Metabolites from the biodegradation of 1,6‐hexanediol dibenzoate,a potential green plasticizer,by Rhodococcus rhodochrous

Metabolites from the biodegradation of a potential plasticizer 1,6‐hexanediol dibenzoate in the presence of n‐hexadecane as a co‐substrate by the common soil organism Rhodococcus rhodochrous were identified using GC/MS and Fourier transform mass spectroscopy (FTMS) techniques. Trimethylsilylation of compounds from the biodegradation broth permitted detection of the following metabolites: 1‐hexadecyl benzoate, 6‐benzoyloxyhexanoic acid, 4‐benzoyloxybutanoic acid, 6‐benzoyloxyhexan‐1‐ol and benzoic acid. The presence of these metabolites was confirmed by repeating the biodegradation with 1,6‐hexanediol di[²H₅]benzoate, by measurement of their exact masses in FTMS and by comparison with available authentic materials. The results show that biodegradation of 1,6‐hexanediol dibenzoate by R. rhodochrous does not lead to the accumulation of persistent metabolites as has been reported for commercial dibenzoate plasticizers. Copyright © 2009 John Wiley & Sons, Ltd.     

Low‐Temperature Growth of Thick Polystyrene Brushes via ATRP

Summary: This contribution describes the graft polymerization of polystyrene (PS) by atom transfer radical polymerization at 50, 60, and 75 °C. Thick PS brushes were grown from initiator‐functionalized PGMA layers on silicon, and constant growth rates provide indirect evidence that the polymerizations were controlled.

Formation of polystyrene brushes at T < T_g by ATRP of styrene from α‐bromoester initiator‐functionalized poly(glycidyl methacrylate) layers.     

Syntheses and spectroscopic investigation of some cyclophosphazanes: Analysis of pseudo‐triplet splitting

Some new phosphoramidates, 1–3 , and the corresponding cyclophosphazanes, 4–6 , with formula Cl₂P(p‐NHC₆H₄CH₃) 1 , Cl₂P(O)(p‐NHC₆H₄NO₂) 2 , (CH₃)₂NP(O)Cl(p‐NHC₆H₄CH₃) 3 , [ClP(p‐NC₆H₄CH₃)]₂ 4 , [ClP(O)(p‐NC₆H₄NO₂)]₂ 5 , and [(CH₃)₂NP(O)(p‐NC₆H₄CH₃)]₂ 6 were synthesized and characterized by ¹H, ¹³C, ³¹P NMR, IR, mass spectroscopy, and elemental analysis. A pseudo‐triplet signal was observed in the ¹H NMR spectrum of molecule 6 for the N(CH₃)₂ protons. The A₆A′ ₆X₂ spin system was suggested for the pseudo‐triplet pattern of ³J_PNCH coupling in this molecule. Ab initio calculations were performed at the HF and B3LYP levels of theory with 6‐311G^** standard basis set on the geometry of compound 6 . Also, the NMR chemical shift calculations were done to compare the computed results with the experimental ones. The calculated results are in good agreement with experimental data. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:337–343, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20229     

Synthesis new Co–Mn mixed oxide catalyst for the production of light olefins by tuning the catalyst structure

In order to increase the catalyst activity for Fischer–Tropsch synthesis (FTS), the preparation methods of two new catalysts were studied. The chemically identical bimetallic Co–Mn/Al₂O₃ catalysts were synthesized by different synthetic methods: (a) via thermal decomposition of the complex [Co_1.33Mn_0.667(C₇H₃NO₄)₂(H₂O)₅].2H₂O ( 1 ) and (b) by the impregnation technique. The complex was characterized by the single‐crystal analysis, elemental analysis, and Fourier‐transform infrared (FT‐IR) spectroscopy. Both catalysts were characterized by powder X‐ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X‐ray spectrometry (EDS), Brunauer–Emmett–Teller (BET) specific surface area, hydrogen temperature‐programmed reduction (H₂‐TPR), and H₂‐chemisorption. The catalysts' activity was investigated for the Fischer–Tropsch synthesis in a fixed bed microreactor. Higher activity was obtained for the catalyst prepared by thermal decomposition of the inorganic precursor due to its small particle size, superior dispersion, and higher surface area. The results show that the catalyst prepared thermal decomposition has 21% ethylene, 10% propylene, and 50% C₅⁺ selectivity, while methane selectivity of this catalyst is 11% at 250°C. On the other hand, the catalyst obtained by the impregnation method displays 15% ethylene, 8% propylene, 29% C₅⁺_, and 29% methane selectivity at the same temperature.     

Dissecting the effect of anions on Hg2+ detection using a FRET based DNA probe

Many biosensors have been developed to detect Hg(2+) using thymine-rich DNA. While sensor response to various cations is often studied to demonstrate selectivity, the effect of anions has been largely overlooked. Anions may compete with DNA for metal binding and thus produce a false negative result. Anions cannot be added alone; the cation part of a salt may cause DNA compaction and other effects, obscuring the role of anions. We find that the sensitivity of a FRET-based Hg(2+) probe is independent of Na(+) concentration. Therefore, by using various sodium salts, any change in sensitivity can be attributed solely to the effect of anions. Halide salts, sulfides, and amines are strong inhibitors; anions containing oxo or hydroxyl groups (e.g. nitrate, sulfate, phosphate, carbonate, acetate, and citrate) do not interfere with Hg(2+) detection even at 100 mM concentration. Mercury hydrolysis and its diffusion into polypropylene containers can also strongly affect the detection results. We conclude that thymine-rich DNA should be useful for Hg(2+) detection in many environmental water samples.     

Solid Phase Extraction of Lead(II) by Sorption on Grinded Eucalyptus Stem and Determination with Flame Atomic Absorption Spectrometry

A sensitive and simple solid‐phase preconcentration procedure for the determination of trace amount of lead by flame atomic absorption spectrometry (FAAS) is developed. The method is based on the adsorption of Pb²⁺ on the column of fine grinded eucalyptus stem adsorbent, elution of the column by nitric acid and subsequent determination by FAAS. The effect of different variables such as pH, eluent type, flow rate and interfering ions on the recovery of the analyte was investigated and optimum conditions were established. The adsorption of lead onto fine grinded eucalyptus stem can formally be described by a Langmuir equation with a maximum adsorption capacity of 4.49 mg g^?1. A preconcentration factor of 50 was achieved using the optimum conditions. The calibration graph was linear in the range 10–125 ng mL^?1 of lead in the initial solution with r = 0.9982. The limit of detection based on 3S_b criterion was 4.5 ng mL^?1 and the relative standard deviation for eight replicate measurements of 30 and 80 ng mL^?1 of iron was 3.6 and 2.8%, respectively. The method was successfully applied to the determination of lead added to well, tap and wastewater samples.     

Synthesis of hydrogenated indazole derivatives starting with α,β-unsaturated ketones and hydrazine derivatives

The reaction of hydrazine derivatives with α,β-unsaturated ketones, such as cyclohexenyl(phenyl)methanone and (E)-2-benzylidenecyclohexanone, were investigated.The reaction between methylhydrazine and e.g., cyclohexenyl(phenyl)methanone was particularly interesting as 3a,4,5,6,7,7a-hexahydro-1-methyl-3-phenyl-1H-indazole was obtained as the major product together with 4,5,6,7-tetrahydro-2-methyl-3-phenyl-2H-indazole as a minor product.     

Microfluidic system for measuring neutrophil migratory responses to fast switches of chemical gradients

Experimental systems that provide temporal and spatial control of chemical gradients are required for probing into the complex mechanisms of eukaryotic cell chemotaxis. However, no current technique can simultaneously generate stable chemical gradients and allow fast gradient changes. We developed a microfluidic system with microstructured membranes for exposing neutrophils to fast and precise changes between stable, linear gradients of the known chemoattractant Interleukin-8 (IL-8). We observed that rapidly lowering the average concentration of IL-8 within a gradient, while preserving the direction of the gradient, resulted in temporary neutrophil depolarization. Fast reversal of the gradient direction while increasing or decreasing the average concentration also resulted in temporary depolarization. Neutrophils adapted and maintained their directional motility, only when the average gradient concentration was increased and the direction of the gradient preserved. Based on these observations we propose a two-component temporal sensing mechanism that uses variations of chemokine concentration averaged over the entire cell surface and localized at the leading edge, respectively, and directs neutrophil responses to changes in their chemical microenvironment.     

Analysis of the magnetic losses in iron-based soft magnetic composites with MgO insulation produced by sol-gel method

This work investigated the magnetic losses of heat treated iron-based soft magnetic composites with a thin MgO insulating layer produced by sol-gel method. The samples were characterized by energy dispersive X-ray spectroscopy, X-ray analysis and Fourier transform infrared spectroscopy. The results show that the surface of the powders contains a thin layer of MgO insulation. The loss results indicate that the hysteresis part for both the core loss and total loss factor was approximately the same for the MgO-insulated compacts and conventional SOMALOY^TM samples with phosphate insulation after annealing at 600 °C. But the MgO-insulated compacts exhibited significantly lower eddy current contribution of both core loss and total loss factor with respect to SOMALOY^TM samples after annealing. Also the contribution of eddy current in the iron particles for MgO insulated compacts (k_p=0.91) was noticeably higher than this contribution for SOMALOY^TM samples (k_p=0.18) after annealing due to the higher electrical resistivity of the MgO-insulated compacts.