Screening of supports for the immobilization of pectinmethylesterase from acerola (Malpighia glabra L)

A partially purified extract of pectinmethylesterase (PME) from acerola fruit was immobilized on various supports: glass, celite, chrysotile, agarose, concanavalin A Sepharose 4B, egg shell, polyacrylamide and gelatin. In addition, reticulation with glutaraldehyde was assessed, as well as the use of gelatin in the presence of celite, glass and silica. The highest immobilization yields were obtained when the pectinmethylesterase was immobilized in concanavalin A Sepharose 4B (81.7%) and in gelatin-water (78.0%). (C) 2004 Society of Chemical Industry.

Synthesis and Physical-Chemical characterization of Metallic Nanoparticles

The stabilization of nanoparticles against their irreversible particle aggregation and oxidation reactions. is a requirement for further advancement in nanoparticle science and technology. For this reason the research aim on this topic focuses on the synthesis of various metal nanoparticles protected with monolayers containing different reactive head groups and functional tail groups. In this work cuprous bromide nanocrystals haave been synthetized with a diameter of about 20 nanometers according to a new sybthetic method adding dropwise ascorbic acid to a water solution of lithium bromide and cupric chloride under continuous stirring and nitrogen flux. Butane thiolate Cu protected nanoparticles have been synthetized according to three different syntesys methods. Their morphologies appear related to the physicochemical conditions during the synthesis and to the dispersing medium used to prepare the sample. Synthesis method II allows to obtain stable nanoparticles of 1-2 nm in size both isolated and forming clusters. Nanoparticle cluster formation was enhanced as water was used as dispersing medium probably due to the idrophobic nature of the butanethiolate layers coating the nanoparticle surface. Synthesis methods I and III lead to large unstable spherical nanoparticles with size ranging between 20 to 50 nm. These nanoparticles appeared in the TEM micrograph with the same morphology independently on the dispersing medium used in the sample preparation. The stability and dimensions of the copper nanoparticles appear inversely related. Using the same methods above described for the butanethiolate protected copper nanoparticles 4-methylbenzenethiol protected copper nanoparticles have been prepared. Diffractometric and spectroscopic data reveal that decomposition processes didn’t occur in both the 4-methylbenzenethiol copper protected nanoparticles precipitates from formic acid and from water in a period of time six month long. Se anticarcinogenic effects by multiple mechanisms have been extensively investigated and documented and Se is defined a genuine nutritional cancer-protecting element and a significant protective effect of Se against major forms of cancer. Furthermore phloroglucinol was found to possess cytoprotective effects against oxidative stress, thanks to reactive oxygen species (ROS) which are associated with cells and tissue damages and are the contributing factors for inflammation, aging, cancer, arteriosclerosis, hypertension and diabetes. The goal of our work has been to set up a new method to synthesize in mild conditions amorphous Se nanopaticles surface capped with phloroglucinol, which is used during synthesis as reducing agent to obtain stable Se nanoparticles in ethanol, performing the synergies offered by the specific anticarcinogenic properties of Se and the antioxiding ones of phloroalucinol. We have synthesized selenium nanoparticles protected by phenolic molecules chemically bonded to their surface. The phenol molecules coating the nanoparticles surfaces form low ordered arrays as can be seen from the wider shape of the absorptions in the FT-IR spectrum with respect to those appearing in that of crystalline phenol. On the other hand, metallic nanoparticles with unique optical properties, facile surface chemistry and appropriate size scale are generating much enthusiasm in nanomedicine. In fact Au nanoparticles has immense potential for both cancer diagnosis and therapy. Especially Au nanoparticles efficiently convert the strongly adsorbed light into localized heat, which can be exploited for the selective laser photothermal therapy of cancer. According to the about, metal nanoparticles-HA nanocrystals composites should have tremendous potential in novel methods for therapy of cancer. 11 mercaptoundecanoic surface protected Au4Ag1 nanoparticles adsorbed on nanometric apathyte crystals we have successfully prepared like an anticancer nanoparticles deliver system utilizing biomimetic hydroxyapatyte nanocrystals as deliver agents. Furthermore natural chrysotile, formed by densely packed bundles of multiwalled hollow nanotubes, is a mineral very suitable for nanowires preparation when their inner nanometer-sized cavity is filled with a proper material. Bundles of chrysotile nanotubes can then behave as host systems, where their large interchannel separation is actually expected to prevent the interaction between individual guest metallic nanoparticles and act as a confining barrier. Chrysotile nanotubes have been filled with molten metals such as Hg, Pb, Sn, semimetals, Bi, Te, Se, and with semiconductor materials such as InSb, CdSe, GaAs, and InP using both high-pressure techniques and metal-organic chemical vapor deposition. Under hydrothermal conditions chrysotile nanocrystals have been synthesized as a single phase and can be utilized as a very suitable for nanowires preparation filling their inner nanometer-sized cavity with metallic nanoparticles. In this research work we have synthesized and characterized Stoichiometric synthetic chrysotile nanotubes have been partially filled with bi and monometallic highly monodispersed nanoparticles with diameters ranging from 1,7 to 5,5 nm depending on the core composition (Au, Au4Ag1, Au1Ag4, Ag). In the case of 4 methylbenzenethiol protected silver nanoparticles, the filling was carried out by convection and capillarity effect at room temperature and pressure using a suitable organic solvent. We have obtained new interesting nanowires constituted of metallic nanoparticles filled in inorganic nanotubes with a inner cavity of 7 nm and an isolating wall with a thick ranging from 7 to 21 nm.

Pyrolysis of peptides and proteins. Analytical study and environmental applications

Analytical pyrolysis was used to investigate the formation of diketopiperazines (DKPs) which are cyclic dipeptides formed from the thermal degradation of proteins. A quali/quantitative procedure was developed combining microscale flash pyrolysis at 500 °C with gas chromatography-mass spectrometry (GC-MS) of DKPs trapped onto an adsorbent phase. Polar DKPs were silylated prior to GC-MS. Particular attention was paid to the identification of proline (Pro) containing DKPs due to their greater facility of formation. The GC-MS characteristics of more than 80 original and silylated DKPs were collected from the pyrolysis of sixteen linear dipeptides and four model proteins (e.g. bovine serum albumin, BSA). The structure of a novel DKP, cyclo(pyroglutamic-Pro) was established by NMR and ESI-MS analysis, while the structures of other novel DKPs remained tentative. DKPs resulted rather specific markers of amino acid sequence in proteins, even though the thermal degradation of DKPs should be taken into account. Structural information of DKPs gathered from the pyrolysis of model compounds was employed to the identification of these compounds in the pyrolysate of proteinaceous samples, including intrinsecally unfolded protein (IUP). Analysis of the liquid fraction (bio-oil) obtained from the pyrolysis of microalgae Nannochloropsis gaditana, Scenedesmus spp with a bench scale reactor showed that DKPs constituted an important pool of nitrogen-containing compounds. Conversely, the level of DKPs was rather low in the bio-oil of Botryococcus braunii. The developed micropyrolysis procedure was applied in combination with thermogravimetry (TGA) and infrared spectroscopy (FT-IR) to investigate surface interaction between BSA and synthetic chrysotile. The results showed that the thermal behavior of BSA (e.g. DKPs formation) was affected by the different form of doped synthetic chrysotile. The typical DKPs evolved from collagen were quantified in the pyrolysates of archaeological bones from Vicenne Necropolis in order to evaluate their conservation status in combination with TGA, FTIR and XRD analysis.

Conductive Polymer Composites

In recent years, nanotechnologies have led to the production of materials with new and sometimes unexpected qualities through the manipulation of nanoscale components. This research aimed primarily to the study of the correlation between hierarchical structures of hybrid organic-inorganic materials such as conductive polymer composites (CPCs). Using a bottom-up methodology, we could synthesize a wide range of inorganic nanometric materials with a high degree of homogeneity and purity, such as thiol capped metal nanoparticles, stoichiometric geomimetic chrysotile nanotubes and metal dioxide nanoparticles. It was also possible to produce inorganic systems formed from the interaction between the synthesized materials. These synthesized materials and others like multiwalled carbon nanotubes and grapheme oxide were used to produce conductive polymer composites. Electrospinning causes polymer fibers to become elongated using an electric field. This technique was used to produce fibers with a nanometric diameter of a polymer blend based on two different intrinsically conducting polymers polymers (ICPs): polyaniline (PANI) and poly(3-hexylthiophene) (P3HT). Using different materials as second phase in the initial electrospun polymer fibers caused significant changes to the material hierarchical structure, leading to the creation of CPCs with modified electrical properties. Further study of the properties of these new materials resulted in a better understanding of the electrical conductivity mechanisms in these electrospun materials.

The Presence of Asbestos-Contaminated Vermiculite Attic Insulation and/or Other Asbestos Containing Materials in Homes and the Potential for Living Space Contamination

Asbestos-contaminated vermiculite attic insulation (VAI) produced from a mine near Libby, Montana, may be present in millions of homes along with other commercial asbestos-containing materials (ACM). The primary goal of the research described here was to develop and test procedures that would allow for the safe and effective weatherization of low-income homes with asbestos. The presence of asbestos insulation was confirmed by bulk sampling of the suspect asbestos material. The homes were then tested for the presence of asbestos fibers in the living spaces. All 40 homes containing VAI revealed the presence of amphibole asbestos in bulk samples. Asbestos (primarily chrysotile) was confirmed in bulk samples of ACM collected from 18 homes. Amphibole asbestos was detected in the living space of 12 (26%) homes, while chrysotile asbestos was detected in the living space of 45 (98%) homes. These results suggest that asbestos sources in homes can contribute to living space contamination

Pressure-temperature estimates of the lizardite/antigorite transition in high pressure serpentinites

Serpentine minerals in natural samples are dominated by lizardite and antigorite. In spite of numerous laboratory experiments, the stability fields of these species remain poorly constrained. This paper presents petrological observations and the Raman spectroscopy and XRD analyses of natural serpentinites from the Alpine paleo-accretionary wedge. Serpentine varieties were identified from a range of metamorphic pressure and temperature conditions from sub-greenschist (P < 4 kbar, T ~ 200–300 °C) to eclogite facies conditions (P > 20 kbar, T > 460 °C) along a subduction geothermal gradient. We use the observed mineral assemblage in natural serpentinite along with the Tmax estimated by Raman spectroscopy of the carbonaceous matter in associated metasediments to constrain the temperature of the lizardite to antigorite transition at high pressures. We show that below 300 °C, lizardite and locally chrysotile are the dominant species in the mesh texture. Between 320 and 390 °C, lizardite is progressively replaced by antigorite at the grain boundaries through dissolution–precipitation processes in the presence of SiO2 enriched fluids and in the cores of the lizardite mesh. Above 390 °C, under high-grade blueschist to eclogite facies conditions, antigorite is the sole stable serpentine mineral until the onset of secondary olivine crystallization at 460 °C.

Effects of asbestos and silica on superoxide anion production in the guinea pig alveolar macrophage

Asbestos and silica are important industrial hazards. Exposure to these dusts can result in pulmonary fibrosis and, in the case of asbestos, cancer. Although the hazards of asbestos and silica exposure have long been known, the pathogenesis of dust-related disease is not well understood. Both silica and asbestos are thought to alter the function of the alveolar macrophage, but the nature of the biochemical alteration is unknown. Therefore, this study examined the effect of asbestos and silica on the activation pathway of the guinea pig alveolar macrophage. Activation of macrophages by physiological agents results in stimulation of phospholipase C causing phosphatidyl inositol turnover and intracellular calcium mobilization. Phosphatidyl inositol turnover produces diacylglycerol which activates protein kinase C causing superoxide anion production.^ Chrysotile stimulated alveolar macrophages to produce superoxide anion. This stimulation proceeded via phospholipase C, since chrysotile stimulated phosphatidyl inositol turnover and intracellular calcium mobilization. The possible involvement of a coupling protein was evaluated by pretreating cells with pertussis toxin. Pertussis toxin pretreatment partially inhibited chrysotile stimulation, suggesting that chrysotile activates a coupling protein in an non-classical manner. Potential binding sites for chrysotile stimulation were examined using a series of nine lectins. Chrysotile-stimulated superoxide anion production was blocked by pretreatment with lectins which bound to N-acetylglucosamine, but not by lectins which bound to mannose, fucose, or N-acetylgalactosamine. In addition, incubation with the N-acetylglucosamine polymer, chitin, inhibited chrysotile-stimulated superoxide anion production, suggesting that chrysotile stimulated superoxide anion production by binding to N-acetylglucosamine residues.^ On the other hand, silica did not stimulate superoxide anion production. The effect of silica on agonist stimulation of this pathway was examined using two stimulants of superoxide anion production, N-formyl-nle-leu-phe (FNLP, which stimulates through phospholipase C) and phorbol-12,13-dibutyrate (which directly activates protein kinase C). Sublethal doses of silica inhibited FNLP-stimulated superoxide anion production, but did not affect phorbol-12,13-dibutyrate-stimulated superoxide anion production, suggesting that the site of inhibition precedes protein kinase C. This inhibition was not due to cell membrane damage, since cell permeability to calcium-45 and rubidium-86 was not increased. It is concluded that chrysotile binds to N-acetylglucosamine residues on macrophage surface glycoproteins to stimulate the physiological pathway resulting in superoxide anion production. In contrast, silica does not stimulate superoxide anion production, but it did inhibit FNLP-stimulated superoxide anion production. ^

Mineralogy of serpentine muds of ODP Leg 125 holes (Table 1)

Large serpentinite seamounts are common in the forearc regions between the trench axis and the active volcanic fronts of the Mariana and Izu-Bonin intraoceanic arcs. The seamounts apparently form both as mud volcanoes, composed of unconsolidated serpentine mud flows that have entrained metamorphosed ultramafic and mafic rocks, and as horst blocks, possibly diapirically emplaced, of serpentinized ultramafics partially draped with unconsolidated serpentine slump deposits and mud flows. The clayand silt-sized serpentine recovered from three sites on Conical Seamount on the Mariana forearc region and from two sites on Torishima Forearc Seamount on the Izu-Bonin forearc region is composed predominantly of chrysotile, brucite, chlorite, and clays. A variety of accessory minerals attest to the presence of unusual pore fluids in some of the samples. Aragonite, unstable at the depths at which the serpentine deposits were drilled, is present in many of the surficial cores from Conical Seamount. Sjogrenite minerals, commonly found as weathering products of serpentine resulting from interaction with groundwater, are found in most of the samples. The presence of aragonite and carbonate-hydroxide hydrate minerals argues for interaction of the serpentine deposits with fluids other than seawater. There are numerous examples of sedimentary serpentinite deposits exposed on land that are very similar to the deposits recovered from the serpentine seamounts drilled on ODP Leg 125. We suggest that Conical Seamount may be a type locality for the study of in situ formation of many of these sedimentary serpentinite bodies. Further, we suggest that both the deposits drilled on Conical Seamount and on Torishima Forearc Seamount demonstrate that serpentinization can continue in situ within the seamounts through interaction of the serpentine deposits with both seawater and subduction-related fluids.

Mineralogy and geochemistry of weathered serpentinites in DSDP Leg 84 sediments

At Sites 566, 567, and 570 of Leg 84, ophiolitic serpentinite basement was covered by a sequence of serpentinitic mud that was formed by weathering of the serpentinites under sea- or pore-water conditions. Several mineralogical processes were observed: (1) The serpentinitic mud that consists mainly of chrysotile was formed from the lizardite component of the serpentinites by alteration. (2) Slightly trioctahedral smectites containing nonexpandable mica layers, trioctahedral smectites containing nonexpandable chlorite layers, and swelling chlorites were presumably formed from detrital chlorite and/or serpentine. (3) The occurrence of tremolite, chlorite, analcime, and talc can be attributed to reworking of gabbroic ophiolite rocks. (4) Dolomite, aragonite, and Mg-calcite, all authigenic, occur in the serpentinitic mud.

Geochemistry of serpentinized peridotites from ODP Holes 207-1272A and 207-1274A

Despite the key importance of altered oceanic mantle as a repository and carrier of light elements (B, Li, and Be) to depth, its inventory of these elements has hardly been explored and quantified. In order to constrain the systematics and budget of these elements we have studied samples of highly serpentinized (>50%) spinel harzburgite drilled at the Mid-Atlantic Ridge (Fifteen-Twenty Fracture zone, ODP Leg 209, Sites 1272A and 1274A). In-situ analysis by secondary ion mass spectrometry reveals that the B, Li and Be contents of mantle minerals (olivine, orthopyroxene, and clinopyroxene) remain unchanged during serpentinization. B and Li abundances largely correspond to those of unaltered mantle minerals whereas Be is close to the detection limit. The Li contents of clinopyroxene are slightly higher (0.44-2.8 µg/g) compared to unaltered mantle clinopyroxene, and olivine and clinopyroxene show an inverse Li partitioning compared to literature data. These findings along with textural observations and major element composition obtained from microprobe analysis suggest reaction of the peridotites with a mafic silicate melt before serpentinization. Serpentine minerals are enriched in B (most values between 10 and 100 µg/g), depleted in Li (most values below 1 µg/g) compared to the primary phases, with considerable variation within and between samples. Be is at the detection limit. Analysis of whole rock samples by prompt gamma activation shows that serpentinization tends to increase B (10.4-65.0 µg/g), H2O and Cl contents and to lower Li contents (0.07-3.37 µg/g) of peridotites, implying that-contrary to alteration of oceanic crust-B is fractionated from Li and that the B and Li inventory should depend essentially on rock-water ratios. Based on our results and on literature data, we calculate the inventory of B and Li contained in the oceanic lithosphere, and its partitioning between crust and mantle as a function of plate characteristics. We model four cases, an ODP Leg 209-type lithosphere with almost no igneous crust, and a Semail-type lithosphere with a thick igneous crust, both at 1 and 75 Ma, respectively. The results show that the Li contents of the oceanic lithosphere are highly variable (17-307 kg in a column of 1 m * 1 m * thickness of the lithosphere (kg/col)). They are controlled by the primary mantle phases and by altered crust, whereas the B contents (25-904 kg/col) depend entirely on serpentinization. In all cases, large quantities of B reside in the uppermost part of the plate and could hence be easily liberated during slab dehydration. The most prominent input of Li into subduction zones is to be expected from Semail-type lithosphere because most of the Li is stored at shallow levels in the plate. Subducting an ODP Leg 209-type lithosphere would mean only very little Li contribution from the slab. Serpentinized mantle thus plays an important role in B recycling in subduction zones, but it is of lesser importance for Li.