Enthalpies of Solution of 1-Butyl-3-methylimidazolium Tetrafluoroborate in 15 Solvents at 298.15 K

Enthalpies of solution of 1-butyl-3-methylimidazolium tetra fluoroborate, [BMIm]BF4, are reported at 298.15 K in a set of 15 hydrogen bond donor and hydrogen bond acceptor solvents, chosen by their diversity, namely, water, methanol, ethanol, 1,2-ethanediol, 2-choroethanol, 2-methoxyethanol, formamide, propylene carbonate, nitromethane, acetonitrile, dimethyl sulfoxide, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, and aniline. These values are shown to be largely independent of [BMIm]BF4 concentration. The obtained enthalpies of solution vary from very endothermic to quite exothermic, thus showing a very high sensitivity of the enthalpies of solution of [BMIm]BF4 to solvent properties. Solvent effects on the solution process of this IL are analyzed by a quantitative structure-property relationship methodology, using the TAKA equation and a modified equation, which significantly improves the model's predictive ability. The observed differences in the enthalpies of solution are rationalized in terms of the solvent properties found to be relevant, that is, pi* and E-T(N).

More than maternal sensitivity shapes attachment : infant coping and temperament

The aim of this longitudinal studywas to investigate the effect of a set of factors from multiple levels of influence: infant temperament, infant regulatory behavior, and maternal sensitivity on infant’s attachment. Our sample consisted of 48 infants born prematurely and their mothers. At 1 and 3 months of age, mothers described their infants’behavior using the Escala de Temperamento do Beb´e. At 3 months of age, infants’ capacity to regulate stress was evaluated during Tronick’s Face-to-Face Still-Face (FFSF) paradigm. At 9 months of age, mothers’ sensitivity was evaluated during free play using the CARE-Index. At 12 months of age, infants’ attachment security was assessed during Ainsworth’s Strange Situation. A total of 16 infants were classified as securely attached, 17 as insecure-avoidant, and 15 as insecure-resistant. Mothers of securely attached infantswere more likely than mothers of insecure infants to describe their infants as less difficult and to be more sensitive to their infants in free play. In turn, secure infants exhibited more positive responses during the Still-Face. Infants classified as insecureavoidant were more likely to self-comfort during the Still-Face and had mothers who were more controlling during free play. Insecure-resistant exhibited higher levels of negative arousal during the Still-Face and had mothers who were more unresponsive in free play. These findings show that attachment quality is influenced bymultiple factors, including infant temperament, coping behavior, and maternal sensitivity.

Synthesis and structural characterization of iron complexes with 2,2,2-tris(1-pyrazolyl)ethanol ligands: Application in the peroxidative oxidation of cyclohexane under mild conditions

The reactions of FeCl2 center dot 2H(2)O and 2,2,2-tris(1-pyrazolyl) ethanol HOCH2C(pz)(3) (1) (pz = pyrazolyl) afford [Fe{HOCH2C(pz)(3)}(2)][FeCl4]Cl (2), [Fe{HOCH2C(pz)(3)}(2)](2)[Fe2OCl6](Cl)(2)center dot 4H(2)O (3 center dot 4H(2)O), [Fe{HOCH2C(pz)(3)}(2)] [FeCl{HOCH2C(pz)(3)}(H2O)(2)](2)(Cl)(4) (4) or [Fe{HOCH2C(pz)(3)}(2)]Cl-2 (5), depending on the experimental conditions. Compounds 1-5 were isolated as air-stable crystalline solids and fully characterized, including (1-4) by single-crystal X-ray diffraction analyses. The latter technique revealed strong intermolecular H-bonds involving the OH group of the scorpionate 2 and 3 giving rise to 1D chains which, in 3, are further expanded to a 2D network with intercalated infinite and almost plane chains of H-interacting water molecules. In 4, intermolecular pi center dot center dot center dot pi interactions involving the pyrazolyl rings are relevant. Complexes 2-5 display a high solubility in water (S-25 degrees C ca. 10-12 mg mL(-1)), a favourable feature towards their application as catalysts (or catalyst precursors) for the peroxidative oxidation of cyclo-hexane to cyclohexanol and cyclohexanone, with aqueous H2O2/MeCN, at room temperature (TON values up to ca. 385). (C) 2011 Elsevier B. V. All rights reserved.

Synthesis of optimization of [11C] Pittsburgh compound B by the captive solvent method

Mestrado em Medicina Nuclear.

Pyrazole or tris(pyrazolyl)ethanol oxo-vanadium(IV) complexes as homogeneous or supported catalysts for oxidation of cyclohexane under mild conditions

The oxovanadium(IV) complexes [VO(acac)(2)(Hpz)].HC(pz)(3) 1.HC(pz)(3) (acac= acetylacetonate, Hpz = pyrazole, pz = pyrazoly1) and [VOCl2{HOCH2C(pz)(3)}] 2 were obtained from reaction of [VO(acac)(2)] with hydrotris(1-pyrazolyl)methane or of VCl(3)with 2,2,2-tris(1-pyrazolyl)ethanol. The compounds were characterized by elemental analysis, IR, Far-IR and EPR spectroscopies, FAB or ESI mass-spectrometry and, for 1, by single crystal X-ray diffraction analysis. 1 and 2 exhibit catalytic activity for the oxidation of cyclohexane to the cyclohexanol and cyclohexanone mixture in homogeneous system (TONS up to 1100) under mild conditions (NCMe, 24h, room temperature) using benzoyl peroxide (BPO), tert-butyl hydroperoxide (TBHP), m-chloroperoxybenzoic acid (mCPBA), hydrogen peroxide or the urea-hydrogen peroxide adduct (UHP) as oxidants. 1 and 2 were also immobilized on a polydimethylsiloxane membrane (1-PDMS or 2-PDMS) and the systems acted as supported catalysts for the cyclohexane oxidation using the above oxidants (TONs up to 620). The best results were obtained with mCPBA or BP0 as oxidant. The effects of various parameters, such as the amount of catalyst, nitric acid, reaction time, type of oxidant and oxidant-to-catalyst molar ratio, were investigated, for both homogeneous and supported systems. (C) 2012 Elsevier B.V. All rights reserved.

Desacyl-ghrelin does not influence insulin sensitivity

Acyl-ghrelin has been reported to increase food intake and adiposity and it is the best studied of the orexigenic gastrointestinal hormones. On the other hand, desacyl-ghrelin – DAG (the unacylated form of the hormone) has been reported as a potential player on carbohydrate metabolism. However, the potential impact of DAG on glucose homeostasis remains uncertain. In this study we aim to assess the association between DAG and insulin sensitivity.

The effects of parental sensitivity and involvement in caregiving on mother–infant and father–infant attachment in a portuguese sample

In the present longitudinal study, we investigated attachment quality in Portuguese mother–infant and in father–infant dyads, and evaluated whether attachment quality was related to parental sensitivity during parent–infant social interaction or to the amount of time each parent spent with the infant during play and in routine caregiving activities (e.g., feeding, bathing, play). The sample consisted of 82 healthy full-term infants (30 girls, 53 boys, 48 first born), and their mothers and fathers from mostly middle-class households. To assess parental sensitivity, mothers and fathers were independently observed during free play interactions with their infants when infants were 9 and 15 months old. The videotaped interactions were scored by masked coders using the Crittenden’s CARE-Index. When infants were 12 and 18 months old, mother–infant and father–infant dyads were videotaped during an adaptation of Ainsworth’s Strange Situation. Parents also described their level of involvement in infant caregiving activities using a Portuguese version of the McBride and Mills Parent Responsibility Scale. Mothers were rated as being more sensitive than fathers during parent–infant free play at both 9 and 15 months. There also was a higher prevalence of secure attachment in mother–infant versus father–infant dyads at both 12 and 18 months. Attachment security was predicted by the amount of time mothers and fathers were involved in caregiving and play with the infant, and with parents’ behavior during parent–infant free play.

Comparative analysis of near and mid-infrared spectroscopy to monitor recombinant cyprosin production

Infrared spectroscopy, either in the near and mid (NIR/MIR) region of the spectra, has gained great acceptance in the industry for bioprocess monitoring according to Process Analytical Technology, due to its rapid, economic, high sensitivity mode of application and versatility. Due to the relevance of cyprosin (mostly for dairy industry), and as NIR and MIR spectroscopy presents specific characteristics that ultimately may complement each other, in the present work these techniques were compared to monitor and characterize by in situ and by at-line high-throughput analysis, respectively, recombinant cyprosin production by Saccharomyces cerevisiae. Partial least-square regression models, relating NIR and MIR-spectral features with biomass, cyprosin activity, specific activity, glucose, galactose, ethanol and acetate concentration were developed, all presenting, in general, high regression coefficients and low prediction errors. In the case of biomass and glucose slight better models were achieved by in situ NIR spectroscopic analysis, while for cyprosin activity and specific activity slight better models were achieved by at-line MIR spectroscopic analysis. Therefore both techniques enabled to monitor the highly dynamic cyprosin production bioprocess, promoting by this way more efficient platforms for the bioprocess optimization and control.