforming. In this study, PLA films were prepared by solution casting method. PLAs which are different molecular weights were plasticized with glycerol and the morphology of films was monitored by optical microscopy. Properties of mechanical and film of PLA were researched with the mechanical testing machine.Keywords: biodegradable, bioplastics, morphology, solution casting, poly(lactic acid)
Procedia PDF Downloads 3781121 Analysis of Road Network Vulnerability Due to Merapi Volcano Eruption
Authors: Imam Muthohar, Budi Hartono, Sigit Priyanto, Hardiansyah Hardiansyah
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The eruption of Merapi Volcano in Yogyakarta, Indonesia in 2010 caused many casualties due to minimum preparedness in facing disaster. Increasing population capacity and evacuating to safe places become very important to minimize casualties. Regional government through the Regional Disaster Management Agency has divided disaster-prone areas into three parts, namely ring 1 at a distance of 10 km, ring 2 at a distance of 15 km and ring 3 at a distance of 20 km from the center of Mount Merapi. The success of the evacuation is fully supported by road network infrastructure as a way to rescue in an emergency. This research attempts to model evacuation process based on the rise of refugees in ring 1, expanded to ring 2 and finally expanded to ring 3. The model was developed using SATURN (Simulation and Assignment of Traffic to Urban Road Networks) program version 11.3. 12W, involving 140 centroid, 449 buffer nodes, and 851 links across Yogyakarta Special Region, which was aimed at making a preliminary identification of road networks considered vulnerable to disaster. An assumption made to identify vulnerability was the improvement of road network performance in the form of flow and travel times on the coverage of ring 1, ring 2, ring 3, Sleman outside the ring, Yogyakarta City, Bantul, Kulon Progo, and Gunung Kidul. The research results indicated that the performance increase in the road networks existing in the area of ring 2, ring 3, and Sleman outside the ring. The road network in ring 1 started to increase when the evacuation was expanded to ring 2 and ring 3. Meanwhile, the performance of road networks in Yogyakarta City, Bantul, Kulon Progo, and Gunung Kidul during the evacuation period simultaneously decreased in when the evacuation areas were expanded. The results of preliminary identification of the vulnerability have determined that the road networks existing in ring 1, ring 2, ring 3 and Sleman outside the ring were considered vulnerable to the evacuation of Mount Merapi eruption. Therefore, it is necessary to pay a great deal of attention in order to face the disasters that potentially occur at anytime.Keywords: model, evacuation, SATURN, vulnerability
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