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High Throughput Screening Of 3d Printable Resins: Adjusting The Surface And Catalytic Properties Of Multifunctional Architectures, J. Sebastián Manzano, Hsin Wang, Igor I. Slowing 2019 Iowa State University and Ames Laboratory

High Throughput Screening Of 3d Printable Resins: Adjusting The Surface And Catalytic Properties Of Multifunctional Architectures, J. Sebastián Manzano, Hsin Wang, Igor I. Slowing

Igor I. Slowing

Identification of 3D printable materials is crucial to expand the breadth of physical and chemical properties attainable by additive manufacturing. Stereolithography (SLA), a widespread 3D printing method based on resin photo-polymerization, is ideally suited for exploring a large variety of monomers to produce functional three-dimensional solids of diverse properties. However, for most of the commercially available SLA 3D printers, screening monomers and resin compositions requires large volumes (~150 mL) in each printing cycle, making the process costly and inefficient. Herein, a high throughput block (HTB) adaptor was developed to screen arrays of monomers and resin compositions, consuming lower volumes (< 2 mL) and less time per print (< 1/16 based on a 44 matrix) than using the original hardware. Using this approach, a library of materials with different surface hydrophobicities were 3D printed by including long chain acrylates in the resins. In addition, several metal salts were dissolved in an acrylic acid-based resin, 3D printed and screened as heterogeneous catalysts for the selective aerobic oxidation of benzyl alcohol to benzaldehyde. Cu(II)-based resins produced the most active structures. Combinations of Cu(II) and long chain acrylate monomers were then used to 3D print complex catalytic architectures with varying degrees of hydrophobicity. Linear relationships were observed between 3D printed surface area, surface hydrophobicity and catalyst performance. For a high surface Schwarz P topology ca. 60 % enhancement in the catalytic activity of Cu(II) was attained by replacing the parent resin with one containing hydrophobic isodecyl groups, indicating that the immediate environment of the catalytic site affected its performance. The HTB enables fast screening of resins for 3D printing multifunctional architectures with intrinsic catalytic activity, tunable surface properties, and minimal waste.


High Throughput Screening Of 3d Printable Resins: Adjusting The Surface And Catalytic Properties Of Multifunctional Architectures, J. Sebastián Manzano, Hsin Wang, Igor I. Slowing 2019 Iowa State University and Ames Laboratory

High Throughput Screening Of 3d Printable Resins: Adjusting The Surface And Catalytic Properties Of Multifunctional Architectures, J. Sebastián Manzano, Hsin Wang, Igor I. Slowing

Chemistry Publications

Identification of 3D printable materials is crucial to expand the breadth of physical and chemical properties attainable by additive manufacturing. Stereolithography (SLA), a widespread 3D printing method based on resin photo-polymerization, is ideally suited for exploring a large variety of monomers to produce functional three-dimensional solids of diverse properties. However, for most of the commercially available SLA 3D printers, screening monomers and resin compositions requires large volumes (~150 mL) in each printing cycle, making the process costly and inefficient. Herein, a high throughput block (HTB) adaptor was developed to screen arrays of monomers and resin compositions, consuming lower volumes (< 2 mL) and less time per print (< 1/16 based on a 44 matrix) than using the original hardware. Using this approach, a library of materials with different surface hydrophobicities were 3D printed by including long chain acrylates in the resins. In addition, several metal salts were dissolved in an acrylic acid-based resin, 3D printed and screened as heterogeneous catalysts for the selective aerobic oxidation of benzyl alcohol to benzaldehyde. Cu(II)-based resins produced the most active structures. Combinations of Cu(II) and long chain acrylate monomers were then used to 3D print complex catalytic architectures with varying degrees of hydrophobicity. Linear relationships were observed between 3D printed surface area, surface hydrophobicity and catalyst performance. For a high surface Schwarz P topology ca. 60 % enhancement in the catalytic activity of Cu(II) was attained by replacing the parent resin with one containing hydrophobic isodecyl groups, indicating that the immediate environment of the catalytic site affected its performance. The HTB enables fast screening of resins for 3D printing multifunctional architectures with intrinsic catalytic activity, tunable surface properties, and minimal waste.


Pre-Methylation Of Lignin To Improve Storage Stability Of Oil Produced By Solvent Liquefaction, Jae-Young Kim, Parinaz Hafezi-Sefat, Sarah D. Cady, Ryan G. Smith, Robert C. Brown 2019 Iowa State University

Pre-Methylation Of Lignin To Improve Storage Stability Of Oil Produced By Solvent Liquefaction, Jae-Young Kim, Parinaz Hafezi-Sefat, Sarah D. Cady, Ryan G. Smith, Robert C. Brown

Sarah Cady

In this study, we methylated hydroxyl groups (phenolic hydroxyl: Phe-OH and aliphatic hydroxyl: Aliph-OH) in soda lignin (SL) prior to solvent liquefaction to improve storage stability of the resulting oil. We investigated two methylating reagents, dimethyl sulfate (DMS) and dimethyl carbonate (DMC), for selective Phe-OH and total hydroxyl group (Phe-OH and Aliph-OH) blocking. Samples of SL, DMS-SL, and DMC-SL were depolymerized into oils under supercritical ethanol (350 °C). Both methylated lignins produced higher amounts of oils and smaller amounts of char compared to untreated SL due to suppressed charring reactions. Oil produced from SL had relatively higher functional group contents ...


Synthesis Of Crosslinkable Poly(Ester Amide)S For Cell Encapsulation And Delivery, Yu Ting (Natalie) Liang 2019 The University of Western Ontario

Synthesis Of Crosslinkable Poly(Ester Amide)S For Cell Encapsulation And Delivery, Yu Ting (Natalie) Liang

Electronic Thesis and Dissertation Repository

Tissue engineering using adipose-derived stromal cells (ASCs) shows promise for soft tissue regeneration. Biodegradable polymers are potential biomaterials as they support the growth and delivery of cells. Specifically, poly(ester amide)s (PEAs) are a class of biodegradable polymers with tunable structures that have been shown to exhibit low cytotoxicity and support the growth of various cell types. This thesis involved the development of new water soluble amino acid-based PEAs with crosslinkable moieties to enable formation of hydrogel scaffolds for ASC encapsulation. These hydrophilic phenylalanine-based and alanine-based PEAs were synthesized by solution polycondensation and photo-crosslinked into a series of hydrogels ...


Synthesis And Characterization Of Multifunctional Transition Metal Oxide Nanoparticles Through A Modified Sol-Gel Method With Application In Energy Storage, Julien Lombardi 2019 The Graduate Center, City University of New York

Synthesis And Characterization Of Multifunctional Transition Metal Oxide Nanoparticles Through A Modified Sol-Gel Method With Application In Energy Storage, Julien Lombardi

All Dissertations, Theses, and Capstone Projects

The Synthesis of transition metal oxide nanoparticles has been studied in great detail over the many years. The most studied transition metal oxide nanoparticles are perovskites of the ABO3 stoichiometry (A and B = transition metal) and more recently double perovskite crystal structures of the AA’BO6 or A2BB’O6 stoichiometry due to the many different properties arising from the many different combinations of elements possible. These materials have proven potentially useful in many fields, but due to properties such as ferroelectricity and ferromagnetism, the desire to integrate these materials into electronics is ever growing. Many ...


Synthesis Of New Aliphatic Pseudo-Branched Polyester Co-Polymers For Biomedical Applications, Zachary Shaw 2019 Pittsburg State University

Synthesis Of New Aliphatic Pseudo-Branched Polyester Co-Polymers For Biomedical Applications, Zachary Shaw

Electronic Thesis Collection

In this study, a hyperbranched polyester co-polymer was designed using a proprietary monomer and diethylene glycol or triethylene glycol as monomers. The synthesis was carried out using standard melt polymerization technique and catalyzed by p-Tolulenesulfonic acid. The progress of the reaction was monitored with respect to time and negative pressure, with samples being subjected to standard characterization protocols. The resulting polymers were purified using the solvent precipitation method and characterized using various chromatographic and spectroscopic methods including GPC, MALDI-TOF, and NMR. We have observed polymers with a molecular weight of 29,643 kDa and 33,996 kDa, which is ideal ...


Photoswitchable Self-Complementary Hydrogen Bond Arrays, Suendues Noori, James A. Wisner 2019 University of Western Ontario

Photoswitchable Self-Complementary Hydrogen Bond Arrays, Suendues Noori, James A. Wisner

Western Research Forum

Background: Photochromism is the reversible transformation of a chemical material to another form by the absorption of electromagnetic radiation (light), where the two metastable forms have distinct absorption spectra and other properties. Photochromism in materials allows for the switching of their function solely based on irradiation with light. Polymers are used frequently as the building blocks for materials as they are versatile, multifunctional, can carry charge and be processed by solution-based deposition methods. Supramolecular polymers share the same definition as polymers with the exception that they are held together by reversible and directional non-covalent interactions such as hydrogen bonds. Synthesizing ...


Non-Einstein Viscosity Phenomenon Of Acrylonitrile–Butadiene–Styrene Composites Containing Lignin–Polycaprolactone Particulates Highly Dispersed By High-Shear Stress, Sing-Hoon Kim, Kisuk Choi, Kyouk Ryeol Choi, Taesung Kim, Jonghwan Suhr, Kwang Jin Kim, Hyoung Jin Choi, Jae-Do Nam 2019 Sungkyunkwan University

Non-Einstein Viscosity Phenomenon Of Acrylonitrile–Butadiene–Styrene Composites Containing Lignin–Polycaprolactone Particulates Highly Dispersed By High-Shear Stress, Sing-Hoon Kim, Kisuk Choi, Kyouk Ryeol Choi, Taesung Kim, Jonghwan Suhr, Kwang Jin Kim, Hyoung Jin Choi, Jae-Do Nam

Mechanical Engineering Faculty Publications

Lignin powder was modified via ring-opening polymerization of caprolactone to form a lignin–polycaprolactone (LPCL) particulate. The LPCL particulates were mixed with an acrylonitrile–butadiene–styrene (ABS) matrix at an extremely high rotational speed of up to 3000 rpm, which was achieved by a closed-loop screw mixer and in-line melt extruder. Using this high-shear extruding mixer, the LPCL particulate size was controlled in the range of 3395 nm (conventional twin-screw extrusion) down to 638 nm (high-shear mixer of 3000 rpm) by altering the mixing speed and time. The resulting LPCL/ABS composites clearly showed non-Einstein viscosity phenomena, exhibiting reduced viscosity ...


Implementation Of Multivariate Artificial Neural Networks Coupled With Genetic Algorithms For The Multi-Objective Property Prediction And Optimization Of Emulsion Polymers, David Chisholm 2019 California Polytechnic State University, San Luis Obispo

Implementation Of Multivariate Artificial Neural Networks Coupled With Genetic Algorithms For The Multi-Objective Property Prediction And Optimization Of Emulsion Polymers, David Chisholm

Master's Theses and Project Reports

Machine learning has been gaining popularity over the past few decades as computers have become more advanced. On a fundamental level, machine learning consists of the use of computerized statistical methods to analyze data and discover trends that may not have been obvious or otherwise observable previously. These trends can then be used to make predictions on new data and explore entirely new design spaces. Methods vary from simple linear regression to highly complex neural networks, but the end goal is similar. The application of these methods to material property prediction and new material discovery has been of high interest ...


Rheological Investigations Of Latex-Surfactant-Associative Thickener Aqueous Systems, Bishop I. Hammack 2019 CalPoly San Luis Obispo

Rheological Investigations Of Latex-Surfactant-Associative Thickener Aqueous Systems, Bishop I. Hammack

Master's Theses and Project Reports

Surfactants and Thickeners are both additives used in fully-formulated waterborne coatings to provide colloidal stability, thickening, and other functionality. The behavior of each ingredient in a coating must be understood and controlled to maintain colloidal stability as well as balance other desired properties of the liquid coating and the dry paint film. In this work, quaternary systems of Water-Latex-Thickener-Surfactant were investigated to further the understanding of their behavior in coatings. The thickener used was a well characterized, hydrophobically-modified, ethoxylated urethane (HEUR) with two C18 terminal hydrophobes and 795 average repeat units of ethylene oxide as the hydrophilic spacer. Two latexes ...


Hairy Nanoparticles With Hydrophobic Polystyrene Cores And Hydrophilic Poly(2-Hydroxyethylmethacrylate) Hairs: Synthesis And Characterization, Azza Habel 2019 Atlanta University Center

Hairy Nanoparticles With Hydrophobic Polystyrene Cores And Hydrophilic Poly(2-Hydroxyethylmethacrylate) Hairs: Synthesis And Characterization, Azza Habel

Electronic Theses & Dissertations Collection for Atlanta University & Clark Atlanta University

The self-assembling properties of a core-shell system are considered to be the most desirable characteristics that allow using this class of polymers in different applications. New hairy nanoparticles (HNPs) with hydrophobic polystyrene cores (PS Cores) and hydrophilic poly(2-hydroxyethylmethacrylate) (PHEMA) shells were synthesized by coupling polymerization methods. Living anionic polymerization in one-pot step was used to synthesize cross-linked polystyrene cores functionalized with hydroxyl groups and atom transfer radical polymerization (ATRP) was then carried out to prepare PHEMA hairs following the grafting form technique. The structural characterizations were carried out by FT-IR and NMR spectroscopy (1H NMR, 13C NMR ...


Melt Electrospinning Designs For Nanofiber Fabrication For Different Applications, Yasseen S. Ibrahim, Essraa A. Hussein, Moustafa M. Zagho, Ghada G. Abdo, Ahmed A. Elzatahry 2019 Qatar University

Melt Electrospinning Designs For Nanofiber Fabrication For Different Applications, Yasseen S. Ibrahim, Essraa A. Hussein, Moustafa M. Zagho, Ghada G. Abdo, Ahmed A. Elzatahry

Student Publications

Nanofibers have been attracting growing attention owing to their outstanding physicochemical and structural properties as well as diverse and intriguing applications. Electrospinning has been known as a simple, flexible, and multipurpose technique for the fabrication of submicro scale fibers. Throughout the last two decades, numerous investigations have focused on the employment of electrospinning techniques to improve the characteristics of fabricated fibers. This review highlights the state of the art of melt electrospinning and clarifies the major categories based on multitemperature control, gas assist, laser melt, coaxial, and needleless designs. In addition, we represent the effect of melt electrospinning process parameters ...


Thermotropic Liquid-Crystalline And Light-Emitting Properties Of Poly(Pyridinium) Salts Containing Various Diamine Connectors And Hydrophilic Macrocounterions, Tae Soo Jo, Haesook Han, Pradip K. Bhowmik, Benoît Heinrich, Bertrand Donnio 2019 University of Nevada, Las Vegas

Thermotropic Liquid-Crystalline And Light-Emitting Properties Of Poly(Pyridinium) Salts Containing Various Diamine Connectors And Hydrophilic Macrocounterions, Tae Soo Jo, Haesook Han, Pradip K. Bhowmik, Benoît Heinrich, Bertrand Donnio

Chemistry and Biochemistry Faculty Publications

A set of poly(pyridinium) salts containing various diamine moieties, as molecular connectors, and poly(ethyleneglycol)-4-nonylphenyl-3-sulfopropyl ether, thereafter referred to as “Macroion”, as the hydrophilic counterion, were prepared by metathesis reaction from the respective precursory tosylated poly(pyridinium)s in methanol. The structure of these ionic polymers was established by spectroscopy and chromatography techniques. The shape-persistent ionic poly(pyridinium) materials, inserting rigid or semi-rigid diamine spacers, display thermotropic liquid-crystalline properties from room-temperature up to their isotropization (in the temperature range around 160–200 °C). The nature of the LC phases is lamellar in both cases as identified by the ...


Bridging The Molecular/Material Divide: An Investigation Into The Properties Of Polyesters, Terra Marie M. Jouaneh 2019 University of Rhode Island

Bridging The Molecular/Material Divide: An Investigation Into The Properties Of Polyesters, Terra Marie M. Jouaneh

Senior Honors Projects

By definition, polymers consist of large molecules composed of small, repeating units called monomers. These monomers give characteristic material properties to polymers, whether they be the melting point, the folding character, or the inherent stability. Many of the objects we encounter on a daily basis are composed of polymers. These polymers may be synthetic, such as the plastic in disposable bags, or natural, like glycogen in the liver. Recent developments in biotechnology have used synthetic polymers in drug delivery, contact lenses, and even organ transplants. Polyesters, in particular, have been utilized pharmacologically due to their biodegradable properties. Understandably, not all ...


Characterizing Flame-Resistant Polymers Using Single-Sided Nmr, Anna Tsutsui 2019 William & Mary

Characterizing Flame-Resistant Polymers Using Single-Sided Nmr, Anna Tsutsui

Undergraduate Honors Theses

Many commonly used polymers are inherently flammable. Manufacturers have been able to make polymers more flame-resistant by incorporating additives in polymer matrices. Current testing methods of these materials are destructive. As a result, there is a lack of data that can characterize the long-term effects of thermal exposure on these materials. This study presents single-sided NMR as an alternative technique to characterize the physical properties of these materials before and after thermal exposure. From single-sided NMR, this study finds that it is possible to characterize the molecular behavior of flame-resistant polymers and that additives cause no significant physical change to ...


Atomic Force Microscopy Measurements Of Interfacial Forces Between Boron Nitride And Polymers For Development Of An Optimum Nano-Composite, Hall Zhang 2019 William & Mary

Atomic Force Microscopy Measurements Of Interfacial Forces Between Boron Nitride And Polymers For Development Of An Optimum Nano-Composite, Hall Zhang

Undergraduate Honors Theses

Boron Nitride Nanotubes (BNNT’s) and their use in a BNNT nano-composite have been the focus of an increasing number of studies due to their theorized high thermal conducitivty (3,000 W(m•K-1)) as well as high thermal stability. One of our hopes is to integrate BNNT’s into polymer composites to transfer their strength and thermal conductivity into said composites. However, there is little information on boron nitride interfacial forces with different composite polymer resins. Here, we chose to look at nanoscale interfacial forces by functionalizing an Atomic Force Microscopy (AFM) probe cantilever with a silica bead ...


A High-Spin Ground-State Donor-Acceptor Conjugated Polymer, Alex E. London, H. Chen, M.A. Sabuj, Joshua Tropp, M. Saghayezhian, Naresh Eedugurala, B.A. Zhang, Y. Liu, Xiaodan Gu, B.M. Wong, N. Rai, M.K. Bowman, Jason D. Azoulay 2019 University of Southern Mississippi

A High-Spin Ground-State Donor-Acceptor Conjugated Polymer, Alex E. London, H. Chen, M.A. Sabuj, Joshua Tropp, M. Saghayezhian, Naresh Eedugurala, B.A. Zhang, Y. Liu, Xiaodan Gu, B.M. Wong, N. Rai, M.K. Bowman, Jason D. Azoulay

Faculty Publications

Interest in high-spin organic materials is driven by opportunities to enable far-reaching fundamental science and develop technologies that integrate light element spin, magnetic, and quantum functionalities. Although extensively studied, the intrinsic instability of these materials complicates synthesis and precludes an understanding of how fundamental properties associated with the nature of the chemical bond and electron pairing in organic materials systems manifest in practical applications. Here, we demonstrate a conjugated polymer semiconductor, based on alternating cyclopentadithiophene and thiadiazoloquinoxaline units, that is a ground-state triplet in its neutral form. Electron paramagnetic resonance and magnetic susceptibility measurements are consistent with a high-to-low spin ...


Nanogels And Microgels: From Model Colloids To Applications, Recent Developments, And Future Trends, Mattias Karg, Andrij Pich, Thomas Hellweg, Todd Hoare, L. Andrew Lyon, J. J. Crassous, Daisuke Suzuki, Rustam A. Gumerov, Stefanie Schneider, Igor I. Potemkin, Walter Richtering 2019 Heinrich-Heine-University

Nanogels And Microgels: From Model Colloids To Applications, Recent Developments, And Future Trends, Mattias Karg, Andrij Pich, Thomas Hellweg, Todd Hoare, L. Andrew Lyon, J. J. Crassous, Daisuke Suzuki, Rustam A. Gumerov, Stefanie Schneider, Igor I. Potemkin, Walter Richtering

Engineering Faculty Articles and Research

Nanogels and microgels are soft, deformable, and penetrable objects with an internal gel-like structure that is swollen by the dispersing solvent. Their softness and the potential to respond to external stimuli like temperature, pressure, pH, ionic strength, and different analytes make them interesting as soft model systems in fundamental research as well as for a broad range of applications, in particular in the field of biological applications. Recent tremendous developments in their synthesis open access to systems with complex architectures and compositions allowing for tailoring microgels with specific properties. At the same time state-of-the-art theoretical and simulation approaches offer deeper ...


Method Development To Quantify The Reinforcing Properties Of Silica Fillers, Hamid Reza Givehchi 2019 Pittsburg State University

Method Development To Quantify The Reinforcing Properties Of Silica Fillers, Hamid Reza Givehchi

Electronic Thesis Collection

Polysiloxane polymers are widely used as a high-temperature resistant materials with the ability to maintain flexibility at extremely low temperatures. Unfortunately, polysiloxane elastomers generally exhibit low strength and poor mechanical properties and have no practical use unless they are reinforced. These elastomers can be mechanically improved through the use of reinforcing silica-based fillers. It is known that silanol groups on the surface of silica filler particles can interact with the polysiloxane backbone. Interactions of silanol groups on the fillers’ surfaces with the polysiloxane backbone through hydrogen bonding may hinder the mobility of the polymer chain and can improve thermal, physical ...


Rgd-Decorated Cholesterol Stabilized Polyplexes For Targeted Sirna Delivery To Glioblastoma Cells., Bo Lou, Kate Connor, Kieron Sweeney, Ian S. Miller, Alice C. O'Farrell, Eduardo Ruiz-Hernandez, David M. Murray, Garry P. Duffy, Alan Wolfe, Enrico Mastrobattista, Annette Byrne, Wim E. Hennink 2019 Utrecht University

Rgd-Decorated Cholesterol Stabilized Polyplexes For Targeted Sirna Delivery To Glioblastoma Cells., Bo Lou, Kate Connor, Kieron Sweeney, Ian S. Miller, Alice C. O'Farrell, Eduardo Ruiz-Hernandez, David M. Murray, Garry P. Duffy, Alan Wolfe, Enrico Mastrobattista, Annette Byrne, Wim E. Hennink

Physiology and Medical Physics Articles

The development of an effective and safe treatment for glioblastoma (GBM) represents a significant challenge in oncology today. Downregulation of key mediators of cell signal transduction by RNA interference is considered a promising treatment strategy but requires efficient, intracellular delivery of siRNA into GBM tumor cells. Here, we describe novel polymeric siRNA nanocarriers functionalized with cRGD peptide that mediates targeted and efficient reporter gene silencing in U87R invasive human GBM cells. The polymer was synthesized via RAFT copolymerization of N-(2-hydroxypropyl)-methacrylamide (HPMA) and N-acryloxysuccinimide (NAS), followed by post-polymerization modification with cholesterol for stabilization, cationic amines for siRNA complexation, and ...


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