Synthesis and reactivity of enediynyl amino acids and peptides: a novel concept in lowering the activation energy of Bergman cyclisation by H-bonding and electrostatic interactions

Novel enediynyl amino acids and peptides 3 and 5-8 were synthesized and their thermal reactivity towards Bergman cyclization studied and compared with the earlier reported amino acid 4, which demonstrated, for the first time, the effect of H-bonding and electrostatic interactions in lowering the activation energy of Bergman cyclization.     

Mileage bands in freight transportation

Contract carriers in the trucking industry are known to offer shippers a per mile rate that decreases stepwise as the shipper’s route lengthens, with a mileage band designated for each rate. While the use of quantity-based pricing discounts in supply chains has been well studied, there has been no research on how shippers should route under such a pricing scheme or how carriers should set such bands. In this paper, we provide methods for both. Route construction is complicated by the fact that the per mile rate cannot be determined until after the route has been created. With this consideration, we develop a model of this problem and then an algorithm for solving it that assists the shipper in constructing the lowest cost route. It is beneficial for the shipper to extend the length of certain routes to incur a lower per mile cost, and we find that most of these routes can be constructed to equal any mileage required to receive the lower rate. As an extended route generates unnecessary expense and energy use for the carrier, theoretical and analytical insights provide guidelines for a carrier to use in developing better mileage bands. These guidelines assist a carrier in constructing bands that maximize profit and minimize the cost associated with a shipper extending a route.     

Transport engineering in microbial cell factories producing plant-specialized metabolites

Transport engineering strategies use altered expression of transporter proteins to change metabolite distribution within an organism. The production of plant specialized metabolites in microbial cell factories encounters a set of challenges that could benefit from the implementation of transport engineering technology. The range of challenges includes premature pathway termination due to secretion of intermediates, feedback inhibition due to inefficient export of final products, low yields in bioconversion processes due to inefficient import of precursors, and poor connectivity between subcellular compartments expressing different parts of complex biosynthetic pathways. We highlight the latest examples of transport engineering in microbial cell factories producing plant specialized metabolites, identify the current knowledge gap, and propose future research for advancing the field.     

Synthesis and characterization of a [3-15N]-labeled cis-syn thymine dimer-containing DNA duplex

Cis-syn thymine dimers are the major photoproducts of DNA and are the principal cause of mutations induced by sunlight. To better understand the nature of base pairing with cis-syn thymine dimers, we have synthesized a decamer oligodeoxynucleotide (ODN) containing a cis-syn thymine dimer labeled at the N3 of both T's with 15N by two efficient routes from [3-15N]-thymidine phosphoramidite. In the postsynthetic irradiation route, an ODN containing an adjacent pair of [3-15N]-labeled T's was irradiated and the cis-syn dimer-containing ODN isolated by HPLC. In the mixed building block route, a mixture of cis-syn and trans-syn dimer-containing ODNs was synthesized from a mixture of [3-15N]-labeled thymine dimer phosphoramidites after which the cis-syn dimer-containing ODN was isolated by HPLC. The N3-nitrogen and imino proton signals of an (15)N-labeled thymine dimer-containing decamer duplex were assigned by 2D 1H-15N heterocorrelated HSQC NMR spectroscopy, and the 15N-1H coupling constant was found to be 1.8 Hz greater for the 5'-T than for the 3'-T. The larger coupling constant is indicative of weaker H-bonding that is consistent with the more distorted nature of the 5'-base pair found in solution state NMR and crystallographic structures.     

Numerical simulation of shear and normal forces in standard and shear flow sequencing batch reactor (SF-SBR)

The purpose of this contribution is to compare the shear and the normal stresses in two different types of bioreactors. In the first one (SBR), the granules are generated by liquid and bubbles flow, whereas in the second one (SF-SBR), the shear rate is achieved by installing a rotating cylinder inside the reactor. Such shear flow can be applied for anaerobic process in the wastewater treatment. The results demonstrate the effective role of the process parameters and the reactor geometry on the shear and normal stresses and consequently on the granulation process. Hereby, the different tendencies of the velocity fields, the particle sedimentation as well as Taylor vortices in (SF-SBR), are observed. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Properties and transport behavior of perfluorotripentylamine (FC-70)-doped amorphous teflon AF 2400 films

Teflon AF 2400 films are known to imbibe solvents, making films in the presence of solvents less fluorous than they might otherwise be. Herein, we demonstrate that doping films with perfluorotripentylamine (Fluorinert FC-70) maintains the fluorous nature of Teflon AF 2400 and improves transport selectivity for fluorine-containing organic compounds. Density measurements on the FC-70-doped films reveal that free volume decreases dramatically as the dopant concentration increases (0-12 wt %) and then increases to approach that of pure FC-70. Remarkably, films from 0 to 12 wt % FC-70 have the same w/v concentration of Teflon AF 2400, indicating that FC-70 fills the free volume of Teflon AF 2400. This is consistent with the observed increased storage modulus and significant decrease (compared to undoped films) of solute diffusion coefficients in the same range of FC-70 concentrations. In contrast, FC-70 at concentrations greater than 12 wt % dilutes Teflon AF 2400, leading to a decrease of storage modulus and dramatic increase in solute diffusion coefficients. Sorption of chloroform decreases from 11.8 g of chloroform/100 g of film (pure Teflon film) to 3.8 g of chloroform/100 g of film (27 wt % FC-70-doped Teflon film), less than the solubility of chloroform in pure FC-70 (4.06 g of chloroform/100 g of FC-70). Solute partition coefficients from chloroform to FC-70-doped films generally decrease with increased dopant concentration. However, within a series of toluenes and nitrobenzenes, selectivity for F-containing solutes over analogous H-containing solutes increases as dopant concentration increases if the substitution is on the aromatic ring but not if it is on the methyl group (toluene). Transport (partitioning × diffusion) rates, as they involve both thermodynamic and kinetic factors, are not simply related to composition.     

Design,synthesis and molecular docking of new [1,2,4] triazolo[4,3-a]quinoxaline derivatives as anticancer agents targeting VEGFR-2 kinase

Molecular Diversity - Vascular endothelial growth factor receptor-2 (VEGFR-2) is critically involved in cancer angiogenesis. Blocking of VEGFR-2 signaling pathway proved effective suppression of...     

Analysis and prediction of single laser tracks geometrical characteristics in coaxial laser cladding process

Direct Laser Fabrication is a promising new manufacturing technology coming from laser cladding process. From a coaxial nozzle, powder is fed through a laser beam on a substrate. The powder melting and solidification processes lead to the fabrication of a part layer by layer. In this work 316L stainless steel powder is used to form laser tracks on a low carbon steel substrate. The layer geometry is an important process characteristic to control the final part of fabrication. This paper presents analytical relationships between the laser tracks geometrical characteristics (width, height, area, penetration depth) and the processing parameters (laser power P, scanning speed V and powder mass flow Q_m). Three values of each processing parameters are fixed and so 27 different experiments have been made and analyzed. The validity of these results is discussed studying the correlation coefficient R, the graphical analysis of the residuals and the uncertainty evaluations. Two kinds of models are studied to predict the form and the geometrical characteristics of the single laser tracks cross sections. The first one is an analytical model in which the distribution of the powder in the feed jet is supposed to govern the laser clad geometry. Three distributions are proposed: Gaussian, uniform and polynomial. In the second model the general form of the clad cross section is supposed to be a disk due to the surface tension forces. Analytical relationships are established between the radius and the center of the disk in one hand and the process parameters in the other hand. This way we show that we can reproduce the laser track geometry in all the area experimentally explored.     

Nuclear magnetic resonance study of speciation of water at low concentrations in hydrogen bond acceptor solvents

Equilibrium constants for the formation of 1:1 and 1:2 complexes of monomeric water with twelve hydrogen bond acceptor solvents were evaluated from the chemical shifts of the water protons in ternary mixtures containing a low concentration of water and varying proportions of the acceptor solvent and carbon tetrachloride. Formation constants of the 1:1 complexes (with the exception of those of dioxane and dimethoxyethane) correlate well with Kamlet-Taft -parameters. A good correlation is also obtained with Gutmann donor numbers if nitromethane and pyridine are excluded. Stepwise formation constants of the 1:2 complexes vary relatively little; this is attributed to a leveling effect of first hydrogen bond formation.     

Electrochemical measurement and speciation of inorganic arsenic in groundwater of Bangladesh

The presence of arsenic in groundwater above the maximum permissible limit of 50 mug l(-1) has threatened the health of more than 50 million people in Bangladesh and neighboring India. We report here the development of an inexpensive anodic stripping voltammetric (ASV) technique for routine measurement and speciation of arsenic in groundwater. The measurements are validated by more expensive atomic absorption, atomic emission and other techniques. To understand the present situation in Bangladesh, we measured As(III) in 960 water samples collected from 18 districts. A random distribution of 238 samples was used to measure both As(III) and As(V). The results from the present study indicate that most toxic form of inorganic arsenic, As(III), has the broad range of 30-98%. It shows 60% of the samples have 10 mug l(-1) and 44% of the samples have 50 mug l(-1) or more As(III). The fractional distribution pattern shows significant skew towards high percent occurrence which may indicate a progressive reduction process with a single source or a single mechanism for the formation of As(III). For direct consumption, this is possibly one of the most toxic groundwater known today. Speciation distribution at groundwater pH value shows H(3)AsO(3) is the predominant species including H(2)AsO(4)(-) and H(2)AsO(4)(2-) whose distribution is significantly pH dependent. This is also supported by E(h)-pH measurements. The depth distribution for Kushtia shows most of the As(III) is located within 100-200 ft deep aquifers. Similar fractional distribution of As(III) is found in deeper aquifers and may indicate contamination by leakage from upper aquifer. This study clearly demonstrates the aquifer environment is reductive and conducive to the formation of As(III) species.