Remember Me
Or use your Academic/Social account:


You have just completed your registration at OpenAire.

Before you can login to the site, you will need to activate your account. An e-mail will be sent to you with the proper instructions.


Please note that this site is currently undergoing Beta testing.
Any new content you create is not guaranteed to be present to the final version of the site upon release.

Thank you for your patience,
OpenAire Dev Team.

Close This Message


Verify Password:
Verify E-mail:
*All Fields Are Required.
Please Verify You Are Human:

OpenAIRE is about to release its new face with lots of new content and services.
During September, you may notice downtime in services, while some functionalities (e.g. user registration, login, validation, claiming) will be temporarily disabled.
We apologize for the inconvenience, please stay tuned!
For further information please contact helpdesk[at]openaire.eu

fbtwitterlinkedinvimeoflicker grey 14rssslideshare1
Kelly, Elizabeth Jane
Languages: English
Types: Doctoral thesis
Subjects: QD
This thesis describes the application of optically active helical polymers to chiral stationary phases for high performance liquid chromatography. The use of porous graphitic carbon as a support for these phases is examined and its implication for the nature of the separation.\ud \ud In the first case 3,5-dimethylphenyl carbamate (CDMPC) was studied. This work continued the study by Grieb and Matlin. The use of porous graphitic carbon as a support for this polymer was examined. PGC is produced by Hypersil under the name Hypercarb. It is a porous carbon phase with virtually no surface functionalities. It was confirmed that a 25% w/w loading ofCDMPC produced using a batch coating method produced the optimum phase. The nature of the cellulose used to synthesise the CDMPC was also studied by gel permeation chromatography. It was found that Avicel cellulose (Merck) gave the best results.\ud \ud CDMPC has certain characteristics which make it an effective phase, these are; a) a-helical secondary structure and b) optical activity within the monomer unit. We decided to examine other polymers which possess these characteristics, in particular poly-L-Ieucine. It is believed that this polymer has an a-helical secondary structure and in its synthesis L-leucine is used as a single pure isomer. This polymer has been shown to be effective as an asymmetric organic catalyst.\ud \ud Poly-L-Ieucine was synthesised using condensation polymerisation with three methods of initiation using both L-Ieucine and N-carboxy anhydride L-Ieucine as monomers. N-carboxy anhydride L-Ieucine was initiated by ethylenediamine in solution and water via a humidity cabinet. L-Ieucine was polymerised using triphenyl phosphite, lithium chloride and N-methyl pyrrolidine. Poly-L-Ieucine containing a maximum of fifteen residues was synthesised using solid phase peptide synthesis techniques.\ud \ud These polymers were examined using MALDI-TOF and ESI mass spectrometry. The polymers synthesised from N-carboxy anhydride L-Ieucine were examined using viscometry. Comparing these results it was considered that the molecular weight of the water-initiated polymer was greater. This polymer was further modified by continuous extraction to remove lower molecular weight fragments. All of these polymers were coated onto the surface of PGC by evaporation. It was shown that a 20% w/w loading level was optimum for this type of phase. The optimum phase was found to be made from the water initiated polymer after\ud continuous extraction.\ud \ud This phase was shown to be capable of the resolution ofa variety of racemic epoxides.
  • The results below are discovered through our pilot algorithms. Let us know how we are doing!

    • L.Pasteur, Comptes Rendus de / 'Academie des Sciences, 1848, 26, 535.
    • J.H. Van't Hoff, Arch. Netherlands Sci. Extracts et Naturelles, 1874, 9,445.
    • S.J. Angyal, Angewantde Chemie, 1969,8,157.
    • RB. Herbert, Natural Product Reports, 1992, 9, 507.
    • G. Blaschke, H.P. Kraft, K Fickentscher and F. Kohler, Arzeim.-Forsch., 1979, 29, 1640.
    • RS. Cahn, Sir C. Ingold and V. Prelog, Angew. Chem. Int. Ed Engl., 1966, 5, 385.
    • A. Piutti, c.R. Hebd. Seances Acad Sci., 1886,103,134.
    • E.L. Eliel and S. H. Wilen, Stereochemistry o/Organic Compounds, Chapter 6- 4, Wiley, 1994.
    • G. Blashke, HP. Kraft, H Markgraf, Chem. Ber., 1980, 113 , 2318.
    • R.J. Baczuk, G.K Landram, R.J. Dubois and H. C. Dehm, J. Chromatogr., 1971, 60, 351.
    • S. Loftier, R Stadler, N. Nagakura and M.H. Zenk, 1. Chem. Soc., Chem. Commun., 1987, 1160.
    • RH. Mazur, lM. Schlatter and A.H. Goldkamp, JAm. Chem. Soc., 1969,91, 2684.
    • T.G. Burlingame and W.H. Pirkle, JAm. Chem. Soc., 1966, 88, 4294.
    • G.M. Whitesides and D. W. Lewis, J. Am. Chem. Soc., 1970,92,6979.
    • M.S. Tswett, Bull. Lab. Bot. Gen., Univ. Geneve., 1896, 1, 123.
    • R Kuhn and E. Lederer, Ber. Deut. Chem. Ges., 1931,61,1349.
    • J.J.Kirkland and L.R. Snyder, Introduction to Modem Liquid Chromatography, 2nd Ed., New York: Wiley, 1979.
    • KK. Unger, Porous Silica, 1. Chromatogr. Library, 16, Elsevier, 1979.
    • M.T. Gilbert, J.H. Knox and B. Kaur, Chromatogr., 1982, 16, 138.
    • Y. Okamoto, M. Kawashima, K. Hatada and K. Yamamoto, Chem. Lett., 1984, 739.
    • Y. Okamoto, R. Aburatani, R. Kawashima, M. Hatada and N. Okamura, Chem. Lett, 1987,386,95.
    • T. Shibata, I. Okamoto and K. Ishii, J. Liq. Chromatogr., 1986, 9, 313.
    • I.W. Wainer and M.C. Alembik, J. Chromatogr.,1986, 358,85.
    • I.W. Wainer, E. Smith and M.C. Alembik, J. Chromatogr.,1987, 388,65.
    • E. Francotte and RM. Wolf, J. Chromatogr., 1992, 595, 63.
    • Y. Okamoto, R Aburatani, R. Kawashima, K. Hatada and N. Okamura, Chem. Lett, 1986, 1767.
    • Y. Okamoto, H. Fukaya and E. Yashima, J. Chromatogr., 1994,677, 11.
    • Y. Okamoto, R. Aburatani and K. Hatada, J. Chromatogr., 1987,389,95.
    • E. Yashima, M. Yamada, Y. Kaida and Y. Okamoto, J. Chromatogr.,1995, 694,347.
    • U. Zogt and P. Zugenmaier, Ber. Bunzenges. Phys. Chem., 1985,89, 1217.
    • S.J. Grieb, S.A Matlin, AM. Belenguer, H.J. Richie and P. Ross, J. Chromatogr., 1995,697,271.
    • T.D. Booth, W.J. Lough, M. Saeed, T.AG. Noctor and I.W. Wainer, Chirality, 1997, 9, 173.
    • T.D. Booth, D. Wahnon and I.W.Wainer, Chirality, 1997,9,96.
    • Q.H. Wan, P.N. Shaw, M.C. Davies and D.A Barrett, J. Chromatogr., 1995, 697,219.
    • S.1. Grieb, PhD Thesis, University of Warwick, 1995.
    • S.M. Wilkins, D.R Taylor and R.J. Smith, J. Chromatogr., 1995,697, 587.
    • Y. Okamoto, M. Kawashima, R. Aburatani, K Hatada, T. Nishiyama and M. Masuda, Chem. Lett., 1986, 1237.
    • Y. Okamoto, R. Aburatani, K Hatada, and Y. Kaida, Chem. Lett., 1988, 1125.
    • C.K Lim, Biomedical Chromatography, 1989,3, 1989.
    • R. S. Brown and 1.1. Lennon, Anal. Chem., 1995,67, 3990.
    • M. Dole, R.L. Hines, L.L. Mack, R.C. Modley, L.D. Ferguson and M.B. Alice, 1. Chem. Phys., 1968, 49, 2240.
  • No related research data.
  • No similar publications.

Share - Bookmark

Cite this article

Cookies make it easier for us to provide you with our services. With the usage of our services you permit us to use cookies.
More information Ok