Ligand substituents effect on 10Dq

Reaction of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline (L) with Ni(ClO4)(2)center dot 6H(2)O in methanol in 3:1 M proportion at room temperature yields [NiL3](ClO4)(2)center dot 2H(2)O. The X-ray crystal structure of the cation Nil(3)(2+) has been determined. Aminolysis of the three epoxide rings in NiL32+ by 4-substituted anilines in boiling water without any Lewis acid catalyst gives a family of Ni(II) complexes with octahedral NiL62+ core. In these complexes, crystal field splitting 10Dq varies from 11601 to 15798 cm(-1) in acetonitrile. The variation in 10Dq is found to be satisfactorily linear (r(2) = 0.951) with the Hammett sigma(R) parameter of the substituent on the anilino fragment. 10Dq increases with the increase in the electron donation ability of the substituent.

Epoxide ring opening in a zinc(II) complex in water without any Lewis acid catalyst: formation of only one diastereomer out of 2

The epoxide ring in 5,6-dihydro-5,6-epoxy-1,10-phenanthroline (L) opens up in its reaction with 4-methylaniline and 4-methoxyaniline in water in equimolar proportion at room temperature without any Lewis acid catalyst to give a monohydrate of 6-(4-methyl-phenylamino)-5,6-dihydro-1,10-phenanthrolin-5-ol (L′·H2O) and 6-(4-methoxyphenyl-amino)-5,6-dihydro-1,10-phenanthrolin-5-ol (L″) respectively. Reaction time decreases from 72 to 14 h in boiling water. But the yields become less. Reaction of L with Zn(ClO4)2·6H2O in methanol in 3:1 molar ratio at room temperature affords white [ZnL3](ClO4)2·H2O. The X-ray crystal structure of the acetonitrile solvate [ZnL3](ClO4)2·MeCN has been determined which shows that the metal has a distorted octahedral N6 coordination sphere. [ZnL3](ClO4)2·2H2O reacts with 4-methylaniline and 4-methoxyaniline in boiling water in 1:3 molar proportion in the absence of any Lewis acid catalyst to produce [ZnL′3](ClO4)2·4H2O and [ZnL″3](ClO4)2·H2O, respectively in 1–4 h time in somewhat low yield. In the 1H NMR spectra of [ZnL′3](ClO4)2·4H2O and [ZnL″3](ClO4)2·H2O, only one sharp methyl signal is observed implicating that only one diastereomer out of the 23 possibilities is formed. The same diastereomers are obtained when L′·H2O and L″ are reacted directly with Zn(ClO4)2·6H2O in tetrahydrofuran at room temperature in very good yields. Reactions of L′·H2O and L″ with Ru(phen)2Cl2·2H2O (phen = 1,10-phenanthroline) in equimolar proportion in methanol–water mixture under refluxing condition lead to the isolation of two diastereomers of [Ru(phen)2L′](ClO4)2·2H2O and [Ru(phen)2L″](ClO4)2·2H2O.

Effects of nitrogen and sulfur fertilization on free amino acids, sugars, and acrylamide-forming potential in potato

Nitrogen (N) fertilizer is used routinely in potato (Solanum tuberosum) cultivation to maximize yield. However, it also affects sugar and free amino acid concentrations in potato tubers, and this has potential implications for food quality and safety because free amino acids and reducing sugars participate in the Maillard reaction during high-temperature cooking and processing. This results in the formation of color, aroma, and flavor compounds, but also some undesirable contaminants, including acrylamide, which forms when the amino acid that participates in the final stages of the reaction is asparagine. Another mineral, sulfur (S), also has profound effects on tuber composition. In this study, 13 varieties of potato were grown in a field trial in 2010 and treated with different combinations of N and S. Potatoes were analyzed immediately after harvest to show the effect of N and S fertilization on concentrations of free asparagine, other free amino acids, sugars, and acrylamide-forming potential. The study showed that N application can affect acrylamide-forming potential in potatoes but that the effect is type- (French fry, chipping, and boiling) and variety-dependent, with most varieties showing an increase in acrylamide formation in response to increased N but two showing a decrease. S application reduced glucose concentrations and mitigated the effect of high N application on the acrylamide-forming potential of some of the French fry-type potatoes.

Evidence for the complex relationship between free amino acid and sugar concentrations and acrylamide-forming potential in potato

Free amino acids and reducing sugars participate in the Maillard reaction during high-temperature cooking and processing. This results not only in the formation of colour, aroma and flavour compounds, but also undesirable contaminants, including acrylamide, which forms when the amino acid that participates in the reaction is asparagine. In this study, tubers of 13 varieties of potato (Solanum tuberosum), which had been produced in a field trial in 2010 and sampled immediately after harvest or after storage for 6 months, were analysed to show the relationship between the concentrations of free asparagine, other free amino acids, sugars and acrylamide-forming potential. The varieties comprised five that are normally used for crisping, seven that are used for French fry production and one that is used for boiling. Acrylamide formation was measured in heated flour, and correlated with glucose and fructose concentration. In French fry varieties, which contain higher concentrations of sugars, acrylamide formation also correlated with free asparagine concentration, demonstrating the complex relationship between precursor concentration and acrylamide-forming potential in potato. Storage of the potatoes for 6 months at 9°C had a significant, variety-dependent impact on sugar and amino acid concentrations and acrylamide-forming potential.

Consumer acceptability and sensory profile of cooked broccoli with mustard seeds added to improve chemoprotective properties

Broccoli, a rich source of glucosinolates, is a commonly consumed vegetable of the Brassica family. Hydrolysis products of glucosinolates, isothiocyanates, have been associated with health benefits and contribute to the flavour of Brassica. However, boiling broccoli causes the myrosinase enzyme needed for hydrolysis to denature. In order to ensure hydrolysis, broccoli must either be mildly cooked or active sources of myrosinase, such as mustard seed powder, can be added post-cooking. In this study, samples of broccoli were prepared in six different ways; standard boiling with and without mustard seeds, sous-vide cooking at low temperature (70 °C) and sous-vide cooking at higher temperature (100 ºC) without mustard and with mustard at two different concentrations. The majority of consumers disliked the mildly cooked broccoli samples (70 ºC, 12 min, sous-vide) which had a hard and stringy texture. The highest mean consumer liking was for standard boiled samples (100 ºC, 7 min). Addition of 1% mustard seed powder developed sensory attributes such as pungency, burning sensation, mustard odour and flavour. One cluster of consumers (32%) found mustard seeds to be a good complement to cooked broccoli, however, the majority disliked the mustard-derived sensory attributes. Where the mustard seeds were partially processed, doubling the addition to 2% led to only the same level of mustard flavour and pungency as 1% unprocessed seeds, and mean consumer liking remained unaltered. This suggests that optimisation of the addition level of partially processed mustard seeds may be a route to enhance bioactivity of cooked broccoli without compromising consumer acceptability.

Calculating Flash Point Numbers from Molecular Structure: An Improved Method for Predicting the Flash Points of Acyclic Alkanes

We report a novel method for calculating flash points of acyclic alkanes from flash point numbers, N(FP), which can be calculated from experimental or calculated boiling point numbers (Y(BP)) with the equation N(FP) = 1.020Y(BP) - 1.083 Flash points (FP) are then determined from the relationship FP(K) = 23.369N(FP)(2/3) + 20.010N(FP)(1/3) + 31.901 For it data set of 102 linear and branched alkanes, the correlation of literature and predicted flash points has R(2) = 0.985 and an average absolute deviation of 3.38 K. N(FP) values can also be estimated directly from molecular structure to produce an even closer correspondence of literature and predicted FP values. Furthermore, N(FP) values provide a new method to evaluate the reliability of literature flash point data.

Simple Method to Evaluate and to Predict Flash Points of Organic Compounds

Flash points (T(FP)) of organic compounds are calculated from their flash point numbers, N(FP), with the relationship T(FP) = 23.369N(FP)(2/3) + 20.010N(FP)(1/3) + 31.901. In turn, the N(FP) values can be predicted from boiling point numbers (Y(BP)) and functional group counts with the equation N(FP) = 0.974Y(BP) + Sigma(i)n(i)G(i) + 0.095 where G(i) is a functional group-specific contribution to the value of N(FP) and n(i) is the number of such functional groups in the structure. For a data set consisting of 1000 diverse organic compounds, the average absolute deviation between reported and predicted flash points was less than 2.5 K.

Soda-Treated Sisal/Polypropylene Composites

Treated sisal fibers were used as reinforcement of polypropylene (PP) composites, with maleic anhydride-grafted PP (MAPP) as coupling agent. The composites were made by melting processing of PP with the fiber in a heated roller followed by multiple extrusions in a single-screw extruder. Injection molded specimens were produced for the characterization of the material. In order to improve the adhesion between fiber and matrix and to eliminate odorous substances, sisal fibers were treated with boiling water and with NaOH solutions at 3 and 10 wt.%. The mechanical properties of the composites were assessed by tensile, bend and impact tests. Additionally, the morphology of the composites and the adhesion at he fiber-matrix interface were analyzed by SEM. The fiber treatment led to very light and odorless materials, with yields of 95, 74 and 62 wt.% for treatments with hot water, 3 and 10 wt.% soda solution respectively. Fiber treatment caused an appreciable change in fiber characteristics, yet the mechanical properties under tensile and flexural tests were not influenced by that treatment. Only the impact strength increased in the composites with alkali-treated sisal fibers.

Characterization of the raw essential oil eugenol extracted from Syzygium aromaticum L.

Eugenol is the main volatile compound extracted oil from clove bud, Syzygium aromaticum L., and used in traditional medicine, as a bactericide, fungicide, anesthetic, and others. Its extraction was performed using hydrodistillation which is the most common extraction technique. Its components and thermal behavior were evaluated using gas chromatography (GC) and differential scanning calorimetry (DSC), which provide a better characterization of these natural compounds. This extracted product was compared to the standard eugenol results. The GC results suggested similar to 90% eugenol was found in the total extracted oil, and some of its boiling characteristics were 270.1 A degrees C for peak temperature and 244.1 J g(-1) for the enthalpy variation.

Choreographic exploration of physical duress: motivation for and responses to exhaustion (a project in performance)

What motivates someone to dance until they are exhausted, sweaty, boiling hot and out of breath? I myself, recalling experiences when I have danced so hard I've nearly fainted, remember how exhilarating that motivation can be. But why? Why is that at all pleasant? Of course, I had several of my own explanations, but I was also interested in doing some scientific research on exhaustion. This question was of ample depth to become the basis of my project.

Comportamento do aco inoxidavel ABNT 304 a corrosao-sob-tensao em solucoes aquosas neutras de nacl a temperatura de ebulicao utilizando a tecnica de carga constante

Estudou-se o comportamento do aço inoxidável ABNT 304 à corrosão-sob-tensão (C.S.T.) em soluções aquosas com 0,1%, 3,5% e 20% de NaCl, na temperatura de 103°C, através de ensaios de carga constante. Com auxílio das técnicas e conceitos de Mecânica de Fratura Linear Elástica e das análises eletroquímicas procurou-se encontrar as condições em que ocorre C.S.T. no sistema aço inoxidável austenítico/solução aquosa de NaCl a 103°C. Utilizou-se o corpo-de-prova do tipo dupla viga em balanço (T-notch double cantilever beam: TN-DCB), com intuito de observar a influência do fator de intensidade de tensão, concentração da solução e potencial eletroquímico. Estimou-se o valor do fator de intensidade de tensão limite (KICST) e a velocidade de propagação das trincas; também foram analisadas outras importantes características em termos mecanísticos. Definiu-se faixas de potenciais e valores de intensidade de tensão a partir dos quais ocorre o surgimento de trincas por C.S.T.. Fêz-se análises metalográficas dos corpos-de-prova onde se pode constatar trincas transgranulares bem típicas do fenômeno de C.S.T.. Foram feitos alguns testes em solução aquosa saturada de MgCl2, em ebulição, para se comparar as diferentes soluções quanto ao fenômeno de C.S.T.. Alterou-se as dimensões do corpo-de-prova para avaliar a orientação da propagação das trincas por C.S.T..

Uma análise energética da cristalização por resfriamento na indústria da cana-de-açúcar

Os mercados dos produtos oriundos da cana-de-açúcar no mundo vêm sofrendo nos últimos anos mudanças estruturais significativas. No cenário brasileiro, houve grande expansão da produção de cana-de-açúcar, impulsionados pela demanda dos carros flex –fuel, além da oportunidade de suprir o volume de açúcar que a União Europeia deixara de colocar no mercado mundial pela eliminação da subvenção aos exportadores de açúcar do bloco. As incertezas dos mercados exigem mudanças de estratégias de negócio, usinas projetadas para produção exclusiva de etanol, alteram sua estratégia para produção conjunta etanol e açúcar. Apesar dos processos comuns para produção de açúcar e etanol, não significa que essa mudança de estratégia seja fácil de ser efetivada, principalmente pelo aspecto energético. Estudos de processo de produção de açúcar mais eficientes energeticamente, com custos menores tem ganhado força na União Europeia, dentre elas a cristalização do açúcar por resfriamento. Vários cenários produtivos inclusive integrados a produção de etanol tem sido desenvolvidos ao longo dos anos. O objetivo do trabalho foi verificar por comparação de cenários, duas tecnologias de cristalização do açúcar (cozimento e resfriamento), em relação ao impacto nos excedentes de energia elétrica quando a produção de açúcar é adicionada a unidades que produzem somente etanol e energia elétrica. Por meio de simulações dos balanços térmicos dos cenários, observou-se uma restrição importante quando adotado a cristalização por cozimento, no que se refere aos volumes de excedentes de energia elétrica, e que pode ser minimizado se adotado o processo de cristalização por resfriamento, podendo assim ser uma alternativa quando se deseja mudar a estratégia do negócio, de produção exclusiva de etanol e energia elétrica para etanol, açúcar e energia elétrica.

Obtenção de pós de tântalo metálico a partir da redução aluminotérmica com ignição a plasma

Metallic tantalum has a high commercial value due to intrinsic properties like excellent ductility, corrosion resistance, high melt and boiling points and good electrical and thermal conductivities. Nowadays, it is mostly used in the manufacture of capacitors, due to excellent dielectric properties of its oxides. In the nature, tantalum occurs in the form of oxide and it is extracted mainly from tantalite-columbite ores. The tantalum is usually produced by the reduction of its oxide, using reductants like carbon, silicon, calcium, magnesium and aluminum. Among these techniques, the aluminothermic reduction has been used as the industrial method to produce niobium, tantalum and their alloys, due to the easy removal of the Al and Al2O3 of the system, easing further refining. In conventional aluminothermic reduction an electrical resistance is used to trigger the reaction. This reaction self-propagates for all the volume of material. In this work, we have developed a novel technique of aluminothermic reduction that uses the hydrogen plasma to trigger the reaction. The results obtained by XRD, SEM and EDS show that is possible to obtain a compound rich in tantalum through this technique of aluminothermic reduction in the plasma reactor