The synthesis of non‐symmetrical stilbene analogs of trans‐resveratrol using the same Pd catalyst in a sequential double‐Heck arylation of ethylene

We have developed a sequential and selective Pd‐catalyzed double‐Heck arylation of ethylene that results in non‐symmetrical nitro‐stilbene analogs of trans‐resveratrol at excellent yields. A catalytic system consisting of Pd(OAc)₂ and P(o‐tolyl)₃ permitted us to carry out the two consecutive Heck arylations without losing activity from the first to the second Heck reaction. After the first Heck arylation of ethylene, no isolation or additional catalyst loading is required for the second Heck arylation reaction. This protocol was applied to the synthesis of methylated trans‐resveratrol, which was obtained at a 65% overall yield. Copyright © 2011 John Wiley & Sons, Ltd.     

Dynamics and Control Strategies for a Butanol Fermentation Process

In this work, mathematical modeling was employed to assess the dynamic behavior of the flash fermentation process for the production of butanol. This process consists of three interconnected units as follows: fermentor, cell retention system (tangential microfiltration), and vacuum flash vessel (responsible for the continuous recovery of butanol from the broth). Based on the study of the dynamics of the process, suitable feedback control strategies [single input/single output (SISO) and multiple input/multiple output (MIMO)] were elaborated to deal with disturbances related to the process. The regulatory control consisted of keeping sugar and/or butanol concentrations in the fermentor constant in the face of disturbances in the feed substrate concentration. Another objective was the maintenance of the proper operation of the flash tank (maintenance of the thermodynamic equilibrium of the liquid and vapor phases) considering that oscillations in the temperature in the tank are expected. The servo control consisted of changes in concentration set points. The performance of an advanced controller, the dynamic matrix control, and the classical proportional-integral controller was evaluated. Both controllers were able to regulate the operating conditions in order to accommodate the perturbations with the lowest possible alterations in the process outputs. However, the performance of the PI controller was superior because it showed quicker responses without oscillations.     

Convenient copper- and solvent-free Sonogashira-type alkynylation of aryl iodides and bromides using Pd EnCat™

A straightforward methodology is described for the copper- and solvent-free alkynylations of aryl iodides and bromides using 0.1-0.01 mol % of Pd as Pd EnCat™ 40 or TPP30. High yielding reactions can be achieved under aerobic conditions for a variety of activated and deactivated aryl iodides; a few examples with aryl bromides are also described. Microwave irradiation is able to enhance yields and rates of these reactions.     

The Structural Stability of Graphene Anticorrosion Coating Materials is Compromised at Low Potentials

Corrosion of engineered structures is a major problem causing an estimated economic loss of more than 2 trillion US dollars annually worldwide. Graphene has recently emerged as highly promising, low‐cost, and transparent anticorrosion coating material. Herein, it is shown that a multilayer graphene film grown on Ni by chemical vapor deposition undergoes abrupt stability failure under galvanic‐corrosion conditions. The multilayer graphene coating was examined by optical microscopy, SEM, energy dispersive X‐ray spectroscopy, Raman spectroscopy, and cyclic voltammetry after exposure to potentials between 600 and 1300 mV in alkaline solution. A fast and simple electrochemical method is proposed to sensitively quantify the damage caused by the applied potential bias. It is based on quantification of the oxidation signals generated by the underlying Ni‐metal catalyst that is exposed by damage to the graphene film. It is shown that film damage can start at potentials as low as 900 mV and that macroscopic and extensive damage can be caused at potentials above 1000 mV. In addition, once the graphene film has been damaged, the corrosion rate of the underlying metal is significantly increased. These findings are of great importance for potential applications of multilayer graphene films in coating metal structures with huge industrial and economic implications.     

Processing of high resolution magic angle spinning spectra of breast cancer cells by the filter diagonalization method

Proton nuclear magnetic resonance ((1)H NMR) spectroscopy for detection of biochemical changes in biological samples is a successful technique. However, the achieved NMR resolution is not sufficiently high when the analysis is performed with intact cells. To improve spectral resolution, high resolution magic angle spinning (HR-MAS) is used and the broad signals are separated by a T(2) filter based on the CPMG pulse sequence. Additionally, HR-MAS experiments with a T(2) filter are preceded by a water suppression procedure. The goal of this work is to demonstrate that the experimental procedures of water suppression and T(2) or diffusing filters are unnecessary steps when the filter diagonalization method (FDM) is used to process the time domain HR-MAS signals. Manipulation of the FDM results, represented as a tabular list of peak positions, widths, amplitudes and phases, allows the removal of water signals without the disturbing overlapping or nearby signals. Additionally, the FDM can also be used for phase correction and noise suppression, and to discriminate between sharp and broad lines. Results demonstrate the applicability of the FDM post-acquisition processing to obtain high quality HR-MAS spectra of heterogeneous biological materials.     

Evaluation of a microHPLC system dedictaed to packed capillary column liquid chromatography

Miniaturization and optimization of the solvent delivery system, mixing device, and detection system for gradient elution at few μl/min is the most important objective of instrumental development in microHPLC using packed capillary columns. Instrumental solutions and evaluation of the performence of a dedicated system for automatic gradient elution with packed capillary columns are reported. Retention time precision shown buy the system results in an RSD of 0.20–0.52% for a PAH model mixture eluted under gradient conditions at few μl/min. Compositional accuracy of gradient profiles is also demonstrated.     

Rhenium(V) complexes with Schiff bases: Synthesis and reaction mechanisms

Summary Some isomers of the ReOX₂LPPh₃ complexes [X = Cl or Br and L =N-methylsalicylideneiminate,N-phenylsalicylideneiminate, halfN,N'-ethylenebis(salicylideneiminate) or 8-hydroxyquinolinate] have been synthesized and characterized. Two different mechanisms for reaction of thetrans-ReOX₃(PPh₃)₂ complexes (X = Cl or Br) with the Schiff bases are supported by qualitative studies on such parameters as the Schiff base ligand form, concentration of free triphenylphosphine ligand, reaction solvent and temperature.     

1,4-Benzodiazepines as ligands. Synthesis,characterization and crystal and molecular structure ofbis(8-chloro-6-(o-chlorophenyl)-1-methyl-4H-s-triazolo[4,3-a]1,4-benzodiazepine (triazolam)) cadmium (II) dichloride

The compound C₃₄H₂₄CdN₈Cl₆ was prepared and characterized by means of X-ray, IR, and Raman measurements. The crystals are monoclinic, space groupC2/c, (No. 14) witha=22.284(3),b=14.501(2),c=14.595(2) Å=129.77(1)° andZ=4. The structure was solved by the heavy-atom method, and least-squares refinement of structural parameters led to a conventionalR factor of 0.040 for 2379 independent reflections. The structure consists of discrete molecules, in which the Cd atom is coordinated in a distorted tetrahedral geometry by two chlorine atoms and by two nitrogens of two triazolic rings of triazolam molecules. Infrared and Raman bands are assigned on the basis of the known structure. An electronic charge calculation has been performed on the unbonded ligand.