Solid-State Experimental and Theoretical Investigation of the Ammonium Salt of Croconate Violet, a Pseudo-Oxocarbon Ion

The present work describes the crystal structure, vibrational spectra, and theoretical calculations of ammonium salts of 3,5-bis-(dicyanomethylene)cyclopentane-1,2,4-trionate, (NH(4))(2)(C(11)N(4)O(3)) [(NH(4))(2)CV], also known as ammonium croconate violet. This compound crystallizes in triclinic P (1) over bar and contains two water molecules per unit formula. The crystal packing is stabilized by hydrogen bonds involving water molecules and ammonium cations, giving rise to a 3D polymeric arrangement. In this structure, a pi-stacking interaction is not observed, as the smaller centroid-centroid distance is 4.35 angstrom. Ab initio electronic structure calculations under periodic boundary conditions were performed to predict vibrational and electronic properties. The vibrational analysis was used to assist the assignments of the Raman and infrared bands. The solid structure was optimized and characterized as a minimum in the potential-energy surface. The stabilizing intermolecular hydrogen bonds in the crystal Structure were characterized by difference charge-density analysis. The analysis of the density of states of (NH(4))(2)CV gives an energy gap of 1.4 eV with a significant contribution of carbon and nitrogen 2p states for valence and conduction bands.

Uncommon mechanism of egg incubation in the endemic Southern hermit crab Loxopagurus loxochelis: how is this phenomenon related to egg production?

The aim of the present work was to characterize the egg production of Loxopagurus loxochelis. A total of 71 ovigerous females were obtained, 28% of which were simultaneously incubating eggs at different developmental stages. This phenomenon can be the result of incomplete fertilization, or may represent a rapid gonadal cycle by this species in this area, which is, to our understanding, the best explanation of this phenomenon. Egg volume decreased 25.6% during the incubation period. The reproductive output based on dry and wet weight was 6.8 and 19.3%, respectively. Water was the prevailing component of the eggs, representing 86.0% of the total weight at initial stage, increasing to 95.1% at the final stage. Ash content increased at the same time as a decrease in the organic content occurred, indicating the consumption of yolk and absorption of salts from the water medium. In conclusion, we hypothesized that this population has the capacity to copulate and deposit another brood even before the release of the larvae from the previous one, intensifying the reproductive effort of these hermit crabs as a strategy of adaptation in a region considered the northern limit of the geographical distribution of this species.

Iron Fortification Strategies for the Control of Childhood Anemia in Brazil

This article presents data on the fortification of foods, necessary as an important public health approach for the success in reducing anemia. The use of food vehicles, iron salts and their costs, as well as recent work on iron fortification of foods in Brazil are reviewed. Recent research serves as a cornerstone for countries that attempt to implement permanent, long-lasting iron fortification programs aimed at the prevention of anemia considering cultural habits, type of iron salts and at-risk groups.

Characterization of a chromium-rich tannery waste and its potential use in ceramics

Leather industries which promote hide stabilization by the conventional chrome-tanning process are a major source of pollution because of the resultant chromium-rich wastes. In this work, an extensive characterization of such a chromium-rich waste sludge is presented, regarding its chemical composition (XRF), crystalline phase contents (XRD), organic carbon content (TOC), thermal behavior by thermogravimetry (TG) and differential scanning calorimetry (DSC), as well as its stability under chemical attack (the concentration of important ions in the leachates being determined by capillary electrophoresis) and when submitted to temperatures as high as 1100 degrees C, in air. The material showed the tendency to produce some undesirable, and previously non-detected hexavalent chromium when exposed to high temperatures, but after washing off the soluble salts and the elimination of the organic matter by firing, the resultant material was succesfully tested as a ceramic pigment in a conventional glaze composition usually employed in the ceramic the industry. (C) 2009 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Postembryonic Development of Rectal Pads in Bees (Hymenoptera, Apidae)

The morphology and development of the digestive tract of insects has been extensively studied, but little attention has been given to the development of the rectal pads. These organs are responsible for absorption of water and salts. In insects where they occur, there are usually six ovoid rectal pads located in the medial-anterior portion of the rectum. The rectal pad has three types of cells: principal, basal, and junctional. The arrangement of these three cell types delimits an intrapapillary lumen. The aim of the current study is to describe the development of the rectal pads during postembryonic development of Melipona quadrifasciata anthidioides and Melipona scutellaris. Specimens were analyzed at the following developmental stages: white-, pink-, brown-, and black-eyed pupae, and adult workers. The development of the rectal pad begins as a thickening of the epithelium in white-eyed pupae at 54 hr. At this stage, there is neither a basal cell layer nor intrapapillary lumen. The basal layers begin to form in the pink-eyed pupa and are completely formed at the end of the development of the brown-eyed pupa. In the brown-eyed pupal stage, the intrapapillary lumen is formed and the junctional cells are positioned and completely differentiated. Necrotic and apoptotic cell death were detected along with cell proliferation in the whole rectum during pupal development, suggesting that the development of the rectal pads involves cell proliferation, death, and differentiation. The rectal pads originate only from the ectoderm. Anat Rec, 292:1602-1611, 2009. (C) 2009 Wiley-Liss, Inc.

Effect of Iron on Matrix Metalloproteinase Inhibition and on the Prevention of Dentine Erosion

It is known that some metal salts can inhibit matrix metalloproteinase (MMP) activity, but the effect of iron has not been tested yet. On the other hand, it has recently been suggested that MMP inhibition might influence dentine erosion. Based on this, the aims of this study were: (1) to test in vitro the effect of FeSO(4) on MMP-2 and -9 activity, and (2) to evaluate in situ the effect of FeSO(4) gel on dentine erosion. MMP-2 and -9 activities were analysed zymographically in buffers containing FeSO(4) in concentrations ranging between 0.05 and 1.5 mmol/l or not. Volunteers (n = 10) wore devices containing bovine dentine blocks (n = 60) previously treated with the following gel treatments: FeSO(4) (1 mmol/l FeSO(4)), F (NaF 1.23%; positive control) and placebo (negative control). The gels were applied once and removed after 1 min. Erosion was performed extraorally with Coca-Cola 4 times per day for 5 min over 5 days. Dentine wear was evaluated by profilometry. The data were analysed by Kruskal-Wallis and Dunn`s tests (p < 0.05). FeSO(4) inhibited both MMP-2 (IC(50) = 0.75 mmol/l) and MMP-9 (IC(50) = 0.50 mmol/l) activities. In the in situ experiment, the mean wear (+/- SD) found for the F gel (0.79 8 +/- 0.08 mu m) was significantly reduced in more than 50% when compared to the placebo gel (1.77 +/- 0.33 mu m), but the FeSO(4) gel completely inhibited the wear (0.05 +/- 0.02 mu m). Since FeSO(4) was able to inhibit MMP in vitro, it is possible that the prevention of dentine wear by the FeSO(4) gel in situ might be due to MMP inhibition, which should be investigated in further studies. Copyright (C) 2010 S. Karger AG, Basel

Immunological parameters related to the adjuvant effect of the ordered mesoporous silica SBA-15

In 2006, the first report of a nanostructured material as adjuvant was described establishing the effectiveness of the ordered mesoporous SBA-15 silica as an immune adjuvant. The present study evaluated the SBA-15 capacity to modulate the immune responsiveness of High and Low responder mice immunized with BSA encapsulated/adsorbed in SBA-15 by the intramuscular or oral route and the adjuvant effect was compared with the responsiveness induced by BSA in aluminum hydroxide salts or emulsified in Incomplete Freund adjuvant. These results demonstrate the ability of the non-toxic SBA-15 nanoparticles to increase the immunogenicity and repair the responsiveness of the constitutively low responder individuals inducing both the IgG2a and the IgG1 isotypes, independently of the immune cell committed and conditioning the low phenotype. This new adjuvant may reveal novel therapeutic targets for immune modulation and vaccine design. (C) 2010 Elsevier Ltd. All rights reserved.

Synthesis and characterization of NiMn(2)O(4) nanoparticles using gelatin as organic precursor

Nanoparticles of NiMn(2)O(4) were successfully obtained by mixing gelatin and inorganic salts NiCl(2) center dot 6H(2)O and MnCl(2) center dot 4H(2)O in aqueous solution. The mixture has been synthesized at different temperatures and resulted in NiMn(2)O(4) nanoparticles with crystallites size in the range of 14-44 nm, as inferred from X-ray powder diffraction (XRPD) data. We have also observed that both the average crystallite size and the unit cell parameters increase with increasing synthesis temperature. Magnetic measurements confirmed the presence of a magnetic transition near 110K. (C) 2008 Published by Elsevier B.V.

Magnetic Fluids Based on gamma-Fe(2)O(3) and CoFe(2)O(4) Nanoparticles Dispersed in Ionic Liquids

The disclosure of magnetic ionic liquids (MILs) as stable dispersions of surface modified gamma-Fe(2)O(3) or CoFe(2)O(4) nanoparticles (NPs) in the 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMIBF(4)) ionic liquid is reported. The magnetic NPs were characterized by X-ray powder diffraction, transmission electron microscopy, and Raman spectroscopy. The surface modified NPs have proved to form stable dispersions in BMIBF(4) in the absence of water and behave like a magnetic ionic liquid. The MILs have been characterized by Raman spectroscopy, magnetic measurements, and DSC. The stability of the magnetic NPs in BMIBF(4) is consistently explained by assuming the formation of a semiorganized protective layer composed of supramolecular aggregates in the form of [(BMI)(2)(BF(4))(3)](-). A superparamagnetic behavior and saturation magnetization of ca. 18 emu/g for a sample containing 30% w/w maghemite NPs/BMIBF(4) have been inferred from static and dynamic magnetic measurements. DSC results have shown that the MIL composed of 30% w/w CoFe(2)O(4) NPs/BMIBF(4) remains a liquid phase down to -84 degrees C.

Influence from the sulfonate group (RSO(3)(-)) on the conversion process and emission efficiency of poly(p-phenylene vinylene)

The discovery of an alternative route to convert poly(xylyliden tetrahydrothiophenium chloride) (PTHT) into poly(p-phenylene vinylene) (PPV) using dodecylbenzenesulfonate (DBS) has allowed the formation of ultrathin films with unprecedented control of architecture and emission properties. In this work, we show that this route may be performed with several sufonated compounds where RSO(3)(-) replaces the counter-ion (Cl(-)) of PTHT, some of which are even more efficient than DBS. Spin-coating films were produced from PTHT and azo-dye molecules, an azo-polymer and organic salts as counter-ions of PTHT. The effects of the thermal annealing step of PTHT/RSO(3)(-) films at 110 and 230 degrees C were monitored by measuring the absorption and emission spectra. The results indicate that the exchange of the counterion Cl(-) of PTHT by a linear long chain with RSO(3)(-) group is a general procedure to obtain PPV polymer at lower conversion temperature (ca. 110 degrees C) with significant increase in the emission efficiency, regardless of the chemical position and the number of sulfonate groups. With the enhanced emission caused by Congo Red and Tinopal as counter-ions, it is demonstrated that the new synthetic route is entirely generic, which may allow accurate control of conversion and emission properties. (C) 2010 Elsevier B.V. All rights reserved.

Crystal Engineering of an Anti-HIV Drug Based on the Recognition of Assembling Molecular Frameworks

A rational strategy was employed for design of an orthorhombic structure of lamivudine with maleic acid. On the basis of the lamivudine saccharinate structure reported in the literature, maleic acid was chosen to synthesize a salt with the anti-HIV drug because of the structural similarities between the salt formers. Maleic acid has an acid-ionization constant of the anti first proton and an arrangement of their hydrogen bonding functionalities similar to those of saccharin. Likewise, there is a saccharin-like conformational rigidity in maleic acid because of the hydrogen-bonded ring formation and the Z-configuration around the C=C double bond. As was conceivably predicted, lamivudine maleate assembles into a structure whose intermolecular architecture is related to that of saccharinate salt of the drug. Therefore, a molecular framework responsible for crystal assembly into a lamivudine saccharinate-like structure could be recognized in the salt formers. Furthermore, structural correlations and structure-solubility relationships were established for lamivudine maleate and saccharinate. Although there is a same molecular framework in maleic acid and saccharin, these salt formers are Structurally different in some aspects. When compared to saccharin, neither out-of-plane SO(2) oxygens nor a benzene group occur in maleic acid. Both features could be related to higher solubility of lamivudine maleate. Here, we also anticipate that multicomponent molecular crystals of lamivudine with other salt formers possessing the molecular framework responsible for crystal assembly can be engineered successfully.

Two New Supramolecular Assemblies Obtained by Reaction Between Saccharin and Long-chain Diamines

The crystal Structures of heptamethylenediammonium bis(saccharinate) monohydrate, [H(3)N-(CH(2))(7)-NH(3)](sac)(2)center dot H(2)O (1) 0 (1) and octamethylenediammonium bis(saccharinate) hemihydrate, [H(3)N-(CH(2))(8)-NH(3)](sac)(2)center dot 0.5H(2)O (2), were determined-by single-crystal X-ray diffraction methods. Compound I crystallizes in the triclinic space group P (1) over bar with 2 molecules per unit cell, and 2 in the monoclinic space group P2(1)/a with Z = 4. The saccharinate moiety is planar in both compounds presenting bonding characteristics comparable to those found in other saccharinate salts. The ionic crystals are further stabilized by an extensive H-bonding network, which links the anions and cations into an infinite three-dimensional Supramolecular assembly. The FTIR spectra of the adducts are briefly discussed in comparison with those of the constituent Molecules.

Acanthoscurrin Fragment 101-132: Total Synthesis at 60 degrees C of a Novel Difficult Sequence

Glycine-rich proteins (GRP), serve a variety of biological functions. Acanthoscurrin is an antimicrobial GRP isolated front hemocytes-of the Brazilian spider Acanthoscurria gomesiana. Aiming to contribute to the knowledge of the secondary structure and stepwise solid-phase synthesis of GRPs` glycine-rich domains, we attempted to prepare G(101)GGLGGGRGGGYG(113) GGGGYGGGYG(123)GGy(126)GGGKYK(132)-NH(2), acanthoscurrin C-terminal amidated fragment. Although a theoretical prediction did not indicate high aggregation potential for this peptide, repetitive incomplete aminoacylations were observed after incorporating Tyr(126) to the growing peptide-MBHA resin (Boc chemistry) at 60 degrees C. The problem was not solved by varying the coupling reagents or solvents, adding chaotropic salts to the reaction media or changing the resin/chemistry (Rink amide resin/Fmoc chemistry). Some improvement was mode when CLEAR amide resin (Fmoc chemistry) was 32 used, as it allowed for obtaining fragment (G(113)-K(132) NIR-FT-Raman spectra collected for samples of the growing peptide-MBHA, -Rink amide resin and -CLEAR amide resin revealed the presence of beta-sheet structures. Only the combination of CLEAR-amide resin, 60 degrees C, Fmoc-(Fmoc-Hmb)Gly-OH and LiCl (the last two used alternately) was able to inhibit the phenomenon, as proven by NIR-FT-Raman analysis of the growing peptide-resin, allowing the total synthesis of desired 132 fragment Gly(101)-K(132). In summary, this work describes a new difficult sequence, contributes to understanding stepwise solid-phase synthesis of this type of peptide and shows that, at least while protected and linked to a resin, this GRPs glycine-rich motif presents all early tendency to assume beta-sheet structures. (c) 2008 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 92: 65-75, 2009.

Diphtheria toxoid conformation in the context of its nanoencapsulation within liposomal particles sandwiched by chitosan

Chitosan (alpha alpha-(1-4)-amino-2-deoxy-beta beta-D-glucan) is a deacetylated form of chitin, a polysaccharide from crustacean shells. Its unique characteristics, such as positive charge, biodegradability, biocompatibility, nontoxicity, and rigid structure, make this macromolecule ideal for an oral vaccine delivery system. We prepared reverse-phase evaporation vesicles (REVs) sandwiched by chitosan (Chi) and polyvinylic alcohol (PVA). However, in this method, there are still some problems to be circumvented related to protein stabilization. During the inverted micelle phase of protein nanoencapsulation, hydrophobic interfaces are expanded, leading to interfacial adsorption, followed by protein unfolding and aggregation. Here, spectroscopic and immunological techniques were used to ascertain the effects of the Hoffmeister series ions on diphtheria toxoid (Dtxd) stability during the inverted micelle phase. A correlation was established between the salts used in aqueous solutions and the changes in Dtxd solubility and conformation. Dtxd alpha alpha-helical content was quite stable, which led us to conclude that encapsulation occurred without protein aggregation or without exposition of hydrophobic residues. Dtxd aggregation was 98% avoided by the kosmotropic, PO

Surface Activity of the Triflate Ion at the Air/Water Interface and Properties of N,N,N-Trimethyl-N-Dodecylammonium Triflate Aqueous Solutions

The surface activity of salts added to water is Air orders of magnitude lower than that of surfactants. Sodium trifluoromethanesulfonate (NaTf) produced a change in surface tension. with concentration, Delta gamma/Delta c, of -13.2 mN.L/m.mol. This value is ca. 4-fold larger than those of simple salts and that of methanesulfonate. This unexpected surface effect suggested that positively charged micelles containing Tf could exhibit interesting properties. Dodecyltrimethylammonium triflate (DTATf) had a higher Kraft temperature (37 degrees C) and a lower cmc (5 x 10(-3)M) and degree of dissociation (0.11) than the chloride and bromide salts of DTA. Above the Kraft temperature, at a characteristic temperature t(1), the addition of NaTf above 0.05 M. to a DTATf solution induced phase separation. By increasing the temperature of the two-phase system to above t(1), a homogeneous, transparent solution was obtained at a characteristic temperature t(2). These results, together with well-known triflate properties, led us to suggest that the Tf ion pairs With DTA and that the -CF(3) group may be dehydrated in the interfacial region, resulting in new and interesting self-aggregated structures.