Hydrolytic stability of terephthaloyl chloride and isophthaloyl chloride

The phthaloyl chloride isomers, terephthaloyl chloride (TCl) and isophthaloyl chloride (ICl), are high production volume chemicals used in polymers to impartflame resistance, chemical resistance, and temperature stability and as water scavengers. In these studies, we determined the hydrolytic stability of TCl and ICl and their hydrolysis products in aqueous solutions. Hydrolysis rates for TCl and ICl were initially determined by gas chromatography/flame ionization detection in water buffered at pH 4.0, 7.0, and 9.0 and 0 degrees C for up to 30 min. Subsequent studies determined the products from TCl and ICl hydrolysis. The parent phthaloyl chlorides (TCl and ICl), their intermediate hydrolysis products (designated as the "half-acids"), and their stable hydrolysis products (terephthalic acid (TPA) and isophthalic acid (IPA)) were determined by high-performance liquid chromatography. The half-lives (t(1/2)) of TCl and ICl ranged from an average of 1.2 to 2.2 min and from 2.2 to 4.9 min, respectively, at pH 4-9 and 0 degrees C. The observed first-order rate constants (k(obs)) ranged from an average of 530 to 1100 (x 10(5) s(-1)) for TCl and 240 to 520 (x 10(5) s(-1)) for ICl. Both phthaloyl chlorides formed their respective short-lived intermediates, in which one of the two carboxylic acid chloride functionalities reacts with water to form the carboxylic acid ("half-acid"). Subsequently, the half-acids underwent further hydrolysis so that greater than 90% of the initial phthaloyl chloride hydrolyzed in less than 60 min at 0 degrees C. The hydrolysis products TPA and IPA were hydrolytically stable, undergoing no further transformations after 20 min at pH 7 and 25 degrees C. This work demonstrated that TCl, ICl, and their respective half-acids will not be persistent in aqueous systems for a time sufficient to have a sustained toxicological effect on aquatic organisms (less than 1 h). Performing additional aquatic toxicity studies, biodegradation studies, and potentially mammalian studies on TCl and ICl are unnecessary since the existing information on TPA and IPA with the hydrolysis data presented here is sufficient to address questions on the fate and effects of these two substances in aqueous environments.     

Antimicrobial resistance of Escherichia coli O157 from cattle in Korea

Of 45 Escherichia coli O157 isolates from cattle feces, which were collected between May 2000 and September 2003 in Korea, 32 were resistant to at least 1 antibiotic and 28 were resistant to 4 or more antibiotics, with 32, 30 and 30 of the isolates being resistant to streptomycin, tetracycline and sulfisoxazole, respectively. Two isolates were resistant to fluoroquinolones and to 10 or more of the 22 other antimicrobial agents that were tested. Thirteen antimicrobial resistant patterns were observed. The most frequent resistance type, which was found for 11 isolates, was streptomycin-tetracycline-kanamycin-ampicillin-piperacillin-cephalothin-sulfisoxazole-ticarcillin. Polymerase chain reaction (PCR) analysis of the isolates for E. coli O157 virulence markers revealed that 25 of the resistant E. coli O157 isolates tested positive for stx2 or both stx1 and stx2 genes. These findings suggest that many of the resistant E. coli O157 isolates might cause disease in humans.     

In vitro incorporation of14C-acetate into lipids of hamster flank organ (Costovertebral organ) sebaceous glands and epidermis

Following in vitro incubation of flank organs from male golden Syrian hamsters with sodium [1-¹⁴C] acetate, sebaceous glands and appendage-freed epidermis were obtained by treating the flank organ tissue with calcium chloride. This method permitted the study of incorporation of carbon-14 into the lipids of these skin components. Extracted lipids were identified by thin layer chromatography and autoradiography and were quantitated by liquid scintillation counting. Mono-, di-, and triglycerides, free sterols, fatty acids, wax monoesters, and squalene were identified as products of sebaceous gland metabolism of labeled acetate. In marked contrast, little incorporation of¹⁴C into triglycerides by the epidermal preparations was noted, although the epidermal lipids showed higher relative proportions of free sterols and polar lipids (including phospholipids). Accumulation of sterol esters did not occur. In both preparations phosphatidylcholine represented the major labeled phospholipid.     

Imaging and Diffraction Study of Continuous α-Fe2O3 Films on (0001)Al2O3

Continuous α-Fe₂O₃ films grown on bulk (0001)Al₂O₂ substrates by low-pressure chemical vapor deposition have been studied by transmission electron microscopy and the observations compared to those obtained from discontinuous films at an earlier stage of the growth process. Plan-view specimens revealed significant thermal stress in the continuous films, while cross-sectional specimens showed that cracking occurs in thicker films. The free surface of the film and the film/substrate interface appeared sharp and flat, apart from growth ledges and steps. Weak-beam imaging revealed a hexagonal misfit dislocation network consisting of perfect edge dislocations. Fine structure in the selected-area diffraction patterns which corroborates these observations is also discussed. The misfit network of partial dislocations previously observed in the discontinuous films was not observed for the continuous films, indicating an effect of film thickness, growth rate, or surface preparation on the Fe₂O₃/(0001)Al₂O₃ interface structure.     

Allocation of energy inputs among the end-uses in the US petroleum and coal products industry

This paper models the allocation of energy inputs in the US petroleum and coal products industry by allocating combustible fuel and renewable energy inputs among generic end-uses, including intermediate conversions through onsite power and steam generation. This analysis, called an energy end-use model, showed that 72% of the fuel input in the US petroleum and coal products industry goes to onsite steam and power generation, whereas 28% goes directly to end-uses. Eight percent of the boiler output is used for power generation, 72% goes directly to end-uses, and 20% is waste heat. Among the end-uses, process heating is the biggest energy user with a total energy consumption of 2338 PJ, whereas machine drive is the biggest electricity consumer with a consumption of 168 PJ. This paper also provides estimates of the uncertainty of the data. The approach to create this model is applicable to all other industries for which data is available and the model is consistent with US Department of Energy data for 1998. When used in conjunction with similar models for other years, it can be used to identify the changes and trends in energy utilization even at the prime mover level of detail.     

Aromatase and dual aromatase-steroid sulfatase inhibitors from the letrozole and vorozole templates

Concurrent inhibition of aromatase and steroid sulfatase (STS) may provide a more effective treatment for hormone‐dependent breast cancer than monotherapy against individual enzymes, and several dual aromatase–sulfatase inhibitors (DASIs) have been reported. Three aromatase inhibitors with sub‐nanomolar potency, better than the benchmark agent letrozole, were designed. To further explore the DASI concept, a new series of letrozole‐derived sulfamates and a vorozole‐based sulfamate were designed and biologically evaluated in JEG‐3 cells to reveal structure–activity relationships. Amongst achiral and racemic compounds, 2‐bromo‐4‐(2‐(4‐cyanophenyl)‐2‐(1H‐1,2,4‐triazol‐1‐yl)ethyl)phenyl sulfamate is the most potent DASI (aromatase: IC₅₀=0.87 nM ; STS: IC₅₀=593 nM ). The enantiomers of the phenolic precursor to this compound were separated by chiral HPLC and their absolute configuration determined by X‐ray crystallography. Following conversion to their corresponding sulfamates, the S‐(+)‐enantiomer was found to inhibit aromatase and sulfatase most potently (aromatase: IC₅₀=0.52 nM ; STS: IC₅₀=280 nM ). The docking of each enantiomer and other ligands into the aromatase and sulfatase active sites was also investigated.     

Δ6 Desaturase mRNA Abundance in HepG2 Cells Is Suppressed by Unsaturated Fatty Acids

The effect of unsaturated fatty acids on the abundance of Δ6 desaturase (D6D) mRNA and the fatty acid composition of HepG2 cell membranes was examined. Supplementation of HepG2 cells with oleic acid (18:1n-9, OA), linoleic acid (18:2n-6, LA), α-linolenic acid (18:3n-3, ALA), arachidonic acid (20:4n-6, AA) or eicosapentaenoic acid (20:5n-3, EPA) reduced D6D mRNA abundance by 39 ± 6.6, 40 ± 2.2, 31 ± 5.2, 55 ± 4.8, and 52 ± 5.0%, respectively, compared with control cells. Despite the reduction in D6D mRNA abundance, the level of D6D conversion products (20:3n-9, EPA and AA) in OA, ALA and LA supplemented cells, respectively, was elevated above that in control cells. Our results suggest that although unsaturated fatty acids decrease the abundance of D6D mRNA by as much as 50%, the conversion of polyunsaturated fatty acids and accumulation of long chain polyunsaturated fatty acids (LCPUFA) in HepG2 cell phospholipids continues to occur.     

A band-ratio algorithm for retrieving open-lake chlorophyll values from satellite observations of the Great Lakes

The U.S. Environmental Protection Agency's Great Lakes National Program Office (GLNPO) has collected water quality data from the five Great Lakes annually since 1993. We used the GLNPO observations made since 2002 along with coincident measurements made by the Sea-viewing Wide Field-of-View Sensor (SeaWiFS) and the Moderate-resolution Imaging Spectroradiometer (MODIS) to develop a new band-ratio algorithm for estimating chlorophyll concentrations in the Great Lakes from satellite observations. The new algorithm is based on a third-order polynomial model using the same maximum band ratios employed in the standard NASA algorithms (OC4 for SeaWiFS and OC3M for MODIS). The sensor-specific coefficients for the new algorithm were obtained by fitting the relationship to several hundred matched field and satellite observations. Although there are some seasonal variations in some lakes, the relationship between the observed chlorophyll values and those modeled using the new coefficients is fairly stable from lake to lake and across years. The accuracy of the satellite chlorophyll estimates derived from the new algorithm was improved substantially relative both to the standard NASA retrievals and to previously published algorithms tuned to individual lakes. Monte-Carlo fits to randomly selected subsets of the observations allowed us to estimate the uncertainty associated with the retrievals purely as a function of the satellite data. Our results provide, for the first time, a single simple band ratio method for retrieving chlorophyll concentrations in the offshore “open” waters of the Great Lakes from satellite observations.