Chemistry Commons^™

Purification Of Synthetic Oligonucleotides, Shiyue Fang

Michigan Tech Patents

This invention provides a method for purifying synthetic oligonucleotides comprising capping, polymerizing and separating any failure sequences produced during oligonucleotide synthesis. The invention also provides a method for purifying synthetic oligonucleotides comprising reacting a full length oligonucleotide with a compound to attach a polymerizable functional group to an end of the full length oligonucleotide, polymerizing the full length oligonucleotides and removing the failure sequences, and recovering the full length oligonucleotides. The invention also provides novel capping agents having a polymerizable functional group, and kits comprising at least one composition of the present invention.

Synthesis And Properties Of Bisimidazolium And Poly(Ethylene Glycol)-Containing Michael Addition Polyester Networks, Joshua Allan Dippie

Murray State Theses and Dissertations

Poly(ionic liquid)s (PILs) have been examined in recent years for applications in various technologies, including solid-state lithium ion batteries and gas separation membranes. In this work, a series of bisimidazolium-containing, Michael addition donors were synthesized and used to produce a series of covalently crosslinked PIL polyester networks containing bis(trifluoromethylsulfonyl)imide as the counteranion. Within the series, the length of alkyl spacer between the two imidazolium cations and the diacrylate to acetoacetate monomer ratio were varied in an attempt to correlate structural variations with the thermal, mechanical, and conductive properties of the PILs. Keeping the diacrylate to acetoacetate ratio constant, increasing the …

Mechanistic Studies Of The Structure-Photostability Relationship Of Organic Conjugated Polymers, Logan Paul Sanow

Electronic Theses and Dissertations

Organic Conjugated polymers (CPs) are a subject of intense research for their application in organic photovoltaics (OPVs), organic light emitting diodes (OLEDs), solid-state dye lasing, biological imaging and sensing, chemical sensing and remote sensing. CPs are key materials in the quest for more sustainable forms of renewable energy, making electronics more versatile and light weight, and increasing the functionality of everyday materials. For these applications and others that use CPs as the photoactive material, one of their main drawbacks is their susceptibility to photodegradation. Photodegradation occurs when the material is exposed to light leading to irreversible changes in the materials, …

Raft Polymerization Of Ph-Responsive, Diblock Copolymers For Nucleic Acid Delivery Vehicles, Annie Katherine Mcclellan

Electronic Theses and Dissertations

Since the development of gene therapy, a variety of non-viral nucleic acid delivery vehicles have been prepared and studied for their transfection efficiencies. Recently, polymeric gene delivery vehicles have gained popularity for their low immunogenicity and high transfection efficiency. With the advent of controlled radical polymerization (CRP) and more specifically reversible addition-fragmentation chain transfer (RAFT) polymerization, it is now possible to develop well-defined polymers with predicted molecular weights and architectures. The work presented here focuses on the RAFT polymerization of a family of amphiphilic, cationic copolymers to be utilized for nucleic acid delivery. These copolymers are composed of a stabilizing …

Targeted Delivery Of Nrf2 Sirna Using Modular Polymeric Micellar Nanodelivery System For Efficient Target Gene Knockdown In Hepatocellular Carcinoma, Shaimaa Mohamed Ibrahim Yousef

Wayne State University Theses

Tumor selective drug delivery as well as chemotherapy associated multi drug resistance (MDR) pose tremendous hurdles for effective cancer therapy. In this regard, designing multifunctional nanocarriers loaded with drug/gene payloads and engineered with tumor targeting ligands can serve as a modular platform for targeted drug/gene delivery. In this study we undertook the synthesis of a self-assembling block copolymer constructed using poly(styrene-co-maleic anhydride, partial iso-octyl ester) (SMAPIE) and branched polyethylenimine (PEI) as building blocks and evaluated its micelle forming ability, siRNA complexation and siRNA delivery potentials. In addition, we engineered galactosamine decorated nanomicelles using modular “click” chemistry based approaches for evaluating …

Improving The Engineering Properties Of Pla For 3d Printing And Beyond, Carmen R. Rocha

Open Access Theses & Dissertations

Additive manufacturing (AM), now more commonly known as 3D printing, has been classified as efficient, fast, and practical in the prototyping sector of product development. In the work presented here, we will use one of the AM techniques known as Material extrusion 3D printing (ME3DP), which has all the advantages of AM. However, one of the biggest challenges facing ME3DP technologies is the limitation of the range of materials used by this technique. Acrylonitrile butadiene styrene (ABS) and poly-lactic acid (PLA) are currently the most common thermoplastics materials used in ME3DP because of their ability to melt and be reprocessed. …

The Synthesis Of Poly(Propylene Fumarate), Brian N. Fitch

Williams Honors College, Honors Research Projects

Poly(propylene fumarate) is a promising material in the field of bone tissue engineering. A recently described chain growth polymerization was developed for the synthesis of poly(propylene fumarate). This pathway uses the ring-opening polymerization of maleic anhydride and propylene oxide with magnesium ethoxide as an initiator to yield poly(propylene maleate). The poly(propylene maleate) was then isomerized to poly(propylene fumarate) using diethyl amine. In order to scale up the reaction to a 20L reactor, several optimizations of the purification schemes was required. The main optimizations were done to the purification of poly(propylene maleate). Several methods were tested including replacing the water washes …

Size And Chemistry Selective Membranes From Block Polymer Templates, Ryan A. Mulvenna

Open Access Dissertations

The use of block polymers continues to gain attention with their myriad applications in industry for advanced applications in biology, medicine, electronics, and separations. The ability of block polymers to self assemble into ordered states on the nanometer level makes these materials suitable for applications that mandate structural order on this scale. By tuning the chemistry of these block domains, we may explore their utilization for advanced separations.

In this dossier, we detail the efforts into the controlled radical polymerization of polyisoprene-b-polystyrene-b-poly( N,N-dimethylacrylamide) (PI-PS-PDMA) via. a facile reversible addition-fragmentation chain transfer (RAFT) mechanism. For this …

Optimizing Solvent Blends For A Quinary System, Thomas L. Hoy

Williams Honors College, Honors Research Projects

The Department of Polymer Engineering had received a grant from the Keck foundation to produce a process in which hundreds of copolymers can be formulated, synthesized, analyzed and then extrapolated to produce the optimal polymer for the desired material property. This process involves synthesizing approximately fifty polymers in a custom apparatus, none of which necessarily have the same monomer components. This leads to issue of which solvent or blend of solvents to use that would sufficiently dissolve both monomers and the resulting copolymer. If the monomers are not completely dissolved, a homogenous reaction will be impossible and if the copolymer …

Organometallic Materials: Ferroceno[C]Thiophenes And 1,2-Bisthienylmetallocenes, Surya R. Banks

Theses and Dissertations--Chemistry

Development of synthetic routes toward two general organometallic frameworks was undertaken. The first project involved synthetic attempts of substituted and unsubstituted ferroceno[c]thiophene while the second one was the synthesis of 1,2-dithienylmetallocenes. The long-term goal of this work is to lay the foundations for study of electronic, electrochromic, redox, and optical properties of thiophene-based materials integrated with organometallic systems such as ferrocene, ruthenocene and cymantrene. The synthetic pathway for the target molecule in the first project involved converting 1,2-bis(hydroxymethyl)ferrocene to 1,2-bis(thiouroniummethyl)ferrocene with thiourea under acidic conditions. Refluxing the salt in base followed by acidification resulted in 1,2-bis(mercaptomethyl)ferrocene, which is …

พอลิเมอร์ผสมของพอลิแล็กทิกแอซิดและเซลลูโลสแอซีเทตจากผักตบชวา, กรองกาญจน์ อมตาริยกุล

Chulalongkorn University Theses and Dissertations (Chula ETD)

เซลลูโลสอะซิเทดถูกสังเคราะห์โดยใช้เซลลูโลสผักตบชวาเป็นวัตถุดิบ ซึ่งส่วนที่ใช้จะเป็นส่วนของก้านขั้นตอนแรกนำเส้นใยผักตบชวาไปกำจัดสิ่งสกปรกก้านแห้งและตามมาด้วยการฟอกสีไฮโปคลอไรเซลลูโลสให้เป็นสีขาวสีขาวแล้ว หลังจากนั้นเตรียมเซลลูโลสเจลโดยใช้โซเดียมไฮดรอกไซด์ / ยูเรีย / น้ำ (7:12:81 โดยน้ำหนัก) จากนั้นนำมาผสม ปริมาณของไวนิลอะซิเตทโดยมีอัตราส่วนต่างกันคือ 3.0, 5.0, 7.0, 9.0, 11.0% โดยน้ำหนักของเซลลูโลส หลังจากนั้นส่วนผสมที่ถูกเก็บไว้ในตู้แช่แข็งเป็นเวลา 6 ชั่วโมงเพื่อให้เกิดปฏิกิริยาแอซิทิเลชันสมบูรณ์ เซลลูโลสอะซิเตทมีความสามารถในการปรับปรุงคุณสมบัติของพอลิแล็กทิกแอซิดโดยการเปลี่ยนเป็นผลึกที่สมบัติเชิงกลและสมบัติทางความร้อน จุดมุ่งหมายของการศึกษาครั้งนี้คือการสังเคราะห์ เซลลูโลสแอซิเทดจากผักตบชวาโดยใช้พอลิไวนิลอะซิเตตสารช่วยเพิมความเข้ากันได้ (Compatiblizer) จากนั้นพอลิแล็กทิกแอซิด / เซลลูโลสอะซิเทดนำไปผสมกันโดยใช้เครื่องอัดรีดเกลียว หลังจากนั้นนำไปวิเคราะผล ดังนี้ วิเคราะห์หมู่ฟังก์ชันโดยใช้ฟูเรียทรานสฟอร์มสเปกโตรสโคปี (FTIR) วิเคราห์ความเป็นผลึกด้วยเครื่องเอกซ์เรย์ดิฟแฟรกโทรมิเตอร์(XRD) และ วิเคราะห์สัณฐานวิทยาด้วยกล้องจุลทรรศน์อิเล็กตรอนแบบส่องกราด(SEM) พบว่าพอลิแล็กทิกแอซิด / เซลลูโลสอะซิเตทโดยความเข้มข้นที่เหมาะสมที่สุดของเซลลูโลสอะซิเตทสำหรับการผสมกับพอลิแล็กทิกแอซิด เป็น 11% โดยน้ำหนักและสัดส่วนของพอลิแล็กทิกแอซิด/เซลลูโลสแอซิเทดคือ 95 : 5

Fabrication Of Multifunctional Nanostructured Porous Materials, Ahmed A. Farghaly

Theses and Dissertations

Nanostructured porous materials generally, and nanoporous noble metals specifically, have received considerable attention due to their superior chemical and physical properties over nanoparticles and bulk counterparts. This dissertation work aims to develop well-established strategies for the preparation of multifunctional nanostructured porous materials based on the combination of inorganic-chemistry, organic-chemistry and electrochemistry. The preparation strategies involved one or more of the following processes: sol-gel synthesis, co-electrodeposition, metal ions reduction, electropolymerization and dealloying or chemical etching. The study did not stop at the preparation limits but extended to investigate the reaction mechanism behind the formation of these multifunctional nanoporous structures in order …

Systematic Postsynthetic Modification Of Nanoporous Organic Frameworks And Their Performance Evaluation For Selective Co2 Capture, Timur Islamoglu

Theses and Dissertations

Porous organic polymers (POPs) with high physicochemical stability have attracted significant attention from the scientific community as promising platforms for small gas separation adsorbents. Although POPs have amorphous morphology in general, with the help of organic chemistry toolbox, ultrahigh surface area materials can be synthesized. In particular, nitrogen-rich POPs have been studied intensively due to their enhanced framework-CO₂ interactions. Postsynthetic modification (PSM) of POPs has been instrumental for incorporating different functional groups into the pores of POPs which would increase the CO₂ capture properties. We have shown that functionalizing the surface of POPs with nitro and amine groups …

Antiviral Peptide Nanocomplexes As Potential Therapeutics For The Treatment Of Infectious Diseases, Jinjin Zhang

Theses & Dissertations

Hepatitis C Virus (HCV) is recognized as a major burden in global public health, which can be further exacerbated by several cofactors such as human immunodeficiency virus (HIV). Currently, there is no vaccine for HCV. The emergence of potent and highly specific direct-acting antivirals (DAA) has marked a new era in HCV therapy, however, the remaining issues like affordability, genotype dependency, and potential resistance still necessitate the development of additional therapeutic approaches to be used instead or in combination with DAA.

Recently, the antiviral peptide C5A (in our studies designated as p1) and its cationic derivative p41 have been identified …

Hybrid Aryl-Ether-Ketone And Hyperbranched Epoxy Networks, John Misasi

Dissertations

In this dissertation, relationships between chemical structures, cure kinetics and network architectures are correlated to bulk mechanical properties for novel, hybrid epoxy-amine networks. The work is split into two primary sections: the first is the synthesis and characterization of multifunctional glassy networks based on aryl-ether-ketone diamine curatives, while the second is based on the synthesis and characterization of hyperbranched epoxy polymers and their resulting networks.

Three aryl-ether-ketone (AEK) diamines of increasing molecular weights were synthesized and used to cure 4,4’-tetraglycidylether of diaminodiphenylmethane (TGDDM); the resulting networks were compared to 4,4’-diaminodiphenyl sulfone cured TGDDM. Architectural differences were created by varying cure …

Development Of Dual-Cure Hybrid Polybenzoxazine Thermosets, Jananee Narayanan Sivakami

Dissertations

Polybenzoxazines are potential high performance thermoset replacements for traditional phenolic resins that can undergo an autocatalytic, thermally initiated ring - opening polymerization, and possess superior processing advantages including excellent shelf-life stability, zero volatile loss and limited volumetric shrinkage. The simplistic monomer synthesis and availability of a wide variety of inexpensive starting materials allows enormous molecular design flexibility for accessing a wide range of tailorable material properties for targeted applications. Despite the fact, once fully cured, benzoxazines are difficult to handle due to their inherent brittleness, leaving a very little scope for any modifications. The motivation of this dissertation is directed …

Hydrogen Bond-Mediated Structural Order In Hydroxylated Bis-Mpa Dendritic Polymers: Experimental And Molecular Dynamics Simulation Study, Maliha N. Syed

Dissertations

Dendritic architectures are echoed throughout nature. While the significance of these pervasive patterns is not entirely clear, connections between their structures and physical properties are fascinating to contemplate. Particular interest has been paid to a family of synthetically manufactured and commercially available dendritic polymers based on 2,2-bis(hydroxymethyl) propionic acid (bis-MPA) as a monomer. Composed of two hydroxyls and a carboxyl group, bis-MPA based structures hydrogen bond (H-bond) profusely. Given the high concentration and unique spatial orientation of end-groups, as well as the multitude of carbonyl, ester, and ether interior H-bond acceptors, a set of distinct H-bond organizations may be observed …

Production And Characterization Of Cut Resistant Acrylic/Copolyaramid Fibers Via Bicomponent Wet Spinning, Stephen Hipp

All Dissertations

A composite fiber system consisting of a sheath core bicomponent polymer fiber loaded with hard ceramic particles was developed and characterized for use in cut protective clothing. The core component was comprised of a copolyaramid in order to provide high base cut resistance. An acrylic-copolyaramid polymer blend was used for the sheath component to improve processability and provide potential benefits such as dyeability. Lastly, aluminum oxide particles were incorporated into the fiber core to deflect and deform the cutting edge, further improving cut resistance. A series of designed experiments was used to explore the effects of the wet spinning and …

Syneresis And Rheology Mechanisms Of A Latex-Heur Associative Thickener System, Travis Bruno Smith

Master's Theses

Rheology modifiers are used in paints and coatings to ease their application to a surface, prevent sagging once applied, and allow the leveling of brushstrokes, among other benefits. The early rheology modifiers were hydroxyethyl celluloses (HECs), a type of non-associative thickener that is relatively inexpensive and synthesized from cellulose, which is abundant. However, coatings that are modified with HECs tend to suffer from poor leveling and syneresis (phase separation). HECs have since been replaced with associative thickeners (ATs). These thickeners, when properly formulated, produce stable dispersions that have improved rheological properties, yet, unlike HECs, are sensitive to changes to the …

Photothermally Induced Optical Property Changes Of Poly (N-Isopropylacrylamide) Microgel-Based Etalons, Molla R. Islam, Jessica Irvine, Michael J. Serpe

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Poly(N-isopropylacrylamide) microgel-based optical devices were designed such that they can be stimulated to change their optical properties in response to light produced by a light-emitting diode (LED). The devices were fabricated by sandwiching the synthesized microgels between two Cr/Au layers all supported on a glass coverslip with gold nanoparticles (AuNPs) deposited. Here, we found that these devices can be stimulated to change their optical properties when exposed to green LED light, which excites the AuNPs and increases the local temperature, causing the thermoresponsive microgels to decrease in diameter, resulting in a change in the devices’ optical properties. We also found …

Determination Of The Polymerisation Rate Of A Low-Toxicity Diacetone Acrylamide-Based Holographic Photopolymer Using Raman Spectroscopy, Dervil Cody, Emilia Mihaylova, Luke O'Neill, Izabela Naydenova

Articles

The polymerisation rate of a low-toxicity Diacetone Acrylamide (DA)-based photopolymer has been measured for the first time using Raman spectroscopy. A value for the polymerisation rate of 0.020 s⁻¹ has been obtained for the DA photopolymer by modelling the polymerisation reaction dynamics as a stretched exponential or Kohlrausch decay function. This is significantly lower than the polymerisation rate of 0.100 s⁻¹ measured for the well known Acrylamide (AA)-based photopolymer composition. The effect of the additive glycerol on the polymerisation rate of the DA-based photopolymer has also been investigated. The inclusion of glycerol is observed to increase the rate …

Large-Pore Mesoporous Organosilicas And Related Polymer Nanocomposites, Amanpreet Singh Manchanda

Dissertations, Theses, and Capstone Projects

The research work in this dissertation covers the synthesis of mesoporous organosilicas and (organo)silica/polymer nanocomposites. The content can be divided into 4 parts (8 chapters).

The first part of the dissertation is the introduction, which covers the background and progress in the field of mesoporous silicas, periodic mesoporous organosilicas and related inorganic/polymer nanocomposites. The second part of the dissertation (Chapter 2-5) involves the synthesis of mesoporous organosilicas from different organosilane precursors at mild acid concentration (0.1 M HCl) and low temperature (0 or 7 ℃) using Pluronic F127 (EO₁₀₆PO₇₀EO₁₀₆) as a surfactant template. Chapter …

Polymer Pen Printing: A Tool For Studying 2d Enzymatic Lithography And Printing 3d Carbon Features, Zhantong Mao

Dissertations, Theses, and Capstone Projects

Polymer Pen Lithography (PPL) is a promising molecular printing approach which combines the advantages of both microcontact printing (low cost, high-throughput) and the dip pen lithography (DPN) (arbitrary writing, high-resolution) into one cohesive lithography method to create 2 dimensional (2-D) patterns with micro/nano-features on different substrates. The goal of this dissertation is to design and develop a new tool based upon PPL, which is not limited to forming 2D parallel patterns, but can also create 3D complex microstructures, finding applications in both biotechnology and Micro-Electro-Mechanical systems (MEMS) technology. This novel approach is named Polymer Pen Printing. Different from PPL using …

Revision-Polyurethane-Graphene Nanocomposites For Corrosion-Resistant Coatings, Alexandra Rose Stevenson

Master's Theses

Corrosion is a prevalent concern throughout the world, causing significant monetary and safety concerns. Research has been dedicated to developing cost-effective solutions for corrosion that will also meet increasingly stringent environmental regulations. The recently discovered nanomaterial graphene has been proposed as a potential component in anticorrosion technology due to its strong air and water barrier properties. However, graphene is a relatively expensive, difficult to synthesize material. By incorporating it into nanocomposites, its properties can be exploited even at low concentrations. Previous work has been conducted involving the preparation of anticorrosive polystyrene-graphene nanocomposites; these materials were found to be effective long-term …

Rational Design Of Materials For The Protection Of Outdoor Metalworks, Natasja Alexandria Swartz

Dissertations and Theses

Protective coatings are commonly used to protect culturally significant works, such as outdoor sculptures and architectural elements. Given the valuable nature of such metalworks, there is a surprising lack of environmentally sustainable coatings available for their conservation. High performance clear coatings are not developed or thoroughly tested for compatibility and longevity on outdoor sculptures. This can make the implementation of both methods and materials, no matter how promising in a lab, a significant hurdle for the conservation science community. This dissertation work initially aims to replace high-VOC formulations such as acrylic lacquers and waxes currently used as protective coatings for …

Analysis Of The Fabrication Conditions In Organic Field-Effect Transistors, Rachel M. Rahn, Yan Zhao, Jianguo Mei

The Summer Undergraduate Research Fellowship (SURF) Symposium

Polymer-based organic field-effect transistors have raised substantial awareness because they enable low-cost, solution processing techniques, and have the potential to be implemented in flexible, disposable organic electronic devices. The performance of these devices is highly dependent on the processing conditions, as well as the intrinsic properties of the polymer. Processing conditions play an important role in semiconductor film formation and device performance. These factors may provide an important link between structure and performance. In this study, an empirical analysis tool, Process Scout, was applied to assess processing factors such as polymer concentration and silicon modification. This sanctioned the creation of …

Development Of A Scalable Synthesis Of Hp-Β-Cd Pluronic Polyrotaxanes, Joseph L. Skulsky, Elizabeth A. Slepko, Bradley P. Loren, David H. Thompson

The Summer Undergraduate Research Fellowship (SURF) Symposium

Polyrotaxanes are polymers that have macrocycles threaded onto them, analogous to beads threaded onto a string. These materials are used for a variety of different biomedical applications.^1-3 The Thompson group has been developing 2-hydroxypropyl-β-cyclodextrin (HP-β-CD) polyrotaxanes as therapeutics for the treatment of Niemann-Pick Type C (NPC) disease. NPC is a debilitating genetic disorder where cholesterol accumulates in the lysosomes of cells.⁴ Developing a scalable process is crucial for the advancement of these materials as NPC therapeutics. The goal of this project is to optimize the only protocol for the synthesis of HP-β-CD/Pluronic polyrotaxanes in order to develop a …

Synthesis, Characterization, And Thermoelectric Properties Of Radical Siloxanes, Arnold J. Eng, Bryan Boudouris, Edward P. Tomlinson, Martha Emily Hay

The Summer Undergraduate Research Fellowship (SURF) Symposium

More than half of the annual energy consumption in the United States is lost as waste heat. Polymer-based thermoelectric devices have the potential to utilize this waste heat both sustainably and cost-effectively. Although conjugated polymers currently dominate research in organic thermoelectrics, the potential of using polymers with radical pendant groups have yet to be realized. These polymers have been found to be as conductive as pristine (i.e., not doped) poly(3-hexylthiophene) (P3HT), a commonly-used charge-transporting conjugated polymer. This could yield promising avenues for thermoelectric material design as radical polymers are more synthetically tunable and are hypothesized to have a high Seebeck …

Forensic Significance Of Teal Colored Cashmere And Black Acrylic Fibers, Nicole M. Martin

Forensic Science Theses

Textile fibers are a valuable type of trace evidence within forensic cases. They have the ability to connect a perpetrator to a victim and or a crime scene. Some types of fibers are more prevalent than others. The purpose of this research was to conduct a target fiber study in order to determine the significance of the selected fibers in a forensic case. Two fibers were selected from two different garments, black acrylic fiber and a teal colored cashmere fiber. Unknown fibers were collected from three local clothing stores and counted. Using light microscopy, all 20,164 fibers were eliminated as …

Morphology-Property Relationship For Binary Organic Thin Films, Alyssa Lynn Griffin

Master's Theses

Organic thin films can be readily mass-produced through solution-based fabrication methods including ink-printing and solution-casting because their light weight, flexibility, and inexpensive sources. Their applications range from organic field-effect transistors (OFET), organic solar cells (OSC), to organic light emitting diodes (OLEDs). Compared with pure component films, binary organic thin films (BOTF) allows for novel characteristics and specialized features to handle more demanding tasks. Due to the complex intermolecular interactions in BOTF, various microscopic phases with different morphological and electronic properties may be formed and this information is difficult to extract through conventional bulk measurements.

Organic thin films can be readily …