Catalytic enantioselective construction of quaternary stereocenters by direct vinylogous Michael addition of deconjugated butenolides to nitroolefins

A direct vinylogous Michael reaction of gamma-substituted deconjugated butenolides with nitroolefins has been developed with the help of a newly identified quinine-derived bifunctional catalyst, allowing the synthesis of densely functionalized products with contiguous quaternary and tertiary stereocenters in excellent yield with perfect diastereoselectivity (>20 : 1 dr) and high enantioselectivity (up to 99 : 1 er).

Enantioselective desymmetrization of prochiral 1,3-dinitropropanes via organocatalytic allylic alkylation

An enantioselective desymmetrization of prochiral 1,3-dinitropropanes has been developed which proceeds via enantiogroup differentiating organocatalytic allylic alkylation. Densely functionalized products with two vicinal stereocenters were obtained generally with good to excellent diastereoselectivity (up to >20:1 dr) and superb enantioselectivity (up to >99:1 er).

Differential viability response of prokaryotes and eukaryotes to high strength pulsed magnetic stimuli

The present study examines the efficacy of a high strength pulsed magnetic field (PMF) towards bacterial inactivation in vitro, without compromising eukaryotic cell viability. The differential response of prokaryotes Staphylococcus aureus (MESA), Staphylococcus epidermidis, and Escherichia coli], and eukaryotes C2C12 mouse myoblasts and human mesenchymal stem cells, hMSCs] upon exposure to varying PMF stimuli (1-4 T, 30 pulses, 40 ms pulse duration) is investigated. Among the prokaryotes, similar to 60% and similar to 70% reduction was recorded in the survival of staphylococcal species and E. coli, respectively at 4 T PMF as evaluated by colony forming unit (CPU) analysis and flow cytometry. A 2-5 fold increase in intracellular ROS (reactive oxygen species) levels suggests oxidative stress as the key mediator in PMF induced bacterial death/injury. The 4 T PMF treated staphylococci also exhibited longer doubling times. Both TEM and fluorescence microscopy revealed compromised membranes of PMF exposed bacteria. Under similar PMF exposure conditions, no immediate cytotoxicity was recorded in C2C12 mouse myoblasts and hMSCs, which can be attributed to the robust resistance towards oxidative stress. The ion interference of iron containing bacterial proteins is invoked to analytically explain the PMF induced ROS accumulation in prokaryotes. Overall, this study establishes the potential of PMF as a bactericidal method without affecting eukaryotic viability. This non-invasive stimulation protocol coupled with antimicrobial agents can be integrated as a potential methodology for the localized treatment of prosthetic infections. (C) 2015 Elsevier B.V. All rights reserved.

Physical insights into salicylic acid release from poly(anhydrides)

Salicylic acid (SA) based biodegradable polyanhydrides (PAHs) are of great interest for drug delivery in a variety of diseases and disorders owing to the multi-utility of SA. There is a need for the design of SA-based PAHs for tunable drug release, optimized for the treatment of different diseases. In this study, we devised a simple strategy for tuning the release properties and erosion kinetics of a family of PAHs. PAHs incorporating SA were derived from related aliphatic diacids, varying only in the chain length, and prepared by simple melt condensation polymerization. Upon hydrolysis induced erosion, the polymer degrades into cytocompatible products, including the incorporated bioactive SA and diacid. The degradation follows first order kinetics with the rate constant varying by nearly 25 times between the PAH obtained with adipic acid and that with dodecanedioic acid. The release profiles have been tailored from 100% to 50% SA release in 7 days across the different PAHs. The release rate constants of these semi-crystalline, surface eroding PAHs decreased almost linearly with an increase in the diacid chain length, and varied by nearly 40 times between adipic acid and dodecanedioic acid PAH. The degradation products with SA concentration in the range of 30-350 ppm were used to assess cytocompatibility and showed no cytotoxicity to HeLa cells. This particular strategy is expected to (a) enable synthesis of application specific PAHs with tunable erosion and release profiles; (b) encompass a large number of drugs that may be incorporated into the PAH matrix. Such a strategy can potentially be extended to the controlled release of other drugs that may be incorporated into the PAH backbone and has important implications for the rational design of drug eluting bioactive polymers.

An Integrated Assessment of the Introduction of Lionfish (Pterois volitans/miles complex) to the Western Atlantic Ocean.

Lionfish (Pterois volitans/miles complex) are venomous coral reef fishes from the Indian and western Pacific oceans that are now found in the western Atlantic Ocean. Adult lionfish have been observed from Miami, Florida to Cape Hatteras, North Carolina, and juvenile lionfish have been observed off North Carolina, New York, and Bermuda. The large number of adults observed and the occurrence of juveniles indicate that lionfish are established and reproducing along the southeast United States coast. Introductions of marine species occur in many ways. Ballast water discharge, a very common method of introduction for marine invertebrates, is responsible for many freshwater fish introductions. In contrast, most marine fish introductions result from intentional stocking for fishery purposes. Lionfish, however, likely were introduced via unintentional or intentional aquarium releases, and the introduction of lionfish into United States waters should lead to an assessment of the threat posed by the aquarium trade as a vector for fish introductions. Currently, no management actions are being taken to limit the effect of lionfish on the southeast United States continental shelf ecosystem. Further, only limited funds have been made available for research. Nevertheless, the extent of the introduction has been documented and a forecast of the maximum potential spread of lionfish is being developed. Under a scenario of no management actions and limited research, three predictions are made: ● With no action, the lionfish population will continue to grow along the southeast United States shelf. ● Effects on the marine ecosystem of the southeast United States will become more noticeable as the lionfish population grows. ● There will be incidents of lionfish envenomations of divers and/or fishers along the east coast of the United States. Removing lionfish from the southeast United States continental shelf ecosystem would be expensive and likely impossible. A bounty could be established that would encourage the removal of fish and provide specimens for research. However, the bounty would need to be lower than the price of fish in the aquarium trade (~$25-$50 each) to ensure that captured specimens were from the wild. Such a low bounty may not provide enough incentive for capturing lionfish in the wild. Further, such action would only increase the interaction between the public and lionfish, increasing the risk of lionfish envenomations. As the introduction of lionfish is very likely irreversible, future actions should focus on five areas. 1) The population of lionfish should be tracked. 2) Research should be conducted so that scientists can make better predictions regarding the status of the invasion and the effects on native species, ecosystem function, and ecosystem services. 3) Outreach and education efforts must be increased, both specifically toward lionfish and more generally toward the aquarium trade as a method of fish introductions. 4) Additional regulation should be considered to reduce the frequency of marine fish introduction into U.S. waters. However, the issue is more complicated than simply limiting the import of non-native species, and these complexities need to be considered simultaneously. 5) Health care providers along the east coast of the United States need to be notified that a venomous fish is now resident along the southeast United States. The introduction and spread of lionfish illustrates the difficulty inherent in managing introduced species in marine systems. Introduced species often spread via natural mechanisms after the initial introduction. Efforts to control the introduction of marine fish will fail if managers do not consider the natural dispersal of a species following an introduction. Thus, management strategies limiting marine fish introductions need to be applied over the scale of natural ecological dispersal to be effective, pointing to the need for a regional management approach defined by natural processes not by political boundaries. The introduction and success of lionfish along the east coast should change the long-held perception that marine fish invasions are a minimal threat to marine ecosystems. Research is needed to determine the effects of specific invasive fish species in specific ecosystems. More broadly, a cohesive plan is needed to manage, mitigate and minimize the effects of marine invasive fish species on ecosystems that are already compromised by other human activities. Presently, the magnitude of marine fish introductions as a stressor on marine ecosystems cannot be quantified, but can no longer be dismissed as negligible. (PDF contains 31 pages)

Optical Remote Sensing of Coastal Habitats, Moss Landing, California, 9-11 January, 2006: workshop proceedings

The Alliance for Coastal Technologies (ACT) Workshop on Optical Remote Sensing of Coastal Habitats was convened January 9-11, 2006 at Moss Landing Marine Laboratories in Moss Landing, California, sponsored by the ACT West Coast regional partnership comprised of the Moss Landing Marine Laboratories (MLML) and the Monterey Bay Aquarium Research Institute (MBARI). The "Optical Remote Sensing of Coastal Habitats" (ORS) Workshop completes ACT'S Remote Sensing Technology series by building upon the success of ACT'S West Coast Regional Partner Workshop "Acoustic Remote Sensing Technologies for Coastal Imaging and Resource Assessment" (ACT 04-07). Drs. Paul Bissett of the Florida Environmental Research Institute (FERI) and Scott McClean of Satlantic, Inc. were the ORS workshop co-chairs. Invited participants were selected to provide a uniform representation of the academic researchers, private sector product developers, and existing and potential data product users from the resource management community to enable development of broad consensus opinions on the role of ORS technologies in coastal resource assessment and management. The workshop was organized to examine the current state of multi- and hyper-spectral imaging technologies with the intent to assess the current limits on their routine application for habitat classification and resource monitoring of coastal watersheds, nearshore shallow water environments, and adjacent optically deep waters. Breakout discussions focused on the capabilities, advantages ,and limitations of the different technologies (e.g., spectral & spatial resolution), as well as practical issues related to instrument and platform availability, reliability, hardware, software, and technical skill levels required to exploit the data products generated by these instruments. Specifically, the participants were charged to address the following: (1) Identify the types of ORS data products currently used for coastal resource assessment and how they can assist coastal managers in fulfilling their regulatory and management responsibilities; (2) Identify barriers and challenges to the application of ORS technologies in management and research activities; (3) Recommend a series of community actions to overcome identified barriers and challenges. Plenary presentations by Drs. Curtiss 0. Davis (Oregon State University) and Stephan Lataille (ITRES Research, Ltd.) provided background summaries on the varieties of ORS technologies available, deployment platform options, and tradeoffs for application of ORS data products with specific applications to the assessment of coastal zone water quality and habitat characterization. Dr. Jim Aiken (CASIX) described how multiscale ground-truth measurements were essential for developing robust assessment of modeled biogeochemical interpretations derived from optically based earth observation data sets. While continuing improvements in sensor spectral resolution, signal to noise and dynamic range coupled with sensor-integrated GPS, improved processing algorithms for georectification, and atmospheric correction have made ORS data products invaluable synoptic tools for oceanographic research, their adoption as management tools has lagged. Seth Blitch (Apalachicola National Estuarine Research Reserve) described the obvious needs for, yet substantial challenges hindering the adoption of advanced spectroscopic imaging data products to supplement the current dominance of digital ortho-quad imagery by the resource management community, especially when they impinge on regulatory issues. (pdf contains 32 pages)

Indol als moglicher Indikator fur nicht einwandfreie hygiensiche Be- bzw. Verbarbeitung tropischer Garnelen

Indole concentrations of 114 samples of tropical shrimp, 3 samples of crayfish, and 3 samples of cold water crustaceans were determined. Cold water crustaceans contained less than 15 μg/kg indole, whereas crayfish contained between 62 and 123 μg indole/kg. In 81 samples (70 %) of tropical shrimp indole content was less than 50 μg/kg, but in 12 samples (11 %) indole content exceeded 250 μg/kg. Different batches of some products with high indole levels as well as of some products with low indole levels were analysed. Except for one sample high as well as low indole levels could be confirmed. Highest indole concentrations were determined in samples which origin was specified as South Pacific, Indo-Pacific, Malaysia, India and India/Vietnam

Enfoque cartogr??fico de los modelos virtuales de elementos patrimoniales

[ES] Los modelos virtuales de edificios hist??ricos u otros elementos patrimoniales cuentan con una gran variedad de aplicaciones relacionadas, sobre todo, con la difusi??n y multimedia. Aunque en muchas ocasiones se trata de productos eminentemente inform??ticos en los que la componente geom??trica y, por lo tanto topogr??fica, es muy limitada, existen aplicaciones, como los estudios hist??ricos, en los cuales, es necesario que estos modelos representen fielmente la geometr??a y las texturas. En estos casos, los modelos pueden considerarse como productos cartogr??ficos. A continuaci??n se hace una recapitulaci??n de las conclusiones a las que hemos llegado durante los ??ltimos dos a??os despu??s de haber desarrollado una veintena de proyectos en este campo.

Directed evolution of terpene synthases for non-natural substrates

Terpenes represent about half of known natural products, with terpene synthases catalyzing reactions to increase the complexity of substrates and generate cyclizations of the linear diphosphate substrates, therefore forming rings and stereocenters. With their diverse functionality, terpene synthases may be highly evolvable, with the ability to accept a wide range of non-natural compounds and with high product selectivity. Our hypothesis is that directed evolution of terpene synthases can be used to increase selectivity of the synthase on a specific substrate. In the first part of the work presented herein, three natural terpene synthases, Cop2, BcBOT2, and SSCG_02150, were tested for activity against the natural substrate and a non-natural substrate, called Surrogate 1, and the relative activities on both the natural and non-natural substrates were compared. In the second part of this work, a terpene synthase variant of BcBOT2 that has been evolved for thermostability, was used for directed evolution for increased activity and selectivity on the non-natural substrate referred to as Surrogate 2. Mutations for this evolution were introduced using random mutagenesis, with error prone polymerase chain reactions, and using site-specific saturation mutagenesis, in which an NNK library is designed with a specific active site amino acid targeted for mutation. The mutant enzymes were then screened and selected for enhancement of the desired functionality. Two neutral mutants, 19B7 W367F and 19B7 W118Q, were found to maintain activity on Surrogate 2, as measured by the screen.

The combinatorics of transcriptional regulation

The ability to regulate gene expression is of central importance for the adaptability of living organisms to changes in their internal and external environment. At the transcriptional level, binding of transcription factors (TFs) in the vicinity of promoters can modulate the rate at which transcripts are produced, and as such play an important role in gene regulation. TFs with regulatory action at multiple promoters is the rule rather than the exception, with examples ranging from TFs like the cAMP receptor protein (CRP) in E. coli that regulates hundreds of different genes, to situations involving multiple copies of the same gene, such as on plasmids, or viral DNA. When the number of TFs heavily exceeds the number of binding sites, TF binding to each promoter can be regarded as independent. However, when the number of TF molecules is comparable to the number of binding sites, TF titration will result in coupling ("entanglement") between transcription of different genes. The last few decades have seen rapid advances in our ability to quantitatively measure such effects, which calls for biophysical models to explain these data. Here we develop a statistical mechanical model which takes the TF titration effect into account and use it to predict both the level of gene expression and the resulting correlation in transcription rates for a general set of promoters. To test these predictions experimentally, we create genetic constructs with known TF copy number, binding site affinities, and gene copy number; hence avoiding the need to use free fit parameters. Our results clearly prove the TF titration effect and that the statistical mechanical model can accurately predict the fold change in gene expression for the studied cases. We also generalize these experimental efforts to cover systems with multiple different genes, using the method of mRNA fluorescence in situ hybridization (FISH). Interestingly, we can use the TF titration affect as a tool to measure the plasmid copy number at different points in the cell cycle, as well as the plasmid copy number variance. Finally, we investigate the strategies of transcriptional regulation used in a real organism by analyzing the thousands of known regulatory interactions in E. coli. We introduce a "random promoter architecture model" to identify overrepresented regulatory strategies, such as TF pairs which coregulate the same genes more frequently than would be expected by chance, indicating a related biological function. Furthermore, we investigate whether promoter architecture has a systematic effect on gene expression by linking the regulatory data of E. coli to genome-wide expression censuses.

Investigations of group IVA transition metal mediated carbon-carbon bond forming reactions

Zirconocene aldehyde and ketone complexes were synthesized in high yield by treatment of zirconocene acyl complexes with trimethylaluminum or diisobutylaluminum hydride. These complexes, which are activated by dialkylaluminum chloride ligands, inserted unsaturated substrates such as alkynes, allenes, ethylene, nitriles, ketenes, aldehydes, ketones, lactones, and acid chlorides with moderate to high conversion. Insertion of aldehyde substrates yielded zirconocene diolate complexes with up to 20:1 (anti:syn) diastereoselectivity. The zirconocene diolates were hydrolyzed to afford unsymmetrical 1,2-diols in 40-80% isolated yield. Unsymmetrical ketones gave similar insertion yields with little or no diastereoselectivity. A high yielding one-pot method was developed that coupled carbonyl substrates with zirconocene aldehyde complexes that were derived from olefins by hydrozirconation and carbonylation. The zirconocene aldehyde complexes also inserted carbon monoxide and gave acyloins in 50% yield after hydrolysis.

The insertion reaction of aryl epoxides with the trimethylphoshine adduct of titanocene methylidene was examined. The resulting oxytitanacyclopentanes were carbonylated and oxidatively cleaved with dioxygen to afford y-lactones in moderate yields. Due to the instability and difficult isolation of titanocene methylidene trimethylphoshine adducts, a one-pot method involving the addition of catalytic amounts of trimethylphosphine to β,β-dimethyltitanacyclobutane was developed. A series of disubstituted aryl epoxides were examined which gave mixtures of diastereomeric insertion products. Based on these results, as well as earlier Hammett studies and labeling experiments, a biradical transition state intermediate is proposed. The method is limited to aryl substituted epoxide substrates with aliphatic examples showing no insertion reactivity.

The third study involved the use of magnesium chloride supported titanium catalysts for the Lewis acid catalyzed silyl group transfer condensation of enol silanes with aldehydes. The reaction resulted in silylated aldol products with as many as 140 catalytic turnovers before catalyst inactivation. Low diastereoselectivities favoring the anti-isomer were consistent with an open transition state involving a titanium atom bound to the catalyst surface. The catalysts were also used for the aldol group transfer polymerization of t-butyldimethylsilyloxy-1-ethene resulting in polymers with molecular weights of 5000-31,000 and molar mass dispersities of 1.5-2.8. Attempts to polymerize methylmethacrylate using GTP proved unsuccessful with these catalysts.

Strategies for the Stereoselective Synthesis of Carbon Quaternary Centers via Transition Metal-Catalyzed Alkylation of Enolate Compounds

Notwithstanding advances in modern chemical methods, the selective installation of sterically encumbered carbon stereocenters, in particular all-carbon quaternary centers, remains an unsolved problem in organic chemistry. The prevalence of all-carbon quaternary centers in biologically active natural products and pharmaceutical compounds provides a strong impetus to address current limitations in the state of the art of their generation. This thesis presents four related projects, all of which share in the goal of constructing highly-congested carbon centers in a stereoselective manner, and in the use of transition-metal catalyzed alkylation as a means to address that goal.

The first research described is an extension of allylic alkylation methodology previously developed in the Stoltz group to small, strained rings. This research constitutes the first transition metal-catalyzed enantioselective α-alkylation of cyclobutanones. Under Pd-catalysis, this chemistry affords all–carbon α-quaternary cyclobutanones in good to excellent yields and enantioselectivities.

Next is described our development of a (trimethylsilyl)ethyl β-ketoester class of enolate precursors, and their application in palladium–catalyzed asymmetric allylic alkylation to yield a variety of α-quaternary ketones and lactams. Independent coupling partner synthesis engenders enhanced allyl substrate scope relative to allyl β-ketoester substrates; highly functionalized α-quaternary ketones generated by the union of our fluoride-triggered β-ketoesters and sensitive allylic alkylation coupling partners serve to demonstrate the utility of this method for complex fragment coupling.

Lastly, our development of an Ir-catalyzed asymmetric allylic alkylation of cyclic β-ketoesters to afford highly congested, vicinal stereocenters comprised of tertiary and all-carbon quaternary centers with outstanding regio-, diastereo-, and enantiocontrol is detailed. Implementation of a subsequent Pd-catalyzed alkylation affords dialkylated products with pinpoint stereochemical control of both chiral centers. The chemistry is then extended to include acyclic β-ketoesters and similar levels of selective and functional group tolerance are observed. Critical to the successful development of this method was the employment of iridium catalysis in concert with N-aryl-phosphoramidite ligands.

Investigation of Fundamental Processes Governing Secondary Organic Aerosol Formation in Laboratory Chambers

Our understanding of the processes and mechanisms by which secondary organic aerosol (SOA) is formed is derived from laboratory chamber studies. In the atmosphere, SOA formation is primarily driven by progressive photooxidation of SOA precursors, coupled with their gas-particle partitioning. In the chamber environment, SOA-forming vapors undergo multiple chemical and physical processes that involve production and removal via gas-phase reactions; partitioning onto suspended particles vs. particles deposited on the chamber wall; and direct deposition on the chamber wall. The main focus of this dissertation is to characterize the interactions of organic vapors with suspended particles and the chamber wall and explore how these intertwined processes in laboratory chambers govern SOA formation and evolution.

A Functional Group Oxidation Model (FGOM) that represents SOA formation and evolution in terms of the competition between functionalization and fragmentation, the extent of oxygen atom addition, and the change of volatility, is developed. The FGOM contains a set of parameters that are to be determined by fitting of the model to laboratory chamber data. The sensitivity of the model prediction to variation of the adjustable parameters allows one to assess the relative importance of various pathways involved in SOA formation.

A critical aspect of the environmental chamber is the presence of the wall, which can induce deposition of SOA-forming vapors and promote heterogeneous reactions. An experimental protocol and model framework are first developed to constrain the vapor-wall interactions. By optimal fitting the model predictions to the observed wall-induced decay profiles of 25 oxidized organic compounds, the dominant parameter governing the extent of wall deposition of a compound is identified, i.e., wall accommodation coefficient. By correlating this parameter with the molecular properties of a compound via its volatility, the wall-induced deposition rate of an organic compound can be predicted based on its carbon and oxygen numbers in the molecule.

Heterogeneous transformation of δ-hydroxycarbonyl, a major first-generation product from long-chain alkane photochemistry, is observed on the surface of particles and walls. The uniqueness of this reaction scheme is the production of substituted dihydrofuran, which is highly reactive towards ozone, OH, and NO3, thereby opening a reaction pathway that is not usually accessible to alkanes. A spectrum of highly-oxygenated products with carboxylic acid, ester, and ether functional groups is produced from the substituted dihydrofuran chemistry, thereby affecting the average oxidation state of the alkane-derived SOA.

The vapor wall loss correction is applied to several chamber-derived SOA systems generated from both anthropogenic and biogenic sources. Experimental and modeling approaches are employed to constrain the partitioning behavior of SOA-forming vapors onto suspended particles vs. chamber walls. It is demonstrated that deposition of SOA-forming vapors to the chamber wall during photooxidation experiments can lead to substantial and systematic underestimation of SOA. Therefore, it is likely that a lack of proper accounting for vapor wall losses that suppress chamber-derived SOA yields contribute substantially to the underprediction of ambient SOA concentrations in atmospheric models.

Cultura de tecidos e análise do potencial antioxidante de Passiflora alata Curtis

Passiflora alata Curtis, comumente conhecida como maracujá-doce, é uma das espécies do gênero Passiflora cultivadas comercialmente, sendo consumida in natura devido ao seu gosto adocicado. Ela também é utilizada em todo o mundo como ornamental e na medicina popular. O objetivo deste trabalho foi o estabelecimento de diferentes estratégias para a cultura in vitro de P. alata e a análise da produção de substâncias antioxidantes nos materiais obtidos in vitro, em comparação com as plantas in vivo. Diferentes tratamentos visando à quebra da dormência das sementes foram avaliados para a germinação in vitro ou in vivo, além da incubação das sementes sob tipos distintos de luz. Para o estabelecimento das culturas primárias, apices caulinares e segmentos nodais das plântulas derivadas da germinação in vitro foram cultivados em meio MSM . A taxa de alongamento dos brotos e o número de nós por brotos das culturas primárias foram aumentados pela adição de água de coco ao meio. Plantas derivadas dessas culturas foram utilizadas como fontes de explantes nodais, internodais e foliares. O potencial morfogênico de sementes sem tegumento foi também avaliado. Calos friáveis foram induzidos a partir de segmentos nodais e foliares na presença de PIC, e aqueles obtidos a partir de folhas em meio suplementado com PIC a 28,9 μM foram selecionados para o estabelecimento de culturas de células em suspensão. Após o desenvolvimento de diferentes estratégias in vitro para P. alata, folhas de plantas in vivo foram utilizadas para a avaliação de parâmetros que afetam a extração de substâncias antioxidante. O potencial antioxidante foi determinado pelo ensaio DPPH e o conteúdo de fenóis totais foi determinado utilizando o método Folin-Ciocalteau. Após o desenvolvimento do protocolo de extração, a atividade antioxidante dos diferentes materiais in vitro foi também avaliada. A eficiência antirradicalar variou entre os sistemas de cultura estudados, sendo diretamente proporcional ao conteúdo de fenóis totais dos extratos. Esses resultados indicam que as estratégias para cultura in vitro de P. alata desenvolvidas neste trabalho representam alternativas para a multiplicação de plantas e produção de substâncias fenólicas com ação antioxidante.

O Poder legislativo e as políticas públicas educacionais no período 1995-2010

Este trabalho versa sobre o papel do Poder Legislativo brasileiro na definição das políticas públicas educacionais. Foi feito o exame de conteúdo de cerca de mil e quinhentos projetos de lei e propostas de emenda à Constituição, apresentados pelos deputados nas legislaturas compreendidas entre os anos de 1995 e 2007. Foram também realizados três estudos de caso sobre duas questões estruturantes das políticas educacionais: o financiamento da educação e a avaliação da educação superior. Nesses casos, analisaram-se as propostas de emendas constitucionais e projetos de lei ou medidas provisórias regulamentadoras, as emendas oferecidas pelos parlamentares, os pareceres e substitutivos apresentados e os textos afinal convertidos em lei. Os resultados encontrados confirmam os estudos que apontam que a iniciativa legislativa dos parlamentares, em algumas áreas de políticas públicas, como a da educação, não está predominantemente vinculada a interesses particularistas ou voltada para a distribuição de benefícios concentrados. Evidenciou-se a predominância de iniciativas legislativas voltadas para benefícios difusos, independentemente da vinculação partidária. O estudo demonstra que, nas questões mais estruturantes de políticas públicas educacionais, normalmente submetidas ao Congresso Nacional pelo Presidente da República, é expressiva a intervenção do Poder Legislativo, por meio da apresentação e à aprovação de emendas, alterando significativamente os textos originais das proposições e freqüentemente levando à aprovação de textos com orientação diversa daquela originalmente pretendida pelo Poder Executivo. Os textos resultantes não são um amontoado de emendas particularistas, mas contribuições para o aperfeiçoamento da legislação, que refletem uma ampla negociação em torno de linhas consensuais de política. Revelam também que a alternância de partidos políticos no Poder Executivo não tem determinado ruptura nessas políticas, mas continuidade com aperfeiçoamento ou ampliação de abrangência. Governos diferentes, com suporte parlamentar diverso, promoveram, com decisiva participação do Poder Legislativo, radical mudança nos mecanismos de financiamento da educação pública, implantando procedimentos redistributivos de recursos e envolvendo o conjunto das três esferas da federação brasileira. Estas iniciativas configuram inovação nas políticas públicas educacionais, estabelecendo novo padrão de financiamento. No campo da avaliação da educação superior, também foram introduzidas normas e procedimentos inovadores, com significativa atuação do Congresso Nacional.