Search results for: cross-linked

Authors: Kamel Agroui, George Collins, Rydha Yaiche

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The objective of this study is to better understand the thermal characteristics and molecular behaviour of cured EVA before and after outdoor exposure. Thermal analysis methods as DSC, TSC and DMTA studies were conducted on EVA material. DSC experiments on EVA show a glass transition at about -33.1° C which is characteristic of crystalline phase and an endothermic peak at temperature of 55 °C characteristic of amorphous phase. The magnitude of the integrated temperature DSC peak for EVA is 14.4 J/g. The basic results by TSC technique is that there are two relaxations that are reproducibly observed in cured EVA encapsulant material. At temperature polarization 85°C, a low temperature relaxation occurs at –24.4°C and a high temperature relaxation occurs at +30.4ºC. DMTA results exhibit two tan peaks located at -14.9°C and +66.6°C. After outdoor exposure cured EVA by DSC analysis revealed two endothermic peaks due to post crystallization phenomenon and TSC suggests that prolonged exposure selectively effects the poly(vinyl acetate)-rich phase, with much less impact on the polyethylene-rich phase.

Keywords: EVA, encapsulation process, PV module, thermal analysis, quality control

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Authors: J. Desbrieres, M. Popa, C. Peptu, S. Bacaita

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Because of their favorable properties (non-toxicity, biodegradability, mucoadhesivity etc.), polysaccharides were studied as biomaterials and as pharmaceutical excipients in drug formulations. These formulations may be produced in a wide variety of forms including hydrogels, hydrogel based particles (or capsules), films etc. In these formulations, the polysaccharide based materials are able to provide local delivery of loaded therapeutic agents but their delivery can be rapid and not easily time-controllable due to, particularly, the burst effect. This leads to a loss in drug efficiency and lifetime. To overcome the consequences of burst effect, systems involving liposomes incorporated into polysaccharide hydrogels may appear as a promising material in tissue engineering, regenerative medicine and drug loading systems. Liposomes are spherical self-closed structures, composed of curved lipid bilayers, which enclose part of the surrounding solvent into their structure. The simplicity of production, their biocompatibility, the size and similar composition of cells, the possibility of size adjustment for specific applications, the ability of hydrophilic or/and hydrophobic drug loading make them a revolutionary tool in nanomedicine and biomedical domain. Drug delivery systems were developed as hydrogels containing chitosan or carboxymethylcellulose (CMC) as polysaccharides and gelatin (GEL) as polypeptide, and phosphatidylcholine or phosphatidylcholine/cholesterol liposomes able to accurately control this delivery, without any burst effect. Hydrogels based on CMC were covalently crosslinked using glutaraldehyde, whereas chitosan based hydrogels were double crosslinked (ionically using sodium tripolyphosphate or sodium sulphate and covalently using glutaraldehyde). It has been proven that the liposome integrity is highly protected during the crosslinking procedure for the formation of the film network. Calcein was used as model active matter for delivery experiments. Multi-Lamellar vesicles (MLV) and Small Uni-Lamellar Vesicles (SUV) were prepared and compared. The liposomes are well distributed throughout the whole area of the film, and the vesicle distribution is equivalent (for both types of liposomes evaluated) on the film surface as well as deeper (100 microns) in the film matrix. An obvious decrease of the burst effect was observed in presence of liposomes as well as a uniform increase of calcein release that continues even at large time scales. Liposomes act as an extra barrier for calcein release. Systems containing MLVs release higher amounts of calcein compared to systems containing SUVs, although these liposomes are more stable in the matrix and diffuse with difficulty. This difference comes from the higher quantity of calcein present within the MLV in relation with their size. Modeling of release kinetics curves was performed and the release of hydrophilic drugs may be described by a multi-scale mechanism characterized by four distinct phases, each of them being characterized by a different kinetics model (Higuchi equation, Korsmeyer-Peppas model etc.). Knowledge of such models will be a very interesting tool for designing new formulations for tissue engineering, regenerative medicine and drug delivery systems.

Keywords: controlled and delayed release, hydrogels, liposomes, polysaccharides

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Authors: Abdulrahman T. Essa, Ahmed Aied, Omar Hamid, Felicity R. A. J. Rose, Kevin M. Shakesheff

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Biodegradable poly(ester amide)s are promising polymers for biomedical applications such as drug delivery and tissue engineering because of their optimized chemical and physical properties. In this study, we developed a biodegradable polyester amide elastomer poly(serinol sebacate) (PSS) composed of crosslinked networks based on serinol and sebacic acid. The synthesized polymers were characterized to evaluate their chemical structures, mechanical properties, degradation behaviors and in vitro cytocompatibility. Analysis of proton nuclear magnetic resonance and Fourier transform infrared spectroscopy revealed the structure of the polymer. The PSS exhibit excellent solubility in a variety of solvents such as methanol, dimethyl sulfoxide and dimethylformamide. More importantly, the mechanical properties of PSS could be tuned by changing the curing conditions. In addition, the 3T3 fibroblast cells cultured on the PSS demonstrated good cell attachment and high viability.

Keywords: biodegradable, biomaterial, elastomer, mechanical properties, poly(serinol sebacate)

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Authors: Fernando G. Torres, Omar P. Troncoso

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Starch is a highly biocompatible, non-toxic, and biodegradable polymer. It is widely used in biomedical applications, including drug delivery systems and tissue engineering scaffolds. Curcumin, a phenolic compound found in the dried root of Curcuma longa, has been used as a nutritional supplement due to its antimicrobial, anti-inflammatory, and antioxidant effects. However, the major problem with ingesting curcumin by itself is its poor bioavailability due to its poor absorption and rapid metabolism. In this study, we report a novel methodology to prepare starch nanoparticles loaded with curcumin. The nanoparticles were synthesized via nanoprecipitation of starch granules extracted from native Andean potatoes (Solanum tuberosum ssp. and Andigena var Huamantanga varieties). The nanoparticles were crosslinked and stabilized by using sodium tripolyphosphate and Tween®80, respectively. The characterization of the nanoparticles loaded with curcumin was assessed by Fourier Transform Infrared Spectroscopy, Dynamic Light Scattering, Zeta potential, and Differential scanning calorimetry. UV-vis spectrophotometry was used to evaluate the loading efficiency and capacity of the samples. The results showed that native starch nanoparticles could be used to prepare promising nanocarriers for the controlled release of curcumin.

Keywords: starch nanoparticle, nanoprecipitation, curcumin, biomedical applications

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Authors: Daihui Zhang, Marie J. Dumont

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A derivative of 5-hydroxymethylfurfural (HMF) was synthesized for the thiol-Michael addition reaction. The efficiency of the catalysts (base and nucleophiles) and side reactions during the thiol-Michael addition were investigated. Dimethylphenylphosphine efficiently initiated the thiol-Michael addition polymerization for synthesizing a series of bio-based furan polymers with different structure and properties. The benzene rings or hydroxyl groups present in the polymer chains increased the glass transition temperature (Tg) of poly (β-thioether ester). Additionally, copolymers with various compositions were obtained via adding different ratio of 1,6-hexanedithiols to 1,4-benzenedithiols. 1H NMR analysis revealed that experimental ratios of two dithiols monomers matched well with theoretical ratios. The occurrence of a reversible Diels-Alder reaction between furan rings and maleimide groups allowed poly (β-thioether ester) to be dynamically crosslinked. These polymers offer the potentials to produce materials from biomass that have both practical mechanical properties and reprocessing ability.

Keywords: copolymers, Diels-Alder reaction, hydroxymethylfurfural, Thiol-Michael addition

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Authors: Budi Hastuti, Mudasir, Dwi Siswanta, Triyono

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Biosorbent, such as pectin and chitosan, are usually produced with low physical stability, thus the materials need to be modified. In this research, the physical characteristic of adsorbent was increased by grafting chitosan using acetate carboxymetyl chitosan (CC). Further, CC and Pectin (Pec) were crosslinked using cross-linking agent BADGE (bis phenol A diglycidyl ether) to get CC-Pec-BADGE (CPB) adsorbent. The cross-linking processes aim to form stable structure and resistance on acidic media. Furthermore, in order to increase the adsorption capacity in removing Pb(II), the adsorbent was added with NaCl to form macroporous adsorbent named CCPec-BADGE-Na (CPB-Na). The physical and chemical characteristics of the porogenic adsorbent structure were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). The adsorption parameter of CPB-Na to adsorb Pb(II) ion was determined. The kinetics and thermodynamics of the bath sorption of Pb(II) on CPB-Na adsorbent and using chitosan and pectin as a comparison were also studied. The results showed that the CPB-Na biosorbent was stable on acidic media. It had a rough and porous surface area, increased and gave higher sorption capacity for removal of Pb(II) ion. The CPB-Na 1/1 and 1/3 adsorbent adsorbed Pb(II) with adsorption capacity of 45.48 mg/g and 45.97 mg/g respectively, whereas pectin and chitosan were of 39.20 mg /g and 24.67 mg /g respectively.

Keywords: porogen, Pectin, Carboxymethyl Chitosan (CC), CC- Pec-BADGE-Na

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Authors: Nikola Toshikj, Michel Ramonda, Sylvain Catrouillet, Jean-Jacques Robin, Sebastien Blanquer

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Biodegradable and biocompatible block copolymers have risen as the golden materials in both medical and environmental applications. Moreover, if their architecture is of controlled manner, higher applications can be foreseen. In the meantime, organocatalytic ROP has been promoted as more rapid and immaculate route, compared to the traditional organometallic catalysis, towards efficient synthesis of block copolymer architectures. Therefore, herein we report novel organocatalytic pathway with guanidine molecules (TBD) for supported synthesis of trimethylene carbonate initiated by poly(caprolactone) as pre-polymer. Pristine PTMC-b-PCL-b-PTMC block copolymer structure, without any residual products and clear desired block proportions, was achieved under 1.5 hours at room temperature and verified by NMR spectroscopies and size-exclusion chromatography. Besides, when elaborating block copolymer films, further stability and amelioration of mechanical properties can be achieved via additional reticulation step of precedently methacrylated block copolymers. Subsequently, stimulated by the insufficient studies on the phase-separation/crystallinity relationship in these semi-crystalline block copolymer systems, their intrinsic thermal and morphology properties were investigated by differential scanning calorimetry and atomic force microscopy. Firstly, by DSC measurements, the block copolymers with χABN values superior to 20 presented two distinct glass transition temperatures, close to the ones of the respecting homopolymers, demonstrating an initial indication of a phase-separated system. In the interim, the existence of the crystalline phase was supported by the presence of melting temperature. As expected, the crystallinity driven phase-separated morphology predominated in the AFM analysis of the block copolymers. Neither crosslinking at melted state, hence creation of a dense polymer network, disturbed the crystallinity phenomena. However, the later revealed as sensible to rapid liquid nitrogen quenching directly from the melted state. Therefore, AFM analysis of liquid nitrogen quenched and crosslinked block copolymer films demonstrated a thermodynamically driven phase-separation clearly predominating over the originally crystalline one. These AFM films remained stable with their morphology unchanged even after 4 months at room temperature. However, as demonstrated by DSC analysis once rising the temperature above the melting temperature of the PCL block, neither the crosslinking nor the liquid nitrogen quenching shattered the semi-crystalline network, while the access to thermodynamical phase-separated structures was possible for temperatures under the poly (caprolactone) melting point. Precisely this coexistence of dual crosslinked/crystalline networks in the same copolymer structure allowed us to establish, for the first time, the shape-memory properties in such materials, as verified by thermomechanical analysis. Moreover, the response temperature to the material original shape depended on the block copolymer emplacement, hence PTMC or PCL as end-block. Therefore, it has been possible to reach a block copolymer with transition temperature around 40°C thus opening potential real-life medical applications. In conclusion, the initial study of phase-separation/crystallinity relationship in PTMC-b-PCL-b-PTMC block copolymers lead to the discovery of novel shape memory materials with superior properties, widely demanded in modern-life applications.

Keywords: biodegradable block copolymers, organocatalytic ROP, self-assembly, shape-memory

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Authors: Shib Shankar Banerjeea, Andreas Ferya, Gert Heinricha, Amit Das

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Recently, the growing need for the development of soft robots consisting of highly deformable and compliance materials emerge from the serious limitations of conventional service robots. However, one of the main challenges of soft robotics is to develop such compliance materials, which facilitates the design of soft robotic structures and, simultaneously, controls the soft-body systems, like soft artificial muscles. Generally, silicone or acrylic-based elastomer composites are used for soft robotics. However, mechanical performance and long-term reliabilities of the functional parts (sensors, actuators, main body) of the robot made from these composite materials are inferior. This work will present the development and characterization of robust super-soft programmable elastomeric materials from crosslinked natural rubber that can serve as touch and strain sensors for soft robotic arms with very high elastic properties and strain, while the modulus is altered in the kilopascal range. Our results suggest that such soft natural programmable elastomers can be promising materials and can replace conventional silicone-based elastomer for soft robotics applications.

Keywords: elastomers, soft materials, natural rubber, sensors

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Authors: Dean Robinson, Miriam Gublebank, Ella Sklan, Tali Tavor Re'em

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Alginate, a natural linear polysaccharide polymer extracted from brown seaweed, is extensively applied due to its biocompatibility, all- aqueous ease of handling, and relatively low costs. Alginate easily forms a hydrogel when crosslinked with a divalent ion, such as calcium. However, Alginate hydrogel holds low mechanical properties and is cell-inert. To overcome these drawbacks and to improve alginate as a bio-ink for bioprinting, we produced a new alginate matrix combined with spider silk, one of the most resilient, elastic, strong materials known to men. Recombinant spider silk biopolymer has a sponge-like structure and is known to be biocompatible and non-immunogenic. Our results indicated that combining synthetic spider-silk into bio-printed cell-seeded alginate hydrogels resulted in improved properties compared to alginate: improved mechanical properties of the matrix, achieving a tunable gel viscosity and high printability, alongside prolonged and higher cell viability in culture, probably due to the improved cell-matrix interactions. The new bio-ink was then used for bilayer bioprinting of epithelial and stromal endometrial cells. Such a co-culture model will be used for the formation of the complex endometrial tissue for studying the embryo implantation process.

Keywords: cell culture, tissue engineering, spider silk, alginate, bioprinting

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Authors: Xin Zhao

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3D printing is used in creating bone grafts of various architectures by printing materials in a layer-by-layer manner. Traditionally, to make materials printable, heating up or dissolving materials in organic solvents have been used, compromising their capability in loading biomolecules. Photocrosslinkable materials which are initially liquid and printable, and solidified upon light exposure are therefore developed. However, the existing photocrosslinkable materials are either too soft to bear load or non-degradable with potential long-term biocompatibility problems. Here, photocrosslinkable nanocomposite ink is developed composed of poly (lactide-co-propylene glycol-co-lactide) dimethacrylate (PmLnDMA) and hydroxyethyl methacrylate-functionalized hydroxyapatite nanoparticles (nHAMA) mimicking the hairy setae of gecko that can strongly interact with its surroundings to bear high load. Incorporation of nHAMA into PmLnDMA endows the nanocomposite ink with several advantages in (1) improved organic/inorganic interfacial compatibility to increase mechanical strength, (2) readily modulated rheological behaviors, wettability, and biodegradation, (3) enhanced osteoconductivity and osteoinductivity. Moreover, the ink can be rapidly crosslinked upon light exposure, load, and long-term release growth factors, and be printed into 3D bone scaffolds of various shapes and structures according to the patients’ needs. Altogether, this innovation will benefit patients all over the world who suffer from bone fractures, tumors, infections.

Keywords: photocrosslinkable nanocomposite, 3D printing, bone ink, personalized medicine

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Authors: Asmaa Selim, Peter Mizsey

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Bio-ethanol is considered of higher potential as a green renewable energy source owing to its environmental benefits and its high efficiency. In the present study, silver nanoparticles were in-situ generated in a poly (vinyl alcohol) in order to improve its potentials for pervaporation of ethanol-water mixture using solution-casting. Effect of silver content on the pervaporation separation index and the enrichment factor of the membrane at 15 percentage mass water at 40ᵒC was reported. Pervaporation data for nanocomposite membranes showed around 100% increase in the water permeance values while the intrinsic selectivity decreased. The water permeances of origin crosslinked PVA membrane, and the 2.5% silver loaded PVA membrane are 26.65 and 70.45 (g/m².kPa.h) respectively. The values of total flux and water flux are closed to each other, indicating that membranes could be effectively used to break the azeotropic point of ethanol-water. Effect of temperature on the pervaporation performance, permeation parameter and diffusion coefficient of both water and ethanol was discussed. The negative heat of sorption ∆Hs values calculated on the basis of the estimated Arrhenius activation energy values indicating that the sorption process was controlled by Langmuir’s mode. The overall results showed that the membrane containing 0.5 mass percentage of Ag salt exhibited excellent PV performance.

Keywords: bio-ethanol, diffusion coefficient, nanocomposite, pervaporation, poly (vinyl alcohol), silver nanoparticles

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Authors: Elbadawy A. Kamoun

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Magnetically responsive hydrogel nanocomposite (NCH) based on composites of superparamagnetic of Fe3O4 nano-particles and temperature responsive hydrogel matrices were developed. The nanocomposite hydrogel system based on the temperature sensitive N-isopropylacrylamide hydrogels crosslinked by poly(ethylene glycol)-400 dimethacrylate (PEG400DMA) incorporating with chitosan derivative, was synthesized and characterized. Likewise, the NCH system was synthesized by visible-light free radical photopolymerization, using carboxylated camphorquinone-amine system to avoid the common risks of the use of UV-light especially in hyperthermia treatment. Superparamagnetic of iron oxide nanoparticles were introduced into the hydrogel system by polymerizing mixture technique and monomer solution. FT-IR with Raman spectroscopy and Wide angle-XRD analysis were utilized to verify the chemical structure of NCH and exfoliation reaction for nanoparticles, respectively. Additionally, morphological structure of NCH was investigated using SEM and TEM photographs. The swelling responsive of the current nanocomposite hydrogel system with different crosslinking conditions, temperature, magnetic field efficiency, and the presence effect of magnetic nanoparticles were evaluated. Notably, hydrolytic degradation of this system was proved in vitro application. While, in-vivo release profile behavior is under investigation nowadays. Moreover, the compatibility and cytotoxicity tests were previously investigated in our studies for photoinitiating system. These systems show promised polymeric material candidate devices and are expected to have a wide applicability in various biomedical applications as mildly.

Keywords: hydrogel nanocomposites, tempretaure-responsive hydrogel, superparamagnetic nanoparticles, hyperthermia therapy

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Authors: Oya A. Urucu, Aslı B. Çiğil, Hatice Birtane, Ece K. Yetimoğlu, Memet Vezir Kahraman

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Chlorpyrifos is an organophosphorus pesticide which can be found in environmental water samples. The efficiency and reuse of a molecularly imprinted polymer (chlorpyrifos - MIP) were investigated for the selective removal of chlorpyrifos residues. MIP was prepared with UV curing thiol-ene polymerization technology by using multifunctional thiol and ene monomers. The thiol-ene curing reaction is a radical induced process, however unlike other photoinitiated polymerization processes, this polymerization process is a free-radical reaction that proceeds by a step-growth mechanism, involving two main steps; a free-radical addition followed by a chain transfer reaction. It assures a very rapidly formation of a uniform crosslinked network with low shrinkage, reduced oxygen inhibition during curing and excellent adhesion. In this study, thiol-ene based UV-curable polymeric materials were prepared by mixing pentaerythritol tetrakis(3-mercaptopropionate), glyoxal bis diallyl acetal, polyethylene glycol diacrylate (PEGDA) and photoinitiator. Chlorpyrifos was added at a definite ratio to the prepared formulation. Chemical structure and thermal properties were characterized by FTIR and thermogravimetric analysis (TGA), respectively. The pesticide analysis was performed by gas chromatography-mass spectrometry (GC-MS). The influences of some analytical parameters such as pH, sample volume, amounts of analyte concentration were studied for the quantitative recoveries of the analyte. The proposed MIP method was applied to the determination of chlorpyrifos in river and tap water samples. The use of the MIP provided a selective and easy solution for removing chlorpyrifos from the water.

Keywords: molecularly imprinted polymers, selective removal, thilol-ene, uv-curable polymer

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Authors: Mohamed Edokali, Robert Menzel, David Harbottle, Ali Hassanpour

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Forward osmosis (FO) process has stood out as an energy-efficient technology for water desalination and purification, although the practical application of FO for desalination still relies on RO-based Thin Film Composite (TFC) and Cellulose Triacetate (CTA) polymeric membranes which have a low performance. Recently, graphene oxide (GO) laminated membranes have been considered an ideal selection to overcome the bottleneck of the FO-polymeric membranes owing to their simple fabrication procedures, controllable thickness and pore size and high water permeability rates. However, the low stability of GO laminates in wet and harsh environments is still problematic. The recent developments of modified GO and hydrophobic reduced graphene oxide (rGO) membranes for FO desalination have demonstrated attempts to overcome the ongoing trade-off between desalination performance and stability, which is yet to be achieved prior to the practical implementation. In this study, acid-functionalized GO nanosheets cooperatively reduced and crosslinked by the hyperbranched polyethyleneimine (PEI) and polyethylene glycol (PEG) polymers, respectively, are applied for fabrication of the FO membrane, to enhance the membrane stability and performance, and compared with other functionalized rGO-FO membranes. PEI/PEG doped rGO membrane retained two compacted d-spacings (0.7 and 0.31 nm) compared to the acid-functionalized GO membrane alone (0.82 nm). Besides increasing the hydrophilicity, the coating layer of PEG onto the PEI-doped rGO membrane surface enhanced the structural integrity of the membrane chemically and mechanically. As a result of these synergetic effects, the PEI/PEG doped rGO membrane exhibited a water permeation of 7.7 LMH, salt rejection of 97.9 %, and reverse solute flux of 0.506 gMH at low flow rates in the FO desalination process.

Keywords: desalination, forward osmosis, membrane performance, polyethyleneimine, polyethylene glycol, reduced graphene oxide, stability

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Authors: Sylvain Caillol, Maxence Fache, Bernard Boutevin

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Recent years have witnessed an increasing demand on renewable resource-derived polymers owing to increasing environmental concern and restricted availability of petrochemical resources. Thus, a great deal of attention was paid to renewable resources-derived polymers and to thermosetting materials especially, since they are crosslinked polymers and thus cannot be recycled. Also, most of thermosetting materials contain aromatic monomers, able to confer high mechanical and thermal properties to the network. Therefore, the access to biobased, non-harmful, and available aromatic monomers is one of the main challenges of the years to come. Starting from phenols available in large volumes from renewable resources, our team designed platforms of chemicals usable for the synthesis of various polymers. One of these phenols, vanillin, which is readily available from lignin, was more specifically studied. Various aromatic building blocks bearing polymerizable functions were synthesized: epoxy, amine, acid, carbonate, alcohol etc. These vanillin-based monomers can potentially lead to numerous polymers. The example of epoxy thermosets was taken, as there is also the problematic of bisphenol A substitution for these polymers. Materials were prepared from the biobased epoxy monomers obtained from vanillin. Their thermo-mechanical properties were investigated and the effect of the monomer structure was discussed. The properties of the materials prepared were found to be comparable to the current industrial reference, indicating a potential replacement of petrosourced, bisphenol A-based epoxy thermosets by biosourced, vanillin-based ones. The tunability of the final properties was achieved through the choice of monomer and through a well-controlled oligomerization reaction of these monomers. This follows the same strategy than the one currently used in industry, which supports the potential of these vanillin-derived epoxy thermosets as substitutes of their petro-based counterparts.

Keywords: lignin, vanillin, epoxy, amine, carbonate

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

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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

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

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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

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

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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

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Authors: Ragi Poyyara, Vijaya Patnana, Mohammed Alam

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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

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

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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

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Authors: G. Krishnamoorthy, S. Anandhakumar

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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

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

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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

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

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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

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

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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

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Authors: Hassiba Benguergoura, Kamal Chanane, Sâad Moulay

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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

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

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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

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Authors: Zhaoyang Liu, Detao Qin, Darren Delai Sun

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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

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

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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

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

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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

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Authors: J. D. Cabral, E. Murray, P. Turner, E. Hewitt, A. Ali, M. McConnell

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Worldwide demand for organ replacement and tissue regeneration is progressively increasing. Three-dimensional (3D) bioprinting, where a physical construct is produced using computer-aided design, is a promising tool to advance the tissue engineering and regenerative medicine fields. In this paper we describe two different approaches to developing 3D bioprinted constructs for use in tissue regeneration. Bioink development is critical in achieving the 3D biofabrication of functional, regenerative tissues. Hydrogels, cross-linked macromolecules that absorb large amounts of water, have received widespread interest as bioinks due to their relevant soft tissue mechanics, biocompatibility, and tunability. In turn, not only is bioink optimisation crucial, but the creation of vascularized tissues remains a key challenge for the successful fabrication of thicker, more clinically relevant bioengineered tissues. Among the various methodologies, cell-laden hydrogels are regarded as a favorable approach; and when combined with novel core/shell 3D bioprinting technology, an innovative strategy towards creating new vessel-like structures. In this work, we investigate this cell-based approach by using human umbilical endothelial cells (HUVECs) entrapped in a viscoelastic chitosan/dextran (CD)-based core hydrogel, printed simulataneously along with a gelatin methacrylate (GelMA) shell. We have expanded beyond our previously reported FDA approved, commercialised, post-surgical CD hydrogel, Chitogel®, by functionalizing it with cell adhesion and proteolytic peptides in order to promote bone marrow-derived mesenchymal stem cell (immortalized BMSC cell line, hTERT) and HUVECs growth. The biocompatibility and biodegradability of these cell lines in a 3D bioprinted construct is demonstrated. Our studies show that particular peptide combinations crosslinked within the CD hydrogel was found to increase in vitro growth of BMSCs and HUVECs by more than two-fold. These gels were then used as a core bioink combined with the more mechanically robust, UV irradiated GelMA shell bioink, to create 3D regenerative, vessel-like scaffolds with high print fidelity. As well, microporous MEW scaffolds made from milk proteins blended with PCL were found to show promising bioactivity, exhibiting a significant increase in keratinocyte (HaCaTs) and fibroblast (normal human dermal fibroblasts, NhDFs) cell migration and proliferation when compared to PCL only scaffolds. In conclusion, our studies indicate that a peptide functionalized CD hydrogel bioink reinforced with a GelMA shell is biocompatible, biodegradable, and an appropriate cell delivery vehicle in the creation of regenerative 3D constructs. In addition, a novel 3D printing technique, melt electrowriting (MEW), which allows fabrication of micrometer fibre meshes, was used to 3D print polycaprolactone (PCL) and bioactive milk protein, lactorferrin (LF) and whey protein (WP), blended scaffolds for potential skin regeneration applications. MEW milk protein/PCL scaffolds exhibited high porosity characteristics, low overall biodegradation, and rapid protein release. Human fibroblasts and keratinocyte cells were seeded on to the scaffolds. Scaffolds containing high concentrations of LF and combined proteins (LF+WP) showed improved cell viability over time as compared to PCL only scaffolds. This research highlights two scaffolds made using two different 3D printing techniques using a combination of both natural and synthetic biomaterial components in order to create regenerative constructs as potential chronic wound treatments.

Keywords: biomaterials, hydrogels, regenerative medicine, 3D bioprinting

Procedia PDF Downloads 243