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.

Galaxy threshing and the origin of intracluster stellar objects

We numerically investigate the dynamical evolution of non-nucleated dwarf elliptical/spiral galaxies (dE) and nucleated ones (dE,Ns) in clusters of galaxies in order to understand the origin of intracluster stellar objects, such as intracluster stars (ICSs), GCs (ICGCs), and ultracompact dwarfs (UCDs) recently discovered by all-object spectroscopic survey centred on the Fornax cluster of galaxies. We find that the outer stellar components of a nucleated dwarf are removed by the strong tidal field of the cluster, whereas the nucleus manages to survive as a result of its initially compact nature. The developed naked nucleus is found to have physical properties (e.g., size and mass) similar to those observed for UCDs. We also find that the UCD formation process, does depend on the radial density profile of the dark halo in the sense that UCDs are less likely to be formed from dwarfs embedded in dark matter halos with central 'cuspy' density profiles. Our simulations also suggest that very massive and compact stellar systems can be rapidly and efficiently formed in the central regions of dwarfs through the merging of smaller GCs. GCs initially in the outer part of dE and dE,Ns are found to be stripped to form ICGCs.

New porphyrins tailored as biodiesel fluorescent markers

This work reports the synthesis, characterization, and evaluation of new porphyrins tailored to become biodiesel fluorescent markers. The compounds were obtained by the synthetic modification of the commercially available porphyrin 5,10,15,20-meso-tetrakis(pentafluorophenyl)porphyrin (TPPF(20)) using ethanol and hexadecan-1-ol (cetylic alcohol) as nucleophilic reagents. The stability of the marked biodiesel fuel solutions was investigated every 15 days for a total period of 3 months, and under different storage temperature and light exposure condition, simulating the conventional stock conditions. The influence of the different substituents of the porphyrins on the fluorescence properties of the biodiesel fuel markers was also assessed. The resulting porphyrins were highly soluble in biodiesel fuel and displayed strong fluorescence characterized by two strong emission bands. The fluorescent markers did not affect the biodiesel physical properties and were stable in storage conditions for at least 3 months at a concentration of 4 ppm. The best storage condition was found to be absence of light and 6 degrees C; the limit of detection by photoluminescence technique had magnitude of 10(-13) mol L(-1). The synthesized porphyrins were characterized by nuclear magnetic resonance ((1)H-NMR and (19)F-NMR), mass spectrometry (HRMS), ultraviolet visible absorption spectroscopy, and photoluminescence spectroscopy. (C) 2011 Elsevier Ltd. All rights reserved.

Photoacoustic investigation of maghemite-based BSA nanocomposite

Maghemite-based bovine serum albumin (BSA) nanocomposites have been investigated using photoacustic spectroscopy (PAS). Features in the PAS spectra were analyzed in terms of three bands (band-C, band-S, and band-L). Though the observed PAS peak positions are insensitive to the nanoparticle concentration the PAS peak intensity displays a different behaviour. For band-C the PAS intensity scales almost linearly with the nanoparticle concentration in the hosting template. Nevertheless, it was found that the PAS intensity of band-L scales sub-linearly with the nanoparticle concentration.

Luminescent and morphological study of Sr(2)CeO(4) blue phosphor prepared from oxalate precursors

Luminescent and morphological studies of Sr(2)CeO(4) blue phosphor prepared from cerium-doped strontium oxalate precursor are reported Powder samples were prepared from 5 and 25 mol% Ce(3+)-doped strontium oxalate as well as from a mechanical mixture of strontium oxalate and cerium oxalate at a 4 1 ratio respectively All the samples were characterized by XRD IR PLS and SEM The luminescent and structural properties of the Sr(2)CeO(4) material are little affected by the SrCO(3) remaining from precursors The Sr(2)CeO(4) material consists in one-dimensional chains of edge-sharing CeO(6) octahedra that are linked together by Sr(2+) ions The carbonate ion might be associated with oxygen ions of the linear chain and also with the oxygen atoms located in the equatorial position which consequently affects the charge transfer bands between O(2-) and Ce(4+). As observed by SEM, the morphological changes are related to each kind of precursor and thermal treatment along with irregular powder particles within the size range 05-2 mu m (c) 2010 Elsevier B V All rights reserved

Syntheses, electrochemistry and photophysical properties of a series of meso-pyridylpentafluorophenylporphyrins

This work presents the synthesis and characterization of a series of substituted pyridylpentafluroporphyrins, including the separation of the cis- and trans-isomers, the latter being characterized by X-ray crystallography. The spectroscopic and electrochemical properties of the series are dependent on the number of electron withdrawing pentafluorophenyl substituent, but they do not depend on the symmetry of the molecule. Ongoing from the monosubstituted to the more substituted pentafluorophenyl porphyrin H(2)(MPyTFPP) derivative, the Soret bands are slightly red-shifted and their quantum fluorescence yields range from 0.035 to 0.046, consistent with the value of 0.045 for the fully substituted 5,10,15,20-tetrapentafluorophenylporphyrin (dichloromethane solutions). The redox potentials of the reductive processes of monoanion and dianion formation are also sensitive to the number of pentafluoro substituents, shifting 180 mV to more positive values for the P(0)/P(-1) process ongoing from the monopentafluoro to the tris-pentafluorophenyl substituted derivative.

Synthesis, characterization and electrochemical behavior of the vanadium pentoxide/cetyl pyridinium chloride hybrid material

In situ and ex situ studies concerning the new hybrid material vanadium pentoxide xerogel in the presence of the cationic surfactant cetyl pyridinium chloride (V(2)O(5)/CPC) are presented. The in situ characterization studies revealed the presence of a lamellar structure for the V(2)O(5)/CPC hybrid material. The intercalation reaction was evidenced on the basis of the increase in the d-spacing as well as the displacement of the infrared bands toward lower energy levels. Electrochemical studies comprising the cyclic voltammetry and the electrochemical impedance spectroscopy techniques showed that the behavior of the hybrid material is considerably influenced by the electrolyte composition. The ion insertion/de-insertion into the V(2)O(5) xerogel structure accompanying the charge transfer process is influenced by the solid-state diffusion process modeled by using the finite-space Warburg element.

Jacobsen catalyst immobilized on chitosan membrane as interface catalyst in organic/aqueous system for alkene oxidation

The Jacobsen catalyst, Mn(salen), was immobilized in chitosan membrane. The obtained Mn(salen)-Chit was characterized by thermogravimetric analysis (TC), differential thermal analysis (DTA), differential scanning calorimetry (DSC), infrared spectroscopy (FT-IR), degree of N-acetylation by (1)H NMR, and UV-vis spectroscopy. The UV-vis absorption spectrum of the encapsulated catalyst displayed the typical bands of the Jacobsen catalyst, and the FT-IR presented an absorption band characteristic of the imines present in the Jacobsen catalyst. The chitosan membranes were available, in a biphasic system, as a catalytic barrier between two different phases: an organic substrate phase (cyclooctene or styrene) and an aqueous solution of either m-CPBA, t-BuOOH or H(2)O(2), and dismissing the need for phase transfer agents and leading to better product yields compared with the catalyst in homogeneous medium. This new catalyst did not leach from the support and was reused many times, leading to high turnover frequencies. (C) 2009 Elsevier B.V. All rights reserved.

Solvent Effects in Optical Spectra of ortho-Aminobenzoic Acid Derivatives

We investigated three amino derivatives of ortho-aminobenzoic or anthranilic acid (o-Abz): a) 2-Amino-benzamide (AbzNH(2)); b) 2-Amino-N-methyl-benzamide (AbzNHCH(3)) and c) 2-Amino-N-N`-dimethyl-bezamide (AbzNH(CH(3))(2)), see Scheme 1. We describe the results of ab-initio calculations on the structural characteristics of the compounds and experimental studies about solvent effects in their absorption and steady-state and time-resolved emission properties. Ab-initio calculations showed higher stability for the rotameric conformation in which the oxygen of carbonyl is near to the nitrogen of ortho-amino group. The derivatives present decrease in the delocalization of pi electron, and absorption bands are blue shifted compared to the parent compound absorption, the extent of the effect increasing from to Abz-NH(2) to Abz-NHCH(3) Abz-NH(CH(3))(2). Measurements performed in several solvents have shown that the the dependence of Stokes shift of the derivatives with the orientational polarizability follows the Onsager-Lippert model for general effects of solvent. However deviation occurred in solvents with properties of Bronsted acids, or electron acceptor characteristics, so that hydrogen bonds formed with protic solvents predominates over intramolecular hydrogen bond. In most solvents the fluorescence decay of AbzNH(2) and AbzNHCH(3) was fitted to a single exponential with lifetimes around 7.0 ns and no correlation with polarity of the solvent was observed. The fluorescence decay of AbzN(CH(3))(2) showed lifetimes around 2.0 ns, consistent with low quantum yield of the compound. The spectroscopic properties of the monoamino derivative AbzNHCH(3) are representative of the properties presented by Abz labelled peptides and fatty acids previously studied.

A new species of Phylloicus Muller, 1880 (Trichoptera: Calamoceratidae), from southeastern Brazil, including descriptions of larval and pupal stages

The cosmopolitan family Calamoceratidae Ulmer, 1906, has 8 living genera, among them Phylloicus Muller, 1880, with species distributed from South to Central America. This genus is characterized by its dark-colored adults (brown to black) with diurnal to crepuscular habits. In this paper, the adults, pupae, and larvae of Phylloicus camargoi n. sp. are described and illustrated. The new species is easily diagnosed by male tergum X bearing a short, digitate, setose, basodorsal process; 2 short, digitate, hairless, lateral processes; and 2 pairs of very short processes on the posterior margin: a pair of digitate, hairless, posterolateral processes, and a pair of posteromesal processes. Additional diagnostic characters are the presence of 3 color bands on the forewings, 2 golden longitudinal bands and a white transversal one.

Two novel reports of semidry stigmatic surface in Asteraceae

Research documents related to the morphology and function of style branches and stigmatic surface of Asteraceae are still rather few, and the literature reports are thus controversial. We report in the present study that the stigmatic surfaces of two non-related species of Asteraceae (Lessingianthus grandiflorus and Lucilia lycopodioides) have features of semidry stigmas. Sporodermis of both species was also analyzed so that we could understand how the stigmatic surface works during pollen deposition and rehydration. Stylar branches and pollen grains (sporodermis) were studied using scanning and transmission electron microscopy (SEM and TEM) and histochemistry techniques. The inner and marginal bands of stylar branches in these species display intermediary features between the dry and wet types of stigma: the cuticle characterizes the dry stigma and cells with secretory activity characterize the wet stigma; these showed differences from what has been described to the Asteraceae family, where stigmatic surface of species from several tribes is considered dry. Pollen grains are medium-size to large with exine ornamentation (echinate and echinolophate) and abundant secretion which latter characterizes pollenkitt. We can assume that two processes might help pollen grain hydration on stigmatic surface in Lessingianthus grandiflorus and Lucilia lycopodioides: (1) the presence of pollenkitt, as observed in the secretory content inside exine cavities and around pollen grains; and (2) the secretory activity of stigmatic surface cells, whose secretion accumulates among intercellular and subcuticular spaces and leads to cuticle disruption during the floral receptive phase. Our results suggest that ultrastructural and histochemical studies should be considered when describing stigmatic surface and that the ""semidry"" feature within Asteraceae should be investigated still more in detail, so that the taxonomic or adaptation value of this trait in the family can be verified. (C) 2010 Elsevier GmbH. All rights reserved.

Adsorption of phenylalanine on layered double hydroxides: effect of temperature and ionic strength

In this work we report the adsorption of phenylalanine (Phe) on Magnesium Aluminum Layered Double Hydroxides (Mg-Al-CO(3)-LDH) at two different temperatures (298 and 310 K) and under two distinct ionic strength conditions (with and without the addition 0.1 M of NaCl). The adsorption isotherms exhibit the same profile in all conditions, and they only differ in the amount of removed Phe. At lower ionic strength, the isotherms are almost identical at both temperatures, except for the last points, where the increase in temperature causes a decrease in the amount of adsorbed Phe. An increase in ionic strength results in a decrease in Phe adsorption. The electrokinetic potential decreases as the amount of adsorbed Phe increases, and only positive values are observed. This indicates that the surface of the adsorbent is not totally neutralized and suggests that more Phe could be removed by adsorption. The presence of Phe on the solid is confirmed by FTIR spectra, which present the specific bands assigned to Phe. The hydrophobicity of the amino acid probably contributes to its extraction, thus enabling the removal of a great amount of Phe. In conclusion, LDH is potentially applicable in the removal of Phe from wastewater.

Prostatic Artery Embolization as a Primary Treatment for Benign Prostatic Hyperplasia: Preliminary Results in Two Patients

Symptomatic benign prostatic hyperplasia (BPH) typically occurs in the sixth and seventh decades, and the most frequent obstructive urinary symptoms are hesitancy, decreased urinary stream, sensation of incomplete emptying, nocturia, frequency, and urgency. Various medications, specifically 5-alpha-reductase inhibitors and selective alpha-blockers, can decrease the severity of the symptoms secondary to BPH, but prostatectomy is still considered to be the traditional method of management. We report the preliminary results for two patients with acute urinary retention due to BPH, successfully treated by prostate artery embolization (PAE). The patients were investigated using the International Prostate Symptom Score, by digital rectal examination, urodynamic testing, prostate biopsy, transrectal ultrasound (US), and magnetic resonance imaging (MRI). Uroflowmetry and postvoid residual urine volume complemented the investigation at 30, 90, and 180 days after PAE. The procedure was performed under local anesthesia; embolization of the prostate arteries was performed with a microcatheter and 300- to 500-mu m microspheres using complete stasis as the end point. One patient was subjected to bilateral PAE and the other to unilateral PAE; they urinated spontaneously after removal of the urethral catheter, 15 and 10 days after the procedure, respectively. At 6-month follow-up, US and MRI revealed a prostate reduction of 39.7% and 47.8%, respectively, for the bilateral PAE and 25.5 and 27.8%, respectively, for the patient submitted to unilateral PAE. The early results, at 6-month follow-up, for the two patients with BPH show a promising potential alternative for treatment with PAE.

Effects of Si content on defect band formation in hypoeutectic Al-Si die castings

Al-3-11% Si alloys have been high-pressure die-cast and characterized microstructurally. Alstruc was used to calculate the solidification characteristics and fraction of eutectic. Defect bands were observed at all Si contents, although their constitution, position and distinctiveness were a function of Si content. The defect bands contain a higher fraction Al-Si eutectic than the surroundings in all alloys, and porosity was additionally found in the band in AlSi3. With decreasing Si content, the defect bands formed closer to the casting surface, became more prevalent and also the width of the bands decreased. These differences are discussed by considering the effect of Si content on the distribution of solid in the mushy wall layers and on the feeding potentials of the alloys. The observations are consistent with the mechanism proposed by Gourlay et al. in which bands form due to deformation within the solidifying mushy wall layers. (c) 2005 Elsevier B.V. All rights reserved.

Collagen and Elastic Content of Abdominal Skin After Surgical Weight Loss

Collapsed skin folds after bariatric weight loss are often managed by plastic procedures, but changes in dermal composition and architecture have rarely been documented. Given the potential consequences on surgical outcome, a prospective histochemical study was designed. The hypothesis was that a deranged dermal fiber pattern would accompany major changes in adipose tissue. Female surgical candidates undergoing postbariatric abdominoplasty (n = 40) and never obese women submitted to control procedures (n = 40) were submitted to double abdominal biopsy, respectively in the epigastrium and hypogastrium. Histomorphometric assessment of collagen and elastic fibers was executed by the Image Analyzer System (Kontron Electronic 300, Zeiss, Germany). Depletion of collagen, but not of elastic fibers, in cases with massive weight loss was confirmed. Changes were somewhat more severe in epigastrium (P = 0.001) than hypogastrium (P = 0.007). Correlation with age did not occur. (1) Patients displayed lax, soft skin lacking sufficient collagen fiber network. (2) Elastic fiber content was not damaged, and was even moderately increased in epigastrium; (3) Preoperative obesity negatively correlated with hypogastric collagen concentration; (4) Future studies should pinpoint the roles of obesity, and especially of massive weight loss, on dermal architecture and response to surgery.