One‐Pot Hydroacetylation of Menadione (Vitamin K3) to Menadiol Diacetate (Vitamin K4) by Heterogeneous Catalysis

Vitamin K₄ (menadiol diacetate, MDD) can be easily synthesized through cleaner and more efficient catalytic alternatives following the green chemistry principles. Ionic gold‐based hydroxylated fluorides are active bi‐functional catalysts for the one‐pot hydroacetylation of menadione leading to MDD with 77% selectivity. Unprecedent results were obtained in the presence of oxide‐fluoride catalysts by using a microwave‐assisted hydrogen‐transfer (Meerwein–Ponndorf–Verley reaction) coupled with an acetylation approach, yielding very high selectivities for the target product (95%).     

Evaluation of child safety seat checkpoint events

Objective

To determine the effectiveness of child safety seat checkpoints in generating change in child restraint practice to reduce the prevalence and extent of misuse.

Methods

Child safety seats underwent an initial checkpoint evaluation and participants received a training session. Participants were asked to return within 6–12 months to a checkpoint for follow-up evaluation. During each visit, a data collection sheet was used to assess the participants’ use of their child safety seat, and to subsequently calculate a restraint misuse score to characterize the child safety seat's usage before and after the intervention.

Results

During the period of study, 42 participants underwent both the initial and follow-up child safety seat check. Before the intervention, at least one misuse was identified in 100% of installed child safety seats. After the intervention, there was a significant reduction in the proportion of rear-facing child safety seats (18.8%) and forward-facing child safety seats (64.0%) that had at least one misuse (p < 0.001). Almost all (93.4%) of those using rear-facing child safety seats and the majority (64.0%) of those using forward-facing child safety seats improved their safety score as measured after the intervention.

Conclusions

Although misuse was universally observed, child safety seat checkpoint events were successful in improving usage practices.     

Scanning tunneling microscopy images of alkane derivatives on graphite: role of electronic effects

Scanning tunneling microscopy (STM) images of self-assembled monolayers of close-packed alkane chains on highly oriented pyrolitic graphite often display an alternating bright and dark spot pattern. Classical simulations suggest that a tilt of the alkane backbone is unstable and, therefore, unlikely to account for the contrast variation. First principles calculations based on density functional theory show that an electronic effect can explain the observed alternation. Furthermore, the asymmetric spot pattern associated with the minimum energy alignment is modulated depending on the registry of the alkane adsorbate relative to the graphite surface, explaining the characteristic moiré pattern that is often observed in STM images with close packed alkyl assemblies.     

Prevalence of Escherichia coli O157:H7, Listeria monocytogenes, and Salmonella in two geographically distant commercial beef processing plants in the United States

For two large beef processing plants, one located in the southern United States (plant A) and one located in the northern United States (plant B), prevalence of Escherichia coli O157:H7, Listeria spp., Listeria monocytogenes, and Salmonella was determined for hide, carcass, and facility environmental samples over the course of 5 months. The prevalence of E. coli O157:H7 (68.1 versus 55.9%) and Salmonella (91.8 versus 50.3%) was higher (P < 0.05), and the prevalence of Listeria spp. (37.7 versus 75.5%) and L. monocytogenes (0.8 versus 18.7%) was lower (P < 0.05) for the hides of cattle slaughtered at plant A versus plant B. Similarly, the prevalence of Salmonella (52.0 versus 25.3%) was higher (P < 0.05) and the prevalence of Listeria spp. (12.0 versus 40.0%) and L. monocytogenes (1.3 versus 14.7%) was lower (P < 0.05) for the fence panels of the holding pens of plant A versus plant B. The prevalence of E. coli O157:H7 (3.1 versus 10.9%), Listeria spp. (4.5 versus 14.6%), and L. monocytogenes (0.0 versus 1.1%) was lower (P < 0.05) for preevisceration carcasses sampled at plant A versus plant B. Salmonella (both plants), Listeria spp. (plant B), and L. monocytogenes (plant B) were detected on fabrication floor conveyor belts (product contact surfaces) late during the production day. For plant B, 21 of 148 (14.2%) late-operational fabrication floor conveyor belt samples were L. monocytogenes positive. For plant B, E. coli O157:H7 and L. monocytogenes were detected in preoperational fabrication floor conveyor belt samples. Overall results suggest that there are regional differences in the prevalence of pathogens on the hides of cattle presented for harvest at commercial beef processing plants. While hide data may reflect the regional prevalence, the carcass data is indicative of differences in harvest practices and procedures in these plants.     

Perfluoroalkyl contaminants in the Canadian Arctic: evidence of atmospheric transport and local contamination

Perfluorosulfonates (PFSAs) and perfluorocarboxylates (PFCAs) have been hypothesized to reach remote locations such as the Canadian Arctic either indirectly as volatile precursor chemicals that undergo atmospheric transport and subsequent degradation, or directly via oceanic and atmospheric transport of the PFSAs and PFCAs themselves. Water, sediment, and air samples were collected from three Arctic lakes (Amituk, Char, and Resolute) on Cornwallis Island, Nunavut, Canada. Samples were analyzed for PFSAs and PFCAs, precursor chemicals including the fluorotelomer alcohols (FTOHs) and polyfluorinated sulfonamides (FSAs), and precursor degradation products such as the fluorotelomer unsaturated carboxylates (FTUCAs). PFSAs and PFCAs were detected in water and sediment of all three Arctic lakes (concentrations ranged from nondetect to 69 ng/L and nondetect to 85 ng/g dry weight, respectively). FTOHs and FSAs were observed in air samples (mean concentrations ranged from 2.8 to 29 pg/m3), and confirm that volatile precursors are reaching Arctic latitudes. The observation of degradation products, including FTUCAs observed in sediment and atmospheric particles, and N-ethyl perfluorooctanesulfonamide (NEtFOSA) and perfluorooctanesulfonamide (PFOSA) in air samples, indicate that degradation of the FTOHs and FSAs is occurring in the Arctic environment. PFSAs and PFCAs were also observed on atmospheric particles (mean concentrations ranged from < 0.1 to 5.9 pg/m3). In addition, results of this study also indicate that local perfluoroalkyl contamination of Resolute Lake, which is located downstream of an airport wastewater input, has occurred.     

Low‐Dose Irradiation Can be Used as a Phytosanitary Treatment for Fresh Table Grapes

Grapes (Vitis vinifera var. Sugraone and Vitis labrusca var. Crimson Seedless) were treated with 400, 600, and 800 Gy and the effects on physicochemical factors were measured alongside sensory testing during 3 wk of storage. Significant changes in texture and color with irradiation and age were measured but little visual difference was seen between control and irradiated grapes. However, age had a greater effect on firmness than irradiation for Sugraone grapes. Irradiation did not significantly (P ≤ 0.05) affect the SSC/TA ratio, which increased during storage. The trained panel detected significant changes in the berry texture and rachis color but rated sweetness and flavor significantly higher (P ≤ 0.05) for irradiated Sugraone as compared to the control. Consumers liked both the untreated and 800 Gy treated Sugraone grapes, but liked the untreated grapes more for texture (P ≤ 0.05). However, there was no difference in liking between irradiated (600 Gy or 800 Gy) and control samples of Crimson Seedless for any attribute. The results show that there are varietal differences in response to irradiation but the overall maintenance in quality of irradiated grapes during 3 wk of storage indicates that irradiation can serve as a viable phytosanitary treatment.     

Spatial distribution of perfluoroalkyl contaminants in lake trout from the Great Lakes

Individual whole body homogenates of 4 year old lake trout (Salvelinus namaycush) samples collected in 2001 from each of the Great Lakes were extracted using a novel fluorophilicity cleanup step and analyzed for perfluoroalkyl compounds (PFCs). Standard addition and internal standardization were used for quantification. Results were reported (+/- SE) for perfluorinated carboxylates (PFCAs), perfluorinated sulfonates (PFSAs), and unsaturated fluorotelomer carboxylates (8:2 and 10:2 FTUCA). The lowest average concentration of sigmaPFC was found in samples from Lake Superior (13+/-1 ng g(-1)), while the highest average concentration was found in samples from Lake Erie (152+/-14 ng g(-1)). Samples from Lake Ontario (60+/-5 ng g(-1)) and Lake Huron (58 +/-10 ng g(-1)) showed similar average sigmaPFC concentrations, although the perfluorinated sulfonate/carboxylate ratios were different. The major perfluoroalkyl contaminant observed was perfluorooctane sulfonate (PFOS) with the highest concentration found in samples from Lake Erie (121+/-14 ng g(-1)), followed by samples from Lake Ontario (46+/-5 ng g(-1)), Lake Huron (39 +/-10 ng g(-1)), Lake Michigan (16+/-3 ng g(-1)), and Lake Superior (5+/-1 ng g(-1)). Perfluorodecane sulfonate (PFDS) was detected in 89% of the samples, with the highest concentration in Lake Erie samples (9.8+/-1.6 ng g(-1)), and lowest concentration in samples from Lake Superior (0.7 +/- 0.1 ng g(-1)). Statistically significant correlations were observed between PFOS and PFDS concentrations, and PFOS concentration and body weight, respectively. The PFCAs were detected in all samples, with the highest total average concentration in samples from Lake Erie (19 ng g(-1)), followed by samples from Lake Huron (16 ng g(-1)), Lake Ontario (10 ng g(-1)), Lake Michigan (9 ng g(-1)) and Lake Superior (7 ng g(-1)). The compounds with significant contributions to the sigmaPFCA concentrations were PFOA and C9-C13-PFCAs. The 8:2 FTUCA was detected at concentrations ranging between 0.1 and 0.2 ng g-1, with the highest level in samples showing also elevated concentrations of PFOA (4.4 ng g(-1) for Lake Michigan vs 1.5 ng g(-1) for all other samples). The 10:2 FTUCA was detected only in 9% of all samples (nd, 45 pg g(-1)). For those PFCs where we determined lake water concentrations, the highest log BAFs were calculated for PFOS (4.1), PFDA (3.9), and PFOSA (3.8).     

Geography and stage of development affect persistent organic pollutants in stranded and wild-caught harbor seal pups from central California

Persistent organic pollutants have been associated with disease susceptibility and decreased immunity in marine mammals. Concentrations of polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), polybrominated diphenyl ethers (PBDEs), chlordanes (CHLDs), and hexachlorocyclohexane isomers (HCHs) were evaluated in terms of stage of development and likely exposure routes (in utero, suckling, fasting) in the blubber of 202 stranded and wild-caught, primarily young of the year (n = 177), harbor seals (Phoca vitulina) in the central California coast. This is the first report of HCH concentrations in the blubber of California seals. Lipid normalized concentrations ranged from 200 to 330,000 ng/g for sum PCBs, 320-1,500,000 ng/g for sum DDTs, 23-63,000 ng/g for sum PBDEs, 29-29,000 ng/g for sum CHLDs, and 2-780 ng/g for sum HCHs. The highest concentrations were observed in harbor seal pups that suckled in the wild and then lost mass during the post-weaning fast. Among the pups sampled in the wild and those released from rehabilitation, there were no differences in mass, blubber depth, or percent lipid although contaminant concentrations were significantly higher in the pups which nursed in the wild. When geographic differences were evaluated in a subset of newborn animals collected near their birth locations, the ratio of sum DDTs to sum PCBs was significantly greater in samples from an area with agricultural inputs (Monterey), than one with industrial inputs (San Francisco Bay). A principal components analysis distinguished between seals from San Francisco Bay and Monterey Bay based on specific PCB and PBDE congeners and DDT metabolites. These data illustrate the important influence of life stage, nutritional status, and location on blubber contaminant levels, and thus the need to consider these factors when interpreting single sample measurements in marine mammals.     

The impact of driver education on self-reported collisions among young drivers with a graduated license

In this study, we assess the impact of driver education on the risk of collisions in a Graduated Licensing System (GLS). Ontario's GLS requires all new drivers to successfully pass through two stages of graduated license (referred to as G1 and G2, respectively) before full licensure is granted. Surveys of driving behaviour and related factors were administered to Grades 11 and 12 students with a graduated license in seven Ontario schools in 1996 and 1998. A total of 1533 students completed the survey in 2 years. Multivariate logistic regression analysis revealed a significantly lower odds of self-reported collision involvement among G1 license holders with driver education (OR: 0.31, 95% CI: 0.12-0.83). No significant effects were observed for G2 license holders. Other significant predictors of collisions include sex of driver, months of licensure and kilometers driven for G2 license holders. These results suggest that the impact of driver education may be dependent on the stage of driver learning in which it occurs.     

Lethality of commercial whole-muscle beef jerky manufacturing processes against Salmonella serovars and Escherichia coli O157:H7

Thermal processes used in making whole-muscle beef jerky include a drying step, which may result in enhanced pathogen thermotolerance and evaporative cooling that reduce process lethality. Several salmonellosis outbreaks have been associated with beef jerky. In this study, a standardized process was used to inoculate beef strips with five-strain cocktails of either Salmonella serovars or Escherichia coli O157:H7, to marinate the strips at pH 5.3 for 22 to 24 h at 5 degrees C, and to convert the strips to jerky using various heating and drying regimes. Numbers of surviving organisms were determined during and after heating and drying. Salmonella reductions of > or = 6.4 log CFU and similar reductions in E. coli O157:H7 were best achieved by ensuring that high wet-bulb temperatures were reached and maintained early in the process (51.7 or 54.4 degrees C for 60 min, 57.2 degrees C for 30 min, or 60 degrees C for 10 min) followed by drying at 76.7 degrees C (dry-bulb temperature). Processes with less lethality that reduced counts of both pathogens by > or = 5.0 log CFU were (i) heating and drying at 76.7 degrees C (dry bulb) within 90 min of beginning the process, (ii) heating for successive hourly intervals at 48.9, 54.4, 60, and 76.7 degrees C (dry bulb), and (iii) heating at 51.7 degrees C (dry bulb) and then drying at 76.7 degrees C (dry bulb), starting before the product water activity dropped below 0.86. In several trials, separate beef strips were inoculated with a commercial Pediococcus acidilactici starter culture as a potential surrogate for evaluating pathogen thermotolerance. The results of these trials suggested that this experimental approach may be useful for in-plant validation of process lethality.