Sob a sombra do eixo: camisas-verdes e o Jornal Integralista Acção (1936-1938)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Optimization of molecular and crystalline forms of drugs, agrochemicals, pesticides in relation to activity, bioavailability, patentability and to the fabrication of polymorphs, solvates, co-crystals with green chemistry methods

This doctorate was funded by the Regione Emilia Romagna, within a Spinner PhD project coordinated by the University of Parma, and involving the universities of Bologna, Ferrara and Modena. The aim of the project was: - Production of polymorphs, solvates, hydrates and co-crystals of active pharmaceutical ingredients (APIs) and agrochemicals with green chemistry methods; - Optimization of molecular and crystalline forms of APIs and pesticides in relation to activity, bioavailability and patentability. In the last decades, a growing interest in the solid-state properties of drugs in addition to their solution chemistry has blossomed. The achievement of the desired and/or the more stable polymorph during the production process can be a challenge for the industry. The study of crystalline forms could be a valuable step to produce new polymorphs and/or co-crystals with better physical-chemical properties such as solubility, permeability, thermal stability, habit, bulk density, compressibility, friability, hygroscopicity and dissolution rate in order to have potential industrial applications. Selected APIs (active pharmaceutical ingredients) were studied and their relationship between crystal structure and properties investigated, both in the solid state and in solution. Polymorph screening and synthesis of solvates and molecular/ionic co-crystals were performed according to green chemistry principles. Part of this project was developed in collaboration with chemical/pharmaceutical companies such as BASF (Germany) and UCB (Belgium). We focused on on the optimization of conditions and parameters of crystallization processes (additives, concentration, temperature), and on the synthesis and characterization of ionic co-crystals. Moreover, during a four-months research period in the laboratories of Professor Nair Rodriguez-Hormedo (University of Michigan), the stability in aqueous solution at the equilibrium of ionic co-crystals (ICCs) of the API piracetam was investigated, to understand the relationship between their solid-state and solution properties, in view of future design of new crystalline drugs with predefined solid and solution properties.

Extracellular matrix of the charophycean green algae

A comprehensive knowledge of cell wallstructure and function throughout the plant kingdom is essential to understanding cell wall evolution. The fundamental understanding of the charophycean green algal cell wall is broadening. The similarities and differences that exist between land plant and algal cell walls provide opportunities to understand plant evolution. A variety of polymers previously associated with higher plants were discovered in the charophycean green algae (CGA), including homogalacturonans, cross-linking glycans, arabinogalactan protein, β-glucans, and cellulose. The cellulose content of CGA cell walls ranged from 6% to 43%, with the higher valuescomparable to that found in the primary cell wall of land plants (20-30%). (1,3)β-glucans were found in the unicellular Chlorokybus atmophyticus, Penium margaritaceum, and Cosmarium turpini, the unbranched filamentous Klebsormidium flaccidum, and the multicellular Chara corallina. The discovery of homogalacturonan in Penium margaritaceum representsthe first confirmation of land plant-type pectinsin desmids and the second rigorous characterization of a pectin polymer from the charophycean algae. Homogalacturonan was also indicated from the basal species Chlorokybus atmophyticus and Klebsormidium flaccidum. There is evidence of branched pectins in Cosmarium turpini and linkage analysis suggests the presence of type I rhamnogalacturonan (RGI). Cross-linking β-glucans are associated with cellulose microfibrils during land plant cell growth, and were found in the cell wall of CGA. The evidence of mixed-linkage glucan (MLG) in the 11 charophytesis both suprising and significant given that MLG was once thought to be specific to some grasses. The organization and structure of Cosmarium turpini and Chara corallina MLG was found to be similar to that of Equisetumspp., whereas the basal species of the CGA, Chlorokybus atmophyticus and Klebsormidium flaccidum, have unique organization of alternating of 3- and 4-linkages. The significance of this result on the evolution of the MLG synthetic pathway has yet to be determined. The extracellular matrix (ECM) of Chlorokybus atmophyticus, Klebsormidium flaccidum, and Spirogyra spp. exhibits significant biochemical diversity, ranging from distinct “land plant” polymers to polysaccharides unique to these algae. The neutral sugar composition of Chlorokybus atmophyticus hot water extract and Spirogyra extracellular polymeric substance (EPS), combined with antibody labeling results, revealed the distinct possibility of an arabinogalactan protein in these organisms. Polysaccharide analysis of Zygnematales (desmid) EPS, indicated a probable range of different EPS backbones and substitution patterns upon the core portions of the molecules. Desmid EPS is predominately composed of a complex matrix of branched, uronic acid containing polysaccharides with ester sulfate substitutions and, as such, has an almost infinite capacity for various hydrogen bonding, hydrophobic interaction and ionic cross-bridging motifs, which characterize their unique function in biofilms. My observations support the hypothesis that members of the CGA represent the phylogenetic line that gave rise to vascular plants and that the primary cell wall of vascular plants many have evolved directly from structures typical of the cell wall of filamentous green algae found in the charophycean green algae.

(Table 1, page 1124), Chemical composition of Lake Michigan manganese nodules

Manganese nodules containing up to 22 percent manganese oxide were found in Green Bay and the western and northern parts of Lake Michigan. The chemical composition of these nodules resembles that of shallow-water lacustrine and marine nodules. The manganese content of interstitial water is in some places enriched as much as 4000 times over that of lake water.

Report of the Michigan State Pomological Society.

1871

John Warren's copy of votes from a meeting of the Boston Medical Society, 1784 May 3

This document lists the eleven votes cast at a meeting of the Boston Medical Society on May 3, 1784. It was authorized as a "true coppy" by Thomas Kast, the Secretary of the Society. The following members of the Society were present at the meeting, all of them doctors: James Pecker, James Lloyd, Joseph Gardner, Samuel Danforth, Isaac Rand, Jr., Charles Jarvis, Thomas Kast, Benjamin Curtis, Thomas Welsh, Nathaniel Walker Appleton, and doctors whose last names were Adams, Townsend, Eustis, Homans, and Whitwell. The document indicates that a meeting had been held the previous evening, as well (May 2, 1784), at which the topics on which votes were taken had been discussed. The votes, eleven in total, were all related to the doctors' concerns about John Warren and his involvement with the emerging medical school (now Harvard Medical School), that school's relation to almshouses, the medical care of the poor, and other related matters. The tone and content of these votes reveals anger on the part of the members of the Boston Medical Society towards Warren. This anger appears to have stemmed from the perceived threat of Warren to their own practices, exacerbated by a vote of the Harvard Corporation on April 19, 1784. This vote authorized Warren to apply to the Overseers of the Poor for the town of Boston, requesting that students in the newly-established Harvard medical program, where Warren was Professor of Anatomy and Surgery, be allowed to visit the hospital of the almshouse with their professors for the purpose of clinical instruction. Although Warren believed that the students would learn far more from these visits, in regards to surgical experience, than they could possibly learn in Cambridge, the proposal provoked great distrust from the members of the Boston Medical Society, who accused Warren of an "attempt to direct the public medical business from its usual channels" for his own financial and professional gain.

Minor element geochemistry of Lake Michigan ferromanganese nodules

Samples of ferromanganese nodules from several localities in Lake Michigan have been analyzed for their minor element content utilizing neutron activation techniques. The thorium and uranium levels in Lake Michigan nodules exhibit marked dissimilarities with marine nodules. The radium content of these freshwater nodules is substantially higher than the reported marine values. The concentrations of barium in the Lake Michigan nodules appear to be abnormally high. Although barium could be present as minute segregations of the mineral barite, patterns obtained using the electron microprobe suggest it is evently dispersed throughout the nodules. The average arsenic content of these freshwater nodules is at least twice as great as that reported for highly oxidized marine sediments. If all this arsenic is dissolved and released into Green Bay as a result of changing environmental conditions (eutrophication), the concentration in the water of Green Bay would be several times the maximum permissible level for drinking water.

1887 University of Michigan Football Team

Fred Bonine at Intercollegiate Championships, 1885, UM Men's track

Final heat of the Intercollegiate Association Championships at Manhattan Athletic Club grounds, 1885. L to R: Bonine - U of M, Dericskon - Columbia, Baker - Harvard, Holden - Harvard, Mapes Columbia.

1969 University of Michigan Football Team

1970 University of Michigan Football Team

1971 University of Michigan Football Team