Browsing by Author "Eubank, Jarrod F."
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- ItemAnalysis of Metal-Organic Framework Stability, Antimicrobial Properties, and Dental Applications(Florida Southern College, 2022-05) Marusko, Benjamin; Eubank, Jarrod F.; Langford, Melanie L.The development of metal-organic frameworks (MOFs), an analysis of their properties, and exploration of their potential biomedical applications, specifically dental, are areas of modern biochemical interest focus on through this study. Previous research has shown these frameworks (and/or their components) have the potential for antimicrobial properties, and we hypothesized that they may be used on dental implants to inhibit the growth of oral bacteria responsible for peri-implantitis. This project has consisted of the development and structural analysis of several different novel frameworks with a high potential for microbial inhibition. Through the incorporation of antimicrobial metal ions, bridging ligands, and possibly terminal ligands there is the potential for a synergistic antimicrobial effect greater than any of the individual components. Structural stability has been monitored under varying environmental conditions, such as humidity; changes have been recorded and analyzed for potential functional applications in biological conditions. A common characteristic of MOFs is the modularity of components, which could allow for the addition of drug compounds or ligands with higher antimicrobial effects for a stronger inhibition of bacterial growth. Key MOFs were selected for antimicrobial analysis through Kirby-Bauer inhibition tests on the common oral bacteria, Streptococcus mutans (S. mutans). The frameworks presenting significant bacterial inhibition were then tested for the potential of growth directly onto the titanium implants used in a majority of oral surgeries. Our research project has resulted in novel MOFs with antimicrobial properties that can be further functionalized and grown directly onto titanium implants for the prevention of infection immediately post oral surgery.
- ItemEffect of pendant isophthalic acid moieties on the adsorption properties of light hydrocarbons in HKUST-1-like tbo -MOFs: Application to methane purification and storage(Royal Society of Chemistry, 2014) Belmabkhout , Youssef; Mouttaki, Hasnaa; Eubank, Jarrod F.; Guillerm, Vincent; Eddaoudi, MohamedEquilibrium adsorption of methane (CH4), C2+ gases (ethane (C2H6), ethylene (C2H4), propane (C3H8), and propylene (C3H6)), and carbon dioxide (CO2) was measured on a series of tbo-MOFs (topological analogues of the prototypical MOF, HKUST-1, correspondingly dubbed tbo-MOF-1), which were developed via the supermolecular building layer (SBL) pillaring strategy. Specifically, tbo-MOF-2 and its isoreticular, functionalized analogue, tbo-MOF-2-{CH2O[Ph(CO2H)2]}2 (or tbo-MOF-3), which is characterized by pendant isophthalic acid moieties freely pointing into the cavities, were evaluated on the basis of potential use in methane storage and C2+/CH4 separation. The parent, tbo-MOF-2, showed high gravimetric and volumetric CH4 uptake, close to the U.S. Department of Energy (DOE) target for methane storage at 35 bar and room temperature. Though the presence of the pendant isophthalic acid moiety in the analogous compound, tbo-MOF-3, led to a decrease in total CH4 uptake, due mainly to the reduced size of the cavities, interestingly, it increased the affinity of the SBL-based tbo-MOF platform for propane, propene, ethane, and ethylene at low pressures compared with CH4, due additionally to the enhanced interactions of the highly polarizable light hydrocarbons with the isophthalic acid moiety. Using Ideal Adsorption Solution Theory (IAST), the predicted mixture adsorption equilibria for the C3H8/CH4, C3H6/CH4, C2H6/CH4, C2H4/CH4, and C3H8/CO2 systems showed high adsorption selectivity for C2+ over methane for tbo-MOF-3 compared with tbo-MOF-2. The high working storage capacity of tbo-MOF-2 and the high affinity of tbo-MOF-3 for C2+ over CH4 and CO2 make tbo-MOF an ideal platform for studies in gas storage and separation.
- ItemExceptional stability and high hydrogen uptake in hydrogen-bonded metal-organic cubes possessing ACO and AST zeolite-like topologies(American Chemical Society, 2009) Sava, Dorina F.; Kravtsov, Victor Ch.; Eckert, Juergen; Eubank, Jarrod F.; Nouar, Farid; Eddaoudi, MohamedA novel approach for targeting zeolite-like metal-organic frameworks (ZMOFs) that utilizes metal-organic cubes and are regarded as double four-membered rings (d4Rs) and are composite building units (BUs) in traditional inorganic zeolites are reported. The implimentation of the new method is demonstrated by two ZMOFs with ACO and AST zeolite-like topologies constructed from d4R BUs exclusively held together by hydrogen bonds.
- ItemHighly effective and fast removal of anionic carcinogenic dyes: Via an In3-cluster-based cationic metal-organic framework with nitrogen-rich ligand(Royal Society of Chemistry, 2019) Liu, Xinyao; Liu, Bing; Eubank, Jarrod F.; Liu, YunlingIn this work, highly effective and rapid removal of anionic carcinogenic organic dye molecules is achieved through the use of a novel cationic metal–organic framework (MOF). The MOF is constructed using a nitrogen-rich triangular organic ligand, 4,4′,4′′-s-triazine-1,3,5-triyltri-p-aminobenzoate (H3TATAB), and trinuclear 6-connected In3-cluster secondary building units (SBUs), [In3O(TATAB)2(H2O)3](NO3)·(DMA)15 (In-TATAB), which gives a structure exhibiting a new topology. As the formula indicates, In-TATAB is inherently cationic due to the [In3O(COO−)6]+ units, which thus favors interaction with anionic guests. Several organic dye molecules of varying charge and size, such as acid chrome blue K, acid red 26, congo red, direct black 38 and, orange II, were used to test the sequestration potential of the MOF material. In addition to electrostatic attraction, it is shown that hydrogen-bonding originating from the highly functional bridging ligand and terminal H2O ligands enhance the interactions between the framework and guest dye molecules, suggesting its potential use for the removal of anionic organic pollutants.
- ItemAn Inquiry into the Synthesis of Zinc/Chelidonate-based MOFs and Their Potential Uses in the Prevention of Hernia Mesh Infections(Florida Southern College, 2022-05) Vassalotti, Ryan; Eubank, Jarrod F.A hernia is one of the most common medical issues that occurs in the entire world, affecting millions of people yearly. As part of the surgery to repair a hernia, the physician will often insert a mesh material to prevent recurrence of the hernia. Despite their high efficacy in preventing recurrence of the hernia, these hernia meshes are unfortunately prone to infection. Hernia mesh infections affect thousands of people every year and cost the individuals large amounts of unnecessary time and money. The field of metal-organic frameworks (MOFs) has opened up a promising path towards solving this issue. The successful synthesis of antimicrobial MOFs and biocompatible MOFs demonstrates that there is merit in pursuing biomedical applications. With the help of antimicrobial materials like MOFs it may be possible to prevent these postoperative infections. Synthesis of a Zn-based analogue to a previously characterized antimicrobial Cu-basedMOF, me137, was successful. The results of this study indicate that control of both morphology and structure in Zn-based MOFs is possible. Additionally, the Zn-based MOFs appear to be more chemically stable than similar Cu-based MOFs. Antimicrobial assays have demonstrated that the Zn-based MOFs are capable of inhibiting the growth of E. coli and S. aureus. Early adhesion tests have shown that growth of Compound 1 (RV22) onto unmodified polypropylene is not an interaction that readily occurs. Thus, methods for modifying polypropylene to take on a form more conducive to MOF adhesion was investigated. A method for oxidizing polypropylene with the use of KMnO4, NaOH, and heat was found to be successful, but adhesion of Compound 1 onto the oxidized polypropylene has not yet been achieved.
- ItemQuest for zeolite-like metal-organic frameworks: on pyrimidinecarboxylate bis-chelating bridging ligands(American Chemical Society, 2008) Sava, Dorina F.; Kravtsov, Victor Ch.; Nouar, Farid; Wojtas, Lukasz; Eubank, Jarrod F.; Eddaoudi, MohamedTwo novel porous zeolitelike metal−organic frameworks (ZMOFs) were constructed via the single metal ion-based molecular building block approach from rigid and directional tetrahedral building units and pyrimidinecarboxylate bridging ligands; their ion exchange and hydrogen sorption properties were evaluated.
- ItemSelf-assembly of two robust 3D supramolecular organic frameworks from a geometrically non-planar molecule for high gas selectivity performance(The Royal Society of Chemistry, 2019-05-29) Zhou, Yue; Kan, Liang; Eubank, Jarrod F.; Li, Guanghua; Zhang, Lirong; Liu, YunlingThe synthesis of highly porous frameworks has received continuous research interest, but achieving the ability to target stable and selective materials remains challenging. Herein, by utilizing a 'direction-oriented' strategy and modulating reaction conditions, two novel 3D porous supramolecular organic framework (SOF) materials ( JLU-SOF2 and JLU-SOF3 , as isomers) are assembled from a non-planar building block (TMBTI = 2,4,6-trimethyl benzene-1,3,5-triyl-isophthalic acid) and they display permanent porosity, high thermal stability, and good recyclability. It is worth mentioning that the CO 2 uptake values of JLU-SOF2 and JLU-SOF3 rank among the highest values for SOF-based materials under ambient conditions. Furthermore, these two materials exhibit preferential adsorption of CO 2 over N 2 and CH 4 , and can effectively separate the mixtures of light hydrocarbons. These studies indicate the possible application of JLU-SOF2 and JLU-SOF3 in trapping greenhouse gases and upgrading natural gas. In addition, this synthetic strategy introduces an effective method for developing remarkable 3D SOFs among other framework materials. Two 3D SOFs were synthesized based on a 'direction-oriented' strategy. The unique and permanent porosity structures exhibit remarkable ability to separate CO 2 from N 2 and light hydrocarbons.
- ItemThermomechanical characterization of thermoplastic polyimide to improve the chain interaction via crystalline domains(Society of Plastics Engineers, Inc., 2019-09) Nicholls, Alejandro Rivera; Craft, Garrett; Perez, Yesenia; Pellisier, Matthew; Stock, John Allan; Testemale, Maxime; Kull, Ken; Eubank, Jarrod F.; Harmon, Julie P.In a previous study on polyimides, we incorporated an aromatic diamine monomer with a methylene linker, 4,4'-methylenebis (2,6-dimethylaniline), to make a robust main chain along with aliphatic polyetherdiamine backbone linkers to decrease rigidity. In this report, we explore the behavior of crystalline regions provided by the organized packing of polyethylene oxide into the formerly characterized polymers. The polymers were designed to exhibit thermal properties in between those of conventional aromatic polyimides and polymers with wholly aliphatic ether diamine links, with a target to improve the mechanical characteristics. Through dynamic mechanical analysis and differential scanning calorimetry, it is shown that the incorporation of polyethylene oxide diamine and the removal of methyl pending groups serve to improve the organized packing of the chains. All of this allows for a broader range in tenability of thermal and mechanical properties of the polyimide. Furthermore, the crystalline regions are an important component to maintain the temperature stability of polyimide while maintaining the processability. The polymers are characterized by Fourier-transform infrared spectroscopy, thermomechanical and calorimetric analysis, microhardness measurements, tensile testing, and wide-angle X-ray scattering. INTRODUCTION Highly ordered aromatic backbones allow polyimides (PIs) to have superb properties demonstrated by elevated thermal stability, solvent resistance, low coefficients of thermal expansion, low dielectric constants, high glass transition [...]
- ItemThermomechanical characterization of thermoplastic polyimides to improve the chain collaboration via ureidopyrimidone endcaps(Society of Plastics Engineers, Inc., 2019-11) Nicholls, Alejandro Rivera; Perez, Yesenia; Pellisier, Matthew; Rodde, Arnaud; Lanusse, Pierre; Stock, John Allan; Kull, Ken; Eubank, Jarrod F. ; Harmon, Julie P.In this report, we explored the effect of incorporating ureidopyrimidone (UPy) linkers in a series of polyimides (Pis) previously studied in our laboratory. The polymers consist of an aromatic diamine monomer with a methylene linker, 4,4'-methylenebis (2,6-dimethylaniline), used to make a robust main chain along with aliphatic polyetherdiamine backbone linkers to decrease rigidity. The polymers were designed to exhibit thermal properties in between those of conventional aromatic PIs and polymers with wholly aliphatic ether diamine links, with an aim to improve the mechanical characteristics. Through dynamic mechanical analysis and differential scanning calorimetry, it is shown that the UPy linkers with their four-hydrogen bond sites are introduced to connect the chains in series. The connection strengthens the chain interactions and increases the range of the thermal and mechanical properties of the PI. Furthermore, the connecting regions are an important component to preserve the thermal stability of PIs while maintaining the processability. The polymers were characterized by FTIR, nuclear magnetic resonance, GPC, thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, microhardness, and tensile testing.
- ItemThermomechanical characterization of thermoplastic polyimide–polyurea to improve the chain interaction via internal hydrogen bonds(Society of Plastics Engineers, Inc, 2019-09) Nicholls, Alejandro Rivera; Pellisier, Matthew; Perez, Yesenia; Stock, John Allan; Kull, Ken; Julien, Tamalia; Eubank, Jarrod F.; Harmon, Julie P.Recently, we have studied polyimides (PIs) synthesized by incorporating an aromatic diamine monomer with a methylene linker, 4,4'-methylenebis(2,6-dimethylaniline), to make a robust main chain along with aliphatic polyetherdiamine backbone linkers to reduce rigidity. In this report, we incorporate a urea linkage into these materials in order to observe the effect of additional hydrogen bonding. The polymers are designed to exhibit thermal properties in between those of conventional aromatic PIs and polymers with wholly aliphatic ether diamine links. Herein, we demonstrate that the addition of 1,6 hexamethylene diisocyanate and the increase of hydrogen bonds at the urea linkage can be used to improve the thermal and mechanical properties of the PI. Furthermore, the imide ring is an important component to maintain the thermal stability characteristics in poly-imidepolyurea hybrids. The polymers were characterized by FTIR, thermomechanical and calorimetric analysis, micro-hardness, and tensile testing. INTRODUCTION A series of thermoplastic polyimide-polyureas (PIUs) with tractable properties and structural improvements are synthesized and characterized in this work. Polyimides (PIs) with highly ordered aromatic backbones demonstrate high thermal [...]
- ItemUnique Fluorescence Turn-On and Turn-Off–On Responses to Acids by a Carbazole-Based Metal–Organic Framework and Theoretical Studies(Journal of the American Chemical Society, 2022-09-21) Qiao, Junyi; Liu, Xinyao; Zhang, Lirong; Eubank, Jarrod F.; Liu, Xin; Liu, Yunling
- ItemZero-periodic metal–organic material, organic polymer composites: tuning properties of methacrylate polymers via dispersion of dodecyloxy-decorated Cu-BDC nanoballs(Royal Society of Chemistry, 2015-02-02) Kim, Mu-Seong; Perry IV, John; Julien, Tamalia C. M.; Marangon, Elisa; Manouat, Cedric; Eubank, Jarrod F.; Harmon, Julie P.A self-assembled metal–organic polyhedron (i.e., MOP or nanoball) with –OC12 external/surface functionality has been incorporated into two polymeric systems: poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(methyl methacrylate) (PMMA). The nanoball, having the chemical formula [(DMSO) (MeOH)Cu2(5-(dodecyloxy)-1,3-benzenedicarboxylate)2]12, possesses 24 saturated 12-carbon chains on the surface. This work characterizes the interactions between OC12-decorated nanoballs and the polymers, revealing interesting effects from the polymer perspective. The resultant nanocomposites were characterized by differential scanning calorimetry (DSC) and microindentation. The dielectric permittivity (ε′) and loss factor (ε′′) were measured via dielectric analysis (DEA) in the frequency range 1 Hz to 100 kHz. The electric modulus formalism was used to reveal α, β, γ and conductivity relaxations. The nanoball interactions with the different polymer matrices allows for tuning of mechanical and electrical properties, by varying polymer structure and/or nanoball loadings, which could be of interest in applications related to electrochemistry, implantable polymeric sensors, drug delivery, energy storage, and beyond.