Regio‐ and Enantioselective Sequential Dehalogenation of rac‐1,3‐Dibromobutane by Haloalkane Dehalogenase LinB

The hydrolytic dehalogenation of rac‐1,3‐dibromobutane catalyzed by the haloalkane dehalogenase LinB from Sphingobium japonicum UT26 proceeds in a sequential fashion: initial formation of intermediate haloalcohols followed by a second hydrolytic step to produce the final diol. Detailed investigation of the course of the reaction revealed favored nucleophilic displacement of the sec‐halogen in the first hydrolytic event with pronounced R enantioselectivity. The second hydrolysis step proceeded with a regioselectivity switch at the primary position, with preference for the S enantiomer. Because of complex competition between all eight possible reactions, intermediate haloalcohols formed with moderate to good ee ((S)‐4‐bromobutan‐2‐ol: up to 87 %). Similarly, (S)‐butane‐1,3‐diol was formed at a maximum ee of 35 % before full hydrolysis furnished the racemic diol product.     

An Efficient New Pyrimidine Synthesis – a pathway to octupoles

The condensation of N,N,N′-tris(trimethylsilyl)-amidines ( 6 , 11 , 22 ) with vinamidinium salts ( 1 , 7 ) in the presence of potassium fluoride is the method of choice for the synthesis of pyrimidines ( 8 , 12 , 20 , 23 ). Octupoles comprising 1,3,5-benzene ( 8 ) and triphenylamine ( 12 , 20 ) derivatives can be prepared in high yields.     

Synthesen und Eigenschaften Mono- und diphenylsubstituierter Monothio-β-dicarbonylverbindungen und ihrer Nickel(II)chelate

Syntheses and Properties of Mono- and Disubstituted Monothio-β-dicarbonyl Compounds and their Nickel(II) chelates Reaction of phenylacetaldehyde with phosphorous oxichloride and dimethylformamide yielded 3-chloro-2-phenyl-propenal, which was converted into 2-phenyl-monothiomalonic dialdehyde 2 by treating with sodium sulfide nonahydrate. Furthermore the reactions of other mono- and diphenylsubstituted monothio-β-dicarbonyl compounds with aniline on the one side and nickel(II)acetate on the other side have been studied. It was shown, that compounds 1–6 react in different way with aniline yielding either sulfur free products or in case of 1 and 4 enaminothioketones, which are of interest as building blocks for syntheses. In contrast to this the nickel complexes of 1–6 indicates an one another similar, typical chelate structure, which have been elucidated by u.v.-vis-, i.r.- and x-ray photoelectron spectroscopy.     

Characterization of the Arcobacter contamination on Belgian pork carcasses and raw retail pork

In the present study, the occurrence of Arcobacter was assessed at four sites on 169 porcine carcasses (foreleg, chest, pelvis and ham) at different stages of slaughter and 47 pork products at retail. Carcass swab samples were enriched in Arcobacter broth containing 5-fluorouracil, amphotericine B, cefoperazone, novobiocine and trimethoprim as selective supplement. After microaerobic incubation, arcobacters were isolated using Arcobacter selective agar plates, containing the selective supplement described above. Some carcass samples and all pork samples were also examined quantitatively. All 862 isolates were identified by a species-specific m-PCR-assay and 182 isolates were further characterized by ERIC-PCR. Arcobacters were isolated from one or more sampling places on 96.4% of the carcasses, with the foreleg and the chest area as the two most contaminated sites. Furthermore, A. cryaerophilus was the most common species. Chilling decreased the number of positive carcasses, but did not eliminate all arcobacters. Direct isolation revealed that only a few carcasses were contaminated with arcobacters on foreleg and/or chest at levels higher than 10(2 )cfu/100 cm(2). Characterization demonstrated a large heterogeneity among the isolates, with ten genotypes present on more then one site per carcass. Fourteen genotypes were simultaneously present on carcasses from different herds slaughtered on the same day, which may indicate cross-contamination. Arcobacters were present in 21% of the pork samples taken at retail, but contamination levels did not exceed 100 cfu per gram. Characterization of the A. butzleri and A. cryaerophilus isolates indicated an additional contamination during processing at retail.     

Prevalence, distribution, and diversity of Listeria monocytogenes in retail environments, focusing on small establishments and establishments with a history of failed inspections

Despite growing concerns about cross-contamination of ready-to-eat foods with Listeria monocytogenes, our knowledge about the ecology and transmission of L. monocytogenes in retail establishments has remained limited. We conducted a cross-sectional study to characterize the prevalence, distribution, and subtype diversity of L. monocytogenes in 120 New York State retail deli establishments that were hypothesized to present an increased risk for environmental L. monocytogenes contamination (i.e., small establishments and establishments with a history of failed New York State Agriculture and Markets inspections). Analysis of these data along with previously reported data for 121 predominantly larger retail establishments in New York State identified establishment size, geographic location, and inspection history as significant predictors of L. monocytogenes presence and prevalence. The odds of an establishment being L. monocytogenes positive were approximately twice as high for large establishments, establishments located in New York City, or establishments with poor inspection history (as compared with establishments without these attributes), even though correlation between location and inspection history complicated interpretation of results. Within an establishment, L. monocytogenes was significantly more prevalent on nonfood contact surfaces than on food contact surfaces; prevalence was particularly high for floors and in floor drains, sinks, the dairy case, and milk crates. L. monocytogenes subtype diversity differed between sites, with lineage I isolates significantly associated with nonfood contact surfaces and lineage II isolates significantly associated with food contact surfaces. Isolates belonging to the same ribotype were often found dispersed across multiple sites within an operation.     

Methods for determining pesticides and polychlorinated biphenyls in food samples--problems and challenges

Determination of residual amounts of pesticides and polychlorinated biphenyls (PCBs) in food samples requires the use of specific techniques regarding sample preparation as well as instrumental analysis which should be characterized by a very low detection limit. A problem associated with the use of pesticides and PCBs is the need for controlling their residues in the environment, particularly in food, as these chemicals show a propensity to accumulate. The analysis of food samples for the presence of pesticides and PCBs brings on many difficulties because of the specificity of sample preparation consisting of multistep purification procedures of samples that contain trace amounts of an analyte. Concentration determinations of pollutants that easily dissolve in complex matrices, particularly in the presence of a large apportionment of interfering substances, pose a big challenge. Therefore, the basic step in food analysis for the presence of pesticides and PCBs is sample preparation which mainly consists of analyte enrichment and the removal of interfering substances. But all steps of the analytical procedure that include sample collection and preparation, extraction of analytes from matrix, extract purification, and final determination, are very significant; their precision and correct application have a decisive effect on the final result.     

Preparation of New Benzoylthiourea-functionalized PVC Resin and Investigation of the Complexation Properties

Poly(vinyl chloride) (PVC) have been modified, using a two-step process with amine and benzoyl isothiocyanate groups. In the present paper, PVC-N,N′-(3,3′-(ethane-1,2-diyl bis(azanediyl))bis (propane-3,1-diyl))bis(azanediyl)bis(thioxomethylene) dibenzamide one have been synthesized. Its complexes have been prepared with CoCl₂, NiCl₂, PtCl₂ and HgCl₂. These compounds have been characterized by elemental analysis, FT-IR, UV-VIS, TGA, SEM, ^IH NMR.     

Fitting smooth curves to noisy indicator-dilution and other unimodal data.

A linear least squares method for fitting noisy unimodal functions such as indicator-dilution curves with piecewise stretched exponential functions is described. Stretched exponential functions have the form z(t) = alpha t beta e gamma t, where alpha, beta, and gamma are constants. These functions are particularly useful for fitting experimental data that spans several orders of magnitude is non-Gaussian, high skewed, and long tailed. In addition, the method allows for specifying external restrictions on the smooth curve that might be required by physical constraints on the data. These constraints can take the form of restrictions on the value of the fitting function at certain points or the value of the derivatives in certain regions. To determine the necessary constants in the fitting functions, a linear least squares problem with linear equality and inequality constraints is solved.     

Säurekatalysierte Umsetzungen von Aromaten mit Alkanen und Cycloalkanen. IX. Alkylierungen mit 2,2,4-Trimethylpentan (Isooctan)

Acid-catalyzed Reactions of Aromatic Hydrocarbons with Alkanes and Cycloalkanes. IX. Alkylations with 2,2,4-Trimethylpentane (Isooctane) The non-conventional alkylation of benzene, toluene, ethyl- and isopropylbenzene, fluoro- and chlorobenzene with 2,2,4-trimethylpentane in the presence of acid catalysts is described. The composition of the rather complex reaction mixtures is determined by gas-liquid chromatography and mass spectrometry, tert. butylarenes being the main products beside alkylsubstituted indanes and tetralines. Their formation is interpreted as a competition between fragmentation and isomerization of the alkylating agent. By use of trifluoromethanesulfonic acid or combinations of catalysts from HF or HSO₃F with variant metallic fluorides at lower temperatures the selectivity of the reaction may be partially raised.