Chemistry Commons^™

Development Of Nanomaterials: Complex Mesoporous Silicas And Highly Functional Multi-Responsive Hybrid Nanogels, Jinhui Yi

Dissertations, Theses, and Capstone Projects

The research work in this dissertation describes the study of the applications of polymers in several important areas. Two synthesis methods for bicontinuous cubic KIT6 silicas with block copolymer Pluronic P123 as templates were developed, expanding the range of available pore size and enchancing mesopore volume. In addition, two types of drug delivery systems were developed based on polymer nanoparticles.

In Chapter 2, it was shown that the addition of a suitable swelling agent at temperatures somewhat lower than those typically used in the syntheses of silicas with cubic Ia3d structure (19−25 °C vs 30−35 °C) allows one to induce …

The Therapeutic Potential Of Natural Products From Vaccinium Berries For Viral And Lung Diseases Through An Improved Lc-Ms-Based Chemometric Approach, Vanya I. Petrova

Dissertations, Theses, and Capstone Projects

Smoking is a global epidemic that creates serious health and economic burden. It is the primary, preventative factor for the majority of causes of death worldwide. Analysis of publicly available data revealed that smoking prevalence rates among the youth in developing countries, especially in Bulgaria, are alarmingly high. The Bulgarian population has one of the highest percentages of smokers and the second highest rate among teenage girls. Consequently, chronic diseases affected by smoking, such as chronic obstructive pulmonary disorder (COPD), have been increasing there in the last five years. Poland, on the other hand, is an exemplary outlier for the …

Organic Photochemistry: Remote Delivery Of Reactive Oxygen Intermediates Via A Heterogeneous Approach, Niluksha Walalawela Abeykoon

Dissertations, Theses, and Capstone Projects

Photosensitized oxidation reactions produce a number of intermediates species, which are generated in varying amounts over time. This complexity presents major challenges in the study of oxidation processes. Mechanistic efforts to separate and deliver reactive oxygen intermediates enable their controlled use in processes such as bacterial inactivation. This thesis describes a heterogeneous reaction approach taken to control the generation and delivery of reactive oxygen intermediates. The mechanistic details of photosensitized reactions were elucidated via synthetic, materials, and physical organic techniques to optimize the delivery of reactive oxygen intermediates. This thesis contains six chapters as described below.

Chapter 1 gives a …

Cooperative Standing-Horizontalstanding Reentrant Transition For Numerous Solid Particles Under External Vibration, Satoshi Takatori, Hikari Baba, Takatoshi Ichino, Chwen-Yang Shew, Kenichi Yoshikawa

Publications and Research

We report the collective behavior of numerous plastic bolt-like particles exhibiting one of two distinct states, either standing stationary or horizontal accompanied by tumbling motion, when placed on a horizontal plate undergoing sinusoidal vertical vibration. Experimentally, we prepared an initial state in which all of the particles were standing except for a single particle that was placed at the center of the plate. Under continuous vertical vibration, the initially horizontal particle triggers neighboring particles to fall over into a horizontal state through tumbling-induced collision, and this effect gradually spreads to all of the particles, i.e., the number of horizontal particles …

Experiential Learning Activity: Biodiesel Inquiry Project, Ji Kim

Open Educational Resources

The activity described herein can be implemented in introductory chemistry and high school chemistry courses. The main goal of the project is to integrate a ubiquitous biodiesel production with experiential learning by providing a community-based project. The students work in groups, research the benefits of using biodiesel over petroleum-based diesel, collect waste cooking oil from home or restaurants, develop simple and cost-effective methods to produce biodiesel.

The Study Of The Degradation Of Hexabromocyclododecane In A Heterogeneous System Containing Fe(Ii) Adsorbed To The Iron Oxide Hematite., Kristian K. Roopnarine

Dissertations and Theses

The reaction of hexabromocyclododecane (HBCDD), a widely used brominated flame retardant, was studied in a heterogenous mixture containing reactive Fe(II) adsorbed to the iron oxide hematite. The adsorbed Fe(II)/iron oxide system has shown to be a potent reductant in the transformation of organic contaminants with relatively water soluble organic contaminants. There currently aren’t many studies involving hydrophobic organic contaminants, such as HBCDD, in this reducing Fe(II)/iron oxide system. The results indicate that across the pHs 6.86, 6.95, 7.15 and 7.35 γ and β-HBCDD are degraded within a couple days. The pseudo-first order rate constants at pH 6.95 are 0.049 hr …

Synthesis Of A Model Of The Bc Ring System Of Oxygenated Angucyclines, Xiaolan Wu, Abdullah Allaoa, Tony E. Nicolas

Publications and Research

Angucycline is a subclass of natural antibiotics, containing a characteristic tetracyclic ring structure, and featuring a wide range of biological functions, including antitumor, antiviral and antifungal properties. This extraordinarily therapeutic character has interested many chemists to develop efficient methodologies for synthesizing the tetracyclic ring system of angucycline. Construction of the BC ring configuration appears as a synthetic challenge. Successful installation of hydroxyl groups at the AB junction would pave the way for efficient syntheses. As a continuation of the previous work done on this system, our synthetic methodology focuses on the coupling of a suitably substituted Phthalide and an activated …

Pretargeting Of Internalizing Trastuzumab And Cetuximab With A 18f-Tetrazine Tracer In Xenograft Models, Outi Keinänen, Kimberly Fung, Jacob Pourat, Vilma Jallinoja, Delphine Vivier, Nagavara Kishore Pillarsetty, Anu J. Airaksinen, Jason S. Lewis, Brian M. Zeglis, Mirkka Sarparanta

Publications and Research

Background: Pretargeting-based approaches are being investigated for radioimmunoimaging and therapy applications to reduce the effective radiation burden to the patient. To date, only a few studies have used short-lived radioisotopes for pretargeting of antibodies, and such examples with internalizing antibodies are even rarer. Herein, we have investigated pretargeting methodology using inverse electron-demand Diels-Alder (IEDDA) for tracing two clinically relevant, internalizing monoclonal antibodies, cetuximab and trastuzumab.

Results: Bioorthogonal reaction between tetrazine and trans-cyclooctene (TCO) was used for tracing cetuximab and trastuzumab in vivo with a fluorine-18 (t½ = 109.8 min) labelled tracer. TCO-cetuximab or TCO-trastuzumab was administered 24, 48, or 72 …

The Role Of Carbon On Copper–Carbon Composites For The Electrooxidation Of Alcohols In An Alkaline Medium, Leticia García-Cruz, Conchi O. Ania, Ana Paula Carvalho, Teresa Bandosz, Vicente Montiel, Jesús Iniesta

Publications and Research

Copper–carbon composites were prepared following various different synthetic routes and using various carbon precursors (i.e., lignocellulose and graphite oxide), andwere used as electrocatalysts for the oxidation of propargyl alcohol (PGA) in an alkaline medium. The electrochemical response of the copper-based catalysts was analyzed in terms of the influence of the metallic species, the carbon matrix incorporated in the composites, and the chemical structure of the ionomers—Nafion and poly (4-vinylpyridine) cross-linked methyl chloride quaternary salt resin (4VP)—used in the fabrication of the electrodes. Data has shown that the incorporation of reduced graphene oxide sheets between the copper metallic particles increased the …

Efficient Air Desulfurization Catalysts Derived From Pig Manure Liquefaction Char, Rajiv Wallace, Sundaramurthy Suresh, Elham H. Fini, Teresa Bandosz

Publications and Research

Biochar from the liquefaction of pig manure was used as a precursor of H2S desulfurization adsorbents. In its inorganic matter, it contains marked quantities of calcium, magnesium and iron, which are known as hydrogen sulfide oxidation catalysts. The char was used either as-received or mixed with 10% nanographite. The latter was added to increase both the content of the carbon phase and conductivity. ZnCl2 in two different ratios of char to an activation agent (1:1 and 1:2) was used to create the porosity in the carbon phase. The content of the later was between 18–45%. The activated samples adsorbed 144 …

Synthesis, Crystal Structure, And Photoluminescent Properties Of 3,3′,4,4′-Tetraethyl-5,5′-Divinyl-2,2′-Bipyrrole Derivatives, Toru Okawara, Reo Kawano, Hiroya Morita, Alan Finkelstein, Renjiro Toyofuku, Kanako Matsumoto, Kenji Takehara, Toshihiko Nagamura, Seiji Iwasa, Sanjai Kumar

Publications and Research

Photoluminescent divinylbipyrroles were synthesized from 3,3′,4,4′-tetraetyl-2,2′-bipyrrole-5,5′-dicarboxaldehyde and activated methylene compounds via aldol condensation.For mechanistic clarity, molecular structures of Meldrum’s acid- and 1,3-dimethylbarbituricacid-derived divinylbipyrroles were determined by single-crystal X-ray diffraction. Photoluminescentproperties of the synthesized divinylbipyrroles in dichloromethane were found to be dependent onthe presence of electron withdrawing groups at the vinylic terminal. The divinylbipyrroles derivedfrom malononitrile, Meldrum’s acid, and 1,3-dimethylbarbituric acid showed fluorescent peaks at553, 576, and 602 nm respectively. Computational studies indicated that the alkyl substituents on thebipyrrole 3 and 3′positions increased energy level of the highest occupied molecular orbital (HOMO)compared to the unsubstituted derivatives and provided rationale for the …

Ligand Modulation Of Sidechain Dynamics In A Wild-Type Human Gpcr, Lindsay D. Clark, Igor Dikiy, Karen Chapman, Karin Ej Rodstrom, James Aramini, Michael V. Levine, George Khelashvili, Soren Gf Rasmussen, Kevin H. Gardner, Daniel M. Rosenbaum

Publications and Research

GPCRs regulate all aspects of human physiology, and biophysical studies have deepened our understanding of GPCR conformational regulation by different ligands. Yet there is no experimental evidence for how sidechain dynamics control allosteric transitions between GPCR conformations. To address this deficit, we generated samples of a wild-type GPCR (A2AR) that are deuterated apart from 1H/13C NMR probes at isoleucine d1 methyl groups, which facilitated 1H/13C methyl TROSY NMR measurements with opposing ligands. Our data indicate that low [Na+] is required to allow large agonist-induced structural changes in A2AR, and that patterns of sidechain dynamics substantially differ between agonist (NECA) and …

Toxic Gas Sensing On Nanoporous Carbons, Nikolina-Eleni Travlou

Dissertations, Theses, and Capstone Projects

Activated carbons, either synthetic, developed in our laboratory, or commercial, were prepared or further modified, in order to introduce specific heteroatoms such as oxygen, nitrogen and sulfur to their matrices. Chips coated with thin layers of the carbon samples were used for the sensing of gaseous ammonia. They were exposed to continuous cycles of various ammonia concentrations (10-500 ppm), and changes in normalized resistance were analyzed. In all cases linear responses were recorded and the chips reached sensitivities as high as 31%, which are comparable to those of modified graphene-based sensors. The applied specific surface chemical modifications were an effective …

Synthesis And Evaluation Of Tetrahydroprotoberberines As Dopamine Receptor Ligands, Satishkumar V. Gadhiya

Dissertations, Theses, and Capstone Projects

Dopamine (DA) receptors belong to the G-protein coupled receptors (GPCRs) family, divided in to two groups based on their high homology transmembrane domains; D1-like DA receptors (D1, D5) and D2-like DA receptors (D2-D4). DA receptor specific ligands have been exploited as a means for studying the prognosis and curing several CNS disorders. Though several efforts have been devoted to discover selective and potent DA receptor ligands, complete selectivity within the DA receptor subtypes remains a challenge.

Tetrahydroprotoberberines (THPBs) are a group of naturally occurring tetracyclic alkaloids that belong to the tetrahydroisoquinoline family. A wide range of biological activities are associated …

Computational Investigation Of The Pore Formation Mechanism Of Beta-Hairpin Antimicrobial Peptides, Richard Lipkin

Dissertations, Theses, and Capstone Projects

β-hairpin antimicrobial peptides (AMPs) are small, usually cationic peptides that provide innate biological defenses against multiple agents. They have been proposed as the basis for novel antibiotics, but their pore formation has not been directly observed on a molecular level. We review previous computational studies of peptide-induced membrane pore formation and report several new molecular dynamics simulations of β-hairpin AMPs to elucidate their pore formation mechanism. We simulated β-barrels of various AMPs in anionic implicit membranes, finding that most of the AMPs’ β-barrels were not as stable as those of protegrin. We also performed an optimization study of protegrin β-barrels …

Heterojunction Engineering For Next Generation Hybrid Ii-Vi Materials, Thor Garcia

Dissertations, Theses, and Capstone Projects

Molecular Beam Epitaxy(MBE) is a versatile thin film growth technique with monolayer control of crystallization. The flexibility and precision afforded by the technique allows for unique control of interfaces and electronic structure of the films grown. This facilitates the realization of novel devices and structures within a research environment normally only achieved though complex industrial processes. In the past, the control of each interface in MBE has been explored to great benefit. In this work, we study the control of these interfaces so as to increase the performance of novel devices material systems. This dissertation focuses on two main areas …

Stereospecific Electrophilic Fluorination Of Alkylcarbastannatrane Reagents, Xinghua Ma

Dissertations, Theses, and Capstone Projects

The introduction of fluorine atoms into organic molecules significantly changes their physical, chemical, and biological properties. Fluorinated organic compounds are used as pharmaceuticals, agrochemicals, materials, and tracers for positron emission tomography (PET). For example, the site-specific fluorination of drugs can block sites of phase I metabolism by cytochrome P450 enzymes as well as improve target-binding affinities. In view of the unique features of fluorine-containing compounds, there has been increasing interest in the development of novel methods for the synthesis of fluorinated molecules, especially the site-specific monofluorination of complex molecules. Herein, we present the enantiospecific conversion of chiral secondary alkylcarbastannatranes into …

The Effect Of Hydrogen Bonding In Enhancing The Ionic Affinities Of Immobilized Monoprotic Phosphate Ligands, Spiro D. Alexandratos, Xiaoping Liu

Publications and Research

Environmental remediation requires ion-selective polymers that operate under a wide range of solution conditions. In one example, removal of trivalent and divalent metal ions from waste streams resulting from mining operations before they enter the environment requires treatment at acidic pH. The monoethyl ester phosphate ligands developed in this report operate from acidic solutions. They have been prepared on polystyrene-bound ethylene glycol, glycerol, and pentaerythritol, and it is found that intra-ligand hydrogen bonding affects their metal ion affinities. The affinity for a set of trivalent (Fe(III), Al(III), La(III), and Lu(III)) and divalent (Pb(II), Cd(II), Cu(II), and Zn(II)) ions is greater …

Chelator-Free Radiolabeling Of Serrs Nanoparticles For Whole-Body Pet And Intraoperative Raman Imaging, Matthew A. Wall, Travis Shaffer, Stefan Harmsen, Darjus-Felix Tschaharganeh, Chun-Hao Huang, Scott W. Lowe, Charles Michael Drain, Moritz F. Kircher

Publications and Research

A single contrast agent that offers whole-body non-invasive imaging along with the superior sensitivity and spatial resolution of surface-enhanced resonance Raman scattering (SERRS) imaging would allow both pre-operative mapping and intraoperative imaging and thus be highly desirable. We hypothesized that labeling our recently reported ultrabright SERRS nanoparticles with a suitable radiotracer would enable pre-operative identification of regions of interest with whole body imaging that can be rapidly corroborated with a Raman imaging device or handheld Raman scanner in order to provide high precision guidance during surgical procedures. Here we present a straightforward new method that produces radiolabeled SERRS nanoparticles for …

Distinct Properties Of The Triplet Pair State From Singlet Fission, M. Tuan Trinh, Andrew Pinkard, Andrew B. Pun, Samuel N. Sanders, Elango Kumarasamy, Matthew Y. Sfeir, Luis M. Campos, Xavier Roy, X.-Y. Zhu

Publications and Research

Singlet fission, the conversion of a singlet exciton (S₁) to two triplets (2 × T₁), may increase the solar energy conversion efficiency beyond the Shockley-Queisser limit. This process is believed to involve the correlated triplet pair state ¹(TT). Despite extensive research, the nature of the ¹(TT) state and its spectroscopic signature remain actively debated. We use an end-connected pentacene dimer (BP0) as a model system and show evidence for a tightly bound ¹(TT) state. It is characterized in the near-infrared (IR) region (~1.0 eV) by a distinct excited-state absorption (ESA) spectral feature, which …

Cross-Dehydrogenative Coupling And Oxidativeamination Reactions Of Ethers And Alcohols With Aromatics And Heteroaromatics, Mahesh K. Lakshman, Prasanna K. Vuram

Publications and Research

Cross-dehydrogenative coupling (CDC) is a process in which, typically, a C–C bond is formed at the expense of two C–H bonds, either catalyzed by metals or other organic compounds, or via uncatalyzed processes. In this perspective, we present various modes of C–H bond-activation at sp3 centers adjacent to ether oxygen atoms, followed by C–C bond formation with aromatic systems as well as with heteroaromatic systems. C–N bond-formation with NH-containing heteroaromatics, leading to hemiaminal ethers, is also an event that can occur analogously to C–C bond formation, but at the expense of C–H and N–H bonds. A large variety of hemiaminal …

The Quantification Of Cocaine From The Erythroxylum Coca Plant And The Comparison On High Performance Liquid Chromatography And Gas Chromatography Mass Spectroscopy As An Analytical Method., Tuesday James

Student Theses

Cocaine is derived from the Erythroxylum coca plant, is a highly addictive stimulant abused all over the world. There are two types of Erythroxylum coca plants that produce cocaine; the E. Coca and E. Novogranatense. Cocaine exists as the salt, and the freebase which is typically referred to as “crack” due to the crackling sound it makes when heated. It is popular because it is inexpensive and easily available on the streets, mainly in poor urban areas. The purpose of this project was to determine the amount of cocaine that can be extracted from E.coca and to assess which analytical …

Species Identification Of Necrophagous Insect Eggs Based On Amino Acid Profile Differences Revealed By Direct Analysis In Real Time-High Resolution Mass Spectrometry, Justine E. Giffen, Jennifer Y. Rosati, Cameron M. Longo, Rabi A. Musah

Publications and Research

The colonization of decomposing remains by necrophagous insects such as blow flies is of forensic importance because the progression through the various stages of insect development can be correlated to time of death. The ability to infer this information hinges on accurate determination of the fly species that are associated with the entomological evidence collected. This evidence can include eggs, larvae, pupae, and puparial casings. Determination of the egg’s identity is particularly challenging because the eggs of multiple species are morphologically very similar. We report here that the species identity of fly eggs can be determined from their chemical fingerprint …

Naturally-Derived Molecular Ensembles In Medicine, Materials Science And Evolutionary Biology: An Interdisciplinary Study, Silvio Panettieri

Dissertations, Theses, and Capstone Projects

The first chapter will introduce the work carried out in collaboration with the Govind laboratory at CCNY. Our quest was set forth to investigate the intimate relationship lying between chronic inflammation and tumor development. For at least the last fifteen years much research has been conducted on this topic; yet, the level of complexity arising from exceedingly interwoven biochemical pathways in mammals has resulted in slow advancements in this field. This is why we resorted to a simple yet powerful immunogenetic model organism, the fruit fly Drosophila melanogaster, in combination with the administration of the most common anti-inflammatory drug, …

Olfactory Receptor Antagonism In The Or-I7 Aldehyde Receptor And The Mammalian Olfactory System, Min Ting Liu

Dissertations, Theses, and Capstone Projects

The detection of smell is initiated when an odorant binds and activates olfactory receptors (ORs) within the nose. Chapter 1 studies the structural requirements for activation of the OR-I7 aldehyde receptor. Octanal is an agonist of the OR-I7 receptor. 4-Ethylcyclohexylacetaldehyde (1.1), with a cyclohexyl ring that locks the C4-C5 bond of octanal in the gauche conformation, was previously found to have higher potency than octanal, suggesting that the OR-I7 receptor prefers the gauche conformation of octanal during activation. However, 1.1 had only been previously tested as a mixture of cis- and trans-isomers, and therefore, it was …

Fabrication And Applications Of Multifunctional Superhydrophobic Surfaces Based On Surface Chemistry And Morphology, Yang Liu

Dissertations, Theses, and Capstone Projects

Superhydrophobic surfaces are gaining great interests in both fundamental researches and technological applications, because of their unique non-wetting and self-cleaning properties. By mimicking the hierarchical surface structure of the natural superhydrophobic surface, i.e. lotus leaf, numerous artificial surperhydrophobic surfaces were developed. However, the challenge is how to fabricate superhydrophobic surfaces by a scalable and economical method. To address this challenge, our group has developed methodologies that enable the fabrication of superhydrophobic surfaces in inexpensive and potentially scalable ways, such as lamination and 3-D printing. To expand on applications, we also combined other desired functionalities into the superhydrophobic surfaces.

The transparent …

Chelating Ligands And Nanomaterials Based On Graphene Oxide For The Reduction And Sequestration Of Radiometals And Protein Purification, Sam Groveman

Dissertations, Theses, and Capstone Projects

Nuclear waste remediation and protein purification using immobilized metals can benefit enormously from the design and implementation of novel chelating nanomaterials. Available commercial resins capable of sequestering metals are based on bulk materials such as organic polymers, ceramics, and their composites. The use of two-dimensional nanoplatforms with large surface areas expands the horizon for the research and development of new systems with higher efficiency and lower cost. Fundamental science challenges remain in the synthesis and characterization of these nanomaterials and their integration with known or novel coordinating ligands.

Chemical exfoliation of graphite under strong oxidizing conditions yields graphene oxide (GO) …

From The Making To The Tuning To The Use Of Chlorins For Biomedical Applications, Junior Gonzales

Dissertations, Theses, and Capstone Projects

Chlorins are porphyrins missing a double bond. These pigments are optimal platforms for the development of novel dyes that display drug-like attributes such as photodynamic therapy (PDT) agents. More recently, it was demonstrated that chlorins can serve both as a PDT agent and as a modality for fluorescence or PET imaging. Thus, multifunctional chlorins eliminate the differences that may occur in specificity, uptake, and distribution between separate compounds or constructs for imaging and therapy. The overall goal of this dissertation is to take advantage of the reputed intrinsic attributes of chlorins as a viable tool in biomedical applications. In this …

The Advanced Spectroscopic Analysis Of Organic Gunshot Residue And Explosives, Jennifer M. Leonard

Dissertations, Theses, and Capstone Projects

With the prevalence of shooting cases and terrorist attacks/or threats that plague the current state of the criminal justice system, it is of paramount importance to be able to detect, identify and interpret the presence of gunshot residue or explosives material. This concern is seen in law enforcement agencies and the media throughout the United States and abroad.

Currently, the typical method of analyzing gunshot residue in most crime laboratories serves to identify the inorganic constituents of the primer residue, namely lead, barium and antimony. However, it is possible that the organic matter from the propellant could provide different information …

The Modified Stereospecific Stille Reaction: Palladium-Catalyzed Cross-Coupling Reactions Involving Secondary And Tertiary Alkyl Carbastannatranes, Chao-Yuan Wang

Dissertations, Theses, and Capstone Projects

Organic chemistry is present in all domains of everyday life, from polymer production to medicine. In order to synthesize complex compounds, it is often necessary to make new carbon-carbon bonds. Transition metal catalysts, particularly those derived from second and third row metals such as Pt, Pd, Rh, and Ir metals, display remarkable efficiency for the formation of carbon-carbon and carbon-heteroatom bonds. In the first chapter, introduction of transition metal-catalyzed cross-coupling reactions is given. While the formation of C(sp²)–C(sp²) bonds has been studied extensively, C(sp³)-C(sp²) bond formation still presents a challenge due to …