Gas Chromatography–Mass Spectrometry Analysis of 4-Methylimidazole in Balsamic Vinegars and Processed Sauces

A gas chromatography–mass spectrometry method was optimized for quantification of 4-methylimidazole [4-MEI] in balsamic vinegars and processed sauces. The method used ion-pair extraction with bis-2-ethylhexylphosphate and derivatization with isobutylchloroformate, followed by Gas Chromatography-Mass Spectrometry (GC–MS) quantification using 2-ethylimidazole as internal standard. Performance characteristics such as linearity, recovery, and repeatability were good in a broad range of concentrations, and the limit of detection was low enough (130 ug/kg) to detect the presence of small quantities of the compound. A total of 35 samples were analyzed, including balsamic vinegars and processed sauces containing caramel in the ingredients list (soy, Worcestershire, Tonkatsu, Marinara, and Oyster sauces). The presence of 4-MEI was consistent with the presence of ammonia caramel (E150 c and d) in the ingredients list, with average values of 2431 ug/kg for balsamic vinegars and 804 ug/kg for processed sauces. These 4-MEI amounts are almost tenfold higher than those described for caramels containing beverages, which support the necessity to take an effective control on these products.     

Extensive N‐methylation of chitosan: evaluating the effects of the reaction conditions by using response surface methodology

The effects of reaction time, concentration of aqueous sodium hydroxide and molar ratio iodomethane/chitosan on the yield of the reaction of chitosan with iodomethane in N‐methyl‐2‐pyrrolidone (NMP) at 25.0 ± 0.1 °C, as well as on the characteristics of the resulting N,N,N‐trimethylchitosan (TMCh), were evaluated by using full‐factorial 2³ design analysis and response surface methodology. This study also aimed to determine the reaction conditions allowing the production of water‐soluble TMCh presenting a high average degree of quaternization and intrinsic viscosity at high reaction yield. ¹H NMR spectroscopy was employed for structural characterization, including the determination of average degrees of acetylation () and quaternization (), while capillary viscometry was used to determine intrinsic viscosity [η]. The results show that when the extensive N‐methylation is carried out for 24 h in NMP/15% NaOH (w/v) employing a lower excess of iodomethane (CH₃I/Ch = 9), water‐soluble highly substituted ( = 46.0%) TMCh ([η] = 213.0 mL g^?1) can be produced in high yield (81.8%). The highly significant mathematical models resulting from this study describe the dependence of the experimental responses on the reaction conditions and allow the characteristics and properties of the resulting TMCh to be defined by properly choosing the reaction conditions. © 2015 Society of Chemical Industry     

Palladium on Calcium Carbonate Combined to 2‐Hydroxypropyl‐α/β‐cyclodextrins: A Selective Catalytic System for Aqueous Heck Coupling and Hydroarylation

An efficient, selective and recoverable catalytic system for ligand‐free aqueous Heck reactions using hydroxypropylated cyclodextrins (HPCDs) and palladium on calcium carbonate (Pd/CaCO₃) is highlighted. Remarkably, stereo‐ and chemoselectivities could be tuned by the cavity size of cyclodextrins, exploiting the relevance of host‐guest interactions. UV‐Vis experiments have led to strong evidence concerning an interplay between Pd(II) and α‐HPCD, possibly ascribed to a reduction/stabilization effect of CDs. Unexpectedly, hydroarylation was the favored pathway with acrylonitrile which provided access to 3‐phenylpropionitrile derivatives without usual hydride donors. Finally, determination of soluble Pd(0/II) via AAS enabled the definition of a predominant homogeneous mechanism in which TONs over 5000 were observed.     

A faster procedure for the calculation of the J(ξ, β) function

One of the biggest difficulties in obtaining an analytical expression for the J(ξ, β) function is its explicit dependence on the Doppler broadening function ψ(x,ξ). The objective of this paper is to present a method for the fast and accurate calculation for the J(ξ, β) function based on the recent advances in the calculation of the Doppler broadening function and on a systematic analysis of its integrand. The methodology proposed uses an analytical formulation for the calculation of ψ(x, ξ) and a representation in series for error functions with complex argument. The results were satisfactory from the accuracy and processing time standpoint and are an option to other calculation methods found in the literature.     

Bibliometric Analysis of Physics in Catalonia: Towards Quality Consolidation?

This paper studies the main bibliometric figures in order to analyse the "states of the art" and the evolution of research in physics in Catalonia (Spain) between 1981 and 1998 via the National Citation Report (NCR) for Catalonia elaborated by ISI (Institute for Scientific Information). The main indicators and parameters used are: bibliometric size, rate of citation, citedness of papers, concentration of scientific categories, journals and types of paper, index of immediacy, international collaboration, and papers and citation distribution by research centres and universities.     

Wax deposition modeling of oil/water stratified channel flow

Wax deposition modeling becomes complicated when multiphase flow is involved. Empirical heat and mass transfer correlations are unreliable for multiphase deposition modeling and full scale computational fluid dynamics calculations require expensive computational intensity. In this work, numerical methods are used to study wax deposition in oil/water stratified flow through a channel. A unidirectional flow analysis is used to calculate the nonisothermal hydrodynamics and mass transfer. It was found that the change in the position of the oil/water interface throughout the channel must be taken into accounted for the mass balance to be valid. Unfortunately, this change has not been accounted for in all previous studies. In addition, the growth of the wax deposit as a function of time along with the effect of oil/water flow rate ratio is discussed. The presence of water significantly reduces the severity of wax deposition by altering the heat and mass transfer characteristics. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Kappa-Opioid Receptor Blockade Ameliorates Obesity Caused by Estrogen Withdrawal via Promotion of Energy Expenditure through mTOR Pathway

Weight gain is a hallmark of decreased estradiol (E2) levels because of menopause or following surgical ovariectomy (OVX) at younger ages. Of note, this weight gain tends to be around the abdomen, which is frequently associated with impaired metabolic homeostasis and greater cardiovascular risk in both rodents and humans. However, the molecular underpinnings and the neuronal basis for these effects remain to be elucidated. The aim of this study is to elucidate whether the kappa-opioid receptor (k-OR) system is involved in mediating body weight changes associated with E2 withdrawal. Here, we document that body weight gain induced by OVX occurs, at least partially, in a k-OR dependent manner, by modulation of energy expenditure independently of food intake as assessed in Oprk1−/−global KO mice. These effects were also observed following central pharmacological blockade of the k-OR system using the k-OR-selective antagonist PF-04455242 in wild type mice, in which we also observed a decrease in OVX-induced weight gain associated with increased UCP1 positive immunostaining in brown adipose tissue (BAT) and browning of white adipose tissue (WAT). Remarkably, the hypothalamic mTOR pathway plays an important role in regulating weight gain and adiposity in OVX mice. These findings will help to define new therapies to manage metabolic disorders associated with low/null E2 levels based on the modulation of central k-OR signaling.     

Metal-catalyzed cross-coupling reactions with supported nanoparticles: Recent developments and future directions

The metal-catalyzed processes are ubiquitous in the modern organic synthesis toolbox. However, a continuous challenge has been related to the design of reactions from a sustainable viewpoint (e.g., easy recovery of the catalyst, ability to perform sequential steps in high yields, avoidance of high amounts of organic solvents). Supported nanocatalysts have prompted special interest because of the synergy involving eletronic and surface effects which can play key roles towards more sustainable processes. In this article, we comprehensively summarize the latest progress in cross-coupling reactions involving supported metal nanoparticles. A background to mechanisms and industrial application will also be presented.     

Prediction of the neutrons subcritical multiplication using the diffusion hybrid equation with external neutron sources

We used the neutron diffusion hybrid equation, in cartesian geometry with external neutron sources to predict the subcritical multiplication of neutrons in a pressurized water reactor, using a 1/M curve to predict the criticality condition. A Coarse Mesh Finite Difference Method was developed for the adjoint flux calculation and to obtain the reactivity values of the reactor. The results obtained were compared with benchmark values in order to validate the methodology presented in this paper.     

Soft computing systems applied to PWR''s xenon

The present work intends to introduce a soft computing technique as an effective and robust tool available to deal with nuclear engineering problems. This goal is reached by the presentation of an application: a genetic programming system (GP) able to automatically design a controller for the axial xenon oscillations in a pressurized water reactors (PWRs). The axial xenon oscillations control methodology is based on three axial offsets: the xenon axial offset (AOx), the iodine axial offset (AOi) and the neutron flux axial offset (AOf), effectively used in former work. Simulations were made using a two-point xenon oscillation model which employs the non-linear xenon and iodine balance equations and the one group, one-dimensional neutron diffusion equation, with non-linear power reactivity feedback, also proposed in the literature. Obtained results showed the ability of the GP in finding a strategy which can effectively control the axial xenon oscillations.