Search results for: telechelic polymers

Authors: O. Squillace, R. L. Thompson

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Migration of small molecules to, and across the surface of polymer matrices is a little-studied problem with important industrial applications. Tackifiers in adhesives, flavors in foods and binding agents in paints all present situations where the function of a product depends on the ability of small molecules to migrate through a polymer matrix to achieve the desired properties such as softness, dispersion of fillers, and to deliver an effect that is felt (or tasted) on a surface. It’s been shown that the chemical and molecular structure, surface free energies, phase behavior, close environment and compatibility of the system, influence the migrants’ motion. When differences in behavior, such as occurrence of segregation to the surface or not, are observed it is then of crucial importance to identify and get a better understanding of the driving forces involved in the process of molecular migration. In this aim, experience is meant to be allied with theory in order to deliver a validated theoretical and computational toolkit to describe and predict these phenomena. The systems that have been chosen for this study aim to address the effect of polarity mismatch between the migrants and the polymer matrix and that of a second migrant over the first one. As a non-polar resin polymer, polyvinyl acetate is used as the material to which more or less polar migrants (sorbitol, carvone, octanoic acid (OA), triacetin) are to be added. Through contact angle measurement a surface excess is seen for sorbitol (polar) mixed with PVAc as the surface energy is lowered compare to the one of pure PVAc. This effect is increased upon the addition of carvon or triacetin (non-polars). Surface micro-structures are also evidenced by atomic force microscopy (AFM). Ion beam analysis (Nuclear Reaction Analysis), supplemented by neutron reflectometry can accurately characterize the self-organization of surfactants, oligomers, aromatic molecules in polymer films in order to relate the macroscopic behavior to the length scales that are amenable to simulation. The nuclear reaction analysis (NRA) data for deuterated OA 20% shows the evidence of a surface excess which is enhanced after annealing. The addition of 10% triacetin, as a second migrant, results in the formation of an underlying layer enriched in triacetin below the surface excess of OA. The results show that molecules in polarity mismatch with the matrix tend to segregate to the surface, and this is favored by the addition of a second migrant of the same polarity than the matrix. As studies have been restricted to materials that are model supported films under static conditions in a first step, it is also wished to address the more challenging conditions of materials under controlled stress or strain. To achieve this, a simple rig and PDMS cell have been designed to stretch the material to a defined strain and to probe these mechanical effects by ion beam analysis and atomic force microscopy. This will make a significant step towards exploring the influence of extensional strain on surface segregation, flavor release in cross-linked rubbers.

Keywords: polymers, surface segregation, thin films, molecular migration

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Authors: Sajjad H. Kasanagh, Perviz Ahmedzade, Alexander Fainleib, Taylan Gunay

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Modification of asphalt is a fundamental method around the world mainly on the purpose of providing more durable pavements which lead to diminish repairing cost during the lifetime of highways. Various polymers such as styrene-butadiene-styrene (SBS) and ethylene vinyl acetate (EVA) make up the greater parts of the all-over asphalt modifiers generally providing better physical properties of asphalt by decreasing temperature dependency which eventually diminishes permanent deformation on highways such as rutting. However, some waste and low-cost materials such as recycled plastics and ground rubber tire have been attempted to utilize in asphalt as modifier instead of manufactured polymer modifiers due to decreasing the eventual highway cost. On the other hand, the usage of recycled plastics has become a worldwide requirement and awareness in order to decrease the pollution made by waste plastics. Hence, finding an area in which recycling plastics could be utilized has been targeted by many research teams so as to reduce polymer manufacturing and plastic pollution. To this end, in this paper, thermoplastic dynamic vulcanizate (TDV) obtained from recycled post-consumer polyethylene and ground tire rubber (GTR) were used to provide an efficient modifier for asphalt which decreases the production cost as well and finally might provide an ecological solution by decreasing polymer disposal problems. TDV was synthesized by the chemists in the research group by means of the abovementioned components that are considered as compatible physical characteristic of asphalt materials. TDV modified asphalt samples having different rate of proportions of 3, 4, 5, 6, 7 wt.% TDV modifier were prepared. Conventional tests, such as penetration, softening point and roll thin film oven (RTFO) tests were performed to obtain fundamental physical and aging properties of the base and modified binders. The high temperature performance grade (PG) of binders was determined by Superpave tests conducted on original and aged binders. The multiple stress creep and recovery (MSCR) test which is relatively up-to-date method for classifying asphalts taking account of their elasticity abilities was carried out to evaluate PG plus grades of binders. The results obtained from performance grading, and MSCR tests were also evaluated together so as to make a comparison between the methods both aiming to determine rheological parameters of asphalt. The test results revealed that TDV modification leads to a decrease in penetration, an increase in softening point, which proves an increasing stiffness of asphalt. DSR results indicate an improvement in PG for modified binders compared to base asphalt. On the other hand, MSCR results that are compatible with DSR results also indicate an enhancement on rheological properties of asphalt. However, according to the results, the improvement is not as distinct as observed in DSR results since elastic properties are fundamental in MSCR. At the end of the testing program, it can be concluded that TDV can be used as modifier which provides better rheological properties for asphalt and might diminish plastic waste pollution since the material is 100% recycled.

Keywords: asphalt, ground tire rubber, recycled polymer, thermoplastic dynamic vulcanizate

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Authors: Mikaela Kutrolli, Noah S. Pereira, Vanessa Scanlon, Mohamadmahdi Samandari, Ali Tamayol

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Bone tissue engineering has drawn significant attention and various biomaterials have been tested. Polymers such as polycaprolactone (PCL) offer excellent biocompatibility, reasonable mechanical properties, and biodegradability. However, PCL scaffolds suffer a critical drawback: a lack of micro/mesoporosity, affecting cell attachment, tissue integration, and mineralization. It also results in a slow degradation rate. While 3D-printing has addressed the issue of macroporosity through CAD-guided fabrication, PCL scaffolds still exhibit poor smaller-scale porosity. To overcome this, we generated composites of PCL, hydroxyapatite (HA), and powdered sucrose (PS). The latter serves as a sacrificial material to generate porous particles after sucrose dissolution. Additionally, we have incorporated dexamethasone (DEX) to boost the PCL osteogenic properties. The resulting scaffolds maintain controlled macroporosity from the lattice print structure but also develop micro/mesoporosity within PCL fibers when exposed to aqueous environments. The study involved mixing PS into solvent-dissolved PCL in different weight ratios of PS to PCL (70:30, 50:50, and 30:70 wt%). The resulting composite was used for 3D printing of scaffolds at room temperature. Printability was optimized by adjusting pressure, speed, and layer height through filament collapse and fusion test. Enzymatic degradation, porogen leaching, and DEX release profiles were characterized. Physical properties were assessed using wettability, SEM, and micro-CT to quantify the porosity (percentage, pore size, and interconnectivity). Raman spectroscopy was used to verify the absence of sugar after leaching. Mechanical characteristics were evaluated via compression testing before and after porogen leaching. Bone marrow stromal cells (BMSCs) behavior in the printed scaffolds was studied by assessing viability, metabolic activity, osteo-differentiation, and mineralization. The scaffolds with a 70% sugar concentration exhibited superior printability and reached the highest porosity of 80%, but performed poorly during mechanical testing. A 50% PS concentration demonstrated a 70% porosity, with an average pore size of 25 µm, favoring cell attachment. No trace of sucrose was found in Raman after leaching the sugar for 8 hours. Water contact angle results show improved hydrophilicity as the sugar concentration increased, making the scaffolds more conductive to cell adhesion. The behavior of bone marrow stromal cells (BMSCs) showed positive viability and proliferation results with an increasing trend of mineralization and osteo-differentiation as the sucrose concentration increased. The addition of HA and DEX also promoted mineralization and osteo-differentiation in the cultures. The integration of PS as porogen at a concentration of 50%wt within PCL scaffolds presents a promising approach to address the poor cell attachment and tissue integration issues of PCL in bone tissue engineering. The method allows for the fabrication of scaffolds with tunable porosity and mechanical properties, suitable for various applications. The addition of HA and DEX further enhanced the scaffolds. Future studies will apply the scaffolds in an in-vivo model to thoroughly investigate their performance.

Keywords: bone, PCL, 3D printing, tissue engineering

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Authors: Irene Carmagnola, Valeria Chiono, Sandra Pacharra, Jochen Salber, Sean McMahon, Chris Lovell, Pooja Basnett, Barbara Lukasiewicz, Ipsita Roy, Xiang Zhang, Gianluca Ciardelli

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Thrombosis and restenosis after stenting procedure can be prevented by promoting fast stent wall endothelialisation. It is well known that surface functionalisation with antifouling molecules combining with extracellular matrix proteins is a promising strategy to design biomimetic surfaces able to promote fast endothelialization. In particular, REDV has gained much attention for the ability to enhance rapid endothelialization due to its specific affinity with endothelial cells (ECs). In this work, a two-step plasma treatment was performed to polymerize a thin layer of acrylic acid, used to subsequently graft PEGylated-REDV and polyethylene glycol (PEG) at different molar ratio with the aim to selectively promote endothelial cell adhesion avoiding platelet activation. PEGylate-REDV was provided by Biomatik and it is formed by 6 PEG monomer repetitions (Chempep Inc.), with an NH2 terminal group. PEG polymers were purchased from Chempep Inc. with two different chain lengths: m-PEG6-NH2 (295.4 Da) with 6 monomer repetitions and m-PEG12-NH2 (559.7 Da) with 12 monomer repetitions. Plasma activation was obtained by operating at 50W power, 5 min of treatment and at an Ar flow rate of 20 sccm. Pure acrylic acid (99%, AAc) vapors were diluted in Ar (flow = 20 sccm) and polymerized by a pulsed plasma discharge applying a discharge RF power of 200 W, a duty cycle of 10% (on time = 10 ms, off time = 90 ms) for 10 min. After plasma treatment, samples were dipped into an 1-(3-dimethylaminopropyl)-3- ethylcarbodiimide (EDC)/N-hydroxysuccinimide (NHS) solution (ratio 4:1, pH 5.5) for 1 h at 4°C and subsequently dipped in PEGylate-REDV and PEGylate-REDV:PEG solutions at different molar ratio (100 μg/mL in PBS) for 20 h at room temperature. Surface modification was characterized through physico-chemical analyses and in vitro cell tests. PEGylated-REDV peptide and PEG were successfully bound to the carboxylic groups that are formed on the polymer surface after plasma reaction. FTIR-ATR spectroscopy, X -ray Photoelectron Spectroscopy (XPS) and contact angle measurement gave a clear indication of the presence of the grafted molecules. The use of PEG as a spacer allowed for an increase in wettability of the surface, and the effect was more evident by increasing the amount of PEG. Endothelial cells adhered and spread well on the surfaces functionalized with the REDV sequence. In conclusion, a selective coating able to promote a new endothelial cell layer on polymeric stent surface was developed. In particular, a thin AAc film was polymerised on the polymeric surface in order to expose –COOH groups, and PEGylate-REDV and PEG were successful grafted on the polymeric substrates. The REDV peptide demonstrated to encourage cell adhesion with a consequent, expected improvement of the hemocompatibility of these polymeric surfaces in vivo. Acknowledgements— This work was funded by the European Commission 7th Framework Programme under grant agreement number 604251- ReBioStent (Reinforced Bioresorbable Biomaterials for Therapeutic Drug Eluting Stents). The authors thank all the ReBioStent partners for their support in this work.

Keywords: endothelialisation, plasma treatment, stent, surface functionalisation

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Authors: Safa Ladhari, Alireza Saidi, Phuong Nguyen-Tri

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During health crises, such as COVID-19, using disposable protective equipment (PEs) (masks, gowns, etc.) causes long-term problems, increasing the volume of hazardous waste that must be handled safely and expensively. Therefore, producing textiles for antimicrobial and reusable materials is highly desirable to decrease the use of disposable PEs that should be treated as hazardous waste. In addition, if these items are used regularly in the workplace or for daily activities by the public, they will most likely end up in household waste. Furthermore, they may pose a high risk of contagion to waste collection workers if contaminated. Therefore, to protect the whole population in times of sanitary crisis, it is necessary to equip these materials with tools that make them resilient to the challenges of carrying out daily activities without compromising public health and the environment and without depending on them external technologies and producers. In addition, the materials frequently used for EPs are plastics of petrochemical origin. The subject of the present work is replacing petroplastics with bioplastic since it offers better biodegradability. The chosen polymer is polyhydroxybutyrate (PHB), a family of polyhydroxyalkanoates synthesized by different bacteria. It has similar properties to conventional plastics. However, it is renewable, biocompatible, and has attractive barrier properties compared to other polyesters. These characteristics make it ideal for EP protection applications. The current research topic focuses on the preparation and rapid evaluation of the biological activity of nanotechnology-based antimicrobial agents to treat textile surfaces used for PE. This work will be carried out to provide antibacterial solutions that can be transferred to a workplace application in the fight against short-term biological risks. Three main objectives are proposed during this research topic: 1) the development of suitable methods for the deposition of antibacterial agents on the surface of textiles; 2) the development of a method for measuring the antibacterial activity of the prepared textiles and 3) the study of the biodegradability of the prepared textiles. The studied textile is a non-woven fabric based on a biodegradable polymer manufactured by the electrospinning method. Indeed, nanofibers are increasingly studied due to their unique characteristics, such as high surface-to-volume ratio, improved thermal, mechanical, and electrical properties, and confinement effects. The electrospun film will be surface modified by plasma treatment and then loaded with hybrid antibacterial silver and titanium dioxide nanoparticles by the dip-coating method. This work uses simple methods with emerging technologies to fabricate nanofibers with suitable size and morphology to be used as components for protective equipment. The antibacterial agents generally used are based on silver, zinc, copper, etc. However, to our knowledge, few researchers have used hybrid nanoparticles to ensure antibacterial activity with biodegradable polymers. Also, we will exploit visible light to improve the antibacterial effectiveness of the fabric, which differs from the traditional contact mode of killing bacteria and presents an innovation of active protective equipment. Finally, this work will allow for the innovation of new antibacterial textile materials through a simple and ecological method.

Keywords: protective equipment, antibacterial textile materials, biodegradable polymer, electrospinning, hybrid antibacterial nanoparticles

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Authors: Mazaher Yarmohamadi-Vasel, Ali Reza Modarresi-Alama, Sahar Shabzendedara

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Purpose/Objectives: The first purpose was synthesize Poly(N-(sulfophenyl)aniline) nanoflowers (PSANFLs) and Poly(N-(sulfophenyl)aniline) nanofibers/titanium dioxide nanoparticles ((PSANFs/TiO2NPs) by a solid-state mechano-chemical reaction and template-free method and use them in hybrid solar cell. Also, our second aim was to increase the solubility and the processability of conjugated nanomaterials in water through polar functionalized materials. poly[N-(4-sulfophenyl)aniline] is easily soluble in water because of the presence of polar groups of sulfonic acid in the polymer chain. Materials/Methods: Iron (III) chloride hexahydrate (FeCl3∙6H2O) were bought from Merck Millipore Company. Titanium oxide nanoparticles (TiO2, <20 nm, anatase) and Sodium diphenylamine-4-sulfonate (99%) were bought from Sigma-Aldrich Company. Titanium dioxide nanoparticles paste (PST-20T) was prepared from Sharifsolar Co. Conductive glasses coated with indium tin oxide (ITO) were bought from Xinyan Technology Co (China). For the first time we used the solid-state mechano-chemical reaction and template-free method to synthesize Poly(N-(sulfophenyl)aniline) nanoflowers. Moreover, for the first time we used the same technique to synthesize nanocomposite of Poly(N-(sulfophenyl)aniline) nanofibers and titanium dioxide nanoparticles (PSANFs/TiO2NPs) also for the first time this nanocomposite was synthesized. Examining the results of electrochemical calculations energy gap obtained by CV curves and UV–vis spectra demonstrate that PSANFs/TiO2NPs nanocomposite is a p-n type material that can be used in photovoltaic cells. Doctor blade method was used to creat films for three kinds of hybrid solar cells in terms of different patterns like ITO│TiO2NPs│Semiconductor sample│Al. In the following, hybrid photovoltaic cells in bilayer and bulk heterojunction structures were fabricated as ITO│TiO2NPs│PSANFLs│Al and ITO│TiO2NPs│PSANFs /TiO2NPs│Al, respectively. Fourier-transform infrared spectra, field emission scanning electron microscopy (FE-SEM), ultraviolet-visible spectra, cyclic voltammetry (CV) and electrical conductivity were the analysis that used to characterize the synthesized samples. Results and Conclusions: FE-SEM images clearly demonstrate that the morphology of the synthesized samples are nanostructured (nanoflowers and nanofibers). Electrochemical calculations of band gap from CV curves demonstrated that the forbidden band gap of the PSANFLs and PSANFs/TiO2NPs nanocomposite are 2.95 and 2.23 eV, respectively. I–V characteristics of hybrid solar cells and their power conversion efficiency (PCE) under 100 mWcm−2 irradiation (AM 1.5 global conditions) were measured that The PCE of the samples were 0.30 and 0.62%, respectively. At the end, all the results of solar cell analysis were discussed. To sum up, PSANFLs and PSANFLs/TiO2NPs were successfully synthesized by an affordable and straightforward mechanochemical reaction in solid-state under the green condition. The solubility and processability of the synthesized compounds have been improved compared to the previous work. We successfully fabricated hybrid photovoltaic cells of synthesized semiconductor nanostructured polymers and TiO2NPs as different architectures. We believe that the synthesized compounds can open inventive pathways for the development of other Poly(N-(sulfophenyl)aniline based hybrid materials (nanocomposites) proper for preparing new generation solar cells.

Keywords: mechanochemical synthesis, PSANFLs, PSANFs/TiO2NPs, solar cell

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Authors: Alejandra Martin-Dominguez, Javier Canto-Rios, Velitchko Tzatchkov

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Electrocoagulation is a water treatment technology that consists of generating coagulant species in situ by electrolytic oxidation of sacrificial anode materials triggered by electric current. It removes suspended solids, heavy metals, emulsified oils, bacteria, colloidal solids and particles, soluble inorganic pollutants and other contaminants from water, offering an alternative to the use of metal salts or polymers and polyelectrolyte addition for breaking stable emulsions and suspensions. The method essentially consists of passing the water being treated through pairs of consumable conductive metal plates in parallel, which act as monopolar electrodes, commonly known as ‘sacrificial electrodes’. Physicochemical, electrochemical and hydraulic processes are involved in the efficiency of this type of treatment. While the physicochemical and electrochemical aspects of the technology have been extensively studied, little is known about the influence of the hydraulics. However, the hydraulic process is fundamental for the reactions that take place at the electrode boundary layers and for the coagulant mixing. Electrocoagulation reactors can be open (with free water surface) and closed (pressurized). Independently of the type of rector, hydraulic head loss is an important factor for its design. The present work focuses on the study of the total hydraulic head loss and flow velocity and pressure distribution in electrocoagulation reactors with single or multiple concentric annular cross sections. An analysis of the head loss produced by hydraulic wall shear friction and accessories (minor head losses) is presented, and compared to the head loss measured on a semi-pilot scale laboratory model for different flow rates through the reactor. The tests included laminar, transitional and turbulent flow. The observed head loss was compared also to the head loss predicted by several known conceptual theoretical and empirical equations, specific for flow in concentric annular pipes. Four single concentric annular cross section and one multiple concentric annular cross section reactor configuration were studied. The theoretical head loss resulted higher than the observed in the laboratory model in some of the tests, and lower in others of them, depending also on the assumed value for the wall roughness. Most of the theoretical models assume that the fluid elements in all annular sections have the same velocity, and that flow is steady, uniform and one-dimensional, with the same pressure and velocity profiles in all reactor sections. To check the validity of such assumptions, a computational fluid dynamics (CFD) model of the concentric annular pipe reactor was implemented using the ANSYS Fluent software, demonstrating that pressure and flow velocity distribution inside the reactor actually is not uniform. Based on the analysis, the equations that predict better the head loss in single and multiple annular sections were obtained. Other factors that may impact the head loss, such as the generation of coagulants and gases during the electrochemical reaction, the accumulation of hydroxides inside the reactor, and the change of the electrode material with time, are also discussed. The results can be used as tools for design and scale-up of electrocoagulation reactors, to be integrated into new or existing water treatment plants.

Keywords: electrocoagulation reactors, hydraulic head loss, concentric annular pipes, computational fluid dynamics model

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Authors: Alberto Fina, Samuele Colonna, Maria del Mar Bernal, Orietta Monticelli, Mauro Tortello, Renato Gonnelli, Julio Gomez, Chiara Novara, Guido Saracco

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Thermally conductive polymer nanocomposites are of high interest for several applications including low-temperature heat recovery, heat exchangers in a corrosive environment and heat management in electronics and flexible electronics. In this paper, the preparation of thermally conductive nanocomposites exploiting graphene-related materials is addressed, along with their thermal characterization. In particular, correlations between 1- chemical and physical features of the nanoflakes and 2- processing conditions with the heat conduction properties of nanocomposites is studied. Polymers are heat insulators; therefore, the inclusion of conductive particles is the typical solution to obtain a sufficient thermal conductivity. In addition to traditional microparticles such as graphite and ceramics, several nanoparticles have been proposed, including carbon nanotubes and graphene, for the use in polymer nanocomposites. Indeed, thermal conductivities for both carbon nanotubes and graphenes were reported in the wide range of about 1500 to 6000 W/mK, despite such property may decrease dramatically as a function of the size, number of layers, the density of topological defects, re-hybridization defects as well as on the presence of impurities. Different synthetic techniques have been developed, including mechanical cleavage of graphite, epitaxial growth on SiC, chemical vapor deposition, and liquid phase exfoliation. However, the industrial scale-up of graphene, defined as an individual, single-atom-thick sheet of hexagonally arranged sp2-bonded carbons still remains very challenging. For large scale bulk applications in polymer nanocomposites, some graphene-related materials such as multilayer graphenes (MLG), reduced graphene oxide (rGO) or graphite nanoplatelets (GNP) are currently the most interesting graphene-based materials. In this paper, different types of graphene-related materials were characterized for their chemical/physical as well as for thermal properties of individual flakes. Two selected rGOs were annealed at 1700°C in vacuum for 1 h to reduce defectiveness of the carbon structure. Thermal conductivity increase of individual GNP with annealing was assessed via scanning thermal microscopy. Graphene nano papers were prepared from both conventional RGO and annealed RGO flakes. Characterization of the nanopapers evidenced a five-fold increase in the thermal diffusivity on the nano paper plane for annealed nanoflakes, compared to pristine ones, demonstrating the importance of structural defectiveness reduction to maximize the heat dissipation performance. Both pristine and annealed RGO were used to prepare polymer nanocomposites, by melt reactive extrusion. Thermal conductivity showed two- to three-fold increase in the thermal conductivity of the nanocomposite was observed for high temperature treated RGO compared to untreated RGO, evidencing the importance of using low defectivity nanoflakes. Furthermore, the study of different processing paremeters (time, temperature, shear rate) during the preparation of poly (butylene terephthalate) nanocomposites evidenced a clear correlation with the dispersion and fragmentation of the GNP nanoflakes; which in turn affected the thermal conductivity performance. Thermal conductivity of about 1.7 W/mK, i.e. one order of magnitude higher than for pristine polymer, was obtained with 10%wt of annealed GNPs, which is in line with state of the art nanocomposites prepared by more complex and less upscalable in situ polymerization processes.

Keywords: graphene, graphene-related materials, scanning thermal microscopy, thermally conductive polymer nanocomposites

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Authors: Ariesny Vera, Rodrigo Montecinos

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The rare-earth elements (REEs) or rare-earth metals (REMs), correspond to seventeen chemical elements composed by the fifteen lanthanoids, as well as scandium and yttrium. Lanthanoids corresponds to lanthanum and the f-block elements, from cerium to lutetium. Scandium and yttrium are considered rare-earth elements because they have ionic radii similar to the lighter f-block elements. These elements were called rare earths because they are simply more difficult to extract and separate individually than the most metals and, generally, they do not accumulate in minerals, they are rarely found in easily mined ores and are often unfavorably distributed in common ores/minerals. REEs show unique chemical and physical properties, in comparison to the other metals in the periodic table. Nowadays, these physicochemical properties are utilized in a wide range of synthetic, catalytic, electronic, medicinal, and military applications. Because of their applications, the global demand for rare earth metals is becoming progressively more important in the transition to a self-sustaining society and greener economy. However, due to the difficult separation between lanthanoid ions, the high cost and pollution of these processes, the scientists search the development of a method that combines selectivity and quantitative separation of lanthanoids from the leaching liquor, while being more economical and environmentally friendly processes. This motivation has favored the design and development of more efficient and environmentally friendly cation extractors with the incorporation of compounds as ionic liquids, membrane inclusion polymers (PIM) and supramolecular systems. Supramolecular chemistry focuses on the development of host-guest systems, in which a host molecule can recognize and bind a certain guest molecule or ion. Normally, the formation of a host-guest complex involves non-covalent interactions Additionally, host-guest interactions can be influenced among others effects by the structural nature of host and guests. The different macrocyclic hosts for lanthanoid species that have been studied are crown ethers, cyclodextrins, cucurbituryls, calixarenes and pillararenes.Among all the factors that can influence and affect lanthanoid (III) coordination, perhaps the most basic of them is the systematic control using macrocyclic substituents that promote a selective coordination. In this sense, macrocycles pillar[n]arenes (P[n]As) present a relatively easy functionalization and they have more π-rich cavity than other host molecules. This gives to P[n]As a negative electrostatic potential in the cavity which would be responsible for the selectivity of these compounds towards cations. Furthermore, the cavity size, the linker, and the functional groups of the polar headgroups could be modified in order to control the association of lanthanoid cations. In this sense, different P[n]As systems, specifically derivatives of the pentamer P[5]A functionalized with amide, amine, phosphate and sulfate derivatives, have been designed in terms of experimental synthesis and molecular dynamics, and the interaction between these P[5]As and some lanthanoid ions such as La³+, Eu³+ and Lu³+ has been studied by physicochemical characterization by 1H-NMR, ITC and fluorescence in the case of Eu³+ systems. The molecular dynamics study of these systems was developed in hexane as solvent, also taking into account the lanthanoid ions mentioned above, and the respective comparison studies between the different ions.

Keywords: lanthanoids, macrocycles, pillar[n]arenes, rare-earth metal extraction, supramolecular chemistry, supramolecular complexes.

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Authors: Dmitriy Berillo, Areej K. A. Al-Jwaid, Jonathan L. Caplin, Andrew Cundy, Irina Savina

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Chlorophenols (CPs) are used as a precursor in the production of higher CPs and dyestuffs, and as a preservative. Contamination by CPs of the ground water is located in the range from 0.15-100mg/L. The EU has set maximum concentration limits for pesticides and their degradation products of 0.1μg/L and 0.5μg/L, respectively. People working in industries which produce textiles, leather products, domestic preservatives, and petrochemicals are most heavily exposed to CPs. The International Agency for Research on Cancers categorized CPs as potential human carcinogens. Existing multistep water purification processes for CPs such as hydrogenation, ion exchange, liquid-liquid extraction, adsorption by activated carbon, forward and inverse osmosis, electrolysis, sonochemistry, UV irradiation, and chemical oxidation are not always cost effective and can cause the formation of even more toxic or mutagenic derivatives. Bioremediation of CPs derivatives utilizing microorganisms results in 60 to 100% decontamination efficiency and the process is more environmentally-friendly compared with existing physico-chemical methods. Microorganisms immobilized onto a substrate show many advantages over free bacteria systems, such as higher biomass density, higher metabolic activity, and resistance to toxic chemicals. They also enable continuous operation, avoiding the requirement for biomass-liquid separation. The immobilized bacteria can be reused several times, which opens the opportunity for developing cost-effective processes for wastewater treatment. In this study, we develop a bioremediation system for CPs based on macroporous materials, which can be efficiently used for wastewater treatment. Conditions for the preparation of the macroporous material from specific bacterial strains (Pseudomonas mendocina and Rhodococus koreensis) were optimized. The concentration of bacterial cells was kept constant; the difference was only the type of cross-linking agents used e.g. glutaraldehyde, novel polymers, which were utilized at concentrations of 0.5 to 1.5%. SEM images and rheology analysis of the material indicated a monolithic macroporous structure. Phenol was chosen as a model system to optimize the function of the cryogel material and to estimate its enzymatic activity, since it is relatively less toxic and harmful compared to CPs. Several types of macroporous systems comprising live bacteria were prepared. The viability of the cross-linked bacteria was checked using Live/Dead BacLight kit and Laser Scanning Confocal Microscopy, which revealed the presence of viable bacteria with the novel cross-linkers, whereas the control material cross-linked with glutaraldehyde(GA), contained mostly dead cells. The bioreactors based on bacteria were used for phenol degradation in batch mode at an initial concentration of 50mg/L, pH 7.5 and a temperature of 30°C. Bacterial strains cross-linked with GA showed insignificant ability to degrade phenol and for one week only, but a combination of cross-linking agents illustrated higher stability, viability and the possibility to be reused for at least five weeks. Furthermore, conditions for CPs degradation will be optimized, and the chlorophenol degradation rates will be compared to those for phenol. This is a cutting-edge bioremediation approach, which allows the purification of waste water from sustainable compounds without a separation step to remove free planktonic bacteria. Acknowledgments: Dr. Berillo D. A. is very grateful to Individual Fellowship Marie Curie Program for funding of the research.

Keywords: bioremediation, cross-linking agents, cross-linked microbial cell, chlorophenol degradation

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Authors: B.L. España-Sánchez, E. Luna-Hernández, R.A. Mauricio-Sánchez, M.E. Cruz-Soto, F. Padilla-Vaca, R. Muñoz, L. Granados-López, L.R. Ovalle-Flores, J.L. Menchaca-Arredondo, G. Luna-Bárcenas

Abstract:

Treatment of burn injured has been considered an important clinical problem due to the fluid control and the presence of microorganisms during the healing process. Conventional treatment includes antiseptic techniques, topical medication and surgical removal of damaged skin, to avoid bacterial growth. In order to accelerate this process, different alternatives for tissue regeneration have been explored, including artificial skin, polymers, hydrogels and hybrid materials. Some requirements consider a nonreactive organic polymer with high biocompatibility and skin adherence, avoiding bacterial infections. Chitin-derivative biopolymer such as chitosan (CS) has been used in skin regeneration following third-degree burns. The biological interest of CS is associated with the improvement of tissue cell stimulation, biocompatibility and antibacterial properties. In particular, antimicrobial properties of CS can be significantly increased when is blended with nanostructured materials. Silver-based nanocomposites have gained attention in medicine due to their high antibacterial properties against pathogens, related to their high surface area/volume ratio at nanomolar concentrations. Silver nanocomposites can be blended or synthesized with chitin-derivative biopolymers in order to obtain a biodegradable/antimicrobial hybrid with improved physic-mechanical properties. In this study, nanocomposites based on chitosan/silver nanoparticles (CS/nAg) were synthesized by the in situ chemical reduction method, improving their antibacterial properties against pathogenic bacteria and enhancing the healing process in thermal burn injuries produced in an animal model. CS/nAg was prepared in solution by the chemical reduction method, using AgNO₃ as precursor. CS was dissolved in acetic acid and mixed with different molar concentrations of AgNO₃: 0.01, 0.025, 0.05 and 0.1 M. Solutions were stirred at 95°C during 20 hours, in order to promote the nAg formation. CS/nAg solutions were placed in Petri dishes and dried, to obtain films. Structural analyses confirm the synthesis of silver nanoparticles (nAg) by means of UV-Vis and TEM, with an average size of 7.5 nm and spherical morphology. FTIR analyses showed the complex formation by the interaction of hydroxyl and amine groups with metallic nanoparticles, and surface chemical analysis (XPS) shows low concentration of Ag⁰/Ag⁺ species. Topography surface analyses by means of AFM shown that hydrated CS form a mesh with an average diameter of 10 µm. Antibacterial activity against S. aureus and P. aeruginosa was improved in all evaluated conditions, such as nAg loading and interaction time. CS/nAg nanocomposites films did not show Ag⁰/Ag⁺ release in saline buffer and rat serum after exposition during 7 days. Healing process was significantly enhanced by the presence of CS/nAg nanocomposites, inducing the production of myofibloblasts, collagen remodelation, blood vessels neoformation and epidermis regeneration after 7 days of injury treatment, by means of histological and immunohistochemistry assays. The present work suggests that hydrated CS/nAg nanocomposites can be formed a mesh, improving the bacterial penetration and the contact with embedded nAg, producing complete growth inhibition after 1.5 hours. Furthermore, CS/nAg nanocomposites improve the cell tissue regeneration in thermal burn injuries induced in rats. Synthesis of antibacterial, non-toxic, and biocompatible nanocomposites can be an important issue in tissue engineering and health care applications.

Keywords: antibacterial, chitosan, healing process, nanocomposites, silver

Procedia PDF Downloads 257

Authors: Agman Gupta, Rajashekar Badam, Noriyoshi Matsumi

Abstract:

Introduction: Recently, silicon has been recognized as one of the potential alternatives as anode active material in Li-ion batteries (LIBs) to replace the conventionally used graphite anodes. Silicon is abundantly present in the nature, it can alloy with lithium metal, and has a higher theoretical capacity (~4200 mAhg-1) that is approximately 10 times higher than graphite. However, because of a large volume expansion (~400%) upon repeated de-/alloying, the pulverization of Si particles causes the exfoliation of electrode laminate leading to the loss of electrical contact and adversely affecting the formation of solid-electrolyte interface (SEI).1 Functional polymers as binders have emerged as a competitive strategy to mitigate these drawbacks and failure mechanism of silicon anodes.1 A variety of aqueous/non-aqueous polymer binders like sodium carboxy-methyl cellulose (CMC-Na), styrene butadiene rubber (SBR), poly(acrylic acid), and other variants like mussel inspired binders have been investigated to overcome these drawbacks.1 However, there are only a few reports that mention the attempt of addressing all the drawbacks associated with silicon anodes effectively using a single novel functional polymer system as a binder. In this regard, here, we report a novel highly robust n-type bisiminoacenaphthenequinone (BIAN)-paraphenylene-based crosslinked polymer as a binder for Si anodes in lithium-ion batteries (Fig. 1). On its application, crosslinked-BIAN binder was evaluated to provide mechanical robustness to the large volume expansion of Si particles, maintain electrical conductivity within the electrode laminate, and facilitate in the formation of a thin SEI by restricting the extent of electrolyte decomposition on the surface of anode. The fabricated anodic half-cells were evaluated electrochemically for their rate capability, cyclability, and discharge capacity. Experimental: The polymerized BIAN (P-BIAN) copolymer was synthesized as per the procedure reported by our group.2 The synthesis of crosslinked P-BIAN: a solution of P-BIAN copolymer (1.497 g, 10 mmol) in N-methylpyrrolidone (NMP) (150 ml) was set-up to stir under reflux in nitrogen atmosphere. To this, 1,6-dibromohexane (5 mmol, 0.77 ml) was added dropwise. The resultant reaction mixture was stirred and refluxed at 150 °C for 24 hours followed by refrigeration for 3 hours at 5 °C. The product was obtained by evaporating the NMP solvent under reduced pressure and drying under vacuum at 120 °C for 12 hours. The obtained product was a black colored sticky compound. It was characterized by 1H-NMR, XPS, and FT-IR techniques. Results and Discussion: The N 1s XPS spectrum of the crosslinked BIAN polymer showed two characteristic peaks corresponding to the sp2 hybridized nitrogen (-C=N-) at 399.6 eV of the diimine backbone in the BP and quaternary nitrogen at 400.7 eV corresponding to the crosslinking of BP via dibromohexane. The DFT evaluation of the crosslinked BIAN binder showed that it has a low lying lowest unoccupied molecular orbital (LUMO) that enables it to get doped in the reducing environment and influence the formation of a thin (SEI). Therefore, due to the mechanically robust crosslinked matrices as well as its influence on the formation of a thin SEI, the crosslinked BIAN binder stabilized the Si anode-based half-cell for over 1000 cycles with a reversible capacity of ~2500 mAhg-1 and ~99% capacity retention as shown in Fig. 2. The dynamic electrochemical impedance spectroscopy (DEIS) characterization of crosslinked BIAN-based anodic half-cell confirmed that the SEI formed was thin in comparison with the conventional binder-based anodes. Acknowledgement: We are thankful to the financial support provided by JST-Mirai Program, Grant Number: JP18077239

Keywords: self-healing binder, n-type binder, thin solid-electrolyte interphase (SEI), high-capacity silicon anodes, low-LUMO

Procedia PDF Downloads 130

Authors: L. Malic, X. Zhang, D. Brassard, L. Clime, J. Daoud, C. Luebbert, V. Barrere, A. Boutin, S. Bidawid, N. Corneau, J. Farber, T. Veres

Abstract:

The incidence of infections caused by foodborne pathogens such as Listeria monocytogenes (L. monocytogenes) poses a great potential threat to public health and safety. These issues are further exacerbated by legal repercussions due to “zero tolerance” food safety standards adopted in developed countries. Unfortunately, a large number of related disease outbreaks are caused by pathogens present in extremely low counts currently undetectable by available techniques. The development of highly sensitive and rapid detection of foodborne pathogens is therefore crucial, and requires robust and efficient pre-analytical sample preparation. Immunomagnetic separation is a popular approach to sample preparation. Microfluidic chips combined with external magnets have emerged as viable high throughput methods. However, external magnets alone are not suitable for the capture of nanoparticles, as very strong magnetic fields are required. Devices that incorporate externally applied magnetic field and microstructures of a soft magnetic material have thus been used for local field amplification. Unfortunately, very complex and costly fabrication processes used for integration of soft magnetic materials in the reported proof-of-concept devices would prohibit their use as disposable tools for food and water safety or diagnostic applications. We present a sample preparation magnetic microfluidic device implemented in low-cost thermoplastic polymers using fabrication techniques suitable for mass-production. The developed magnetic capture chip (M-chip) was employed for rapid capture and release of L. monocytogenes conjugated to immunomagnetic nanoparticles (IMNs) in buffer and beef filtrate. The M-chip relies on a dense array of Nickel-coated high-aspect ratio pillars for capture with controlled magnetic field distribution and a microfluidic channel network for sample delivery, waste, wash and recovery. The developed Nickel-coating process and passivation allows generation of switchable local perturbations within the uniform magnetic field generated with a pair of permanent magnets placed at the opposite edges of the chip. This leads to strong and reversible trapping force, wherein high local magnetic field gradients allow efficient capture of IMNs conjugated to L. monocytogenes flowing through the microfluidic chamber. The experimental optimization of the M-chip was performed using commercially available magnetic microparticles and fabricated silica-coated iron-oxide nanoparticles. The fabricated nanoparticles were optimized to achieve the desired magnetic moment and surface functionalization was tailored to allow efficient capture antibody immobilization. The integration, validation and further optimization of the capture and release protocol is demonstrated using both, dead and live L. monocytogenes through fluorescence microscopy and plate- culture method. The capture efficiency of the chip was found to vary as function of listeria to nanoparticle concentration ratio. The maximum capture efficiency of 30% was obtained and the 24-hour plate-culture method allowed the detection of initial sample concentration of only 16 cfu/ml. The device was also very efficient in concentrating the sample from a 10 ml initial volume. Specifically, 280% concentration efficiency was achieved in 17 minutes only, demonstrating the suitability of the system for food safety applications. In addition, flexible design and low-cost fabrication process will allow rapid sample preparation for applications beyond food and water safety, including point-of-care diagnosis.

Keywords: array of pillars, bacteria isolation, immunomagnetic sample preparation, polymer microfluidic device

Procedia PDF Downloads 247

Authors: Leila Safazadeh, Brad Berron

Abstract:

Self-assembled monolayers have tremendous impact in interfacial science, due to the unique opportunity they offer to tailor surface properties. Low-density self-assembled monolayers are an emerging class of monolayers where the environment-interfacing portion of the adsorbate has a greater level of conformational freedom when compared to traditional monolayer chemistries. This greater range of motion and increased spacing between surface-bound molecules offers new opportunities in tailoring adsorption phenomena in sensing systems. In particular, we expect low-density surfaces to offer a unique opportunity to intercalate surface bound ligands into the secondary structure of protiens and other macromolecules. Additionally, as many conventional sensing surfaces are built upon gold surfaces (SPR or QCM), these surfaces must be compatible with gold substrates. Here, we present the first stable method of generating low-density self assembled monolayer surfaces on gold for the analysis of their interactions with protein targets. Our approach is based on the 2:1 addition of thiol-yne chemistry to develop new classes of y-shaped adsorbates on gold, where the environment-interfacing group is spaced laterally from neighboring chemical groups. This technique involves an initial deposition of a crystalline monolayer of 1,10 decanedithiol on the gold substrate, followed by grafting of a low-packed monolayer on through a photoinitiated thiol-yne reaction in presence of light. Orthogonality of the thiol-yne chemistry (commonly referred to as a click chemistry) allows for preparation of low-density monolayers with variety of functional groups. To date, carboxyl, amine, alcohol, and alkyl terminated monolayers have been prepared using this core technology. Results from surface characterization techniques such as FTIR, contact angle goniometry and electrochemical impedance spectroscopy confirm the proposed low chain-chain interactions of the environment interfacing groups. Reductive desorption measurements suggest a higher stability for the click-LDMs compared to traditional SAMs, along with the equivalent packing density at the substrate interface, which confirms the proposed stability of the monolayer-gold interface. In addition, contact angle measurements change in the presence of an applied potential, supporting our description of a surface structure which allows the alkyl chains to freely orient themselves in response to different environments. We are studying the differences in protein adsorption phenomena between well packed and our loosely packed surfaces, and we expect this data will be ready to present at the GRC meeting. This work aims to contribute biotechnology science in the following manner: Molecularly imprinted polymers are a promising recognition mode with several advantages over natural antibodies in the recognition of small molecules. However, because of their bulk polymer structure, they are poorly suited for the rapid diffusion desired for recognition of proteins and other macromolecules. Molecularly imprinted monolayers are an emerging class of materials where the surface is imprinted, and there is not a bulk material to impede mass transfer. Further, the short distance between the binding site and the signal transduction material improves many modes of detection. My dissertation project is to develop a new chemistry for protein-imprinted self-assembled monolayers on gold, for incorporation into SPR sensors. Our unique contribution is the spatial imprinting of not only physical cues (seen in current imprinted monolayer techniques), but to also incorporate complementary chemical cues. This is accomplished through a photo-click grafting of preassembled ligands around a protein template. This conference is important for my development as a graduate student to broaden my appreciation of the sensor development beyond surface chemistry.

Keywords: low-density self-assembled monolayers, thiol-yne click reaction, molecular imprinting

Procedia PDF Downloads 195

Authors: Z. S. Haidar

Abstract:

Millions of teeth are removed annually, and dental extraction is one of the most commonly performed surgical procedures globally. Whether due to caries, periodontal disease, or trauma, exodontia and the ensuing wound healing and bone remodeling processes of the resultant socket (hole in the jaw bone) usually result in serious deformities of the residual alveolar osseous ridge and surrounding soft tissues (reduced height/width). Such voluminous changes render the placement of a proper conventional bridge, denture, or even an implant-supported prosthesis extremely challenging. Further, most extractions continue to be performed with no regard for preventing the onset of alveolar osteitis (also known as dry socket, a painful and difficult-to-treat/-manage condition post-exodontia). Hence, such serious resorptive morphological changes often result in significant facial deformities and a negative impact on the overall Quality of Life (QoL) of patients (and oral health-related QoL); alarming, particularly for the geriatric with compromised healing and in light of the thriving longevity statistics. Despite advances in tissue/wound grafting, serious limitations continue to exist, including efficacy and clinical outcome predictability, cost, treatment time, expertise, and risk of immune reactions. For cases of dry socket, specifically, the commercially available and often-prescribed home remedies are highly-lacking. Indeed, most are not recommended for use anymore. Alveogyl is a fine example. Hence, there is a great market demand and need for alternative solutions. Herein, SockGEL/PLUG (patent pending), an innovative, all-natural, drug-free, and injectable thermo-responsive hydrogel, was designed, formulated, characterized, and evaluated as an osteogenic, angiogenic, anti-microbial, and pain-soothing suture-free intra-alveolar dressing, safe and efficacious for use in fresh extraction sockets, immediately post-exodontia. It is composed of FDA-approved, biocompatible and biodegradable polymers, self-assembled electro-statically to formulate a scaffolding matrix to (1) prevent the on-set of alveolar osteitis via securing the fibrin-clot in situ and protecting/sealing the socket from contamination/infection; and (2) endogenously promote/accelerate wound healing and bone remodeling to preserve the volume of the alveolus. The intrinsic properties of the SockGEL/PLUG hydrogel were evaluated physical-chemical-mechanically for safety (cell viability), viscosity, rheology, bio-distribution, and essentially, capacity to induce wound healing and osteogenesis (small defect, in vivo) without any signaling cues from exogenous cells, growth factors or drugs. The proposed animal model of cranial critical-sized and non-vascularized bone defects shall provide new and critical insights into the role and mechanism of the employed natural bio-polymer blend and gel product in endogenous reparative regeneration of soft tissues and bone morphogenesis. Alongside, the fine-tuning of our modified formulation method will further tackle appropriateness, reproducibility, scalability, ease, and speed in producing stable, biodegradable, and sterilizable thermo-sensitive matrices (3-dimensional interpenetrating yet porous polymeric network) suitable for the intra-socket application. Findings are anticipated to provide sufficient evidence to translate into pilot clinical trials and validate the innovation before engaging the market for feasibility, acceptance, and cost-effectiveness studies.

Keywords: hydrogel, nanotechnology, bioengineering, bone regeneration, nanogel, drug delivery

Procedia PDF Downloads 80

Authors: Ziyad S. Haidar

Abstract:

Millions of teeth are removed annually, and dental extraction is one of the most commonly performed surgical procedures globally. Whether due to caries, periodontal disease or trauma, exodontia and the ensuing wound healing and bone remodeling processes of the resultant socket (hole in the jaw bone) usually result in serious deformities of the residual alveolar osseous ridge and surrounding soft tissues (reduced height/width). Such voluminous changes render the placement of a proper conventional bridge, denture or even an implant-supported prosthesis extremely challenging. Further, most extractions continue to be performed with no regard for preventing the onset of alveolar osteitis (also known as dry socket, a painful and difficult-to-treat/-manage condition post-exodontia). Hence, such serious resorptive morphological changes often result in significant facial deformities and a negative impact on the overall Quality of Life (QoL) of patients (and oral health-related QoL), alarming, particularly for the geriatric with compromised healing and in light of the thriving longevity statistics. Opportunity: Despite advances in tissue/wound grafting, serious limitations continue to exist, including efficacy and clinical outcome predictability, cost, treatment time, expertise and risk of immune reactions. For cases of dry sockets, specifically, the commercially-available and often-prescribed home remedies are highly lacking. Indeed, most are not recommended for use anymore. Alveogyl is a fine example. Hence, there is a great market demand and need for alternative solutions. Solution: Herein, SockGEL/PLUG (patent pending), an all-natural, drug-free and injectable stimuli-responsive hydrogel, was designed, formulated, characterized and evaluated as an osteogenic, angiogenic, anti-microbial and pain-soothing suture-free intra-alveolar dressing, safe and efficacious for use in several oro-dental and cranio-maxillo-facial interventional applications; for example: in fresh dental extraction sockets, immediately post-exodontia. It is composed of FDA-approved, biocompatible and biodegradable polymers, self-assembled electro-statically to formulate a scaffolding matrix to (a) prevent the onset of alveolar osteitis via securing the fibrin-clot in situ and protecting/sealing the socket from contamination/infection; and (b) endogenously promote/accelerate wound healing and bone remodeling to preserve the volume of the alveolus. Findings: The intrinsic properties of the SockGEL/PLUG hydrogel were evaluated physico-chemico-mechanically for safety (cell viability), viscosity, rheology, bio-distribution and essentially, capacity to induce wound healing and osteogenesis (small defect, in vivo) without any signaling cues from exogenous cells, growth factors or drugs. The performed animal model of cranial critical-sized and non-vascularized bone defects shall provide vitally critical insights into the role and mechanism of the employed natural bio-polymer blend and gel product in endogenous reparative regeneration of soft tissues and bone morphogenesis. Alongside, the fine-tuning of our modified formulation method will further tackle appropriateness, reproducibility, scalability, ease and speed in producing stable, biodegradable and sterilizable stimuli (thermo-sensitive and photo-responsive) matrices (3-dimensional interpenetrating yet porous polymeric network) suitable for an intra-socket application, and beyond. Conclusions and Perspective: Findings are anticipated to provide sufficient evidence to translate into pilot clinical trials and validate the bionanomaterial before engaging the market for feasibility, acceptance and cost-effectiveness studies. The SockGEL/PLUG platform is patent pending: SockGEL is a bio-inspired drug-free hydrogel; SockPLUG is a drug-loaded hydrogel designed for complex indications.

Keywords: hydrogel, injectable, dentistry, craniomaxillofacial complex, bioinspired, nanobiotechnology, biopolymer, sol-gel, stimuli-responsive, matrix, tissue engineering, regenerative medicine

Procedia PDF Downloads 41