Search results for: crosslinked copolymers

Authors: Lucas Kurth de Azambuja, Loise Silveira da Silva, Gean Vitor Salmoria, Darlan Dallacosta, Carlos Rodrigo de Mello Roesler

Abstract:

This work provides a physicochemical and thermal characterization assessment of three different hyaluronic acid (HA)-based injections used for rejuvenation skin treatments. The three products analyzed are manufactured by the same manufacturer and commercialized for application on different skin levels. According to the manufacturer, all three HA-based injections are crosslinked and have a concentration of 23 mg/mL of HA, and 0.3% of lidocaine. Samples were characterized by Fourier-transformed infrared (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and scanning electron microscope (SEM) techniques. FTIR analysis resulted in a similar spectrum when comparing the different products. DSC analysis demonstrated that the fusion points differ in each product, with a higher fusion temperature observed in specimen A, which is used for subcutaneous applications, when compared with B and C, which are used for the middle dermis and deep dermis, respectively. TGA data demonstrated a considerable mass loss at 100°C, which means that the product has more than 50% of water in its composition. TGA analysis also showed that Specimen A had a lower mass loss at 100°C when compared to Specimen C. A mass loss of around 220°C was observed on all samples, characterizing the presence of hyaluronic acid. SEM images displayed a similar structure on all samples analyzed, with a thicker layer for Specimen A when compared with B and C. This series of analyses demonstrated that, as expected, the physicochemical and thermal properties of the products differ according to their application. Furthermore, to better characterize the crosslinking degree of each product and their mechanical properties, a set of different techniques should be applied in parallel to correlate the results and, thereby, relate injection application with material properties.

Keywords: hyaluronic acid, characterization, soft-tissue fillers, injectable gels

Procedia PDF Downloads 71

Authors: Salma E. Ahmed

Abstract:

Since the mid 50’s, enormous attention has been paid towards nanocarriers and their applications in drug and gene delivery. Among these vesicles, liposomes and micelles have been heavily investigated due to their many advantages over other types. Liposomes, for instance, are mostly distinguished by their ability to encapsulate hydrophobic, hydrophilic and amphiphilic drugs. Micelles, on the other hand, are self-assembled shells of lipids, amphiphilic or oppositely charged block copolymers that, once exposed to aqueous media, can entrap hydrophobic agents, and possess prolonged circulation in the bloodstream. Both carriers are considered compatible and biodegradable. Nevertheless, they have limited stabilities, chemical versatilities, and drug encapsulation efficiencies. In order to overcome these downsides, strategies for optimizing a novel drug delivery system that has the architecture of liposomes and polymeric characteristics of micelles have been evolved. Polymersomes are vehicles with fluidic cores and hydrophobic shells that are protected and isolated from the aqueous media by the hydrated hydrophilic brushes which give the carrier its distinctive polymeric bilayer shape. Similar to liposomes, this merit enables the carrier to encapsulate a wide range of agents, despite their affinities and solubilities in water. Adding to this, the high molecular weight of the amphiphiles that build the body of the polymersomes increases their colloidal and chemical stabilities and reduces the permeability of the polymeric membranes, which makes the vesicles more protective to the encapsulated drug. These carriers can also be modified in ways that make them responsive when targeted or triggered, by manipulating their composition and attaching moieties and conjugates to the body of the carriers. These appealing characteristics, in addition to the ease of synthesis, gave the polymersomes greater potentials in the area of drug delivery. Thus, their design and characterization, in comparison with liposomes and micelles, are briefly reviewed in this work.

Keywords: controlled release, liposomes, micelles, polymersomes, targeting

Procedia PDF Downloads 170

Authors: Dafna Knani, Sarit S. Sivan

Abstract:

Aggrecan, one of the main components of the intervertebral disc (IVD), belongs to the family of proteoglycans (PGs) that are composed of glycosaminoglycan (GAG) chains covalently attached to a core protein. Its primary function is to maintain tissue hydration and hence disc height under the high loads imposed by muscle activity and body weight. Significant PG loss is one of the first indications of disc degeneration. A possible solution to recover disc functions is by injecting a synthetic hydrogel into the joint cavity, hence mimicking the role of PGs. One of the hydrogels proposed is GAG-analogues, based on sulfate-containing polymers, which are responsible for hydration in disc tissue. In the present work, we used molecular dynamics (MD) to study the effect of the hydrogel crosslinking (type and degree) on the swelling behavior of the suggested GAG-analogue biomimetics by calculation of cohesive energy density (CED), solubility parameter, enthalpy of mixing (ΔEmix) and the interactions between the molecules at the pure form and as a mixture with water. The simulation results showed that hydrophobicity plays an important role in the swelling of the hydrogel, as indicated by the linear correlation observed between solubility parameter values of the copolymers and crosslinker weight ratio (w/w); this correlation was found useful in predicting the amount of PEGDA needed for the desirable hydration behavior of (CS)₄-peptide. Enthalpy of mixing calculations showed that all the GAG analogs, (CS)₄ and (CS)₄-peptide are water-soluble; radial distribution function analysis revealed that they form interactions with water molecules, which is important for the hydration process. To conclude, our simulation results, beyond supporting the experimental data, can be used as a useful predictive tool in the future development of biomaterials, such as disc replacement.

Keywords: molecular dynamics, proteoglycans, enthalpy of mixing, swelling

Procedia PDF Downloads 48

Authors: Soney C. George, Thomasukutty Jose, Sabu Thomas

Abstract:

Membrane based separation is the most important energy –efficient separation processes. There are wide ranges of membrane based separation process such as Micro-filtration, ultra filtration, reverse osmosis, electro-dialysis etc. Among these pervaporation is one of the most promising techniques. The promising technique is in the sense that it needs an ease of process design, low energy consumption, environmentally clean, economically cost effective and easily separate azeotropic composition without losing any components, unlike distillation in a short period of time. In the present work, we developed a new bentonite clay reinforced cross-linked PVA nano-composite membranes by solution casting method. The membranes were used for the pervaporation separation of azeotropic composition of isopropanol and water mixtures. The azeotropic composition of water and isopropanol is difficult to separate and we can’t get a better separation by normal separation processes. But the better separation was achieved here using cross-linked PVA/Clay nano-composite membranes. The 2wt% bentonite clay reinforced 5vol% GA cross-linked nano-composite membranes showed better separation efficiency. The selectivity of the cross-linked membranes increases 65% upon filler loading. The water permeance is showed tremendous enhancement upon filler loading. The permeance value changes from 4100 to 8200, due to the incorporation hydrophilic bentonite clay to the cross-linked PVA membranes. The clay reinforced membranes shows better thermal stability upon filler loading was confirmed from TGA and DSC analysis. The dispersion of nanoclay in the polymeric matrix was clearly evident from the TEM analysis. The better dispersed membranes showed better separation performance. Thus the developed cross-linked PVA/Clay membranes can be effectively used for the separation of azeotropic composition of water and isopropanol.

Keywords: poly(vinyl alcohol), membrane, gluraldehyde, permeance

Procedia PDF Downloads 281

Authors: Rui He, Seung-Eun Baik, Min-Jae Lee, Myong-Hoon Lee

Abstract:

The polarizer is one of the most essential optical elements in LCDs. Currently, the most widely used polarizers for LCD is the derivatives of the H-sheet polarizer. There is a need for coatable polarizers which are much thinner and more stable than H-sheet polarizers. One possible approach to obtain thin, stable, and coatable polarizers is based on the use of highly ordered guest-host system. In our research, we aimed to fabricate coatable polarizer based on highly ordered liquid crystalline monomer and dichroic dye ‘guest-host’ system, in which the anisotropic absorption of light could be achieved by aligning a dichroic dye (guest) in the cooperative motion of the ordered liquid crystal (host) molecules. Firstly, we designed and synthesized a new reactive liquid crystalline monomer containing polymerizable acrylate groups as the ‘host’ material. The structure was confirmed by 1H-NMR and IR spectroscopy. The liquid crystalline behavior was studied by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). It was confirmed that the monomers possess highly ordered smectic phase at relatively low temperature. Then, the photocurable ‘guest-host’ system was prepared by mixing the liquid crystalline monomer, dichroic dye and photoinitiator. Coatable polarizers were fabricated by spin-coating above mixture on a substrate with alignment layer. The in-situ photopolymerization was carried out at room temperature by irradiating UV light, resulting in the formation of crosslinked structure that stabilized the aligned dichroic dye molecules. Finally, the dichroic ratio (DR), order parameter (S) and polarization efficiency (PE) were determined by polarized UV/Vis spectroscopy. We prepared the coatable polarizers by using different type of dichroic dyes to meet the requirement of display application. The results reveal that the coatable polarizers at a thickness of 8μm exhibited DR=12~17 and relatively high PE (>96%) with the highest PE=99.3%, which possess potential for the LCD or flexible display applications.

Keywords: coatable polarizer, display, guest-host, liquid crystal

Procedia PDF Downloads 233

Authors: Susmita Roy, Madhavan Nallani

Abstract:

In recent years' polymersomes, self-assembled polymeric vesicles emerge from block copolymers, have been widely investigated due to their enhance stability and unique advantageous properties compared to their phospholipid counterpart, liposomes, dendrimers, and micelles. It provides a distinctive platform for advanced therapeutics and the creation of complex (bio) catalytically active systems for research in Nanomedicine and synthetic biology. Inspired by nature, where compartmentalization of biological components is all ubiquitous, we are interested in developing a platform technology of self-assembled multifunctional compartments with applications in areas from targeted drug/gene delivery, biosensing, pharmaceutical to cosmetics. Polymersome surfaces can be a proper choice of derivatization with a controlled amount of functional groups. To achieve site-specific targeting of polymersomes, biological recognition motives can be attached to the polymersomes surface by standard bioconjugation techniques, (like esterification, amidation, thiol-maleimide coupling, click-chemistry routes or other coupling methods). Herein, we are developing easy going, one-step bioconjugation strategies for site-specific surface functionalized biodegradable polymeric and/or polymer-lipid hybrid vesicles for targeted drug delivery. Biodegradable polymer, polycaprolactone-b-polyethylene glycol (PCL-PEG), polylactic acid-b-polyethylene glycol (PLA-PEG) and phospholipid, 1-palmitoyl-2- oleoyl-sn-glycero-3-phosphocholine (POPC) has been widely used for numerous vesicle formulations. Some of these drug-loaded formulations are being tested on mice for controlled release. These surface functionalized polymersomes are also appropriate for membrane protein reconstitution/insertion, antibodies conjugation and various bioconjugation with diverse targeted molecules for controlled drug delivery.

Keywords: drug delivery, membrane protein, polymersome, surface modification

Procedia PDF Downloads 135

Authors: Ragi Poyyara, Vijaya Patnana, Mohammed Alam

Abstract:

When acid is pumped into damaged reservoirs for damage removal/stimulation, distorted inflow of acid into the formation occurs caused by acid preferentially traveling into highly permeable regions over low permeable regions, or (in general) into the path of least resistance. This can lead to poor zonal coverage and hence warrants diversion to carry out an effective placement of acid. Diversion is desirably a reversible technique of temporarily reducing the permeability of high perm zones, thereby forcing the acid into lower perm zones. The uniqueness of each reservoir can pose several challenges to engineers attempting to devise optimum and effective diversion strategies. Diversion techniques include mechanical placement and/or chemical diversion of treatment fluids, further sub-classified into ball sealers, bridge plugs, packers, particulate diverters, viscous gels, crosslinked gels, relative permeability modifiers (RPMs), foams, and/or the use of placement techniques, such as coiled tubing (CT) and the maximum pressure difference and injection rate (MAPDIR) methodology. It is not always realized that the effectiveness of diverters greatly depends on reservoir properties, such as formation type, temperature, reservoir permeability, heterogeneity, and physical well characteristics (e.g., completion type, well deviation, length of treatment interval, multiple intervals, etc.). This paper reviews the mechanisms by which each variety of diverter functions and discusses the effect of various reservoir properties on the efficiency of diversion techniques. Guidelines are recommended to help enhance productivity from zones of interest by choosing the best methods of diversion while pumping an optimized amount of treatment fluid. The success of an overall acid treatment often depends on the effectiveness of the diverting agents.

Keywords: diversion, reservoir, zonal coverage, carbonate, sandstone

Procedia PDF Downloads 396

Authors: R. S. Komartin, B. Balanuca, R. Stan

Abstract:

the last decades, studies about the use of polymeric materials of plant origin, considering environmental concerns, have captured the interest of researchers because these represent an alternative to petroleum-derived materials. Vegetable oils are one of the preferred alternatives for petroleum-based raw materials having long aliphatic chains similar to hydrocarbons which means that can be processed using conventional chemistry. Epoxidized vegetable oils (EVO) are among the most interesting products derived from oil both for their high reactivity (epoxy group) and for the potential to react with compounds from various classes. As in the case of epoxy resins starting from petrochemical raw materials, those obtained from EVO can be crosslinked with different agents to build polymeric networks and can also be reinforced with various additives to improve their thermal and mechanical performances. Among the multitude of known EVO, the most common in industrial practice are epoxidized linseed oils (ELO) and epoxidized soybean oils (ESO), the first with an iodine index over 180, the second having a lower iodine index but being cheaper. On the other hand, lignin (Ln) is the second natural organic material as a spread, whose use has long been hampered because of the high costs associated with its isolation and purification. In this context, our goal was to obtain new composite materials with satisfactory intermediate properties in terms of stiffness and elasticity using the characteristics of ELO and Ln and choosing the proper curing procedure. In the present study linseed oil (LO) epoxidation was performed using peracetic acid generated in situ. The obtained bio-based epoxy resin derived from linseed oil was used further to produce the new composites byloading Ln in various mass ratios. The resulted ELO-Ln blends were subjected to a dual-curing protocol, namely photochemical and thermal. The new ELO-Ln composites were investigated by FTIR spectrometry, thermal stability, water affinity, and morphology. The positive effect of lignin regarding the thermal stability of the composites could be proved. The results highlight again the still largely unexplored potential of lignin in industrial applications.

Keywords: composite materials, dual curing, epoxidized linseed oil, lignin

Procedia PDF Downloads 135

Authors: Selim Kara, Ertan Arda, Fahrettin Dolastir, Önder Pekcan

Abstract:

Biomaterials and thin film coatings play a fundamental role in medical, food and pharmaceutical industries. Carrageenan is a linear sulfated polysaccharide extracted from algae and seaweeds. To date, such biomaterials have been used in many smart drug delivery systems due to their biocompatibility and antimicrobial activity properties. Poly (N-isopropylacrylamide) (PNIPAm) gels and copolymers have also been used in medical applications. PNIPAm shows lower critical solution temperature (LCST) property at about 32-34 °C which is very close to the human body temperature. Below and above the LCST point, PNIPAm gels exhibit distinct phase transitions between swollen and collapsed states. A special class of gels are microgels which can react to environmental changes significantly faster than microgels due to their small sizes. Quartz crystal microbalance (QCM) measurement technique is one of the attractive techniques which has been used for monitoring the thin-film formation process. A sensitive QCM system was designed as to detect 0.1 Hz difference in resonance frequency and 10-7 change in energy dissipation values, which are the measures of the deposited mass and the film rigidity, respectively. PNIPAm microgels with the diameter around few hundred nanometers in water were produced via precipitation polymerization process. 5 MHz quartz crystals with functionalized gold surfaces were used for the deposition of the carrageenan molecules and microgels in the solutions which were slowly pumped through a flow cell. Interactions between charged carrageenan and microgel particles were monitored during the formation of the film layers, and the Sauerbrey masses of the deposited films were calculated. The critical phase transition temperatures around the LCST were detected during the heating and cooling cycles. It was shown that it is possible to monitor the interactions between PNIPAm microgels and biopolymer molecules, and it is also possible to specify the critical phase transition temperatures by using a QCM system.

Keywords: carrageenan, phase transitions, PNIPAm microgels, quartz crystal microbalance (QCM)

Procedia PDF Downloads 206

Authors: Supriya Gupta, Paresh Chokshi

Abstract:

Polymer-particle interactions can be effectively utilized to produce composites that possess physicochemical properties superior to that of neat polymer. The incorporation of fillers with dimensions comparable to polymer chain size produces composites with extra-ordinary properties owing to very high surface to volume ratio. The dispersion of nanoparticles is achieved by inducing steric repulsion realized by grafting particles with polymeric chains. A comprehensive understanding of the interparticle interaction between these functionalized nanoparticles plays an important role in the synthesis of a stable polymer nanocomposite. With the focus on incorporation of clay sheets in a polymer matrix, we theoretically construct the polymer mediated interparticle potential for two nanosheets grafted with polymeric chains. The self-consistent field theory (SCFT) is employed to obtain the inhomogeneous composition field under equilibrium. Unlike the continuum models, SCFT is built from the microscopic description taking in to account the molecular interactions contributed by both intra- and inter-chain potentials. We present the results of SCFT calculations of the interaction potential curve for two grafted nanosheets immersed in the matrix of polymeric chains of dissimilar chemistry to that of the grafted chains. The interaction potential is repulsive at short separation and shows depletion attraction for moderate separations induced by high grafting density. It is found that the strength of attraction well can be tuned by altering the compatibility between the grafted and the mobile chains. Further, we construct the interaction potential between two nanosheets grafted with diblock copolymers with one of the blocks being chemically identical to the free polymeric chains. The interplay between the enthalpic interaction between the dissimilar species and the entropy of the free chains gives rise to a rich behavior in interaction potential curve obtained for two separate cases of free chains being chemically similar to either the grafted block or the free block of the grafted diblock chains.

Keywords: clay nanosheets, polymer brush, polymer nanocomposites, self-consistent field theory

Procedia PDF Downloads 231

Authors: G. Krishnamoorthy, S. Anandhakumar

Abstract:

The effect of D-Lysine (D-Lys) on collagen with 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide(EDC)/N-hydroxysuccinimide(NHS) initiated cross linking using experimental and modelling tools are evaluated. The results of the Coll-D-Lys-EDC/NHS scaffold also indicate an increase in the tensile strength (TS), percentage of elongation (% E), denaturation temperature (Td), and decrease the decomposition rate compared to L-Lys-EDC/NHS. Scanning electron microscopic (SEM) and atomic force microscopic (AFM) analyses revealed a well ordered with properly oriented and well-aligned structure of scaffold. The D-Lys stabilizes the scaffold against degradation by collagenase than L-Lys. The cell assay showed more than 98% fibroblast viability (NIH3T3) and improved cell adhesions, protein adsorption after 72h of culture when compared with native scaffold. Cell attachment after 74h was robust, with cytoskeletal analysis showing that the attached cells were aligned along the fibers assuming a spindle-shape appearance, despite, gene expression analyses revealed no apparent alterations in mRNA levels, although cell proliferation was not adversely affected. D-Lysine (D-Lys) plays a pivotal role in the self-assembly and conformation of collagen fibrils. The D-Lys assisted EDC/NHS initiated cross-linking induces the formation of an carboxamide by the activation of the side chain -COOH group, followed by aminolysis of the O-iso acylurea intermediates by the -NH2 groups are directly joined via an isopeptides bond. This leads to the formation of intra- and inter-helical cross links. Modeling studies indicated that D-Lys bind with collagen-like peptide (CLP) through multiple H-bonding and hydrophobic interactions. Orientational changes in collagenase on CLP-D-Lys are observed which may decrease its accessibility to degradation and stabilize CLP against the action of the former. D-Lys has lowest binding energy and improved fibrillar-assembly and staggered alignment without the undesired structural stiffness and aggregations. The proteolytic machinery is not well equipped to deal with Coll-D-Lys than Coll-L-Lys scaffold. The information derived from the present study could help in designing collagenolytically stable heterochiral collagen based scaffold for biomedical applications.

Keywords: collagen, collagenase, collagen like peptide, D-lysine, heterochiral collagen scaffold

Procedia PDF Downloads 369

Authors: Ujjawal Kumar Bhagat, Kamaluddin, Rama Krishna Peddinti

Abstract:

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

Procedia PDF Downloads 297

Authors: Mauricio A. Sarabia-Vallejos, Carmen M. Gonzalez-Henriquez, Adolfo Del Campo-Garcia, Aitzibier L. Cortajarena, Juan Rodriguez-Hernandez

Abstract:

In this study, it was explored the formation and the morphological differences between wrinkled hydrogel patterns obtained via generation of surface instabilities. The slight variations in the polymerization conditions produce important changes in the material composition and pattern structuration. The compounds were synthesized using three main components, i.e. an amphiphilic monomer, hydroxyethyl methacrylate (HEMA), a hydrophobic monomer, trifluoroethyl methacrylate (TFMA), and a hydrophilic crosslinking agent, poly(ethylene glycol) diacrylate (PEGDA). The first part of this study was related to the formation of wrinkled surfaces using only HEMA and PEGDA and varying the amount of water added in the reaction. The second part of this study involves the gradual insertion of TFMA into the hydrophilic reaction mixture. Interestingly, the manipulation of the chemical composition of this hydrogel affects both surface morphology and physicochemical characteristics of the patterns, inducing transitions from one particular type of structure (wrinkles or ripples) to different ones (creases, folds, and crumples). Contact angle measurements show that the insertion of TFMA produces a slight decrease in surface wettability of the samples, remaining however highly hydrophilic (contact angle below 45°). More interestingly, by using confocal Raman spectroscopy, important information about the wrinkle formation mechanism is obtained. The procedure involving two consecutive thermal and photopolymerization steps lead to a “pseudo” two-layer system. Thus, upon photopolymerization, the surface is crosslinked to a higher extent than the bulk and water evaporation drives the formation of wrinkled surfaces. Finally, cellular, and bacterial proliferation studies were performed to the samples, showing that the amount of TFMA included in each sample slightly affects the proliferation of both (bacteria and cells), but in the case of bacteria, the morphology of the sample also plays an important role, importantly reducing the bacterial proliferation.

Keywords: antibiofouling properties, hydrophobic/hydrophilic balance, morphologic characterization, wrinkled hydrogel patterns

Procedia PDF Downloads 136

Authors: Mohamed H. Sorour, Hayam F. Shaalan, Heba A. Hani, Eman S. Sayed

Abstract:

Ion exchange adsorption has a long standing history of success for seawater softening and selective ion removal from saline sources. Strong, weak and mixed types ion exchange systems could be designed and optimized for target separation. In this paper, different types of adsorbents comprising zeolite 13X and kaolin, in addition to, poly acrylate/zeolite (AZ), poly acrylate/kaolin (AK) and stand-alone poly acrylate (A) hydrogel types were prepared via microwave (M) and ultrasonic (U) irradiation techniques. They were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The developed adsorbents were evaluated on bench scale level and based on assessment results, a composite bed has been formulated for performance evaluation in pilot scale column investigations. Owing to the hydrogel nature of the partially crosslinked poly acrylate, the developed adsorbents manifested a swelling capacity of about 50 g/g. The pilot trials have been carried out using magnesium enriched Red Seawater to simulate Red Seawater desalination brine. Batch studies indicated varying uptake efficiencies, where Mg adsorption decreases according to the following prepared hydrogel types AU>AM>AKM>AKU>AZM>AZU, being 108, 107, 78, 69, 66 and 63 mg/g, respectively. Composite bed adsorbent tested in the up-flow mode column studies indicated good performance for Mg uptake. For an operating cycle of 12 h, the maximum uptake during the loading cycle approached 92.5-100 mg/g, which is comparable to the performance of some commercial resins. Different regenerants have been explored to maximize regeneration and minimize the quantity of regenerants including 15% NaCl, 0.1 M HCl and sodium carbonate. Best results were obtained by acidified sodium chloride solution. In conclusion, developed cation exchange adsorbents comprising clay or zeolite support indicated adequate performance for Mg recovery under saline environment. Column design operated at the up-flow mode (approaching expanded bed) is appropriate for such type of separation. Preliminary cost indicators for Mg recovery via ion exchange have been developed and analyzed.

Keywords: batch and dynamic magnesium separation, seawater, polyacrylate hydrogel, cost evaluation

Procedia PDF Downloads 115

Authors: Vanda Ferreira Ribeiro, Daiane Tomacheski, Douglas Naue Simões, Michele Pitto, Ruth Marlene Campomanes Santana

Abstract:

Indoor environments, such as car cabins and public transportation vehicles are places where users are subject to air quality. Microorganisms (bacteria, fungi, yeasts) enter these environments through windows, ventilation systems and may use the organic particles present as a growth substrate. In addition, atmospheric pollutants can act as potential carbon and nitrogen sources for some microorganisms. Compounds base SEBS copolymers, poly(styrene-b-(ethylene-co-butylene)-b-styrene, are a class of thermoplastic elastomers (TPEs), fully recyclable and largely used in automotive parts. Metals, such as cooper and silver, have biocidal activities and the production of the SEBS compounds by melting blending with these agents can be a good option for producing compounds for use in plastic parts of ventilation systems and automotive air-conditioning, in order to minimize the problems caused by growth of pathogenic microorganisms. In this sense, the aim of this work was to evaluate the effect of copper microparticles as antimicrobial agent in compositions based on SEBS/PP/oil/calcite. Copper microparticles were used in weight proportion of 0%, 1%, 2% and 4%. The compounds were prepared using a co-rotating double screw extruder (L/D ratio of 40/1 and 16 mm screw diameter). The processing parameters were 300 rpm of screw rotation rate, with a temperature profile between 150 to 190°C. SEBS based TPE compounds were injection molded. The compounds emission were characterized by gravimetric fogging test. Compounds were characterized by physical (density and staining by contact), mechanical (hardness and tension properties) and rheological properties (melt volume rate – MVR). Antibacterial properties were evaluated against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) strains. To avaluate the abilities toward the fungi have been chosen Aspergillus niger (A. niger), Candida albicans (C. albicans), Cladosporium cladosporioides (C. cladosporioides) and Penicillium chrysogenum (P. chrysogenum). The results of biological tests showed a reduction on bacteria in up to 88% in E.coli and up to 93% in S. aureus. The tests with fungi showed no conclusive results because the sample without copper also demonstrated inhibition of the development of these microorganisms. The copper addition did not cause significant variations in mechanical properties, in the MVR and the emission behavior of the compounds. The density increases with the increment of copper in compounds.

Keywords: air conditioner, antimicrobial, cooper, SEBS

Procedia PDF Downloads 253

Authors: Yihenew Simegniew Birhan, Hsieh Chih Tsai

Abstract:

The recent advancements in synthetic chemistry and nanotechnology fostered the development of different nanocarriers for enhanced intracellular delivery of pharmaceutical agents to tumor cells. Polymeric micelles (PMs), characterized by small size, appreciable drug loading capacity (DLC), better accumulation in tumor tissue via enhanced permeability and retention (EPR) effect, and the ability to avoid detection and subsequent clearance by the mononuclear phagocyte (MNP) system, are convenient to improve the poor solubility, slow absorption and non-selective biodistribution of payloads embedded in their hydrophobic cores and hence, enhance the therapeutic efficacy of chemotherapeutic agents. Recently, redox-responsive polymeric micelles have gained significant attention for the delivery and controlled release of anticancer drugs in tumor cells. In this study, we synthesized redox-responsive diselenide bond containing amphiphilic polymer, Bi(mPEG-PLGA)-Se₂ from mPEG-PLGA, and 3,3'-diselanediyldipropanoic acid (DSeDPA) using DCC/DMAP as coupling agents. The successful synthesis of the copolymers was verified by different spectroscopic techniques. Above the critical micelle concentration, the amphiphilic copolymer, Bi(mPEG-PLGA)-Se₂, self-assembled into stable micelles. The DLS data indicated that the hydrodynamic diameter of the micelles (123.9 ± 0.85 nm) was suitable for extravasation into the tumor cells through the EPR effect. The drug loading content (DLC) and encapsulation efficiency (EE) of DOX-loaded micelles were found to be 6.61 wt% and 54.9%, respectively. The DOX-loaded micelles showed initial burst release accompanied by sustained release trend where 73.94% and 69.54% of encapsulated DOX was released upon treatment with 6mM GSH and 0.1% H₂O₂, respectively. The biocompatible nature of Bi(mPEG-PLGA)-Se₂ copolymer was confirmed by the cell viability study. In addition, the DOX-loaded micelles exhibited significant inhibition against HeLa cells (44.46%), at a maximum dose of 7.5 µg/mL. The fluorescent microscope images of HeLa cells treated with 3 µg/mL (equivalent DOX concentration) revealed efficient internalization and accumulation of DOX-loaded Bi(mPEG-PLGA)-Se₂ micelles in the cytosol of cancer cells. In conclusion, the intelligent, biocompatible, and the redox stimuli-responsive behavior of Bi(mPEG-PLGA)-Se₂ copolymer marked the potential applications of diselenide-linked mPEG-PLGA micelles for the delivery and on-demand release of chemotherapeutic agents in cancer cells.

Keywords: anticancer drug delivery, diselenide bond, polymeric micelles, redox-responsive

Procedia PDF Downloads 88

Authors: Douglas N. Simoes, Michele Pittol, Vanda F. Ribeiro, Daiane Tomacheski, Ruth M. C. Santana

Abstract:

Thermoplastic elastomers (TPE) compounds are used in a wide range of applications, like home appliances, automotive components, medical devices, footwear, and others. These materials are susceptible to microbial attack, causing a crack in polymer chains compounds based on SEBS copolymers, poly (styrene-b-(ethylene-co-butylene)-b-styrene, are a class of TPE, largely used in domestic appliances like refrigerator seals (gaskets), bath mats and sink squeegee. Moisture present in some areas (such as shower area and sink) in addition to organic matter provides favorable conditions for microbial survival and proliferation, contributing to the spread of diseases besides the reduction of product life cycle due the biodegradation process. Zinc oxide (ZnO) has been studied as an alternative antibacterial additive due its biocidal effect. It is important to know the influence of these additives in the properties of the compounds, both at the beginning and during the life cycle. In that sense, the aim of this study was to evaluate the effect of accelerated aging in oven on antibacterial and mechanical properties of ZnO loaded SEBS based TPE compounds. Two different comercial zinc oxide, named as WR and Pe were used in proportion of 1%. A compound with no antimicrobial additive (standard) was also tested. The compounds were prepared using a co-rotating double screw extruder (L/D ratio of 40/1 and 16 mm screw diameter). The extrusion parameters were kept constant for all materials, screw rotation rate was set at 226 rpm, with a temperature profile from 150 to 190 ºC. Test specimens were prepared using the injection molding machine at 190 ºC. The Standard Test Method for Rubber Property—Effect of Liquids was applied in order to simulate the exposition of TPE samples to detergent ingredients during service. For this purpose, ZnO loaded TPE samples were immersed in a 3.0% w/v detergent (neutral) and accelerated aging in oven at 70°C for 7 days. Compounds were characterized by changes in mechanical (hardness and tension properties) and mass. The Japan Industrial Standard (JIS) Z 2801:2010 was applied to evaluate antibacterial properties against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). The microbiological tests showed a reduction up to 42% in E. coli and up to 49% in S. aureus population in non-aged samples. There were observed variations in elongation and hardness values with the addition of zinc The changes in tensile at rupture and mass were not significant between non-aged and aged samples.

Keywords: antimicrobial, domestic appliance, sebs, zinc oxide

Procedia PDF Downloads 227

Authors: Majid Farsadrouh Rashti, Alireza Mohammadinejad, Amir Shafiee Kisomi

Abstract:

Lead (Pb²⁺), a cation, is a prime constituent of the majority of the industrial effluents such as mining, smelting and coal combustion, Pb-based painting and Pb containing pipes in water supply systems, paper and pulp refineries, printing, paints and pigments, explosive manufacturing, storage batteries, alloy and steel industries. The maximum permissible limit of lead in the water used for drinking and domesticating purpose is 0.01 mg/L as advised by Bureau of Indian Standards, BIS. This becomes the acceptable 'safe' level of lead(II) ions in water beyond which, the water becomes unfit for human use and consumption, and is potential enough to lead health problems and epidemics leading to kidney failure, neuronal disorders, and reproductive infertility. Superabsorbent hydrogels are loosely crosslinked hydrophilic polymers that in contact with aqueous solution can easily water and swell to several times to their initial volume without dissolving in aqueous medium. Superabsorbents are kind of hydrogels capable to swell and absorb a large amount of water in their three-dimensional networks. While the shapes of hydrogels do not change extensively during swelling, because of tremendously swelling capacity of superabsorbent, their shape will broadly change.Because of their superb response to changing environmental conditions including temperature pH, and solvent composition, superabsorbents have been attracting in numerous industrial applications. For instance, water retention property and subsequently. Natural-based superabsorbent hydrogels have attracted much attention in medical pharmaceutical, baby diapers, agriculture, and horticulture because of their non-toxicity, biocompatibility, and biodegradability. Novel superabsorbent hydrogel nanocomposites were prepared by graft copolymerization of acrylamide and itaconic acid in the presence of nanoclay (laponite), using methylene bisacrylamide (MBA) and potassium persulfate, former as a crosslinking agent and the second as an initiator. The superabsorbent hydrogel nanocomposites structure was characterized by FTIR spectroscopy, SEM and TGA Spectroscopy adsorption of metal ions on poly (AAm-co-IA). The equilibrium swelling values of copolymer was determined by gravimetric method. During the adsorption of metal ions on polymer, residual metal ion concentration in the solution and the solution pH were measured. The effects of the clay content of the hydrogel on its metal ions uptake behavior were studied. The NC hydrogels may be considered as a good candidate for environmental applications to retain more water and to remove heavy metals.

Keywords: adsorption, hydrogel, nanocomposite, super adsorbent

Procedia PDF Downloads 165

Authors: Hassiba Benguergoura, Kamal Chanane, Sâad Moulay

Abstract:

Pervaporation (PV), a membrane-based separation technology, has gained much attention because of its energy saving capability and low-cost, especially for separation of azeotropic or close-boiling liquid mixtures. There are two crucial issues for industrial application of pervaporation process. The first is developing membrane material and tailoring membrane structure to obtain high pervaporation performances. The second is modeling pervaporation transport to better understand of the above-mentioned structure–pervaporation relationship. Many models were proposed to predict the mass transfer process, among them, solution-diffusion model is most widely used in describing pervaporation transport including preferential sorption, diffusion and evaporation steps. For modeling pervaporation transport, the permeation flux, which depends on the solubility and diffusivity of components in the membrane, should be obtained first. Traditionally, the solubility was calculated according to the Flory–Huggins theory. Separation of the benzene (Bz)/cyclohexane (Cx) mixture is industrially significant. Numerous papers have been focused on the Bz/Cx system to assess the PV properties of membrane materials. Membranes with both high permeability and selectivity are desirable for practical application. Several new polymers have been prepared to get both high permeability and selectivity. Styrene-butadiene rubbers (SBR), dense membranes cross-linked by chloromethylation were used in the separation of benzene/cyclohexane mixtures. The impact of chloromethylation reaction as a new method of cross-linking SBR on the pervaporation performance have been reported. In contrast to the vulcanization with sulfur, the cross-linking takes places on styrene units of polymeric chains via a methylene bridge. The partial pervaporative (PV) fluxes of benzene/cyclohexane mixtures in styrene-butadiene rubber (SBR) were predicted using Fick's first law. The predicted partial fluxes and the PV separation factor agreed well with the experimental data by integrating Fick's law over the benzene concentration. The effects of feed concentration and operating temperature on the predicted permeation flux by this proposed model are investigated. The predicted permeation fluxes are in good agreement with experimental data at lower benzene concentration in feed, but at higher benzene concentration, the model overestimated permeation flux. The predicted and experimental permeation fluxes all increase with operating temperature increasing. Solvent sorption levels for benzene/ cyclohexane mixtures in a SBR membrane were determined experimentally. The results showed that the solvent sorption levels were strongly affected by the feed composition. The Flory- Huggins equation generates higher R-square coefficient for the sorption selectivity.

Keywords: benzene, cyclohexane, pervaporation, permeation, sorption modeling, SBR

Procedia PDF Downloads 300

Authors: Ana Maria Muț, Georgeta Coneac, Ioana Olariu, Ștefana Avram, Ioana Zinuca Pavel, Ionela Daliana Minda, Lavinia Vlaia, Cristina Adriana Dehelean, Corina Danciu

Abstract:

Oregano essential oil is obtained from different parts of the plant Origanum vulgare (fam. Lamiaceae) and carvacrol and thymol are primary components, widely recognized for their antimicrobial activity, as well as their antiviral and antifungal properties. Poloxamers are triblock copolymers (Pluronic®), formed of three non-ionic blocks with a hydrophobic polyoxypropylene central chain flanked by two polyoxyethylene hydrophilic chains. They are known for their biocompatibility, sensitivity to temperature changes (sol-to-gel transition of aqueous solution with temperature increase), but also for their amphiphilic and surface active nature determining the formation of micelles, useful for solubilization of different hydrophobic compounds such as the terpenes and terpenoids contained in essential oils. Thus, these polymers, listed in European and US Pharmacopoeia and approved by FDA, are widely used as solubilizers and gelling agents for various pharmaceutical preparations, including topical hydrogels. The aim of this study was to investigate the posibility of solubilizing oregano essential oil (OEO) in polymeric micelles using polyoxypropylene (PPO)-polyoxyethylene (PEO)-polyoxypropylene (PPO) triblock polymers to obtain semisolid systems suitable for topical application. A formulation screening was performed, using Pluronic® F-127 in concentration of 20%, Pluronic® L-31, Pluronic® L-61 and Pluronic® L-62 in concentration of 0.5%, 0.8% respectively 1% to obtain the polymeric micelles-based systems. Then, to each selected system, with or without 10% absolute ethanol, 5% or 8% OEO was added. The obtained transparent poloxamer-based hydrogels containing solubilized OEO were further evaluated for pH, rheological characteristics (flow behaviour, viscosity, consistency and spreadability), using consacrated techniques like potentiometric titration, stationary shear flow test, penetrometric method and parallel plate method. Also, in vitro release and permeation of carvacrol from the hydrogels was carried out, using vertical diffusion cells and synthetic hydrophilic membrane and porcine skin respectively. The pH values and rheological features of all tested formulations were in accordance with official requirements for semisolid cutaneous preparations. But, the formulation containing 0.8% Pluronic® L-31, 10% absolute ethanol, 8% OEO and water and the formulation with 1% Pluronic® L-31, 5% OEO and water, produced the highest cumulative amounts of carvacrol released/permeated through the membrane. The present study demonstrated that oregano essential oil can be successfully solubilized in the investigated poloxamer-based hydrogels. These systems can be further investigated as potential topical therapy for cutaneous papillomas. Funding: This research was funded by Project PN-III-P1-1.1-TE2019-0130, Contract number TE47, Romania.

Keywords: oregano essential oil, carvacrol, poloxamer, topical hydrogels

Procedia PDF Downloads 87

Authors: Sonia Kudlacik-Kramarczyk, Anna Drabczyk, Dagmara Malina, Bozena Tyliszczak, Agnieszka Sobczak-Kupiec

Abstract:

Introduction: In the preparation of polymer materials, compounds of natural origin are currently gaining more and more interest. This is particularly noticeable in the case of synthesis of materials considered for biomedical use. Then, selected material has to meet many requirements. It should be characterized by non-toxicity, biodegradability and biocompatibility. Therefore special attention is directed to substances such as polysaccharides, proteins or substances that are the basic building components of proteins, i.e. amino acids. These compounds may be crosslinked with other reagents that leads to the preparation of polymer matrices. Such amino acids as e.g. cysteine or histidine. On the other hand, previously mentioned requirements may be met by polymers obtained as a result of biosynthesis, e.g. polyhydroxybutyrate. This polymer belongs to the group of aliphatic polyesters that is synthesized by microorganisms (selected strain of bacteria) under specific conditions. It is possible to modify matrices based on given polymer with substances of various origin. Such a modification may result in the change of their properties or/and in providing the material with new features desirable in viewpoint of specific application. Described materials are synthesized using UV radiation. Process of photopolymerization is fast, waste-free and enables to obtain final products with favorable properties. Methodology: Polymer matrices have been prepared by means of photopolymerization. First step involved the preparation of solutions of particular reagents and mixing them in the appropriate ratio. Next, crosslinking agent and photoinitiator have been added to the reaction mixture and the whole was poured into the Petri dish and treated with UV radiation. After the synthesis, polymer samples were dried at room temperature and subjected to the numerous analyses aimed at the determining their physicochemical properties. Firstly, sorption properties of obtained polymer matrices have been determined. Next, mechanical properties have been characterized, i.e. tensile strength. The ability to deformation under applied stress of all prepared polymer matrices has been checked. Such a property is important in viewpoint of the application of analyzed materials e.g. as wound dressings. Wound dressings have to be elastic because depending on the location of the wound and its mobility, such a dressing has to adhere properly to the wound. Furthermore, considering the use of the materials for biomedical purposes it is essential to determine its behavior in environments simulating these ones occurring in human body. Therefore incubation studies using selected liquids have also been conducted. Conclusions: As a result of photopolymerization process, polymer matrices based on natural compounds have been prepared. These exhibited favorable mechanical properties and swelling ability. Moreover, biocompatibility in relation to simulated body fluids has been stated. Therefore it can be concluded that analyzed polymer matrices constitute an interesting materials that may be considered for biomedical use and may be subjected to the further more advanced analyses using specific cell lines.

Keywords: photopolymerization, polymer matrices, simulated body fluids, swelling properties

Procedia PDF Downloads 101

Authors: Zhaoyang Liu, Detao Qin, Darren Delai Sun

Abstract:

The onshore production of oil and gas (for example, shale gas) generates large quantities of wastewater, referred to be ‘produced water’, which contains high contents of oils and salts. The direct discharge of produced water, if not appropriately treated, can be toxic to the environment and human health. Membrane filtration has been deemed as an environmental-friendly and cost-effective technology for treating oily wastewater. However, conventional polymeric membranes have their drawbacks of either low salt rejection rate or high membrane fouling tendency when treating oily wastewater. Recent years, forward osmosis (FO) membrane filtration has emerged as a promising technology with its unique advantages of low operation pressure and less membrane fouling tendency. However, until now there is still no report about FO membranes specially designed and fabricated for treating the oily and salty produced water. In this study, a novel nanocomposite FO membrane was developed specially for treating oil- and salt-polluted produced water. By leveraging the recent advance of nanomaterials and nanotechnology, this nanocomposite FO membrane was designed to be made of double layers: an underwater oleophobic selective layer on top of a nanomaterial infused polymeric support layer. Wherein, graphene oxide (GO) nanosheets were selected to add into the polymeric support layer because adding GO nanosheets can optimize the pore structures of the support layer, thus potentially leading to high water flux for FO membranes. In addition, polyvinyl alcohol (PVA) hydrogel was selected as the selective layer because hydrated and chemically-crosslinked PVA hydrogel is capable of simultaneously rejecting oil and salt. After nanocomposite FO membranes were fabricated, the membrane structures were systematically characterized with the instruments of TEM, FESEM, XRD, ATR-FTIR, surface zeta-potential and Contact angles (CA). The membrane performances for treating produced waters were tested with the instruments of TOC, COD and Ion chromatography. The working mechanism of this new membrane was also analyzed. Very promising experimental results have been obtained. The incorporation of GO nanosheets can reduce internal concentration polarization (ICP) effect in the polymeric support layer. The structural parameter (S value) of the new FO membrane is reduced by 23% from 265 ± 31 μm to 205 ± 23 μm. The membrane tortuosity (τ value) is decreased by 20% from 2.55 ± 0.19 to 2.02 ± 0.13 μm, which contributes to the decrease of S value. Moreover, the highly-hydrophilic and chemically-cross-linked hydrogel selective layer present high antifouling property under saline oil/water emulsions. Compared with commercial FO membrane, this new FO membrane possesses three times higher water flux, higher removal efficiencies for oil (>99.9%) and salts (>99.7% for multivalent ions), and significantly lower membrane fouling tendency (<10%). To our knowledge, this is the first report of a nanocomposite FO membrane with the combined merits of high salt rejection, high oil repellency and high water flux for treating onshore oil/gas produced waters. Due to its outstanding performance and ease of fabrication, this novel nanocomposite FO membrane possesses great application potential in wastewater treatment industry.

Keywords: nanocomposite, membrane, polymer, graphene oxide

Procedia PDF Downloads 228

Authors: Barbara Urasinska-Wojcik, Neil Chilton, Peter Todd, Christopher Elsworthy, Gregory J. Gibbons

Abstract:

The recent increase in the application of Additive Manufacturing (AM) of products has resulted in new demands on capability. The ability to integrate both form and function within printed objects is the next frontier in the 3D printing area. To move beyond prototyping into low volume production, we demonstrate a UK-designed and built AM hybrid system that combines polymer based structural deposition with digital deposition of electrically conductive elements. This hybrid manufacturing system is based on a multi-planar build approach to improve on many of the limitations associated with AM, such as poor surface finish, low geometric tolerance, and poor robustness. Specifically, the approach involves a multi-planar Material Extrusion (ME) process in which separated build stations with up to 5 axes of motion replace traditional horizontally-sliced layer modeling. The construction of multi-material architectures also involved using multiple print systems in order to combine both ME and digital deposition of conductive material. To demonstrate multi-material 3D printing, three thermoplastics, acrylonitrile butadiene styrene (ABS), polyamide 6,6/6 copolymers (CoPA) and polyamide 12 (PA) were used to print specimens, on top of which our high viscosity Ag-particulate ink was printed in a non-contact process, during which drop characteristics such as shape, velocity, and volume were assessed using a drop watching system. Spectroscopic analysis of these 3D printed materials in the IR region helped to determine the optimum in-situ curing system for implementation into the AM system to achieve improved adhesion and surface refinement. Thermal Analyses were performed to determine the printed materials glass transition temperature (Tg), stability and degradation behavior to find the optimum annealing conditions post printing. Electrical analysis of printed conductive tracks on polymer surfaces during mechanical testing (static tensile and 3-point bending and dynamic fatigue) was performed to assess the robustness of the electrical circuits. The tracks on CoPA, ABS, and PA exhibited low electrical resistance, and in case of PA resistance values of tracks remained unchanged across hundreds of repeated tensile cycles up to 0.5% strain amplitude. Our developed AM printer has the ability to fabricate fully functional objects in one build, including complex electronics. It enables product designers and manufacturers to produce functional saleable electronic products from a small format modular platform. It will make 3D printing better, faster and stronger.

Keywords: additive manufacturing, conductive tracks, hybrid 3D printer, integrated manufacture

Procedia PDF Downloads 143

Authors: Gondrexon, Gonon, Mendil-Jakani, Mareau

Abstract:

Proton Exchange Membrane Fuel Cells (PEMFCs) seems to be a promising device used for converting hydrogen into electricity. PEMFC is made of a Membrane Electrode Assembly (MEA) composed of a Proton Exchange Membrane (PEM) sandwiched by two catalytic layers. Nowadays, specific performances are targeted in order to ensure the long-term expansion of this technology. Current polymers used (perfluorinated as Nafion®) are unsuitable (loss of mechanical properties) for the high-temperature range. To overcome this issue, sulfonated polyaromatic polymers appear to be a good alternative since it has very good thermomechanical properties. However, their proton conductivity and chemical stability (oxidative resistance to H2O2 formed during fuel cell (FC) operating) are very low. In our team, we patented an original concept of hybrid membranes able to fulfill the specific requirements for PEMFC. This idea is based on the improvement of commercialized polymer membrane via an easy and processable stabilization thanks to sol-gel (SG) chemistry with judicious embeded chemical functions. This strategy is thus breaking up with traditional approaches (design of new copolymers, use of inorganic charges/additives). In 2020, we presented the elaboration and functional properties of a 1st generation of hybrid membranes with promising performances and durability. The latter was made by self-condensing a SG phase with 3(mercaptopropyl)trimethoxysilane (MPTMS) inside a commercial sPEEK host membrane. The successful in-situ condensation reactions of the MPTMS was demonstrated by measures of mass uptakes, FTIR spectroscopy (presence of C-Haliphatics) and solid state NMR 29Si (T2 & T3 signals of self-condensation products). The ability of the SG phase to prevent the oxidative degradation of the sPEEK phase (thanks to thiol chemical functions) was then proved with H2O2 accelerating tests and FC operating tests. A 2nd generation made of thiourea functionalized SG precursors (named HTU & TTU) was made after. By analysing in depth the morphologies of these different hybrids by direct space analysis (AFM/SEM/TEM) and reciprocal space analysis (SANS/SAXS/WAXS), we highlighted that both SG phase morphology and its localisation into the host has a huge impact on the PEM functional properties observed. This relationship is also dependent on the chemical function embedded. The hybrids obtained have shown very good chemical resistance during aging test (exposed to H2O2) compared to the commercial sPEEK. But the chemical function used is considered as “sacrificial” and cannot react indefinitely with H2O2. Thus, we are now working on a 3rd generation made of both sacrificial/regenerative chemical functions which are expected to inhibit the chemical aging of sPEEK more efficiently. With this work, we are confident to reach a predictive approach of the key parameters governing the final properties.

Keywords: fuel cells, ionomers, membranes, sPEEK, chemical stability

Procedia PDF Downloads 46

Authors: Douglas N. Simões, Michele Pittol, Vanda F. Ribeiro, Daiane Tomacheski, Ruth M. C. Santana

Abstract:

The increasing demand of thermoplastic elastomers is related to the wide range of applications, such as automotive, footwear, wire and cable industries, adhesives and medical devices, cell phones, sporting goods, toys and others. These materials are susceptible to microbial attack. Moisture and organic matter present in some areas (such as shower area and sink), provide favorable conditions for microbial proliferation, which contributes to the spread of diseases and reduces the product life cycle. Compounds based on SEBS copolymers, poly(styrene-b-(ethylene-co-butylene)-b-styrene, are a class of thermoplastic elastomers (TPE), fully recyclable and largely used in domestic appliances like bath mats and tooth brushes (soft touch). Zinc oxide and zinc ions loaded in personal and home care products have become common in the last years due to its biocidal effect. In that sense, the aim of this study was to evaluate the effect of zinc as antimicrobial agent in compounds based on SEBS/polypropylene/oil/ calcite for use as refrigerator seals (gaskets), bath mats and sink squeegee. Two zinc oxides from different suppliers (ZnO-Pe and ZnO-WR) and one masterbatch of zinc ions (M-Zn-ion) were used in proportions of 0%, 1%, 3% and 5%. The compounds were prepared using a co-rotating double screw extruder (L/D ratio of 40/1 and 16 mm screw diameter). The extrusion parameters were kept constant for all materials. Tests specimens were prepared using the injection molding machine. A compound with no antimicrobial additive (standard) was also tested. Compounds were characterized by physical (density), mechanical (hardness and tensile properties) and rheological properties (melt flow rate - MFR). The Japan Industrial Standard (JIS) Z 2801:2010 was applied to evaluate antibacterial properties against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). The Brazilian Association of Technical Standards (ABNT) NBR 15275:2014 were used to evaluate antifungal properties against Aspergillus niger (A. niger), Aureobasidium pullulans (A. pullulans), Candida albicans (C. albicans), and Penicillium chrysogenum (P. chrysogenum). The microbiological assay showed a reduction over 42% in E. coli and over 49% in S. aureus population. The tests with fungi showed inconclusive results because the sample without zinc also demonstrated an inhibition of fungal development when tested against A. pullulans, C. albicans and P. chrysogenum. In addition, the zinc loaded samples showed worse results than the standard sample when tested against A. niger. The zinc addition did not show significant variation in mechanical properties. However, the density values increased with the rise in ZnO additives concentration, and had a little decrease in M-Zn-ion samples. Also, there were differences in the MFR results in all compounds compared to the standard.

Keywords: antimicrobial, home device, SEBS, zinc

Procedia PDF Downloads 296

Authors: Siddhant Sethi, Yasuharu Takashima, Shigetaka Nakamura, Kenzo Fujimoto

Abstract:

Site-directed mutagenesis is a renowned technique to introduce specific mutations in the genome. To achieve site-directed mutagenesis, many chemical and enzymatic approaches have been reported in the past like disulphite induced genome editing, CRISPR-Cas9, TALEN etc. The chemical methods are invasive whereas the enzymatic approaches are time-consuming and expensive. Most of these techniques are unusable in the cellular application due to their toxicity and other limitations. Photo-chemical cytosine deamination, introduced in 2010, is one of the major technique for enzyme-free single-point mutation of cytosine to uracil in DNA and RNA, wherein, 3-cyanovinylcarbazole nucleoside (CNVK) containing oligodeoxyribonucleotide (ODN) having CNVK at -1 position to that of target cytosine is reversibly crosslinked to target DNA strand using 366 nm and then incubated at 90ºC to accommodate deamination. This technique is superior to enzymatic methods of site-directed mutagenesis but has a disadvantage that it requires the use of high temperature for the deamination step which restricts its applicability in the in vivo applications. This study has been focused on improving the technique by reducing the temperature required for deamination. Firstly, the photo-cross-linker, CNVK has been modified by replacing cyano group attached to vinyl group with methyl ester (OMeVK), amide (NH2VK), and carboxylic acid (OHVK) to observe the acceleration in the deamination of target cytosine cross-linked to vinylcarbazole derivative. Among the derivatives, OHVK has shown 2 times acceleration in deamination reaction as compared to CNVK, while the other two derivatives have shown deceleration towards deamination reaction. The trend of rate of deamination reaction follows the same order as that of hydrophilicity of the vinylcarbazole derivatives. OHVK being most hydrophilic has shown highest acceleration while OMeVK is least hydrophilic has proven to be least active for deamination. Secondly, in the related study, the counter-base of the target cytosine, guanine has been replaced by inosine, 2-aminopurine, nebularine, and 5-nitroindole having distinct hydrogen bonding patterns with target cytosine. Among the ODNs with these counter bases, ODN with inosine has shown 12 fold acceleration towards deamination of cytosine cross-linked to CNVK at physiological conditions as compared to guanosine. Whereas, when 2-aminopurine, nebularine, and 5-nitroindole were used, no deamination reaction took place. It can be concluded that inosine has potential to be used as the counter base of target cytosine for the CNVK mediated photo-cross-linking induced deamination of cytosine. The increase in rate of deamination reaction has been attributed to pattern and number of hydrogen bonding between the cytosine and counter base. One of the important factor is presence of hydrogen bond between exo-cyclic amino group of cytosine and the counter base. These results will be useful for development of more efficient technique for site-directed mutagenesis for C → U transformations in the DNA/RNA which might be used in the living system for treatment of various genetic disorders and genome engineering for making designer and non-native proteins.

Keywords: C to U transformation, DNA editing, genome engineering, ultra-fast photo-cross-linking

Procedia PDF Downloads 211

Authors: Nino Kupatadze, Mzevinar Bedinashvili, Tamar Memanishvili, Manana Gurielidze, David Tugushi, Ramaz Katsarava

Abstract:

Bacteria easily colonize the surfaces of tissues, surgical devices (implants, orthopedics, catheters, etc.), and instruments causing surgical device related infections. Therefore, the battle against bacteria and the prevention of surgical devices from biofilm formation is one of the main challenges of biomedicine today. Our strategy to the solution of this problem consists in using antimicrobial polymeric coatings as effective “shields” to protect surfaces from bacteria’s colonization and biofilm formation. As one of the most promising approaches look be the use of antimicrobial bioerodible polymeric nanocomposites containing silver nanoparticles (AgNPs). We assume that the combination of an erodible polymer with a strong bactericide should put obstacles to bacteria to occupy the surface and to form biofilm. It has to be noted that this kind of nanocomposites are also promising as wound dressing materials to treat infected superficial wounds. Various synthetic and natural polymers were used for creating biocomposites containing AgNPs as both particles' stabilizers and matrices forming elastic films at surfaces. One of the most effective systems to fabricate AgNPs is an ethanol solution of polyvinylpyrrolidone(PVP) with dissolved AgNO3–ethanol serves as a AgNO3 reductant and PVP as AgNPs stabilizer (through the interaction of nanoparticles with nitrogen atom of the amide group). Though PVP is biocompatible and film-forming polymer, it is not a good candidate to design either "biofilm shield" or wound dressing material because of a high solubility in water – though the solubility of PVP provides the desirable release of AgNPs from the matrix, but the coating is easily washable away from the surfaces. More promising as matrices look water insoluble but bioerodible polymers that can provide the release of AgNPs and form long-lasting coatings at the surfaces. For creating bioerodible water-insoluble antimicrobial coatings containing AgNPs, we selected amino acid based biodegradable polymers(AABBPs)–poly(ester amide)s, poly(ester urea)s, their copolymers containing amide and related groups capable to stabilize AgNPs. Among a huge variety of AABBPs reported we selected the polymers soluble in ethanol. For preparing AgNPs containing nanocompositions AABBPs and AgNO3 were dissolved in ethanol and subjected to photochemical reduction using daylight-irradiation. The formation of AgNPs was observed visually by coloring the solutions in brownish-red. The obtained AgNPs were characterized by UV-spectroscopy, transmission electron microscopy(TEM), and dynamic light scattering(DLS). According to the UV and TEM data, the photochemical reduction resulted presumably in spherical AgNPs with rather high contribution of the particles below 10 nm that are known as responsible for the antimicrobial activity. DLS study showed that average size of nanoparticles formed after photo-reduction in ethanol solution ranged within 50 nm. The in vitro antimicrobial activity study of the new nanocomposite material is in progress now.

Keywords: nanocomposites, silver nanoparticles, polymer, biodegradable

Procedia PDF Downloads 378

Authors: G. M. Vlasceanu, H. Iovu, E. Vasile, M. Ionita

Abstract:

Herein, the synthesis and characterization of chitosan-gelatin highly porous scaffold reinforced with graphene oxide, and hydroxyapatite (HAp), crosslinked with genipin was targeted. In tissue engineering, chitosan and gelatin are two of the most robust biopolymers with wide applicability due to intrinsic biocompatibility, biodegradability, low antigenicity properties, affordability, and ease of processing. HAp, per its exceptional activity in tuning cell-matrix interactions, is acknowledged for its capability of sustaining cellular proliferation by promoting bone-like native micro-media for cell adjustment. Genipin is regarded as a top class cross-linker, while graphene oxide (GO) is viewed as one of the most performant and versatile fillers. The composites with natural bone HAp/biopolymer ratio were obtained by cascading sonochemical treatments, followed by uncomplicated casting methods and by freeze-drying. Their structure was characterized by Fourier Transform Infrared Spectroscopy and X-ray Diffraction, while overall morphology was investigated by Scanning Electron Microscopy (SEM) and micro-Computer Tomography (µ-CT). Ensuing that, in vitro enzyme degradation was performed to detect the most promising compositions for the development of in vivo assays. Suitable GO dispersion was ascertained within the biopolymer mix as nanolayers specific signals lack in both FTIR and XRD spectra, and the specific spectral features of the polymers persisted with GO load enhancement. Overall, correlations between the GO induced material structuration, crystallinity variations, and chemical interaction of the compounds can be correlated with the physical features and bioactivity of each composite formulation. Moreover, the HAp distribution within follows an auspicious density gradient tuned for hybrid osseous/cartilage matter architectures, which were mirrored in the mice model tests. Hence, the synthesis route of a natural polymer blend/hydroxyapatite-graphene oxide composite material is anticipated to emerge as influential formulation in bone tissue engineering. Acknowledgement: This work was supported by the project 'Work-based learning systems using entrepreneurship grants for doctoral and post-doctoral students' (Sisteme de invatare bazate pe munca prin burse antreprenor pentru doctoranzi si postdoctoranzi) - SIMBA, SMIS code 124705 and by a grant of the National Authority for Scientific Research and Innovation, Operational Program Competitiveness Axis 1 - Section E, Program co-financed from European Regional Development Fund 'Investments for your future' under the project number 154/25.11.2016, P_37_221/2015. The nano-CT experiments were possible due to European Regional Development Fund through Competitiveness Operational Program 2014-2020, Priority axis 1, ID P_36_611, MySMIS code 107066, INOVABIOMED.

Keywords: biopolymer blend, ectopic osteoinduction, graphene oxide composite, hydroxyapatite

Procedia PDF Downloads 86

Authors: Natia Jalagonia, Tinatin Kuchukhidze

Abstract:

Polymer electrolytes (PE) play an important part in electrochemical devices such as batteries and fuel cells. To achieve optimal performance, the PE must maintain a high ionic conductivity and mechanical stability at both high and low relative humidity. The polymer electrolyte also needs to have excellent chemical stability for long and robustness. According to the prevailing theory, ionic conduction in polymer electrolytes is facilitated by the large-scale segmental motion of the polymer backbone, and primarily occurs in the amorphous regions of the polymer electrolyte. Crystallinity restricts polymer backbone segmental motion and significantly reduces conductivity. Consequently, polymer electrolytes with high conductivity at room temperature have been sought through polymers which have highly flexible backbones and have largely amorphous morphology. The interest in polymer electrolytes was increased also by potential applications of solid polymer electrolytes in high energy density solid state batteries, gas sensors and electrochromic windows. Conductivity of 10-3 S/cm is commonly regarded as a necessary minimum value for practical applications in batteries. At present, polyethylene oxide (PEO)-based systems are most thoroughly investigated, reaching room temperature conductivities of 10-7 S/cm in some cross-linked salt in polymer systems based on amorphous PEO-polypropylene oxide copolymers.. It is widely accepted that amorphous polymers with low glass transition temperatures Tg and a high segmental mobility are important prerequisites for high ionic conductivities. Another necessary condition for high ionic conductivity is a high salt solubility in the polymer, which is most often achieved by donors such as ether oxygen or imide groups on the main chain or on the side groups of the PE. It is well established also that lithium ion coordination takes place predominantly in the amorphous domain, and that the segmental mobility of the polymer is an important factor in determining the ionic mobility. Great attention was pointed to PEO-based amorphous electrolyte obtained by synthesis of comb-like polymers, by attaching short ethylene oxide unit sequences to an existing amorphous polymer backbone. The aim of presented work is to obtain of solid polymer electrolyte membranes using PMHS as a matrix. For this purpose the hydrosilylation reactions of α,ω-bis(trimethylsiloxy)methyl¬hydrosiloxane with allyl triethylene-glycol mo¬nomethyl ether and vinyltriethoxysilane at 1:28:7 ratio of initial com¬pounds in the presence of Karstedt’s catalyst, platinum hydrochloric acid (0.1 M solution in THF) and platinum on the carbon catalyst in 50% solution of anhydrous toluene have been studied. The synthesized olygomers are vitreous liquid products, which are well soluble in organic solvents with specific viscosity ηsp ≈ 0.05 - 0.06. The synthesized olygomers were analysed with FTIR, 1H, 13C, 29Si NMR spectroscopy. Synthesized polysiloxanes were investigated with wide-angle X-ray, gel-permeation chromatography, and DSC analyses. Via sol-gel processes of doped with lithium trifluoromethylsulfonate (triflate) or lithium bis¬(trifluoromethylsulfonyl)¬imide polymer systems solid polymer electrolyte membranes have been obtained. The dependence of ionic conductivity as a function of temperature and salt concentration was investigated and the activation energies of conductivity for all obtained compounds are calculated

Keywords: synthesis, PMHS, membrane, electrolyte

Procedia PDF Downloads 220

Authors: Vishal Kumar, Soumitra Satapathi

Abstract:

Föster Resonance Energy Transfer (FRET) is a powerful technique used to probe close-range molecular interactions. Physically, the FRET phenomenon manifests as a dipole–dipole interaction between closely juxtaposed fluorescent molecules (10–100 Å). Our effort is to employ this FRET technique to make a prototype device for highly sensitive detection of environment pollutant. Among the most common environmental pollutants, nitroaromatic compounds (NACs) are of particular interest because of their durability and toxicity. That’s why, sensitive and selective detection of small amounts of nitroaromatic explosives, in particular, 2,4,6-trinitrophenol (TNP), 2,4-dinitrotoluene (DNT) and 2,4,6-trinitrotoluene (TNT) has been a critical challenge due to the increasing threat of explosive-based terrorism and the need of environmental monitoring of drinking and waste water. In addition, the excessive utilization of TNP in several other areas such as burn ointment, pesticides, glass and the leather industry resulted in environmental accumulation, and is eventually contaminating the soil and aquatic systems. To the date, high number of elegant methods, including fluorimetry, gas chromatography, mass, ion-mobility and Raman spectrometry have been successfully applied for explosive detection. Among these efforts, fluorescence-quenching methods based on the mechanism of FRET show good assembly flexibility, high selectivity and sensitivity. Here, we report a FRET-based sensor system for the highly selective detection of NACs, such as TNP, DNT and TNT. The sensor system is composed of a copolymer Poly [(N,N-dimethylacrylamide)-co-(Boc-Trp-EMA)] (RP) bearing tryptophan derivative in the side chain as donor and dansyl tagged copolymer P(MMA-co-Dansyl-Ala-HEMA) (DCP) as an acceptor. Initially, the inherent fluorescence of RP copolymer is quenched by non-radiative energy transfer to DCP which only happens once the two molecules are within Förster critical distance (R0). The excellent spectral overlap (Jλ= 6.08×10¹⁴ nm⁴M⁻¹cm⁻¹) between donors’ (RP) emission profile and acceptors’ (DCP) absorption profile makes them an exciting and efficient FRET pair i.e. further confirmed by the high rate of energy transfer from RP to DCP i.e. 0.87 ns⁻¹ and lifetime measurement by time correlated single photon counting (TCSPC) to validate the 64% FRET efficiency. This FRET pair exhibited a specific fluorescence response to NACs such as DNT, TNT and TNP with 5.4, 2.3 and 0.4 µM LODs, respectively. The detection of NACs occurs with high sensitivity by photoluminescence quenching of FRET signal induced by photo-induced electron transfer (PET) from electron-rich FRET pair to electron-deficient NAC molecules. The estimated stern-volmer constant (KSV) values for DNT, TNT and TNP are 6.9 × 10³, 7.0 × 10³ and 1.6 × 104 M⁻¹, respectively. The mechanistic details of molecular interactions are established by time-resolved fluorescence, steady-state fluorescence and absorption spectroscopy confirmed that the sensing process is of mixed type, i.e. both dynamic and static quenching as lifetime of FRET system (0.73 ns) is reduced to 0.55, 0.57 and 0.61 ns DNT, TNT and TNP, respectively. In summary, the simplicity and sensitivity of this novel FRET sensor opens up the possibility of designing optical sensor of various NACs in one single platform for developing multimodal sensor for environmental monitoring and future field based study.

Keywords: FRET, nitroaromatic, stern-Volmer constant, tryptophan and dansyl tagged copolymer

Procedia PDF Downloads 105