Spectroscopic characterization and investigation of the dynamic of charge compensation process of supramolecular films derived from tetra-2-pyridyl-1,4-pyrazine ligand

This work describes the infrared spectroscopy characterization and the charge compensation dynamics in supramolecular film FeTPPZFeCN derived from tetra-2-pyridyl-1,4-pyrazine (TPPZ) with hexacyanoferrate, as well as the hybrid film formed by FeTPPZFeCN and polypyrrole (PPy). For supramolecular film, it was found that anion flux is greater in a K+ containing solution than in Li+ solution, which seems to be due to the larger crystalline ionic radius of K+. The electroneutralization process is discussed in terms of electrostatic interactions between cations and metallic centers in the hosting matrix. The nature of the charge compensation process differs from others modified electrodes based on Prussian blue films, where only cations such as K+ participate in the electroneutralization process. In the case of FeTPPZFeCN/PPy hybrid film, the magnitude of the anions’s flux is also dependent on the identity of the anion of the supporting electrolyte.

Metal-free synthesis of indanes by iodine(III)-mediated ring contraction of 1, 2-dihydronaphthalenes

A metal-free protocol was developed to synthesize indanes by ring contraction of 1, 2-dihydronaphthalenes promoted by PhI(OH)OTs (HTIB or Koser's reagent). This oxidative rearrangement can be performed in several solvents (MeOH, CH3CN, 2 , 2, 2-trifluoroethanol (TFE), 1 , 1, 1, 3, 3, 3-hexafluoroisopropanol (HFIP), and a 1:4 mixture of TFE:CH2Cl2) under mild conditions. The ring contraction diastereoselectively gives functionalized trans-1, 3-disubstituted indanes, which are difficult to obtain in synthetic organic chemistry

Elementos protetores do leite materno na prevenção de doenças gastrintestinais e respiratórias

A Epistemologia Genética defende que o indivíduo passa por várias etapas de desenvolvimento ao longo da sua vida. O desenvolvimento é observado pela sobreposição do equilíbrio entre a assimilação e a acomodação, resultando em adaptação. Assim, nesta formulação, o ser humano assimila os dados que obtém do exterior, mas uma vez que já tem uma estrutura mental que não está vazia, precisa adaptar esses dados à estrutura mental já existe. O processo de modificação de si próprio é chamado de acomodação. Este esquema revela que nenhum conhecimento chega do exterior sem que sofra alguma alteração pelo indivíduo, sendo que tudo o que se aprende é influenciado por aquilo que já havia sido aprendido. A assimilação ocorre quando a informação é incorporada às estruturas já pré-existentes nessa dinâmica estrutura cognitiva, enquanto que a adaptação ocorre quando o organismo se modifica de alguma maneira de modo a incorporar dinamicamente a nova informação. Por fim, de um pensamento moderno que, buscando a síntese inusitada entre o biológico e o lógico-matemático, parece encontrar seus limites na desconstrução ainda mais inusitada a que tende sistematicamente todo o pensamento na atualidade: a de si mesmo se construindo de modo essencialmente esclarecido

Effect of protein intake on bone and muscle mass in the elderly

The aging process is frequently characterized by an involuntary loss of muscle (sarcopenia) and bone (osteoporosis) mass. Both chronic diseases are associated with decreased metabolic rate, increased risk of falls fracture, and, as a result, increased morbidity and loss of independence in the elderly. The quality and quantity of protein intake affects bone and muscle mass in several ways and there is evidence that increased essential amino acid or protein availability can enhance muscle protein synthesis and anabolism, as well as improve bone homeostasis in older subjects. A thorough evaluation of renal function is important, since renal function decreases with age. Finally, protein and calcium intake should be considered in the prevention or treatment of the chronic diseases osteoporosis and sarcopenia

A epistemologia genética de Piaget e o construtivismo

A Epistemologia Genética defende que o indivíduo passa por várias etapas de desenvolvimento ao longo da sua vida. O desenvolvimento é observado pela sobreposição do equilíbrio entre a assimilação e a acomodação, resultando em adaptação. Assim, nesta formulação, o ser humano assimila os dados que obtém do exterior, mas uma vez que já tem uma estrutura mental que não está vazia, precisa adaptar esses dados à estrutura mental já existe. O processo de modificação de si próprio é chamado de acomodação. Este esquema revela que nenhum conhecimento chega do exterior sem que sofra alguma alteração pelo indivíduo, sendo que tudo o que se aprende é influenciado por aquilo que já havia sido aprendido. A assimilação ocorre quando a informação é incorporada às estruturas já pré-existentes nessa dinâmica estrutura cognitiva, enquanto que a adaptação ocorre quando o organismo se modifica de alguma maneira de modo a incorporar dinamicamente a nova informação. Por fim, de um pensamento moderno que, buscando a síntese inusitada entre o biológico e o lógico-matemático, parece encontrar seus limites na desconstrução ainda mais inusitada a que tende sistematicamente todo o pensamento na atualidade: a de si mesmo se construindo de modo essencialmente esclarecido

The Process of Simulation Authoring/Creation by Chemistry Teachers: A Service Learning Experience

Two case studies are presented to describe the process of public school teachers authoring and creating chemistry simulations. They are part of the Virtual Didactic Laboratory for Chemistry, a project developed by the School of the Future of the University of Sao Paulo. the documental analysis of the material produced by two groups of teachers reflects different selection process for both themes and problem-situations when creating simulations. The study demonstrates the potential for chemistry learning with an approach that takes students' everyday lives into account and is based on collaborative work among teachers and researches. Also, from the teachers' perspectives, the possibilities of interaction that a simulation offers for classroom activities are considered.

Architecture for machining process and production monitoring based in open computer numerical control

This paper proposes an architecture for machining process and production monitoring to be applied in machine tools with open Computer numerical control (CNC). A brief description of the advantages of using open CNC for machining process and production monitoring is presented with an emphasis on the CNC architecture using a personal computer (PC)-based human-machine interface. The proposed architecture uses the CNC data and sensors to gather information about the machining process and production. It allows the development of different levels of monitoring systems with mininium investment, minimum need for sensor installation, and low intrusiveness to the process. Successful examples of the utilization of this architecture in a laboratory environment are briefly described. As a Conclusion, it is shown that a wide range of monitoring solutions can be implemented in production processes using the proposed architecture.

Bond Strength of Multicomponent White Cast Iron Coatings Applied by HVOF Thermal Spray Process

Multicomponent white cast iron is a new alloy that belongs to system Fe-C-Cr-W-Mo-V, and because of its excellent wear resistance it is used in the manufacture of hot rolling mills rolls. To date, this alloy has been processed by casting, powder metallurgy, and spray forming. The high-velocity oxyfuel process is now also considered for the manufacture of components with this alloy. The effects of substrate, preheating temperature, and coating thickness on bond strength of coatings have been determined. Substrates of AISI 1020 steel and of cast iron with preheating of 150 A degrees C and at room temperature were used to apply coatings with 200 and 400 mu m nominal thickness. The bond strength of coatings was measured with the pull-off test method and the failure mode by scanning electron microscopic analysis. Coatings with thickness of 200 mu m and applied on substrates of AISI 1020 steel with preheating presented bond strength of 87 +/- A 4 MPa.

Importance of considering a material micro-failure criterion in the numerical modelling of the shot peening process applied to parabolic leaf springs

Shot peening is a cold-working mechanical process in which a shot stream is propelled against a component surface. Its purpose is to introduce compressive residual stresses on component surfaces for increasing the fatigue resistance. This process is widely applied in springs due to the cyclical loads requirements. This paper presents a numerical modelling of shot peening process using the finite element method. The results are compared with experimental measurements of the residual stresses, obtained by the X-rays diffraction technique, in leaf springs submitted to this process. Furthermore, the results are compared with empirical and numerical correlations developed by other authors.

Synthesis and total H-1- and C-13-NMR assignment of cephem derivatives for use in ADEPT approaches

We report the synthesis and total NMR characterization of 5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid-3-[[[(4''-nitrophenoxy)carbonyl]oxy]-methyl]-8-oxo-7[(2-thienyloxoacetyl)amino]-diphenylmethyl ester-5-dioxide (5), a new cephalosporin derivative. This compound can be used as the carrier of a wide range of drugs containing an amino group. The preparation of the intermediate product, 5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid-3-[methyl-4-(6-methoxyquinolin-8-ylamino) pentylcarbamate]-8-oxo-7-[(2-thienyloxoacetyl)amino]-diphenylmethyl ester-5-dioxide (6), as well as the synthesis of the antimalarial primaquine prodrug 5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid-3-[methyl-4-(6-methoxyquinolin-8-ylamino) pentylcarbamate]-8-oxo-7-[(2-thienyloxoacetyl)amino]-5-dioxide (7) are also described, together with their total H-1- and C-13-NMR assignments.

Mechanistic aspects of the isomerization of Z-vinylic tellurides double bonds in the synthesis of potassium Z-vinyltrifluoroborate salts

Through direct transmetalation reaction of Z-vinylic tellurides with nBuLi was observed the unexpected isomerization of double bonds leading to potassium E-vinyltrifluoroborates salts in low to moderate yields. Using EPR spin trapping experiments the radical species that promoted the stereoinversion of Z-vinylic organometallic species during the preparation of potassium vinyltrifluoroborate salts was identified. The experiments support the proposed mechanism, which is based on the homolytic cleavage of the TenBu bond.

Synthesis of diaryl selenides using electrophilic selenium species and nucleophilic boron reagents in ionic liquids

We described herein the use of imidazolium ionic liquids [bmim]PF(6) and [bmim]BF(4) in the selective, metal and catalyst-free synthesis of unsymmetrical diaryl selenides by electrophilic substitution in arylboron reagents with arylselenium halides (Cl and Br) at room temperature. This is a general substitution reaction and it was performed with arylboronic acids or potassium aryltrifluoroborates bearing electron-withdrawing or electron-donating groups, affording the corresponding diaryl selenides in good to excellent yields. The ionic liquid [bmim][PF(6)] was easily recovered and utilized for further substitution reactions.

The inducing NO-vasodilation by chemical reduction of coordinated nitrite ion in cis-[Ru(NO(2))L(bpy)(2)](+) complex

The synthesis of [Ru(NO(2)) L(bpy)(2)](+) (bpy = 2,2'-bipyridine and L = pyridine (py) and pyrazine (pz)) can be accomplished by addition of [Ru(NO) L(bpy) 2](PF(6))(3) to aqueous solutions of physiological pH. The electrochemical processes of [Ru(NO2) L(bpy) 2]+ in aqueous solution were studied by cyclic voltammetry and differential pulse voltammetry. The anodic scan shows a peak around 1.00 V vs. Ag/AgCl attributed to the oxidation process centered on the metal ion. However, in the cathodic scan a second peak around-0.60 V vs. Ag/AgCl was observed and attributed to the reduction process centered on the nitrite ligand. The controlled reduction potential electrolysis at-0.80 V vs. Ag/AgCl shows NO release characteristics as judged by NO measurement with a NO-sensor. This assumption was confirmed by ESI/MS(+) and spectroelectrochemical experiment where cis-[Ru(bpy)(2)L(H(2)O)](2+) was obtained as a product of the reduction of cis-[Ru(II)(NO(2)) L(bpy)(2)](+). The vasorelaxation observed in denuded aortic rings pre-contracted with 0.1 mu mol L(-1) phenylephrine responded with relaxation in the presence of cis-[RuII(NO2) L(bpy) 2]+. The potential of rat aorta cells to metabolize cis-[RuII(NO(2)) L(bpy)(2)](+) was also followed by confocal analysis. The obtained results suggest that NO release happens by reduction of cis-[RuII(NO(2)) L(bpy)(2)](+) inside the cell. The maximum vasorelaxation was achieved with 1 x 10(-5) mol L(-1) of cis-[RuII(NO(2)) L(bpy)(2)](+) complex.

Cyclooligomerisation of azido-alkyne-functionalised sugars: synthesis of 1,6-linked cyclic pseudo-galactooligosaccharides and assessment of their sialylation by Trypanosoma cruzi trans-sialidase

Cyclic pseudo-galactooligosaccharides were synthesized by cyclooligomerisation of isomeric azido-alkyne derivatives of beta-D-galactopyranose under Cu(I)-catalysed azide-alkyne 1,3-dipolar cycloaddition reaction conditions. The principal products isolated were cyclic dimers and trimers, with lower amounts of cyclic tetramer and pentamer also evident in some cases. Molecular mechanics calculations suggest very compact but flexible structures for the cyclic trimers, with secondary OH groups exposed outside the macrocycle and available for enzymatic glycosylation. The cyclic dimers and trimers represent a new type of acceptor substrate for Trypanosoma cruzi trans-sialidase, giving rise to doubly and triply sialylated glycomacrocycles, respectively.

Intrinsic colony conditions affect the provisioning and oviposition process in the stingless bee Melipona scutellaris

The cell provisioning and oviposition process (POP) is a unique characteristic of stingless bees (Meliponini), in which coordinated interactions between workers and queen regulate the filling of brood cells with larval resources and subsequent egg laying. Environmental conditions seem to regulate reproduction in stingless bees; however, little is known about how the amount of food affects quantitative sequences of the process. We examined intrinsic variables by comparing three colonies in distinct conditions (strong, intermediate and weak state). We predicted that some of these variables are correlated with temporal events of POP in Melipona scutellaris colonies. The results demonstrated that the strong colony had shorter periods of POP.