On the equation of state and atomic mean square displacement of crystals

We have presented a Green's function method for the calculation of the atomic mean square displacement (MSD) for an anharmonic Hamil toni an . This method effectively sums a whole class of anharmonic contributions to MSD in the perturbation expansion in the high temperature limit. Using this formalism we have calculated the MSD for a nearest neighbour fcc Lennard Jones solid. The results show an improvement over the lowest order perturbation theory results, the difference with Monte Carlo calculations at temperatures close to melting is reduced from 11% to 3%. We also calculated the MSD for the Alkali metals Nat K/ Cs where a sixth neighbour interaction potential derived from the pseudopotential theory was employed in the calculations. The MSD by this method increases by 2.5% to 3.5% over the respective perturbation theory results. The MSD was calculated for Aluminum where different pseudopotential functions and a phenomenological Morse potential were used. The results show that the pseudopotentials provide better agreement with experimental data than the Morse potential. An excellent agreement with experiment over the whole temperature range is achieved with the Harrison modified point-ion pseudopotential with Hubbard-Sham screening function. We have calculated the thermodynamic properties of solid Kr by minimizing the total energy consisting of static and vibrational components, employing different schemes: The quasiharmonic theory (QH), ).2 and).4 perturbation theory, all terms up to 0 ().4) of the improved self consistent phonon theory (ISC), the ring diagrams up to o ().4) (RING), the iteration scheme (ITER) derived from the Greens's function method and a scheme consisting of ITER plus the remaining contributions of 0 ().4) which are not included in ITER which we call E(FULL). We have calculated the lattice constant, the volume expansion, the isothermal and adiabatic bulk modulus, the specific heat at constant volume and at constant pressure, and the Gruneisen parameter from two different potential functions: Lennard-Jones and Aziz. The Aziz potential gives generally a better agreement with experimental data than the LJ potential for the QH, ).2, ).4 and E(FULL) schemes. When only a partial sum of the).4 diagrams is used in the calculations (e.g. RING and ISC) the LJ results are in better agreement with experiment. The iteration scheme brings a definitive improvement over the).2 PT for both potentials.

Applications of dihydroarenediols to chemoenzymatic synthesis : approaches to total synthesis of morphine alkaloids

The present studies describe, as a primary goal, our recent progess toward the synthesis of morphine alkaloids from aromatic precursors. Model substrates were synthesized which allowed investigation into Diels-Alder, radical cascade, and palladium-catalyzed bond-forming reactions as possible routes to the morphine alkaloid skeleton. As a secondary objective, three separate series of aromatic substrates were subjected to whole-cell oxidation with Escherichia coli JM 109 (pDTG601), a recombinant organism over-expressing the enzyme toluene dioxygenase. Included in this study were bromothioanisoles, dibromobenzenes, and cyclopropylbenzene derivatives. The products of oxidation were characterized by chemical conversion to known intermediates. The synthetic utility of one of these bacterial metabolites, derived from oxidation of o-dibromobenezene, was demonstrated by chemical conversion to (-)conduritol E.

Application of [Lambda] to the fourth perturbation theory in calculating the equation of state of rare gas solids and fcc metals

We have calculated the thermodynamic properties of monatomic fcc crystals from the high temperature limit of the Helmholtz free energy. This equation of state included the static and vibrational energy components. The latter contribution was calculated to order A4 of perturbation theory, for a range of crystal volumes, in which a nearest neighbour central force model was used. We have calculated the lattice constant, the coefficient of volume expansion, the specific heat at constant volume and at constant pressure, the adiabatic and the isothermal bulk modulus, and the Gruneisen parameter, for two of the rare gas solids, Xe and Kr, and for the fcc metals Cu, Ag, Au, Al, and Pb. The LennardJones and the Morse potential were each used to represent the atomic interactions for the rare gas solids, and only the Morse potential was used for the fcc metals. The thermodynamic properties obtained from the A4 equation of state with the Lennard-Jones potential, seem to be in reasonable agreement with experiment for temperatures up to about threequarters of the melting temperature. However, for the higher temperatures, the results are less than satisfactory. For Xe and Kr, the thermodynamic properties calculated from the A2 equation of state with the Morse potential, are qualitatively similar to the A 2 results obtained with the Lennard-Jones potential, however, the properties obtained from the A4 equation of state are in good agreement with experiment, since the contribution from the A4 terms seem to be small. The lattice contribution to the thermal properties of the fcc metals was calculated from the A4 equation of state, and these results produced a slight improvement over the properties calculated from the A2 equation of state. In order to compare the calculated specific heats and bulk moduli results with experiment~ the electronic contribution to thermal properties was taken into account~ by using the free electron model. We found that the results varied significantly with the value chosen for the number of free electrons per atom.

Effectiveness of life skills training on the total behaviour of six individuals in a job preparation program

In the first week of a Job preparation Program all twelve female members of the class were invited to be part of a study to determine the effect of Life Skills training on their behaviour over the twelve-week period of the program. Six females volunteered and each was interviewed four times during the Job preparation Program and once after the program ended. The interviews focused on three areas of skill deficiency addressed in Life Skills lessons: their knowledge about themselves and attitude towards themselves; their interpersonal relationships; and their problem-solving ability. The participants' comments over the sixteen-week period of the interviews were used to decide if the total behaviour of the participants, (i.e., what they did, thought, and felt) changed so that each became more effective in satisfying her needs. The study suggested that the total behaviour of three of the six women changed so that they became more effective in satisfying their needs. The fourth female's total behaviour changed in only two of the three areas focused on in the interviews, and the total behaviour of the fifth and sixth females showed no change.

Total synthesis of (S)-4-hydroxy-[a]-Lapachone

(S)-4-Hydroxy-a-lapachone has been prepared for the first time. The commercially available compound 2-acetyl-1-naphthol was used as the starting material. The synthesis involved methylation, followed by Baeyer-Villiger oxidation, and hydrolysis of the acetate to give 1-methoxy-2-naphthol. After protecting of the hydroxyl group, t-BuLi was used to form 3-(3',3'-dimethyl-acryloyl)-1- meth oxy-2- (meth oxymethoxy)-naphthalen e. eycl izationand oxidation then gave 4-keto-a-lapachone. Finally enzymic biotransformation by Mortierella isabellina ATCC 42613 was used to yield the target compound. The enantiomeric excess of the product was determined to be ~98% by using 1H NMR chiral shift analysis. The overall yield is 80/0. The biological activity of (S)-4-hydroxy-alapachone and its acetate are under investigation.

Special report of New York State Survey on the preservation of the scenery of Niagara Falls ; and fourth annual report on the triangulation of State. For the Year 1879 /

Notes by F. L. Olmsted.

Letter from the Secretary of State to Mr. Monroe, on the subject of the attack on the Chesapeake : the correspondence of Mr. Monroe with the British Government ; and also Mr. Madison's correspondence with Mr. Rose on the same subject. --

March 23, 1808. Printed by order of the House of Representatives.

Message from the President of the United States, transmitting of a report of the Secretary of State, in relation to individuals selected from American prisoners of war, and sent to Great Britain for trial, and also in relation to any orders for retaliation, &c., &c.--

April 16, 1814. Printed by order of the Senate of the United States.

Message from the President of the United States, transmitting a report of the Secretary of State, in obedience to a resolution of the thirteenth inst. "requesting the President to lay before this House such documents relative to the Russian mediation as in his opinion it may not be improper to communicate." --

United States,13th Congress, 2d session, 1813-1814. House. Doc. no. 35.

Message from the President of the United States, transmitting copies of a letter from the British Secretary of State for Foreign Affairs, to the Secretary of State, with the answer of the latter.--

January 6, 1814. Ordered to lie on the table.

Report of the Committee to whom was Referred the Correspondence between Mr. Monroe and Mr. Canning, and between Mr. Madison and Mr. Rose, relative to the attacked of Chesapeake : and also a communication from the President of the United States of the 30 March last, with a letter from Mr. Erskine to the Secretary of State, and a letter from M. Champagny to Gen. Armstrong.--

April 16, 1808. Printed by Order of the Senate.

Advocating recognition and redistribution in poverty alleviation programs in Ghana : an examination of state and NGO programs and policies

Abstract This thesis argues that poverty alleviation strategies and programs carried out by the government and Non Governmental Organizations in Ghana provide affirmative solutions to poverty. This is because, these intervention strategies have been influenced by conventional discourses on poverty that fail to adequately address non-economic issues of poverty such as powerlessness, marginalization and tmder-representation. The study is carried out in a two-pronged manner; first, it analyses state policies and strategies, particularly the Ghana Poverty Reduction Strategy (GPRS), on poverty alleviation and compares these to NGO programs, implemented with funds and support from external donor organizations. Specifically, I focus on how NGOs and the governnlent of Ghana negotiate autonomy and financial dependency with their funding donor-partners and how these affect their policies and programs. Findings from this study reveal that while external influences dominate poverty alleviation policies and strategies, NGOs and the government of Ghana exercise varying degrees of agency in navigating these issues. In particular, NGOs have been able to adapt their programs to the changing needs of donor markets, and are also actively engaged in re-orienting poverty back to the political domain through advocacy campaigns. Overall, rural communities in Ghana depend on charitable NGOs for the provision of essential social services, while the Ghanaian government depends on international donor assistance for its development projects.

Chemoenzymatic synthesis of amaryllidaceae alkaloids and their C-1 analogues : symmetry based approach to total synthesis of thebaine

Described herein is the chemoenzymatic total synthesis of several Amaryllidaceae constituents and their unnatural C-I analogues. A new approach to pancratistatin and related compounds will be discussed along with the completed total synthesis of 7 -deoxypancratistatin and trans-dihydrolycoricidine. Evaluation of all new C-l analogues as cancer cell growth inhibitory agents is described. The enzymatic oxidation of dibromobenzenes by Escherichia coli 1M 109 (pDTG60 1) is presented along with conversion of their metabolites to (-)-conduritol E. Investigation into the steric and functional factors governing the enzymatic dihydroxylation of various benzoates by the same organism is also discussed. The synthetic utility of these metabolites is demonstrated through their conversion to pseudo-sugars, aminocyclitols, and complex bicyclic ring systems. The current work on the total synthesis of some morphine alkaloids is also presented. Highlighted will be the synthesis of several model systems related to the efficient total synthesis of thebaine.

Development of thermally stable versions of the Burgess Reagent : approaches to the chemoenzymatic total synthesis of morphine

The present studies describe our recent work on expanding the use of the Burgess reagent and its reaction with oxiranes. Several new variants of the Burgess reagent and its chiral auxiliary version were evaluated for their thermal stability by NMR spectroscopy. Three new versions of the reagent were synthesized and their stability was determined. The reactivity of all five Burgess reagents was compared in a dehydration reaction and reactions with epoxides and diols. Progress toward a chemoenzymatic synthesis of morphine is also included in this report. The synthesis began with the whole cell oxidation of bromobenzene by Escherichia coli JMI09(pDTG601). The preparation of several precursors for a key step involving the lohnson-Claisen rearrangement and progress toward the total synthesis are described.

Letter from the Secretary of State to Mr. Monroe, on the subject of the attack on the Chesapeake : the correspondence of Mr. Monroe with the British Government; and also Mr. Madison's correspondence with Mr. Rose on the same subject

March 23, 1808. Printed by order of the House of Representatives.