Iodine(III)-promoted ring expansion of 1-vinylcycloalkanol derivatives: A metal-free approach toward seven-membered rings

A versatile and metal-free approach for the synthesis of molecules bearing seven- and eight-membered rings is described. The strategy is based on the ring expansion of 1-vinylcycloalkanols (or the corresponding silyl or methyl ether) mediated by the hypervalent iodine reagent HTIB (Phl(OH)OTs). The reaction condition can be easily adjusted to give seven-membered rings bearing different functional groups. A route to medium-ring lactones was also developed.

Ligand-Assisted Preparation of Palladium Supported Nanoparticles: a Step toward Size Control

Supported nanoparticles (SNPs) with narrow size distribution were prepared by H(2) reduction of Pd(2+) previously bound, to ligand-modified silica surfaces. Interestingly, the size of the Pd SNPs was tuned by the ligand grafted on the support surface. Amino- and ethylenediamino-functionalized supports formed Pd(0) SNPs of ca. 6 and 1 nm, respectively. The catalytic properties of both Pd(0) SNPs were investigated.

Reactivity of Beer Bitter Acids Toward the 1-Hydroxyethyl Radical as Probed by Spin-Trapping Electron Paramagnetic Resonance (EPR) and Electrospray Ionization-Tandem Mass Spectrometry (ESI-MS/MS)

The iso-alpha-acids or isohumulones are the major contributors to the bitter taste of beer, and it is well-recognized that they are degraded during beer aging. In particular, the trans-isohumulones seem to be less stable than the cis-isohumulones. The major radical identified in beer is the 1-hydroxyethyl radical; however, the reactivity between this radical and the isohumulones has not been reported until now. Therefore, we studied the reactivity of isohumulones toward the 1-hydroxyethyl radical through a competitive kinetic approach. It was observed that both cis- and trans-isohumulones and dihydroisohumulones are decomposed in the presence of 1-hydroxyethyl radicals, while the reactivities are comparable. On the other hand, the tetrahydroisohumulones did not react with 1-hydroxyethyl radicals. The apparent second-order rate constants for the reactions between the 1-hydroxyethyl radical and these compounds were determined by electron paramagnetic resonance (EPR) spectroscopy and electrospray ionization-tandem mass spectrometry [ESI(+)-MS/MS]. It follows that degradation of beer bitter acids is highly influenced by the presence of 1-hydroxyethyl radicals. The reaction products were detected by liquid chromatography electrospray ionization-ion trap-tandem mass spectrometry (LC-ESI-IT-MS/MS), and the formation of oxidized derivatives of the isohumulones was confirmed. These data help to understand the mechanism of beer degradation upon aging.

Synthesis, Characterization, and Electrocatalytic Activity toward Methanol Oxidation of Carbon-Supported Pt(x)-(RuO(2)-M)(1-x) Composite Ternary Catalysts (M = CeO(2), MoO(3), or PbO(x))

Carbon-supported platinum is commonly used as an anode electrocatalyst in low-temperature fuel cells fueled with methanol. The cost of Pt and the limited world supply are significant barriers for the widespread use of this type of fuel cell. Moreover, Pt used as anode material is readily poisoned by carbon monoxide produced as a byproduct of the alcohol oxidation. Although improvements in the catalytic performance for methanol oxidation were attained using Pt-Ru alloys, the state-of-the-art Pt-Ru catalyst needs further improvement because of relatively low catalytic activity and the high cost of noble Pt and Ru. For these reasons, the development of highly efficient ternary platinum-based catalysts is an important challenge. Thus, various compositions of ternary Pt(x)-(RuO(2)-M)(1-x)/C composites (M = CeO(2), MoO(3), or PbO(x)) were developed and further investigated as catalysts for the methanol electro-oxidation reaction. The characterization carried out by X-ray diffraction, energy-dispersive X-ray analysis, transmission electron microscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry point out that the different metallic oxides were successfully deposited on the Pt/C, producing small and well-controlled nanoparticles in the range of 2.8-4.2 nm. Electrochemical experiments demonstrated that the Pt(0.50)(RuO(2)-CeO(2))(0.50)/C composite displays the higher catalytic activity toward the methanol oxidation reaction (lowest onset potential of 207 mV and current densities taken at 450 mV, which are 140 times higher than those at commercial Pt/C), followed by the Pt(0.75)(RuO(2)-MoO(3))(0.25)/C composite. In addition, both of these composites produced low quantities of formic acid and formaldehyde when compared to a commercially available Pt(0.75)-Ru(0.25)/C composite (from E-Tek, Inc.), suggesting that the oxidation of methanol occurs mainly by a pathway that produces CO(2) forming the intermediary CO(ads).

Studies toward the structural optimization of novel thiazolylhydrazone-based potent antitrypanosomal agents

In previous studies, we identified promising anti-Trypanosoma cruzi cruzain inhibitors based on thiazolylhydrazones. To optimize this series, a number of medicinal chemistry directions were explored and new thiazolylhydrazones and thiosemicarbazones were thus synthesized. Potent cruzain inhibitors were identified, such as thiazolylhydrazones 3b and 3j, which exhibited IC(50) of 200-400 nM. Furthermore, molecular docking studies showed concordance with experimentally derived structure-activity relationships (SAR) data. In the course of this work, lead compounds exhibiting in vitro activity against both the epimastigote and trypomastigote forms of T. cruzi were identified and in vivo general toxicity analysis was subsequently performed. Novel SAR were documented, including the importance of the thiocarbonyl carbon attached to the thiazolyl ring and the direct comparison between thiosemicarbazones and thiazolylhydrazones. (C) 2010 Elsevier Ltd. All rights reserved.

Opting out of oppositionality : toward an informed and engaged "third wave" feminism

I begin by citing a definition of "third wave" from the glossary in Turbo Chicks: Talking Young Feminisms at length because it communicates several key issues that I develop in this project. The definition introduces a tension within "third wave" feminism of building and differentiating itself from second wave feminism, the newness of the term "third wave," its association with "young" women, complexity of contemporary feminisms, and attention to multiple identities and oppressions. Uncovering explanations of "third wave" feminism that go beyond, like this one, generational associations, is not an easy task. Authors consistently group new feminist voices together by age under the label "third wave" feminists without questioning the accuracy of the designation. Most explorations of "third wave" feminism overlook the complexities and distinctions that abound among "young" feminists ; not all young feminists espouse similar ideas, tactics, and actions; and for various reasons, not all young feminists identify with a "third wave" of feminism. Less than a year after I began to learn about feminism I discovered Barbara Findlen's Listen Up: Voices From the Next Feminist Generation. Although the collection nor its contributors declare association with "third wave" feminism, consequent reviews and citations in articles identify it, along with Rebecca Walker's To Be Real: Telling the Truth and Changing the Voice of Feminism, as a major text of "third wave" feminism. Re-reading Listen Up since beginning to research "third wave" feminism, I now understand its fundamental influence on my research questions as a starting point for assessing persistent exclusion in contemporary feminism, rather than as a revolutionary text (as it is claimed to be in many reviews). Findlen begins the introduction with the bold claim, "My feminism wasn't shaped by antiwar or civil rights activism ..." (xi). Framing the collection with a disavowal of the influence women of color's organizational efforts negates, for me, the project's proclaimed commitment to multivocality. Though several contributions examine persistent exclusion within contemporary feminist movement, the larger project seems to rely on these essays to reflect this commitment, suggesting that Listen Up does not go beyond the "add and stir" approach to "diversity." Interestingly, this statement does not appear in the new edition of Listen Up published in 2001. And the content has changed with this new edition, including several more Latina contributors and other "corrective" additions.

An empirical approach toward understanding the linkage between legal and financial institutions

Researchers have made different attempts to investigate the interaction between the quality and efficiency of a country’s institutions and a country’s economic performance. Within this framework, emphasis has been put on the relationship between the legal institutions and the financial system as essential factors in creating and enhancing overall economic growth. The link between legal institutions and the financial systems, however, is still somewhat controversial. This paper reports on a survey administered to 1,362 participants regarding preferences for investment under different legal and financial institutions. Results suggest that the performance of a country‘s legal institutions affects the willingness to invest money in that country and that people of different gender, age, political traditions, and professional experience react differently to these institutions.