Fungi with history: Unveiling the mycobiota of historic documents of Costa Rica.

We studied the physicochemical characteristics and mycobiota associated to five key historic documents from Costa Rica, including the Independence Act of Costa Rica from 1821. We used nondestructive techniques (i.e., ATR-FTIR and XRF) to determine paper and ink composition. Results show that some documents are composed of cotton-based paper, whereas others were made of wood cellulose with an increased lignin content. We also determined that the ink employed in some of the documents is ferrogallic. Cultivation and molecular techniques were used to characterize the fungi inhabiting the documents. In total, 22 fungal isolates were obtained: 15 from the wood-cellulose-based documents and seven from the other three cotton-based. We also tested the cellulolytic activity of the recovered fungi; 95% of the fungi presented cellulolytic activity correlated to their ability to cause deterioration of the paper. Results suggest that cotton-based paper is the most resistant to fungal colonization and that most of the isolates have cellulolytic activity. This work increases the knowledge of the fungal diversity that inhabits historic documents and its relationship with paper composition and provides valuable information to develop strategies to conserve and restore these invaluable documents.

Model to subtract contributions of scattered radiation from measured direct transmittance and specular reflectance by light diffusing materials.

The formalism of the Lorenz-Mie (LM) theory is used to estimate the contributions of radiation being scattered into the detector acceptance angle of spectrophotometers (with or without an integrating sphere) to the apparent direct transmittance and specular reflectance measurements. These contributions are subtracted from the measurements before doing the inversion to obtain the spectral variation of the scattering and absorption (S&A) coefficients of optically particulate liquid samples, decoupling the contribution to extinction from these two mechanisms. The method is applied to transmittance spectra of Pickering emulsions of dodecane oil (DO) and DO micelles with saturated dissolved Nile red dye, stabilized with anatase (T i O 2) in water. What we believe to be novel expressions are given to estimate the forward and backward average path-length parameters of propagating diffuse radiation from its equivalent quantities defined within the formalism of the LM theory and to relate these single particle average path-length parameters with the forward scattering ratio, asymmetry parameter, and higher-order coefficients in the expansion of the LM phase function. This novel approach makes it possible to avoid the underestimation of the S&A coefficients, which arises when the correction is not made by subtracting that contribution due to scattered radiation that is reaching the detectors from the directional reflectance and transmittance measurements.

Influence of surface roughness on the spectroscopic characterization of jadeite and greenstones archaeological artifacts: The axe-god pendants case study.

Spectroscopic techniques are commonly used for the non-invasive characterization of the molecular and elemental composition of greenstone archaeological artifacts. The surface topography of these artifacts is greatly influenced by the crafting and polishing techniques employed in their making. However, no study of the effect of roughness on spectra has ever been reported for greenstones. Here we show that infrared, Raman and X-ray fluorescence spectra are strongly influenced by the sample's surface roughness. Spectral changes were seen in both geological (45 jadeite and green stone samples) and archaeological artifacts (12 axe-God pendants); in every case, the variations were more prominent in samples with higher arithmetic average height values. The results show that these changes can affect the interpretation of the spectroscopic data and limit the efficacy of statistical analysis. Consequently, any spectroscopic characterization of this type of samples should be performed preferably in areas with lower values of roughness parameters. Overall, FT-IR appears to be the most advantageous technique to distinguish the differences in mineral composition of this type of samples during in situ studies; its performance was evaluated with an innovative statistical analysis that treats the spectra as functional data. Additionally, the results suggest that confocal Raman spectroscopy is an ideal complementary technique that enhances mineralogical characterization, nevertheless its applicability is limited to laboratory settings.

Structural and functional role of anions in electrochemical water oxidation probed by arsenate incorporation into cobalt-oxide materials.

Direct (photo)electrochemical production of non-fossil fuels from water and CO2 requires water-oxidation catalysis at near-neutral pH in the presence of appropriate anions that serve as proton acceptors. We investigate the largely enigmatic structural role of anions in water oxidation for the prominent cobalt-phosphate catalyst (CoCat), an amorphous and hydrated oxide material. Co3([(P/As)O]4)2·8H2O served, in conjunction with phosphate-arsenate exchange, as a synthetic model system. Its structural transformation was induced by prolonged operation at catalytic potentials and probed by X-ray absorption spectroscopy not only at the metal (Co), but for the first time also at the anion (As) K-edge. For initially isostructural microcrystals, anion exchange determined the amorphization process and final structure. Comparison to amorphous electrodeposited Co oxide revealed that in CoCat, the arsenate binds not only at oxide-layer edges, but also arsenic substitutes cobalt positions within the layered-oxide structure in an unusual AsO6 coordination. Our results show that in water oxidation catalysis at near-neutral pH, anion type and exchange dynamics correlate with the catalyst structure and redox properties.

Comparison of the adjuvant activity of emulsions with different physicochemical properties on the antibody response towards the venom of West African carpet viper (Echis ocellatus).

Adjuvant emulsions are widely used to enhance the antibody response of the animals used as immunoglobulin source for producing antivenoms. Usually, the adjuvant activity of emulsions is attributed both to their ability to trigger "danger" signals from cells in which they induce death, and to form depots from which immunogens are slowly released. However, there is contradictory evidence suggesting that adjuvant activity of emulsions is independent of the dispersion type and the rate of immunogen release. In order to test how physical properties of emulsions, composed of mineral oil and water, affect their ability to enhance the antibody response towards snake venoms, we compared water-in-oil (W/O) emulsions prepared at volume ratios of 70/30, 50/50 or 30/70, a 50/50 oil-in-water (O/W) emulsion, and a water-in-oil-in-water (W/O/W) multiple emulsion. Comparison included their droplet-size, viscosity, rate of immunogen release and ability to enhance the antibody response of mice immunized with the venom of the African viperid snake Echis ocellatus. It was found that all emulsions released a low amount of venom, and that the 50/50 (W/O) and the multiple emulsion (W/O/W) were those that induced the higher anti-venom antibody response. Our results suggest that the ability of emulsions to enhance the anti-venom response is not associated to their ability to form depots from which the venom is slowly released.

Heterogeneous water oxidation: surface activity versus amorphization activation in cobalt phosphate catalysts.

Is water oxidation catalyzed at the surface or within the bulk volume of solid oxide materials? This question is addressed for cobalt phosphate catalysts deposited on inert electrodes, namely crystallites of pakhomovskyite (Co3(PO4)2⋅8 H2O, Pak) and phosphate-containing Co oxide (CoCat). X-ray spectroscopy reveals that oxidizing potentials transform the crystalline Pak slowly (5-8 h) but completely into the amorphous CoCat. Electrochemical analysis supports high-TOF surface activity in Pak, whereas its amorphization results in dominating volume activity of the thereby formed CoCat material. In the directly electrodeposited CoCat, volume catalysis prevails, but not at very low levels of the amorphous material, implying high-TOF catalysis at surface sites. A complete picture of heterogeneous water oxidation requires insight in catalysis at the electrolyte-exposed "outer surface", within a hydrated, amorphous volume phase, and modes and kinetics of restructuring upon operation.

Comparison of the adjuvant activity of aluminum hydroxide and calcium phosphate on the antibody response towards Bothrops asper snake venom.

The adjuvanticity of aluminum hydroxide and calcium phosphate on the antibody response in mice towards the venom of the snake Bothrops asper was studied. It was found that, in vitro, most of the venom proteins are similarly adsorbed by both mineral salts, with the exception of some basic phospholipases A2, which are better adsorbed by calcium phosphate. After injection, the adjuvants promoted a slow release of the venom, as judged by the lack of acute toxicity when lethal doses of venom were administered to mice. Leukocyte recruitment induced by the venom was enhanced when it was adsorbed on both mineral salts; however, venom adsorbed on calcium phosphate induced a higher antibody response towards all tested HPLC fractions of the venom. On the other hand, co-precipitation of venom with calcium phosphate was the best strategy for increasing: (1) the capacity of the salt to couple venom proteins in vitro; (2) the venom ability to induce leukocyte recruitment; (3) phagocytosis by macrophages; and (4) a host antibody response. These findings suggest that the chemical nature is not the only one determining factor of the adjuvant activity of mineral salts.

Self-assembly of a catechol-based macrocycle at the liquid-solid interface: experiments and molecular dynamics simulations.

This combined experimental (STM, XPS) and molecular dynamics simulation study highlights the complex and subtle interplay of solvent effects and surface interactions on the 2-D self-assembly pattern of a Schiff-base macrocycle containing catechol moieties at the liquid-solid interface. STM imaging reveals a hexagonal ordering of the macrocycles at the n-tetradecane/Au(111) interface, compatible with a desorption of the lateral chains of the macrocycle. Interestingly, all the triangular-shaped macrocycles are oriented in the same direction, avoiding a close-packed structure. XPS experiments indicate the presence of a strong macrocycle-surface interaction. Also, MD simulations reveal substantial solvent effects. In particular, we find that co-adsorption of solvent molecules with the macrocycles induces desorption of lateral chains, and the solvent molecules act as spacers stabilizing the open self-assembly pattern.

Identification of new snake venom metalloproteinase inhibitors using compound screening and rational Peptide design.

The majority of snakebite envenomations in Central America are caused by the viperid species Bothrops asper, whose venom contains a high proportion of zinc-dependent metalloproteinases that play a relevant role in the pathogenesis of hemorrhage characteristic of these envenomations. Broad metalloproteinase inhibitors, such as the peptidomimetic hydroxamate Batimastat, have been shown to inhibit snake venom metalloproteinases (SVMP). However, the difficulty in having open public access to Batimastat and similar molecules highlights the need to design new inhibitors of SVMPs that could be applied in the treatment of snakebite envenomations. We have chosen the SVMP BaP1 as a model to search for new inhibitors using different strategies, that is, screening of the Prestwick Chemical Library and rational peptide design. Results from these approaches provide clues on the structural requirements for efficient BaP1 inhibition and pave the way for the design of new inhibitors of SVMP.

Formation of Adamantane-Like Structures by Reaction of Titanocene Fluorides with an Iminoalane.

Fluorine-nitrogen metathesis in the reaction of a cyclic iminoalane with titanocene fluorides results in unexpected cage compounds. Treatment of one of these compounds with diethyl ether leads to 1, which contains a titanium-nitrogen double bond stabilized intramolecularly by fluorine.