Bacterial Reduction of Chromium

A mixed culture was enriched from surface soil obtained from an eastern United States site highly contaminated with chromate. Growth of the culture was inhibited by a chromium concentration of 12 mg/L. Another mixed culture was enriched from subsurface soil obtained from the Hanford reservation, at the fringe of a chromate plume. The enrichment medium was minimal salts solution augmented with acetate as the carbon source, nitrate as the terminal electron acceptor, and various levels of chromate. This mixed culture exhibited chromate tolerance, but not chromate reduction capability, when growing anaerobically on this medium. However, this culture did exhibit chromate reduction capability when growing anaerobically on TSB. Growth of this culture was not inhibited by a chromium concentration of 12 mg/L. Mixed cultures exhibited decreasing diversity with increasing levels of chromate in the enrichment medium. An in situ bioremediation strategy is suggested for chromate contaminated soil and groundwater.

     

Low‐density extraction solvent based solvent‐terminated dispersive liquid–liquid microextraction for quantitative determination of ionizable pesticides in environmental waters

A rapid, efficient, and new solvent terminated dispersive liquid–liquid microextraction technique coupled with HPLC was developed for selective extraction and analysis of s‐triazine herbicides from environmental water samples. Important parameters influencing the extraction process including type and volume of extraction and disperser solvent, extraction time, sample pH, ionic strength, and extraction temperature were successfully optimized. Under the optimal conditions, there are excellent linear relationships between the analytical results and concentration in the range of 10–400 mg/L for atrazine, propazine, prometryn, and terbutryn. LOD and LOQ ranged from 0.60 to 2.33 μg/L and 2.0 to 7.7 μg/L, respectively. Performance of the analytical technique was evaluated by carrying out the repeatability and reproducibility analyses that were ranged from 2.86 to 5.66% and 4.64 to 5.89% for 100 μg/L of each target analyte, respectively. The proposed method has been successfully applied to the analysis of real water samples and acceptable relative recoveries over the range of 65.93–101.46%, with RSDs ≤ 8.80%, were obtained. The overall results have been compared with the literature values. Thus, the method developed could efficiently be used for selective extraction of the target analytes from complex matrices, particularly environmental waters.     

Copper‐Catalyzed Intramolecular Oxidative Amination of Unactivated Internal Alkenes

A copper‐catalyzed oxidative amination of unactivated internal alkenes has been developed. The Wacker‐type oxidative alkene amination reaction is traditionally catalyzed by a palladium through a mechanism involving aminopalladation and β‐hydride elimination. Replacing the precious and scarce palladium with a cheap and abundant copper for this transformation has been challenging because of the difficulty associated with the aminocupration of internal alkenes. The combination of a simple copper salt, without additional ligand, as the catalyst and Dess–Martin periodinane as the oxidant, promotes efficiently the oxidative amination of allylic carbamates and ureas bearing di‐ and trisubstituted alkenes leading to oxazolidinones and imidazolidinones. Preliminary mechanistic studies suggested a hybrid radical–organometallic mechanism involving an amidyl radical cyclization to form the key C?N bond.     

Electrochemical C−H/N−H Functionalization for the Synthesis of Highly Functionalized (Aza)indoles

Indoles and azaindoles are among the most important heterocycles because of their prevalence in nature and their broad utility in pharmaceutical industry. Reported herein is an unprecedented noble‐metal‐ and oxidant‐free electrochemical method for the coupling of (hetero)arylamines with tethered alkynes to synthesize highly functionalized indoles, as well as the more challenging azaindoles.     

Density of universal classes of series‐parallel graphs

A class of graphs ordered by the homomorphism relation is universal if every countable partial order can be embedded in . It is known (see [ 1 , 3 ]) that the class of k‐colorable graphs, for any fixed , induces a universal partial order. In 4 , a surprisingly small subclass of which is a proper subclass of the series‐parallel graphs (the K₄‐minor‐free graphs) is shown to be universal. On another side, Pan and Zhu in 7 proved a density result that for each rational number , there is a K₄‐minor‐free graph with circular chromatic number equal to a/b. In this note, we show for each rational number a/b within this interval the class of K₄‐minor‐free graphs with circular chromatic number a/b is universal if and only if , 5/2 or 3. This shows yet another surprising richness of the K₄‐minor‐free class that it contains universal classes as dense as the rational numbers. © 2006 Wiley Periodicals, Inc. J Graph Theory     

Electrochemical Synthesis of Imidazo‐Fused N‐Heteroaromatic Compounds through a C−N Bond‐Forming Radical Cascade

We have developed a unified strategy for preparing a variety of imidazo‐fused N‐heteroaromatic compounds through regiospecific electrochemical (3+2) annulation reaction of heteroarylamines with tethered internal alkynes. The electrosynthesis employs a novel tetraarylhydrazine as the catalyst, has a broad substrate scope, and obviates the need for transition‐metal catalysts and oxidizing reagents.     

Determination of D[C6F5-I] by the toluene carrier method

The pyrolysis of C₆F₅I has been studied by the toluene carrier method over the temperature range of 900–978°K with contact times of 0.4–2.0 seconds and total pressures of 11.2–19.5 torr. Percent decomposition ranged from 8.6 to 97.7%. With toluene-to-C₆F₅I molar ratios of greater than 150, 85–100% of the C₆F₅ released abstracts a hydrogen atom from toluene to produce C₆F₅H. No significant quantities of I₂ were observed and the only major gaseous product was HI. Within the limits of the experimental method the decomposition of C₆F₅I was first order and homogeneous. Least squares analysis of log k₁ and 10³/T(C₆F₅I → C₆F₅ + I) values gives while a weighted line of best fit yields. Based on this latter equation D[C₆F₅? I] at 298°K is estimated as 66.2 kcal/mole.     

Phenolic glycosides from Lindera fruticosa root and their inhibitory activity on osteoclast differentiation

Two new compounds were found in the phenolic glycosides isolated from the roots of Lindera fruticosa: 5-O-[beta-D-apiofuranosyl-(1'-->2')-O-beta-D-xylopyranosyl]gentisic acid-7,5'-ester (3), named linderofruticoside A; and 5-O-[beta-D-apiofuranosyl-(1'-->3')-O-beta-D-xylopyranosyl]gentisic acid methyl ester (4), linderofruticoside B. Two previously known phenolic glycosides were also identified: beta-D-(3,4-disinapoyl)fructofuranosyl-alpha-D-(6-sinapoyl)glucopyranoside (1) and beta-D-(3-sinapoyl)fructofuranosyl-alpha-D-(6-sinapoyl)glucopyranoside (2). Compounds 1 and 2 inhibited osteoclast differentiation in a dose-dependent manner at concentrations higher than 1.04 microM and 0.132 microM, respectively.