Thermodynamic, spectroscopic, and computational evidence for the irreversible conversion of beta- to alpha-endosulfan.     

W F Schmidt  S Bilboulian  C P Rice  J C Fettinger  L L McConnell  C J Hapeman 《Journal of agricultural and food chemistry》2001,49(11):5372-5376

Previous studies have provided unequivocal evidence for the symmetry of beta-endosulfan and the corresponding asymmetry of alpha-endosulfan; the conversion of beta-endosulfan to alpha-endosulfan was identified. In this study, evidence from differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR) experiments combined with computational chemistry calculations was used to propose a molecular mechanism for the corresponding conformational changes that occur in this process. DSC and NMR data of mixtures indicated that both isomers can influence the conformer populations in the solid, solution, and vapor phase. Computational chemistry demonstrated that the relative S==O configuration between alpha- and beta-isomers can be the intermediate state through which the conformations of alpha- and beta-isomers affect each other. Furthermore, calculations for mixtures indicated that the asymmetrical conformation of the sulfite in alpha-endosulfan can induce asymmetry in beta-endosulfan, and conversion to alpha-endosulfan occurs from this transition state.  相似文献   

Genetically modified organisms in food-screening and specific detection by polymerase chain reaction   总被引：20，自引：0，他引：20  

Vollenhofer S  Burg K  Schmidt J  Kroath H 《Journal of agricultural and food chemistry》1999,47(12):5038-5043

PCR methods for the detection of genetically modified organisms (GMOs) were developed that can be used for screening purposes and for specific detection of glyphosate-tolerant soybean and insect-resistant maize in food. Primers were designed to amplify parts of the 35S promoter derived from Cauliflower Mosaic Virus, the NOS terminator derived from Agrobacterium tumefaciens and the antibiotic marker gene NPTII (neomycin-phosphotransferase II), to allow for general screening of foods. PCR/hybridization protocols were established for the detection of glyphosate-tolerant RoundUp Ready soybean and insect-resistant Bt-maize. Besides hybridization, confirmation of the results using restriction analysis was also possible. The described methods enabled a highly sensitive and specific detection of GMOs and thus provide a useful tool for routine analysis of raw and processed food products.  相似文献   

Carbon and nitrogen isotope composition of bulk soils, particle-size fractions and organic material after treatment with hydrofluoric acid   总被引：5，自引：1，他引：5  

M. W. I. Schmidt  & G. Gleixner 《European Journal of Soil Science》2005,56(3):407-416

Soils and sediments contain only small amounts of organic matter, and large concentrations of paramagnetic metals can give poor solid‐state nuclear magnetic resonance (NMR) spectra of organic matter. Pretreatment of samples with hydrofluoric acid (HF) dissolves significant proportions of the mineral matrix and extracts paramagnetic elements. We investigated the effects of 10% HF treatment on the stable isotope content of carbon (C) and nitrogen (N) of organic matter from soils, composts and shales. Additionally we inferred molecular and isotopic characteristics of lost materials from calculations of isotope mass balances. Treatment with HF enriched C and N in mineral samples substantially (factors 2.5–42.4), except for Podzol B horizons (1.1–1.7) and organic material (1.0–1.3). After treatment most of the C (59.7–91.7%) and N (53.7–86.6%) was recovered, although changing C/N ratios often indicated a preferential loss of N‐rich material. Isotope ratios of C and N in the remaining material became more negative when net alterations exceeded 0.3‰. The isotope ratios of the lost material contained more ¹³C (1–2‰) and ¹⁵N (1–4‰) than the initial organic matter. Acid hydrolysis typically removes proteins, amino acids and polysaccharides, all of which are enriched in ¹³C, and in the case of proteins and amino acids, enriched in ¹⁵N as well. We conclude that HF treatment released fresh, soluble, probably microbial, biomass in addition to carbohydrates. Net changes of the bulk chemical composition of organic matter were small for most soils, size fractions and plant material, but not for samples containing little organic matter, or those rich in easily soluble organic matter associated with iron oxides, such as Podzol B horizons.  相似文献   

Translocation, penetration, and metabolism of O-(4-bromo-2,5-dichlorophenyl)-O,O-dimethylphosphorothioate (bromophos) in tomato plants     

Stiasni M  Deckers W  Schmidt K  Simon H 《Journal of agricultural and food chemistry》1969,17(5):1017-1020

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Effective separation of potent antiproliferation and antiadhesion components from wild blueberry (Vaccinium angustifolium Ait.) fruits     

Schmidt BM  Howell AB  McEniry B  Knight CT  Seigler D  Erdman JW  Lila MA 《Journal of agricultural and food chemistry》2004,52(21):6433-6442

Extracts from wild blueberry (Vaccinium angustifolium Ait.) were separated into proanthocyanidin-rich fractions using liquid vacuum and open column chromatography on Toyopearl and Sephadex LH-20, respectively. Fractions were characterized using analytical tools including mass spectrometry and NMR spectroscopy; fraction composition was correlated with bioactivity using antiproliferation and antiadhesion in vitro assays. There was a significant positive correlation between proanthocyanidin content of different fractions and biological activity in both the antiproliferation and antiadhesion assays. Two fractions containing primarily 4-->8-linked oligomeric proanthocyanidins with average degrees of polymerization (DPn) of 3.25 and 5.65 inhibited adhesion of Escherichia coli responsible for urinary tract infections. Only the fraction with a DPn of 5.65 had significant antiproliferation activity against human prostate and mouse liver cancer cell lines. These findings suggest both antiadhesion and antiproliferation activity are associated with high molecular weight proanthocyanidin oligomers found in wild blueberry fruits.  相似文献   

Long-term sulfate dynamics at lange bramke (Harz) used for testing two acidification models     

H. Lange  M. Hauhs  S. Schmidt 《Water, air, and soil pollution》1995,79(1-4):339-351

At Lange Bramke (Harz) soil solution and runoff concentrations of major elements were observed over 16 yr. During this period acid deposition was high but showed a marked decrease of H⁺ and SO ₄ ^2? both in concentrations and fluxes over the last five years. Among others, this record reveals the following patterns: seasonality in the signals for SO ₄ ^2? and NO ₃ ^? in runoff which are synchronous; an accumulation of SO ₄ ^2? in the soil, initially up to 50% of the deposition fluxes; apparently no correlation between runoff and SO ₄ ^2? concentration, and no long-term trend in runoff concentration of SO ₄ ^2? . In this paper we use these patterns in the data set from Lange Bramke to test two established acidification models. The test criterion is that the algorithms employed by the SO ₄ ^2? modules of these models must be able to reproduce these features. To that end, both models need not to be run as it can be shown that even with completely unrestricted parameter values the two algorithms are unable to match the observed SO ₄ ^2? dynamics. The MAGIC model (Cosbyet al., 1985) is unable to reproduce, given the existence of net SO ₄ ^2? accumulation, the constant SO ₄ ^2? concentration in runoff during the last 16 years. The second model, BEM (Prenzel, 1986), is succesful in reconstructing the constant SC>4~ levels in runoff. However, on a monthly time scale BEM predicts a shift between the periodic maximum concentrations of SO ₄ ^2? and NO ₃ ^? which is not observed in the data.  相似文献   

Fate and dispersal of recombinant bacteria in a soil microcosm containing the earthworm Lumbricus terrestris     

R. B. Henschke  E. Nücken  F. R. J. Schmidt 《Biology and Fertility of Soils》1989,7(4):374-376

Summary A model ecosystem was designed containing Lumbricus terrestris in soil. The microcosm is suitable for assessing the dispersal and survival of genetically engineered microorganisms. After the inoculation of genetically engineered microorganisms their number in the worm excretions decreased continuously to reach the level of the detection limit within 50 days.  相似文献   

Repräsentanz und Vergleichbarkeit von Daten und Flächen der Bodendauerbeobachtung     

Winfried Schrder  Gunther Schmidt  Roland Pesch 《植物养料与土壤学杂志》2003,166(5):649-659

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Isotopic labelling of earthworms: comments on the paper by Whalen and Janzen (2002)     

O. Schmidt  J. DyckmansC.M. Scrimgeour 《Soil biology & biochemistry》2003,35(6):875-876

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Microbial immobilization and mineralization of dissolved organic nitrogen from forest floors     

Bettina H.M. Schmidt  Sabine Braun  William H. McDowell 《Soil biology & biochemistry》2011,43(8):1742-1745

Dissolved organic nitrogen (DON) plays a key role in the N cycle of many ecosystems, as DON availability and biodegradation are important for plant growth, microbial metabolism and N transport in soils. However, biodegradation of DON (defined as the sum of mineralization and microbial immobilization) is only poorly understood. In laboratory incubations, biodegradation of DON and dissolved organic carbon (DOC) from Oi and Oa horizons of spruce, beech and cypress forests ranged from 6 to 72%. Biodegradation of DON and DOC was similar in most samples, and mineralization of DON was more important than microbial immobilization. Nitrate additions (0-10 mg N L⁻¹) never influenced either DON immobilization by microorganisms or mineralization. We conclude that soil microorganisms do not necessarily prefer mineral N over DON for meeting their N demand, and that biodegradation of DON seems to be driven by the microbial demand for C rather than N. Quantifying the dynamics of DON in soils should include consideration of both C and N demands by microbes.  相似文献