Chemistry Commons^™

Synthesis Of Oligonucleotides Containing Unnatural Backbone And Regulation Of Crispr Activity Using Inverse Electron Demand Diels-Alder Chemistry, Alyssa Hoy

Legacy Theses & Dissertations (2009 - 2024)

This thesis describes the synthesis of an oligonucleotide containing an unnatural neutralbackbone. The backbone was constructed using bio-orthogonal inverse electron demand Diels- Alder chemistry between trans-cyclooctene (TCO) and tetrazine (Tz). A TCO phosphoramidite was synthesized and attached to solid support for strand propagation. Uridine monomers containing either bis-TCO or bis-Tz were also synthesized. The oligonucleotide strand was formed by sequential ligation of the bis-Tz and bis-TCO monomers. The oligonucleotide was analyzed using mass spectrometry. This thesis also describes the synthesis of sgRNAs containing non-canonical nucleobases, m1A, m6A, s2U and s4U using the ‘split-and-click’ methodology. The synthetic sgRNAs were assembled using …

Development And Applications Of Touch Chemistry Biometrics Analysis Of Latent Fingermarks By Maldi-Ms, Cameron M. Longo

Legacy Theses & Dissertations (2009 - 2024)

Fingerprint evidence has long been a pillar of forensic science and has been used for over a century as a means of identifying an individual. This is accomplished through the comparison of friction ridge patterns, which are inherently unique to each individual, and the practice of visualizing fingerprints and comparing them has become a well-studied field. While these techniques have been optimized and improved over time, they generally rely only on the physical pattern to provide information about the donor, and not the content of the fingerprint material itself. In the modern era, steps have been made to extract from …

First Homoleptic Rare Rarth Metal Complexes With Doubly-Reduced Dibenzocyclooctatetraene, James C. Mahoney

Legacy Theses & Dissertations (2009 - 2024)

A set of novel complexes of rare earth elements, M(III) = Y, La, Gd, Tb, and Dy, with the doubly-reduced dibenzo[a,e]cyclooctatetraene (DBCOT) anion has been synthesized and crystallographically characterized for the first time. Preparation of new complexes has been accomplished through the ligand-metathesis reaction of M(III) triiodides with K2(DBCOT) in THF at ambient conditions. Subsequent crystallization via slow solvent evaporation afforded single crystals of good quality. X-ray diffraction technique confirmed that all complexes are isomorphous and conform to the [M(DBCOT)(THF)4][M(DBCOT)2] composition. In their crystal structures, the monoanionic double-decker sandwiches, [M(DBCOT)2], weakly interact with the cationic counterparts, [M(DBCOT)(THF)4]+. In both parts, …

Uio-Type Metal-Organic Framework Derivatives As Sorbents For The Detection Of Gas-Phase Explosives, Matthew Ryan Sherrill

Legacy Theses & Dissertations (2009 - 2024)

The detection of energetic compounds – better known to the public as explosives – has is an important cornerstone of counterterrorism and homeland security . While significant advances have been achieved for the detection of trace explosives in various matrices such as soil, wastewater, and clothing, the detection of explosives in the gas phase remains challenging due to their infamously low vapor pressures. In this thesis, we leverage the high sensitivity of direct analysis in real-time mass spectrometry (DART-MS) and the microporosity of metal-organic frameworks (MOFs) to adsorb and therefore concentrate explosives from the vapor phase and subsequently detect them …

Photopolymers : Environmentally Benign Technology For A Variety Of Industries, Tatyana Tarasevich

Legacy Theses & Dissertations (2009 - 2024)

Photopolymerization is a well-known process with applications in a variety of industries. Photopolymers are formed by a reaction of monomers or oligomers, photoinitiators and in some cases crosslinkers. Upon irradiation with UV or visible light, monomers undergo conformational change to form polymers via a photochemical process. Several photopolymerization types will be discussed in this thesis. End products of photopolymerizations included epoxies, inks, coatings, photoresists, etc.

Extensive Thiol Profiling For Assessment Of Intracellular Redox Status In Cultured Cells By Hplc-Ms/Ms, Jiandong Wu, Anna Chernatynskaya, Annalise Pfaff, Huari Kou, Nan Cen, Nuran Ercal, Honglan Shi

Computer Science Faculty Research & Creative Works

Oxidative stress may contribute to the pathology of many diseases, and endogenous thiols, especially glutathione (GSH) and its metabolites, play essential roles in the maintenance of normal redox status. Understanding how these metabolites change in response to oxidative insult can provide key insights into potential methods of prevention and treatment. Most existing methodologies focus only on the GSH/GSH disulfide (GSSG) redox couple, but GSH regulation is highly complex and depends on several pathways with multiple redox-active sulfur-containing species. In order to more fully characterize thiol redox status in response to oxidative insult, a high-performance liquid chromatography with tandem mass spectrometry …

Establishing The Relative Composition Of Functionalized Thiols In Mixed Ligand Gold Nanoparticles By 1h-Nmr Spectroscopy, Matthias Carroll

All Master's Theses

Functionalized gold nanoparticles (AuNPs) are of interest for their optical and electrical properties, specifically the surface plasmon resonance phenomenon and potential applications for medicine and nano-circuitry. In this study, the ligand composition of small (~5 nm diameter) thiol functionalized AuNPs with mixed ligand monolayers was investigated to better understand how the molar feed ratio of ligands used during their synthesis influences the composition of ligands on the particle’s surface. The system under study was a combination of two ω-functionalized thiols, mercapto ethoxy ethoxy ethanol (MEEE) and mercapto pentyl trimethyl ammonium chloride (MPTMA). UV/Visible spectrophotometry, dynamic light scattering, and electron …

Isolation Of Ace2 Inhibitors From Rice Bran Oil By-Product, Muhammad Waqar Nasir

Chulalongkorn University Theses and Dissertations (Chula ETD)

This study aimed to isolate γ-oryzanol from the crude oil acid fraction (a by-product of rice bran oil refinery) and to evaluate their Angiotensin-Converting Enzyme 2 (ACE2) inhibitory activity. Chromatographic fractionation of the crude oil acid fraction gave 3 isolated fractions of γ-oryzanol containing cycloartenyl ferulate, campesteryl ferulate, sitosteryl ferulate, stigmasteryl ferulate, and cyclobranyl ferulate. The γ-oryzanol containing cycloartenyl ferulate and campesteryl ferulate as major component showed good ACE2 inhibitory activity with the IC50 value 10.57 μg/mL. Furthermore, the 19 structures of γ-oryzanol were also studied for its interaction against ACE2 through molecular docking. Based on the in-silico study, ADME …

Development Of [3,3]-Sigmatropic Rearrangements Of Zwitterionic And Cationic Intermediates Formed By Intramolecular Cyclization Of Tertiary Allylic Amines Tethered To Heterocumulenes, Joseph Pisano

Graduate College Dissertations and Theses

Guanidines are ubiquitous in nature and serve as useful building blocks in biologically active natural products as well as non-nucleophilic bases and organocatalysts. There is thus a need for methods for the synthesis of guanidine compounds as well as isoelectronic groups such as isothioureas. The 1,3-diaza-Claisen rearrangement represents a powerful reaction by which to synthesize highly substituted guanidines.

The scope of the zwitterionic 1,3-diaza-Claisen rearrangement has been further investigated through the introduction of a two-carbon tether. Electron-deficient carbodiimides can be synthesized through desulfurization of isothioureas, which undergo intramolecular cyclization through a tethered tertiary amine bearing an allylic group to afford …

The Acute Physiological Response Of Polar Bears To Helicopter Capture, John P. Whiteman, Henry J. Harlow, George M. Durner, Eric V. Regehr, Steven C. Amstrup, Anthony M. Pagano, Merav Ben-David

Biological Sciences Faculty Publications

Many wildlife species are live captured, sampled, and released; for polar bears (Ursus maritimus) capture often requires chemical immobilization via helicopter darting. Polar bears reduce their activity for approximately 4 days after capture, likely reflecting stress recovery. To better understand this stress, we quantified polar bear activity (via collar‐mounted accelerometers) and body temperature (via loggers in the body core [T_abd] and periphery [T_per]) during 2–6 months of natural behavior, and during helicopter recapture and immobilization. Recapture induced bouts of peak activity higher than those that occurred during natural behavior for 2 of 5 bears, …

Gene Vectors With Fluorescence Tracking Capabilities, Sophia Despina Angelopoulos

Browse all Theses and Dissertations

This project focuses on the optimization of benzothiazole-based chromophores to utilize them as fluorescent tags functionalized onto stimuli-responsive, or “smart,” polymers as non-viral gene delivery vectors for gene therapy applications. Blue-fluorescent emissive chromophores will allow tracking capabilities for the transfection pathway of the vector to be monitored as it delivers the DNA payload within intercellular space. The most appropriate chromophore must be covalently bound to a free amine within the vector, which is accomplished through NAS chemistry from fluorophenyl-benzothiazoles (F-BTZ-CBz) derivatives to amidated hyperbranched poly(ethyleneimine)(HPEI-IBAm0.61). HPEI is considered to be a synthetic polycation, which promotes tunable solubility through characteristics of …

Fabrication And Characterization Of Novel Agnps Functionalized With Chlorothymol (C@Agnps), Lirim Sopaj

Browse all Theses and Dissertations

In this study, novel silver nanoparticles (AgNPs) were successfully synthesized and functionalized with an antibacterial agent, namely chlorothymol (denoted C@AgNPs). The resulting colloid (C@AgNPs) was purified by two comparative methods: ultrafiltration and ultracentrifugation. Ultrafiltration proved to be more efficient in purifying and size selecting (10 kD filter) and concentrating the C@AgNPs than ultracentrifugation. The physicochemical properties of the filtered C@AgNPs were then characterized by UV-Vis absorption spectroscopy, inductively coupled plasma optical emission spectroscopy (ICP-OES), Raman spectroscopy, Cytoviva hyperspectral imaging, and Scanning electron microscopy. These measurements confirmed the functionalization of the core AgNPs with chlorothymol and suggest the proposed mechanism of …

Understanding And Harnessing The Structural Features That Govern Hmg-Coa Reductase Activity, Edwin Ragwan

Bryn Mawr College Dissertations and Theses

The enzyme 3-hydroxy-3-methylglutaryl coenzyme-A reductase (HMGR), which catalyzes the reduction of HMG-CoA to mevalonate using two equivalents of the cofactor NAD(P)H, is part of the mevalonate pathway, found in all kingdoms of life. This pathway is at the heart of natural product biosynthesis constituting one of the obligate routes to producing the building blocks for isoprenoids, which represent the largest and most diverse class of natural products. Natural products and its derivatives continue to provide important compounds in the fields of drug development, biomedical engineering, and commercially-driven products. Therefore, HMGR, which performs the rate-limiting step of the mevalonate pathway garners …

Electrocatalytic Processes For Energy Storage & Conversion, Apurv Saxena

Doctoral Dissertations

"The continuous excessive usage of fossil fuels has resulted in its fast depletion leading to an escalating energy crisis as well as several environmental issues leading to increased research towards sustainable energy conversion. Electrocatalysts play crucial role in the development of numerous novel energy conversion devices including fuel cells and solar fuel generators.

High-efficiency and cost-effective catalysts are required for large-scale implementation of these new devices. Over the last few years transition metal chalcogenides have emerged as highly efficient electrocatalysts for several electrochemical devices such as water splitting, carbon dioxide electroreduction and, solar energy converters. These transition metal chalcogenides exhibit …

Synthesis And Characterization Of Multimetallic Clusters Featuring Iron, Cobalt, And 2,6-Bis(Trialkylsilylamino)Pyridines, Lynn Nguyen

Electronic Theses and Dissertations

Extended metal atom chain (EMAC) complexes are multimetallic complexes of three or more metals, often containing M-M bonds, with the metal ions arranged linearly. These complexes have significant potential as molecular wires. They can elicit unique physical properties and reactivities, sometimes a result of direct magnetic exchange between metal centers, especially when incorporating first row transition metals. The synthesis of the first linear, triiron (II) complex with 2,6-bis[(trimethylsilyl)amino]pyridine (H₂L^Me) featuring Fe-Fe bonding from our group, Fe₃L^Me₃, motivated the expansion of linear multimetallic EMAC complexes with Fe and Co, incorporating M-M bonds. …

Ozonized Biochar Filtrate Effects On The Growth Of Pseudomonas Putida And Cyanobacteria Synechococcus Elongatus Pcc 7942, Oumar Sacko, Nancy L. Engle, Timothy J. Tschaplinski, Sandeep Kumar, James Weifu Lee

Chemistry & Biochemistry Faculty Publications

Background

Biochar ozonization was previously shown to dramatically increase its cation exchange capacity, thus improving its nutrient retention capacity. The potential soil application of ozonized biochar warrants the need for a toxicity study that investigates its effects on microorganisms.

Results

In the study presented here, we found that the filtrates collected from ozonized pine 400 biochar and ozonized rogue biochar did not have any inhibitory effects on the soil environmental bacteria Pseudomonas putida, even at high dissolved organic carbon (DOC) concentrations of 300 ppm. However, the growth of Synechococcus elongatus PCC 7942 was inhibited by the ozonized biochar filtrates at …

Microbial Labilization And Diversification Of Pyrogenic Dissolved Organic Matter, Aleksandar I. Goranov, Andrew S. Wozniak, Kyle W. Bostick, Andrew R. Zimmerman, Siddhartha Mitra, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

With the increased occurrence of wildfires around the world, interest in the chemistry of pyrogenic organic matter (pyOM) and its fate in the environment has increased. Upon leaching from soils by rain events, significant amounts of dissolved pyOM (pyDOM) enter the aquatic environment and interact with microbial communities that are essential for cycling organic matter within the different biogeochemical cycles. To evaluate the biodegradability of pyDOM, aqueous extracts of laboratory-produced biochars were incubated with soil microbes, and the molecular changes to the composition of pyDOM were probed using ultrahigh-resolution mass spectrometry (Fourier transform–ion cyclotron resonance–mass spectrometry). Given that solar irradiation …

การศึกษาปัจจัยที่ส่งผลต่อสมบัติของยางแผ่นรมควันเกรดพรีเมียม, สายสุณี จิตกล้า

Chulalongkorn University Theses and Dissertations (Chula ETD)

ถึงแม้ว่าสมบัติเชิงกลของยางแผ่นรมควันจะเหนือกว่ายางแห้งชนิดอื่นก็ตาม แต่ความไม่สม่ำเสมอในคุณภาพของยางส่งผลให้ปริมาณการใช้งานยางแผ่นรมควันในอุตสาหกรรมล้อยางลดลงอย่างต่อเนื่อง ปัจจุบันการยางแห่งประเทศไทยได้กำหนดมาตรฐานการผลิตยางแผ่นรมควันขึ้นเพื่อควบคุมและให้ได้ยางแผ่นรมควันที่มีสมบัติต่าง ๆ คงที่ ซึ่งยางที่ได้จะเรียกว่า “ยางแผ่นรมควันเกรดพรีเมียม” หรือ “ยางแผ่นรมควันเกรด P” เพื่อให้เข้าใจถึงสาเหตุที่ส่งผลให้สมบัติต่าง ๆ ของยางแผ่นรมควันแปรปรวนดียิ่งขึ้น งานวิจัยนี้ได้ศึกษาถึงอิทธิพลด้านภาวะการผลิต ช่วงฤดูกาลกรีดยาง รวมไปถึงพิ้นที่ปลูกยางต่อสมบัติทั้งทางกายภาพและเชิงกลของยางแผ่นรมควัน ผลการทดลองที่ได้พบว่า เมื่อใช้น้ำยางที่มีปริมาณเนื้อยางแห้งแตกต่างกันและใช้ความเข้มข้นกรดฟอร์มิกในการจับตัวเนื้อยางแตกต่างกัน สมบัติของยางแผ่นรมควันจะแตกต่างกันไป โดยพบว่าเมื่อปริมาณเนื้อยางแห้งและความเข้มข้นกรดฟอร์มิกเพิ่มขึ้นส่งผลให้ค่าสิ่งระเหยในยางแผ่นรมควันเพิ่มขึ้น เนื่องจากก้อนยางที่ได้จากการจับตัวของเนื้อยางด้วยกรดค่อนข้างแข็ง ทำให้เมื่อนำไปรีดเป็นแผ่นบางทำได้ยาก น้ำในเนื้อยางจึงระเหยออกมาได้ไม่ดี เมื่อเพิ่มปริมาณเนื้อยางแห้งจะทำให้ค่า PO, PRI และความหนืดมูนีเพิ่มขึ้น การแปรปริมาณเนื้อยางแห้งในน้ำยางจาก 20% (ภาวะใช้ในการผลิตยางแผ่นรมควันพรีเมียม) เป็น 18, 20 และ 25% โดยน้ำหนัก ส่งผลให้ความทนต่อแรงดึงของยางแตกต่างกันมากที่สุดอยู่ที่ 2.1 MPa การเพิ่มความเข้มข้นกรดฟอร์มิกจะส่งผลทำให้ค่า PO, PRI และความหนืดมูนีลดลง การแปรความเข้มข้นกรดฟอร์มิกจาก 4% (ภาวะที่ใช้ในการผลิตยางแผ่นรมควันเกรดพรีเมียม) เป็น 2, 3, 5, 8 และ 10% โดยปริมาตร ส่งผลให้ความทนต่อแรงดึงของยางแตกต่างกันมากที่สุดอยู่ที่ 3.2 MPa เมื่อพิจารณาฤดูกาลกรีดยางแตกต่างกัน น้ำยางที่ได้จากช่วงการผลัดใบของต้นยางจะมีปริมาณเนื้อยางแห้งในน้ำยางลดลง และปริมาณธาตุต่างๆ ในยางเพิ่มขึ้น ซึ่งจะส่งผลต่อค่าเถ้าและไนโตรเจนในยางแผ่นรมควันแตกต่างกัน ค่าความหนืดมูนีของยางแผ่นรมควันขึ้นอยู่กับช่วงฤดูกาลกรีดยางค่อนข้างชัดเจน โดยยางแผ่นรมควันที่เตรียมจากน้ำยางที่ได้จากการกรีดในช่วงกรีดปกติจะมีความหนืดมูนีที่สูงกว่ายางแผ่นรมควันที่เตรียมจากน้ำยางที่ได้จากการกรีดในช่วงก่อนปิดกรีด ยางแผ่นรมควันที่ได้จากภาคตะวันออกเฉียงเหนือมีปริมาณเถ้ามากกว่าที่ได้จากภาคใต้ ซึ่งปริมาณเถ้าเกิดจากปริมาณสารและแร่ธาตุต่าง ๆ ในดินที่ไม่เหมือนกัน อย่างไรก็ตาม ยางที่ได้จากทั้งสองบริเวณที่มีค่า PO , PRI และ ความหนืดมูนี ไม่ได้แตกต่างกันอย่างเห็นได้ชัด

Improvement Of Hydrodynamics And Heat Transfer In Biomass Fluidized Bed Combustor With Immersed Tubes Using Cfd-Dem, Krittin Korkerd

Chulalongkorn University Theses and Dissertations (Chula ETD)

Computational Fluid Dynamics coupled with Discrete Element Method (CFD-DEM) has been extensively utilized for studying hydrodynamics and heat transfer in fluidization processes. This study specifically focuses on improving hydrodynamics and heat transfer in a biomass fluidized bed combustor with immersed tubes. The investigation involves the use of mixed biomass, exploring the effects of biomass types, biomass loading, and blending ratios to propose criteria for selecting suitable biomass fuel for the system. Design parameters related to the immersed tubes, such as the angle between tubes, tube diameters, and distance between tubes, were also considered. A data-driven model was developed based on …

Chemical Constituents From The Fresh Pericarps Of Mature Mangosteen Fruit Garcinia Mangostana, Ahmad Tijani Azeez

Chulalongkorn University Theses and Dissertations (Chula ETD)

α-Mangostin has been identified as a major chemical constituent in the pericarps of mangosteen (Garcinia mangostana Linn.) Over time, dried pericarps of mangosteen have been subjected to studies in literature. This study aimed to explore isolation of α-mangostin and other chemical constituents from the fresh pericarps of mature mangosteen fruits and investigate their relative antioxidant and anticancer activities. Repeated column chromatography on ethyl acetate and methanol extracts of fresh mature mangosteen pericarps led to the isolation of α-mangostin (33.25% of crude extracts) as the major compound, beta-mangostin (0.225%) and gartanin (7.57%). Their antioxidant scavenging activity was investigated against 2,2-diphenyl-1-picrylhydrazyl (DPPH) …