Keep making sense

In a number works Jerry Fodor has defended a reductive, causal and referential theory of cognitive content. I argue against this, defending a quasi-Fregean notion of cognitive content, and arguing also that the cognitive content of non-singular concepts is narrow, rather than wide.

Beyond the environmentalist's paradox and the debate on weak versus strong sustainability

Environmentalists generally argue that ecological damage will (eventually) lead to declines in human well-being. From this perspective, the recent introduction of the “environmentalist’s paradox” in BioScience by Raudsepp-Hearne and colleagues (2010) is particularly significant. In essence, Raudsepp-Hearne and colleagues (2010) claimed that although ecosystem services have been degraded, human well-being—paradoxically—has increased. In this article, we show that this debate is in fact rooted in a broader discussion on weak sustainability versus strong sustainability(the substitutability of human-made capital for natural capital). We warn against the reductive nature of focusing only on a stock–flow framework in which a natural-capital stock produces ecosystem services. Concretely, we recommend a holistic approach in which the complexity, irreversibility, uncertainty, and ethical predicaments intrinsic to the natural environment and its connections to humanity are also considered.

Caribbean Irish connections

There has been an Irish presence within the Caribbean since at least the 1620s and yet the historical and cultural dimensions of this encounter remain relatively under-researched and are often conceived of in reductive terms by crude markers such as redlegs or poor whites. While there are some striking reminders of this hitory throughout the region, this collection explores how the complications and contradictions of Irish Caribbean relations are much richer and deeper than previously recognized. Caribbean Irish Connections makes an important contribution to Irish studies by challenging the dominance of a US diasporic history and a disciplinary focus on cultural continuity and ancestry. Likewise, within Caribbean studies, the Irish presence troubles the orthodox historical models for understanding race and the plantation, race and class structures, as well as questions of ethnic and religious minorities. The contributors emphasize the importance of understanding the transatlantic nexus between Ireland and the Caribbean in terms of the shared historical experiences of dislocation, diaspora and colonization, as well as of direct encounter. This collection pays tribute to the extraordinarily rich tradition of cultural expression that informs both cultures and their imagination of each other.

Interactions between cocoa flavanols and inorganic nitrate: additive effects on endothelial function at achievable dietary amounts

Dietary intervention studies have shown that flavanols and inorganic nitrate can improve vascular function, suggesting that these two bioactives may be responsible for beneficial health effects of diets rich in fruits and vegetables. We aimed to study interactions between cocoa flavanols (CF) and nitrate, focusing on absorption, bioavailability, excretion, and efficacy to increase endothelial function. In a double-blind randomized, dose-response crossover study, flow-mediated dilation (FMD) was measured in 15 healthy subjects before and at 1, 2, 3, and 4 h after consumption of CF (1.4-10.9 mg/kg bw) or nitrate (0.1-10 mg/kg bw). To study flavanol-nitrate interactions, an additional intervention trial was performed with nitrate and CF taken in sequence at low and high amounts. FMD was measured before (0 h) and at 1h after ingestion of nitrate (3 or 8.5 mg/kg bw) or water. Then subjects received a CF drink (2.7 or 10.9 mg/kg bw) or a micro- and macronutrient-matched CF-free drink. FMD was measured at 1, 2, and 4 h thereafter. Blood and urine samples were collected and assessed for CF and nitric oxide (NO) metabolites with HPLC and gas-phase reductive chemiluminescence. Finally, intragastric formation of NO after CF and nitrate consumption was investigated. Both CF and nitrate induced similar intake-dependent increases in FMD. Maximal values were achieved at 1 h postingestion and gradually decreased to reach baseline values at 4 h. These effects were additive at low intake levels, whereas CF did not further increase FMD after high nitrate intake. Nitrate did not affect flavanol absorption, bioavailability, or excretion, but CF enhanced nitrate-related gastric NO formation and attenuated the increase in plasma nitrite after nitrate intake. Both flavanols and inorganic nitrate can improve endothelial function in healthy subjects at intake amounts that are achievable with a normal diet. Even low dietary intake of these bioactives may exert relevant effects on endothelial function when ingested together.

Revisiting cangitoxin, a sea anemone peptide: Purification and characterization of cangitoxins II and III from the venom of Bunodosoma cangicum

Sodium channel toxins from sea anemones are employed as tools for dissecting the biophysical properties of inactivation in voltage-gated sodium channels. Cangitoxin (CGTX) is a peptide containing 48 amino acid residues and was formerly purified from Bunodosoma cangicum. Nevertheless, previous works reporting, the isolation procedures for such peptide from B. cangicum secretions are controversial and may lead to incorrect information. In this paper, we report a simple and rapid procedure, consisting of two chromatographic steps, in order to obtain a CGTX analog directly from sea anemone venom. We also report a substitution of N16D in this peptide sample and the co-elution of an inseparable minor isoform presenting the R14H substitution. Peptides are named as CGTX-II and CGTX-III, and their effects over Nav1.1 channels in patch clamp experiments are demonstrated. (c) 2008 Elsevier Ltd. All rights reserved.

The opportunistic fungal pathogen Scedosporium prolificans: Carbohydrate epitopes of its glycoproteins

Isolated from the mycelium, of Scedosporium prolificans were complex glycoproteins (RMP-Sp), with three structurally related components (HPSEC). RMP-Sp contained 35% protein and 62% carbohydrate with Rha, Ara, Man, Gal, Glc, and GlcNH(2) in a 18:1:24:8:6:5 molar ratio. Methylation analysis showed mainly nonreducing end- of Galp (13%), nonreducing end- (9%),2-O-(13%), and 3-O-subst. Rhap (7%), nonreducing end-(11%), 2-O-(10%), 3-O-(14%), and 2,6-di-O-subst. Manp units (13%). Mild reductive P-elimination of RMP-Sp gave alpha-L-Rhap-(1-->2)-alpha-L-Rhap-(1-->3)-alpha-L-Rhap-(1-->3)-alpha-D-Manp-(1-->2)-D-Man-ol, with Man-ol substituted at O-6 with beta-D-Galp units, a related pentasaccharide lacking beta-D-Galp units, and beta-D-Galp-(1-->6)-[alpha-D-Manp-(1-->2)]-D-Man-ol in a 16:3:1 w/w ratio. Traces of Man-ol and Rha-ol were detected. ESI-MS showed HexHex-o1 and HCX(3-6)Hex-ol components. Three rhamnosyl units were peeled off successively from the penta- and hexasaccharide by ESI-MS-MS. The carbohydrate epitopes of RMP-Sp differ from those of the glycoprotein of Pseudallescheria boydii, a related opportunistic pathogen. (C) 2007 Elsevier B.V. All rights reserved.

Rock magnetism in soils of the Pampean plain. Buenos Aires province, Argentina. Linking climate and magnetic behaviour

Results of the study of Argiudolls in two localities (Zarate and Veronica) of the Pampean plain, Argentina, are presented in this contribution. This is a typical area covered by loess. The magnetic studies carried out allowed to determine the presence of detrital magnetite and titanomagnetite, as well as maghemite, pedogenic goethite and superparamagnetic particles (SP). In Veronica soils, a depletion of ferromagnetic minerals is recorded The dominant process in these soils has been the reductive loss of detrital magnetite and titanomagnetite. This is associated with a greater degree of evolution of the soil, which is determined by the concentration and type of detected clays. The higher clay concentration in these soils facilitated reducing conditions and a greater loss of detrital magnetic particles. The loss is reinforced under poor drainage conditions. In the poorly drained soil of Zarate, a concentration of magnetic particles is observed in the Bt horizon, which is associated with an illuviation process. The well drained soil of the same locality shows neoformation of SP particles. These particles would have an ephemeral life until a new wet period in the annual cycle occurs. Although some characteristics of the magnetic signal appear reinforced by the conditions of drainage, this aspect does not seem to be too significant, at least in the Pampean region with low topographic gradients.

Fluorimetric determination of intra- and extracellular free amino acids in the microalgae Tetraselmis gracilis (Prasinophyceae) using monolithic column in reversed phase mode

This paper describes the development and application of an RP HPLC method using a C(18) monolithic stationary phase for the separation and quantification of extra- and intracellular amino acids in a batch cultivation of the marine alga Tetraselmis gracilis. Fluorimetric detection was made after separation of the o-phthaldialdehyde 2-mercaptoethanol (OPA-2MCE) derivatives using a binary gradient elution. Separation of 19 amino acids was achieved with resolution >1.5 in about 39 min at a flow rate of 1.5 mL/min. RSD of analyses in seawater medium ranged from 0.36% for Orn (0.50 mu mol/L) to 12% for Ile (0.10 mu mol/L). The main constituents of the intracellular dissolved free amino acids (DFAAs) in the exponential growth phase were arginine (Arg), asparagine (Asn), alanine (Ala), aspartic acid (Asp), glutamic acid (Glu), serine (Ser), glycine (Gly), glutamine (Gln), and leucine (Leu). The major amino acids excreted to the media were valine (Val), Ala, Ser, and Gly. The monolithic phase facilitates the analysis by shortening the separation time and saving solvents and instrumentation costs (indeed conventional HPLC instrumentation can be used, running at lower pressures than those ones used with packed particle columns).

Selective Sulfenylative Desulfonylation or Decarbalkoxylation of -Sulfonyl Malonates with DABCO or Bu3N: Reactivity and Conformational Analysis

The study on reactivity of several -substituted -sulfonyl malonates toward 1,4-diazabicyclo[2.2.2]octane (DABCO) and Bu3N is described. The reactivity with DABCO revealed the possible competition between decarbalkoxylation and unexpected desulfonylation, depending on the -substituent, because of sterical hindrance around the electrophilic centers (SO2 and CO2R). The derivatives with crowded -substituents suffer selective desulfonylation, and a novel and efficient desulfonylation method can be proposed. The dependence of the reactivity of -sulfonyl malonates on the sterical hindrance around the electrophilic centers is confirmed by conformational analysis (Macromodel/MM2* and Mopac/MP3). The carbanionic mechanism is proved because the corresponding protonated, deuterated, and sulfenylated products were obtained by addition of the corresponding electrophilic agents. Bu3N showed itself to be a novel selective decarbalkoxylation agent for any -substituted -sulfonyl malonate.

Mutagenicity and DNA adduct formation of PAH, nitro-PAH, and oxy-PAH fractions of atmospheric particulate matter from Sao Paulo, Brazil

Urban particulate matter (UPM) contributes to lung cancer incidence. Here, we have studied the mutagenic activity and DNA adduct-forming ability of fractionated UPM extractable organic matter (EOM). UPM was collected with a high-volume sampler in June 2004 at two sites, one at street level adjacent to a roadway and the other inside a park within the urban area of the city of Sao Paulo, Brazil. UPM was extracted using dichloromethane, and the resulting EOM was separated by HPLC to obtain PAH, nitro-PAH, and oxy-PAH fractions which were tested for mutagenicity with the Salmonella strains TA98 and YG1041 with and without S9 metabolic activation. The PAH fraction from both sites showed negligible mutagenic activity in both strains. The highest mutagenic activity was found for the nitro-PAH fraction using YG1041 without metabolic activation; however, results were comparable for both sites. The nitro-PAH and oxy-PAH fractions were incubated with calf thymus DNA under reductive conditions appropriate for the activation of nitro aromatic compounds, then DNA adduct patterns and levels were determined with thin-layer chromatography (TLC) (32)p-postlabeling method using two enrichment procedures-nuclease PI digestion and butanol extraction. Reductively activated fractions from both sites produced diagonal radioactive zones (DRZ) of putative aromatic DNA adducts on thin layer plates with both enrichment procedures. No such DRZ were observed in control experiments using fractions from unexposed filters or from incubations without activating system. Total adduct levels produced by the nitro-PAH fractions were similar for both sites ranging from 30 to 45 adducts per 10(8) normal nucleotides. In contrast, the DNA binding of reductively activated oxy-PAH fractions was three times higher and the adduct pattern consisted of multiple discrete spots along the diagonal line on the thin layer plates. However, DNA adduct levels were not significantly different between the sampling sites. Both samples presented the same levels of mutagenic activity. The response in the Salmonella assay was typical of nitroaromatics. Although, more mutagenic activity was related to the nitro-PAH fraction in the Salmonella assay, the oxy-PAH fractions showed the highest DNA adduct levels. More studies are needed to elucidate the nature of the genotoxicants occurring in Sao Paulo atmospheric samples. (C) 2008 Elsevier B.V. All rights reserved.

Surface-enhanced Raman study of electrochemical and photocatalytic degradation of the azo dye Janus Green B

The photocatalytic degradation of Janus Green B azo dye over silver modified titanium dioxide films was investigated by surface-enhanced Raman spectroscopy (SERS). An optimized SERS-active substrate was employed to study the photodegradation reaction of Janus Green B. Considering that photocatalytic degradation processes of organic molecules adsorbed on TiO2 might involve either their oxidation or reduction reaction, the vibrational spectroelectrochemical study of the dye was also performed, in order to clarify the transformations involved in initial steps of its photochemical decomposition. In order to understand the changes in Raman spectra of Janus Green B after photodegradation and/or electrochemical processes, a vibrational assignment of the main Raman active modes of the dye was carried out, based on a detailed resonance Raman profile. Products formed by electrochemical and photochemical degradation processes were compared. The obtained results revealed that the first steps of the degradation process of Janus Green B involve a reductive mechanism. (C) 2007 Published by Elsevier B.V.

Interfacial Electron Transfer Dynamics Following Laser Flash Photolysis of [Ru(bpy)(2)((4,4 `-PO(3)H(2))(2)bpy)](2+) in TiO(2) Nanoparticle Films in Aqueous Environments

Nanosecond laser flash photolysis has been used to investigate injection and back electron transfer from the complex [(Ru-(bpy)(2)(4,4`-(PO(3)H(2))(2)bpy)](2+) surface-bound to TiO(2) (TiO(2)-Ru(II)). The measurements were conducted under conditions appropriate for water oxidation catalysis by known single-site water oxidation catalysts. Systematic variations in average lifetimes for back electron transfer, - were observed with changes in pH, surface coverage, incident excitation intensity, and applied bias. The results were qualitatively consistent with a model involving rate-limiting thermal activation of injected electrons from trap sites to the conduction band or shallow trap sites followed by site-to-site hopping and interfacial electron transfer, TiO(2)(e(-))-Ru(3+) -> TiO(2)-Ru(2+). The appearance of pH-dependent decreases in the efficiency of formation of TiO(2)-Ru(3+) and in incident-photon-to-current efficiencies with the added reductive scavenger hydroquinone point to pH-dependent back electron transfer processes on both the sub-nanosecond and millisecond-microsecond time scales, which could be significant in limiting long-term storage of multiple redox equivalents.

Multimilligram enantioresolution of sulfoxide proton pump inhibitors by liquid chromatography on polysaccharide-based chiral stationary phase

The enantiomers of sulfoxide proton pump inhibitors - omeprazole, lansoprazole, rabeprazole and Ro 18-5364 - were enantiomerically separated by liquid chromatography at multimilligram scale on a poly saccharide-based chiral stationary phase using normal and polar organic conditions as mobile phase. The values of the recovery and production rate were significant for each enantiomer; better results were achieved using a solid-phase injection system. However, this system was applied just for the enantionteric separation of omeprazole to demonstrate the applicability of this injection mode at milligram scale. The chiroptical characterization of the compounds was performed using a polarimeter and a circular dichroism detector. The higher enantiomeric purity obtained for the isolated enantiomers suggests that the methods here described should be considered as a simple and rapid way to obtain enantiomeric pure standards for analytical purpose. (C) 2007 Elsevier B.V. All rights reserved.

Fluoxetine and norfluoxetine analysis by direct injection of human plasma in a column switching liquid chromatographic system

A column switching LC method is presented for the analysis of fluoxetine (FLU) and norfluoxetine (NFLU) by direct injection of human plasma using a lab-made restricted access media (RAM) column. A RAM-BSA-octadecyl silica (C-18) column (40 min x 4.6 mm, 10 mu m) is evaluated in both backflush and foreflush elution modes and coupled with a C-18 lab-made (50 mm x 4.6 mm, 3 pm) analytical column in order to perform online sample preparation. Direct injection of 100 mu L, of plasma samples is possible with the developed approach. In addition, reduction of sample handling is obtained when compared with traditional liquid-liquid extraction (LLE) and SPE. The total analysis time is around 20 min. A LOQ of 15 ng/mL is achieved in a concentration range of 15-500 ng/mL, allowing the therapeutic drug monitoring of clinical samples. The precision values achieved are lower than 15% for all the evaluated points with adequate recovery and accuracy. Furthermore, no matrix interferences are found in the analysis and the proposed method shows to be an adequate alternative for analysis of FLU in plasma.

Quenching of excited states of red-pigment zinc protoporphyrin IX by hemin and natural reductors in dry-cured hams

Zinc protoporphyrin IX (ZnPP), the major red pigment in hams dry-cured without nitrates/nitrites, is an efficient photosensitizer, which upon absorption of visible light forms short-lived excited singlet state ((1)ZnPP*) and by intersystem crossing yields the very reactive triplet-excited state ((3)ZnPP*). Using nano-second laser flash photolysis and transient absorption spectroscopy NADH, ascorbic acid, hemin and dehydroascorbic acid were each found to be efficient quenchers of (3)ZnPP*. The deactivation followed, in homogeneous dimethyl sulfoxide (DMSO) or DMSO:water (1:1) solutions, second-order kinetics. The rate constant for ascorbic acid and NADH for reductive quenching of (3)ZnPP* was at 25 A degrees C found to be 7.5 +/- A 0.1 x 10(4) L mol(-1) s(-1) and 6.3 +/- A 0.1 x 10(5) L mol(-1) s(-1), respectively. The polyphenols catechin and quercetin had no effect on (3)ZnPP*. The quenching rate constant for oxidative deactivation of (3)ZnPP* by dehydroascorbic acid and hemin was at 25 A degrees C: 1.6 +/- A 0.1 x 10(5) L mol(-1) s(-1) and 1.47 +/- A 0.1 x 10(9) L mol(-1) s(-1), respectively. Oxidized glutathione did not act as an oxidative quencher for (3)ZnPP*. After photoexcitation of ZnPP to (1)ZnPP*, fluorescence was only found to be quenched by the presence of hemin in a diffusion-controlled reaction. The efficient deactivation of (3)ZnPP* and (1)ZnPP* by the metalloporphyrin (hemin) naturally present in meat may accordingly inherently protect meat proteins and lipids against ZnPP photosensitized oxidation.