Vibrational spectra and crystal structure of the di-amino acid peptide cyclo(L-Met-L-Met): Comparison of experimental data and DFT calculations

Experimental Raman and FT-IR spectra of solid-state non-deuterated and N-deuterated samples of cyclo(L-Met-L-Met) are reported and discussed. The Raman and FT-IR results show characteristic amide I vibrations (Raman: 1649 cm-1, infrared: 1675 cm-1) for molecules exhibiting a cis amide conformation. A Raman band, assigned to the cis amide II vibrational mode, is observed at sim1493 cm-1 but no IR band is observed in this region. Cyclo(L-Met-L-Met) crystallises in the triclinic space group P1 with one molecule per unit cell. The overall shape of the diketopiperazine (DKP) ring displays a (slightly distorted) boat conformation. The crystal packing employs two strong hydrogen bonds, which traverse the entire crystal via translational repeats. B3-LYP/cc-pVDZ calculations of the structure of the molecule predict a boat conformation for the DKP ring, in agreement with the experimentally determined X-ray structure. Copyright © 2009 John Wiley & Sons, Ltd.

Vibrational spectroscopy and crystal structure analysis of two polymorphs of the di-amino acid peptide cyclo(L-Glu-L-Glu)

Cyclo(L-Glu-L-Glu) has been crystallised in two different polymorphic forms. Both polymorphs are monoclinic, but form 1 is in space group P21 and form 2 is in space group C2. Raman scattering and FT-IR spectroscopic studies have been conducted for the N,O-protonated and deuterated derivatives. Raman spectra of orientated single crystals, solid-state and aqueous solution samples have also been recorded. The different hydrogen-bonding patterns for the two polymorphs have the greatest effect on vibrational modes with N&bond;H and C&dbond;O stretching character. DFT (B3-LYP/cc-pVDZ) calculations of the isolated cyclo(L-Glu-L-Glu) molecule predict that the minimum energy structure, assuming C2 symmetry, has a boat conformation for the diketopiperazine ring with the two L-Glu side chains being folded above the ring. The calculated geometry is in good agreement with the X-ray crystallographic structures for both polymorphs. Normal coordinate analysis has facilitated the band assignments for the experimental vibrational spectra. Copyright © 2009 John Wiley & Sons, Ltd.

REDUCING DIESEL DEPENDENCE IN NUNAVUT: INTEGRATING RENEWABLE ENERGY TECHNOLOGIES THROUGH POLICY ACTIONS

In the last fifty years, Nunavut has developed a deep dependence on diesel for virtually all of its energy needs, including electricity. This dependence has created a number of economic, environmental and health related challenges in the territory, with an estimated 20% of the territory’s annual budget being spent on energy, thereby limiting the Government of Nunavut’s ability to address other essential infrastructure and societal needs, such as education, nutrition and health care and housing. One solution to address this diesel dependency is the use of renewable energy technologies (RETs), such as wind, solar and hydropower. As such, this thesis explores energy alternatives in Nunavut, and through RETScreen renewable energy simulations, found that solar power and wind power are technically viable options for Nunavut communities and a potentially successful means to offset diesel-generated electricity in Nunavut. However, through this analysis it was also discovered that accurate data or renewable resources are often unavailable for most Nunavut communities. Moreover, through qualitative open-ended interviews, the perspectives of Nunavut residents with regards to developing RETs in Nunavut were explored, and it was found that respondents generally supported the use of renewable energy in their communities, while acknowledging that there still remains a knowledge gap among residents regarding renewable energy, stemming from a lack of communication between the communities, government and the utility company. In addition, the perceived challenges, opportunities and gaps that exist with regards to renewable energy policy and program development were discussed with government policy-makers through further interviews, and it was discovered that often government departments work largely independently of each other rather than collaboratively, creating gaps and oversights in renewable energy policy in Nunavut. Combined, the results of this thesis were used to develop a number of recommended policy actions that could be undertaken by the territorial and federal government to support a shift towards renewable energy in order to develop a sustainable and self-sufficient energy plan in Nunavut. They include: gathering accurate renewable resource data in Nunavut; increasing community consultations on the subject of renewable energy; building strong partnerships with universities, colleges and industry; developing a knowledge sharing network; and finally increasing accessibility to renewable energy programs and policies in Nunavut.