Reduced face preference in infancy: a developmental precursor to callous-unemotional traits?

Background Children with callous-unemotional (CU) traits, a proposed precursor to adult psychopathy, are characterized by impaired emotion recognition, reduced responsiveness to others’ distress, and a lack of guilt or empathy. Reduced attention to faces, and more specifically to the eye region, has been proposed to underlie these difficulties, although this has never been tested longitudinally from infancy. Attention to faces occurs within the context of dyadic caregiver interactions, and early environment including parenting characteristics has been associated with CU traits. The present study tested whether infants’ preferential tracking of a face with direct gaze and levels of maternal sensitivity predict later CU traits. Methods Data were analyzed from a stratified random sample of 213 participants drawn from a population-based sample of 1233 first-time mothers. Infants’ preferential face tracking at 5 weeks and maternal sensitivity at 29 weeks were entered into a weighted linear regression as predictors of CU traits at 2.5 years. Results Controlling for a range of confounders (e.g., deprivation), lower preferential face tracking predicted higher CU traits (p = .001). Higher maternal sensitivity predicted lower CU traits in girls (p = .009), but not boys. No significant interaction between face tracking and maternal sensitivity was found. Conclusions This is the first study to show that attention to social features during infancy as well as early sensitive parenting predict the subsequent development of CU traits. Identifying such early atypicalities offers the potential for developing parent-mediated interventions in children at risk for developing CU traits.

Kinetic resolution of a drug precursor by Burkholderia cepacia lipase immobilized by different methodologies on superparamagnetic nanoparticles

Burkholderia cepacia lipase was immobilized on superparamagnetic nanoparticles using three different methodologies (adsorption, chemisorption with carboxibenzaldehyde and chemisorption with glutaraldehyde) and employed in the kinetic resolution of a chiral drug precursor, (RS)-2-bromo-1-(phenyl)ethanol, via enantioselective acetylation reaction. An excellent improvement of lipase catalytical performance was observed. Free B. cepacia lipase gave the ester (S)-2 with poor E-value <30, and after its immobilization to magnetic nanoparticles the E-value was up to >200. The effect of several reaction parameters in the kinetic resolution was studied. The best results for kinetic resolution were obtained using vinyl acetate as acetyl donor and toluene as solvent, typically yielding the ester in high enantiomeric excess (>99%) and E-value (E > 200). Of the three tested immobilization methods, chemisorption with glutaraldehyde was the best one in terms of temperature stability and yield product. (C) 2010 Elsevier B.V. All rights reserved.

Urea amperometric biosensors based on a multifunctional bipolymeric layer: Comparing enzyme immobilization methods

This paper outlines the results obtained with biosensors designed for urea amperometric detection. The incorporation of urease into a bipolymeric substrate consisting of poly(pyrrole) and poly(5-amino-1-naphthol) was performed through four different approaches: direct adsorption, entrapment in cellulose acetate layer. cross-linking with glutaraldehyde, and also covalent attachment to the polymeric matrix. Poly(pyrrole) acts as amperometric transducer in these biosensors, while poly(5-amino-1-naphthol) drastically reduces the interference signal of agents such as ascorbic and uric acids. The biosensors containing urease covalently attached to the substrate provided interesting results in terms of sensitivity towards urea (0.50 mu A cm(-2) mmol(-1) L), lifetime (20 days) and short response times, due to the enzyme immobilization method used. All biosensors analyzed showed also a wide linear concentration range (up to 100 mmol L(-1)) and low detection limits (0.22-0.58 mmol L(-1)). (C) 2009 Elsevier B.V. All rights reserved.

Synthesis and characterization of mono and polymeric cyclopalladated compounds: Crystal and molecular structure of [{Pd(dmba)(ONO(2))}(2)(mu-pz)] center dot H(2)O (pz = pyrazine)

In the treatment of cyclometallated dimer [Pd(dmba)(mu-Cl)](2) (dmba = N,N-dimethylbenzylamine) with AgNO(3) and acetonitrile the result was the monomeric cationic precursor [Pd(dmba)(NCMe)(2)](NO(3)) (NCMe=acetonitrile) (1). Compound 1 reacted with m-nitroaniline (m-NAN) and pirazine (pz), originating [Pd(dmba)(ONO(2))(m-NAN)] (2) and [{Pd(dmba)(ONO(2))}(2)(mu-pz)] center dot H(2)O (3), respectively. These compounds were characterized by elemental analysis, IR and NMR spectroscopy. The IR spectra of (2-3) display typical bands of monodentade O-bonded nitrate groups, whereas the NMR data of 3 are consistent with the presence of bridging pyrazine ligands. The structure of compound 3 was determined by Xray diffraction analysis. This packing consists of a supramolecular chain formed by hydrogen bonding between the water molecule and nitrato ligands of two consecutive [Pd(2)(dmba)(2)(ONO(2))2(mu-pz)] units. (c) 2008 Elsevier Ltd. All rights reserved.

Nanotechnological delivery systems for the oral administration of active molecules: Polymeric microparticles and microemulsions applied to anti-inflammatory and anti-infectious drugs

This thesis was devoted to the development of innovative oral delivery systems for two different molecules. In the first part, microparticles (MPs) based on xylan and Eudragit® S- 100 were produced and used to encapsulate 5-aminosalicylic acid for colon delivery. Xylan was extracted from corn cobs and characterized in terms of its physicochemical, rheological and toxicological properties. The polymeric MPs were prepared by interfacial cross-linking polymerization and spray-drying and characterized for their morphology, mean size and distribution, thermal stability, crystallinity, entrapment efficiency and in vitro drug release. MPs with suitable physical characteristics and satisfactory yields were prepared by both methods, although the spray-dried systems showed higher thermal stability. In general, spraydried MPs would be preferable systems due to their thermal stability and absence of toxic agents used in their preparation. However, drug loading and release need to be optimized. In the second part of this thesis, oil-in-water microemulsions (O/W MEs) based on mediumchain triglycerides were formulated as drug carriers and solubility enhancers for amphotericin B (AmB). Phase diagrams were constructed using surfactant blends with hydrophiliclipophilic balance values between 9.7 and 14.4. The drug-free and drug-loaded MEs presented spherical non-aggregated droplets around 80 and 120 nm, respectively, and a low polydispersity index. The incorporation of AmB was high and depended on the volume fraction of the disperse phase. These MEs did not reduce the viability of J774.A1 macrophage-like cells for concentrations up to 25 μg/mL of AmB. Therefore, O/W MEs based on propylene glycol esters of caprylic acid may be considered as suitable delivery systems for AmB

Structure and Physical Properties of EVA/Starch Precursor Materials for Foaming Applications

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Synthesis and characterization of mono and polymeric cyclopalladated compounds: Crystal and molecular structure of [{Pd(dmba)(ONO2)}(2)(mu-pz)] center dot H2O (pz = pyrazine)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Nanoindentation mechanical properties characterization of glassy polymeric carbon treated with ion beam

Phenolic resins when heat treated in inert atmosphere up to 1000 degreesC become glassy polymeric carbon (GPC), a chemically inert and biocompatible material useful for medical applications, such as in the manufacture of heart valves and prosthetic devices. In earlier work we have shown that ion bombardment can modify the surface of GPC, increasing its roughness. The enhanced roughness, which depends on the species, energy and fluence of the ion beam, can improve the biocompatibility of GPC prosthetic artifacts. In this work, ion bombardment was used to make a layer of implanted ions under the surface to avoid the propagation of microcracks in regions where cardiac valves should have pins for fixation of the leaflets. GPC samples prepared at 700 and 1500 degreesC were bombarded with ions of silicon. carbon, oxygen and gold at energies of 5, 6, 8 and 10 MeV, respectively, and fluences between 1.0 x 10(13) and 1.0 x 10(16) ions/cm(2). Nanoindentation hardness characterization was used to compare bombarded with non-bombarded samples prepared at temperatures up to 2500 degreesC. The results with samples not bombarded showed that the hardness of GPC increases strongly with the heat treatment temperature. Comparison with ion bombarded samples shows that the hardness changes according to the ion used, the energy and fluence. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Erbium and ytterbium co-doped SiO2 : GeO2 planar waveguide prepared by the sol-gel route using an alternative precursor

The sol-gel method combined with a spin-coating technique has been successfully applied for the preparation of rare-earth doped silica:germania films used for the fabrication of erbium-doped waveguide amplifiers (EDWA), presenting several advantages over other methods for the preparation of thin films. As with other methods, the sol-gel route also shows some drawbacks, such as cracks related to the thickness of silica films and high hydrolysis rate of certain precursors such as germanium alkoxides. This article describes the preparation and optical characterization of erbium and ytterbium co-doped SiO2:GeO2 crack-free thick films prepared by the sol-gel route combined with a spin-coating technique using a chemically stable non-aqueous germanium oxide solution as an alternative precursor. The non-crystalline films obtained are planar waveguides exhibiting a single mode at 1,550 nm with an average thickness of 3.9 mu m presenting low percentages of porosity evaluated by the Lorentz-Lorenz Effective Medium Approximation, and low stress, according to the refractive index values measured in both transversal electric and magnetic polarizations. Weakly confining core layers (0.3% < Delta n < 0.75%) were obtained according to the refractive index difference between the core and buffer layers, suggesting that low-loss coupling EDWA may be obtained. The life time of the erbium I-4(13/2) metastable state was measured as a function of erbium concentration in different systems and based on these values it is possible to infer that the hydroxyl group was reduced and the formation of rare-earth clusters was avoided.

Structural and phenomenological characterization of the thermoreversible sol-gel transition of a zirconyl aqueous precursor modified by sulfuric acid

The thermoreversible sol-gel transition is well-known in biological and organic polymeric systems but has not been reported for inorganic systems. In this paper we put in evidence a thermoreversible sol-gel transition for zirconyl chloride aqueous solutions modified by sulfuric acid in the ratio 3:1 Zr:SO4. The synthesis conditions are detailed and a variety of experimental techniques (turbidimetry, dynamic rheology, and EXAFS) have been employed for investigating the thermal reversibility and the chemical structure of this new material. Turbidimetric measurements performed for solutions containing different concentrations of precursor have evidenced that the sol-gel transformation temperature increases from 50 to 80 degrees C as the concentration of zirconyl chloride decreases from 0.22 to 0.018 mol L-1. A more detailed study has been done for the sample with [Zr] = 0.156 mol L-1, in which the sol-gel-sol transformation has been repeated several times by a cyclic variation of the temperature. The mechanical properties of this sample, evaluated by measuring the storage and the loss moduli, show a change from liquid like to viscoelastic to elastic behavior during the sol-gel transition and vice versa during the gel-sol one. In situ EXAFS measurements performed at the Zr K-edge show that no change of the local order around Zr occurs during the sol-gel-sol transition, in agreement with the concept of physical gel formation. We have proposed for the structure of the precursor an inner core made of hydroxyl and oxo groups bridging together zirconium atoms surrounded in surface by complexing sulfate ligands, the sulfate groups act as a protective layer, playing a key role in the linking propagation among primary particles during sol-gel-sol transition.

Synthesis and characterization of 9.5/65/35 PLZT prepared from the polymeric precursors

The 9.5/65/35 PLZT was prepared from the polymeric precursors (the Pechini and partial oxalate process) and by sintering in two stages in an oxygen atmosphere. After thermal treatment at 400 degreesC, the powders were calcinated and sintered at 1200 degreesC with slow heating and cooling rates. The second stage of sintering consisted of hot pressing at the same temperature in oxygen atmosphere. After calcination of PLZT powders obtained by both methods, as well as after sintering of PLZT obtained by Pechini process, the paraelectric cubic phase was formed. After sintering of PLZT obtained by partial oxalate procedure, small tetragonality of crystal structure was observed. After hot pressing PLZT was pseudocubic. SEM microstructural analyses were carried out of the sintering and hot pressed samples and indicated the small grain size less than 2 mum. (C) 2001 Elsevier B.V. B.V. All rights reserved.

SrTiO3 preparation through coprecipitation methods

Precursor powders to obtain SrTiO3 were prepared by using 8-hydroxyquinoline precipitant agent. The residues from the thermal decomposition, followed by TG/DTG/DTA, were characterized by XRD and it could be verified that the mixed oxides could be obtained varying the thermal decomposition conditions like atmosphere and heating rate. However, the morphology and crystallinity of these residues is highly affected by such variations. (C) 2000 Elsevier B.V. B.V. All rights reserved.

High sinterability of Ca-PZT, synthesized by polymeric and partial oxalate process

This study includes Ca-PZT in the morphotropic phase boundary, MPB process combining the Pechini method, (ZT) and the Partial oxalate method (Ca-PZT) by obtaining single phase particles of ZT phase with a high specific surface area (similar to 110 m(2)/g at 550 degrees C) and narrow particle size distribution. Lead and calcium oxalates were precipitated onto the ZT particle surface and reacted to a solid state interface ZT/Ca-PZT/PbO-CaO. A deviation of a coexistence region from F-T- and F-R-phases to F-R-phase (Zr rich region) was observed. Strong surface area reduction occurs by Ca-PZT crystallization at about 700 degreesC, and demonstrated high sinterability (2.40 m(2)/g - 350 nm) with apparent densities near to 99.9%. Different processing methods did not demonstrate superior results. Studies of calcined powder shows a high sinterability of powder calcined 3 h at 700 degrees C and sintered 3 h at 1000 degreesC coming up to 99.8% of relative density. (C) 2001 Kluwer Academic Publishers.

Synthesis and sintering of ultra fine NaNbO3 powder by use of polymeric precursors

Ultra-fine NaNbO3 powder was prepared by the use of polymeric precursors. X-ray diffraction (XRD) results showed that this niobate nucleates from the amorphous precursor, with no intermediate phases, at low temperature (500°C). Studies by XRD and nitrogen adsorption/desorption showed that powders with high crystallinity ( ≈ 100%) and high surface areas (>20 m2/g) are obtained after calcination at 700°C for 5 h. Compacts of calcined powders showed high sinterability reaching 98% of theoretical density when sintered at 1190°C for 3 h.

A brief discussion about image quality and SEM methods for quantitative fractography of polymer composites

The methodology for fracture analysis of polymeric composites with scanning electron microscopes (SEM) is still under discussion. Many authors prefer to use sputter coating with a conductive material instead of applying low-voltage (LV) or variable-pressure (VP) methods, which preserves the original surfaces. The present work examines the effects of sputter coating with 25 nm of gold on the topography of carbon-epoxy composites fracture surfaces, using an atomic force microscope. Also, the influence of SEM imaging parameters on fractal measurements is evaluated for the VP-SEM and LV-SEM methods. It was observed that topographic measurements were not significantly affected by the gold coating at tested scale. Moreover, changes on SEM setup leads to nonlinear outcome on texture parameters, such as fractal dimension and entropy values. For VP-SEM or LV-SEM, fractal dimension and entropy values did not present any evident relation with image quality parameters, but the resolution must be optimized with imaging setup, accompanied by charge neutralization. © Wiley Periodicals, Inc.