The racemic (±)-2,4-di-tert-butyl-6-(((2-(dimethylamino)cyclohexyl)(methyl) amino)methyl)phenol ((±)-(NNMeOtBu)H), (±)-2,4-di-tert-butyl-6-((2-(dimethylamino) cyclohexylamino)methyl)phenol ((±)-(NNHOtBu)H), and (±)-2-(((2-(dimethylamino) cyclohexyl)(methyl)amino) methyl)phenol ((±)-(NNMeOH)H) are chiral ancillary NNO proligands, which synthesis was adapted from a published procedure. Reaction of (±)-(NNMeOtBu)H ((±)-2), (±)-(NNMeOH)H ((±)-3) and (±)-(NNHOtBu)H ((±)-1) with ZnEt2 successfully yielded the corresponding zinc ethyl complexes (±)-5, (±)-6 and (±)-7 respectively; the enantiomerically pure (R,R)-5 was synthesized from (R,R)-2. NMR spectroscopy experiments and X-ray crystallography allowed identification of two stereoisomers for (±)-5, which were observed in solution and in the solid state. The two stereoisomers, 5-α and 5-β, are in equilibrium in solution, with 5-β being thermodynamically favored. The zinc ethyl complexes were found to be unreactive towards weakly acidic alcohols (methanol, ethanol, isopropanol). However, the zinc chloride complex (±)-(NNMeOtBu)ZnCl ((±)-8) and the zinc phenoxide (NNMeOtBu)ZnOPh ((±)-9 and (R,R)-9) could be isolated and characterized. Comparison of the reactivity of both (±)-5 and the reported L₁ZnEt (L₁ = 2,4-di-tert-butyl-6- {[(2'-dimethylaminoethyl) methylamino]methyl}phenolate) in presence of pyridine led to the proposal of a dissociative mechanism explaining the fundamental difference between the two zinc ethyl species. Polymerization of rac-lactide catalyzed by 9 showed that the complex, in its racemic or enantiomerically pure version, has a slow activity and is not stereoselective.

Thesis (Ph. D.)--University of Missouri-Columbia, 2007. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on December 28, 2007) Includes bibliographical references.

Thesis (Ph.D.)--Biomedical Engineering, Georgia Institute of Technology, 2008. / Committee Chair: Dr. Niren Murthy; Committee Member: Dr. Carson Meredith; Committee Member: Dr. Julia Babensee; Committee Member: Dr. Mark Prausnitz; Committee Member: Dr. Ravi Bellamkonda.

M.Sc. (Chemistry) / Please refer to full text to view abstract

The racemic (±)-2,4-di-tert-butyl-6-(((2-(dimethylamino)cyclohexyl)(methyl) amino)methyl)phenol ((±)-(NNMeOtBu)H), (±)-2,4-di-tert-butyl-6-((2-(dimethylamino) cyclohexylamino)methyl)phenol ((±)-(NNHOtBu)H), and (±)-2-(((2-(dimethylamino) cyclohexyl)(methyl)amino) methyl)phenol ((±)-(NNMeOH)H) are chiral ancillary NNO proligands, which synthesis was adapted from a published procedure. Reaction of (±)-(NNMeOtBu)H ((±)-2), (±)-(NNMeOH)H ((±)-3) and (±)-(NNHOtBu)H ((±)-1) with ZnEt2 successfully yielded the corresponding zinc ethyl complexes (±)-5, (±)-6 and (±)-7 respectively; the enantiomerically pure (R,R)-5 was synthesized from (R,R)-2. NMR spectroscopy experiments and X-ray crystallography allowed identification of two stereoisomers for (±)-5, which were observed in solution and in the solid state. The two stereoisomers, 5-α and 5-β, are in equilibrium in solution, with 5-β being thermodynamically favored. The zinc ethyl complexes were found to be unreactive towards weakly acidic alcohols (methanol, ethanol, isopropanol). However, the zinc chloride complex (±)-(NNMeOtBu)ZnCl ((±)-8) and the zinc phenoxide (NNMeOtBu)ZnOPh ((±)-9 and (R,R)-9) could be isolated and characterized. Comparison of the reactivity of both (±)-5 and the reported L₁ZnEt (L₁ = 2,4-di-tert-butyl-6- {[(2'-dimethylaminoethyl) methylamino]methyl}phenolate) in presence of pyridine led to the proposal of a dissociative mechanism explaining the fundamental difference between the two zinc ethyl species. Polymerization of rac-lactide catalyzed by 9 showed that the complex, in its racemic or enantiomerically pure version, has a slow activity and is not stereoselective. / Science, Faculty of / Chemistry, Department of / Graduate

The ability of a peptide vaccine derived from the human T-lymphotropic virus type 1 (HTLV-1) surface envelope glycoprotein protein (gp46) to mimic the native protein and elicit a protective immune response has been examined. This peptide construct, designated MVFMF2, comprises amino acids (aa) 175-218 of gp46 linked by a four residue turn (GPSL) to a promiscuous T-cell epitope from the measles virus fusion protein (MVF, aa 288-302). The peptide was structurally characterized by circular dichroism (CD) spectroscopy and was found to contain α-helical secondary structure. The immunogenicity of MVFMF2 in rabbits and mice was evaluated by direct ELISA and competitive ELISA using peptide constructs and the recombinant protein ACH-RE3 (aa 165-306). This peptide, when administered with adjuvant (N-acetyl-glucosamine-3yl-acetyl-L-alanyl-D-isoglutamine, nor-MDP) was immunogenic in an outbred population of both rabbits and mice. Furthermore, the peptide construct was encapsulated in biodegradable microspheres of poly(D,L-lactide-co-glycolide) to eliminate booster immunization and to examine adjuvant requirements. The data indicate that MVFMF2 shows enhanced immunogenicity when encapsulated in biodegradable microspheres. Inoculation of the encapsulated peptide produced a similar humoral response to that of the free peptide, but did not require the use of adjuvant. Elicited anti-rabbit and anti-mouse antibodies recognized whole viral preparations and the recombinant protein ACH-RE3 in ELISA assays. Additionally, inoculated rabbits exhibited enhanced reactivity to viral antigens by western blot compared to non-vaccinated controls. Although anti-rabbit and anti-mouse antibodies were capable of inhibiting syncytium formation at low dilutions, rabbits were not protected from cell-associated viral challenge. Future development of vaccines to HTLV-1 may need to incorporate the ability to elicit cell-mediated immune responses in order to protect against cell-associated viral infection.

No description available.

Chlorine is used as a powerful disinfectant in water-related industries and in the food industry to remove bacteria and other harmful contaminants. We present a solution-based fabrication process for a biodegradable electrochemical free chlorine sensor using asparagine that is functionalized onto graphene oxide (GO). An ink solution of the GO functionalized with asparagine was fabricated then deposited onto a screen-printed carbon electrode (SPCE) using a spin-coater. The sensor showed high a sensitivity of 0.30 μA ppm−1 over a linear range of 0 to 8 ppm with a hysteresis-limited resolution of 0.2 ppm, very high selectivity in the presence of commonly interfering ions, and an operating voltage well below the reduction potential of dissolved oxygen. The sensor response time to achieve a steady state was 50 s, and it showed little change in its drift response over 16 h and over a temperature range of 10 to 45 °C. From the development of the free chlorine sensor, over 9000 datapoints were collected and used for training a neural network model to quantify and characterize factors affecting the free chlorine sensor performance. A readout system was designed with a printed circuit board and an android app to simplify free chlorine sensing for an end user. / Thesis / Master of Applied Science (MASc) / Free chlorine is used to disinfectant sources of water, and eliminate pathogens. The World Health Organization (WHO) maintains strict amounts of free chlorine in water due to its widespread usage owed to its low cost and persistence in water systems. Too little, and it will not be an effective disinfectant, and too much and the high consumption of free chlorine increases the risk cancer or the formation of hazardous chemicals. Recently, free chlorine sensors that measure an electrical response proportional to the amount of free chlorine are gaining interest for fast, accurate, and repeatable measurements. This thesis focuses on the design, fabrication, and evaluation of these sensors made using biodegradable materials in a solution-based fabrication processes with the aim of working towards large-scale fabrication of a printable ink. First, we review the results achieved by the sensors within recent literature. Second, we present the design of a sensor that aims to achieve environmentally friendly goals and maintain competitive performance characteristics. The, the sensor is tested under various conditions with its performance quantified under different conditions. Third, the sensor is characterized using a neural network to measure its performance and identify sources of improvement for future designs. Finally, we incorporate the sensor with an android app to measure free chlorine in remote water systems.

No description available.

Yes / With antimicrobial resistance (AMR) increasing at an alarming rate, there is a need to develop better antibiotic delivery platforms at the point of need, to reduce over-exposure to antibiotics that are delivered systemically. Recent studies have suggested the use of metal-organic frameworks (MOFs) as potential vehicles for controlled and efficient delivery of various active pharmaceutical ingredients (APIs). Development of MOF-polymer composite materials can assist in the development of medical devices that can deliver APIs to local sites in a targeted approach. This study reports the encapsulation of a widely used antibiotic - ciprofloxacin (CIP) - into two Zr-based MOFs (UiO-66 and UiO-66-NH2) and their subsequent integration into a biodegradable polymer; polycaprolactone (PCL), via solvent casting, to obtain a PCL-MOF composite membrane. The MOFs and PCL-MOF composites were characterised by Fourier-transformed infrared (FT-IR) spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The results demonstrated that the structural integrity of the pristine MOFs was maintained after drug loading and incorporation into the PCL membranes. The ciprofloxacin release was studied using ultraviolet–visible (UV–Vis) spectroscopy, and the results showed that the PCL-MOF composites had a more controlled drug release profile compared to the MOF alone, when monitored for seven days in phosphate buffered saline (PBS) and accelerated ageing (AA) release media. In addition, release studies showed pH-dependence with faster release of ciprofloxacin at both acidic and basic conditions. Antimicrobial assay showed excellent efficacy for both CIP-loaded MOFs and their PCL composites against S. aureus and E. coli, a Gram-negative and Gram-positive bacterium, respectively, with inhibition zone as high as >50 mm against E. coli for UiO-66-NH2-CIP, indicating their potential applications in purpose-specific medical devices. / LAMM and SN acknowledge an Erasmus + exchange studentship. VPT and LRT acknowledge funding via an EPSRC Research Fellowship for VPT [EP/R01650×/1].