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You searched for subject:(enantioselective sensing). Showing records 1 – 2 of 2 total matches.

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University of Texas – Austin

1. Joyce, Leo Anthony. Molecular sensing paradigms : enantioselective recognition of chiral carboxylic acids and interfacial sensing.

Degree: Chemistry, 2012, University of Texas – Austin

Determining the presence of an analyte of interest, and finding the enantiomeric purity of chiral molecules are challenging tasks. This work in molecular recognition is carried out routinely by many different researchers, including both academic as well as industrial research groups. The following dissertation presents original research directed toward two different areas of interest to the molecular recognition community: enantioselective sensing in solution, and sensing at a defined interfacial environment. This work begins with a review of the non-chromatographic ways that the enantiomeric purity of chiral carboxylic acids is determined, presented in Chapter 1. Carboxylic acids are important functional groups, both for organic synthesis as well as pharmaceutical drug development. Chapter 2 presents efforts that have been made to rapidly assess both the enantiomeric purity and identity of chiral carboxylic acids, utilizing the technique of exciton-coupled circular dichroism (ECCD). A twist is imparted on a complex, and can be correlated with the absolute configuration of the stereocenter. The enantiomeric composition can be rapidly determined. After creating the assay, the focus of the work shifted toward applying this system to new classes of analytes. Chapter 3 covers chemo- and enantioselective differentiation of [mathematical symbol]-amino acids, and continues to discuss the expansion to [mathematical symbol]-homoamino acids. Then a synthetic substrates was tested, and a series of reactions screened to determine if any enantioselectivity had been imparted by a Baeyer-Villiger oxidation. Finally, the enantiomeric composition of a biaryl atropisomer, a compound lacking a stereocenter, was determined. The signal produced from this assay is at a relatively short wavelength, and efforts were undertaken to push this signal to longer wavelength. Chapter 4 is a compendium of the lessons that were learned upon attempting to create a self-assembled sensing system. The final chapter details work that was done in collaboration with Professor Katsuhiko Ariga at the National Institute of Materials Science in Tsukuba, Japan. In this chapter, an indicator displacement assay was carried out for the first time at the air-water interface. This contribution opens the door for sensing to be carried out at defined regions, rather than free in bulk solution. Advisors/Committee Members: Anslyn, Eric V., 1960- (advisor).

Subjects/Keywords: Enantioselective sensing; Chiral recognition; Exciton-coupled circular dichroism; Carboxylic acids; Indicator displacement assay; Air-water interface

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6th Edition):

Joyce, L. A. (2012). Molecular sensing paradigms : enantioselective recognition of chiral carboxylic acids and interfacial sensing. (Thesis). University of Texas – Austin. Retrieved from http://hdl.handle.net/2152/22182

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16th Edition):

Joyce, Leo Anthony. “Molecular sensing paradigms : enantioselective recognition of chiral carboxylic acids and interfacial sensing.” 2012. Thesis, University of Texas – Austin. Accessed August 23, 2019. http://hdl.handle.net/2152/22182.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7th Edition):

Joyce, Leo Anthony. “Molecular sensing paradigms : enantioselective recognition of chiral carboxylic acids and interfacial sensing.” 2012. Web. 23 Aug 2019.

Vancouver:

Joyce LA. Molecular sensing paradigms : enantioselective recognition of chiral carboxylic acids and interfacial sensing. [Internet] [Thesis]. University of Texas – Austin; 2012. [cited 2019 Aug 23]. Available from: http://hdl.handle.net/2152/22182.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Joyce LA. Molecular sensing paradigms : enantioselective recognition of chiral carboxylic acids and interfacial sensing. [Thesis]. University of Texas – Austin; 2012. Available from: http://hdl.handle.net/2152/22182

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

2. Null, Eric L. Functional dna: Biochemical/biophysical characterization & sensing applications.

Degree: PhD, 0335, 2011, University of Illinois – Urbana-Champaign

In 1990 the Szostak and Gold groups independently discovered that short pieces of RNA can bind to small molecule or biological targets. In 1994 the Joyce group showed that DNA, long thought to be solely for information storage, was capable of catalysis. Naturally occurring ribozymes were discovered in the 1980s by the Cech group. Since then aptamers, which bind targets, and ribozymes or deoxyribozymes, which are catalytically active, have become known collectively as “functional nucleic acids.” The common theme of the works presented herein involves manipulating functional nucleic acids to further increase our understanding of their fundamental properties and to also develop applications for these molecules. Chapter 1 is an introduction to the works presented herein. Chapter 2 discusses conversion of aptamers into sensors for the determination of enantiomeric ratio, leading to a rapid method of detection with high selectivity and portability. Chapters 3, 4, and 5 are tied together through the common thread of the 8-17 DNAzyme and involve biochemical and biophysical characterization of the 8-17 DNAzyme as well as characterization of a novel red Pb2+ species formed upon cleavage of a modified 8-17 DNAzyme. Determination of the enantiomeric ratio is important as many monetarily and functionally valuable molecules are chiral, such as pharmaceuticals and chiral catalysts. For example, Xopenex,® a single enantiomer form of albuterol, has higher efficacy than the racemic mixture. There are currently multiple methods for determining the enantiomeric ratio, all of which work well, with their own particular caveats. Separations-based methods, using a variety of detectors, may require 30 minute runs and often require solvents. NMR and fluorescence-based methods are rapid, though the development of a chiral reporter requires many iterative cycles of design and synthesis. Herein, we use the power of aptamers generated by in vitro selection to design a fluorescence-based system capable of detecting 0.1% L-arginine in a solution of D-arginine in five minutes. The 8-17 DNAzyme is a RNA-cleaving DNAzyme which is active with divalent metal ions, showing the highest activity with Pb2+. The 8-17 DNAzyme has been isolated multiple times by different groups and has been the subject of many studies – both fundamental and practical. Mutational studies by the Peracchi and Lu groups have shown that certain bases in the DNAzyme are highly conserved, though the metal ion binding site is still unknown. FRET studies by the Lu group have shown that a folding step is necessary before catalysis with either Zn2+ or Mg2+, though Pb2+ does not require a folding step, leading to the postulation of a pre-arranged binding site. FRET, however, is a low-resolution technique and does not provide information on local folding, or rather changes in the conformation of the active site upon metal ion binding. Herein we show that the 8-17 DNAzyme is prearranged for Pb2+ as minimal changes in the 1H NMR spectrum are seen upon Pb2+ titration, supporting a true… Advisors/Committee Members: Lu, Yi (advisor), Lu, Yi (Committee Chair), Shapley, Patricia A. (committee member), Silverman, Scott K. (committee member), Suslick, Kenneth S. (committee member).

Subjects/Keywords: DNAzyme; biochemical characterization; biophysical characterization; aptamer; enantioselective sensing

…7 1.2 3 Sensing applications… …8 1.2.2 Aptamer-based sensing… …9 1.2.3 Deoxyribozyme-based sensing… …biological systems. 1.2 1.2.1 Sensing applications Signal output A good sensor must be both… …interfering species may be present. In order for sensing to take place, three general steps are… 

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6th Edition):

Null, E. L. (2011). Functional dna: Biochemical/biophysical characterization & sensing applications. (Doctoral Dissertation). University of Illinois – Urbana-Champaign. Retrieved from http://hdl.handle.net/2142/24505

Chicago Manual of Style (16th Edition):

Null, Eric L. “Functional dna: Biochemical/biophysical characterization & sensing applications.” 2011. Doctoral Dissertation, University of Illinois – Urbana-Champaign. Accessed August 23, 2019. http://hdl.handle.net/2142/24505.

MLA Handbook (7th Edition):

Null, Eric L. “Functional dna: Biochemical/biophysical characterization & sensing applications.” 2011. Web. 23 Aug 2019.

Vancouver:

Null EL. Functional dna: Biochemical/biophysical characterization & sensing applications. [Internet] [Doctoral dissertation]. University of Illinois – Urbana-Champaign; 2011. [cited 2019 Aug 23]. Available from: http://hdl.handle.net/2142/24505.

Council of Science Editors:

Null EL. Functional dna: Biochemical/biophysical characterization & sensing applications. [Doctoral Dissertation]. University of Illinois – Urbana-Champaign; 2011. Available from: http://hdl.handle.net/2142/24505

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